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Title: The manufacture of mineral and lake pigments : Containing directions for the manufacture of all artificial artists' and painters' colours, enamel colours, soot and metallic pigments
Author: Bersch, Josef
Language: English
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THE MANUFACTURE OF MINERAL AND LAKE PIGMENTS
THE MANUFACTURE OF
MINERAL AND LAKE PIGMENTS
CONTAINING DIRECTIONS FOR THE MANUFACTURE
OF ALL ARTIFICIAL ARTISTS’ AND PAINTERS’ COLOURS,
ENAMEL COLOURS, SOOT AND METALLIC PIGMENTS
A Text-Book For
Manufacturers, Merchants, Artists and Painters
BY
DR. JOSEF BERSCH
TRANSLATED FROM THE SECOND, REVISED EDITION
BY
ARTHUR C. WRIGHT, M.A. (OXON.), B. SC. (LOND.)
FORMERLY ASSISTANT LECTURER AND DEMONSTRATOR
IN CHEMISTRY AT THE YORKSHIRE COLLEGE, LEEDS
_WITH FORTY-THREE ILLUSTRATIONS IN THE TEXT_
LONDON
SCOTT, GREENWOOD & CO.
Publishers of the “Oil and Colourman’s Journal”
19 LUDGATE HILL, E.C.
1901
[_The sole right of publishing this work
in English rests with the above firm._]
PREFACE.
We know hardly another branch of chemical technology which has made
such remarkable advances of late as the manufacture of colours; a large
number of pigments have been recently discovered, distinguished by
beauty of shade and permanence. Chemists are continually endeavouring
to replace handsome and poisonous colours by others equally handsome
but non-poisonous.
In writing this work I have endeavoured to give it such a character
that it may be a text-book for the practical man, only those methods
have been given which certainly lead to a good result; in the case of
new pigments I have only described methods of preparation which I have
myself found to give good results.
Since it cannot be imagined that any one quite ignorant of chemistry
could successfully manufacture colours (colours being always made by
chemical processes which occasionally are rather complicated), I have,
therefore, presupposed a knowledge of the principles of chemistry. In
the short sketch of the chemical properties of the raw materials used
in making ordinary pigments, the principal properties of the materials
used by the colour maker are given.
In order to make this treatise useful to dealers in and consumers of
colours, the chapters dealing with the examination of pigments have
been so arranged that the nature or adulteration of a pigment can be
determined quickly and with certainty by any one.
Recipes, which originated at a time when empiricism ruled in chemistry,
have been omitted, since they would only detract from the clearness of
the matter.
As far as it is possible I have avoided the “recipe fetish,” and have
endeavoured to make clear to the reader the chemical processes to which
regard must be had in the manufacture of the different pigments. Since
the appearance of the first edition there have been many valuable
innovations in the mineral colour industry, to which regard has been
given in preparing this second edition in so far as they possess a
really practical value.
A critical examination of proposals and formulæ, which are found in
large numbers in the journals, has been avoided, since I wished to
keep for my book that character of a reliable text-book and book of
reference which was ascribed to it in the form of its first edition.
DR. JOSEF BERSCH.
TRANSLATOR’S PREFACE.
If excuse be needed for presenting a translation of Dr. Bersch’s book
at so long an interval after the publication of the original (1893),
it must be sought in the paucity of the English literature on the
subject. It is hoped that the practical nature of the work will make it
acceptable to the English reader.
The subject-matter of the original has been preserved in the
translation without alteration or addition, with the exception of an
unimportant change in the order of arrangement.
The metric system of weights and measures has been used throughout;
for the convenience of those who are not familiar with this system,
directions are given in an appendix for converting into English weights
and measures.
The section on paint grinding (Chapter LXIX.) is perhaps somewhat
incomplete; for a more detailed and modern account of this branch of
the subject the reader is referred to _Practical Paint Grinding_, by
Mr. J. Cruickshank Smith, B. Sc., shortly to be issued by the same
publishers.
A. C. WRIGHT.
HULL, _January, 1901_.
TABLE OF CONTENTS.
PAGE
CHAPTER I. INTRODUCTION 1
CHAPTER II. THE PHYSICO-CHEMICAL BEHAVIOUR OF PIGMENTS 8
CHAPTER III. RAW MATERIALS EMPLOYED IN THE MANUFACTURE
OF PIGMENTS 14
CHAPTER IV. ASSISTANT MATERIALS 16
Water—Chlorine—Ammonia—The Hydrometer—Sal Ammoniac or
Ammonium Chloride—Ammonium Sulphide.
Acids.—Hydrochloric Acid—Sulphuretted Hydrogen
—Sulphuric Acid: Oil of Vitriol, Nordhausen
Sulphuric Acid—Nitric Acid—_Aqua Regia_
—Carbon—Carbonic Acid Gas.
Organic Acids.—Acetic Acid—Oxalic Acid—Tartaric Acid.
CHAPTER V. METALLIC COMPOUNDS 32
Alkalis.—Potassium Compounds—Potassium Carbonate
—Potassium Hydroxide—Potassium Nitrate—Potassium
Bitartrate—Potassium Bichromate—Potassium Sodium
Chromate—Chrome Alum—Potassium Ferrocyanide
—Potassium Ferricyanide—Sodium Salts—Sodium
Carbonate—Sodium Hydroxide—Sodium Thiosulphate
—Sodium Chloride—Salts of the Alkaline Earth Metals.
Calcium Compounds.—Calcium Oxide—Calcium Hydroxide
—Calcium Carbonate—Calcium Sulphate—Calcium Phosphate
—Magnesium Carbonate—Barium Compounds—Barium Chloride.
Aluminium Compounds—Aluminium Sulphate.
The Alums.—Potassium Aluminium Alum—Roman Alum—Soda
Alum—Ammonia Alum—Alumina and Hydrate of Alumina.
Compounds of the Heavy Metals.—Zinc Compounds—Cadmium
Compounds—Iron Compounds—Ferrous Sulphate—Ferrous
Chloride—Manganese Compounds—Nickel Compounds—Cobalt
Compounds—Chromium Compounds—Molybdenum, Tungsten and
Vanadium Compounds—Antimony Compounds—Bismuth Compounds
—Tin Compounds—Arsenic Compounds—Lead Compounds
—Lead Sulphate—Lead Nitrate—Lead Acetate—Basic Lead
Acetate—Lead Chloride—Copper Compounds—Copper Sulphate
—Copper Nitrate—Copper Acetate—Mercury Compounds
—Mercurous Nitrate—Mercuric Nitrate—Mercurous Chloride
—Mercuric Chloride—Silver Compounds—Gold Compounds.
CHAPTER VI. THE MANUFACTURE OF MINERAL PIGMENTS 71
White Mineral Pigments—White Lead.
CHAPTER VII. THE MANUFACTURE OF WHITE LEAD 77
Manufacture of White Lead from Metallic Lead.—Dutch
Process: Casting the Lead into Sheets—Building
up the Stacks—Removal and Grinding of the White
Lead—White Lead Mills—Hard White Lead—Soft White
Lead.—German Process.—French Process: Preparation
of the Solution of Basic Lead Acetate—Preparation
of the Carbonic Acid and Precipitation of the White
Lead—Manufacture of White Lead by Means of Natural
Carbonic Acid.—English Process.—Other Methods.
—Oxychloride White Lead: Lead Sulphite—Lewis
& Bartlett’s White Lead Pigment.—White Lead
-Antimony Pigments: Lead Antimonite—Lead Antimonate.
CHAPTER VIII. ENAMEL WHITE 116
Lithopone.
CHAPTER IX. WASHING APPARATUS 120
Filter Presses.
CHAPTER X. ZINC WHITE 126
Griffith’s Zinc White—Tungsten White—White Antimony
Pigments: Antimony Trioxide—Antimony Oxychloride
—Bismuth White—Tin White—Manganese White
—Magnesia White or Mineral White—Annaline.
CHAPTER XI. YELLOW MINERAL PIGMENTS 133
CHAPTER XII. CHROME YELLOWS 134
Lead Chrome Yellow—Preparation of the Lead Solution
—Precipitation of the Chrome Yellow
—The Pale Chrome Yellows.
CHAPTER XIII. LEAD OXIDE PIGMENTS 143
Red Lead, Minium.
CHAPTER XIV. OTHER YELLOW PIGMENTS 148
Cassel Yellow—Montpellier Yellow—Turner’s Yellow
or English Yellow—Naples Yellow—Antimony Yellow
—Calcium Chrome Yellow—Barium Yellow, Yellow
Ultramarine or Permanent Yellow—Zinc Chrome Yellow
—Cadmium Chrome Yellow—Cadmium Yellow—Lead Iodide
—Mars Yellow—Siderin Yellow—Aureolin—Tungsten
Yellow—Nickel Yellow—Mercury Yellow or Turpeth
Mineral—Yellow Arsenic Pigments—Lead Arsenite
—Thallium Pigments.
CHAPTER XV. MOSAIC GOLD 160
Chrysean.
CHAPTER XVI. RED MINERAL PIGMENTS 163
Vermilion—Black Mercuric Sulphide—Red Mercuric Sulphide.
CHAPTER XVII. THE MANUFACTURE OF VERMILION 166
Dry Method: Chinese Vermilion.—Wet Method:
Firmenich’s Method—Liebig’s Process—Infusible
White Precipitate—Electrolytic Process
—Mercuric Iodide.
CHAPTER XVIII. ANTIMONY VERMILION 178
Appendix—Antimony Blue.
CHAPTER XIX. FERRIC OXIDE PIGMENTS 180
Vogel’s Iron Red—Macay’s English Red—Indian Red.
CHAPTER XX. OTHER RED MINERAL PIGMENTS 186
Chrome Red or Chrome Vermilion—Cobalt Red—Cobalt
Magnesia Red—Cobalt Arsenate—Chromium Stannate
—Silver Chromate.
CHAPTER XXI. PURPLE OF CASSIUS 190
Magnesia Gold Purple—Alumina Gold Purple.
CHAPTER XXII. BLUE MINERAL PIGMENTS—IRON-CYANOGEN PIGMENTS 194
Chinese Blue—Prussian Blue—Mineral Blue—Soluble
Prussian Blue—Special Processes for the
Manufacture of Chinese Blue—Turnbull’s Blue
—Antwerp Blue.
CHAPTER XXIII. ULTRAMARINE 204
CHAPTER XXIV. THE MANUFACTURE OF ULTRAMARINE 211
Preparation of Mixtures for Ultramarine—Ultramarine
Violet—Chlorine and Steam Process—Hydrochloric
Acid and Air Process—Ammonium Chloride Process
—Pale Blue Ultramarine—Ultramarine Red.
CHAPTER XXV. BLUE COPPER PIGMENTS 226
Bremen Blue and Green—Neuberg Blue—Lime Blue
—Payen’s Mountain Blue—Oil Blue—Copper Hydroxide.
CHAPTER XXVI. BLUE COBALT PIGMENTS 230
Cobalt Blue, Thénard’s Blue, Cobalt Ultramarine,
King’s Blue, Leyden Blue—Cæruleum—Cobalt
Zinc Phosphate.
CHAPTER XXVII. SMALTS 233
Preparation of the Charge—Fusion of the Charge
—Grinding the Fused Mass—Tungsten Blue
—Tessié du Motay’s Blue—Molybdenum Blue.
CHAPTER XXVIII. GREEN MINERAL PIGMENTS—GREEN COPPER PIGMENTS 240
Green Copper Pigments: Copper Carbonate—Copper Arsenite
—Scheele’s Green—Swedish Green—Brunswick Green
—Green Verditer—Neuwied Green—Copper Oxychloride.
CHAPTER XXIX. EMERALD GREEN 244
Manufacture of Emerald Green from Verdigris—Manufacture
of Emerald Green from Copper Sulphate—Mitis
Green or Vienna Green—Copper Stannate—Kuhlmann’s
Green—Elsner’s Green—Casselmann’s Green—Lime
Green—Patent Green—Copper Borate—Copper Silicate
(Egyptian Blue).
CHAPTER XXX. VERDIGRIS 252
Blue Verdigris—Distilled or Crystallised Verdigris
—German Verdigris.
CHAPTER XXXI. CHROMIUM OXIDE 260
Chrome Green.
CHAPTER XXXII. OTHER GREEN CHROMIUM PIGMENTS 264
Guignet’s Green—Emerald Green—Chrome Green Lake
—Turkish Green—Leaf Green.—Chromium Phosphate
Pigments: Arnaudan’s Green—Plessy’s Green
—Schnitzer’s Green—Chromaventurine—Chrome
Blue (Garnier).
CHAPTER XXXIII. GREEN COBALT PIGMENTS 268
Cobalt Green.
CHAPTER XXXIV. GREEN MANGANESE PIGMENTS 270
Manganese Green—Rosenstiehl’s Green—Böttger’s Barium
Green—Manganous Oxide—Manganese Blue.
CHAPTER XXXV. COMPOUNDED GREEN PIGMENTS 273
Chrome Green—Elsner’s Chrome Green—Silk Green
—Natural Green—Non-arsenical Green.
CHAPTER XXXVI. VIOLET MINERAL PIGMENTS 276
Chromic Chloride—Manganese Violet—Tin Violet,
Mineral Lake—Copper Violet, Guyard’s Violet.
CHAPTER XXXVII. BROWN MINERAL PIGMENTS 279
Lead Brown—Manganese Brown—Pyrolusite Brown
—Prussian Brown—Iron Brown—Copper Brown
—Chrome Brown—Cobalt Brown.
CHAPTER XXXVIII. BROWN DECOMPOSITION PRODUCTS 283
Humins—Bistre.
CHAPTER XXXIX. BLACK PIGMENTS 285
Charcoal Blacks: True Charcoal Black—Vine Black
—Vine Black from Wine Lees—Vine Black from
Pressed Grapes—Bone Black or Ivory Black.
CHAPTER XL. MANUFACTURE OF SOOT PIGMENTS 294
The Manufacture of Soot Blacks on the Large Scale.
CHAPTER XLI. MANUFACTURE OF LAMP BLACK 307
Calcination of the Soot—Pine Black.
CHAPTER XLII. THE MANUFACTURE OF SOOT BLACK WITHOUT CHAMBERS 313
CHAPTER XLIII. INDIAN INK 316
Neutral Tint Black—Appendix: Black Mineral Pigments
—Chrome Copper Black—Chrome Black.
CHAPTER XLIV. ENAMEL COLOURS 319
White Enamels—Coloured Enamels: Yellow Enamels—Red
Enamel—Blue Enamels—Green Enamel—Violet Enamel
—Black Enamel.
CHAPTER XLV. METALLIC PIGMENTS 326
Shell-Gold—Shell-Silver—Imitation Silver.
CHAPTER XLVI. BRONZE PIGMENTS 329
Electrolytic Copper Bronze—Tungsten Bronze Pigments.
CHAPTER XLVII. VEGETABLE BRONZE PIGMENTS 339
Appendix: The Brocade Pigments.
PIGMENTS OF ORGANIC ORIGIN.
CHAPTER XLVIII. LAKES 343
CHAPTER XLIX. YELLOW LAKES 348
Dutch Pink—Weld Lake—Gamboge Lake—Prepared
Gamboge—Fustic Lake—Quercitron Lake—Purree
or Indian Yellow—The Colouring Matter of
Saffron—Colouring Matter of Gardinia Grandiflora.
CHAPTER L. RED LAKES 354
Cochineal and Carmine
CHAPTER LI. THE MANUFACTURE OF CARMINE 357
Cenette’s Method—Munich, Vienna, Paris or Florentine
Lake—Ammonia-Cochineal.
CHAPTER LII. THE COLOURING MATTER OF LAC 363
Lac Dye.
CHAPTER LIII. SAFFLOWER OR CARTHAMINE RED 366
Safflower Carmine—Alkanet.
CHAPTER LIV. MADDER AND ITS COLOURING MATTERS 370
Garancin—Garanceux—Madder Extract—The Constituents
of Madder.
CHAPTER LV. MADDER LAKES 375
Madder Carmine.
CHAPTER LVI. MANJIT (INDIAN MADDER) 378
Chica Red, Curucuru, Carajuru—Bigonia Chica.
CHAPTER LVII. LICHEN COLOURING MATTERS 380
Archil—French Purple—Cudbear—Litmus.
CHAPTER LVIII. RED WOOD LAKES 384
CHAPTER LIX. THE COLOURING MATTERS OF SANDALWOOD
AND OTHER DYE-WOODS 388
CHAPTER LX. BLUE LAKES 390
Indigo—The Constituents of Indigo.
CHAPTER LXI. INDIGO CARMINE 394
Indigo Mills—Blue Lake.
CHAPTER LXII. THE COLOURING MATTER OF LOGWOOD 398
Logwood Extract—Kohlrausch’s Process for Obtaining
Concentrated Extracts of Colouring Matters
and Tannins.
CHAPTER LXIII. GREEN LAKES 409
Chlorophyll—Sap Green—Chinese Green, Lokao
—Charvin’s Green.
CHAPTER LXIV. BROWN ORGANIC PIGMENTS 414
Asphaltum—Sepia.
CHAPTER LXV. SAP COLOURS 416
CHAPTER LXVI. WATER COLOURS 419
Moist Water Colours.
CHAPTER LXVII. CRAYONS 423
Crayons for Earthenware.
CHAPTER LXVIII. CONFECTIONERY COLOURS 427
CHAPTER LXIX. THE PREPARATION OF PIGMENTS FOR PAINTING 429
Paint Mills.
CHAPTER LXX. THE EXAMINATION OP PIGMENTS 434
Mineral Pigments—Examination with the Blowpipe
—Reactions of the White Pigments—Reactions
of the Yellow Pigments—Reactions of the Red
Pigments—Reactions of the Blue Pigments
—Reactions of the Green Pigments—Reactions
of the Brown Pigments—Reactions of the Black
Pigments.
CHAPTER LXXI. EXAMINATION OF LAKES 445
Reactions of the Organic Colouring Matters.
CHAPTER LXXII. THE TESTING OF DYE-WOODS 449
The Colorimeter.
CHAPTER LXXIII. THE DESIGN OF A COLOUR WORKS 457
CHAPTER LXXIV. COMMERCIAL NAMES OF PIGMENTS 460
APPENDIX.
THE CONVERSION OF METRIC INTO ENGLISH WEIGHTS AND MEASURES
—CENTIGRADE AND FAHRENHEIT THERMOMETER SCALES 469
INDEX.
CHAPTER I.
INTRODUCTION.
It is doubtful whether another branch of applied chemistry is recorded
of so great an age as the colour industry; at the present time there
is hardly a race on the face of the earth which does not make use of
colours in some form, either for the decoration of their persons or
surroundings. The art of preparing colours is as ancient as their
use. It is true that we find from the most remote historical records
that the so-called earth colours were almost solely employed, and
principally those which exist ready formed in nature. But these natural
colours also require their particular process of preparation before
they fulfil their object, even though this be merely a mechanical
operation, such as powdering or levigating. That the oldest nations of
whom we possess lasting records, either written or otherwise, really
understood the preparation of colours by chemical processes is shown
by the common occurrence in the Egyptian mural pictures of figures
clad in brightly coloured garments, a proof that the Egyptians not
only understood the science of colour manufacturing, but also the more
advanced art of fastening colours upon fabrics—dyeing.
The writings of the ancient Greeks, and in part also the scanty remains
of their buildings, prove to us completely that they understood the
use of colours to such an advanced degree that they already employed
them for pictures as works of art. That the Greeks were also acquainted
with the preparation of colours and dyeing follows from various
passages from the classical writers, in which magnificently decorated
rooms and beautifully coloured garments are often described.
Among the Romans, who were the pupils of the Greeks in the arts and
manufactures, the prodigal luxury which existed in Rome, especially
under the emperors, caused a great demand for colours, which were used
in the most profuse manner for the decoration of house and attire. The
Roman colour makers had advanced so far in their art that they could
colour the human hair rose-red.
A glance at East Indian fabrics and pictures, or at the ancient Chinese
buildings, whose colouring is a matter of marvel to-day, shows that
the Oriental were not behind the Western nations in the discovery of
colours and the art of manufacturing them.
In so old an industry it is not remarkable that great changes have
taken place in the course of time. The thousands and thousands of
experiments made by the alchemists in the attempt to prepare gold
failed in their main object, but the tremendous expenditure of time and
trouble in this work was not fruitless; upon the great mass of chemical
facts discovered by the alchemists were laid the foundations of
scientific chemistry. We find on reading the writings of the alchemists
that the colour industry is indebted to them for an immense number of
its products; the reason being that the alchemists worked by preference
on metals, earths and mineral compounds, and from these substances a
large number of colours are obtainable, of which many are still in use
to-day, and, on account of their cheapness, will continue in use.
The period in which the painters were also the colour makers lies not
far behind us. The preparation of many a colour of particular beauty
was treated by the fortunate owner of the recipe as a great secret. It
was sold by him at a great price. What a difference between that time
and the present! There is now no painter among civilised races to whom
it would occur to prepare his own colours; the chemical works provide
them for him at a low price and in such a condition that they can be
immediately used for painting. The Italian painters prepared the highly
prized blue pigment, ultramarine, by laborious toil from the costly
_lapis lazuli_; to-day, this same colour, more beautiful and deeper
in hue, is made by several works, and sold at a price which bears no
comparison with that of the colour obtained from the mineral. The
latter was worth many times its weight in gold: a pound of the finest
ultramarine can now be bought for a shilling or two.
We find a similar comparison in the case of the fine scarlet pigment
known as vermilion: formerly the natural vermilion, cinnabar, was
sold at a very high price; at the present time the finest vermilion,
prepared artificially, can be bought at a low rate. It is no longer
necessary for any one to use natural Chinese vermilion as an artists’
colour.
Whilst formerly mineral colours were used in great preponderance, we
now know a great number of vegetable and animal colouring matters. The
discovery of the sea route to India and the discovery of America had an
important influence in this development. From these countries, as from
other tropical lands, come the majority of the plants which contain
colouring matters. The attempt to change these colouring matters into
insoluble compounds led to the discovery of the lake pigments.
With the advance of chemical knowledge the number of colours grew
apace; _e.g._, the discovery of chromium was of great importance
to the colour industry: it presented us with a large number of new
colours. To a more limited extent, the discovery and study of uranium,
molybdenum and other metals were the occasions for the invention of new
colours.
In more recent times, efforts in the colour industry have been
especially directed to making colours more permanent and, at the same
time, harmless. In the first respect, the position at present leaves
much to be desired; but, as regards the second property, great advances
have been made. The colours in use in former days were almost all very
poisonous compounds; the greater number were derived from lead, copper,
mercury or arsenic. More recently these poisonous substances have
been in many cases replaced by innocuous materials, so that among the
colours now in use, though the list is much more comprehensive than of
old, there are but few poisonous to a high degree.
In all civilised states the use of poisonous colours has been much
restricted by law, and in those cases in which an article is to be
manufactured for use as food the employment of such colouring matters
has been absolutely forbidden. For example, in Germany by the law
of 5th July, 1887, concerning the use of dangerous colours in the
preparation of foods and condiments, the application of the permissible
colours has been exactly defined.
During the last decades the colour industry and, still more, dyeing
have undergone a complete change. The momentous discoveries which have
been made in these departments leave far behind the advances which have
been made in other branches of chemical technology, the manufacture
of explosives, perhaps, excepted. We allude here to the beautiful
colours which have been made from coal-tar, colours which far surpass
in beauty all hitherto known, and which we can already prepare in
every shade and hue. Unfortunately, we can only employ the coal-tar
colours, as such, in a restricted measure among the pigments; they
are of more importance in dyeing. We use the term pigments here in
the narrow sense of such substances which, when spread out on certain
materials, provoke a certain sensation of colour. Dyeing is, on the
contrary, that branch of colour chemistry which generally has for its
object the simultaneous production of the colour and its fixation upon
a fabric. This definition was at least applicable to the majority of
the colours which were in use before the discovery of the coal-tar
colours and their introduction into the industry. Since, however,
the latter have acquired so great a preponderance in dyeing, it is
no longer applicable, for the dyers use at present a large number of
substances which are included in the narrow definition of pigments. The
greater part of the coal-tar colours are substances which, in solution,
when brought in contact with a fabric, adhere to it and colour it
permanently.
According to their use and preparation, pigments are divided into a
number of classes, and one speaks of painters’, artists’, enamel,
porcelain and glass colours, also of oil, honey, water and cake
colours. Although this division is important for trade purposes, it
is of little moment for the colour maker, for he can prepare the same
colour for both purposes, either for oil or water colour. What is of
the greatest interest for the colour maker is the preparation of the
pigment itself. The conversion of the prepared pigment into (oil or
water) paint is unaccompanied by difficulties.
When we look for a practical classification for pigments, we find that
there are colours which exist ready formed in nature, and others which
can only be obtained by certain chemical processes, at times very
complicated.
As regards the first group of pigments—those which exist ready formed
in nature—the processes which they undergo at the hands of the colour
maker are almost entirely mechanical treatments—grinding, sieving,
levigating and similar operations—in order to convert them into such
a condition that they can be used for painting. Since a large number
of these pigments belong to that class of minerals which mineralogists
call earths, these pigments have also been designated earth pigments,
a term which we shall retain on account of its general use, although
it is incorrect, since many of the so-called earth pigments are not
obtained from “earths” in the mineralogical sense.
Among the pigments which are prepared by human skill many divisions can
be drawn. A large number of pigments are prepared from mineral sources;
an equally important number are derived from the animal and vegetable
kingdom, the latter consisting of combinations of organic materials
with certain inorganic substances. Some few pigments (putting aside the
coal-tar colours) are simply organic products, as, for example, the
majority of the black pigments, which consist of carbon.
The following classification is drawn up on the lines indicated above:—
1. _Natural Colours or Earth Pigments._—Found ready formed in nature
and requiring only mechanical preparation to be usable. A large number
of handsome and also cheap colours belong to this class.
2. _Artificially Prepared Mineral Pigments._—Obtained by certain
chemical processes, and, according to their composition, either
compounds of metals with sulphur, oxygen, iodine, cyanogen, etc., or of
oxides with acids, i.e., salts.
3. _Lakes._—Compounds of colouring matters from the animal or vegetable
kingdom with a mineral substance, such as lead oxide or alumina.
As a fourth group we might take those colours which do not fall into
the previous classes, as, for example, the black pigments composed of
carbon; but since this division is not made in practice we shall not
regard this species of pigment as a particular group, but shall discuss
them in the proper place.
As an entirely new group of colours are to be classed those which are
generally called coal-tar colours. These colours, which, at present,
are the most important in dyeing and calico printing, are prepared from
so-called organic compounds (more properly, carbon compounds). The
manufacture of these colours is a separate branch of chemical industry.
CHAPTER II.
THE PHYSICO-CHEMICAL BEHAVIOUR OF PIGMENTS.
In a work which, as its title indicates, is devoted to a description of
the manufacture of pigments, the properties of those substances which
are necessary for the preparation of colours cannot be exhaustively
considered; we must, therefore, presuppose a knowledge of the elements
of chemistry. We have to consider in this book the chemistry of
colours; the reader will, therefore, not expect an exposition of
general chemical laws; we shall only state certain facts which are of
value to the manufacturer. With the description of the manufacture of
each pigment and of the materials required for that manufacture, we
shall still discuss the chemical processes which must be conducted in
the preparation of the colours, so far as it is necessary in order to
understand them. In this chapter we shall say a few words about the
physical and chemical behaviour of pigments in general.
The great majority of pigments are prepared by the process of
precipitation, generally by mixing the solutions of two substances,
upon which an interchange of the constituents occurs and the less
soluble compound separates in pulverulent form from the solution as a
precipitate. Most of these colours are obtained by the admixture of
the solutions of two salts; the preparation of the so-called chrome
yellow may be taken as an example. In the preparation of this pigment,
a solution of a lead salt, sugar of lead (lead acetate), is mixed
with a solution of bichromate of potash, whereupon a precipitate of
lead chromate (chrome yellow) is formed, whilst potassium acetate
remains dissolved. The lead chromate is formed because the acetic acid
has a greater affinity for potash than for lead oxide, wherefore an
interchange of acid and base takes place, but the lead chromate being
insoluble in water consequently separates in the form of a precipitate.
Many mineral pigments are produced in the form of precipitates by
passing sulphuretted hydrogen or carbonic acid gas into certain metal
solutions. In these cases a similar exchange takes place between the
reacting substances to that given in the case of chrome yellow; the
metals have a greater affinity for the sulphur or for the carbonic
acid than for the substances with which they are already united, they
unite with the former, and the new compound separates as an insoluble
substance. We have examples of such compounds in cadmium sulphide,
which is obtained by passing sulphuretted hydrogen into the solution
of cadmium in an acid, and in white lead, which is formed by the
saturation of a solution of lead acetate by carbonic acid.
Many organic colouring matters, soluble in water, have the property
of forming compounds with metallic oxides, soluble with great
difficulty, when their solutions are mixed with a salt of lead, tin or
aluminium, and the oxide is separated from the solution by an alkali.
The precipitates obtained in this way are insoluble compounds of the
colouring matter and the oxide of the metal; they are called lake
pigments, or, briefly, lakes. A large number of pigments, often of
great beauty, is obtained in this manner. The lakes are widely used in
all branches of painting and dyeing.
Of great importance for the quality of the pigment is the physical
condition of the precipitate; this is either crystalline or amorphous,
that is, non-crystalline. When a crystalline precipitate is examined
under the microscope, it is seen to consist of very small, coloured,
transparent crystals. The amorphous precipitates are, however, in such
a fine state of division that even with the highest magnification
they transmit little or no light, and consequently appear opaque.
These different characters of precipitates have the greatest influence
on that property of pigments which we call _covering power_. In
consequence of its transparency, a crystalline precipitate will allow
the colour of the surface upon which it is spread to appear through,
hence it must be laid on much more thickly than is necessary with an
opaque pigment, of which a thin coating is sufficient to make the
colour of the surface beneath invisible.
How extremely important is the crystalline or non-crystalline nature
of a precipitate in practice is seen by a consideration of white lead.
This pigment, lead carbonate, can be made by mixing solutions of a
lead salt and a soluble carbonate (soda); but in this case a lead
carbonate of crystalline nature is formed, which, being transparent, is
of so small covering power that this process has no application in the
manufacture of white lead; but a far more troublesome method is used by
which a non-crystalline product, amorphous lead carbonate, is obtained.
Many pigments are formed by burning (oxidising) metals, as, for
example, zinc white; others are prepared by melting salts together, as
Naples yellow; others again are formed by very complicated processes
still partially unexplained, as is the case with ultramarine. In the
manufacture of colours we find all chemical processes in use.
It may be here remarked that it is quite possible to manufacture some
colours, indeed a large number, according to fixed directions, without
any particular chemical knowledge being necessary to carry on the
processes. Indeed, in works we find most processes being carried out
by ordinary labourers who are quite destitute of any knowledge of
chemistry. We must, however, add that we are convinced that any colour
maker who works simply in a purely empirical manner, according to a
stereotyped recipe, will never be in the position to raise himself
above the position of a workman; he will not be able, when a slight
mishap occasions a change in the ordinary course of the process, to
devise a means of overcoming the defect, but will be compelled to
dispose of the faulty product in the condition in which it exists. Such
a manufacturer is in a condition of blind dependence on the chemical
works and dealers from whom he receives the raw materials requisite
for the preparation of his colours. If he should receive materials
which contain impurities not to be detected by empirical methods, the
inevitable result will be that the colours produced from them will not
be equal to the standard. If, in making a colour which is the outcome
of several processes, a workman once makes a mistake, the product will
not be of the required quality.
On the contrary, if the manufacturer possesses a certain amount of
chemical knowledge, it will not be difficult for him to ascertain the
causes of a failure in a process, and, at the same time, to devise
means by which the defects may be removed. The manufacturer is more and
more in the habit of buying the chemicals which he requires for his
manufactures rather than of making them himself. He should, therefore,
be in a position to form an opinion as to the usability and purity of
these substances, which will only be possible when he has the knowledge
requisite for subjecting them to a chemical examination.
Although we shall presuppose, as we have said, that those who intend to
concern themselves with colour manufacturing possess an acquaintance
with the principles of chemistry, yet this book has been so planned
that it may be of use (we hope) to the practical man who is innocent
of chemical knowledge. On this account, we have devoted care to the
description of those raw materials which are bought in large quantity,
and to the simple investigation of their purity.
When the manufacturer has the advantage of a chemical education, apart
from his endeavours to produce colours lacking nothing in beauty or
depth of shade, he will direct his endeavours in two directions, in
respect of which great advances are yet to be made—the permanence and
harmlessness of his colours.
Many pigments possess the undesirable property of losing their
brightness under atmospheric influences; many, indeed, fade away
completely in the course of time. We have only to examine a picture
some centuries old; in spite of the care bestowed on its preservation,
we can say with certainty that, in the course of time, it will be so
completely altered that nothing will remain of the original colours.
It is the endeavour of the sensible manufacturer of colours to make
only such as remain unaltered by atmospheric action, and also undergo
no change when they are mixed with other pigments. Although it may be
highly desirable that the painter should possess a knowledge of the
chemical properties of the colours he uses, still it should be the
first object of the maker to take care that he places on the market
only colours which will remain as much as possible unaltered when used
alone, and will remain undecomposed when mixed. This is, unfortunately,
not the case with many colours now in use. We shall return later to
this point, of such extraordinary importance to the artist.
The second point to be observed, is to produce only harmless colours.
The advances of chemistry have made known to us a series of colours
which have the advantage over others known for a longer period that
they are non-poisonous. Unluckily, these harmless colours frequently
fall behind the poisonous colours in brilliance, and generally they are
more expensive. Here, too, is opened to the manufacturer a wide field
of activity. The more completely poisonous substances disappear from
the colours in use, the more widespread will be the use of colours. We
should remark that the expression “poisonous colours” is to be used
with a certain reserve. Many pigments which contain lead, copper,
antimony, mercury, etc., are poisonous, because they contain poisonous
metals; but poisoning with them will not readily take place on account
of their insolubility. It is different with the very poisonous arsenic
compounds, which should be removed from the list of colours in common
use; many a misfortune caused by them would then be avoided.
Endeavours to produce innocuous colours have been more successful than
the efforts after permanence. There are now very few commonly used
colours which can be accounted very poisonous compounds, and which
cannot be replaced by other colours of equal beauty. On the whole, we
are now in the position to prepare harmless colours suited to most
purposes. Special endeavours should be made to sell these, so that
such cases of poisoning should not occur as, for example, caused by
gingerbread which had been wrapped in paper coloured by emerald green.
CHAPTER III.
RAW MATERIALS EMPLOYED IN THE MANUFACTURE OF PIGMENTS.
As we have mentioned before, the manufacturer of colours now generally
uses materials supplied to him by chemical works. The purer these are,
the easier it will be to work with them, and the finer will the colours
turn out. We have indicated that it is important for the manufacturer
to know accurately the properties of his materials in order to be
able to estimate their value. Many substances required in certain
cases must be made by the colour manufacturer, since, on account of
their condition, they cannot form articles of commerce—chlorine and
sulphuretted hydrogen, for example.
In addition to the substances which are not to be bought, there are
others which do occur in commerce, but are sold at so high a price that
the manufacturer is compelled to make them himself. This is the case
with the cobalt compounds, from which many beautiful colours are made.
The producers of these demand such prices that it is to the interest of
the colour maker to prepare them for his own use.
In the following chapters, we shall deal with the more important
raw materials which are employed in colour manufacturing, and shall
restrict our remarks to what is of particular importance thereto. For
more detailed accounts of these raw materials the reader is referred
to the text books of chemistry, in which he will find them minutely
described, in so far as they are chemical products.
The materials employed may be divided into assistants in the processes
and components of the manufactured pigment. The assisting substances
are those which are used in the manufacture of a colour without
entering into its composition; from the component materials the colours
are directly derived. For example, in the manufacture of Prussian blue,
yellow prussiate of potash, an iron salt, water (in which the salts are
dissolved) and nitric acid are used. In the blue obtained are contained
portions of the iron salt and of the yellow prussiate, these are,
therefore, component materials, whilst water and nitric acid are simply
assistants, since they do not enter into the composition of the pigment.
In colour making a large number of assisting materials are employed,
which comprise a considerable number of elements and compounds. Since
these are of great importance for our purpose, we shall describe their
properties, and, when necessary, briefly the method of preparation.
Among the component materials are to be reckoned a large number of
salts of the alkaline earth and earth metals and of all the heavy
metals. In addition, there are also the substances of animal or
vegetable origin used in lake making.
In the description of the raw materials, if we were to overstep the
line drawn here, we could include a great variety of compounds, those,
for example, used in the manufacture of the so-called aniline dyes.
These substances form, however, as we have stated, the object of a
particular branch of manufacture, which forms a separate division of
colour chemistry, but with which is not to be confounded what has been
hitherto designated the manufacture of colours.
CHAPTER IV.
ASSISTANT MATERIALS.
=Water=, H₂O = 18.[1]—This substance plays a tremendous part in colour
making; almost all the substances which are used in solution are
dissolved in water; the removal from precipitates of admixed foreign
bodies, the so-called washing, is always accomplished with water. The
chemist does not understand by water quite that liquid which in general
speech is so designated. We must consider the water which is at the
disposal of the colour maker.
[1] We append the chemical formula and the molecular weight to the
description of each compound.
Water, in the chemical meaning of the word, is a liquid composed only
of hydrogen and oxygen, and leaving no residue when evaporated. Such
water is not found in nature; it can only be obtained by distillation
of well or river water. The water which falls in long continued rain,
or is obtained by melting snow, is most nearly like distilled water; it
contains only small quantities of dissolved substances, and generally
such as would be without influence in colour making. Water of this
description is available for but a limited use; the large quantities of
water required in a colour works must be taken from springs or streams.
These waters contain, however, more or less large amounts of dissolved
salts, which act in a marked manner upon the substances dissolved in
them.
In almost all spring and well waters is found carbonate of lime;
such waters are called “hard”. River water contains generally little
carbonate of lime; it is then called “soft water”. The influence of the
carbonate of lime is especially evident when salts of lead, copper,
iron and other heavy metals are dissolved in water; the carbonate of
the particular metal gradually separates from solution, and the liquid
becomes very turbid.
When only hard waters containing much lime are at the service of the
manufacturer, turbid solutions are often obtained, which must be
filtered before use. In many cases this can be avoided by adding milk
of lime to the water in a large vessel; the free carbonic acid unites
with the lime, and thus the carbonate of lime, which is only soluble in
water containing free carbonic acid, separates as a fine precipitate.
Water which has been treated in this way becomes clear after some time,
through the deposition of the carbonate of lime; it is then soft water.
In order to separate the carbonate of lime in this way, no more than
the requisite quantity of milk of lime should be added, so that no lime
remains in excess, since this would cause precipitates when salts of
lead, copper, iron, etc., were dissolved. In many cases—for example,
when lead or barium salts are dissolved—the lime contained in the water
can be made harmless by slightly acidifying with acetic or nitric acid.
Water which contains sulphate of lime (gypsum) is equally useless for
many purposes, as, for example, the solution of lead and barium salts.
These metals form insoluble compounds with the sulphuric acid, which
render the solution turbid, and can be removed only with difficulty by
filtering, on account of their great fineness. They are more easily
removed by allowing to settle.
Water containing gypsum often contains in addition small quantities of
sulphuretted hydrogen. However small the quantities of this gas may
be, they still make the water absolutely useless for certain purposes
in the manufacture of colours; for example, for the preparation of
all pigments containing lead which are obtained by precipitation. The
sulphuretted hydrogen forms black compounds with lead, copper, bismuth,
mercury and other metals, which impair the brilliance of the colour. A
colour made under these conditions is never clean, its hue is injured
by the admixture of the black substance.
Water which contains much common salt (sodium chloride) is unsuitable
for the solution of lead, mercury and silver salts. In consequence of
the great affinity of these metals for chlorine, turbid solutions are
obtained when their salts are dissolved in water containing common salt.
Some waters contain a considerable quantity of iron. Such waters
deposit on evaporation, and often on standing exposed to the air, a
brown powder of ferric hydrate, which would have considerable influence
on the shade of a pigment. White pigments, in the preparation of which
such a water is used, have always a brownish tinge; yellow and red
pigments are also unfavourably affected.
Carbonate of lime and common salt occur in small quantities in every
well water. The colour maker must do the best he can with such a water;
its use will not particularly harm the shade of the colours prepared
with it if the amount of the impurities is not very large. Water
containing much iron is practically useless; the oxide of iron would
injure the colours so much that it would not be possible to obtain
brilliant shades. Water from wells in the neighbourhood of deposits of
turf or cemeteries often contains considerable quantities of organic
substances which act injuriously on the shade of pigments; such water
should not be used in colour making.
The impurities in a water are more or less harmful according to the
purpose for which it is to be used. Sulphate of lime is generally
more injurious than carbonate of lime, since the precipitates which
the latter causes in solutions of the salts of certain metals can be
prevented by the addition of acids. This is not the case with sulphate
of lime; when lead or barium salts are dissolved in water containing
this substance, a precipitate of lead or barium sulphate is obtained,
which is insoluble.
In dealing with the salts of costly metals, such as mercury or silver,
it is better to dissolve them in distilled water, or, at least, very
pure rain water. The rain water which runs from zinc or well tiled
roofs is generally very pure; for practical purposes it may be regarded
as free from carbonate and sulphate of lime, sulphuretted hydrogen and
common salt. The colour maker should take care to obtain as much of
this pure water as possible by erecting large rain-water tanks.
The less impurity a water contains the more useful it is for our
purpose. After rain water soft river water is the best, and after this
the softer well waters. All mineral waters distinguished by a high
content of salts or gases are quite useless for colour making; for this
reason sea water is disqualified.
An accurate analysis of a water is much too complicated for the
manufacturer; it is sufficient for him to convince himself of the
absence of certain substances. Water which, some time after the
addition of a little tannic acid solution, acquires a clear green or a
bluish to black shade contains much iron, and is useless. Water which
coagulates a large quantity of a solution of soap in alcohol is very
rich in carbonate or sulphate of lime. In order to decide approximately
in what relative proportion these salts are present, a solution of
barium chloride is added to the water so long as a precipitate forms.
If this disappears completely on the addition of nitric acid, the
water contains only carbonate of lime; if it only partly dissolves,
sulphate of lime is also present. The presence of chlorine is shown
by a considerable turbidity on acidifying the water with nitric acid,
boiling and adding silver nitrate. If the precipitate obtained on the
addition of a lead salt is not pure white, but discoloured, the water
contains sulphuretted hydrogen, which has formed black lead sulphide.
In order to test the water for organic substances, about a litre is
evaporated to dryness in a porcelain dish, and the residue heated to
redness; if it turns brown and black, and possibly gives off a smell of
burnt feathers, the water contains much organic matter.
Pure water is coloured permanently red by a solution of potassium
permanganate; but if it contains organic matter, the solution is
decolourised after some time and a brown precipitate is deposited at
the bottom. From the amount of this precipitate an idea of the quantity
of organic matter present may be obtained.
It is only necessary to be very scrupulous concerning the quality
of the water when it is to be used for the solution of salts or the
extraction of dye-woods. For washing precipitates, which requires a
large volume of water, there can generally be used, without detriment,
water containing much lime, but it must be free from iron and
sulphuretted hydrogen. The latter is particularly harmful to most of
the lead colours, which would lose in beauty by washing with water
containing this substance.
It is hardly necessary to say that the water used in colour making must
be quite clear. Muddy river water must in every case be completely
freed from the solid particles contained in it, either by settling or
by filtering. Filters filled with well washed sand give good results
for this purpose.
=Chlorine=, Cl = 35·5.—For some operations in colour making it is
necessary to employ chlorine. This is a greenish yellow gas at
ordinary temperatures, which is characterised by a suffocating smell
and the energy with which it unites with most elements. On account of
its injurious effects on man certain precautions have to be observed
in preparing chlorine, and it is advisable to erect the apparatus
necessary for its production in a separate room, so that the workmen
are not injured by the gas.
[Illustration: FIG. 1.]
Formerly chlorine was exclusively made in lead apparatus, because this
metal is one of the least readily attacked. When such an apparatus is
used for the first time a layer of lead chloride is formed, which,
like a varnish, protects the metal beneath from further attack. Fig.
1 represents an apparatus formerly employed for the preparation of
chlorine in chemical works. In the upper part of the pear-shaped
vessel, K, there are four openings, two of which, D and C, are provided
with water lutes. This means that the opening is surrounded by a moat
containing water, into which the rim of the cover dips, thus making
a joint. Through the middle opening goes the axle of the stirring
apparatus, R; in the fourth is a lead safety funnel, J. Solid materials
are introduced through D, liquid through J; the tube C carries away the
chlorine formed; the tube A, furnished with a stop cock, can draw off
the fluid contents of the apparatus.
Since lead melts at low temperature, the apparatus cannot be heated
over the fire without danger, therefore it is surrounded by an iron
jacket, W, which is filled with water, or else the apparatus is heated
by steam introduced into W. Larger quantities of chlorine are more
conveniently prepared in an apparatus, of similar structure, made of
stone or earthenware, which have the advantage over lead that they are
not at all attacked by chlorine.
[Illustration: FIG. 2.]
Fig. 2 exhibits the construction of such an apparatus of medium size.
It is constructed of sandstone or earthenware; the lid and some of the
smaller parts can be made of either earthenware or lead. The pyrolusite
is introduced at _G_ in large pieces; _H_ is the funnel for pouring
in the acid; _E K D_, the steam pipe; _C_, the perforated false
bottom upon which the pyrolusite lies; _F_, the delivery tube for the
chlorine; _J_, the opening for running off the manganese chloride; _a_,
the leaden cover.
To prepare chlorine, 1 part (by weight) of common salt, 1 part of
powdered pyrolusite, 2½ parts of vitriol and 1¼ part of water are
used. The salt and the pyrolusite are introduced through _D_ into the
apparatus (Fig. 1); the acid, diluted with the water, is poured in
through the funnel, the materials are mixed by the stirrer and gently
warmed until chlorine appears, when the application of heat must be
considerably diminished or the chlorine will be violently evolved.
Pyrolusite and hydrochloric acid are now generally used for the
preparation of chlorine, because the solution of manganese chloride,
left at the end of the operation, is valuable.
If all the chlorine made in one operation is not at once required for
the manufacture of a colour, it can be utilised by sending it into a
box filled with slaked lime, which is converted into chloride of lime
or bleaching powder. The liquid run away from the apparatus at the
conclusion of the operation contains manganese and sodium sulphates,
or manganese chloride as the case may be, and can be used for the
preparation of manganese pigments.
=Ammonia=, NH₃ = 17.—Ammonia is obtained from chemical works in the
form of a strong solution of ammonia gas in water, which is generally
very pure. The density of an aqueous solution of ammonia is the smaller
the more ammonia it contains, and thus the strength of a solution of
ammonia can easily be formed by means of the hydrometer. The following
table shows the percentage of ammonia, NH₃, in a liquid of known
specific gravity at the temperature of 14° C.:—
+-------------+------------+------------+------------+
| Specific | Ammonia | Specific | Ammonia |
| Gravity. | per cent. | Gravity. | per cent. |
+-------------+------------+------------+------------+
| 0·885 | 36·00 | 0·953 | 11·50 |
| 0·886 | 35·00 | 0·955 | 11·00 |
| 0·889 | 34·00 | 0·957 | 10·50 |
| 0·891 | 33·00 | 0·959 | 10·00 |
| 0·893 | 32·50 | 0·961 | 9·50 |
| 0·895 | 32·00 | 0·963 | 9·00 |
| 0·897 | 31·30 | 0·965 | 8·50 |
| 0·900 | 26·00 | 0·968 | 8·00 |
| 0·905 | 25·39 | 0·970 | 7·50 |
| 0·925 | 19·54 | 0·972 | 7·00 |
| 0·932 | 17·52 | 0·974 | 6·50 |
| 0·947 | 13·46 | 0·976 | 6·00 |
| 0·951 | 12·00 | 0·978 | 5·50 |
+-------------+------------+------------+------------+
_The Hydrometer._—In the above table the percentage content of the
ammonia solution is given according to its specific gravity, that is,
according to the ratio between the weight of any volume of the liquid
and the weight of an equal volume of water. According to scientific
principles, only those hydrometers should be used which are graduated
in specific gravities. In spite of all exertions in this direction,
manufacturers have not yet been induced to use such instruments in
every case. Hydrometers, with quite arbitrary scales, such as those of
Baumé and Twaddell, are frequently found in works. These hydrometers
generally only show that a liquid is of so many degrees on the
particular scale, and the manufacturer in using them is restricted
to the following out of a certain recipe which requires the use of
a liquid of a certain strength which is expressed in degrees Baumé,
etc. He does not learn by this how many per cent. of the particular
substance are dissolved in the water when the liquid has a certain
hydrometric strength.
For the sake of uniformity, it is urgently to be desired that all
manufacturers who use the hydrometer to estimate the content of a
liquid in ammonia, potash, soda, hydrochloric, sulphuric, nitric acids,
etc., should employ simple specific gravities. This is desirable,
because the percentage strength of a solution, corresponding to the
specific gravity, can be at once accurately found from tables. On
these grounds, in the present work, we have restricted ourselves to
tables showing simply the specific gravities of solutions and the
corresponding composition.
=Sal Ammoniac or Ammonium Chloride=, NH₄Cl = 53·5.—This substance comes
into commerce in the form of a white crystalline meal, more rarely in
the form of sugar loaves (crystallised sal ammoniac) or of flat cakes
(sublimed sal ammoniac). It is usually very pure, since impure forms,
generally containing much iron, are difficult of sale. At a particular
temperature sal ammoniac is volatile; it is used in certain mixtures
in order to prevent the temperature, on heating, from rising beyond a
certain point. Like ammonia, it is more used in dyeing.
=Ammonium Sulphide=, NH₄HS.—This compound is obtained by leading
sulphuretted hydrogen into ammonia solution so long as it is dissolved,
and a test portion of the liquid still gives a white precipitate with
a solution of magnesium sulphate. Ammonium sulphide decomposes by long
standing in the air, sulphur being separated. It gives precipitates
with the salts of certain metals, for example, iron, cobalt, manganese,
zinc, nickel. These precipitates, which consist of the sulphides of the
metals, are not formed by sulphuretted hydrogen in acid solutions.
ACIDS.
In colour making many acids are used for the solution of metals, the
production of precipitates, for oxidations and so forth. Commercial
acids, especially inorganic acids, generally contain not inconsiderable
quantities of impurities which are injurious in the manufacture of many
colours.
=Hydrochloric Acid=, HCl = 36·5.—The commercial acid (muriatic acid,
spirits of salt) generally contains large quantities of iron,
which colour it yellow—fortunately, in many cases, this is not a
disadvantage, and also at times the iron can be removed from solutions
made in the acid. Another impurity is sulphuric acid. This can be
detected by diluting and adding barium chloride; if sulphuric acid be
present, a white precipitate, or, at least, a cloudiness, appears.
Ordinary hydrochloric acid is a solution of hydrochloric acid gas in
water. The strongest acid contains 42·85 per cent. of the gas, and has
the specific gravity 1·21. The following table gives the strengths of
acids of various specific gravities:—
+------------+--------------+-------------+--------------+
| Specific | Hydrochloric | Specific | Hydrochloric |
| Gravity. | Acid | Gravity. | Acid |
| | per cent. | | per cent. |
+------------+--------------+-------------+--------------+
| 1·21 | 42·85 | 1·10 | 20·20 |
| 1·20 | 40·80 | 1·09 | 18·75 |
| 1·19 | 38·88 | 1·08 | 16·71 |
| 1·18 | 36·36 | 1·07 | 15·49 |
| 1·17 | 34·34 | 1·06 | 13·86 |
| 1·16 | 32·32 | 1·05 | 11·49 |
| 1·15 | 30·30 | 1·04 | 8·97 |
| 1·14 | 28·28 | 1·03 | 6·93 |
| 1·13 | 26·26 | 1·02 | 4·89 |
| 1·12 | 24·24 | 1·01 | 2·03 |
| 1·11 | 22·22 | | |
+------------+--------------+-------------+--------------+
=Sulphuretted Hydrogen=, H₂S = 34.—This is a gas of acid properties
smelling like rotten eggs; it precipitates the sulphur compounds of
many metals when led into the acid solution of the corresponding
salt. This substance is seldom required in colour works, so that it
is convenient to have an apparatus which permits of the preparation
of any required quantity. Fig. 3 represents an apparatus devised by
the author, which is well adapted for the preparation of sulphuretted
hydrogen. It consists of a small, wooden tub, on whose upper edge lies
a thick paper ring, so that the lid may be pressed down air-tight by
the screws B. Through the lid pass a tap-funnel, T, a movable screw,
S, and a tube, R, to carry away the gas. On the screw S hangs a basket,
K, by a handle; this is filled with pieces of iron sulphide as large as
nuts. The tub is filled to about one-third of its height with a mixture
of 9 parts of water and 1 part of sulphuric acid.
[Illustration: FIG. 3.]
When sulphuretted hydrogen is required the basket is lowered by the
screw, S, until it dips in the liquid; according as the basket dips
more or less into the liquid a fast or slow current of the gas is
obtained. When the gas is no longer required the basket is raised out
of the liquid, and the evolution of gas at once ceases. The funnel, T,
serves for the introduction of the liquid, the tap, H, for drawing off
the iron sulphate solution, which can be used with advantage for the
preparation of fine iron colours. The apparatus should not be opened so
long as sulphide of iron remains in the basket.
=Sulphuric Acid= comes into the market in two different forms: oil
acid; both are used in colour making. _Oil of Vitriol_, H₂SO₄ = 98, is
a colourless, oily liquid of high specific gravity; it is generally
tolerably pure, and contains, as a rule, only a small quantity of
lead, the presence of which is indicated by a turbidity on largely
diluting the acid. The amount of pure sulphuric acid in the liquid
is practically determined by taking the specific gravity. The table
indicates the relation between the specific gravity and the content of
sulphuric acid.
+-----------------+--------------+-----------------+--------------+
|Specific Gravity.|Sulphuric Acid|Specific Gravity.|Sulphuric Acid|
| | per cent. | | per cent. |
+-----------------+--------------+-----------------+--------------+
| 1·8485 | 100 | 1·8043 | 89 |
| 1·8475 | 99 | 1·7962 | 88 |
| 1·8460 | 98 | 1·7870 | 87 |
| 1·8439 | 97 | 1·7774 | 86 |
| 1·8410 | 96 | 1·7673 | 85 |
| 1·8376 | 95 | 1·7570 | 84 |
| 1·8336 | 94 | 1·7465 | 83 |
| 1·8290 | 93 | 1·7360 | 82 |
| 1·8233 | 92 | 1·7245 | 81 |
| 1·8179 | 91 | 1·7120 | 80 |
| 1·8115 | 90 | | |
+-----------------+--------------+-----------------+--------------+
_Nordhausen Sulphuric Acid_, H₂S₂O₇ = H₂SO₄ + SO₃, is generally a
yellowish brown liquid, which gives off white fumes in the air. It
contains varying quantities of sulphur trioxide dissolved in sulphuric
acid. It often contains selenium, which separates as a red powder when
the acid is diluted. The presence of this impurity does not interfere
with the use of the acid for dissolving indigo, the only purpose for
which it is required in the colour factory.
=Nitric Acid=, HNO₃ = 63.—This acid, which is used in the preparation
of many colours, is distinguished by the readiness with which it gives
up part of its oxygen, and thus converts metals like antimony and
bismuth into oxides, and transforms other compounds into a higher state
of oxidation. There are two kinds of nitric acid: ordinary nitric
acid, a colourless liquid which is more or less pure; and fuming nitric
acid, a yellow or orange-coloured liquid, fuming strongly in the air,
which consists of a solution of nitrogen peroxide, NO₂, and nitric
oxide, NO, in nitric acid.
+----------------+--------------+----------------+--------------+
|Specific Gravity| Nitric Acid |Specific Gravity| Nitric Acid |
| at 15° C. | per cent. | at 15° C. | per cent. |
+----------------+--------------+----------------+--------------+
| 1·530 | 100·00 | 1·323 | 55·00 |
| 1·520 | 97·00 | 1·284 | 50·49 |
| 1·509 | 94·00 | 1·251 | 45·00 |
| 1·503 | 92·00 | 1·211 | 40·00 |
| 1·499 | 91·00 | 1·185 | 33·86 |
| 1·495 | 90·00 | 1·157 | 30·00 |
| 1·478 | 85·00 | 1·138 | 25·71 |
| 1·460 | 80·00 | 1·120 | 23·00 |
| 1·442 | 75·00 | 1·089 | 20·00 |
| 1·423 | 69·96 | 1·067 | 15·00 |
| 1·400 | 65·07 | 1·022 | 11·41 |
| 1·346 | 60·00 | 1·010 | 4·00 |
+----------------+--------------+----------------+--------------+
Since the action of nitric acid chiefly depends on its oxidising
properties, which are possessed by both kinds, it generally does not
matter which is used. The usual impurities are chlorine and sulphuric
acid; the presence of the first is shown by silver nitrate solution,
of the latter by barium chloride, in each case added after diluting.
When the acid is used for oxidations these impurities do not interfere,
but nitric acid containing chlorine cannot be used to dissolve silver,
because the chlorine would form insoluble silver chloride.
The strength of nitric acid is gauged by its specific gravity as given
in the table.
=Aqua Regia.=—A mixture of 2 parts of hydrochloric acid and 1 part of
nitric acid gradually turns orange or yellow and evolves chlorine. This
liquid, which can dissolve gold in consequence of the free chlorine it
contains (hence its alchemistic name, from gold, the “king of metals”),
is used as a very powerful oxidising agent in colour making.
=Carbon=, C = 12, is the only one of the non-metallic elements to be
mentioned here; by itself it forms a group of very important pigments,
which we shall describe in detail at a later stage.
=Carbonic Acid Gas=, CO₂ = 44, is used in the manufacture of white
lead, which it precipitates from lead acetate. This is, however, a
particular branch of colour making carried on in special works. In
describing this manufacture we shall return to the preparation of
carbonic acid on a large scale.
ORGANIC ACIDS.
The organic acids which are important in colour making are acetic,
oxalic and tartaric acids.
=Acetic Acid=, C₂H₄O₂ = 58.—The very dilute form of this substance
is known commonly as vinegar, the stronger as pyroligneous acid, and
the purest as glacial acetic acid; the latter is, however, scarcely
used. Formerly in colour making ordinary vinegar was used, but now
pyroligneous acid is almost exclusively employed. This is distinguished
by its strong empyreumatic smell, which, however, is without importance
in colour making.
The strength of a solution of acetic acid cannot be found by a simple
estimation of specific gravity, since the density does not increase
with the percentage of acetic acid. If an accurate estimation of
the strength of acetic acid is required, it must be obtained by
neutralising the acid with an alkali by a process of volumetric
analysis.
For practical purposes, where it is generally known whether a very
strong or a more dilute acetic acid is under consideration, the
following table, showing the connection between specific gravity and
percentage strength, is sufficient.
+--------+---------+--------+---------+
|Specific| Acetic |Specific| Acetic |
|Gravity.| Acid |Gravity.| Acid |
| |per cent.| |per cent.|
+--------+---------+--------+---------+
| 1·0635 | 100 | 1·058 | 48 |
| 1·0670 | 98 | 1·055 | 46 |
| 1·0690 | 96 | 1·054 | 44 |
| 1·0706 | 94 | 1·052 | 42 |
| 1·0716 | 92 | 1·051 | 40 |
| 1·0730 | 90 | 1·049 | 38 |
| 1·0730 | 88 | 1·047 | 36 |
| 1·0730 | 86 | 1·045 | 34 |
| 1·0730 | 84 | 1·042 | 32 |
| 1·0730 | 82 | 1·040 | 30 |
| 1·0735 | 80 | 1·038 | 28 |
| 1·0732 | 78 | 1·035 | 26 |
| 1·0730 | 76 | 1·033 | 24 |
| 1·0720 | 74 | 1·031 | 22 |
| 1·0710 | 72 | 1·027 | 20 |
| 1·0700 | 70 | 1·025 | 18 |
| 1·0700 | 68 | 1·023 | 16 |
| 1·0690 | 66 | 1·020 | 14 |
| 1·0680 | 64 | 1·017 | 12 |
| 1·0670 | 62 | 1·015 | 10 |
| 1·0670 | 60 | 1·012 | 8 |
| 1·0660 | 58 | 1·008 | 6 |
| 1·0640 | 56 | 1·005 | 4 |
| 1·0630 | 54 | 1·002 | 2 |
| 1·0620 | 52 | 1·001 | 1 |
| 1·0600 | 50 | —— | —— |
+--------+---------+--------+---------+
=Oxalic Acid=, C₂H₂O₄.2H₂O = 126, has but a limited use in colour
making. It comes into commerce in the form of more or less pure white
crystals which readily dissolve in water, and are almost pure oxalic
acid, containing only small quantities of oxalate of lime, the presence
of which is without importance for the purposes to which the acid is
put in colour making. Frequently, instead of oxalic acid, the acid
potassium oxalate (salt of sorrel) is used.
=Tartaric Acid=, C₄H₆O₆ = 150, occurs as white or yellowish crystals,
with a slightly burnt smell, which dissolve readily in water, and have
a strong acid taste. The pure acid, which is white and without smell,
is considerably dearer than the yellow variety. The impurities of the
latter, which are small in quantity, are without influence on the
colours prepared by its help, so that this form is generally used.
CHAPTER V.
METALLIC COMPOUNDS.
ALKALIS.
The compounds of the alkali metals, potassium and sodium, play a
considerable part in colour making. Formerly the potassium compounds
were in general use, but the sodium compounds are at present obtainable
at a much lower price, and in most cases they can be used equally well.
Thus, in colour making, sodium compounds are chiefly employed. The
cyanogen compounds are an exception; their potassium compounds are used
exclusively.
=Potassium Compounds.=—The potassium compounds which are chiefly
used in colour making are potassium carbonate (potashes, pearl-ash),
potassium hydroxide (caustic potash), potassium nitrate (saltpetre),
potassium tartrate (tartar), and potassium ferrocyanide and
ferricyanide (yellow and red prussiate of potash). The cyanogen
compounds have peculiar properties. We shall describe them separately
after the potassium and sodium compounds.
=Potassium Carbonate= (carbonate of potash), K₂CO₃ = 138, is known
commercially as potashes, a name derived from its former method of
preparation by heating the ashes of plants in pots. At present potashes
are prepared in large quantities from other sources.
Pure potash forms crumbling lumps with a slight yellow or bluish grey
tinge, rapidly absorbing moisture from the air, and in time completely
liquefying. The yellowish tinge is caused by oxide of iron, the bluish
by manganese compounds. The so-called calcined potash has been strongly
heated, and thus all organic substances contained in it have been
destroyed.
Potashes are in no way pure potassium carbonate; they contain a mixture
of all those salts which are found in plants—potassium sulphate and
chloride, small quantities of silicic acid, etc. These impurities are
rarely harmful, still it is generally necessary to know the percentage
of pure potassium carbonate contained in potashes.
Although at present in commerce the strength of potashes is frequently
guaranteed, it is still desirable to estimate the strength. It is
sufficient for practice to allow a small quantity, say 100 grammes, to
stand with an equal quantity of very cold water for some hours, then
to filter and pour a similar quantity of water over the residue on
the filter. The weight of undissolved substance subtracted from 100
gives with sufficient accuracy the weight of pure potassium carbonate
contained in 100 parts of potashes. This method is founded on the fact
that potassium carbonate dissolves readily even in cold water, but the
other salts with difficulty. This procedure can also be used to obtain
pure potassium carbonate from crude potashes; it is only necessary to
filter and evaporate to dryness the solution obtained by pouring very
cold water on crude potashes.
=Potassium Hydroxide= (Potassium Hydrate, Caustic Potash), KOH =
56.—The commercial variety consists of very deliquescent white lumps,
generally containing a large quantity of impurities. On this account
caustic potash, or rather a solution of it, is prepared in the colour
works.
With this object 11 parts of potash, contained in a tub with an opening
at the bottom, are mixed with 100 parts of cold water. Two hours
later, the clear solution is run off into a clean iron pan, in which
it is heated to boiling. To the boiling solution is added milk of
lime prepared from water and 3·5 parts of quicklime. After the liquid
has boiled a few minutes, a small portion is filtered and hydrochloric
acid added to the clear filtrate; if no effervescence occurs, then
all the potassium carbonate is converted into caustic potash. Should
effervescence occur, milk of lime is added until a new portion no
longer effervesces on the addition of hydrochloric acid. Then the pan
is covered with a well-fitting lid, and the cooled liquid, if not
required for immediate use, preserved in well-corked glass bottles.
The strength of a caustic potash solution can be found by means of a
hydrometer. The following table shows the relation between the specific
gravity of a solution and the percentage of caustic potash it contains:—
+----------+----------------+
| Specific | Caustic Potash |
| Gravity. | per cent. |
+----------+----------------+
| 1·06 | 4·7 |
| 1·11 | 9·5 |
| 1·15 | 13·0 |
| 1·19 | 16·2 |
| 1·23 | 19·5 |
| 1·28 | 23·4 |
| 1·39 | 32·4 |
| 1·52 | 42·9 |
| 1·60 | 46·7 |
| 1·68 | 51·2 |
+----------+----------------+
=Potassium Nitrate= (Saltpetre), KNO₃ = 101, consists of large
crystals, which quickly dissolve in water. On heating it readily gives
up oxygen, and thus finds use as an oxidising agent. In former times,
when the colour manufacturer was compelled to make his own materials,
saltpetre was of great importance in colour making; at present, when
such materials are to be bought at low prices and no colour maker
prepares his own, saltpetre is little used.
=Potassium Bitartrate=, C₄H₅KO₆ = 188.—This salt, known as tartar
in large crystals, and as cream of tartar in the form of meal, is
occasionally used in colour making. It is little soluble in cold water,
but more easily in hot. The hot solution is generally used.
=Potassium Bichromate= (Bichromate of Potash), K₂Cr₂O⁷ = 295.—This salt
is made in special works, by melting chrome iron ore with saltpetre and
extracting the mass with water, when a yellow solution of potassium
chromate is obtained; to this sulphuric acid is added, which unites
with half the potassium, thus leaving potassium bichromate, which is
obtained by evaporation of the solution in fine red crystals. These
are purified by recrystallisation. At present, in place of the above
method, calcium chromate is formed by roasting chrome iron ore with
lime; the calcium chromate is then decomposed by a soluble potassium
salt, thus forming potassium chromate.
Potassium bichromate is unaltered in air; it dissolves easily in
water, and is of great importance in the preparation of many colours,
in particular chromium oxide and the lead pigments. The commercial
salt generally contains potassium sulphate, with which at times it is
intentionally adulterated. The adulteration is detected by dissolving
in water, adding half the volume of pure hydrochloric acid, and
cautiously and carefully dropping in spirits of wine. A rapid action
takes place, which is only assisted by warming when necessary. The red
liquid changes to emerald green. If barium chloride be now added, a
white precipitate is obtained in the presence of potassium sulphate.
=Potassium Sodium Chromate=, KNaCrO₄ = 279, is also used in colour
making. Its solution is made by adding soda to a solution of potassium
bichromate so long as an effervescence of carbonic acid occurs, and
until the liquid turns red litmus paper blue; the solution of the
double salt is yellow.
=Chrome Alum=, KCr(SO₄)₂.12H₂O = 499.—This salt occurs in commerce
as beautiful violet crystals. It is obtained as a by-product in the
manufacture of aniline and anthracene dyes, and may often be bought
at lower prices than other chromium salts; 100 parts of water dissolve
approximately 20 parts of chrome alum.
=Potassium Ferrocyanide=, K₄Fe(CN)₆.3H₂O = 422.—The potassium iron
cyanogen compounds are made in special works, particularly in the
neighbourhood of large towns, by melting potashes with nitrogenous
organic substances and iron, washing out the mass and purifying the
salt so obtained by recrystallisation. Potassium ferrocyanide (yellow
prussiate of potash) forms large transparent crystals of a peculiar
soft nature, which dissolve readily in water. It often contains
considerable quantities of potassium sulphate, up to 5 per cent., and
it is to be noted that the impurity is much the cheaper of the two
salts. When barium chloride is added to a solution of the salt, a white
precipitate forms if sulphate be present.
The behaviour of yellow prussiate towards iron salts is noteworthy.
With ferrous salts, for example green vitriol (copperas), it gives a
white precipitate which gradually turns blue in the air; with ferric
salts, for example ferric chloride (“nitrate of iron”), it at once
gives a blue precipitate.
=Potassium Ferricyanide= (Red Prussiate of Potash), K₃Fe(CN)₆ = 329,
is obtained by passing chlorine through a solution of yellow prussiate
until the liquid smells strongly of chlorine and no longer gives
a precipitate with a solution of a ferric salt. The solution then
contains potassium ferricyanide and chloride. The former is obtained by
evaporating and allowing to crystallise.
Pure potassium ferricyanide forms beautiful dark red crystals, which
readily dissolve in water. The solution gives a blue precipitate with
ferrous salts, but only a brown colouration and no precipitate with
ferric salts. Both yellow and red prussiate are used in the preparation
of several much used colours, for Prussian and Chinese blues, and
several others. All cyanogen compounds, with the exception of yellow
prussiate, are extremely poisonous. The following table gives the
solubility of potassium ferricyanide at different temperatures:—
+-----------------------+------------+----------------+
| 100 Parts of Water |Temperature.|Specific Gravity|
|dissolve Parts of Salt.+------------+ of Solution. |
| | °C. | |
+-----------------------+------------+----------------+
| 33 | 4.44 | 1.151 |
| 36 | 10.00 | 1.164 |
| 40.8 | 15.50 | 1.178 |
| 58.8 | 37.80 | 1.225 |
| 77.5 | 100.00 | 1.250 |
| 82.6 | 104.40 | 1.265 |
+-----------------------+------------+----------------+
=Sodium Salts.=—In chemical properties the sodium salts are very
similar to the potassium salts, and, being cheaper, they are generally
used in place of the latter.
=Sodium Carbonate= (Soda Crystals), Na₂CO₃.10H₂O = 286, is made in
enormous quantities in great works and in a very pure state. It forms
large transparent crystals, which effloresce in the air, losing a
large quantity of water, and so falling to a white powder. Although
this property does not interfere with the use of soda, since it is
generally used in solution, yet efflorescence should be as far as
possible avoided by keeping the salt in well-closed packages, because
effloresced soda dissolves more slowly than crystallised, since it has
to combine with water before it can enter into solution.
In the retail trade a form of soda is found which is adulterated with
very large quantities of Glauber’s salt. This is recognised by the
different form of the crystals. Manufacturers sell soda stating its
strength. The colour maker should only buy with this guarantee.
=Sodium Hydroxide= (Sodium Hydrate, Caustic Soda), NaOH = 40, comes
into commerce in the form of hard masses, the use of which would be
very convenient for the colour maker if it were not often very impure.
Thus it is better to prepare a solution oneself, which is accomplished
in the manner given above for caustic potash.
Caustic soda and caustic potash have similar properties; they have a
corrosive action on the skin, readily unite with carbonic acid from the
air, and separate the heavy metals from their solutions in the form of
hydrated oxides.
The strength of caustic soda solutions is given in the following table:—
+----------+----------+----------+----------+
| Specific | Caustic | Specific | Caustic |
| Gravity. | Soda | Gravity. | Soda |
| | per cent.| | per cent.|
+----------+----------+----------+----------+
| 2·00 | 77·8 | 1·40 | 29·0 |
| 1·85 | 63·6 | 1·36 | 26·0 |
| 1·72 | 53·8 | 1·32 | 23·0 |
| 1·63 | 46·6 | 1·29 | 19·0 |
| 1·56 | 41·2 | 1·23 | 16·0 |
| 1·50 | 36·8 | 1·18 | 13·0 |
| 1·47 | 34·0 | 1·12 | 9·0 |
| 1·44 | 31·0 | 1·06 | 4·7 |
+----------+----------+----------+----------+
Besides soda and caustic soda, few soda salts are used in colour
making. However, sodium nitrate (Chili saltpetre), NaNO₃, is frequently
used instead of ordinary saltpetre, from which it differs in being
deliquescent.
=Sodium Thiosulphate= (Hyposulphite), Na₂S₂O₃.5H₂O = 248, is a common
article of commerce, being much used by photographers; it is used in
a few cases in colour making. It forms large crystals with a somewhat
bitter taste, permanent in air and readily soluble in water.
=Sodium Chloride= (Common Salt), NaCl = 58·5, which has a little
application in colour making, is sufficiently pure in the form in which
it is generally used for household purposes.
SALTS OF THE ALKALINE EARTH METALS.
The metals which are known as the alkali earth metals have much
similarity with the alkali metals in their compounds, with the
difference that their alkalinity is much less, and that their salts
are much less soluble in water. For colour making the compounds of
three of these metals—calcium, barium and magnesium—are used.
CALCIUM COMPOUNDS.
The most important calcium compounds are lime and carbonate and
phosphate of lime. Carbonate of lime is used as a pigment, and will be
dealt with in detail among the mineral colours; it will be but briefly
described here.
=Calcium Oxide= (Quicklime), CaO = 56.—When chalk and limestone, which
consist of calcium carbonate, are heated, carbonic acid is evolved, and
calcium oxide, commonly called quicklime, is left. For our purposes
only very pure quicklime is to be used. Its ordinary impurities are
iron oxide and magnesia: the former is found in lime made from red or
brown limestone; the latter in lime made from dolomitic limestone. The
presence of oxide of iron is recognised by the reddish tinge of the
quicklime; if magnesia be present, a small quantity of the quicklime,
when mixed with a very large quantity of water, leaves an insoluble
residue which consists of magnesia.
When quicklime and water are brought together they unite very
energetically and form calcium hydroxide or slaked lime. According to
the quantity of water used for slaking, either dry slaked lime, lime
paste, or milk of lime is produced, all of which find a use in colour
making.
=Calcium Hydroxide= (Slaked Lime), Ca(OH)₂ = 74.—In order to prepare
slaked lime, which contains lime united with just the necessary
quantity of water, the pieces of quicklime are sprinkled with water
from a watering can. The water is rapidly taken up and the sprinkling
is repeated until the lumps begin to fall to a fine powder; in the
process the lime becomes very hot. The slaked lime is then passed
through a sieve in order to separate the larger pieces of quicklime
which have not been slaked; the powder must be kept in well closed
packages, since it energetically absorbs carbonic acid out of the air.
If so much water is added to the lime that a homogeneous wet mass is
formed which can be readily moved with a shovel, one has then lime
paste, which can be conveniently kept in pits as the masons do; it may
be stored in this way for many months without appreciable alteration,
still it is better to keep it covered. To prepare milk of lime, so
much water is used in slaking that a milky liquid is formed, or the
lime paste is mixed up in the proper quantity of water. Slaked lime
dissolves in 700 to 800 parts of water; on standing, the undissolved
slaked lime settles to the bottom of the milk of lime: thus it is
better to prepare milk of lime immediately before use, and to stir it
well to prevent the settling of the solid particles.
Slaked lime in one of its forms is often used instead of the more
costly caustic soda in order to precipitate metallic oxides from their
salts.
At times one finds a too strongly burnt lime, so-called “dead-burnt”
lime, which is very slowly slaked by water. Such quicklime is slaked by
allowing it to lie in water for days, or by means of hot water, which
accomplishes the slaking more quickly.
=Calcium Carbonate=, CaCO₃ = 100, is found naturally in large
quantities as chalk, which consists of the skeletons of extremely small
animals. By powdering and levigating, it is converted into a soft
powder, which is used to lighten the shade of lakes and other colours.
=Calcium Sulphate= (Gypsum), CaSO₄.2H₂O = 172.—This mineral, when
finely powdered, is added to some colours.
=Calcium Phosphate= (Bone Ash), Ca₃(PO₄)₂ = 310, is sometimes used to
lighten the shade of certain colours which might be injured by calcium
carbonate. It comes in large quantities as a fine, white powder from
South America. Naturally, only quite white bone ash can be used; if not
completely burnt it is grey, and will then impair the shade of colours
with which it is mixed.
=Magnesium Carbonate= (Magnesia), MgCO₃ = 84, is also used as an
addition to colours in order to obtain pale shades. It is most cheaply
obtained by dissolving magnesium sulphate (Epsom salts) in water and
adding soda solution so long as a precipitate forms, which is then
washed and dried. The magnesium carbonate prepared in this way is a
very fine, light powder, insoluble in water, which can be mixed with
the most delicate colours without harming them. White magnesia is an
extremely light powder, which may be used when it can be bought at as
low a price as the above preparation.
=Barium Compounds.=—The raw material used for the preparation of barium
pigments is either barium sulphate (barytes, heavy spar) or barium
carbonate (witherite). The latter is much more rare than barytes, which
is almost exclusively employed in the preparation of barium compounds.
The barium compounds of particular importance for our purpose are
barium chloride and nitrate.
=Barium Chloride=, BaCl₂.2H₂O = 244.—This salt is now a common article
of trade, and can be bought at a low price. When pure it forms
colourless crystals readily soluble in water. If the colour maker is
able to get cheap barytes and fuel, it may be advantageous for him to
prepare barium chloride himself.
To prepare barium chloride from barytes, the latter is very finely
ground and levigated, intimately mixed with coal, and the mixture
subjected to a very high temperature, when barium sulphide is formed,
which is dissolved by washing out the mass with water and converted
into barium chloride by adding hydrochloric acid, sulphuretted hydrogen
being evolved.
The best method is to mix 4 parts of barytes with 1 part of bituminous
coal and so much coal-tar that a plastic mass is formed, which is well
kneaded and made into small cylinders 3 centimetres in diameter and 10
centimetres long. These cylinders are placed in layers in a cylindrical
furnace with a good draught, which contains at the bottom a layer of
coal 15 to 20 centimetres thick, then a layer of the cylinders, then
again coal, and so on until the furnace is full. The lowest layer
of coal is lighted, and the whole burnt at a bright red heat, when
the barium sulphate is changed into sulphide. Hydrochloric acid is
poured over the residue and the insoluble part, consisting chiefly of
unaltered barytes, is used for the next operation.
Witherite (barium carbonate) can be converted into barium chloride in a
very simple manner. Hydrochloric acid is added, in which it dissolves
with the evolution of carbonic acid. The solution is allowed to stand
twenty-four hours with excess of witherite; the whole of the dissolved
iron is thus precipitated. The solution is then filtered, evaporated
down and left, when pure barium chloride crystallises out.
Barium chloride and all soluble barium salts should only be dissolved
in pure water (rain or distilled). Water which contains carbonates
or sulphates always gives a turbid solution by precipitating barium
carbonate or sulphate.
ALUMINIUM COMPOUNDS.
The compounds of the earth metal aluminium play a very important part
in colour making, since they form beautifully coloured compounds with
many organic colouring matters. Formerly alum was the only material
used in colour factories for the preparation of the alumina compounds;
at present aluminium sulphate is used, and when it is sufficiently pure
it is the most valuable material, because it contains the greatest
quantity of alumina.
Under the designation of alum only one compound, the so-called potash
alum, was at one time found in commerce, but now there are other alums,
which contain soda or ammonia in place of potash. These salts are of
equal use in colour making to potash alum. The preference is to be
given to the compound which contains the largest proportion of alumina.
The chief point to be observed in connection with alumina compounds for
use in colour making is that they shall be free from iron, because iron
oxide, which would be precipitated out of the solution along with the
colours, in consequence of its red colour would spoil the shade of the
pigment.
=Aluminium Sulphate= (Sulphate of Alumina), Al₂(SO₄)₃.18H₂O = 664.—Any
manufacturer who can obtain cheap china clay (kaolin) and sulphuric
acid can himself prepare this compound with advantage. The apparatus
used for this purpose is an iron pan containing sand, in which is
placed a large earthenware dish. In this dish are put very finely
ground kaolin and strong sulphuric acid, and the mixture is heated so
strongly that the acid boils, evolving heavy, white vapours. It is
absolutely necessary to heat in this manner in order to avoid dangerous
accidents. Sulphuric acid bumps so violently on boiling that it may
even break a thick earthenware dish. The use of a sand bath makes the
bumping harmless.
China clay, which consists of silicate of alumina, is decomposed by
heating with sulphuric acid into silicic acid and sulphate of alumina.
The original milky liquid becomes more transparent during boiling, and
has at last the appearance of starch paste. Kaolin contains varying
quantities of silica. The quantity of sulphuric acid necessary for its
decomposition can only be found by trial. The quantities are chosen so
that a small amount of kaolin remains undecomposed in order that the
aluminium sulphate shall contain no free sulphuric acid.
When the decomposition is finished the pan is allowed to cool and the
solid mass is brought into a vat filled with water, in which it is
stirred until dissolved; then the liquid is left until the jelly-like
mass of silicic acid has sunk to the bottom, when the clear solution of
aluminium sulphate is drawn off and can at once be used.
If solid aluminium sulphate is required—and this is to be recommended
when large quantities are to be prepared—the solution is evaporated
in earthenware dishes until a portion solidifies when dropped on a
cold plate. The molten aluminium sulphate is then cast in prismatic
blocks, which are preserved in boxes. These blocks are of a pure white
colour and very crystalline; they dissolve with difficulty in cold, but
readily in hot water without residue. The solution has an acid taste,
even when it contains no excess of sulphuric acid. When the blocks have
a yellowish tinge, this denotes the presence of iron, and the solution
must be freed from this impurity. Nowadays sulphate of alumina can be
obtained so cheaply that it is hardly of advantage to make it.
THE ALUMS.
These are double salts of aluminium sulphate and potassium, sodium or
ammonium sulphate. There are also other double sulphates known as alums
which, in place of aluminium, contain chromium, iron, etc., but they
are not of interest here. It may still be observed that all alums,
whatever their composition, possess the property of crystallising
together from mixed solutions, so that crystals can be obtained in
which every existing alum is contained.
The potassium, sodium and ammonium aluminium alums are used in colour
making.
=Potassium Aluminium Alum=, KAl(SO₄)₂.12H₂O = 474.—This is the
substance commonly called alum. Like all alums it crystallises in
fine octahedral crystals, which at first are quite transparent, but
slowly effloresce in the air and become covered by a white powder.
It dissolves with difficulty in cold, but readily in hot water. The
solution has at first a sweet taste, with an astringent after-taste.
Alum comes into the market in different forms, of which the following
are the most important: as crystallised alum, in the form of large
crystals united together; as alum meal, a coarse crystalline powder
obtained by rapidly cooling and stirring a hot alum solution. On
account of the larger surface this form dissolves more quickly than the
large crystals. Roman alum is the name of a variety chiefly imported
from Italy; it owes its reputation to its great purity—it contains a
very small quantity of iron.
In order to prepare alum quite free from iron from the ordinary alum
containing iron, it is recrystallised, that is, as much as possible
is dissolved in boiling water and the solution quickly cooled with
continual stirring; the small crystals so obtained are then washed with
cold water. The residual saturated solution of alum, which contains
the greater part of the iron, can be used for the preparation of those
colours which are not injured by the presence of iron.
The solubility of alum in water varies greatly at different
temperatures. The table gives the weight of alum dissolved by 100 parts
of water at different temperatures.
+------------+------------------+---------------+
|Temperature.|Crystallised Alum.|Anhydrous Alum.|
+------------+------------------+---------------+
| 0° C. | 3·90 | 2·10 |
| 10° ” | 9·52 | 4·99 |
| 20° ” | 15·13 | 7·74 |
| 30° ” | 22·01 | 10·94 |
| 40° ” | 30·92 | 14·88 |
| 50° ” | 44·11 | 20·09 |
| 60° ” | 66·65 | 26·76 |
| 70° ” | 90·67 | 35·11 |
| 80° ” | 134·47 | 45·66 |
| 90° ” | 209·31 | 58·64 |
| 100° ” | 357·48 | 74·53 |
+------------+------------------+---------------+
When potash alum is heated it loses water, 75 per cent. of the total
at 61° C.; at 92° C. it melts completely, and all the water is lost by
continued heating at 100° C. The residue is known as burnt alum.
In alum the whole acidity of the sulphuric acid is not neutralised;
the solution has always an acid reaction; if soda solution is added,
the escaping carbonic acid causes the liquid to effervesce. If soda
solution is added until a further addition would cause a precipitate,
a solution of so-called neutral alum is formed which has no longer
an acid reaction. Neutral alum is occasionally required in colour
making. In preparing it the soda solution must be added with great care
when the liquid is near its point of neutralisation. Any addition of
soda solution after this point is reached will cause a separation of
alumina. This is not desirable, since it is generally only wished to
precipitate the alumina in combination with colouring matters.
=Roman Alum.=—Under this name, or that of “cubic alum,” a variety of
alum is sold, generally at a rather higher price than ordinary alum,
from which it is distinguished by its crystalline form. Ordinary alum
forms octahedral crystals often the size of a child’s head, but cubic
alum well formed cubes.
The property of crystallising in cubes may be imparted to any alum
solution by the addition of a little potash. Much so-called Roman alum
is made in German works in this way. When this alum contains very
little iron it is quite equal in quality to the best Roman alum, for
the higher value of the latter is entirely due to its small content of
iron. The alum prepared in the province of Naples is still better than
Roman alum; it contains less iron.
When alum is required for the preparation of lakes of bright and
delicate shades, it is indispensable to use a preparation free from
iron, because the brownish yellow oxide of iron would appreciably
injure the shade. Alum, free from iron, is most simply prepared by
dissolving alum in boiling water, running the boiling solution quickly
through a cloth, and quickly cooling with constant stirring. The alum
meal prepared in this way contains much less iron than the original
alum, the iron salts remaining dissolved in the mother liquor. When
this alum meal is collected and cold water poured over it to free it
from mother liquor, it is generally sufficiently pure to be used for
any purpose, but if not, it is again recrystallised. The alum liquors
containing the iron are used for the preparation of colours which are
not injured by the presence of iron.
To test alum for iron yellow prussiate of potash is used, which gives
a blue precipitate with ferric salts. The test is carried out by
dissolving 10 grammes of alum in 1 litre of water, placing the solution
in a tall, narrow cylinder standing on white paper, adding 10 to 20
drops of a saturated solution of yellow prussiate, and well stirring.
On looking down through the liquid, if a distinct colouration is at
once evident, the alum contains much iron, and must be recrystallised;
indeed, the crystals would generally be coloured yellow. On the
contrary, if the solution does not show a blue tint until after
standing several days, the alum contains but a small quantity of
iron, and can be used for most purposes without further purification.
Alum quite free from iron is a rare commercial article; the test will
generally show a feeble blue colouration. If this is not intense and
no blue precipitate is deposited at the bottom, the alum is tolerably
pure, and can be used in colour works. The longer the time before the
blue colouration appears the poorer is the alum in iron.
=Soda Alum=, NaAl(SO₄)₂.12H₂O = 458, is made in some alum works. It
has the greatest similarity in properties with the potash salt, but
is distinguished by a much greater solubility in water and more rapid
efflorescence in air. Soda alum can be bought at varying prices; that
containing iron is much cheaper than that free from iron. When the
latter is to be bought at a fair price it is to be preferred to potash
alum, since, as we shall show later, it contains a larger proportion of
alumina.
=Ammonia Alum=, (NH₄)Al(SO₄)₂.12H₂O = 453.—This compound of aluminium
sulphate and ammonium sulphate is now often met with; the more
expensive potassium sulphate in ordinary alum is replaced by ammonium
sulphate, which is cheaply obtained from the ammoniacal liquor of the
gas works.
Ammonia alum is better for our purpose than potash alum since it
contains more alumina, is generally cheaper and dissolves more easily
in water. Unfortunately most commercial ammonia alum contains so much
iron that it has to be recrystallised before it can be used in colour
works.
One hundred parts of water dissolve at different temperatures the
quantities of ammonia alum given in the table:—
+------------+--------------------------+-----------------------+
|Temperature.|Crystallised Ammonia Alum.|Anhydrous Ammonia Alum.|
+------------+--------------------------+-----------------------+
| 0° C. | 5·22 | 2·62 |
| 10° ” | 9·16 | 4·50 |
| 20° ” | 13·66 | 6·57 |
| 30° ” | 19·29 | 9·05 |
| 40° ” | 27·27 | 12·35 |
| 50° ” | 36·51 | 15·90 |
| 60° ” | 51·29 | 21·95 |
| 70° ” | 71·97 | 26·09 |
| 80° ” | 103·08 | 35·19 |
| 90° ” | 187·82 | 50·30 |
| 100° ” | 421·90 | 70·83 |
+------------+--------------------------+-----------------------+
Of the different alums, ammonia alum contains the largest and potash
alum the smallest proportion of alumina. The composition of the three
commonly occurring alums is given in the following table:—
+--------------------+------------+----------+-------------+
| |Potash Alum.|Soda Alum.|Ammonia Alum.|
+--------------------+------------+----------+-------------+
|Potash, K₂O | 9·95 | | |
|Soda, Na₂O | | 6·80 | |
|Ammonia, NH₃ | | | 3·89 |
|Alumina, Al₂O₃ | 10·83 | 11·20 | 11·90 |
|Sulphuric acid, SO₃ | 33·71 | 34·90 | 36·10 |
|Water, H₂O₄ | 45·51 | 47·10 | 48·11 |
+--------------------+------------+----------+-------------+
Thus ammonia alum is to be preferred to soda alum and soda to potash
alum, whilst the latter is used on account of its greater purity. In
a colour works, in which large quantities of alum are used, it is
advantageous to work with ammonia alum which is recrystallised on the
works.
The alums and aluminium sulphate are the alumina compounds in ordinary
use in colour works; aluminium acetate could also be used if it were to
be had at a reasonable price.
=Alumina=, Al₂O₃ = 102, =and Hydrate of Alumina=.—Pure alumina, or
rather hydrate of alumina, is required in the preparation of many
colours. When the solution of an aluminium salt is precipitated by
soda, the carbonic acid escapes with effervescence, and a gelatinous
precipitate is formed which it is extremely difficult to wash clean.
The precipitate, which consists of hydrate of alumina, shrinks very
greatly in drying, and turns to a horny mass; when strongly heated it
loses water, and becomes a white, insoluble powder of anhydrous alumina.
A variety of hydrate of alumina, heavy, and therefore easily washed, is
obtained by boiling a solution of alum with a plate of zinc lying on a
copper plate until all the alumina has separated. By collecting this on
a filter and pouring hot water over it a number of times it is obtained
quite pure.
Alumina plays a particularly important part in the manufacture of
cobalt colours. When treated with a cobalt salt and heated it takes a
fine blue shade.
In the foregoing those metals and their compounds have been treated
which are extensively used in preparing colours without themselves
forming coloured compounds. The chromates and prussiates are an
exception to this. The ammonia compounds, the alkalis and alkaline
earths, also the acids, are used in making many colours, although
they do not contain colouring principles. The alumina compounds are
in similar case. Themselves colourless, they form at the same time a
carrier for the coloured compound and bring it into a suitable form for
use as a pigment.
An example will explain what we mean by “carrier” of the colouring
matter. Logwood contains a very handsome colouring matter which can be
extracted by water. In order to be able to employ this colouring matter
as a pigment it is combined with alumina, a compound insoluble in water
being formed, which is called a lake. In this compound the alumina is
to be regarded as the carrier of the colouring matter, which it has
fixed in an insoluble form.
In dyeing, which in many respects is closely allied to colour making,
the property of certain metallic compounds, themselves colourless, of
fixing dyes is commonly utilised, the metallic compound being called
the mordant. The fabric is first prepared with the metallic compound or
mordant, and the colour then formed by bringing the mordanted material
in contact with the colouring matter.
The “heavy metals” form, among their numerous compounds, a great number
of coloured substances, and several of them are distinguished by a
great wealth of coloured derivatives; for example, copper, chromium
and cobalt form coloured compounds only. Although the use of pigments
derived from the heavy metals has been considerably restricted in
recent years by the discovery of a series of colouring matters which
replace them, yet they are now, and always will be, of very great
importance in the manufacture of colours. It is, therefore, necessary
briefly to describe the various metals which are used in colour making,
so that the manufacturer may know what metals produce harmless colours,
permanent and unaltered by the atmosphere, and what do not.
The metals are divided into two great groups, designated, according
to their specific gravities, the group of the light and of the heavy
metals. The light metals comprise the alkali, alkaline earth and earth
metals, whose important compounds we have just described. The specific
gravity of each of these metals is less than five times that of water.
The heavy metals have a specific gravity exceeding 5; they are
generally divided into groups, which are known by the name of the
commonest metal in the group. These are as follows:—
Zinc group Zinc, Zn = 65.
Iron group Iron, Fe = 56.
Tungsten group Tungsten, W = 184.
Antimony group Antimony, Sb = 120.
Tin group Tin, Sn = 119.
Lead group Lead, Pb = 207.
Silver group Silver, Ag = 108.
Gold group Gold, Au = 197.
Platinum group Platinum, Pt = 194.
To the zinc group belong the metals zinc, cadmium and indium, of which
only the two first are of importance here. The iron group comprises
iron, manganese, cobalt, nickel, chromium and uranium, all of which
are used in the manufacture of colours. The antimony group contains
antimony and bismuth, the latter of which is of little importance.
To the tin group belong tin and the rare metals titanium, zirconium,
thorium, niobium and tantalum; of these tin alone is important in
colour making. In the lead group are lead and thallium; lead produces
many important pigments. The silver group contains silver, copper and
mercury, the two latter of which are important. Of the gold group gold
alone is of interest, and its importance has been diminished by the
discovery of far cheaper substances which replace it. In the platinum
group, which contains platinum, iridium, rhodium, ruthenium, palladium
and osmium, only platinum itself is used as a colour; it is employed
in porcelain painting to produce the peculiar metallic shimmer known
technically as “lustre.”
The behaviour of the compounds, of the metals mentioned above towards
sulphuretted hydrogen is of the greatest importance to the colour
maker, since on it depends the alterability of the pigments when
exposed to the atmosphere. Many metallic compounds are unaltered by the
sulphuretted hydrogen present in the air, whilst others are in a high
degree affected by it and become gradually darker, so that their colour
may in the end approximate to black.
The pigments containing lead, copper, mercury and bismuth are extremely
susceptible to the action of sulphuretted hydrogen, by the action of
which they form black compounds. Since colours which contain these
metals are not permanent, but darken considerably, endeavours have been
made for a long time to replace them by others not susceptible to the
action of sulphuretted hydrogen. Thus it is desirable to manufacture
only colours free from metals forming black compounds with sulphuretted
hydrogen. For the same reason pigments which contain sulphur should
not be mixed with those containing metals which form black sulphur
compounds.
The rules laid down in the preceding paragraphs are of the greatest
importance for the artist, for by following them he will succeed in
composing a “permanent palette,” that is, containing only such colours
as will not, by their composition, bring about the speedy ruin of the
painting.
Although the majority of the compounds of the heavy metals are
poisonous, some possess this property in an eminent degree. These are
chiefly colours which contain arsenic, antimony, copper and lead. So
far as it is possible, these colours should be dispensed with and
harmless pigments sold in their place, though this is not always
possible, since several poisonous colours cannot be replaced by
innocuous ones.
COMPOUNDS OF THE HEAVY METALS.
=Zinc Compounds.=—Zinc oxide, ZnO, and zinc sulphate, ZnSO₄.7H₂O, are
the compounds of this metal used in the colour industry. Zinc oxide,
which is used as a white pigment, is a powder which turns yellow when
heated, and is not acted upon by sulphuretted hydrogen. Zinc sulphate
(white vitriol) occurs as colourless crystals, or more frequently as
greyish white crystalline masses. The freedom of zinc sulphate from
iron is of particular importance; the commercial article is seldom
satisfactory in this respect. In order to free commercial zinc sulphate
from iron, the property of zinc hydroxide of precipitating iron oxide
from neutral solutions may be employed. The zinc sulphate is dissolved
in water, and ammonia added in small quantities until the precipitate
of zinc hydroxide remains on stirring. When the liquid is left in
contact with the precipitate and stirred up once or twice a day, if
iron is present the precipitate will turn yellowish brown, owing to the
separation of ferric hydroxide, and in the course of a few days all the
iron will be removed from solution. The liquid should then give no blue
colouration with yellow prussiate of potash.
Zinc oxide is used as a white pigment, zinc chromate as a yellow, and
zinc cobalt compounds as green colours.
=Cadmium Compounds.=—Cadmium is a metal which possesses great
similarity to zinc, with which it occurs in nature. In the preparation
of cadmium compounds the metal is generally used. This is dissolved in
dilute sulphuric acid, hydrogen is evolved, and a solution of cadmium
sulphate obtained.
Cadmium is used in colour making only for the preparation of the
beautiful cadmium yellows.
=Iron Compounds.=—These are of the greatest importance to the colour
maker. Several, in which iron alone is the colour principle, are very
valuable: ochre, rouge, Venetian red, sienna and umber, for example.
Iron compounds are also used in the preparation of many colours. The
most important is:—
=Ferrous Sulphate= (Green Vitriol, Copperas), FeSO₄.7H₂0.—This
substance, which occurs commercially in a form of great purity at a
very low price, is generally the starting point in the preparation
of iron pigments. When pure, it forms fine sea-green crystals, with
an astringent metallic taste, which are not poisonous and are easily
soluble in water. After long exposure to the air, ferrous sulphate
becomes covered with an ochre-coloured crust, consisting of basic
ferric sulphate. The ferrous oxide contained in the green vitriol has
united with oxygen and been converted into ferric oxide. The latter
requires a larger quantity of acid than ferrous oxide for the formation
of soluble salts, so that an insoluble basic salt is separated. The
same thing occurs when a solution of ferrous sulphate is exposed to the
air.
When green vitriol, or any other ferrous salt, is exposed to the
action of oxidising agents, such as chlorine or nitric acid, the iron
is rapidly changed into the ferric state. This transformation is of
particular importance in the manufacture of certain blue pigments.
We give in a table the relation between the percentage of crystallised
ferrous sulphate (FeSO₄.7H₂O) contained in a solution at 15° C. and its
specific gravity:—
+--------+-----------------+--------+-----------------+
|Specific| Percentage of |Specific| Percentage of |
|Gravity.|Ferrous Sulphate.|Gravity.|Ferrous Sulphate.|
+--------+-----------------+--------+-----------------+
| 1·000 | 0 | 1·118 | 21 |
| 1·005 | 1 | 1·125 | 22 |
| 1·011 | 2 | 1·131 | 23 |
| 1·016 | 3 | 1·137 | 24 |
| 1·021 | 4 | 1·143 | 25 |
| 1·027 | 5 | 1·149 | 26 |
| 1·032 | 6 | 1·155 | 27 |
| 1·037 | 7 | 1·161 | 28 |
| 1·043 | 8 | 1·168 | 29 |
| 1·048 | 9 | 1·174 | 30 |
| 1·054 | 10 | 1·180 | 31 |
| 1·059 | 11 | 1·187 | 32 |
| 1·065 | 12 | 1·193 | 33 |
| 1·071 | 13 | 1·200 | 34 |
| 1·077 | 14 | 1·206 | 35 |
| 1·082 | 15 | 1·213 | 36 |
| 1·088 | 16 | 1·219 | 37 |
| 1·094 | 17 | 1·226 | 38 |
| 1·100 | 18 | 1·232 | 39 |
| 1·106 | 19 | 1·239 | 40 |
| 1·112 | 20 | —— | —— |
+--------+-----------------+--------+-----------------+
Yellow and red prussiate, which have been already mentioned, also
belong to the iron compounds. They have been separately mentioned
because the iron is contained in them in a peculiar form as a portion
of an organic radical.
=Ferrous Chloride=, FeCl₂, may sometimes be used instead of green
vitriol. When iron is dissolved in hydrochloric acid hydrogen is given
off and a solution of ferrous chloride is obtained; but when rouge is
dissolved in the same acid, ferric chloride is formed. When iron is
dissolved in nitric acid, in consequence of the oxidising properties of
this acid a ferric salt is obtained. Iron forms two series of salts:
in the ferrous compounds the iron is in the same form as in green
vitriol and the corresponding salts; in the ferric compounds the iron
is contained in a higher state of oxidation. By powerful oxidising
agents, as nitric acid or chlorine, ferrous compounds are converted
into ferric.
=Manganese Compounds.=—Manganese (Mn) is a metal whose compounds show
great similarity with those of iron, like which it forms two oxides
(also others), manganous oxide (MnO) and manganic oxide (Mn₂O₃). The
salts of manganous oxide are not oxidised in the air like those of
ferrous oxide.
The raw material used in the preparation of manganese compounds is the
mineral pyrolusite, which is manganese dioxide (MnO₂).
Manganese sulphate (MnSO₄) forms rose-red crystals containing varying
quantities of water. The residues from the preparation of chlorine can
be used as the material for the preparation of colours. According as
pyrolusite and hydrochloric acid or pyrolusite, salt and sulphuric acid
are used for this purpose a solution of manganous chloride or sulphate
is obtained.
Manganese compounds have but a restricted use in colour making.
=Nickel Compounds= are generally coloured green, but they are not used
as pigments.
=Cobalt Compounds.=—Among these are found many important pigments. All
cobalt compounds are coloured; in beauty and variety of shade they can
only be compared with those of chromium. In properties cobalt is very
similar to iron and nickel.
The form in which cobalt is used in preparing colours is either cobalt
nitrate, Co(NO₃)₂.6H₂O, or cobalt chloride, CoCl₂.6H₂O. Both salts are
articles of commerce, but generally they are so dear that it is more
profitable for the colour maker to prepare them direct from the cobalt
minerals. A simple method for preparing cobalt compounds from the ores
is therefore given. The most important cobalt ores are speiss cobalt,
a compound of cobalt and arsenic, and cobalt glance, a compound of
cobalt, arsenic and sulphur. The former mineral often contains only
small quantities of cobalt, and it is advisable for our purposes to use
cobalt glance, which contains from thirty to forty per cent. of cobalt.
This mineral is first roasted, that is, is heated with a plentiful air
supply, by which means the arsenic is driven off. On account of the
poisonous nature of the arsenic vapours the roasting must be conducted
in a furnace with a very good draught.
Under the name of zaffre, roasted cobalt ores come into commerce. These
may be used in the preparation of cobalt compounds, by which means
the operation of roasting is avoided. According to the quality of the
ore which has been used to obtain zaffre, it contains a very varying
proportion of cobalt. The varieties richer in cobalt must be used; they
are technically known by the mark FS, or FFS (the best).
The roasted cobalt ores or zaffre are treated with fused acid potassium
sulphate, when the salts of iron and manganese are decomposed, whilst
cobalt and nickel sulphates remain unchanged. In a Hessian crucible
are melted 300 parts of acid potassium sulphate, and 100 parts of the
powdered zaffre are gradually added, mixed with one part of green
vitriol and one part of saltpetre; the mixture is heated so long as
sulphuric acid escapes. The mass is then boiled with water and the red
solution treated with sulphuretted hydrogen so long as a precipitate
is formed; this may contain copper, manganese, and bismuth. After
filtering, soda is added to the boiling liquid; cobalt carbonate is
precipitated, which can be converted into nitrate or chloride by
solution in the corresponding acid. If cobalt sulphate is required,
the solution, after treatment with sulphuretted hydrogen, need only be
evaporated to crystallisation, when the sulphate separates in fine red
crystals. Cobalt nitrate and chloride are very soluble in water; to
obtain them their solutions must be strongly evaporated and quickly
cooled whilst stirring. The crystals of cobalt nitrate and chloride
absorb moisture from the air and deliquesce; they must be kept in glass
vessels with well-ground stoppers.
The cobalt compounds which are to be used in colour making must be free
from iron, nickel and arsenic, which would detract from the cleanness
of the colours. If the precipitate produced by soda contains iron it
is mixed with excess of solution of oxalic acid, and after a few hours
the cobalt oxalate is filtered from the liquid, in which all the iron
is dissolved. The cobalt oxalate can then be converted into nitrate or
chloride by treatment with nitric or hydrochloric acids.
These salts form the material for the preparation of the cobalt
compounds, a large number of which are used as extremely durable red,
blue and green pigments; several of them, such as cobalt blue, cannot
be exactly replaced by other pigments. On account of the industrial
importance of the cobalt colours, these directions for the preparation
of the soluble cobalt salts from the ores have been given with some
detail. The preparation of the cobalt colours will be given _in
extenso_ later on.
=Chromium Compounds.=—As the name indicates, this metal yields numerous
coloured compounds (χρῶμα, colour); in fact, only coloured chromium
compounds are known, and the colours are most varied—yellow, green, red
and violet. On this account the chromium compounds are among the most
important used in colour making; a great number of colours are prepared
by their aid. Chrome ironstone, as we have already stated, is the raw
material for the preparation of chromium compounds. From it potassium
bichromate is made on a large scale in special works, so that no colour
maker is compelled to prepare chromium salts himself.
When the chromium pigments contain no metal blackened by sulphuretted
hydrogen, they have the desirable property of being unaltered by the
atmosphere. Like the cobalt compounds, they are distinguished by their
great stability when heated; on this account, they have a large use in
porcelain painting.
=Molybdenum, Tungsten and Vanadium Compounds= on account of their cost
have a very limited use as pigments. Molybdenum compounds are obtained
from molybdic acid; compounds of tungsten from the metal; and those of
vanadium from ammonium vanadate.
=Antimony Compounds= can be used in the preparation of several
pigments, but, on account of their behaviour towards sulphuretted
hydrogen, the pigments cannot be regarded as really permanent, and
their use is generally diminishing. The so-called antimony vermilion is
the only antimony compound at all extensively employed.
=Bismuth Compounds= possess properties very similar to those of
antimony. Only one bismuth preparation is used as a pigment, and this
is very sensitive to the action of sulphuretted hydrogen, being changed
into black bismuth sulphide.
=Tin Compounds= are employed in two ways: some are themselves colours,
such as stannic sulphide (mosaic gold); others, themselves colourless,
are used in making pigments, as stannous and stannic chlorides.
Stannous Chloride, SnCl₂.2 H₂O, is obtained when tin is dissolved in
hydrochloric acid, hydrogen being evolved. Stannic Chloride, SnCl₄, is
formed when tin is dissolved in a mixture of hydrochloric and nitric
acids (_aqua regia_).
Tin compounds have, similarly to aluminium salts, the property of
forming coloured insoluble compounds (lakes) with many organic
colouring matters. Their use for this purpose is extensive.
=Arsenic Compounds= formerly played an important part in colour making.
They were used in the manufacture of a large number of pigments,
very beautiful but extremely poisonous. At the present time, we can,
fortunately, entirely dispense with arsenic in colour making; the
arsenic colours can be replaced by others equally handsome and less,
or not at all poisonous. The most important of the arsenic compounds
is the trioxide As₂O₃, or Arsenious Acid, commercially known as white
arsenic. This substance is obtained in large quantities as a by-product
in the extraction of several metals. It forms masses which are either
glassy or have the appearance of porcelain. Freshly sublimed arsenic
trioxide is glassy; this form gradually changes into the porcellaneous
variety, it dissolves with difficulty in water. A strong solution can
only be obtained by boiling for many hours.
The compounds of arsenic with sulphur, formerly extensively used as
pigments, have now almost fallen into disuse.
=Lead Compounds= belong to the substances most largely used in making
colours. Unfortunately all lead colours have two very important
drawbacks. They are all very poisonous and at the same time extremely
sensitive to sulphuretted hydrogen, so that they are very considerably
altered by the action of the small quantities of that gas contained in
the atmosphere of an ordinary dwelling. A striking example of this is
seen in the lead paints used on the doors of water-closets. The paint,
at first pure white, becomes gradually darker, and at last almost
black, the lead compound having been changed into black lead sulphide.
On account of this great sensitiveness of lead compounds, it would
be better if they could be excluded from the list of colours. Great
care must be taken not to mix lead compounds with others which contain
sulphur; a discolouration of the mixture would be the inevitable result
in a very short time.
The oxides of lead and a number of its salts are themselves pigments,
for example, litharge, PbO, red lead, Pb₃O₄, and white lead (basic lead
carbonate). These pigments are prepared on a large scale in particular
works. At this point only those lead compounds will be mentioned which
are generally used for the preparation of other lead pigments; they
are: lead sulphate, nitrate, acetate and chloride.
=Lead Sulphate=, PbSO₄, is formed when sulphuric acid or the solution
of a sulphate is added to the solution of a lead salt; so obtained it
is a white crystalline powder insoluble in water. This substance is
generally not made in colour works, but is purchased from chemical
works or dye houses, of which it is a by-product. In this form
(lead bottoms) it is generally not sufficiently pure, but contains
admixtures of sulphuric acid or aluminium salts, from which it is
freed by washing. The lead sulphate is stirred up in water, the heavy
precipitate allowed to settle, the wash water drawn off, and after
repeating this process until the wash water no longer shows an acid
reaction, the purified precipitate is dried. In this condition it is a
heavy, white powder, and can alone be ground into paint. But on account
of its crystalline nature, which reduces the covering power, such use
is inadvisable.
=Lead Nitrate=, Pb(NO₃)₂.—This very important compound may be bought,
but it is advisable to prepare it in the works. Water is placed in a
wooden tub, then half the volume of nitric acid is added, and finely
powdered litharge gradually stirred in, the liquid being kept in
constant movement. When it is seen that the litharge is only slowly
dissolved, the liquid is well stirred after each addition of litharge
and then tested by litmus paper. When this is no longer reddened, the
nitric acid is completely saturated, and the liquid contains only
lead nitrate in solution. It is allowed to stand until the insoluble
portions have settled, and then drawn off into another vessel where
crystals of lead nitrate separate in a few days. If the salt be
required in solid form, the solution may be evaporated in earthenware
dishes; generally the solution is used as it is obtained.
Pure lead nitrate forms white crystals which are not particularly
soluble in water, 1 part requiring 2 parts of water at the ordinary
temperature. Lead nitrate is decomposed on heating, like all nitrates,
and litharge remains. The solution of this salt is used in the
preparation of those lead pigments which are obtained by precipitation,
for example, chrome yellow.
=Lead Acetate=, Pb(C₂H₃O₂)₂.3H₂O.—The compounds of lead with acetic
acid are of great importance. Two of these are to be considered:
neutral lead acetate, commonly known as sugar of lead, and basic lead
acetate. It may be advisable to manufacture both these compounds, the
latter always. Neutral lead acetate comes into commerce in the form of
colourless heavy crystals, which are often covered by a white powder
of the basic acetate; they dissolve readily in water, and the solution
has a sweetish taste, hence the name “sugar of lead”. Frequently the
solution is very turbid; this is caused by the carbonates contained in
the water. The turbidity may be removed by the addition of a little
acetic acid. It is only economical for the colour maker to prepare
sugar of lead when he can obtain cheap raw materials, lead or litharge
and vinegar. Pyroligneous acid may also be used if it is colourless,
its odour being without importance for this purpose.
The best method for preparing lead acetate from litharge is to place
the vinegar in a tub and hang in it a strong linen bag filled with
finely ground litharge. The tub is kept covered for a few days and its
contents then tested with red litmus paper. When this is turned blue,
the liquid is drawn off and vinegar gradually added whilst stirring,
until blue litmus paper is just turned red. In this process, after
neutral lead acetate has been formed, more lead oxide is dissolved, and
the liquid thus acquires an alkaline reaction. The further addition of
acetic acid reconverts the basic salt into neutral lead acetate.
Lead acetate solution may, with advantage, be prepared directly from
metallic lead. For this purpose, lead is granulated by melting and
pouring in a thin stream into cold water, where it solidifies in
irregular pieces. This is done in order to give the lead as large a
surface as possible. Three high narrow tubs placed one above the other
so that liquid may flow from the highest to the middle, and from this
into the lowest, are filled with granulated lead. Vinegar is placed
in the uppermost vessel to cover the lead; after twenty-four hours it
is allowed to flow into the middle, and after a further twenty-four
hours into the lowest tub. In this way, a solution of basic lead
acetate is formed, to which the necessary quantity of acetic acid is
added to bring it into the neutral condition. If crystalline lead
acetate is required, the liquid is evaporated down and quickly cooled
with stirring, so that small crystals are formed. Generally, however,
evaporation is unnecessary, since lead acetate is always used in
solution in preparing colours.
If the lead acetate solution be not colourless, which is generally
the case when coloured acetic acid is used, the defect may be removed
by stirring a little bone black into the liquid and filtering after
twenty-four hours, when a completely colourless solution is obtained.
It is always necessary to know exactly how much lead acetate is
contained in the solutions prepared by these processes. The lead or
the litharge is therefore weighed and the volume of the lead acetate
solution measured. One hundred parts by weight of crystallised lead
acetate are obtained from 62·54 parts of lead.
Lead acetate solutions must be kept in well-covered vessels. The
carbonic acid of the air will turn the liquid turbid. The turbidity may
be removed by the addition of acetic acid.
In the following table is given the percentage of crystallised lead
acetate contained in solutions of different specific gravities:—
+--------+------------+--------+------------+
|Specific|Crystallised|Specific|Crystallised|
|Gravity.|Lead Acetate|Gravity.|Lead Acetate|
| | per cent. | | per cent. |
+--------+------------+--------+------------+
| 1·0000 | 0 | 1·1869 | 26 |
| 1·0064 | 1 | 1·1955 | 27 |
| 1·0127 | 2 | 1·2040 | 28 |
| 1·0191 | 3 | 1·2126 | 29 |
| 1·0255 | 4 | 1·2211 | 30 |
| 1·0319 | 5 | 1·2303 | 31 |
| 1·0386 | 6 | 1·2395 | 32 |
| 1·0453 | 7 | 1·2486 | 33 |
| 1·0520 | 8 | 1·2578 | 34 |
| 1·0587 | 9 | 1·2669 | 35 |
| 1·0654 | 10 | 1·2768 | 36 |
| 1·0725 | 11 | 1·2867 | 37 |
| 1·0796 | 12 | 1·2966 | 38 |
| 1·0867 | 13 | 1·3064 | 39 |
| 1·0939 | 14 | 1·3163 | 40 |
| 1·1010 | 15 | 1·3269 | 41 |
| 1·1084 | 16 | 1·3376 | 42 |
| 1·1159 | 17 | 1·3482 | 43 |
| 1·1234 | 18 | 1·3588 | 44 |
| 1·1309 | 19 | 1·3695 | 45 |
| 1·1384 | 20 | 1·3810 | 46 |
| 1·1464 | 21 | 1·3925 | 47 |
| 1·1544 | 22 | 1·4041 | 48 |
| 1·1624 | 23 | 1·4156 | 49 |
| 1·1704 | 24 | 1·4271 | 50 |
| 1·1784 | 25 | —— | —— |
+--------+------------+--------+------------+
=Basic Lead Acetate=, Pb(C₂H₃O₂)₂.2PbO.—This salt may be regarded as
a compound of neutral lead acetate with lead oxide. It is obtained
by digesting vinegar with excess of litharge or with metallic lead,
and also by treating lead acetate solution with litharge so long as
the latter is dissolved. In the method last given, 100 parts of sugar
of lead require about 118 parts of litharge to produce a saturated
solution of basic acetate. The solution of this compound is alkaline;
it turns red litmus paper blue. When exposed to the air, a turbidity
is quickly produced owing to the separation of lead carbonate. In one
white lead process basic lead acetate is the starting point of the
manufacture.
=Lead Chloride=, PbCl₂, is seldom used in making colours. It may
be prepared by stirring powdered litharge in common salt solution
until the powder appears white. This, when washed, constitutes basic
lead chloride. On adding hydrochloric acid to the washed mass until
the liquid remains acid, lead chloride is obtained in the form of
crystalline needles, which are very little soluble in cold, but more
easily in hot, water.
Like any other soluble lead salt, lead chloride may be used in the
precipitation of colours, but is seldom employed on account of its
small solubility. Basic lead chloride was, at one time, used as a white
pigment, and after melting, by which it is turned yellow, as a yellow
pigment; it is no longer in use for these purposes.
=Copper Compounds.=—These are generally green or blue, and have an
extended use in the production of colours. The metallic copper which
is used in the preparation of colours is of the ordinary commercial
quality. The impurities which it contains are generally so small in
quantity that they are without importance for our purpose.
=Copper Sulphate= (Bluestone, Blue Vitriol), CuSO₄.5H₂O.—This is the
commonest of the commercial copper salts, and on that account deserves
our especial attention. It forms large sky-blue crystals, which
effloresce slightly in the air, possess an unpleasant metallic taste,
and are poisonous, like all soluble copper compounds.
Copper sulphate comes into commerce in a very pure form, but some
qualities contain zinc sulphate or ferrous sulphate. The presence of
zinc may be detected most easily by boiling the solution with excess
of caustic soda, when copper oxide separates as a black powder, whilst
zinc oxide remains dissolved. When sulphuretted hydrogen is passed
through the liquid, a white precipitate of zinc sulphide is formed.
Iron is detected by passing sulphuretted hydrogen through the solution
so long as a precipitate is formed, allowing the liquid to stand in
a covered vessel, pouring it off from the precipitate, adding nitric
acid, boiling and adding a solution of potassium ferrocyanide; a blue
precipitate denotes the presence of iron.
Copper sulphate is rarely found which is quite free from iron and zinc.
If these impurities are present in but small quantity, the zinc not
exceeding 1 per cent. and the iron at most 0·5 per cent., the copper
sulphate may be regarded as sufficiently pure for our purposes.
It may be here remarked that copper sulphate obtained from mints is
generally of great purity, and hence particularly adapted for colour
making.
When copper sulphate and other copper salts are dissolved in water,
pale blue flocks of copper carbonate generally separate. This is due
to the carbonate of lime contained in the water. An addition of a few
drops of sulphuric, nitric or hydrochloric acid suffices to prevent
this separation.
=Copper Nitrate=, Cu(NO₃)₂.6H₂O.—This salt may occasionally be
obtained in colour works as a by-product. When nitric acid is poured
over copper, there follows a copious evolution of nitric oxide, which
produces brown fumes of nitrogen peroxide in air. Nitric oxide may be
used to convert ferrous into ferric salts, a transformation required
in making Prussian blue. In working in this way, nitric acid is poured
over copper contained in a vessel provided with a delivery tube for the
gas. The blue solution is at once used. Pure copper nitrate forms fine
blue crystals, which very readily deliquesce in the air. The solution
is therefore generally used as it is prepared.
=Copper Acetate=, Cu(C₂H₃O₂)₂.H₂O.—Copper is readily attacked by acetic
acid. A number of salts are formed, of which some are used as pigments.
For our purpose it will be sufficient to describe the manufacture of
verdigris; few colour makers prepare any other copper acetate. A
solution of this salt is most simply prepared in the following manner:
Slaked lime is stirred with strong vinegar, and the solution left in
contact with the excess of lime so long as it has a weak acid reaction.
The solution, which contains acetate of lime, is poured into a solution
of copper sulphate so long as a precipitate of sulphate of lime is
formed. When this has been separated from the liquid, the latter is
ready for further treatment. It contains only a very small quantity of
dissolved sulphate of lime, which is not harmful in the preparation of
colours.
In addition to the copper compounds mentioned here, several others were
formerly used as pigments, or in the preparation of pigments which are
no longer employed, because copper compounds of good colour can be
obtained in a cheaper manner.
The same precautions should be taken in the use of copper colours
which were mentioned for lead pigments; copper compounds are equally
sensitive towards sulphuretted hydrogen, by which they are gradually
discoloured.
=Mercury Compounds.=—Mercury forms compounds which, vermilion in
particular, are used as pigments, and others which are used in the
preparation of pigments. In many cases metallic mercury is the starting
point in the preparation of the mercury compounds. The compounds
commonly known as calomel and corrosive sublimate are also used.
=Mercurous Nitrate=, HgNO₃.—Nitric acid acts upon mercury in a manner
differing according to its strength, and according to whether the
mercury or the nitric acid is used in excess. In order to prepare
mercurous nitrate, acid free from chlorine must be diluted at least
with four times its volume of water, and the mercury must be in excess.
On warming, the mercury is gradually dissolved, and, on cooling,
the solution deposits colourless crystalline needles of the salt. A
further crop of crystals is obtained after evaporating the solution.
When the action of nitric acid is over, the solution must be at once
separated from the excess of mercury to prevent the formation of basic
salts. If the salt has been properly made, it is completely soluble in
water, but if a lemon yellow precipitate is formed on dissolving, the
nitrate contains a basic salt, which can only be dissolved by warming
and adding more nitric acid.
=Mercuric Nitrate=, Hg(NO₃)₂, is most simply obtained by warming
mercury with very strong nitric acid. The heating must be continued
until a test portion of the solution no longer gives a precipitate with
hydrochloric acid. When this solution is evaporated, nitric acid is
given off, and a salt crystallising in white needles is obtained, which
dissolves in water with the separation of a yellow basic salt. It is
therefore better to use the hot solution, which contains a little free
acid, without evaporating.
Instead of mercurous and mercuric nitrates, the corresponding sulphates
may be used, but the chlorides are more frequently employed since they
can be readily obtained from the makers.
=Mercurous Chloride= (Calomel), HgCl, is obtained pure by adding common
salt solution to a solution of mercurous nitrate and washing the
precipitate, which is insoluble in water.
=Mercuric Chloride= (Corrosive Sublimate), HgCl₂ a common article of
commerce, is prepared by heating a carefully made mixture of mercuric
sulphate and common salt, when mercuric chloride sublimes. It is a
white crystalline mass, soluble in 13·5 parts of water at 20° C., and
soluble in 3 parts of alcohol. Although all mercury compounds are very
poisonous, corrosive sublimate requires particular care in handling,
since its easy solubility makes it surpass all other mercury compounds
in poisonousness.
The mercuric sulphate required in the above preparation is obtained by
heating mercury with sulphuric acid. Corrosive sublimate can also be
prepared by adding hydrochloric acid to mercurous nitrate, and heating,
with gradual addition of hydrochloric acid until a clear solution is
formed, from which mercuric chloride crystallises on cooling.
=Silver Compounds.=—Silver nitrate, AgNO₃, is the only one of
importance here. It is obtained by dissolving silver in nitric acid,
when a blue solution is obtained because commercial silver contains
copper, evaporating the solution to dryness, melting the residue, and
keeping it molten until all the copper nitrate is decomposed. This
point is recognised when a small portion of the melt dissolved in water
does not give a blue colouration with excess of ammonia. Fused silver
nitrate forms a white crystalline mass readily soluble in water and
turning black when exposed to light, like many other silver compounds.
=Gold Compounds.=—Gold is now very little used in preparing colours.
The compound used for this purpose is gold chloride, AuCl₃, which is
obtained by heating gold with hydrochloric acid, and adding nitric
acid in small quantities until all the metal is dissolved. By careful
evaporation of the yellow solution gold chloride is obtained in
brownish yellow crystals, which easily dissolve in water.
The compounds of molybdenum, vanadium and uranium are less used than
those of gold, yet these metals find a special use in the preparation
of colours for porcelain painting and for colouring glass, for which
they are of great importance. The preparation of their compounds from
the raw materials is complicated and not remunerative to the colour
maker; they should be obtained from chemical works.
* * * * *
In the foregoing, the most important compounds of inorganic origin
used in making colours have been briefly described, less in order to
teach the methods for their preparation than to give the manufacturer
the means of learning their properties. Since the great development of
chemical industries during the last decades it is more advantageous for
the colour maker in most cases to draw his supply of these substances
from works of good reputation than to make them himself; only in the
case of a few substances, which are sold at unreasonably high prices,
will it be profitable for him to prepare them himself.
CHAPTER VI.
THE MANUFACTURE OF MINERAL PIGMENTS.
By mineral pigments we understand those which consist of compounds of
metals with elements such as sulphur, chlorine and iodine, or with
compound radicals, such as cyanogen, or of metallic salts.
Looking at the classification of mineral pigments from the chemical
standpoint, a grouping according to the constituents would appear
preferable, and we should have groups of colours consisting of metallic
oxides, sulphides, salts, etc. In such a division of pigments,
according to their constituents, no regard would be taken of the colour
of the pigment. The white zinc oxide would be placed in the same group
with yellow lead oxide and red lead oxide; and red mercury sulphide and
yellow cadmium sulphide would fall into the same group of the sulphur
compounds.
The chemical composition of a pigment is of less importance to the
colour manufacturer than its shade, and it therefore appears to us
more reasonable to prefer to classify mineral pigments according to
similarity of colour. We shall therefore place all those mineral
pigments together which possess the same colour.
Common usage differs from the scientific in the description of colours.
In the physical sense, yellow, red and blue are the so-called “simple
colours,” between which lie orange, green and violet as “mixed
colours”. Physics knows no white colour and no black colour, but
describes white as a mixture of all the simple colours and black as
the absence of colour. A grey or brown shade, produced by different
mixtures of simple colours, is just as little known in the scale of
colours as white or black.
The colour maker follows, as we have said above, the common manner of
speaking; to him white and black are equally as much colours as red
and green. Besides the pure principal colours (yellow, red and blue),
and the mixed colours obtained from them (orange, green and violet),
colour makers distinguish many shades of each colour—lemon yellow,
sulphur yellow, cherry red, blood red, violet blue, etc. For the
present purpose it is of great importance to accurately distinguish
the several shades, for the value of many colours is in proportion to
their beauty of shade. The colour maker is often required to produce a
colour of some particular shade, which he accomplishes in many cases by
a suitable alteration in the process by which the colour is made, in
other cases by mixing different colours, in which event chemistry is
of no help to him; he must depend on the sensitiveness of his eyes to
colour.
=White Mineral Pigments.=—We are acquainted with a great number of
white or, more properly, colourless mineral compounds; they possess the
property of reflecting, undecomposed, all the rays of light which fall
upon them, in consequence of which they produce that impression upon
the eye which we call white. According as a white substance reflects
every ray of light or absorbs a portion, we see it as a brilliant pure
white or, in the latter case, as a white with a grey tinge. If a white
body reflects the majority of the rays of light falling on it, but
decomposes a small number, we perceive a white which has a yellow, blue
or red tinge.
The most valuable white for the colour maker is evidently that which
reflects, unaltered, all the rays of light; it is the most brilliant,
and free from every tinge of colour. The physical condition of the
substance is most important. Solid substances are either crystalline,
that is, possess definite shapes formed according to a regular law,
or they are amorphous, that is, are composed of irregularly formed
particles. Snow and white lead may serve as representatives of these
two classes. Snow is composed of small colourless crystals of ice, the
flat surfaces of which reflect, undecomposed, the light falling on
them. The smaller are the crystals, the more pure appears to us the
whiteness of the snow, and the thinner is the layer of snow required
to produce the sensation of whiteness. But if the snow crystals are
larger, the white appears to have a bluish tinge, and only a thick
layer of snow is opaque. White lead, being an amorphous substance in a
condition of very fine division, reflects the light very regularly, so
that a thin layer of white lead appears quite opaque.
Among the artificial pigments, crystalline or amorphous, exactly the
same conditions hold good as between snow and white lead. Of amorphous
pigments a very thin layer is in most cases sufficient to make the
surface upon which they are spread invisible, or, as the technical
expression runs, “to cover,” whilst crystalline substances possess
a smaller covering power. A striking example of this is seen by a
comparison of two white pigments, white lead and “patent white” (lead
oxychloride). The former is amorphous, the latter crystalline. Both are
completely colourless and reflect white light, but in consequence of
its amorphous condition and finer particles, white lead possesses far
greater covering power than “patent white”.
Among all other colours the same rule holds. Amorphous pigments have
always a greater covering power than crystalline. The smaller the
crystals of the latter the greater is their covering power, so that in
preparing pigments of a crystalline character care must be taken to
make the crystals as small as possible.
From the above definition of white pigments it follows that an immense
number must exist, since every colourless substance in a state of fine
division appears white. Generally only those bodies are used which
are insoluble in water, or almost insoluble, and which possess great
covering power. The following may be mentioned as white pigments, only
a few of which are in use: white lead, white zinc, permanent white,
lead oxychloride, lead sulphate and sulphite, zinc oxychloride, lead
antimoniate, antimony white, tin white, tungsten white, and in addition
certain earths, pipe clay, china clay, etc. Several of these pigments
are far too expensive for ordinary use, and have no advantage over much
cheaper pigments except for very special purposes, such, for example,
as bismuth white for cosmetics.
In general use we find very few artificial white pigments; these are
lead, zinc and barium compounds. Circumstances may arise which make it
expedient for the colour maker to manufacture other white pigments, for
example, a demand for them, or favourable opportunities for obtaining
the requisite raw materials.
The white lead pigments, of which there is a large number, as we have
indicated, all have the great disadvantage that they are not permanent,
that is, are changed by atmospheric influences. It is well known that
lead is a very delicate reagent for sulphuretted hydrogen, with the
sulphur of which it forms a black compound. Now the air, especially
in towns, contains sulphur in the form of sulphuretted hydrogen or
ammonium sulphide; though the quantity is very small, the fate of
every white or coloured lead pigment is decided by it; after a longer
or shorter time it will be discoloured, will gradually darken, and
finally be turned black. In spite of this great changeableness of lead
pigments they are used by artists and painters, although the majority
could be replaced by more permanent pigments entirely unaltered by the
atmosphere.
WHITE LEAD.
This pigment, which in addition to other good properties has remarkable
covering power, was amongst the earliest known artificial pigments.
Already in the fourth century before Christ, Dioscorides described the
preparation of white lead, which was obtained by exposing lead to the
action of the vapours of vinegar, removing the white layer and treating
it with water. The Roman writers describe a similar method; they use
the name _cerussa_, under which white lead is known to-day in commerce.
Although white lead has been so long known, it was left to Bergmann,
in 1774, to show that it contained carbonic acid; before that it was
believed to be lead acetate. The development of analytical chemistry
was followed by a knowledge of its constitution and the use of more
rational methods of manufacture. Whilst in the middle ages the
manufacture of white lead was almost exclusively in the hands of the
Dutch and Venetians, in later years it gradually spread, and now
many works are concerned in the manufacture of this pigment. That
adulterations of white lead were not rare in former times appears from
the writings of Basil Valentine, an alchemist of the fifteenth century.
Commercially white lead is known under most varied titles, of which the
following are the principal: White lead, Venetian white, Dutch white,
Krems white, Kremnitz white, flake white, etc.
According to its chemical composition, white lead is a compound of
lead carbonate and lead hydroxide, that is, a basic lead carbonate.
Commercial white lead, apart from intentional admixtures of other white
substances, contains lead carbonate and lead hydroxide in varying
proportions, as is shown by the following analyses by Mulder, who found
that all the samples examined by him were composed according to one or
other of the following formulæ:—
2 PbCO₃.Pb(OH)₂, containing 86·27 per cent. of PbO.
5 PbCO₃.2Pb(OH)₂ ” 85·86 ” ”
3 PbCO₃.Pb(OH)₂ ” 85·45 ” ”
4 PbCO₃.Pb(OH)₂ ” 85·00 ” ”
According to Hochstetter, the manufacture of white lead must be
directed to obtaining the compound 2 PbCO₃.(OH)₂, which possesses the
following percentage composition:—
PbO 86·32
CO₂ 11·36
H₂O 2·32
The compound of this composition is distinguished by being completely
amorphous, and so possesses the greatest covering power. Commercial
white leads, as is seen from the formulæ of Mulder, may differ
appreciably from this composition, when they will have a smaller
covering power, since they will contain some quantity of neutral
lead carbonate, PbCO₃ (containing 83·46 per cent. of PbO), which is
crystalline.
White lead is prepared according to very different methods, the
principle of which consists in subjecting a solution of tribasic lead
acetate to the action of carbonic acid, by which the basic carbonate
is produced and the neutral acetate formed, the latter being then
reconverted into the basic acetate, which again serves to produce white
lead and so on.
CHAPTER VII.
THE MANUFACTURE OF WHITE LEAD.
The processes by which white lead is or was manufactured may be
divided, according to the principal operations, in the following
manner:—
1. Processes in which metallic lead is subjected to the action of
acetic acid vapour, whilst the vessel in which this operation is
conducted is exposed to a higher temperature. In the oldest so-called
Dutch method this increase of temperature is effected by the
decomposition of manure, by which the vessels containing the lead and
acetic acid are surrounded. In consequence of the heat produced by this
fermentation, acetic acid and water are volatilised, and oxygen also
being present, lead acetate is formed.
Also, as a consequence of the oxidation of the lead, heat is produced,
which accelerates the process, and lead oxide is formed in large
quantity, which unites with the neutral acetate already formed to
produce a basic compound. The vessels in which this process is taking
place are in an atmosphere containing much carbonic acid produced by
the fermentation of the surrounding organic matter; this carbonic acid
converts the basic lead acetate into white lead.
The German or Austrian method is to be regarded as an improvement on
this rough process. The heat necessary for the normal course of the
chemical reactions is produced from fuel; the carbonic acid formed by
the combustion of the fuel is used to convert the basic lead acetate
into white lead.
2. In the above methods the manufacture of white lead commences with
the production of white lead from metallic lead and acetic acid. In the
so-called French method a solution of basic lead acetate is decomposed
by carbonic acid into white lead and neutral lead acetate, which latter
is again converted into basic acetate.
3. The English method. The principle of this process consists in
moistening litharge with a solution of lead acetate and exposing it to
the action of carbonic acid, whereby white lead is formed.
Methods for manufacturing white lead, which are often advanced as
entirely new processes, may be always traced to one of the above, from
which they deviate but little in principle, and the deviations cannot
always be regarded as improvements. In the following detailed account
of the manufacture of white lead we shall adhere to the classification
just given, according to which there are three principal methods: (1)
Manufacture of white lead from metallic lead, acetic acid and carbonic
acid (Dutch and German processes); (2) manufacture of white lead from
basic lead acetate (French process); and (3) from litharge moistened
with lead acetate solution (English process).
We should remark that every year “new” processes for the manufacture of
white lead are patented. The majority of these will not be mentioned;
to those acquainted with the principles of chemistry they at once
appear impracticable.
MANUFACTURE OF WHITE LEAD FROM METALLIC LEAD.
(a) DUTCH PROCESS.
This essentially primitive process, when properly conducted, produces
white lead of good colour and covering power, which are the properties
for which this pigment is valued. It is now seldom used,[2] because
other methods give a product of equal colour in a shorter time. It is,
however, of economic interest, as showing how a branch of industry
may rise from crude beginnings to a high state of perfection. The
operations comprised in the Dutch process are as follows:—
[2] In England the Dutch process is in general use.—TRANSLATOR.
(1) Casting the lead into sheets; (2) placing these sheets in pots and
arranging the pots in the stacks (placing the pots containing lead
and acetic acid in the bed of manure); (3) removing the pots from the
stack; (4) separating the white lead formed in the pots; (5) further
purification of the impure white lead by grinding, washing and drying.
1. =Casting the Lead into Sheets.=—At first sight it would appear
unsuitable to cast lead in sheets, since this metal can be readily
rolled into sheets of any thickness. Experience has, however, shown
that rolled lead is only slowly attacked by acetic acid vapours, whilst
cast sheets are rapidly attacked.
An iron pan about one metre in diameter, with an iron cover furnished
with a pipe opening into a flue, is used for melting the lead. This
arrangement is designed to protect the workman from the dangerous
vapours evolved from the molten metal. At the workman’s side of this
cover is a counterpoised slide, which only remains open when the
counterpoise is held in check by a lever. In front of the kettle
there is an iron plate movable about a horizontal axis. The lead
being heated to just above its melting point, the workman takes 7 to
8 kilogrammes of metal in a ladle, and pours it on the plate, which
is horizontal. The lead solidifies in a very short time, but before
it is completely solid the plate is inclined towards the pan so that
the still liquid lead runs back into it, leaving a very thin sheet on
the plate. The hard sheet is removed from the plate, and the latter
cooled by cold water to be ready for a new casting. The sheets made in
this way are not more than 1 to 2 millimetres thick. They are then cut
into strips of a width to suit the size of the pots in which they are
converted into white lead; the width of the sheets is generally 5 to 6
centimetres. Since the rate at which the white lead is formed depends
on the surface of the metallic lead, instead of continuous sheets the
lead is generally cast into gratings. For this purpose an iron plate,
upon which are intersecting strips, is used instead of the flat plate.
Plates for the casting are also used containing grooves intersecting
at right angles. In the first case, plates are obtained in which are
openings meeting at right angles, and in the second case, according to
the distance of the grooves apart, a more or less wide-meshed lattice
work.
[Illustration: FIG. 4.]
2. =Building up the Stacks.=—The rolled-up lead plates are placed in
the pots. These (Fig. 4) are somewhat conical in shape; they have at
some distance from the bottom a projecting ring, or sometimes three
projections only, upon which the lead spiral rests. Before the spirals
are put in position, a quantity of ordinary vinegar, about a quarter of
a litre, is poured in. There must be sufficient room below the spiral
so that it shall not be in contact with the vinegar. The insides of
the pots are glazed at least half-way up, so that the liquid does not
penetrate the porous earthenware.
The pots have a capacity of about 1 litre, and a diameter at the top
of 10 centimetres. If lead plates are used, the pots are about 20
centimetres high; if gratings are used the pots may be lower, by which
there is economy in room and a larger number can be placed in one stack.
The stacks, built up of pots and manure, are of different sizes; it
is not advisable to make them too small, or the loss of heat would
be considerable. A stack 4 to 5 metres long, 3½ metres wide and 6 to
7 metres high will contain 6,000 to 8,000 pots and 9,000 to 11,000
kilogrammes of lead.
The stack consists of a rectangular pit walled on three sides; the
fourth side is open, with the earth dug out in the form of an inclined
plane, in order to permit the introduction of the pots and the manure.
The construction of the stack is commenced by placing the pots at the
bottom in rows, avoiding interspaces as much as possible. In a stack of
the size mentioned a layer contains 1,000 to 1,200 pots. Between the
pots containing lead and acetic acid are arranged a number of larger
ones containing acid only; the object of these is to furnish acetic
acid vapour. When the pots are in place, 3 or 4 lead plates are placed
on each spiral, the top plate forming the cover; immediately over the
pots strong wooden planks are laid, and upon them a layer of boards,
which must fit so tightly that nothing can fall through. On the boards
is spread out a layer of fresh stable manure, with which the space
between the outside row of pots and the wall is also filled. The layer
of manure is 30 to 40 centimetres thick.
Upon the lowest layer of pots, a second, third and so on are built up
exactly in the same manner, so that the whole stack is filled with
alternating layers of pots and manure. In order to prevent the cooling
of the uppermost layer of pots, it is covered with a thicker layer of
manure 60 to 70 centimetres thick. When lead plates and the taller pots
are used, a stack will generally contain 15 layers; but when gratings
and the smaller pots are employed, 18 layers can be packed into the
same space. In arranging the layers of pots, care should be taken to
leave spaces at tolerably equal distances, so that the air necessary
for the oxidation of the lead may enter. To prevent the cooling of the
stack at the front, where it is not protected by masonry, when full it
is walled up with boards; a board roof also protects the erection from
rain.
In place of manure, spent tanners’ bark can be used, which in the
same manner ferments, producing heat and carbonic acid. In places in
the neighbourhood of large tanneries this spent bark is generally
obtainable at lower prices than stable manure, which is more valuable
for agricultural purposes; the former has also a very considerable
advantage, white lead made by means of spent tanners’ bark being
generally of a purer white than that made with manure. The reason for
this is that in the decomposition of animal excrement small quantities
of sulphuretted hydrogen are produced, a gas which produces black lead
sulphide when it comes into contact with lead compounds.
According to the results of practical experience, pigs’ dung cannot be
used in the manufacture of white lead; so much sulphuretted hydrogen
is evolved from it that the white lead is not white, but has a greyish
tinge.
When bark is used in place of manure, a discolouration of white lead by
sulphuretted hydrogen is not to be feared, but there is the drawback
that a longer time is necessary for the corrosion of the lead, because
the bark decomposes more slowly than the manure, and accordingly gives
out less heat and carbonic acid.
According to the climate of the country, the stacks may be differently
erected. In colder countries it is necessary to sink them in the earth
and surround them with masonry, as directed above; but in warmer
climates such effectual protection against cooling is unnecessary, yet
in all cases it is better to sink the stack in the earth on account of
the regularity of temperature so obtained.
Instead of sinking the stacks in the earth, they may be built in the
open when there is a plentiful supply of manure or bark; but they must
then be surrounded by a very thick layer of manure to prevent cooling.
It is a desirable alteration in the construction of the stacks to
provide the pots with lids, and so avoid the use of the layer of boards
separating each two layers of pots. The object of the cover is simply
to prevent dirt from falling into the pot. It should not fit tightly on
the edge, or the entry of carbonic acid into the interior of the pot
would be made difficult. The lids are therefore rounded and fit loosely
on the pot. When pots with lids are used, the lowest layer is covered
with manure in the ordinary way; upon this again comes a layer of pots,
and so on.
The transformation of the lead may be regarded as complete in four
to six weeks when manure is used, but with bark the time extends to
ten weeks. The quantity of white lead obtained varies in different
cases; for example, from a stack 5 metres long, 4 metres wide, and 6
metres high, into which 12,000 kilogrammes of lead were put, 10,000
kilogrammes of white lead were obtained, and 4,000 kilogrammes of
lead remained unaltered. In another case, for a stack of 8 layers 280
kilogrammes of vinegar and 9,600 to 12,000 kilogrammes of lead were
used, and there was a residue of 10 to 15 per cent. of lead.
3. =Removal and Grinding of the White Lead.=—The stack is pulled down
after the lapse of the necessary time; the lead plates and rolls are
collected in wooden boxes and brought into the room where the white
lead is separated from the metallic lead. Formerly the white lead was
removed from the sheets exclusively by manual labour, an operation
extremely dangerous to the workman. It is quite impossible to prevent
the formation of white lead dust, so that the men were continuously
in an atmosphere charged with the poisonous material, and, as a
consequence, suffered from the various forms of lead poisoning.
In order to diminish as much as possible the injurious effects of white
lead on the health of the workmen, manual labour has been, as far as
possible, replaced by machinery, yet the greatest care is necessary in
the different manipulations of so poisonous a substance as white lead.
When the white lead is removed by manual labour, an operation which
ought to be forbidden, the lead sheets are unrolled and struck
together, whereupon the greater part of the white lead falls off. To
remove the remainder of the white lead the plates are laid one upon the
other and struck with a hammer until the white lead is loosened; or the
plates are cleaned with metal brushes.
The masses of white lead obtained in this way are contaminated by
larger or smaller quantities of metallic lead, from which they must
be freed by a further mechanical operation, namely grinding. The
larger pieces of the white lead, which have a thickness of several
millimetres, were picked out and sold separately under the name of
flake white. This was formerly a highly prized quality of white lead,
its appearance being a guarantee of its purity. The flake white
generally found in the market nowadays is not obtained in this manner,
but by mixing white lead with a solution of dextrin, forming plates
from the paste and drying them slowly in the air.
In order to separate the white lead mechanically from the remains of
the lead sheets, grooved rollers are used, between which the sheets are
passed. In order to guard against dust, the rollers are surrounded by a
closed casing, in which there is also a sieve which serves to separate
the larger pieces of white lead (flake white) from the fine dust. The
arrangement is represented in Fig. 5. The unrolled plates pass through
the opening, B, on to an endless leather band, by means of which they
are carried between the grooved rollers, D and E; after they have
passed through these they go between a second pair of rollers, F and G,
which are placed nearer together; they then fall into the drum-shaped
sieve, H, out of which they leave the apparatus in the direction of K.
The white lead falls through the sieve, is caught in trucks placed at
J, and carried away to the mills.
[Illustration: FIG. 5.]
A mechanical arrangement for the separation of white lead from the
unaltered metallic lead, due to Horn, is represented in Figs. 6 and
7. It consists of a drum, in which is the spindle, _b_, provided with
the arms, _c_. The teeth, _e_, on the arms reach nearly to the lower
curve of the drum, but pass at a somewhat greater distance from the
upper portion so that the pieces of lead can fall down again after
they are carried up. The material is fed in through the hopper, _t_,
the rotation of the arms loosens the white lead from the pieces of
metallic lead, and it is carried on by the water which passes through
the sieve, 3, and the stop cock, _h_, into the settling tank. The
lead pieces which are carried forward have their progress checked by
the bridge, _o_, they are collected by the perforated scoop, _n_, are
raised above the hopper, _m_, and fall out of the apparatus at _r_. If
it is required to continue the treatment of the material in the drum
for a longer period it is only necessary to close the hopper, _m_, by
the slide, _n_.
[Illustration: FIG. 6.]
[Illustration: FIG. 7.]
_White Lead Mills._—Before the white lead is subjected to the real
process of grinding, it is generally first ground dry, or, more
properly, pressed or crushed. This crushing is accomplished by means
of vertical or edge-runner mills, which consist of mill-stones running
round upon a stone bed about a vertical axis. The mill is surrounded by
a wooden casing to prevent the escape of dust.
Wet grinding, which is done between mill-stones, may be carried out in
two ways, with the production of hard or soft white lead. The former is
obtained when the lead acetate is not removed, the latter when all the
lead acetate is washed out.
[Illustration: FIG. 8.]
_Hard White Lead_ presents a shining mass, broken with difficulty. This
appearance is a guarantee against adulteration with barytes; white
lead, which contains this adulterant, does not give a smooth, but an
uneven earthy fracture. Hard white lead is rather difficult to grind,
and requires very careful treatment to be brought into that state of
fine division in which it is usable.
The dry white lead, after powdering under the edge-runners, must pass
through a sieve, which retains the particles of metallic lead, before
it is subjected to wet grinding. The mills used for wet grinding differ
little, or not at all, from the ordinary pattern.
[Illustration: FIG. 9.]
A mill designed by Richter of Königsee, in Thuringia, for wet grinding,
is constructed as follows (Figs. 8 and 9). The shaft, _F E_, is driven
by a water-wheel and the necessary gearing at 60 revolutions per
minute; the bevelled cog-wheel _G_, by means of the cog-wheels _H_ and
_J_, drives the shafts _K_ and _L_, which, by means of the bevelled
cog-wheels _a_ and _b_, communicate to the runner stones of the mills,
_M_, _N_ and _O_, a speed of 140 revolutions per minute. _C D_ is the
framework for the support of the storied arrangement of mills, _f_ and
_g_ are bearings with cast-iron cups to receive the escaping oil, _i_
is a clamp fastening the axle _d_ to _k_. A steel cup in _k_ rests upon
the hardened top of the spindle, _l_; the bed stone rests upon the beam
_n_ (80 millimetres thick) and is prevented from lateral movement by
the surrounding _oo_; _p_ is a wooden support in the opening in the bed
stone, carrying the stuffing box, _q_, which prevents the white lead
from running out, and connects the spindle, _l_, with the bed stone.
The runner stone, _r_, is surrounded by the box, _s_, cemented with
white clay inside and out and fastened to the bed stone. The lever,
_t_, turning about _w_, moved by the screw, _u_, and handle, _v_,
regulates the position of the runner. The diameter of the stones is 95
centimetres.
Thirty kilogrammes of white lead, mixed with water, are fed into the
top mill of the series shown on the right; the mixture flows by the
spouts, _e_, into the lower mills, and is received in vessels, from
which it is emptied into the holder, _P_. From _P_ it goes through the
3 mills on the left. After passing through 6 mills, white lead without
barytes is ready for use. If the white lead contains an admixture of
barytes, it is put through the 3 mills on the left a second time. In 24
hours 900 to 1,200 kilogrammes (18 to 24 cwt.) of white lead are ground.
In dry grinding, mills are used arranged so that the formation of dust
is avoided, a matter which is of particular importance. The usual
size of these mills has a diameter of 90 to 95 centimetres for both
runner and bed stone. The grinding surfaces of both stones have radial
grooves.
[Illustration: FIG. 10.]
Fig. 10 represents the construction of Lefèbre’s white lead mill, which
is designed to give the greatest protection possible to the workmen. At
A, the white lead masses are enclosed in a hopper lined with bronze,
with internal angular projections; by means of M, which is grooved in
a similar manner, the larger lumps are broken up and enter the mill
itself by means of the hopper under A. The mill consists of bed stone,
H, and runner, K. The grinding surfaces are grooved to facilitate the
delivery of the ground white lead. As the illustration shows, the
stones are completely covered by M, so that the escape of dust is
almost completely prevented. The ground white lead is conducted by the
tubes, O O, to the drums, O′ O′, from which it is packed.
In order to obtain hard white lead, the material which has been ground
dry under the edge-runners is mixed with water to a soft paste, or if
water has been added whilst the lead was under the edge stones, more
is now added to make the paste thin enough to be ready for the mills,
where it is ground, being fed in regularly by means of a copper spoon.
The paste issuing from the mill is collected in earthenware pans or
plaster of Paris moulds, in which it is dried.
These pans have usually the shape of a truncated cone, which was the
form in which white lead was formerly brought into trade from Holland.
In drying, water is lost, and the mass of white lead shrinks, so that
the lump can be removed from the mould after a few days on turning
it upside down. The drying is accomplished either in the air or in
artificially heated stoves. The heating must at first be gradual, or
the mass of white lead would shrink so rapidly that the cone would be
full of cracks, and then easily fall to pieces. When once the drying
has reached a certain stage, the temperature of the stove may be
raised to 50° C. (122° F.) without danger of breaking the lumps. When
quite dry, the surface of the white lead, which is now rough, must be
smoothed by scraping, when it is ready for the market.
_Soft White Lead._—The hard white lead prepared as just described
consists of very heavy and very hard lumps of the purest white. When
soft white lead is required, the admixed lead acetate must be removed
by washing. This is accomplished by adding a larger quantity of water,
either when grinding under the edge-runners or in the mills, so that
a thin pulp is formed; this is run into a receiver, in which is a
stirrer. The white lead is not completely prevented from sinking by the
stirrer; a soft mud is deposited at the bottom of the vessel, which
can only be stirred up with difficulty on account of its high density.
When this vessel is full, the stirrer is stopped and the milky liquid
allowed to settle, which happens in a short time on account of the
high specific gravity of white lead. The clear liquid above the white
lead is drawn off into a tank lined with cement. It is advisable to
arrange the stirrer so that it may be placed at any height in the
vessel; if this is the case, by gradually lowering the stirrer whilst
in motion, the white lead lying at the bottom can be mixed up with
fresh water. These operations are repeated until all the lead acetate
is removed.
Soda solution is added to the wash waters in order to recover the lead
dissolved in them as lead acetate; lead carbonate is precipitated and
settles at the bottom of the tank. This precipitation may also be
effected by putting lumps of limestone in the tank. The paste remaining
in the washing tubs, which now contains only pure white lead and water,
is filled into bags of closely woven material and the water pressed out
by a gradually increasing pressure, until a stiff pulp remains behind.
This is then completely dried, either in the air or in drying stoves.
Soft white lead forms either irregular lumps or a soft, heavy powder.
The lower qualities of white lead contain a smaller or larger quantity
of finely ground barytes; the higher the proportion of barytes the
smaller is the covering power of the mixture. A very simple method for
detecting barytes in white lead will be given later.
(b) GERMAN PROCESS.
The German or Austrian method of making white lead is also known as the
chamber process, since the formation takes place in closed chambers,
constructed of wood or masonry. In the older processes, cast lead
sheets were bent double and hung on cross bars in a wooden box with
a water-tight bottom, with the precaution that the plates did not
touch. A number of these boxes, generally 90, were arranged in a hot
room, each box being about 1·6 metre long, 0·4 metre wide and 0·3
metre high. On the bottom of each box was poured a mixture of vinegar
or dilute acetic acid and wine refuse, and the box was covered with
a well-fitting lid. The temperature of the room was gradually raised
week by week; during the first week remaining at 25° C., during the
second at 38° C., the third at 45° C. At the commencement of the
fourth week the temperature was raised to 50° C., at which it was kept
for a fortnight. At this high temperature a considerable quantity of
acetic acid is evaporated, causing the formation of lead acetate,
which is converted, by the carbonic acid evolved from the wine refuse,
into basic lead carbonate. When the proper temperatures have been
maintained, on opening the boxes almost all the lead is found changed
into white lead, which is knocked off, and the residual lead used in
casting new plates. It is easy to conceive that the boxes may be well
replaced by brick chambers, in which a large number of lead plates
are brought and into which acetic acid vapours and carbonic acid are
introduced after the room has been closed. Chambers are used which can
contain 12,000 to 12,500 kilogrammes of lead.
These chambers, in which the lead plates are hung upon wooden supports,
have an opening immediately above the bottom, which is connected with
a retort in which vinegar, containing 4 to 5 per cent. of acetic acid,
is boiled. After about 12 hours, by the simultaneous action of the
vapours of acetic acid and the oxygen of the air, lead acetate is
formed. Carbonic acid is now led into the chambers. The carbonic acid
is obtained by burning charcoal in a cylindrical furnace; it is cooled
by being passed through a long iron tube before it enters the chamber.
For 12,500 kilogrammes of lead there are required every day about 482
litres of dilute acetic acid, obtained by mixing strong acetic acid
with water until the mixture contains 4·5 per cent. of the acid, and
18 kilogrammes of charcoal, from which the carbonic acid is obtained.
The time required is 5 or 6 weeks, and the residue of unaltered lead
varies from 10 to 35 per cent.
The white lead obtained by this process is quite usable, but the
process has the considerable disadvantage that there is no control
over the quantities of materials used. In order to produce a certain
quantity of white lead of a certain composition, definite quantities
of lead, oxygen, acetic acid and carbonic acid are necessary. If,
then, the apparatus can be so arranged that the quantities of material
employed can be accurately measured, a great advance will have been
made, for the operation will be no longer conducted at random, but
under definite unchangeable conditions. The quantities of carbonic acid
and acetic acid can be calculated beforehand. The volumes of the gases
required may be measured without difficulty by meters of the type used
for measuring coal gas. Upon this principle are based a number of more
modern methods.
[Illustration: FIG. 11.]
According to the process of Major, the vapours of water and acetic
acid are introduced at the same time into the chambers filled with
lead plates, in order to produce basic lead acetate. This part of the
process requires about 12 hours. Then carbonic acid is introduced; it
is produced by burning charcoal in an iron cylinder, through which air
is forced. By means of this carbonic acid, which is at a comparatively
high temperature, about 60° C., the lead acetate is quickly changed
into white lead. A portion of the lead acetate remains undecomposed;
in order to remove this, at the close of the operation ammonia is
injected, which decomposes the lead salt. The ammonia salts now present
are finally driven out by means of superheated steam. Major’s apparatus
is depicted in Fig. 11. _A_ and _B_ are chambers with horizontal
gratings upon which the lead lies; _C_ is the furnace for burning the
charcoal, provided with a fan. The products of combustion from _C_ pass
under the boiler _D_, their passage being regulated by the valve, _a_;
they then heat the boiler _E_, containing acetic acid, and enter the
chambers, _A_ and _B_, through the flue, _b_, or are directed by the
valve in _b_ into the chimney, _d_. The gases, after passing through
the chamber, find an exit at _e_. The steam pipe, _f_, conducts steam
into the boiler _E_, through _g_, and also into the chambers, _A_ and
_B_, thus heating them and providing the necessary moisture; _h_ is the
funnel for filling _E_; the pipe, _k_, carries the acetic acid vapours
into the chambers. After the thin lead plates have been brought into
the chambers they are closed and the temperature raised to 49° to 60°
C., steam and acetic acid vapours are led in for 10 to 20 hours in
order to form the basic acetate, then the furnace gases are introduced
at a temperature of 60° C. The white lead obtained in this manner can
be finished in the ordinary way by washing and grinding, but it is
better to remove the lead acetate by introducing ammonia, and then hot
air or superheated steam, as previously stated.
[Illustration: FIG. 12.]
[Illustration: FIG. 13.]
The process is complete in 2 to 4 weeks. Gartner, working according to
this process with 150 kilogrammes of lead in a chamber 1·26 metre long,
0·78 metre high and 0·78 metre wide, obtained good white lead in 28
days.
The apparatus designed by H. Kirberg for the manufacture of white lead
is illustrated in Figs. 12, 13 and 14. The lead plates are hung upon
the laths, _a_, in the chambers; the supports of the laths, _b_, go
through the slits, _c_, in the supports, _d_, and project through the
walls at _e_. The carriers, _b_, hang from bolts by brass wire. By
striking the end of the laths, _e_, they are made to swing so that the
white lead loosely adhering to the lead plates is shaken off and fresh
surfaces of metal are exposed. The openings in the walls through which
the ends of the laths project are closed by indiarubber. In order to
prevent the production of dust when the chambers are emptied, water is
introduced in a fine spray upon the lead plates from the copper tubes,
_v_, placed under the roof of the chamber. The water washes off the
remains of the white lead from the plates.
[Illustration: FIG. 14.]
In a similar manner, the white lead process may be carried out in a
shorter time when the gases enter the chamber under increased pressure;
but this is attended with difficulties, since continuous supervision of
the apparatus and of the tightness of the chamber is necessary.
[Illustration: FIG. 15.]
The apparatus of W. Thompson (Fig. 15) consists of a chamber, _A_,
constructed with a false roof, _B_, to carry off the condensed vapours,
and provided at both sides with doors, through which the waggons,
carrying the lead, are introduced and removed. The pipes, _n_, which
convey air and carbonic acid, are provided with branches, _e_, which
reach to the sides of the chamber, and are joined to the perforated
tubes, _D_. The pipes, _n_, are provided with reservoirs, _b_, which
prevent the too rapid entry of the air or carbonic acid, and at the
same time give a sufficient heating surface. Upon the waggon, _E_, are
the frames, _v_, which support the lead plates. The plates may be solid
or gratings; they are 3 to 12 millimetres thick, and are arranged at
intervals of about 25 millimetres in the frames. The troughs, _F_, for
the reception of the acetic acid are filled from the reservoir, _Z_.
The steam pipe, _C_, effects the evaporation of the acid; the steam
pipe, _d_, heats the chamber at the commencement of the process, and
also when _C_ is out of use. When the chamber is filled with lead, the
troughs, _F_, are filled with acetic acid of 5 per cent. strength. The
chambers are closed, and steam is led through _C_ and _d_ until the
temperature in the chamber reaches 25° to 50° C., and the evaporation
of the acid begins. Then air is forced in under a small pressure
through _n_, _e_, _D_ during 3 to 4 days, after which follows a mixture
of equal parts of carbonic acid and air, continued until the formation
of white lead is complete. When plates 3 millimetres thick are used,
and the temperature is gradually raised from 25° to 50° C., about 12
days are required; but if the plates are 12 millimetres thick, 28
days are necessary. For the proper carrying out of this process it is
important that the temperature of the chamber should be very gradually
raised from 25° to 50° C.
In the process of P. Rey molten lead is poured in a thin stream into
water, and the “granulated” metal then placed in vessels, in a layer
30 centimetres thick, upon a grating 5 centimetres above the bottom.
In the bottom are narrow tubes which, reaching above the lead, serve
to admit air. Acetic acid is allowed to flow over the lead from vessel
to vessel. In order to obtain the proper solution, a layer of lead, 2
metres thick, is necessary, so that 6 to 7 vessels are arranged, one
above the other. If lead acetate solution be used, the layer of lead
need only be 1·2 metre thick. The solution of basic lead acetate is
then treated with carbonic acid according to the ordinary process.
In addition to the modifications of the German white lead process which
have been described, many others have been proposed. The principle of
many of these methods is, that finely divided lead is much more rapidly
converted into white lead than lead in the form of plates; finely
divided lead exposes an enormously greater surface to the action of the
acetic acid and other materials than do lead plates.
In Rostaing’s method the lead is changed into very small pellets, by
allowing the melted metal to flow on to a rapidly rotating iron disc;
the molten lead, in consequence of the centrifugal force due to the
rapid rotation, assumes the form of very small drops, which are thrown
off the disc and cooled in a vessel of cold water.
Torassa recommends that lead, obtained in pellets by pouring into
cold water, should be brought into a rapidly rotating vessel, whereby
the greater part will be converted into fine dust (?). This lead dust
is said to be then converted into white lead by simple exposure to
air, lead oxide being first formed, and from it basic lead carbonate.
This process is not workable on a large scale. The rapid oxidation of
finely divided lead by air has been applied by several inventors to
the manufacture of white lead. The processes of Woods, M’Cannel and
Grüneberg are founded upon this transformation. In essentials they are
as follows: lead is finely divided in iron or earthenware cylinders,
and either carbonic acid and air, or a mixture of these with acetic
acid vapour, are introduced by means of the axle of the cylinders.
If a special apparatus is not provided, as it should be, on the large
scale, to separate the unaltered lead from the white lead, the lumps
coming from the chambers must be subjected to a process of levigation,
in which the lead, being the heaviest body, will be first deposited;
the last portions deposited consist of the purest white lead, the lower
layers of which will be tinged more or less grey by an admixture of
finely divided lead and lead peroxide.
White lead manufactured by the German process occasionally exhibits
perceptible reddish or greyish tinges, the cause of which lies in the
defective execution of the process. The red tinge denotes the presence
of free lead oxide, caused by the use of an insufficient quantity of
acetic acid. A grey tint is due to the presence of metallic lead or an
excess of lead carbonate.
(c) FRENCH PROCESS.
The French process for making white lead is based upon the reaction
which occurs when carbonic acid is passed into a solution of basic lead
acetate; basic lead carbonate is precipitated and neutral lead acetate
remains dissolved; the latter is again converted into basic acetate,
from which carbonic acid again separates white lead and so on. This
process, at present used on an enormous scale, is due to the French
chemist Thénard, who first put it into operation on the large scale at
Clichy, near Paris. The method is also known as the Clichy process.
The operations of this process are divided into the production of the
basic acetate and the treatment of its solution with pure carbonic
acid, whereby the basic carbonate is precipitated.
1. =Preparation of the Solution of Basic Lead Acetate.=—The preparation
of this compound has been already described; the following is
supplementary to what was previously given. If litharge be used, it is
dissolved in wooden tubs heated by steam. The acetic acid is brought
nearly to boiling by open steam, and the finely ground litharge
gradually added. In consequence of its high specific gravity, the
litharge would quickly sink to the bottom, so that it is advisable
to keep the liquid in motion by means of a stirrer, and to allow the
litharge to fall in in a thin stream. The introduction of the latter is
continued until the specific gravity of the solution indicates that the
liquid contains three equivalents of lead oxide to one equivalent of
acetic acid.
In working with metallic lead, this must be used in a finely divided
form; it is cast, as in the Dutch process, into thin sheets or
gratings, or into flat wires or ribbons. These ribbons are easily
made by melting the lead in a pan provided with a delivery pipe with
stop cock; beneath the latter is brought a vessel, which can be moved
backwards and forwards upon a tram line, filled with water. When the
melted lead is allowed to flow into this vessel, which is being moved
backwards and forwards, the metal forms long, thin ribbons, which
possess a large surface. A wooden tub is almost completely filled with
these lead ribbons, which are then covered with acetic acid. After a
short time the acid is run off, when, by the action of the air, so
energetic an oxidation of the lead takes place that the contents of the
tub become heated, and steam and acetic acid vapours begin to rise.
When this is seen, the original acetic acid is pumped back into the
tub, and left there for some hours in contact with the lead in order
that it may dissolve the lead oxide. When the solution has reached
a specific gravity of 1·1326 to 1·1415, it is drawn off from the
undissolved lead, which again, in a short time, in consequence of the
rapid oxidation, becomes warm, and is treated with fresh acetic acid.
The lead ribbons become finally so thin that they fall together by
their own weight, and form tight masses, upon which air and acetic
acid can no longer act. These residues are then removed from the
solution vessel and new ribbons introduced. The residues have a velvety
appearance; when they are mixed up with water they make it dark, and
from the turbid liquid a fine, velvet-black powder soon separates,
which consists of finely divided silver. The liquid still remains
turbid owing to the suspension of fine particles of carbon. The lead
ores, especially galena, often contain notable quantities of silver;
silver lead is generally desilverised before use; usually, however,
small quantities of silver remain in the lead. When the lead is
dissolved in acetic acid, this silver settles as a soft powder at the
bottom of the vessels in which the lead residues from the solution tubs
are washed.
2. =Preparation of the Carbonic Acid and Precipitation of the White
Lead.=—The carbonic acid required for precipitating the basic carbonate
is obtained either by heating limestone in a small furnace, from which
the gas is drawn by a pump, or directly by burning charcoal. In the
former case very pure carbonic acid is obtained, and, as a by-product,
valuable quicklime; in the latter case precautions must be taken to
produce pure carbonic acid.
[Illustration: FIG. 16.]
The furnace designed by Kindler for preparing carbonic acid (Fig. 16)
consists of a conical furnace, burning coal or coke upon the hearth,
_a_. The passage, _c_, is divided by a vertical wall, in order to avoid
obstruction from the piling up of fuel. The space, _K_, is filled with
limestone, through which the carbonic acid passes; the tanks, _e_,
filled with water, cool the limestone, and the gas, which then passes
through the water in the washing vessel, _D_, is drawn off by a pump.
In the old process at Clichy the apparatus depicted in Fig. 17 was
used. The basic lead acetate was made in the wooden tub, A, provided
with the stirrer, B C. The solution was run off from this vessel
by means of the cock, b, into the settling tank, E, in which the
mechanical impurities separated from the solution. The clear liquid
ran into the decomposing vessel, a large shallow covered tank, holding
9,000 to 10,000 litres. In this tank opened 800 copper tubes, given
off from the large pipe, S. The small furnace, D, in which limestone
was burnt with coke, produced the carbonic acid; from the pipe at the
top of the furnace the carbonic acid was brought into the Archimedean
screw, h K, was washed with water, and pumped into the solution of lead
acetate. The introduction of the carbonic acid was continued from 10 to
12 hours, after which the apparatus was left at rest until the liquid
in the decomposing tank had become quite clear, through deposition
of the white lead. The clear solution, now containing neutral lead
acetate, was run off into the receiver, m, from which the pump, P,
carried it back into the dissolving tub, A, where it was treated with
fresh quantities of litharge. The solution of neutral lead acetate
drawn off from the white lead had approximately a specific gravity of
1·0901. The white lead at the bottom of the decomposing tank was a
tolerably thick paste. It was transferred to the tank, O, and washed
several times with water. The first wash waters, which contained small
quantities of lead acetate, were returned to the dissolving tub. The
resulting white lead formed a very soft powder; it was at once placed
in the drying pans. The white lead prepared by this process is a
precipitate containing no coarse lumps, so that grinding is unnecessary.
[Illustration: FIG. 17.]
Theoretically, the quantity of acetic acid with which the process is
commenced is sufficient to form an unlimited quantity of white lead,
since all the acetic acid brought into the decomposing tank in the form
of basic acetate is returned to the dissolving tub as neutral acetate.
In practice, however, matters are somewhat different. Small quantities
of acetic acid are lost in the wash waters; each time the solution of
lead acetate is pumped back into the dissolving tub, a small quantity
of acetic acid must be added to make up the loss.
[Illustration: FIG. 18.]
The method pursued by Ozouf, in France, is a considerable improvement
on Thénard’s process. Pure carbonic acid is used for the precipitation,
and white lead of similar composition to that produced by the Dutch
process is obtained, since the introduction of the carbonic acid can be
regulated according to the volume and strength of the lead solution,
and thus white lead of any desired composition can be produced. The
most elaborate precautions for the health of the work-people are taken.
The preparation of pure carbonic acid gas is based upon the absorption
of this gas from a mixture of gases by a solution of sodium carbonate,
and its evolution on heating the solution. The apparatus is shown in
Figs. 18 and 19. The products of combustion obtained from the stove,
_A_, are drawn by the air pump, _E_, through the pipe, _C_, into the
cooler, _B_, which is regularly fed with cold water by _D_. The gases
compressed in the receiver, _E´_, deposit moisture there, and then
proceed through 3 horizontal cylinders, _F_, of sheet-iron, provided
with agitators, in which the carbonic acid is absorbed by a cold
solution of sodium carbonate of 9° B. The unabsorbed gases escape
into the atmosphere through _G_ (Fig. 19). The sodium bicarbonate
solution is received in the wooden tank, _H_, after passing through
the 3 cylinders, _F_. The pump, _I_, of the alternating pump, _I I´_,
lifts the sodium bicarbonate solution out of _H_ and sends it through
the pipe, _K_, into the tubular cylinder, _J_, which stands upon a
cylinder of larger diameter, _J´_, communicating with it only by the
vertical tubes. The bicarbonate solution rises between the tubes in
_J_, passes through the pipe, _L_, drops in a fine spray through the
rose forming its mouth, and by means of the vertical tubes passes into
_J´_ and thence into _M_, where it is heated by means of a steam coil
to 100° C. Carbonic acid is then evolved, and the residual solution of
neutral sodium carbonate, after cooling in the vessel, _R_, by means
of the cold coil, is drawn off by the pump, _I´_, again to enter the
cylinders, _F_, by means of the pipe, _K_. The carbonic acid evolved
in _M_, together with steam, enters _J´_ through _N_, and in rising
in the tubes of the cylinder, _J_, is cooled by the falling spray
of bicarbonate solution. The cooling is completed in the coil, _O_,
surrounded by water; the vessel, _P_, separates the condensed water
and passes the gas on into the holder, _Q_. The pipe, _S_, connecting
_P_ with the suction pipe of the pump, _J´_, serves to restore to the
solution of sodium carbonate the water it has lost, thus maintaining
the proper concentration. The cost of 1 cubic metre of carbonic acid is
10 centimes, of 1 kilogramme 5 centimes.
[Illustration: FIG. 19.]
For the production of white lead, the carbonic acid, by means of the
pipe, _U_ (Figs. 19 and 20), enters the cylinder, _T_, provided with
an agitator and containing a solution of basic lead acetate. By means
of the pump, _V_, the lead solution is fed into the cylinder, _T_,
through _W_. The absorption of the gas proceeds rapidly; the progress
of the operation is followed by the observation of a pointer moving
over a scale; as the gas holder sinks the pointer moves upwards. After
the precipitation of white lead, the contents of _T_ are emptied into
the tub, _b_, in which rotate rakes attached to a vertical axis of iron
plated with copper. When the white lead has settled, the supernatant
solution of neutral lead acetate is drawn off through the pipe,
_c_, by means of the pump, _d_, and conducted into the water-tight
vessel, _X_, containing a stirrer on the vertical axis, _W_, made of
coppered steel. Here litharge is added, and the resulting solution
of basic lead acetate is conveyed to the cylinders, _T_, by means of
the pump, _V_, as already described. The white lead in the tub, _b_,
by putting the stirrer in motion, is washed once with water which has
been previously purified by a little lead acetate. It then goes into
another tub provided with stirrers, where it is several times washed,
sodium carbonate being added to the last wash water until a sample of
the white lead is not coloured by a drop of potassium iodide solution.
In this way the wash water is obtained free from lead, and the product
is said to be of better quality. This, however, is not in accordance
with the fact that good Dutch white lead generally contains some lead
acetate. The two-cylinder pump, _h_, which is in connection with the
gas holder, forces gas over the surface of the liquid in T in order
to drive it into tubs which are not in the position shown for _b_ in
the illustration, and into which there is no direct flow. The washed
white lead is brought into bags which are pressed in a hydraulic press,
dried, ground, sieved and packed in casks. These troublesome and often
dangerous operations have been modified by Ozouf in the following
manner. The pulp white lead runs from the tub, _b_, into the hopper,
_g_, where it is kept mixed by a small stirrer, and from which it
passes on to the cylinder, _f_, heated by gas from the inside. In its
rotation the cylinder carries along the white lead and dries it, it is
then removed by a knife below the hopper, and falls on to an inclined
plane. The hopper and cylinder are in a room provided with a good
draught.
[Illustration: FIG. 20.]
The lumps coming from the drying room are placed by workmen wearing
respirators in buckets on an endless chain, are carried to the mills,
ground and sieved; then, by means of an Archimedean screw, the white
lead is conveyed to a cask in which it is evenly pressed by means of a
special mechanism. A bell announces when a cask is full.
=Manufacture of White Lead by means of Natural Carbonic Acid.=—In
districts where currents of carbonic acid gas issue from the ground,
they can be used in the manufacture of white lead, and are actually
utilised for this purpose. Natural carbonic acid may, of course, be
used for any of the white lead processes.
(d) ENGLISH PROCESS.
In this process, now no longer in use, white lead was obtained by
mixing litharge to a stiff paste with a weak solution of lead acetate
and exposing the paste to the action of carbonic acid. By continually
kneading the mass by means of grooved rollers or of rotating cylinders,
through the hollow axis of which carbonic acid was led, the paste was
thoroughly brought into contact with the carbonic acid.
By this process a good product is only obtained when pure litharge,
entirely free from the oxides of iron and copper, is used. The copper
oxide may be removed from the litharge by means of ammonia if this can
be obtained at a low price; but oxide of iron cannot be removed, and
very small quantities of it are sufficient to impart a yellow tinge to
the white lead.
(e) OTHER METHODS.
In Payen’s process the lead sulphate obtained in considerable
quantities as a by-product in calico printing is the raw material
employed. By treating this lead sulphate with a solution of ammonium
or sodium carbonate, white lead and ammonium or sodium sulphate are
produced. The white lead is then freed from the soluble salts by
washing, mixed with a small quantity of lead acetate, and pressed into
the drying moulds.
By boiling lead sulphate with caustic soda and passing in carbonic
acid (Puissant’s process), a white lead is obtained which differs
considerably in composition from ordinary white lead.
Many methods have been proposed with the object of converting insoluble
lead salts, obtained as by-products or by an inexpensive process, by
treatment with alkaline or alkaline earth carbonates, into white lead.
The fact that none of these methods has obtained a permanent footing in
the industry shows that each must be accompanied by serious defects, or
can only be practicable under peculiar conditions.
Magnesium carbonate is used in Pattison’s process to decompose lead
chloride. Dolomite (magnesian limestone) is the raw material for
the magnesium carbonate. Coarsely powdered, it is heated at a low
red heat, when magnesia is formed, the calcium carbonate remaining
almost entirely unaltered, since it requires nearly a white heat for
its decomposition. The powder ground in water was, when treated with
carbonic acid under a high pressure, soluble, magnesium bicarbonate
being formed, the saturated solution of which contains 2·3 per cent.
of magnesia, and has a specific gravity of 1·028. The solution of
lead chloride contains 1 part of the salt in 126 parts of water; it
is mixed with a slight excess of the magnesium carbonate solution as
quickly as possible. The liquid is drawn off from the mixing vessel
into a large receiver in which a precipitate deposits, consisting of
white lead and a little oxychloride. After drying, the precipitate
is ground with a small quantity of caustic soda to decompose the
oxychloride. A few days afterwards the mass is washed to remove sodium
chloride and the product dried.
The process of Dale and Milner is similar to the above magnesia
process. Litharge, lead hydroxide or insoluble lead salts are mixed
with sodium bicarbonate solution, and, with repeated additions of
water, ground until the formation of white lead is completed. The lead
compound and sodium bicarbonate are used in equivalent proportions.
According to the process of P. Bronner (German patent 52,262), 3
molecules of freshly precipitated lead sulphate are heated with a
solution of 2 molecules of caustic soda, when the basic sulphate 2
PbSO₄.Pb(OH)₂ is formed according to the equation—
3 PbSO₄ + 2 NaOH = 2 PbSO₄.Pb(OH)₂ + Na₂SO₄.
Or 4 molecules of lead sulphate are decomposed by 2 molecules of
caustic soda, according to the equation—
4 PbSO₄ + 2 NaOH = 3 PbSO₄.Pb(OH)₂ + Na₂SO₄.
This transformation takes place at a temperature of 70° C. The
resulting basic sulphate, although pure white, cannot be used as a
pigment on account of its lack of covering power; but by heating with a
solution of sodium carbonate it is converted into white lead.
2 PbSO₄.Pb(OH)₂ + 2 Na₂CO₃ = 2 PbCO₃.Pb(OH)₂ + 2 Na₂SO₄.
3 PbSO₄.Pb(OH)₂ + 3 Na₂CO₃ = 3 PbCO₃.Pb(OH)₂ + 3 Na₂SO₄.
By this process, which is harmless to the workmen, the lead sulphate
obtained as a by-product in the preparation of mordants for calico
printing, can be converted into good saleable white lead. The lead
sulphate may also be obtained from litharge, lead acetate or nitrate.
It occasionally happens that white lead has a rose tint, which is
clearly perceptible by comparison with a pure white sample. This
colouration occurs in white lead made from argentiferous lead. A very
small quantity of silver is sufficient to produce the tinge of colour.
Occasionally white lead which has been ground in oil and used for
painting turns perceptibly yellow, the colouration being similar to
that observed on a surface painted with white lead from which light
is almost excluded. The yellow colouration is due to lead oxide. This
has been proved by suspending such a white lead in water and treating
it with carbonic acid, after which a surface painted with it remains
permanently white.
(f) OXYCHLORIDE WHITE LEAD.
Under the name of white lead, but differing from it in composition,
various products are found which consist of lead oxychloride. This
compound is also known as Pattison’s white lead.
Pattison’s white lead can be much more cheaply manufactured than
real white lead, the raw material employed being the cheap galena.
The finely-powdered mineral is boiled with strong hydrochloric acid
in closed lead vessels. Sulphuretted hydrogen is evolved, which may
be burnt to sulphur dioxide and so used to make sulphuric acid. A
hot saturated solution of lead chloride remains, from which the salt
separates in small crystals on cooling. The crystals are drained in a
basket and washed with cold water to remove the acid. The pure lead
chloride is then dissolved in hot water and mixed with lime water.
Pattison obtained lime water from dolomite by burning it, treating
with a little water to remove the easily soluble salts, and, after
the removal of this wash water, treating the residue repeatedly with
water in order to obtain a clear solution of pure hydrate of lime. When
pure limestone is used, it may be treated with water immediately after
burning without any preliminary preparation.
Two equivalents of lead chloride are used to one equivalent of calcium
hydroxide. Practical experience showed that the best product was
obtained when the precipitation was very rapidly brought about. With
this object, both solutions entered the precipitation tanks through
pipes with narrow slits at the side, so that the liquids met in a thin
layer, in which the precipitation of the pigment was instantaneous. It
is also necessary that lead chloride should be in excess throughout.
The liquid is allowed to stand for the precipitate to settle, which
it does in a brief time on account of its high specific gravity. The
solution now contains the small excess of lead chloride in addition to
calcium chloride; lime water is added until the liquid turns red litmus
paper blue. From the alkaline solution all the lead soon separates as
lead hydroxide, which is dissolved in hydrochloric acid, and thus again
comes into the process.
In order to utilise the large quantities of hydrochloric acid obtained
in the manufacture of soda, Percy described a process in which galena
is ground with hydrochloric acid, whereby in 30 to 40 hours all the
lead is converted into lead chloride, whilst the stony admixtures are
unattacked. The lead chloride is then separated by levigation from
the undissolved minerals and washed until free from iron, when it is
dissolved in hot water and converted into oxychloride by means of lime
water.
=Lead Sulphite=, PbSO₃, can be obtained by passing sulphur dioxide into
a solution of basic lead acetate; lead sulphite is precipitated and a
solution of neutral lead acetate remains. The process is similar to the
French white lead process, with the difference that sulphur dioxide is
used instead of carbon dioxide. Lead sulphite has no advantages over
white lead, and is more expensive; it has thus never found practical
application.
=Lewis and Bartlett’s White Lead Pigment.=—In the lead works at Zoplin,
in Missouri, galena is smelted with limestone and coal, lead fume being
obtained in addition to metallic lead. The lead fume deposits are
ignited, and again worked for lead and lead fume. This last lead fume
can at once be used as a white pigment; it consists principally of lead
sulphate, lead oxide and zinc oxide.
WHITE LEAD-ANTIMONY PIGMENTS.
Lead antimonite and antimonate are both heavy, white powders which can
be used as pigments. They are dearer than white lead, to which they are
inferior in covering power, and which they do not exceed in permanence.
=Lead Antimonite= is obtained by heating 5 parts of finely powdered
antimony with 20 parts of sulphuric acid until a dry, white mass of
antimony sulphate is left. This is fused with soda ash, the melt is
extracted with water, and lead antimonite obtained by precipitating
with lead acetate.
=Lead Antimonate= is formed by introducing in small quantities at
a time a mixture of 1 part of finely powdered stibnite (antimony
trisulphide) with 5 parts of sodium nitrate into a red-hot crucible,
boiling the mass with water and precipitating the solution with lead
acetate.
CHAPTER VIII.
ENAMEL WHITE.
Barium sulphate, known as permanent white, enamel white, _blanc fixe_,
barytes white, is the only white pigment which is absolutely unaltered
by exposure to the atmosphere. Lead pigments are discoloured in the
course of time, and in the end turn black; bismuth white behaves in the
same manner; zinc white is much more lasting, but not quite permanent.
Enamel white is really permanent; it deserves the greatest attention
from the colour manufacturer, especially as it can be made by a very
simple and cheap method. When sulphuric acid or a soluble sulphate
is added to the solution of a barium salt, all the barium is at once
precipitated in the form of barium sulphate.
When quite pure, barium sulphate forms an extremely soft, brilliantly
white powder, which offers complete resistance to the action of the
atmosphere, and also of strong acids and alkalis. It is extremely
insoluble, and can be precipitated from the most dilute solutions,
and is then obtained in so fine a state of division that it cannot be
filtered from the liquid; it passes through the closest filter together
with the liquid. When the barium solution is heated to boiling before
precipitation, the precipitate is somewhat coarser, and can be filtered
off without difficulty.
Barium sulphate occurs ready formed in nature as the mineral barytes
or heavy spar. Finely ground barytes may be used alone as a pigment,
but more commonly is used for reducing white lead, for which purpose
it is particularly applicable on account of its high specific gravity.
This admixture must be regarded as diminishing the quality of the
pigment, because ground barytes has far less covering power than white
lead. Artificial barium sulphate is in a state of division which cannot
be reached by grinding barytes, consequently it considerably surpasses
the latter in covering power.
The raw material for the manufacture of enamel white is either barytes
or witherite (barium carbonate); the latter, however, occurs so rarely,
in comparison with barytes, that the greater quantity of all barium
compounds is obtained from barytes.
If witherite is obtainable in large quantity, enamel white can be
prepared from it by dissolving in hydrochloric acid and precipitating
the solution of barium chloride so obtained by sulphuric acid. If the
witherite is very pure, the process may be simplified by treating the
mineral directly with sulphuric acid, and separating the enamel white
by a process of levigation from the impurities. In this case it is,
however, necessary to add a small quantity of hydrochloric acid to the
sulphuric acid, for the latter forms on the surface of the witherite,
at the commencement of the reaction, a thin layer of barium sulphate,
which is quite sufficient to prevent the further action of the acid on
the witherite lying below. The hydrochloric acid forms barium chloride,
which is at once decomposed by the sulphuric acid into barium sulphate
and free hydrochloric acid; this again dissolves a fresh quantity of
witherite, and this process is repeated until the mineral is completely
and quickly dissolved.
Enamel white is, however, generally prepared from barytes, which is
ground into a very fine powder and converted into barium sulphide by
heating with coal (see pages 41 and 42). Hydrochloric acid acting on
the sulphide produces barium chloride and sulphuretted hydrogen.
The covering power of a pigment is greater the finer its state
of division, so that it would appear advisable to precipitate a
weak solution of barium chloride by sulphuric acid at the ordinary
temperature. When the barium sulphate has been completely precipitated,
a solution of pure hydrochloric acid remains, which ought to be
utilised; but when very dilute barium chloride solution is used, the
hydrochloric acid is so dilute as to be useless. The barium chloride
is, therefore, given in practice such a strength that it has a specific
gravity of about 1·198; when the barium sulphate has been precipitated
from this solution the residual hydrochloric acid has a specific
gravity of 1·043.
Water of considerable purity must be used to dissolve the barium
chloride. Experience has shown that water which contains appreciable
quantities of organic matter does not give a pure white product. The
presence of sulphate of lime in the water, which precipitates barium
sulphate, need not be regarded, because the barium sulphate is so
finely divided that it remains suspended in the liquid, and is carried
down on precipitation of the enamel white by sulphuric acid. Carbonate
of lime in the water causes the separation of barium carbonate; this
may be avoided by slightly acidifying the barium chloride solution,
thus converting the calcium carbonate into chloride.
According to C. A. F. Meissner, artificial barytes, suitable for use
in oil paints, is obtained by precipitating barium salts by soluble
sulphates in place of sulphuric acid, then quickly heating the washed
and dried precipitate in a muffle to a red heat and throwing into cold
water.
As has been already stated, enamel white is the most permanent pigment
that exists; it appears destined in course of time to replace white
lead and all other white pigments, especially as its cost is generally
lower than that of the other white pigments. It costs, for example,
only half as much as white lead. At present, the principal uses of
enamel white are found in paper staining; it is not used to any extent
in oil paints. On account of its permanence, it should be used in
the place of white lead and white zinc. It also appears particularly
suitable for obtaining pale shades; it can be mixed with any other
pigment in any quantity without altering it in the least. This is, of
course, only true when the enamel white is completely pure, and when it
has been freed from every trace of hydrochloric acid by careful washing.
LITHOPONE.
A white pigment is obtained, according to Orr’s process, by lixiviating
crude barium sulphide, obtained by igniting barytes with coal, with
water and dividing the solution into two parts. Zinc chloride is added
to the first portion, then zinc sulphate, and finally the second
portion of barium sulphide solution. The white precipitate obtained
by this process contains one equivalent of barium sulphate to two
equivalents of zinc sulphide. It is collected, quickly dried, heated
in retorts to redness, and, whilst still hot, thrown into cold water,
by which its density and therefore covering power are increased. The
pigment is finally washed and ground. It is a good white, but when
mixed with lead pigments discolours them by reason of the sulphide it
contains.
CHAPTER IX.
WASHING APPARATUS.
In all colour works operating on a large scale, special apparatus is
used, in which are carried out the washing, pressing and drying of the
pigments obtained as precipitates. Only pigments prepared in small
quantities are filtered through filter paper. The treatment of enamel
white and white lead requires the use of apparatus for this purpose in
a special degree. We insert a short description here.
The preparation of enamel white takes place most conveniently in tubs
provided with a stirring apparatus. When the precipitate of barium
sulphate has once settled to the bottom, it is very difficult to
again mix it up with water by means of a hand stirrer, an operation
which must be often performed in washing. If vessels be used provided
with a suitable mechanical stirrer, the precipitates are rapidly and
thoroughly washed. We have already stated that vessels with a stirrer
capable of being raised out of the liquid were specially suitable for
washing white lead. Such an arrangement can with advantage be used in
washing all precipitates. Many of the mineral pigments have to be freed
from admixed salts by washing. A description follows of an effective
washing apparatus with movable stirrer. In the cylindrical vessel (Fig.
21), which may be of any size, is a vertical iron shaft rotating upon
a pin in the bottom of the vessel. On this axis is a horizontal wooden
crosspiece, the under surface of which is studded with brushes; the
disc, which this crosspiece carries, is united by means of two bars
with a second, in which is cut a screw moving on the screwed shaft. The
shaft is rotated by means of the cog-wheels shown in the illustration.
The handle fastened to the upper disc enables the crosspiece carrying
the brushes to be raised or lowered. When the handle is held fast, this
crosspiece rises or falls according to the direction of rotation of the
axis. The pipe shown at the side supplies the water for washing the
precipitates.
[Illustration: FIG. 21.]
In the preparation of colours liquids have often to be brought into
the precipitating vessel which would attack the iron of the stirring
apparatus, so that it is advisable to make the connecting rods between
the two discs of such a length that the screws may be above the vessel.
All iron parts of the apparatus dipping into the liquid should be
protected by asphaltum varnish.
When a specially heavy precipitate is to be washed, such as enamel
white, chrome yellow or white lead, the stirrer is raised as high
as possible before the commencement of the operation. When the
precipitate has formed and settled, the liquid is run off, the water
tap opened, and the stirrer slowly brought down to the precipitate;
the brushes fastened to the crosspiece stir up first the top of the
precipitate, then the next portions, and so on until the whole of the
precipitate has been stirred up into the liquid. When this has been
accomplished, the stirrer is kept going for some time, so that the
water may take up as much of the soluble materials as possible; it is
then raised out of the vessel, in which the precipitate again settles.
As a rule, two or three washings of permanent white, in an apparatus of
the construction described, are sufficient to render it quite free from
acid. Washing must be continued until the wash water leaves blue litmus
paper quite unchanged. When dry, precipitated barium sulphate is a very
soft powder of great whiteness, which, on account of the fineness of
its particles, can be readily ground with binding materials.
Enamel white loses, in a remarkable manner when completely dry, a great
portion of its covering power and of its valuable property of being
easily ground with oil or size to a homogeneous paste. It is not known
whether this alteration is caused by a molecular change of the barium
sulphate, as is not altogether improbable. In order to preserve the
valuable properties of enamel white it is not, as a rule, completely
dried, but is brought into the market in the form of pulp, which is
obtained by bringing the washed precipitate into strong linen bags
and allowing the water to drop through. This object is more quickly
accomplished when the last wash water is drawn off only to such a point
that, when the precipitate is again mixed up by means of the stirrer,
a thin paste is formed. This paste is run into a centrifugal machine,
of which Fig. 22 is an illustration. In the drum, B, provided with an
outflow, R, the smaller removable drum, C, with perforated walls, is
caused to rotate by gearing, G, to which it is attached by the screw,
V. The drum, C, is lined by a tight linen bag.
[Illustration: FIG. 22.]
When the drum is in rapid motion, the thick liquid in the washing
vessel is run in. In consequence of the centrifugal force due to the
rapid rotation, the whole mass is at once thrown on the sides of
the drum, the liquid penetrates the fine openings, is caught in the
outer vessel, and runs away to a receiver, in which it is kept until
the finest particles of the precipitate, which will penetrate even
the closest fabric, have settled. The operation is continued until
the excess of water has been separated, when the bag containing the
precipitate is lifted out of the drum. Centrifugalised enamel white is
a fairly stiff, white paste, which should be packed in sacks lined with
oiled paper to prevent drying.
[Illustration: FIG. 23.]
FILTER PRESSES.
In recent years the use of filter presses for separating liquids from
precipitates and for washing the latter has become general. A filter
press consists, as shown in Fig. 23, of a number of frames, between
which are perforated plates and sheets of filter cloth, and which can
be pressed tight together by a screw. A powerful pump forces the liquid
containing the precipitate into the hollow spaces of the frames (known
as chambers), in which the solid body remains, whilst the liquid goes
through the filter cloth. By afterwards pumping fresh water through,
the solid remaining in the chambers is soon completely washed.
CHAPTER X.
ZINC WHITE.
Zinc oxide, known as a pigment under the name of zinc white, is one of
the most important white pigments. Although not absolutely permanent,
yet it has, in common with enamel white, the valuable property of
preserving its whiteness in air containing sulphuretted hydrogen. Its
low price has brought it into general use.
Although zinc white is a most important pigment, it is very seldom
made in colour works, because on account of its origin it is a product
of metallurgical processes. Zinc white in chemical composition is
pure zinc oxide; it is formed when zinc vapour burns in air. In
zinc-smelting works zinc white is obtained by putting zinc in tubes
which are heated to whiteness; the zinc vapours burn when they come
in contact with the air, and the zinc oxide is caught by special
arrangements.
The retorts used for this purpose are similar to those employed in the
manufacture of coal gas. From 8 to 18 of these retorts are arranged in
a furnace, in two rows, one above the other. In the lid of the retorts
is an opening, which serves for charging and for carrying off the zinc
vapours. When the operation is commenced, the retorts being heated
to a white heat, two zinc plates are brought into each, the metal is
soon volatilised, and the vapours pass through the above-mentioned
openings. A current of air, heated to 300° C., is blown in to meet the
zinc vapours, which take fire and burn with a blinding white flame,
producing a very fine white powder, which is carried by the current of
air through a series of chambers in which it deposits.
[Illustration: FIG. 24.]
C. Freitag recommends for the production of zinc white the use of
retorts of oval section, _A_, Fig. 24. These retorts, containing crude
zinc, are heated to a white heat, and then a mixture of generator gas
from coke and air is introduced by _B_ and the pipe running through
_B_. The zinc burns completely in the flame of the generator gas, which
contains excess of oxygen. A product of faultless nature is said to be
obtained in this way.
In zinc works zinc white is always made in the manner which has
been described. It may also be obtained as a by-product in another
metallurgical operation, the desilverisation of lead by Parkes’
process. In this process an alloy of silver and zinc is obtained. By
sending a current of superheated steam over the molten alloy the zinc
decomposes the steam, hydrogen and zinc oxide being formed. The zinc
white is carried by the current of gas into chambers, in which it
deposits.
The zinc white obtained by burning zinc is, as has been said, a very
fine pure white powder, which can at once be used for paint without
further preparation. The price of zinc white is rather higher than
that of white lead, but the difference is counterbalanced by the
greater covering power of the zinc white. Ten parts by weight of zinc
white completely cover a surface for which 13 parts of white lead are
required.
Whilst white lead cannot be mixed with many pigments, such as those
which contain sulphur, zinc white may be mixed with all without fear of
alteration. Zinc white is even better than enamel white for producing
pale pigments from lakes; it has a lower specific gravity than enamel
white, so that the mixture with the light lake can be more easily made.
Zinc grey, which is produced by some works, is zinc oxide discoloured
by metallic zinc. Pure zinc white always has a pure white colour; if
it is tinged with grey it is contaminated by metallic zinc, whilst a
brownish hue denotes the presence of cadmium oxide. The latter impurity
will be rarely met with in commercial samples, since cadmium is worth
much more than zinc. Zinc oxide is used by the colour maker in the
preparation of Rinmann’s green; it is also used, as stated above, as an
addition to other pigments.
=Griffith’s Zinc White.=—This pigment, which is equal in covering
power to white lead, consists of zinc oxysulphide. It is obtained by
precipitating a zinc solution with a solution of barium sulphide,
washing, drying, igniting and grinding the precipitate. As it contains
sulphur, it should not be mixed with copper or lead pigments.
=Tungsten White= (Lead Tungstate), PbWO₄, is obtained as a heavy powder
by precipitating a solution of sodium tungstate with lead acetate and
treating the precipitate, which consists of basic lead tungstate, with
dilute acetic acid, by which lead oxide is dissolved and a salt of the
above composition left. This white pigment is dearer than other lead
pigments, and has no special advantages over them; it is, therefore,
seldom used.
WHITE ANTIMONY PIGMENTS.
Antimony forms a number of white compounds which can be made by a
simple and inexpensive process, and might, therefore, be used as
pigments. Two antimony compounds in particular are so used—antimony
trioxide and oxychloride (powder of algaroth).
=Antimony Trioxide= occurs ready formed in nature as white antimony or
antimony bloom. It is very simply prepared by burning the metal in air,
when it forms soft needles with a silvery lustre. It is only necessary
to heat melted antimony to a little above its melting point in a
crucible placed in a slanting position, when the metal takes fire and
burns with a blue flame. Nitric acid converts metallic antimony very
quickly into antimony oxide with a copious evolution of brown fumes.
Antimony trioxide may be more cheaply prepared from antimony sulphide,
artificial or natural (stibnite), by finely powdering, moistening with
water, and gently warming on plates. Oxidation takes place, the sulphur
is converted into sulphur dioxide and the antimony to trioxide. The
heating should not be carried too far, or the antimony takes up further
oxygen and forms the tetroxide.
=Antimony Oxychloride, or Powder of Algaroth=, is obtained by
dissolving stibnite in strong hydrochloric acid, the operation being
performed under a chimney to carry off the sulphuretted hydrogen. The
solution of antimony trichloride, when the impurities have settled, is
poured into a large vessel of water. At once a pure white precipitate
is formed, which quickly sinks; it is washed with water until the
washings have no acid reaction. Washing should not be continued
too long or the oxychloride will be further decomposed; by washing
with hot water it is almost entirely changed to antimony trioxide.
The precipitate, after washing with cold water, has generally the
composition expressed by the formula SbOCl.
Antimony oxide and oxychloride are both very crystalline powders, and
have in consequence small covering power.
=Bismuth White= is not used as a painters’ pigment; it has no advantage
over the white pigments previously described, and is much more
expensive. Its only use as a pigment is for the preparation of white
cosmetics, and even for this purpose zinc white is now frequently used;
it is cheaper and quite as satisfactory.
Bismuth white is prepared by treating metallic bismuth with fuming
nitric acid. The white precipitate at first formed completely dissolves
in an excess of acid, and when the solution is poured into a large
quantity of water, basic bismuth nitrate—bismuth white—separates.
Pure bismuth white is a soft, heavy powder, brilliantly white; it must
be preserved in air-tight vessels as soon as it is dry, otherwise it
acquires a yellowish tinge. Bismuth compounds are, if possible, more
susceptible to the action of sulphuretted hydrogen than lead compounds.
The yellow colouration, turning to black in the course of time, is due
to black bismuth sulphide.
=Tin White= is used for earthenware enamels. It is obtained by treating
granulated metallic tin with very strong fuming nitric acid. The heavy,
white powder which is formed is separated from the undissolved tin by
floating. Tin white has no application as a pigment; when mixed with
glazes it gives them a handsome, milky appearance.
=Manganese White.=—When large quantities of a solution of impure
manganese chloride are at hand, such as are produced in the preparation
of chlorine, manganese carbonate may be obtained. A small quantity of
soda solution is first added and the liquid left for several days so
that the oxide of iron may separate. When this is the case an addition
of soda gives a pure white precipitate.
=Magnesia White or Mineral White= is obtained, according to T. H.
Cobley, by mixing a solution of magnesium sulphate with calcium
chloride, adding 10 per cent. of aluminium chloride to the mixture and
stirring in slaked lime so long as a precipitate is formed. A cheaper
process is to precipitate mixed solutions of magnesium and aluminium
sulphates by slaked lime.
=Annaline.=—A white pigment is recommended for use under this name; it
consists of dead-burnt gypsum, which has been converted into a fine
powder by grinding and levigating. (Dead-burnt gypsum has been so
strongly heated that it is not able to again unite with water.)
To obtain paler shades of certain colours, additions are made of
natural pigments, such as chalk, which has been converted into a very
fine powder by levigation. An addition of chalk to a heavy mineral
pigment, such as chrome yellow, is not advisable; it would, besides,
seriously diminish its covering power.
* * * * *
In the preceding pages, a large number of white pigments has been
enumerated. It would be easily possible to increase the list, but the
result would be of no practical interest, for other pigments, neither
in respect of quality nor price, can compete with the cheaper white
pigments. Although white lead has at the present time an enormous
use, it is to be hoped that this pigment, of good colour but little
permanence, may be replaced entirely in the course of time by zinc
white, and for some purposes by enamel white.
White pigments, in addition to their use alone, are employed to produce
tints, which are obtained by mixing deeper colours with the white
pigment. By adding the proper quantity of white to a colour it is
possible to produce all paler shades of that colour. For example, the
different varieties of the red lakes which are found in commerce are
obtained by mixing white pigments with the deep red lakes.
The particular white pigment to be employed in these mixtures depends
on the nature of the colour and on its specific gravity. It should
always be remembered that white lead will not increase the permanence
of a colour, since it will be discoloured in a short time by the action
of the atmosphere. In the manufacture of fine colours for artists lead
pigments should be absolutely excluded.
To produce paler shades of colours which contain lead and therefore
have a high specific gravity, _e.g._, chrome yellow, white lead may be
used; for other colours, barytes or zinc white should be employed. In
the case of lakes enamel white is too heavy; zinc white or magnesia is
suitable.
CHAPTER XI.
YELLOW MINERAL PIGMENTS.
As was the case with white pigments, so with yellow: of the large
number known very few are in extensive use. In former times the number
of yellow pigments employed in painting was far greater than at
present; several, formerly in general use, have dropped out, partially
or entirely, owing either to their poisonous character or to their
replacement by others, deeper and more handsome. Especially since the
discovery of cadmium yellow and the development of the manufacture of
chrome yellows, many colours once in general use have properly fallen
into disuse.
Again, unfortunately, the most important of the yellow mineral pigments
contain lead, and have little stability; but a series of yellow colours
free from lead is known, and though some of them are inferior in shade
to the lead pigments they surpass the latter in permanence.
In addition to lead compounds, pigments derived from barium, zinc,
antimony and cadmium are in general use. The yellow lead pigments were
formerly preferred, and at present, so far as concerns beauty, they
must be regarded as superior to other mineral yellows. The endeavour
to provide the artist with permanent colours has resulted in the use
of others, perhaps less brilliant, but very lasting. Under the name of
chrome yellow a single pigment consisting of lead chromate was formerly
understood; to-day, under this title is comprised a series of pigments
containing zinc or barium in place of lead, but all commercially known
as chrome yellow.
CHAPTER XII.
CHROME YELLOWS.
The chrome yellows are the lead, zinc or barium salts of chromic acid.
In describing the different methods used in making these colours, lead
chrome yellow will be taken first, since this is the one most largely
used.
LEAD CHROME YELLOW.
Both neutral and basic lead salts of chromic acid are known. Neutral
lead chromate is found in nature as the somewhat rare mineral
crocoisite, which is found in very small but perfectly shaped crystals
in many lead mines.
=Neutral Lead Chromate=, PbCrO₄, is formed as a very heavy precipitate
of a fine deep yellow colour when a solution of potassium chromate or
bichromate is added to a solution of a lead salt in water. When exactly
equivalent quantities of potassium chromate and lead solution are used,
and the strength of the solutions is the same, the product has the
same shade each time the operation is performed. It is not immaterial
whether the one or the other salt is in excess, or whether strong or
weak solutions are used; all these conditions modify the shade of
the chrome yellow produced. Many colour makers are apparently of the
opinion that some particular skill of the workman is necessary to
produce chrome yellow of a particular shade. This is, however, not the
case; manufacturers who know the simple conditions which are important
in making chrome yellows may produce any desired shade without
difficulty.
Neutral lead chromate readily parts with half the chromic acid it
contains. When treated with alkalis, such as lime or caustic soda, or
even when digested with finely ground litharge, the neutral salt gives
up half of its chromic acid, and is converted into the basic chromate
or chrome red, Pb₂CrO₅.
Basic lead chromate has, as the name chrome red indicates, a fine red
colour. If the quantity of lime or caustic soda used is sufficient to
decompose only a portion of the neutral lead chromate, a mixture of the
yellow neutral and the red basic chromate is formed, the shade of which
will incline to yellow or red according as it contains a preponderance
of one or the other compound. The pigment known as orange chrome is
a mixture of approximately equal parts of the neutral and basic lead
chromates.
In order to brighten the deep yellow shade which distinguishes
neutral lead chromate, it is either mixed with a white pigment, or
a white substance (lead sulphate) is precipitated from the solution
simultaneously with the lead chromate. In this manner all the
imaginable pale yellow shades, lemon yellow, sulphur yellow, etc., can
be obtained.
Just as the quantities of the solutions used and their strength
influence the shade of the chrome yellow they produce, so it also
appears to be not immaterial which lead salt is employed. Colour makers
are generally agreed that the finest product is obtained from neutral
lead acetate. Any lead salt, even insoluble in water, may be used for
the preparation of chrome yellow. The affinity of chromic acid for
lead is so great that an interchange of constituents occurs between
the insoluble salt and the potassium chromate. Chrome yellow may be
made from lead acetate, chloride or sulphate; the resulting substances
are the same, but there is a considerable difference in regard to the
beauty of the product. The finest chrome yellow, which leaves nothing
to be desired in beauty of shade, is obtained by proceeding in the
following manner: Lead acetate is dissolved in water, the solution
diluted with an equal volume of water, and then mixed, under constant
stirring, with a similarly diluted solution of potassium chromate or
bichromate. The precipitate is immediately formed, and quickly sinks to
the bottom in consequence of its high specific gravity. It is washed
with clean water so long as this removes soluble salts. The precipitate
is then drained on cloths and dried in the air.
The finest product is obtained by working with the following
proportions:—
Sugar of lead 100
Potassium bichromate, or 50
Potassium chromate 40
If lead sulphate is used the following quantities are to be employed:—
Lead sulphate 100
Potassium bichromate 25
In the case of lead chloride the following is the proportion:—
Lead chloride 100
Potassium bichromate 27
The chrome yellows prepared from insoluble lead salts have no
particular beauty, but they may be used for mixed colours such as the
spurious chrome green.
=Preparation of the Lead Solution.=—Many makers of chrome yellow do not
use commercial lead acetate, but prepare its solution themselves. The
preparation of this solution requires neither much space nor labour, so
that considering the high price of lead acetate this procedure may be
regarded as advisable, but only when acetic acid is obtainable at a low
rate.
The following is the method by which lead acetate solution is made.
Lead is granulated by pouring the molten metal from a height of
several yards into cold water, which is kept in rapid motion. The
smaller the particles of lead, the larger surface they will possess,
and the more quickly they will dissolve. For the solution of the
lead small tubs are used, 50 centimetres in diameter and 90 to 100
centimetres in height, provided with a tap immediately above the bottom
to run off the liquid. Four of these vessels are so placed, one above
the other, that the contents of each may be run into the one next below
it. The lead in the top vessel is covered with acetic acid; in a few
minutes this is allowed to flow into the second vessel, and similarly
after a few minutes from the second to the third, from the third to
the fourth, from which it runs away into a receiver below. After this
treatment it contains but a small quantity of lead acetate; the object
of the operation is to start the oxidation of the lead, which quickly
follows when air has sufficient access, the lead particles lose their
metallic appearance and become covered with a white layer. When this is
the case, the acetic acid is pumped from the receiver back into the top
vessel, where it is left one to two hours in contact with the lead. It
is then run off into the second, and thence into the third and fourth,
remaining in each vessel for about the same time; the resulting liquid
is an almost completely neutral solution of lead acetate. The treatment
with acetic acid is continued so long as lead remains undissolved.
The solution of potassium chromate is prepared in a tub. The salt is
easily soluble, and warming is unnecessary if the chromate is placed in
a basket, lined with close linen cloth, hung in the liquid so that it
is immersed to half its depth. The salt rapidly dissolves, its solution
has a greater density than water, in consequence of which it sinks and
fresh quantities of water continually come in contact with the salt.
=Precipitation of the Chrome Yellow.=—Before the chrome yellow can be
precipitated it is necessary to estimate the quantity of lead acetate
contained in the solution, since upon this depends the quantity of
potassium chromate solution to be used. If the lead solution contained
only acetate and water, its strength could be simply found by means
of the hydrometer. It contains, however, varying quantities of acetic
acid, on which account the hydrometer would give very inaccurate
results. The test by which the relation between lead solution and
potassium chromate solution is found is performed in the following
manner: The lead solution is measured off in a cylinder divided into
100 divisions; the same volume of potassium chromate solution is
measured and placed in a high narrow vessel; the lead solution is
gradually added to the chromate solution so long as a precipitate is
formed. The precipitate settles rapidly, and there is no particular
difficulty with a little practice in finding with sufficient accuracy
the quantities required for the precipitation. In order to precipitate
100 litres of potassium chromate solution, there are required as many
litres of lead solution as were used divisions of the cylinder.
The preparation of the chrome yellow is now a very simple matter.
Whilst steadily stirring, the measured quantity of lead solution is run
into the solution of potassium chromate; the precipitate is allowed to
settle, is well washed and dried. It does not make any difference to
the colour whether potassium chromate or bichromate is used; the same
product is obtained in each case.
It is stated by Dullo that chrome yellow prepared by the preceding
process alters in colour on long keeping. This is ascribed to the
formation of a basic compound. According to the same author, a chrome
yellow free from this objectionable property is obtained by using
lead nitrate in place of acetate and an excess of potassium chromate
solution. The writer has kept chrome yellow, made from lead acetate,
for years without observing the slightest alteration in the colour.
On chemical grounds, it is incomprehensible that a chrome yellow
prepared from lead nitrate should have different properties to the
same substance prepared from another soluble lead salt, and freed from
foreign substances by sufficient washing.
The product of this process is that which _par excellence_ is known
as chrome yellow, the chemist’s neutral lead chromate; it exhibits a
characteristic deep yellow colour, a shade which is known as chrome
yellow. Under the microscope chrome yellow is seen to be a crystalline
mass; it will possess greater covering power the smaller the crystals.
Now, the motion of a liquid in which crystals are forming prevents the
production of large crystals, thus the reason is clear for the rapid
stirring of the solutions in the preparation of this pigment.
According to C. O. Weber, who has published an exhaustive account
of chrome pigments (_Dingler’s Journal_, 282), the cost of the
lead chrome pigments varies greatly according to the raw materials
employed. Assuming that 100 kilogrammes of litharge cost 35 marks, 100
kilogrammes of 30 per cent. acetic acid 25 marks, and 100 kilogrammes
of 60 per cent. nitric acid 26 marks, Weber calculates that 100
kilogrammes of litharge, in a form suitable for making chrome yellow,
will cost as follows:—
From lead acetate at 56 marks per 100 kilogrammes 96 marks
” ” solution made in the works 80 ”
” lead nitrate at 50 marks per 100 kilogrammes 75 ”
” ” solution made in the works 64 ”
By the basic lead acetate method 51 ”
” ” chloride ” 40 ”
White lead method 55 ”
=The Pale Chrome Yellows.=—When the solution of the chromate used
for the precipitation of the lead solution is mixed with sulphuric
acid, then a mixture of lead sulphate and lead chromate is formed
on precipitation. Lead sulphate is white, so that the colour of the
precipitate would be paler according to the quantity of sulphuric acid
added to the potassium chromate solution. There are, however, compounds
of lead chromate and lead sulphate, of which we know two. Their
composition is expressed by the formulæ:—
PbCrO₄.PbSO₄ and PbCrO₄.2PbSO₄.
The former is a beautiful lemon yellow shade, the latter nearly
approaches sulphur yellow. By corresponding alterations in the quantity
of sulphuric acid added, all intermediate shades can be obtained. On
the works these shades are made in the following manner: buckets are
used for taking the potassium chromate solution out of the vessel
in which it was made; these buckets hold 12·5 litres. Now, if the
solution of potassium chromate has been made from 25 kilogrammes of
the salt and 750 kilogrammes of water, one of these buckets holds
exactly 0·43 kilogramme of chromic acid. In order to obtain the lemon
yellow compound, 0·39 kilogramme of sulphuric acid must be added to
a bucketful of solution; 0·78 kilogramme must be added to obtain the
sulphur yellow chrome. These liquids are prepared by pouring the
sulphuric acid in a thin stream into the potassium chromate solution
made as above, the liquid must be stirred whilst the sulphuric acid is
being added. The lemon chrome has the peculiar property of increasing
considerably in volume soon after formation, a property to which
regard must be had in the manufacture. A description of the rational
preparation of the lemon and sulphur yellow shades of chrome yellow on
the manufacturing scale follows.
In making lemon chrome, the tub in which the precipitation is to take
place is two-thirds filled with water, the lead solution is stirred
in, and then the chromate solution, mixed with the proper quantity
of sulphuric acid, is run in; the liquid is well stirred so that
the precipitate may form as quickly as possible throughout the whole
liquid. The precipitate is allowed to settle, the liquid drawn off, and
the colour washed twice with water as quickly as possible. The paste
is then removed from the tub and poured on a strong linen strainer.
At first, the fine precipitate goes through the strainer, the liquid
is poured back on the strainer until the size of its pores is so far
diminished by the precipitate itself that only clear liquid runs
through. The precipitate is left on the strainer until it forms a stiff
mass, which can be easily spread out upon boards by spatulas.
To obtain a good, that is, a loose product, it is necessary to carry
out the processes so quickly that the swelling mentioned above does not
take place while the colour is being strained, but when it has been
spread out on the boards. This swelling only takes place completely
when the layer of precipitate is fairly thin. Large boards should be
used, upon which the precipitate is spread out in a very thin layer.
To prevent the mass—which is still fairly fluid—from running off the
boards, they are provided with raised edges, and the paste is spread
out smoothly in these flat trays. If the operations have been properly
performed, the precipitate at once begins to swell and becomes of
a loose nature. When it has acquired a buttery consistency it is
cut up, by means of a thin sheet of brass, into prisms, which are
placed near one another standing on the narrow side, and dried first
in the shade and then in the sun. It is necessary that the drying
should take place slowly at first, or the cakes will crack or even
fall to pieces. The precipitate cannot be washed completely in the
tub, because it often begins to swell on the strainers, consequently
a crystalline crust covers the surface of the cakes during drying.
This layer must be removed by scraping the cakes of colour, in which
operation small quantities of chrome yellow dust become suspended
in the air. To protect the workman against poisoning by this lead
compound, precautions must be taken against breathing in the dust. The
simplest and most efficacious is to tie a wet sponge over mouth and
nose; this retains the particles of dust in the inspired air. The dust,
scraped off the cakes, is put into water, in which the salts dissolve,
whilst the chrome yellow sinks to the bottom. In this process for
preparing chrome yellow the solution of potassium acetate left after
the precipitation contains a considerable quantity of free acetic acid,
which may be utilised to dissolve lead.
When sulphur yellow chrome is to be made, the process is substantially
the same as for the preparation of the lemon shade, but with the
difference that everything is done to prevent the swelling of the
precipitate. The precipitation and washing of the precipitate are done
as quickly as possible: the washed precipitate is filled into press
bags and strongly pressed. Care must be taken in the pressing that the
pressure is only gradually increased; if powerful pressure is applied
at once, even the strongest cloths will be burst. The more thoroughly
the precipitate is pressed, the closer will be the fracture of the
chrome, a property which is regarded as a sign of good quality in this
species of chrome yellow.
The manufacture of chrome yellow is intimately connected with that of
a number of colours, varying from orange to dark red, which are known
under the names of chrome orange or chrome red. In accordance with the
division adopted of pigments according to their colour, chrome orange
and chrome red will be considered among the red mineral pigments.
CHAPTER XIII.
LEAD OXIDE PIGMENTS.
Lead monoxide, PbO, exists in two different modifications; in the
crystalline form, as litharge, which is generally pale yellow with a
reddish tinge, and amorphous, as massicot, which is yellowish red.
Lead monoxide is a product of metallurgical works rather than of colour
works; still the preparation of the crude oxide falls in the domain of
the colour maker, since from litharge several pigments may be prepared
by a simple treatment.
Massicot is obtained by heating white lead, lead nitrate or red lead,
and also by heating melted lead in the air, with the precaution that
the oxide formed does not itself melt.
Litharge is obtained as a by-product in several metallurgical
processes, such as the cupellation of lead containing silver, in
which the lead is melted in a furnace with a shallow hearth and a
powerful current of air blown over the melted metal. The lead is
oxidised, the oxide melts at the high temperature approaching 1000°
C., and flows through an orifice in the wall of the furnace, whilst
the silver remains on the cupel. The litharge is ground and levigated
and, according as it is pale yellow or reddish, sold under the name of
silver or gold litharge.
Both massicot and litharge have no particularly striking colour; they
are seldom used as pigments. Litharge has an extensive use in oil
boiling and for the manufacture of lead peroxide, which is used for
matches.
=Red Lead, Minium.=—Lead forms a number of other oxygen compounds, one
of which, red lead, has the composition, Pb₃O₄. It is a bright red
powder, used as a pigment and as a constituent of certain cements (for
gas and water pipes).
Red lead is, like litharge and massicot, a metallurgical product,
but, by working on a small scale, products can be obtained of a much
brighter colour than the produce of the large scale.
[Illustration: FIG. 25.]
Red lead is made in two ways—directly from metallic lead or by heating
easily decomposed lead salts. When it is made from the metal, the
following is the process: the lead, which must be very pure, is melted
in a reverberatory or calcining furnace, oxidised to massicot by the
air passing over it, and the massicot then, by careful heating, changed
into red lead, a process in which particular care must be taken that
the mass is not melted. By continued heating the massicot absorbs about
2 per cent. of oxygen, and changes in colour to a bright red.
The art in making red lead by this process lies in maintaining
the proper temperature; the furnaces are constructed so that the
temperature may be regulated during the heating. A reverberatory
furnace is used, in which is a stirring apparatus, so that the heated
mass may be continually turned over to accelerate the oxidation. Muffle
furnaces are also used, in which the massicot is placed in crucibles on
an iron plate, which can be pulled out of the furnace for observation
of the change of colour. Whatever method is used, the temperature must
be so regulated that over-heating of the material is avoided, otherwise
litharge is formed, which is only very slowly converted into red lead.
[Illustration: FIG. 26.]
Mercier states that the muffle furnaces are arranged as shown in Fig.
25. The muffle, _a_, is 2·5 metres long and 2 metres wide; its bottom
rests on an iron plate. The passage, _d_, running under the muffle
is 20 centimetres high; it is divided by a partition, and at each
end are two hearths, _c_, 70 centimetres long and wide. The products
of combustion pass from the long passages into side channels, _f_,
provided with dampers, go round the muffle and unite in the space, _g_.
The flue, _k_, at the back of the muffle is provided with dampers, _m_,
which exactly regulate the current of air through the muffle; _n_ is
the chamber in which are collected the particles of oxide carried over
by the draught. The furnaces used for manual labour consist, according
to Percy (Figs. 26 and 27) of a rectangular or circular hearth, _a_,
of about 3 metres diameter, which is deeper in the middle and has two
fireplaces, _b_. The low arch surmounting the hearth is covered with
sand in order to prevent cooling.
[Illustration: FIG. 27.]
When finished, the red lead is drawn out of the furnace and finely
ground under edge-runners, or occasionally levigated. The temperature
necessary in making red lead is that at which the angles of the
muffles, when these are used, begin to show a dark red glow.
Orange lead, which is a brighter variety of red lead, is prepared from
lead salts; white lead or lead nitrite is used for this purpose. The
latter salt is made by the process of Pischon, by heating 1 equivalent
of lead nitrate with 4 equivalents of granulated lead and water at
a temperature between 50° and 60° C. After about 2 hours, the lead
nitrite separates in the form of a granular yellow mass. According
to Burton’s process, lead carbonate is oxidised by heating with 20
per cent. of sodium nitrate and extracting the mass with water. There
are also other methods by which red lead is obtained from litharge
by the use of potassium chlorate or saltpetre; but these methods,
without producing a finer product than those previously given, are more
expensive, and consequently have found no application on the large
scale.
CHAPTER XIV.
OTHER YELLOW PIGMENTS.
=Cassel Yellow=, also known as mineral or Veronese yellow, has now a
very restricted use; it has been replaced by the deeper and cheaper
chrome yellow. Much of the Cassel yellow of commerce is nothing but
chrome yellow shaded with barytes. As regards chemical composition,
Cassel yellow has the following formula: PbCl₂.7PbO. It is obtained
by heating litharge, red lead or white lead with ammonium chloride.
To 10 parts of the lead compound 1 part of ammonium chloride is used;
on melting, ammonia is set free, by which part of the lead oxide
is decomposed, metallic lead separating. The melted mass is poured
off from the lead into iron moulds, in which it solidifies to a
very crystalline substance of a fine yellow colour. By grinding and
levigating, the Cassel yellow is prepared for use. Pale yellow shades,
obtained by admixtures of barytes, are occasionally encountered.
=Montpellier Yellow= consists, like the preceding pigment, of basic
lead chloride. It is obtained by gradually mixing 400 parts of powdered
litharge with a solution of 100 parts of common salt in 400 parts of
water. After each addition of salt solution the pasty mass must be
thoroughly stirred, or it will harden. When all the salt solution has
been mixed with the litharge to a homogeneous white mass, the latter is
treated with water to remove excess of salt, and the washed material
dried and melted in earthenware crucibles. The melt, which has a bright
yellow colour, is ground and levigated, when it forms a handsome
pigment.
There are several other yellow pigments of similar composition, of
which one only need be mentioned, obtained by treating a solution of
zinc chloride with lead hydroxide.
=Turner’s Yellow or English Yellow= is prepared by two methods: either
by melting 7 parts of finely ground litharge with 1 part of common
salt; or by treating litharge with a solution of common salt and
converting the white oxychloride into a yellow pigment by melting.
=Naples Yellow.=—This handsome pigment, which is, unfortunately,
susceptible to the action of sulphuretted hydrogen, is known
commercially under different names. Naples yellow takes its names from
the fact that it was formerly exclusively made in Italy, where the
method was kept secret, a secret which disappeared with the advance of
analytical chemistry. Naples yellow is now known to be lead antimoniate.
Naples yellow is a handsome pigment. Its preparation is more tedious
than that of chrome yellow, hence it is now rarely employed. The author
has had practical experience that much of the so-called Naples yellow
of commerce is nothing but a suitably shaded chrome yellow.
Naples yellow can be prepared by different methods. According to the
oldest, given by Brunner, 1 part of pure tartar emetic is carefully and
thoroughly ground with 2 parts of lead nitrate and 4 parts of common
salt. The mixture is melted at a low heat in a Hessian crucible, and
the fluid mass poured on a cold iron plate. After cooling, it is boiled
out with water, when lead antimoniate remains as a powder of a more
or less deep yellow colour. It is not easy to obtain this favourable
result with certainty in every case. If a certain temperature is
exceeded only by a little, a hard mass results, which by long boiling
does not become a fine powder, but a sandy substance of little
brilliance. Even when the operation succeeds, the product often varies
considerably in shade, sometimes a sulphur yellow, at other times an
orange pigment being formed. As a rule, the paler product is obtained
at a lower temperature; by stronger heating, darker products of a red
shade are obtained.
According to another recipe, 2 parts of tartar emetic are melted with 4
parts of lead nitrate and 8 parts of common salt. The mass is treated
with very dilute hydrochloric acid for a long time, which extracts some
quantity of lead oxide, a deeper product being thus obtained. Care is,
however, necessary in this treatment; acid of too great strength would
spoil the whole product.
The Paris method for Naples yellow is as follows: metallic antimony is
oxidised by melting in air; to 12 parts of antimony, 8 parts of red
lead and 4 parts of zinc oxide are used, and the mixture is melted at a
low red heat.
A cheap, but not particularly bright product, can be obtained from old
printer’s type. The metal, which is an alloy of antimony and lead, is
powdered, mixed with 3 parts of saltpetre and 4 parts of common salt,
melted, and the mass washed out with water.
Other formulæ which are said to yield a good result are as follows:
12 parts of white lead, 3 parts of antimony oxide, 1 part of ammonium
chloride, 1 part of alum. Or: 16 parts of stibnite, 24 parts of lead,
1 part of common salt and 1 part of ammonium chloride. The intimate
mixture of these materials is first gently heated with access of air,
then more strongly, and the mass extracted with water. There are many
other recipes for the preparation of Naples yellow, the majority of
which are distinguished by an apparently arbitrary arrangement of the
materials; for there is no scientific reason. If it were possible to
accurately obtain any desired high temperature in a furnace, the
manufacture of Naples yellow would no longer be a matter of skill, but
the same product could be obtained at every attempt. Since this is not
yet the case, the exact procedure for the preparation of this colour
can only be found by careful experiments.
Naples yellow is, as has been said, a handsome colour, and offers a
great resistance to varied reagents. It is only changed by one of them,
sulphuretted hydrogen, by the prolonged action of which it is turned
completely black.
=Antimony Yellow= is very similar in composition to Naples yellow.
It consists of a mixture of lead antimoniate with the oxides of lead
and bismuth. It is prepared by the process recommended by Meromé by
intimately mixing 3 parts of finely powdered bismuth with 24 parts
of powdered stibnite and 64 parts of saltpetre, melting the mixture
and shaking it whilst molten into water. The brittle mass is finely
powdered, washed and dried, then melted with 128 parts of litharge
and 8 parts of sal ammoniac. The mass obtained has a fine pale yellow
colour; when powdered it is antimony yellow. This pigment has almost
fallen into disuse because of its instability and the high price of
bismuth.
=Calcium Chrome Yellow.=—Calcium forms a yellow pigment with chromic
acid, which, although far surpassed by the lead chromes in fineness of
shade, has the advantage over them of greater stability and cheapness.
For purposes for which cheap and at the same time permanent colours
are required calcium chrome yellow can be recommended. It is most
simply prepared from potassium chromate and calcium chloride, which,
as a by-product of many chemical operations, is obtainable at very low
prices. The deepest pigment is obtained when the precipitation is done
with a boiling solution of the chromate. Calcium chromate, in addition
to its use alone, may be employed instead of white pigments to produce
pale shades from deep lead chromes. This addition should not be carried
to a great extent or the chrome will be made too light, since calcium
chromate has a much lower specific gravity than lead chromate.
=Barium Yellow, Yellow Ultramarine or Permanent Yellow.=—This pigment
consists of barium chromate. The finest product is obtained when a
solution of a barium salt, generally barium chloride, is precipitated
boiling by a solution of potassium chromate. The very finely divided
precipitate has a pale yellow colour very similar to that of pale
lead chromes. This handsome pigment is distinguished by the valuable
property of being practically unaltered by the atmosphere; it is only
attacked by strong acids and alkalis. By long heating, the colour of
this compound is gradually changed to a handsome green, which consists
of a compound of barium and chromic oxides, and has occasional use as
an artists’ colour. In order to obtain this pigment, the heating must
be intense and long continued. According to the author’s experiments,
it is not sufficient to heat for a short time to a very high
temperature; in that way a mass is obtained of very unequal colour. The
best result was obtained by spreading barium yellow in a thin, even
layer in a flat porcelain dish and heating to whiteness for 10 hours.
=Zinc Chrome Yellow.=—Zinc chromate is inferior to lead chromate in
beauty, but has the advantage of permanence. It does not blacken in an
atmosphere of pure sulphuretted hydrogen, and resists very well the
action of other agents. Zinc yellow may be prepared by the immediate
precipitation of a solution of zinc sulphate by a solution of potassium
chromate, both being boiling, but the very bright precipitate obtained
in this way is not stable; on washing, it gives up chromic acid
continually to the wash water, and only a pale yellow residue remains.
A very fine colour is obtained in the following manner: zinc sulphate
is dissolved in water and boiled for half an hour with 1 per cent.
of white zinc whilst stirring. This operation effects the separation
of iron oxide and the neutralisation of the free acid generally
present in commercial zinc sulphate. When the solution has cleared by
standing, it is precipitated by a solution of potassium chromate, the
precipitate collected on a filter and allowed to drain completely; it
is then washed with very small quantities of water and finally dried.
A pure yellow precipitate is only obtained when all the iron oxide has
been removed by boiling the zinc sulphate solution with white zinc;
if the liquid contains only a very small quantity of iron, it has yet
a very considerable influence on the colour, the yellow is not pure,
but has a brownish tinge. Zinc yellow is used alone, and mixed with
other pigments. Chrome yellows of all possible shades may be obtained
in this way. Chrome yellows are often found in commerce which consist
essentially of zinc chromate.
=Cadmium Chrome Yellow.=—When a solution of cadmium sulphate, or any
other cadmium salt, is mixed with a solution of potassium chromate, a
precipitate of cadmium chromate, CdCrO₄, is formed. This pigment has
a beautiful, deep yellow colour, in no way inferior in shade to the
finest lead chromes, and having the great advantage over the latter of
being entirely unaltered by the atmosphere; it is thus to be highly
recommended for artistic purposes. The high price at which it is sold
prevents its general use, though now that cadmium compounds are to be
obtained at so much lower prices than formerly, the price of cadmium
chromate appears to be excessively high.
=Cadmium Yellow= is cadmium sulphide, CdS; in nature it occurs as
the somewhat rare mineral greenockite. Cadmium yellow is obtained by
dissolving metallic cadmium in sulphuric acid, and precipitating the
solution with sulphuretted hydrogen. The solution of cadmium sulphate
must be digested for some time with excess of cadmium, in order to
separate the foreign metals present as impurities; the colour is not so
fine when a quite pure cadmium solution is not used.
Cadmium yellow is a very bright yellow. Several shades are obtained
according as the solution of cadmium sulphate used in its precipitation
is neutral or acid. The reason of this difference in shade lies
apparently in the different size of the crystals of which the
precipitate is composed. The deep, pure yellow colour becomes still
deeper by fusion, which takes place at a white heat. Weak alkalis,
acids and sulphuretted hydrogen do not alter cadmium yellow; it is
thus to be regarded as a durable artists’ colour. It can be mixed
with ultramarine without decomposition, when a fine green is formed;
but mixed colours cannot be made from cadmium yellow and blue copper
pigments, since these would blacken in the light.
=Lead Iodide.=—On precipitating a solution of lead nitrate with
potassium iodide, lead iodide is formed. This is but slightly
soluble in water, and, when dry, has a handsome, deep yellow colour.
Unfortunately it is not permanent, but is decomposed on exposure to
light. It can be used for bronzing, but other and cheaper pigments are
available for this purpose.
On account of the great solubility of lead iodide in a solution of
potassium iodide, it is prepared in another way, and accurately
weighed quantities are used. Calcium iodide may be used instead of the
potassium salt; 100 parts of iodine, 15 parts of fine iron filings and
25 parts of lime are mixed with sufficient water to form a thin paste,
which is warmed until all the iodine is dissolved, when water is added,
the liquid filtered, and the residue washed in order to extract all
the calcium iodide. The solution and wash waters are united, then a
solution of 152 parts of lead acetate is added, when all the iodine is
precipitated as lead iodide.
A simpler method is to dissolve equal parts of lead nitrate and
potassium iodide separately, each in 20 parts of hot water, to mix the
solutions and cool quickly, when lead iodide separates in very small
crystals. When pure lead iodide is melted in the absence of air, and
the fused mass powdered, a product of yet finer colour is formed. It
is necessary to completely imbed the crucible in which the fusion is
performed in the fire. The action of air on the melted mass would
produce a basic iodide. The fine golden yellow colour of lead iodide
adapts it especially for the production of gold bronzes on wall papers
and fabrics.
=Mars Yellow=, which is generally reckoned among the best artists’
colours, is usually a mixture of ferric oxide and calcium sulphate
or alumina. The pigment is prepared by mixing a solution of ferrous
sulphate with milk of lime, when ferrous oxide is precipitated, which
becomes yellowish brown on exposure to air, in consequence of the
oxidation of the ferrous oxide. By heating the precipitate, according
to the temperature different shades are obtained, varying between
yellow and red. In addition to Mars yellow, Mars orange and Mars red
are found in commerce.
The manufacture of this pigment is very simple: 1 part of ferrous
sulphate is dissolved in 10 parts of water, and the solution mixed with
milk of lime made from 1 part of quicklime and 40 parts of water. If it
is desired to produce a darker shade, and especially a product to be
afterwards converted into Mars orange, the amount of ferrous sulphate
is increased to 2 parts. When the mixture has been made, it must be
stirred for a long time, in order that the reacting substances may come
thoroughly into contact. The precipitate, which at first is greenish
grey, soon acquires by the action of the air the colour of ferric
hydroxide, which becomes deeper on drying.
When dried and finely ground Mars yellow is heated in thin layers, it
changes to dark yellow, and finally to orange red, a similar alteration
taking place to that occurring when ferric hydroxide itself is heated.
A Mars yellow of a deeper shade, consisting of a mixture of ferric
hydroxide and alumina, is obtained by precipitating with caustic soda
a solution of ferrous sulphate and alum. The sodium sulphate which is
formed at the same time must be removed as completely as possible by
washing with boiling water.
By calcining Mars yellow for a long time at a high temperature, Mars
brown is produced, a fine brown pigment. The value of Mars yellow and
the pigments obtained from it lies not only in their fine shade, but in
their permanence, which distinguishes the majority of the iron colours.
=Siderin Yellow.=—This not very handsome yellow consists of ferric
chromate; it is obtained by adding a neutral solution of ferric
chloride to a strong boiling solution of potassium bichromate so long
as a precipitate is formed. Siderin yellow is said to be used both
in oil and water, and to be particularly adapted for use in sodium
silicate paints, since in the course of time it forms a stony mass with
that substance.
The low price of iron salts would make it desirable to employ chromates
of iron, but it appears to be difficult to obtain a compound of
constant composition. In experiments with this object the author did
not succeed in obtaining products of the same shade. Others have
probably been equally unsuccessful, for siderin yellow has never been
used in quantity, as it would have been were there no difficulties in
the way of its preparation.
=Aureolin= is a double nitrite of cobalt and potassium, Co(NO₂)₂.3
KNO₂. This pigment is prepared by adding excess of potassium nitrite to
a solution of cobalt nitrate acidified with acetic acid. As the liquid
cools, a deep lemon yellow crystalline powder separates, which, when
dry, is known as Indian yellow or aureolin. It is distinguished from
other yellow pigments by being unaffected by sulphuretted hydrogen.
The potassium nitrite required in the preparation of this pigment
is most easily made by melting saltpetre in a thick iron vessel and
stirring in fine iron filings in small quantities as soon as the
saltpetre begins to decompose. The iron glows brightly and burns
to oxide, the saltpetre changes to potassium nitrite. The mass is
dissolved in a little hot water, the solution filtered and cooled,
when most of the undecomposed saltpetre crystallises out, whilst the
nitrite remains in solution. After further evaporation and separation
of another crop of potassium nitrate crystals, the solution can be used
to precipitate the aureolin.
It is advisable to use strong solutions in the precipitation of
aureolin; the finest precipitate is obtained in this way. If dilute
solutions are used, the precipitate forms gradually; it is then coarse
and has little covering power.
According to the method of Hayes, aureolin is prepared by passing into
a solution of cobalt nitrate the vapours produced by pouring nitric
acid over copper and allowing air to enter. Caustic potash is added
to the liquid from time to time. In this way all the cobalt can be
obtained in the form of a yellow precipitate.
=Tungsten Yellow.=—Finely powdered tungsten is introduced in small
quantities into fused potassium carbonate so long as effervescence
occurs. After boiling with water and filtering, calcium tungstate is
precipitated from the filtrate by means of calcium chloride. The moist
precipitate is added to hot dilute nitric acid until the liquid is only
slightly acid, when it is boiled for half an hour and allowed to cool.
The precipitate, after washing with a little water and drying, is a
deep lemon yellow powder.
=Nickel Yellow= consists of nickel phosphate. It is obtained by adding
sodium phosphate to a solution of nickel sulphate or nitrate, and
heating the pale green precipitate to redness. Nickel yellow has a
pleasing shade, and is distinguished by great permanence. Up to the
present it has found little use as an artists’ colour, but on account
of its permanence, which does not distinguish many yellow pigments, its
use is to be recommended.
=Mercury Yellow or Turpeth Mineral= is a basic mercuric sulphate of the
formula Hg₃SO₆. It is obtained by heating 10 parts of mercury with 15
parts of sulphuric acid in a porcelain dish in a good draught, until a
white crystalline mass of neutral mercury sulphate remains. This salt,
HgSO₄, is decomposed in contact with water into free sulphuric acid and
a basic salt of the above composition. The decomposition is effected
by treating the finely powdered neutral sulphate with hot water so
long as the washings are acid, when a handsome lemon yellow substance
remains. The wash waters contain acid mercuric sulphate. They are
allowed to stand with mercuric oxide so long as this is dissolved, and
the solution then used to prepare new quantities of mercury yellow.
Turpeth mineral has a very bright shade and great covering power,
but it has little permanence. Sunlight soon turns it grey, and air
containing sulphuretted hydrogen in a short time turns it quite black,
mercury sulphide being formed.
=Yellow Arsenic Pigments.=—The extremely poisonous character of arsenic
pigments has practically banished these handsome and cheap colours
from use. In many countries their use is justly illegal. The majority
of arsenic pigments have, therefore, merely historic interest. The two
yellow arsenic pigments are found in nature as realgar and orpiment;
though these are not rare minerals, the artificial products were
generally used as pigments, and when they were in common use they were
generally made in metallurgical works, in which minerals containing
arsenic were treated.
Realgar, As₂S₂, has an orange red colour, whilst orpiment, As₂S₃, is a
pure yellow. When these substances were used as pigments they had the
same drawbacks in regard to mixing with other pigments as other sulphur
compounds. King’s yellow is finely powdered natural or artificial
orpiment.
=Lead Arsenite= is a permanent deep yellow, but extremely poisonous. It
can be made by fusing an intimate mixture of 100 parts of white arsenic
with 75 parts of gold litharge, grinding and levigating the mass.
Cadmium yellow, which has still more permanence and is less poisonous,
replaces this pigment.
=Thallium Pigments.=—Thallium is a metal which exhibits certain
similarities to lead. By precipitating a solution of a thallium salt
with potassium chromate or bichromate, according to the proportion
between the quantities of the two salts, precipitates are obtained of
yellow, orange or deep red colour, or, after fusion, brown. By the
addition of a mixture of potassium chromate and ferricyanide to a
mixture of a thallium salt and ferrous sulphate an olive green pigment
is obtained. On account of the rarity of thallium compounds, technical
employment is out of the question, and the sensitiveness of thallium
pigments towards sulphuretted hydrogen prevents their use for artistic
purposes.
CHAPTER XV.
MOSAIC GOLD.
Mosaic gold consists of tin disulphide, SnS₂, fine scales of a golden
yellow colour, which sublime undecomposed at a fairly high temperature
and withstand the action of chemical reagents. It has a peculiar greasy
nature, and can be easily ground. It is, therefore, much used for
bronzing picture frames, as a pigment for painters and for wall papers.
Tin disulphide can be prepared either in the wet or the dry way; in
the wet way, by the action of sulphuretted hydrogen on a solution of
tin tetrachloride. The yellow precipitate so obtained has no handsome
colour. A far finer product is obtained in the dry way. The process
is often regarded as accompanied by particular difficulties, but
in reality it is quite simple. It is only necessary in preparing
this pigment to take care not to raise the temperature above a
certain point, otherwise a great portion of the tin disulphide will
be decomposed into sulphur and tin monosulphide. To prevent the
temperature from rising too high, an addition of ammonium chloride
is made. This salt is volatile at a certain temperature; heat which
would otherwise raise the temperature above this point is used in
volatilising the ammonium chloride. With a little care it is easy to
interrupt the operation before all the ammonium chloride has been
driven off. The mosaic gold then obtained has a real golden glitter.
If the temperature rises too high, grey tin monosulphide is formed,
which naturally considerably diminishes the brilliancy of the product.
Ammonium chloride may be replaced by mercury or mercury compounds,
which are volatile at a temperature below that at which mosaic gold
is decomposed. When mercury compounds are used, both on account of
their cost and poisonous nature the heating must be conducted in glass
retorts in order to recover the mercury. This operation requires great
care if loss due to the breakage of the glass vessels at the high
temperature is to be avoided. The process in which metallic mercury is
used gives the finest product of all, and is to be recommended when a
pigment is to be prepared which shall as nearly as possible approximate
to the appearance of gold.
In order to obviate the danger and loss associated with the use of
glass vessels, manufacturers who make mosaic gold in large quantity
should use an iron vessel. This will last a very long time. Such an
apparatus consists of an iron pan with a broad rim, upon which is
fastened a head which has the form of a retort neck; to this are
connected short, wide tubes leading to a chamber in which substances
not condensed in the retort neck may deposit, so that the use of this
inexpensive apparatus will not only be without danger, but will be
accompanied by the recovery of almost the whole of the volatilised
substances. The pan is filled with the materials, the head placed on,
the joint tightly luted, and the retort neck connected with the chamber
by the wide iron tubes.
There are many formulæ for the preparation of mosaic gold. Some of the
most important are given, which in every case will yield a good result:—
Tin filings 40 parts
Sulphur 35 ”
Ammonium chloride 25 ”
The tin filings, which must be very fine, are well mixed in a mortar
with the sulphur and ammonium chloride. The heating is gradual at
first; when the evolution of vapours has ceased the temperature is
very slowly increased to a dark red heat. The mosaic gold is found as
a yellow mass at the bottom of the vessel, but partly in crystalline
scales on the walls and head of the retort.
Other recipes are as follows:—
Tin dioxide 80 parts
Sulphur 60 ”
Ammonium chloride 30 ”
Tin filings 45 ”
Sulphur 35 ”
Ammonium chloride 25 ”
In all these cases the chief endeavour should be not to raise the
temperature too high; a dark red heat is sufficient to give a perfectly
satisfactory result.
When metallic mercury is used, it is employed in the form of an amalgam
with tin, which is then in such a finely divided condition that it
readily enters into chemical combination with the sulphur. The amalgam
is most simply obtained by heating 1 part of mercury almost to boiling,
and stirring 2 parts of tin filings into the hot metal; 18 parts of
this amalgam mixed with 7 parts of sulphur and 6 of ammonium chloride
are heated together.
The mosaic gold made after any of these methods may be used for gilding
gold frames or as a painter’s pigment. Much so-called gold paint
consists of mosaic gold ground with a thick gum solution.
=Chrysean.=—Wallach found that when a current of sulphuretted hydrogen
was passed through a saturated solution of potassium cyanide a
precipitate was formed, which had the formula C₄H₅N₃S₃. This substance,
chrysean, is similar in appearance to mosaic gold; its technical
employment is prevented by its extremely poisonous nature and its high
cost as compared with mosaic gold.
CHAPTER XVI.
RED MINERAL PIGMENTS.
VERMILION.
This beautiful scarlet red pigment, which has been used for so long
a time, consists of mercuric sulphide, HgS. The same compound occurs
ready formed in nature as cinnabar; picked pieces of this mineral come
into the market under the name of mountain vermilion (_Bergzinnober_).
A far larger quantity of vermilion is made artificially.
Mercuric sulphide exists in two forms—as a black non-crystalline
powder and in the crystalline form, which is used as a pigment.
Each modification may be transformed into the other by suitable
treatment, and each may pass into the other spontaneously under certain
conditions. In the manufacture of vermilion, the black form of mercuric
sulphide plays an important part; it is, therefore, necessary to give
an account of the chemical behaviour of the two modifications before
proceeding to an account of the method by which vermilion is made.
=Black Mercuric Sulphide= may be obtained either by the direct union
of metallic mercury with sulphur, or by precipitating the solution of
a mercuric salt with sulphuretted hydrogen. It is most simply formed
by rubbing together equal parts of sulphur and mercury moistened with
water, until the mixture is uniformly black. It is, however, difficult
in this way to convert all the mercury into sulphide. A better result
is obtained when the mixture is moistened by ammonium sulphide instead
of water. In this case the time required for the operation is shortened
by warming the vessel. If the mortar is placed in hot water it is
generally sufficient to grind for about two hours to bring about the
combination of the mercury and sulphur.
This compound can also be easily obtained by heating mercury with
sulphur. In a vessel, placed under a chimney with a good draught, which
is necessary to carry away the poisonous mercury vapours, 6 parts of
the metal are heated nearly to boiling and 1 part of sulphur added.
Combination takes place at this temperature with a slight explosion,
and pure mercuric sulphide results when the heating is continued until
the excess of sulphur is driven off.
For the purpose of the manufacture of vermilion, black mercuric
sulphide is most simply made by filling a thick-walled vessel with
equal weights of mercury and sulphur, moistening the mixture with water
and shaking or rotating the vessel for several hours. This can be done
either in a rotating cylinder containing iron balls, or the vessel can
be fastened to any rotating object—to a water-wheel or to the fly-wheel
of a steam-engine. The vessel in which the combination is effected
should of course not be quite full. It has been found that a more jerky
motion than that of rotation effects the combination of the mercury and
sulphur in a shorter time. For example, an opportunity of fastening the
vessel to a saw-mill would be of great advantage.
The mercuric sulphide made by the above methods is a velvety black
mass, which, even when exactly equivalent weights of sulphur and
mercury have been used, is never quite pure. Carbon bisulphide will
always extract a certain quantity of uncombined sulphur. The most
important property of the black sulphide for the present purpose is
that it is changed into the crystalline modification by heating to the
temperature at which it volatilises. The sublimed mercuric sulphide has
the well-known fiery scarlet colour characteristic of vermilion.
=Red Mercuric Sulphide=, or vermilion, exhibits, for a sulphur
compound, considerable resistance to the action of chemical reagents;
dilute mineral acids do not decompose it. Unfortunately, vermilion has
another property which makes it quite unsuitable for the artist’s use:
in the course of time it gradually turns dull and at last is completely
discoloured. This alteration of colour can only be ascribed to a return
of the red crystalline modification into the black non-crystalline.
When a white pigment is tinted by vermilion it should not be a lead
pigment, or in a brief time it will turn black. A white pigment such
as zinc white, which is not acted upon by sulphur compounds, should be
used.
CHAPTER XVII.
THE MANUFACTURE OF VERMILION.
The red modification of mercuric sulphide can be prepared in the wet or
the dry way. The latter was formerly in general use, but at present the
wet method is more generally employed, as it more easily and certainly
produces a handsome pigment. Each method has its advantages, and both
will be described.
(a) DRY METHOD.
The numerous prescriptions which have been given for the manufacture
of vermilion by the dry method are all founded on endeavours to
convert black mercuric sulphide into the red form. Many of these
prescriptions contain directions for the soundness of which no reason
can be discovered, and it is not going too far to say that none exists,
and that operations described as essential for the success of the
process have been inserted merely to give the recipe the appearance
of novelty. It cannot be denied that certain manipulations impart a
greater brilliancy to the product, although it is impossible to assign
a physical or chemical reason; but the manufacturer will quickly
be able to differentiate the valuable from the worthless in these
processes. Two conditions have the greatest influence on the beauty of
the pigment—the temperature at which the black sulphide is sublimed,
and the complete freedom of the vermilion from excess of sulphur. Of
less importance is the repeated grinding of the vermilion; the oftener
it is ground, the smaller the crystals become and the paler the shade.
The operation of grinding the pigment in ordinary mills is known
practically as “preparing,” the extraction of excess of sulphur by
boiling with alkaline liquids as “refining,” the product.
The usual process in Holland, especially in the Amsterdam works, is as
follows: The black sulphide is made by heating 270 parts of mercury
with 37·5 parts of sulphur in copper pans—the fire is so regulated that
the temperature is not high enough to ignite the sulphur. If properly
prepared the product has now a pure black colour. It is immediately
finely ground and preserved in earthenware bottles containing only 0·7
kilogramme each. It is sublimed from hemispherical vessels, provided
with iron covers carefully joined to the rim of the sublimation vessel
by a suitable fire-resisting cement. Generally 3 such vessels are
contained in one furnace. The operation is commenced by heating them
until the bottom shows a dark red heat. The temperature should now
be increased to such an extent that, when the contents of one of the
above-mentioned small bottles are poured into the vessel, a small flame
only appears; if on the contrary the contents burn explosively, the
temperature is too high, and further quantities of the black sulphide
must not be added until the vessels have cooled down to a certain
extent. If, on introducing the first quantity of mercuric sulphide, a
flame appears unaccompanied by an explosion, the contents of several of
the bottles may be introduced; the openings through which this addition
is made are immediately closed by a well-fitting iron plate. From time
to time this cover is raised and fresh quantities of mercuric sulphide
added. The operation lasts about 36 hours, when double the quantity of
mercuric sulphide, made from the above mixture of mercury and sulphur,
will have been introduced into the 3 vessels. For the complete success
of the process, the accurate regulation of the temperature to which
the vessels are exposed is particularly important; in practice, the
temperature is judged by the height of the flame which issues on
removing the iron plates: if this reaches to 1 metre the fire is too
fierce, but if the flame is very small the fire must be increased.
Towards the end of the sublimation the mass in the vessels is stirred
about every 15 minutes. As soon as the sublimation is finished the
fire is extinguished. The vessels are broken when completely cold; the
vermilion is then found in the upper portion as a sublimate of fibrous
character. The vermilion made by this process requires simply wet
grinding under ordinary mills and drying to be ready for market.
In the great mercury works at Idria, in Austria, vermilion is also
made from the black sulphide. The latter is made by mixing 84 parts
of mercury with 16 parts of finely powdered sulphur in rotating
vessels driven by water power, the operation lasting about 3 hours.
This quantity of sulphur is larger than is required to form mercuric
sulphide; experience has shown that the combination takes place more
rapidly when more than the equivalent quantity of sulphur is used.
Heat is developed by the reaction and the temperature of the mixture
rises to over 30° C. The black sulphide is then sublimed in cast-iron
vessels, which are pear-shaped and built 6 together in a furnace; each
holds a charge of 315 kilogrammes of black.
Several periods are distinguished during the heating of the mass in
the sublimation vessels. The operation is commenced by heating 2 of
the vessels first. As soon as the vapours of sulphur, issuing from the
neck of the vessels, take fire with explosion, the fire is made to
heat the adjacent vessels. When the contents of all the vessels have
exploded, the first part of the process known as the “evaporation” is
at an end. Earthenware heads are then placed on the vessels and the
fire is increased until the excess of sulphur present begins to distil;
its vapours take fire in the air with a slight explosion. When this
takes place, earthenware receivers are attached which have only a small
opening for the escape of uncondensed vapours. The sulphur condenses
in these. When sulphur vapours are no longer given off in quantity,
the intermediate period (_stϋckperiode_) is finished and the real
sublimation of the vermilion commences. The fire is now considerably
increased and the sublimed vermilion collects in the cooler parts of
the apparatus. When the sublimation is completely finished, small blue
flames, which quickly vanish, appear at the joints of the apparatus.
The furnace is allowed to get quite cold, when the various parts of
the apparatus are taken apart, the vermilion deposited in the tubes
is carefully removed, so that they may be again used, whilst the
receivers and head are broken, so that the vermilion they contain can
be collected.
The larger pieces form lump vermilion; the fragments of the receivers
are cleaned with a wet brush to collect what adheres. The whole process
of sublimation from the introduction of the black to the end lasts
about 7 hours.
The sublimed vermilion is ground in mills which differ little from
ordinary grinding mills. To prevent the formation of dust, water is
added and the stones are surrounded by wooden casings. The red paste
from the mills, which is now known as vermilion, is then refined.
The refining consists in extracting the excess of sulphur by means of
boiling potash solution; 300 kilogrammes of the ground vermilion are
stirred up with water in a tub, the water is drawn off and the wet mass
brought into an iron pan, in which it is heated with 22·5 kilogrammes
of potash lye for about 10 minutes. According to the composition of
the crude vermilion the lye has a strength of from 10° to 13° B. The
smaller the quantity of sulphur, the weaker is the potash solution; it
is, or was, made in Idria in a very primitive manner, by extracting
wood ashes. For vermilion of a bright red shade potash solution of 10°,
for the dark red of 11°, and for “Chinese vermilion” of 13° is used.
The excess of sulphur, together with a trace of mercuric sulphide,
dissolves in the potash solution; the sulphur chiefly forms potassium
pentasulphide. When the boiling is finished, the vermilion is carefully
washed and dried in dishes placed in a heated furnace. During drying,
the vermilion agglomerates; finally the lumps are broken and sieved.
=Chinese Vermilion= is in similar case to Indian ink. Both substances
are in common use in Europe, they far surpass in quality our own
manufacture, and in neither case do we know the exact method by which
they are made. Genuine Chinese vermilion so far surpasses European in
brightness that it is bought at five or six times the price. It is
said on unauthenticated authority to be made by subliming a mixture
of 4 parts of quicksilver with 1 part of sulphur in earthenware pots
closed by an iron plate, which is kept constantly wet and serves as a
receiver, on which the vermilion deposits. The sublimed masses adhering
to the lid are sorted, ground and repeatedly washed with water.
According to Callum’s description of the manufacture of vermilion at
Hong Kong, mercury and sulphur are heated in a large iron pan, with
continual stirring at about the melting point of sulphur (111° C.),
until the whole has changed to a black mass. After cooling, this is
mixed with water and mercury, the mixture thoroughly stirred, dried,
placed in a hemispherical dish and covered over with broken porcelain.
A similar dish is cemented on the top of the first, and the dishes are
heated for 16 hours; the vermilion adhering to the porcelain fragments
is removed, wet ground and dried.
A vermilion approaching Chinese in beauty is said to be obtained by
mixing ordinary vermilion with 1 per cent. of antimony sulphide and
again subliming the mixture. The dark grey sublimate produces a reddish
brown powder, which is repeatedly boiled with a solution of “liver of
sulphur” (potassium polysulphide), washed with water and digested for
a long time with hydrochloric acid. The author has repeatedly made
vermilion by this process, but could never obtain a product differing
appreciably from the original vermilion.
(b) WET METHODS.
The manufacture of vermilion in the wet way is founded on the
conversion of metallic mercury or its compounds into mercuric sulphide
by heating with alkaline sulphides, such as ammonium sulphide and liver
of sulphur. The product always contains uncombined sulphur, which is
eliminated by treatment with alkalis.
Apart from the danger to the health of the workmen caused by the
poisonous mercury vapours, which are present in rooms where mercury or
its compounds are heated in apparatus even of the best construction,
and which is not to be feared in a wet process, the vermilion prepared
in the latter manner has a finer and brighter shade than that prepared
by a dry process. The greater cost of the wet process is covered by the
higher value of the product.
The starting point of the wet method may be either metallic mercury,
black mercuric sulphide or another mercury salt. When metallic mercury
is used, according to an old process, 100 parts are ground with 23
parts of flowers of sulphur and a little caustic potash solution to
a homogeneous mass, which is then heated with a solution of 53 parts
of caustic potash in an equal quantity of water, the evaporated water
being continually replaced, until the colour changes from brownish-red
to the fiery red of vermilion. When the colour approaches the desired
shade a careful watch must be kept, and immediately the proper shade
is obtained the heating must be stopped. If it is continued beyond
this point for but a short time, the vermilion at once loses its fire
and cannot be again brightened. An interruption in the heating is
equally harmful, a dull shade being produced. When the proper shade has
appeared, the contents of the vessel are poured into a large quantity
of water. The vermilion is then washed with dilute caustic potash and
afterwards with water until the alkaline reaction disappears. It is
finally dried. The alkaline solutions obtained in this process contain
considerable quantities of mercury in solution. They are collected, and
when a sufficient quantity has accumulated the mercury is extracted.
Barff recommends the following method: Mercury is rubbed with ⅙ to ⅕
of its weight of sulphur until a uniform grey powder results. This is
heated in a porcelain dish with caustic potash solution (133 parts of
potash in 150 parts of water) at 45° C. until the powder has become
bright red. Heating above 45° C. is to be avoided; it would impart a
brown tinge to the vermilion.
A convenient process for making vermilion in the wet way is to first
produce the black sulphide in the dry way and then treat this with
alkalis. Brunner’s method is founded on this procedure: 100 parts
of mercury and 38 parts of sulphur are used to prepare the black
sulphide. This is heated with a solution of 25 parts of caustic potash
in 150 parts of water. The operation is best conducted in a vessel
placed in a water bath, the temperature of which does not exceed 45°
C. After heating 7 to 8 hours, the mass begins to turn red, when the
change proceeds more quickly, and the greatest care must be taken
not to exceed the point at which the colour has reached its greatest
brilliance. As soon as the desired shade has appeared, the temperature
of the water bath is lowered, but it is kept warm for several hours.
Caustic solutions of different strengths produce different shades.
Thus, in order always to obtain the same product from the same
quantities, it is necessary to replace the evaporated water at short
intervals. In this process some quantity of mercury remains uncombined;
it is separated from the vermilion by a process of levigation in the
washing.
=Firmenich’s Method.=—Many wet methods for the manufacture of vermilion
differ but little from the preceding. In Firmenich’s method the
production of the black sulphide is united with the formation of
vermilion in one operation.
A solution of potassium sulphide of a certain strength is made by
igniting 20 parts of potassium sulphate with 6 parts of coal, boiling
the mixture with 1·5 time the quantity of rain water, cooling the
solution, separating from the potassium sulphate which crystallises
out, and boiling the solution with sulphur so long as it is dissolved.
A mixture of 4·5 parts of this solution, 100 parts of mercury, and 2
parts of sulphur is placed in flasks, which are subjected for several
hours to a shaking or rocking motion. The liquid becomes greenish, and
its temperature rises in consequence of the combination of mercury
with a portion of the sulphur of the potassium sulphide. The latter
immediately dissolves the free sulphur present, and again gives it
up to the mercury, which in the course of a few hours is completely
converted into the black sulphide. The shaking is discontinued when
the contents of the flasks have acquired a deep brownish-red colour.
The flasks are then placed in a room heated to 45° C., and their
contents repeatedly shaken up. At this temperature the transformation
of the black into the red mercuric sulphide is completed. The deposit
in the flasks acquires more and more a scarlet shade. As soon as the
colour is found to have reached its greatest intensity the liquid
is carefully poured off, and the vermilion treated with caustic soda
solution in order to dissolve free sulphur; it is then very carefully
washed.
In this process, the temperature at which the operation commences is
important. The cooler the mixture which is placed in the flasks before
shaking, the paler will be the colour of the vermilion obtained. It is
to be supposed that the reaction, which is but slow in the cold, forms
in consequence of its slowness a black sulphide of such character that
in its subsequent transformation into the red crystalline sulphide very
small crystals are produced.
The Gautier-Bouchart method for the preparation of vermilion from
mercury and ammonium sulphide is applied on the large scale as follows:
1,000 parts of mercury are shaken for 7 hours with 200 parts of flowers
of sulphur and 400 parts of ammonium sulphide saturated with sulphur;
the dark-coloured mixture is exposed for several days to a temperature
of 60° C., when the colour changes to red. In addition to the usual
washings, the mass is further treated with nitric acid. The purpose of
this operation is to oxidise all the free sulphur to sulphuric acid.
For a colour works in which, in addition to vermilion, are made
other pigments, especially such as are sensitive to the action of
sulphuretted hydrogen, this process, which produces vermilion of a
good shade, although not particularly stable, is not to be recommended
on account of the evolution of sulphuretted hydrogen, which cannot be
completely prevented even by the greatest care.
=Liebig’s Process.=—The starting point in the manufacture of vermilion
by this process is the compound known as white precipitate (see below).
It is only necessary to heat white precipitate with a solution of
ammonium sulphide saturated with sulphur, at 40° to 50° C., for a long
time. The operation may be conducted in well-closed flasks in a place
the temperature of which is, as nearly as possible, 45° to 50° C., such
as the flues leading from a furnace in constant use. The change of
colour is gradual; this is an advantage, since it is easier to obtain
the correct shade. By treating the product with weak caustic potash
solution it may be made still brighter. After washing and drying at a
gentle heat the pigment is finished.
This method is especially adapted for manufacturers not exclusively
engaged in making vermilion. No special arrangement of apparatus is
necessary; the apparatus for making ammonium sulphide and a number of
glass flasks are the only essentials. There is another considerable
advantage, that the product cannot be completely spoiled. The process
of formation of the vermilion is tolerably slow; a careful observation
of the progress of the earlier operations is sufficient to determine
the time required. In order to be able to do this with certainty, it is
necessary to work always under exactly the same conditions; the same
quantity of white precipitate must always be used and the solution of
ammonium sulphide must always have the same strength.
=Mercuric Ammonium Chloride, Infusible White Precipitate=,
HgClNH₂.—This compound, which is required in the last-mentioned process
for the manufacture of vermilion, is most cheaply made in the following
way: to a solution of 1 part of common salt in 32 parts of water, 2
parts of dry mercuric sulphate are added in small quantities, whilst
thoroughly stirring. It is absolutely necessary to work in this way,
because mercuric sulphate is decomposed by water into free sulphuric
acid and a basic salt, which is much more slowly converted into white
precipitate than the neutral salt. The liquid now contains mercuric
chloride; on the addition of ammonia to alkaline reaction it gives a
heavy white precipitate. The liquid is poured off and the precipitate
washed with water containing a little ammonia, until the washings
give only a slight turbidity with barium chloride. This process may
also be commenced with mercuric chloride, but the above method is
cheaper. White precipitate should volatilise without fusing when heated
on platinum foil and should keep its white colour when treated with
ammonia.
=Electrolytic Process.=—In a wooden vessel 1 metre in diameter and
2 metres deep are placed, at the sides, dishes 15 centimetres wide,
containing a layer of mercury 1 centimetre deep. These dishes are
connected with the positive pole of a dynamo. The negative pole is
connected to an iron plate, electrolytically coated by copper, placed
at the bottom of the vessel, which is filled with a solution containing
8 per cent. of ammonium nitrate and 8 per cent. of sodium nitrate. A
regular current of sulphur dioxide is introduced through a perforated
coil. The excess of gas escapes by a tube in the cover. When the
current is passed a precipitate of red mercuric sulphide is at once
formed. Attempts have been made to dispense with the current of sulphur
dioxide. The bath then contains 100 litres of water and 8 kilogrammes
each of ammonium nitrate, sodium nitrate, sodium sulphide and sulphur.
Under these conditions it is only necessary to add sulphur and mercury
in order to obtain, at the end of the operation, vermilion which is in
no way inferior to that made by the first process.
Vermilion is frequently grossly adulterated by cheaper pigments.
Substances are often found under the name of vermilion which contain no
trace of mercury, but consist of bright orange lead mixed with a few
per cent. of ferric oxide, and having a deceptive similarity in colour
to the best vermilion.
=Mercuric Iodide.=—When corrosive sublimate solution is precipitated
with exactly the necessary quantity of potassium iodide, mercuric
iodide is obtained as a scarlet precipitate which surpasses in beauty
even the best samples of vermilion. Unfortunately, this substance
cannot be used as an artists’ colour. Exposure to light soon turns it
brown and finally black. It appears to be unaltered in the dark; the
author possesses a sample which has been so kept for 30 years without
losing its shade in any way.
CHAPTER XVIII.
ANTIMONY VERMILION.
Antimony vermilion is a red pigment which will bear comparison in
fineness of shade with mercury vermilion, over which it has the
advantage of cheapness. In composition it is antimony trisulphide,
Sb₂S₃. This compound is obtained by precipitating a solution of
antimony trichloride with sulphuretted hydrogen. However, the
precipitate, which is a very fine red whilst wet, loses its colour in
drying, and the product is almost worthless as a pigment.
In another way it can be obtained in such a condition that it loses
nothing of its beauty in drying, but retains its brilliance. Böttger
gives the following process: a solution of antimony trichloride is
mixed with a solution of sodium hyposulphite (thiosulphate) and the
liquid heated so long as a precipitate forms, which is then washed on
a filter with water containing acetic acid. If pure water were used
for washing, the antimony chloride still present would be decomposed,
forming the white oxychloride, which would detract from the shade of
the antimony vermilion. In this process particular regard is to be paid
to the use of exact quantities of materials. The finest product is
obtained when 2 parts of a solution of antimony trichloride, which has
exactly the specific gravity 1·35, are mixed with a solution of 3 parts
of sodium hyposulphite in 6 parts of water.
According to R. Wagner, antimony vermilion is obtained by dissolving
4 parts of tartar emetic and 3 parts of tartaric acid in 18 parts of
water, heating to 60° C., mixing with a solution of sodium hyposulphite
(thiosulphate) and heating to 90° C. The precipitate is then carefully
washed and dried.
Pure antimony vermilion closely approaches, as we have said, ordinary
vermilion in shade, and for a sulphur compound shows a remarkable
resistance towards chemical reagents. By dilute acids, ammonia and
alkaline carbonates, it is attacked only on long continued contact, but
it is easily decomposed by very dilute hydrochloric acid and by caustic
alkalis. A mixture with white lead keeps for a long time, but there
can be no question of the permanence of such a mixture, in consequence
of the oft-repeated properties of lead pigments. Antimony vermilion is
well adapted for oil painting. When ground with oil it exhibits a red
of a brilliance in no way inferior to that of genuine vermilion. It may
also be used as a water colour, but is not adapted for fresco work,
since it is quickly decomposed by lime.
In spite of these favourable properties antimony vermilion has so
far been little used. Considering the small cost of its preparation,
especially when calcium hyposulphite, which gives an equally good
result, is used in place of the sodium salt, its use is to be
recommended in the place of mercury vermilion. It appears as if the
high price demanded for this substance by several manufacturers has
prevented its general employment.
=Appendix. Antimony Blue.=—This fine blue pigment can be prepared by
the addition of a dilute solution of potassium ferrocyanide to a clear
solution of antimony in _aqua regia_. According to Krauss, it contains
no antimony as colouring principle, but is a Prussian blue obtained
from the ferrocyanide, which is decomposed by the strong acid, with
evolution of hydrocyanic acid.
CHAPTER XIX.
FERRIC OXIDE PIGMENTS.
The pigments composed of ferric oxide are used in enormous quantity.
They are distinguished by a high degree of permanence. Large deposits
of ferric oxide occur in nature, and in places where it is found in
considerable quantity iron is manufactured from it on the spot. Several
varieties of natural ferric oxide are distinguished: specular iron ore
forms crystalline masses of brilliant lustre; another variety in small
crystals is called iron glance; micaceous iron ore consists of shining
scales; red hæmatite has the appearance of bundles of fibres; an earthy
variety of hæmatite is also common.
The compound of ferric oxide with water, ferric hydroxide, is still
more abundant than hæmatite; brown hæmatite, limonite and other iron
ores consist essentially of this compound. The pigment known as ochre
is also ferric hydrate.
Very pure red hæmatite has so fine a red colour that it may often be
used as a pigment after grinding or levigating. The famous red of
Pompeii, which has been found on the ruined walls of the town, still
shows, after eighteen centuries’ exposure to damp, the brightest
shade, certainly a striking proof of the extraordinary permanence of
this pigment. Considering its great permanence, its easy preparation,
and its low price, it is surprising that ferric oxide is not more
extensively used by artists than it is at present. It is used,
however, extensively in colouring earthenware, for which purpose
its stability at high temperatures makes it suitable. Principally on
account of its cheapness it is largely used in ordinary painting, but
for artistic purposes it is not used to the extent it deserves.
Every colour maker well knows that artists justly complain that
the pigments offered to them have generally but a small degree of
permanence. They are surprised that the paintings of the old masters
show now, after the lapse of centuries, their colours unaltered, whilst
the pigments manufactured at the present day, instead of corresponding
to the high standard of chemical knowledge, are often discoloured
within a few months after use. But it was just the restricted knowledge
of chemistry which the ancients possessed which compelled them to
make extensive use of the permanent earth pigments, to which class of
permanent colours ferric oxide belongs. The advances of science have
succeeded in preparing ferric oxide, not only as a red pigment, but in
the different shades of red, from yellow to brown and deep violet, all
consisting entirely of pure ferric oxide. Ferric oxide has the property
of altering its molecular condition on protracted heating; this change
is accompanied by an alteration in colour. If ferric oxide is heated
for a very long time at the highest temperatures its colour changes at
last to black.
Ferric oxide can be prepared by different methods for artists’
purposes. The process by which it is made is not unimportant. Either
ferrous or ferric salts can be employed as the raw material. With
the latter, pure ferric oxide is at once formed, or hydroxide, which
is converted into oxide by heating. The ferrous salts are generally
cheaper than ferric salts; they are therefore commonly used for the
preparation of ferric oxide, as well as of the other iron pigments.
Even in combination with the strongest acids, ferrous oxide has but
little stability; when separated from its salts as ferrous hydroxide,
the greatest precautions must be taken to obtain it pure; in contact
with the air it at once takes up oxygen and changes to ferric
hydroxide. Ferrous carbonate shows this same degree of instability; the
natural substance, occurring in large crystals as spathic ironstone, is
no exception: on exposure to the air it is gradually changed to ferric
oxide.
There is another reason for the advisability of using ferrous salts to
prepare ferric oxide. When ferric hydroxide is made by precipitating
the solution of a ferric salt with ammonia or caustic potash, the least
excess of the precipitant unites with the hydroxide to form a compound
which is only decomposed by long washing with water. The precipitate
is, however, gelatinous, and consequently very difficult to wash.
In order to prepare ferric oxide suitable for an artists’ pigment the
following process may be used: 17 parts of soda are dissolved in 68
parts of water; the solution is boiled in an iron pan, and 10 parts
of crystallised ferrous sulphate are added in small quantities with
continual stirring. The boiling and stirring are continued until
the green vitriol has completely dissolved, when the greenish white
precipitate is allowed to settle, washed several times with water,
and then exposed to the air in thin layers. The precipitate, which
begins to turn yellow during washing, becomes in a short time ochre
yellow in the air, being changed into ferric hydroxide. After drying
and calcining, a fine red powder of pure ferric oxide is formed. The
shade depends on the temperature at which the substance is calcined:
the higher the temperature and the longer the heating is continued, the
darker is the product.
=Vogel’s Iron Red.=—This preparation, which is particularly brilliant
and therefore highly suitable for an artists’ colour, is made by
adding a saturated solution of oxalic acid to a boiling solution of
green vitriol. The greenish yellow precipitate of ferrous oxalate is
collected on a filter and well washed with water. After drying, the
precipitate is heated in a shallow iron dish to a temperature of 200°
C., at which the ferrous oxalate decomposes and is converted into a
soft fiery red powder consisting of pure ferric oxide. By igniting this
powder in covered crucibles the different shades of ferric oxide can be
obtained.
=Macay’s English Red.=—Seven hundred and four parts of ferrous
sulphate, 1,000 parts of copper chloride, and 1,678 parts of common
salt are dissolved, the solution boiled and the precipitate ignited.
In the manufacture of fuming or Nordhausen sulphuric acid, ferric oxide
is obtained as a residue. It is then known under the names of English
red, _caput mortuum_, colcothar, rouge and Indian red as a very cheap
pigment. It is also used as a polishing material. Fuming sulphuric acid
is made by heating green vitriol at a white heat in retorts placed
in furnaces; sulphur dioxide and trioxide are evolved, whilst in the
retorts there remains a residue of almost pure ferric oxide, containing
small quantities of basic ferric sulphate, which can only be decomposed
by long continued violent heating. The vapours of sulphur trioxide are
caught in receivers containing oil of vitriol, in which they dissolve
and produce fuming sulphuric acid.
The residue in the retorts, which has only a low commercial value,
can be converted into a good pigment without the expenditure of much
money or labour. It is ground in mills as finely as possible, and,
if necessary, afterwards levigated. The fine powder is mixed with
varying quantities of common salt, the object of which is to prevent
the temperature from rising too high in the calcining process. Common
salt is volatile at a temperature approaching a strong red heat; when
the temperature has once risen so far, a further rise is prevented by
the heat taken up in volatilising the salt. In order to make ferric
oxide of a yellow tinge, 2 per cent. of salt are added, and the mixture
heated with a moderate fire for 1 hour. To obtain the deeper shades,
the addition of common salt is increased even to 6 per cent. For a
brownish-red oxide, 4 per cent. of salt are added and the mixture
heated for 4 hours; for a dark violet oxide, 6 per cent. of salt are
used, and the mixture is heated for 6 hours with the fiercest fire.
It has been observed that the shade of the product is finer the more
completely air is excluded from the glowing mass and the more quickly
the product, after sufficient heating, is cooled down to the ordinary
temperature.
Fire-clay tubes are used for heating the ferric oxide, which are
similar to gas retorts, and are built one above the other in furnaces.
The number in one furnace may reach 60. Each retort is closed by a
well-fitting lid, which is luted with clay after the retorts are
filled, a small opening being left through which the heated air may
escape. If the retorts were closed completely air-tight they would
burst on heating.
Ferric oxide pigments are made in very large quantity by several works,
which bring up to 20 different shades, varying from reddish yellow to
dark violet, into the market.
On account of their great resistance to the action of the atmosphere
and of chemical agents, the ferric oxide pigments are particularly
suitable for painting iron and other metals which are exposed to air or
water. They are also suited to fresco work.
Lower qualities of iron reds are made by calcining ochres, large
deposits of which occur in nature, and also from the residues of basic
ferric sulphate obtained in the alum manufacture. These varieties
are at the best usable for ordinary painting, but never for artists’
pigments.
According to the method of Steinau, iron pigments can be made from
wrought-iron scraps, turnings, etc., by causing them to rust through
alternate contact with air and water. The resulting ferric hydrate is
either at once used as a pigment or converted into other shades by
calcining. By heating in the air a red pigment is formed; by heating
with coal in the absence of air a black; and from mixtures of red and
black different shades of brown. If the iron turnings can be obtained
cheap, this process should be well adapted to the manufacture of fine
iron pigments.
=Indian Red= consists of ferric oxide. It was originally obtained from
a very pure hæmatite, occurring in India, by grinding and levigating.
It can, however, also be artificially made, in shades varying between
bright red and dark brownish-red, by heating pure ferric oxide. This
valuable pigment is extremely brilliant and durable.
The darkest brownish-red shades can be obtained from Indian red by
mixing it with varying quantities of litharge, and heating the mixture
very strongly in a covered crucible.
CHAPTER XX.
OTHER RED MINERAL PIGMENTS.
=Chrome Red or Chrome Vermilion.=—Under the most varied names, chrome
orange, Persian red, Derby red, Chinese red, Indian red, chrome
vermilion, etc., there occur in commerce numerous pigments, orange to
dark red in colour, which can all be made from neutral lead chromate.
When this salt, _i.e._, ordinary chrome yellow, is treated with
smaller or larger quantities of a strong base, such as caustic potash
or caustic soda, “basic” lead chromates are formed, which exhibit a
more intense red shade the more lead they contain. These compounds can
be made either by adding caustic potash to the solution of potassium
chromate used for making the chrome, or the precipitated chrome yellow
may be treated with caustic potash. The latter process readily yields
good results, so that it is generally followed.
Recent researches have shown that differences in the shade of chrome
red are due to the varying size of the single microscopic crystals
of which it consists. When chrome reds of the most different shades
are ground the powder has almost the same colour. The larger are the
crystals the deeper is the shade of the red, so that the art of making
deep chrome red lies in working so as to produce large crystals.
As was said in describing the preparation of chrome yellow, the lead
liquors used in its manufacture contain varying quantities of acetic
acid, which affect the shade of the product. The quantities of caustic
potash necessary to turn a certain quantity of chrome yellow into
chrome red of a certain shade can, therefore, only be estimated from
time to time in an empirical manner. This estimation may be performed
by the method of Habich with great certainty. The precipitate of chrome
yellow is made in the ordinary way, and well washed 6 to 8 times.
Equal portions of the paste are brought into vessels of equal height
and diameter. To the first of these portions caustic soda solution of
a certain strength is added; to the second rather stronger caustic
soda solution; in each succeeding vessel the strength of the solution
is increased to a known extent. After the addition of caustic soda
the vessels are energetically shaken. They are then set aside for the
precipitate to settle in a place completely free from vibration. In
one of the vessels, an orange or red shade will be seen very similar
to that it is desired to make. Now, it is known how much caustic soda
solution of a certain strength has been added to this quantity of
colour, so that the quantity necessary for the whole of the chrome
yellow precipitate may be found by a simple calculation. In working on
the large scale, the process is exactly the same as in the preliminary
test; the calculated amount of caustic soda solution is added to the
precipitate in the tub, it is well stirred, and left at rest for some
hours. When the proper shade appears, the liquid above the precipitate,
which contains sodium chromate in proportion to the strength of the
caustic soda solution used, can be drawn off and used to precipitate
fresh lead acetate solution. The precipitate is washed first in the tub
and then on the strainers.
Since, as has been said, the depth of colour depends upon the size of
the single crystals, care should be taken in washing the precipitate
not to agitate it too vigorously, or the pigment will lose in depth by
the breakage of a large number of crystals.
Special formulæ for the manufacture of chrome red are abundant, but if
the above process be followed they are superfluous, and it is only for
the sake of completeness that one or two are given. Deep chrome red is
made by the action of 25 parts of caustic soda on 100 parts of pure
chrome yellow.
A noteworthy process is due to Liebig. Saltpetre is melted in a
crucible, and heated to a temperature below that at which oxygen is
evolved. Dry chrome yellow is introduced so long as effervescence
occurs; the fused mass appears, whilst liquid, deep black. As soon as
it is in quiet fusion it is poured on a cold plate. In consequence of
the rapid cooling it becomes brittle and can be easily powdered. The
hot mass is broken up and boiled with water, potassium chromate going
into solution. The chrome red made by this process is little inferior
in brilliance to vermilion.
According to Prinveault a handsome chrome red is obtained by treating
25 grammes of neutral lead carbonate with 10 grammes of yellow
potassium chromate dissolved in 5 litres of water, boiling for half
an hour, washing the violet precipitate, and finally treating with 1
gramme of sulphuric acid diluted with 100 grammes of water.
=Cobalt Red= consists of cobalt phosphate. It was first recommended
by Salvetat. It is obtained by precipitating a solution of a cobalt
salt by sodium phosphate. After drying at the ordinary temperature the
precipitate has a beautiful rose-red colour. By careful heating, the
shade becomes more violet according to the temperature used.
=Cobalt-Magnesia Red.=—When magnesia is moistened with the solution
of a cobalt salt and strongly heated, a rose-red mass is obtained
which can be used as an extremely durable artists’ colour. It probably
consists of a compound of cobalt oxide with magnesia. The method of
preparation is as follows: Magnesium carbonate is mixed to a thin paste
with a dilute solution of cobalt nitrate; this is heated and stirred
until quite dry, when the residue is strongly heated in a covered
crucible. In the manufacture of this and other cobalt pigments it is of
particular importance to prevent the entry of the fire gases into the
crucible. Unless this is done a product of good colour is not obtained.
=Cobalt Arsenate.=—By precipitating a cobalt salt with sodium arsenate,
a violet-red precipitate is obtained which leaves a fine durable red on
heating. The mineral erythrite has a similar composition and colour.
This pigment has a bright shade, is permanent, and although it contains
arsenic is not particularly poisonous, since after fusion it is little
soluble.
=Chromium Stannate.=—This artists’ pigment, which may be used in oil
and porcelain painting, is made in the following manner (Gentele): 1
kilogramme of tin is converted by strong nitric acid into metastannic
acid, 50 grammes of potassium chromate are dissolved in 1 litre of
water, the solution mixed with 2 kilogrammes of chalk and 1 kilogramme
of powdered quartz, and finally with the metastannic acid. The mixture
is dried and strongly heated. The temperature must be raised to a white
heat, at which the mass sinters and acquires a dark rose-red colour. It
is then completely extracted with boiling water, when a fine powder is
left.
This pigment, which is known in the market as “pink colour,” may be
used with advantage in oil painting in the place of rose madder lake,
over which it has the advantage in durability.
=Silver Chromate.=—A solution of silver nitrate gives, with potassium
chromate, a deep red precipitate of silver chromate, which is
occasionally used as an artists’ pigment under the name of “purple
red”. Not only is the price of this pigment high, but it has little
durability, since, like all silver compounds, it is acted upon by
sulphuretted hydrogen and turned dark, owing to the formation of black
silver sulphide.
CHAPTER XXI.
PURPLE OF CASSIUS.
Purple of Cassius, or gold purple, is not a pigment for painters’ use;
it is employed for colouring glass, for porcelain painting and for
coloured glazes. For these last purposes we know nothing which can
completely replace purple of Cassius, so that its preparation will be
described here. Its costliness prevents its general use.
As regards the chemical constitution of purple of Cassius very diverse
views are held. Chemists have not yet succeeded in explaining it;
some regard it as aurous stannate, others as stannic acid, in which a
particular form of gold of a red colour is contained in an extremely
finely divided condition. There are reasonable grounds for both
opinions. Theoretical considerations are of little interest to the
manufacturer, who is chiefly interested in the method by which he can
prepare a product which satisfies the demands of the consumer.
Purple of Cassius has been known for nearly two hundred years,
hence there are many formulas for its preparation. Before these are
enumerated it is necessary to give an account of the conditions under
which this substance is formed. In order to obtain gold purple,
a solution is required which contains both stannous and stannic
chlorides; if this solution is mixed with a very dilute solution of
gold chloride a precipitate is obtained which is generally brownish
red, and only acquires its fine red shade on igniting. The colour
shown by the purple after precipitation is no guide to the shade of
the finished product; a purple which shows a very fine colour whilst
wet often produces a pigment of much less beauty than an actually
ugly precipitate. These differences are to be ascribed to the varying
molecular condition of the purple, for the different varieties show
very small differences in chemical composition.
According to the directions of Fuchs, a fine purple is obtained by
mixing a solution of stannous chloride with sufficient ferric chloride
solution to give the mixture a green colour. Part of the ferric salt is
then reduced to ferrous salt, whilst the stannous chloride is partially
oxidised. At the same time a solution of gold chloride is made; this
must be quite free from nitric acid and contain 1 part of the salt in
400 to 500 parts of water. The tin solution is added drop by drop to
the gold solution with constant stirring; the mixture becomes turbid,
but the precipitate requires a long time to settle on account of its
fine state of division. The depth of colour shown by the purple varies
according to the strength of the solutions.
M. Müller states that the following process gives the best results: The
quantity of stannic chloride equivalent to 9 grammes of stannic acid
is dissolved in 200 cubic centimetres of water; potassium carbonate
is added to alkaline reaction, then 1 gramme of gold in the form of
chloride. Grape sugar is added to the mixture, which is made up to 300
cubic centimetres by water, and warmed until the brightest shade is
reached. When a very gelatinous mass is formed after the addition of
the potassium carbonate it is heated for a short time before adding the
gold solution and grape sugar.
Wächter gives directions for obtaining pale and deep shades. To obtain
the pale purple 5 grammes of tin are dissolved in _aqua regia_, the
solution evaporated to dryness on the water bath, the solid residue
mixed with a solution of 2 grammes of stannous chloride and dissolved
in 10 litres of water. To this liquid is added a solution of 0·5
gramme of gold in _aqua regia_, and immediately 50 grammes of ammonia
to neutralise free acid. The precipitate separates spontaneously from
the dark red liquid; its formation may be hastened by adding sulphuric
acid. The washed precipitate is mixed whilst moist by means of a
silver spatula with 20 grammes of lead flux, 2 grammes of red lead, 1
gramme of quartz sand, and 1 gramme of calcined borax. The mixture is
then dried; it produces a purple red colour. If 3 grammes of silver
carbonate are added, a clean, pale purple pigment results.
The deep purple is made by mixing a solution of 0·5 gramme of gold
in 10 litres of water with 7·5 grammes of stannous chloride solution
(specific gravity, 1·7) whilst stirring, and adding a few drops of
sulphuric acid. The washed precipitate is mixed with 10 grammes of lead
flux and 0·5 gramme of silver carbonate.
A rose-red shade of gold purple is obtained by dissolving 1 gramme
of gold and mixing the solution simultaneously with solutions of 50
grammes of alum in 20 litres of water, and of 1·5 gramme of stannous
chloride (specific gravity, 1·7). Ammonia is now added until all the
alumina is precipitated. In order to prepare from the dried precipitate
the mixture which will produce the colour on fusion, it is mixed with
50 grammes of lead flux and 2·5 grammes of silver carbonate.
=Magnesia Gold Purple.=—According to M. Müller, the colour of gold
purple is produced by covering the particles of a very finely divided
white substance with metallic gold. Thus, when calcined magnesia is
stirred up with water, gold chloride solution added, and the mixture
warmed to 100° C., the gold is precipitated upon the magnesia; the wet,
yellow powder acquires a reddish shade on drying, which at a red heat
becomes so beautiful a carmine-red that it surpasses purple of Cassius
in fineness of shade. A purple which contains 20 grammes of gold as
chloride to 84 grammes of magnesia has the most pure carmine tint; the
shade varies with the proportion of gold to magnesia. The different
shades of purple contain the following percentages of gold:—
_Percentage of Gold._ _Shade of the Purple._
33·5 Brownish-red (excess of gold).
25·0 Deep carmine-red.
20·0 Medium carmine-red.
10·0 Pale carmine.
5·0 A good rose-red.
3·0 Rose-red.
1·0 Pale rose.
0·2 Delicate rose.
0·1 Appreciable red tint.
=Alumina Gold Purple= is obtained, according to Müller, by adding
gold chloride and excess of potassium carbonate to alum solution and
boiling. The purple obtained in this way is as deep in colour with 10
per cent. of gold as a magnesia purple with 20 per cent. of gold, but
has a more bluish violet shade. If, in the preparation of purple, the
alumina is precipitated by potassium carbonate and the gold chloride
reduced by grape sugar, a different shade of purple is obtained to that
in the precipitation of which ammonia is used. The alumina gold purple
is specially adapted for the production of porcelain enamels.
CHAPTER XXII.
BLUE MINERAL PIGMENTS—IRON-CYANOGEN PIGMENTS.
The pigments occurring in commerce under the names of Prussian,
Chinese, Berlin or Paris blue consist, when pure, of ferric
ferrocyanide, Fe₄[Fe(CN)₆]₃. This compound is obtained as a deep blue
precipitate when yellow prussiate (potassium ferrocyanide) is mixed
with the solution of a ferric salt.
The precipitate shows certain differences in composition according
to the exact method by which it is obtained. A different result is
obtained when the solution of the ferric salt is poured into that
of a ferrocyanide, to that produced by the reverse procedure, the
precipitate produced in the one case has properties which it does not
possess in the other. Similar differences often occur in precipitating
pigments.
If the solution of the ferrocyanide is poured into the iron solution,
the latter being in excess, an insoluble precipitate is formed; but if
the iron solution is poured into the ferrocyanide solution of which an
excess is present, the blue precipitate is formed, but it is soluble
in pure water, though not in water containing salts. Thus when this
precipitate is separated from the liquid and washed, the washings are
at first quite colourless and remain so whilst salts are present, but
when these have been completely washed away, a fine blue solution of
the ferric ferrocyanide is formed, from which the addition of a salt
solution again separates the dissolved Prussian blue.
Before proceeding to the manufacture of Prussian blue on the large
scale, it is necessary to consider the behaviour of ferrous salts
towards yellow prussiate, since these are commonly used instead of
ferric salts. When a solution of potassium ferrocyanide is mixed with
a solution of a ferrous salt, there is formed a pure white precipitate
of potassium ferrous ferrocyanide, K₂FeFe(CN)₆. In order to obtain a
completely white precipitate, it is necessary that the ferrous salt
should be completely free from ferric salts and that the solutions
should contain no dissolved oxygen; the solutions would therefore
have to be boiled before mixing. If one of the solutions contains the
smallest quantity of oxygen a bluish precipitate is formed. When the
white precipitate of potassium ferrous ferrocyanide is exposed to the
air it immediately acquires at the surface a dark blue colour, and is
completely changed to Prussian blue by sufficiently long contact with
air.
In accordance with this behaviour of ferrous and ferric salts different
methods may be used to obtain Prussian blue. Either the process is
commenced with a ferric salt from which a precipitate of Prussian blue
is at once obtained, or the solution of a ferrous salt is converted
into ferric salt by a powerful oxidising agent, such as chlorine or
nitric acid, or a solution of a ferrous salt is precipitated with
yellow prussiate and the white or bluish precipitate, which consists
chiefly of potassium ferrous ferrocyanide, converted into ferric
ferrocyanide or Prussian blue by treatment with nitric acid.
Prussian blue is also known, as we have said, as Chinese blue, Berlin
blue and Paris blue; Brunswick blue or mineral blue is another form.
Generally the product under the name of Chinese or Paris blue,
which has an intense dark blue colour, is quite pure, whilst under
the names of Prussian blue and Berlin blue mixtures with starch or
alumina are included, which consequently have a more or less pale
colour. The pigments known as mineral or Brunswick blue are the
least valuable, they have generally a less deep colour and are quite
without the metallic lustre which distinguishes Chinese blue and the
better varieties of Prussian blue. Mineral blue often contains very
large quantities of alumina, chalk, or even barytes; the addition of
the last is to be regarded as irrational, since it makes the pigment
conspicuously heavy.
=Chinese Blue.=—Pure Chinese blue appears in the form of deep blue
masses, characterised by a peculiar metallic lustre, which is
especially marked when the surface of a lump is rubbed with the finger
nail. This metallic lustre is accompanied by a copper-red shimmer
which is similar to that exhibited by fine indigo. In large pieces
pure Chinese blue appears very dark by artificial light; it possesses
enormous strength of colour. The following test serves for the
recognition of the complete purity of Chinese blue: A small quantity
is powdered and rubbed in a thin layer on white paper; if the metallic
lustre shows in undiminished strength the blue may be regarded as quite
pure, for Chinese blue quickly loses this property by additions of
other substances.
From what has been said above concerning the different behaviour of
ferrous and ferric salts, the simplest method of making Chinese blue
would be to precipitate the solution of a ferric salt with yellow
prussiate, keeping the ferric salt in excess, to wash and dry the
precipitate. Ferric salts are, however, dearer than ferrous salts, so
that the latter are generally used.
In making Chinese blue from a ferrous salt ferrous sulphate or green
vitriol is generally taken. This salt is dissolved in water; it is
advisable to add a small quantity of sulphuric acid, since the water
will contain carbonates, which produce ferrous carbonate. Air oxidises
the latter to ferric hydroxide, which is brown, and if present even
in small quantity will spoil the shade of the blue. This addition of
sulphuric acid is of special importance when the white precipitate
produced by the prussiate solution is to be oxidised by the air.
A solution of yellow prussiate is added to the iron solution in such
quantity that a very small excess of iron salt is left; there results
a white or rather, since the ferrous sulphate always contains small
quantities of ferric oxide, a pale blue precipitate. This is allowed
to settle, the liquid drawn off as completely as possible from the
precipitate, and nitric acid then added, or a solution of bleaching
powder, followed by the amount of sulphuric acid required to decompose
it. The nitric acid or the chlorine liberated from the bleaching powder
speedily effects the oxidation, changing the pale blue colour to the
deep blue of Chinese blue. The precipitate should be left for several
days in contact with the liquid in order to complete the oxidation;
it is then well washed and dried. Pieces of definite shape and size
bearing the trade mark of the firm are often pressed from the blue when
it has acquired a stiff consistency.
There are many formulæ for the preparation of Chinese blue, differing
in regard to the quantities of green vitriol, yellow prussiate, and
nitric acid or bleaching powder to be used. It is, however, clear
that only _one_ formula can be correct, that in which the quantities
of materials are equivalent, since the reactions take place between
equivalent quantities. In practice the equivalent quantities would not
be weighed to the tenth of a gramme—there would be no object in such a
proceeding, since in works chemically pure substances are not used; but
manufacturers should work according to equivalent quantities in order
to use up their materials as completely as possible. No increase in
labour is involved, the same labour weighs one or another quantity.
The proportion of materials in which the least loss is involved is here
given. Nine kilogrammes of green vitriol are dissolved in 100 litres of
water, 15 kilogrammes of strong sulphuric acid are added, and then a
solution of 15 kilogrammes of yellow prussiate in 100 litres of water.
The solutions are kept in constant motion during the mixing. As soon
as the decomposition is finished, without waiting for the precipitate
to settle, steam is led in and 20 kilogrammes of nitric acid of 1·3298
specific gravity added in small portions. The heating by direct steam
is continued until red vapours are no longer evolved from the liquid,
which is a sign that the oxidation is finished.
Although the use of direct steam is very convenient for heating, since
wooden vessels can be used and the heating quickly accomplished, it
may be dispensed with, and the solutions heated in pans or even not at
all. In this case the oxidation lasts considerably longer than when the
liquid is heated. In the process recommended by Gentele 109 parts of
yellow prussiate are used to 20 parts of green vitriol, each dissolved
in much water. The precipitate is heated for a short time with 51 parts
of nitric acid of 1·2285 specific gravity and 16 parts of sulphuric
acid. The mixture is allowed to stand for several days to complete the
oxidation before the precipitate is separated from the liquid.
In Hochstätter’s method, solutions of 6 parts of yellow prussiate in
15 parts of water and of 6 parts of green vitriol in 5 parts of water
are mixed. To the precipitate 24 parts of strong hydrochloric acid and
1 part of sulphuric acid are added, and then a solution of bleaching
powder in 80 parts of water until the liquid smells distinctly of
chlorine. Apart from the fact that this method does not employ
equivalent quantities of iron salt and yellow prussiate, it is also
to be regarded as unsuitable, since the addition of sulphuric acid
produces calcium sulphate, which, being soluble with great difficulty,
will be precipitated along with the blue, making the shade lighter. The
addition of sulphuric acid should be omitted and only hydrochloric acid
used, the calcium chloride formed by the decomposition of the bleaching
powder being very soluble in water. Many formulæ given for the
manufacture of Chinese blue are said to produce a pigment of special
beauty. This, however, is incorrect. Chinese blue is a compound of
fixed composition, which is always formed when equivalent quantities of
the salts are used and the precipitate converted into the blue compound
by one of the oxidising agents given. It is most simple to use nitric
acid as the oxidising agent; for this purpose the presence of chlorine
in the acid is harmless. When sufficient space and time are allowed, a
special oxidising agent may be omitted and the oxidation of the white
precipitate accomplished by atmospheric air.
In working in this manner the precipitate is washed several times
with water, and spread in a thin layer upon boards which are placed
in rows one above the other. In a short time the mass turns blue on
the surface, but the pale colour remains underneath much longer, since
the access of oxygen to the interior is difficult. The boards must be
left until the mass has a uniform colour throughout. In order that the
paste shall not dry too thoroughly whilst on the boards it is desirable
to make it very fluid. If the precipitate has been completely washed
before the oxidation the product is finished after drying, but if a
portion when completely dried shows a crystalline incrustation, salts
are still present, which must be removed by careful washing.
=Prussian Blue.=—As we have already stated, Prussian blue is identical
in chemical nature with Chinese blue, from which it differs only by
certain additions which are made in order to reduce the price. Prussian
blue should therefore be regarded as a more or less impure Chinese
blue; less pure materials are used in its preparation than for the
fine Chinese blue. Instead of pure potassium ferrocyanide, the crude
salt, which is sold by the prussiate makers at a lower price, is used
for Prussian blue; in addition to the ferrocyanide this crude salt
contains a considerable proportion of other salts, including a quantity
of potassium carbonate.
The ferrous sulphate used for Prussian blue is mixed with alum, which
neutralises the potassium carbonate, precipitating alumina, by which
the precipitate formed from the yellow prussiate and ferric salt is
made paler. If the pale blue precipitate were treated with acids they
would first dissolve out the alumina; this should be avoided, since the
alum has been added with the intention of increasing the quantity of
precipitate and making the pigment paler. The precipitate can therefore
only be changed into the blue pigment by spontaneous oxidation; this
is accomplished by the oxygen of the air in the manner previously
described. The oxidation is more rapid according to the quantity of
ferric salt contained in the green vitriol at the commencement; it
is convenient to prepare a large quantity of green vitriol solution
and expose it in shallow vessels to the air so that the oxidation may
proceed. But if the solution of green vitriol were exposed alone to
the action of the air a rust-coloured precipitate of basic salt would
be deposited at the bottom of the vessels. To prevent the formation of
this basic salt, sulphuric acid is added in small quantity, and, as the
oxidation proceeds, further small quantities of acid are added. In this
way a solution of ferric sulphate is slowly formed, which gives with
yellow prussiate a blue precipitate requiring little further oxidation.
=Mineral Blue, Brunswick Blue.=—This pigment, the most reduced of the
colours of this class, is obtained by mixing white pigments, barytes,
pipe clay, etc., with the already impure Prussian blue.
=Soluble Prussian Blue.=—The modification of ferric ferrocyanide easily
soluble in water is obtained by adding a solution of a ferric salt
to a solution of yellow prussiate, the latter being in considerable
excess. Brücke gives the following method: a solution is prepared of
217 grammes of yellow prussiate in 11 kilogrammes of water. Another
solution contains 100 grammes of ferric chloride in 1 litre, 1 litre
of which is mixed with 2 litres of a saturated solution of Glauber’s
salt and the mixture added to the prussiate solution so long as a blue
precipitate forms. The Glauber’s salt plays no part in the formation
of the colour; it is added to prevent the solution of the precipitate,
which is insoluble in salt solutions. The precipitate is brought on to
a filter and washed with water until the washings begin to be blue,
which is a sign that the salts have been almost completely removed.
The precipitate cannot be further washed without the loss of a large
quantity which would be dissolved by the water; without further washing
it is slowly dried in the air.
Soluble Prussian blue has but a limited application; anatomists use its
solution to inject specimens, and it was formerly used for blue writing
inks, for which purpose aniline dyes are now preferred. It may also be
remarked that ordinary Prussian blue readily dissolves in a solution of
oxalic acid; the solution was also used as a writing ink, but since it
attacks steel pens, it has now been replaced by solutions of dyes which
have no action on steel.
=Special Processes for the Manufacture of Chinese Blue.=—In place of
chlorine or nitric acid manganic chloride can be used to oxidise the
white precipitate obtained from yellow prussiate and green vitriol.
This process is based upon the property of manganic chloride to readily
give up part of its chlorine and be changed into manganous chloride
(the ordinary chloride of manganese). The conversion of the white
precipitate into the blue is thus also in this case indirectly effected
by chlorine.
Many varieties of pyrolusite contain considerable quantities of
manganic oxide which are of little use in the manufacture of chlorine,
for which pyrolusite is chiefly employed. If such pyrolusite be
digested with crude hydrochloric acid for several days, the manganic
oxide is dissolved with the production of manganic chloride.
The oxidation of the white precipitate is performed in the usual way;
after running off the liquid an excess of manganic chloride solution is
added, as soon as two tests taken at an interval of a few minutes show
no further increase in the depth of the colour, the reaction is ended
and the solution of manganous chloride is drawn off.
Any powerful oxidising agent may be used to oxidise the white
precipitate; chromic acid has been proposed for this purpose, but up to
the present the chromates are too dear to be used in place of the cheap
oxidising agents previously mentioned.
In regard to the present endeavours to utilise by-products of the
chemical industries, a method for preparing this pigment may be
mentioned which would certainly be very profitable on the large scale.
Coal gas before purification contains some quantity of ammonium
cyanide, which is decomposed by ferric oxide with the production of
Prussian blue. This pigment might be made by passing coal gas over
very finely divided ferric oxide, until it was completely converted
into Prussian blue. The process is, however, not practicable on the
large scale: the ferric oxide would have to be exposed in an extremely
thin layer to be completely converted into Prussian blue, and the
transformation would require a long time. A better process is to make
yellow prussiate instead of Prussian blue. A mixture of ferric oxide
with coarse sawdust is spread out in thin layers, over which the impure
coal gas passes. When the mass has acquired a blue colour owing to the
Prussian blue produced, it is treated with a mixture of quicklime and
potassium sulphate. Potassium ferrocyanide is formed; it is obtained
in crystals by the evaporation of the solution and can be used in the
preparation of Prussian blue.
The “Laming’s mass,” now generally used in gas works, contains, after
use, a considerable quantity of cyanogen compounds, and it would only
require a short trial to decide whether it was more advantageous
to make this mixture by exposure to air again suitable for the
purification of coal gas, or to use it to obtain yellow prussiate.
=Turnbull’s Blue.=—When a solution of a ferrous salt is precipitated
by potassium ferrocyanide, a fine blue precipitate is formed,
identical in physical properties with Chinese blue, but differing in
chemical constitution. It is ferrous ferrocyanide, Fe₃[Fe(CN)₆]₂.
The manufacture of Turnbull’s blue is expensive; the pigment has no
specially advantageous properties and is therefore seldom made.
In preparing this pigment, a solution of yellow prussiate is
transformed into red prussiate by passing chlorine through it so long
as it is absorbed by the liquid; the mother liquors from which red
prussiate has been crystallised may be used with advantage. When to the
solution of red prussiate green vitriol solution is added so that the
former remains in excess, a soluble Turnbull’s blue is obtained, but
when excess of green vitriol is used the insoluble form is produced.
Chinese blue and Turnbull’s blue are used both as oil and water
colours, and these handsome but not particularly durable pigments are
also employed in colouring wall papers.
=Antwerp Blue= is a mixture of Prussian blue with zinc cyanogen
compounds. It is obtained by precipitating a solution of 2 parts of
zinc sulphate and 1 to 2 parts of green vitriol (according as pale or
deep blue is required) by a dilute solution of yellow prussiate.
CHAPTER XXIII.
ULTRAMARINE.
At the present time blue, green, red and violet pigments come into the
market under the name of ultramarine. The green and blue have been
commercial articles for about seventy years; the violet and red were
introduced about the year 1860.
At first the name ultramarine was restricted to a natural blue pigment
obtained from _lapis lazuli_, which was extremely costly. Accounts
of the payments of Italian artists, still extant, show the expensive
nature of the ultramarine blue used in their paintings. At that time,
when artists were compelled themselves to make the majority of their
pigments, ultramarine was made in a most laborious manner from _lapis
lazuli_, for which incredibly high prices were paid. In order to make
the mineral easier to powder the lumps were heated, and, whilst hot,
thrown into water. They were then powdered as finely as possible. The
powder was mixed with melted resin, and the mixture kneaded under
water for a long time. The ultramarine suspended in the water by this
crude method of levigation was obtained by allowing the wash waters
to settle. Few places are known at which _lapis lazuli_ occurs in
quantity. It is chiefly obtained in China and Thibet, and, considering
the little intercourse between Europe and these distant countries at
that time, it is no wonder that the price of ultramarine was fabulously
high. One ounce cost about £8—a price which is explained by the small
yield of ultramarine from the best _lapis lazuli_. By the most careful
work not more than from 2 to 3 per cent. of the mineral was obtained,
the residue consisted of foreign minerals.
The enormously high price of this pigment was the stimulus for the
endeavours to make it artificially. The attempts are to be regarded not
only as completely successful, but it must be allowed that science has
gone a considerable step further than nature, since the researches have
made it known that there is not only a blue ultramarine, but also a
green, and, according to the latest researches, there exist in addition
violet, red and white compounds, also to be described as ultramarines.
With the discovery of the methods by which ultramarine can be made
artificially, the preparation of this pigment from _lapis lazuli_
came to an end, and has now but historic interest. The discovery of
artificial ultramarine is due to the French chemist Guimet and to the
great German chemist Gmelin. Ultramarine was first manufactured in
Germany in the year 1828 by A. Köttig, as a branch of the porcelain
works at Meissen in Saxony, where the manufacture was continued for
about fifty years.
The discovery of the aniline dyes is rightly called a triumph of human
intellect. The artificial manufacture of ultramarine deserves the same
description in no less degree, although it has not effected so great a
revolution as the former.
Attempts to make ultramarine artificially would naturally be based on
the analysis of the natural product. The following comparison of the
compositions of natural and artificial ultramarines shows how nearly
the artificial product approaches the natural:—
NATURAL ULTRAMARINE.
Clément and Desormes. Gmelin.
Silica 35·8 per cent. 47·31 per cent.
Alumina 34·8 ” 22·00 ”
Soda 23·2 ” 12·06 ”
Lime 3·1 ” 1·55 ”
Sulphuric acid —— ” 4·68 ”
Sulphur 3·1 ” 0·19 ”
Water and organic matter —— ” 12·21 ”
ARTIFICIAL ULTRAMARINE.
+------------------------------------------------------------------+
| | Blue. | Green. |
+-------------+------------+------+--------+-----+-----------------+
| Observer. |Warrentrapp.|Elfen.|Brunner.|Pohl.| Gentele. |
| | | | | | |
| Silica | 45·60 | 40·0 | 32·54 |36·67|} 47·31 |
| Alumina | 23·31 | 29·5 | 25·25 |32·12|} |
| Soda | 21·47 | 23·0 | 16·91 |21·45| 39·93 |
| | | | | |(sodium silicate)|
| Potash | 1·75 | —— | —— | —— | 3·92 |
| Lime | 0·02 | —— | 2·38 | —— | 1·13 |
| Sulphuric | | | | | |
| Acid | 3·83 | 3·4 | —— | 2·08| —— |
| Sulphur | 1·69 | 4·1 | 11·63 | 7·22| 6·62 |
| Iron | 1·06 | 1·0 | 2·25 |trace| 1·95 |
| | | | | |(ferric silicate)|
| Water | —— | —— | —— | —— | —— |
| Oxygen | —— | —— | 9·04 | 0·58| —— |
+-------------+------------+------+--------+-----+-----------------+
I. Szilasi found three samples of green ultramarine to have the
following composition:—
Water 2·20 1·20 1·19
Aluminous residue 1·80 1·42 1·41
Silica 16·73 17·18 16·74
Aluminium 15·92 15·87 16·15
Sodium 18·42 18·18 18·10
Sulphur 7·19 6·97 6·85
There are many other analyses in addition to those we have given and
agreeing with them, so that there is no doubt as to the composition of
ultramarine, but as to the manner in which the elements are grouped
nothing is definitely known. Some chemists are of the opinion that
the colouring principle of ultramarine is a sulphur compound of iron,
whilst others oppose this view and consider that the colour is due
to the combination of a double silicate of alumina and soda with an
unknown sulphide of sodium. Although no blue or green compound is
known of corresponding composition, the majority of chemists incline
to the latter view. Experience has shown that the presence of iron in
any of the materials used in the manufacture of artificial ultramarine
is very dangerous to the success of the operation, and at the least
considerably injures the beauty of the product.
Although the manufacture of ultramarine is now very well known, it
cannot be denied that some works produce a pigment of a shade which
cannot be obtained by others. These works keep their method very
secret, so that it is not possible to say with certainty whether they
have introduced a process varying from that commonly known, or whether,
by carefully watching the process, they have achieved great technical
dexterity in the manufacture of this product. The latter appears the
most probable, for in order to obtain a good result, many experiments,
and an accurate knowledge of the raw materials, are necessary.
The raw materials used are as follows: pure aluminium silicate, sodium
sulphate, soda, sulphur, coal. The aluminium silicate is used in the
form of fine china clay or kaolin, sodium sulphate and soda must be
used in the anhydrous form, the sulphur is the ordinary commercial
substance purified by distillation. Charcoal or coal containing little
ash can be used.
Whilst the remaining raw materials are always of similar composition,
the china clay from different localities possesses a very varying
composition. This substance must be carefully chosen. There is hardly
any kaolin which is naturally of sufficient purity to be used without
purification; it is well known that the china clay used for porcelain
is subjected to a thorough preparation before it is used. Kaolin, like
all clays, has been produced by the decomposition of feldspar; when
the aluminium silicate so formed was able to deposit without foreign
admixtures, that mineral was formed which is the purest of all clays
and is called kaolin. The more foreign substances are mixed with
the aluminium silicate the further is the clay removed from kaolin.
The impurities which generally accompany the aluminium silicate are
quartz sand, chalk and ferric oxide. We distinguish accordingly
between kaolin, white clay or pipe clay, clay, and lastly marl, a clay
containing much chalk.
Even the purest kaolin contains certain impurities, of which quartz
sand is the principal and the least harmful. Before kaolin can be
used in the ultramarine manufacture it must always be purified by
levigation; it is then ignited at a low temperature and powdered under
stamps or in mills. The other materials required are generally produced
by the chemical works in a condition of such purity that they can be at
once used.
Occasionally Glauber’s salt contains iron, which would spoil the shade
of the ultramarine. The iron can be easily removed by dissolving the
crystallised salt in water, adding a little milk of lime and leaving
the liquid for several days, stirring frequently. The lime neutralises
every trace of free acid, and at the same time produces an ochre-yellow
precipitate of ferric hydrate. The solution of Glauber’s salt thus
freed from iron is evaporated in reverberatory furnaces, in which
the salt is then calcined. This operation is not only simpler than
evaporating the solution in iron pans to crystallisation and subjecting
the dried salt alone to calcination, but it also guards against fresh
contamination by iron, which might be caused by the use of iron
evaporating pans.
The sulphur and coal are employed in a soft powder, which is most
readily obtained by placing the coarsely powdered materials in rotating
drums containing a number of iron balls. By continued rotation the
materials are converted to any desired degree of fineness without the
production of dust. The powder is then put through fine sieves by which
the larger particles are retained.
The proportions in which the raw materials are mixed vary within
certain limits; fixed quantities can only be given for a kaolin of
definite composition. Definite formulæ are known by which ultramarine
is made, but these can only be regarded as approximate. The proportions
employed by French manufacturers differ considerably from those usual
in German works. This variation is chiefly due to the difference in
the composition of the kaolin employed in the two countries.
From the composition of the different mixtures one conclusion may be
drawn with certainty—sufficient sodium is always used to neutralise
half the silicic acid of the kaolin and to form some quantity of
sodium sulphur compounds. In the successful process of the German
makers a portion of the soda unites with the silica during heating. By
the action of the coal on the Glauber’s salt it is reduced to sodium
sulphide, which, since sulphur is present, unites with a further
quantity of that element. The sodium sulphur compounds then unite with
the silicates of aluminium and sodium to form a green compound, which
is converted into blue ultramarine by a further treatment with sulphur
in the presence of air.
Instead of using Glauber’s salt, which must always be decomposed in
the first process, the sodium sulphide may be formed by the action of
sulphur on soda in the presence of coal. This procedure is adopted in
the French process. The proportions of the mixture used in different
works vary. If the kaolin employed is assumed to be bisilicate of
alumina—a somewhat arbitrary assumption—the following mixture can be
successfully used:—
Anhydrous kaolin 100
” Glauber’s salt 42
” soda 42
Sulphur 60
Coal 13
In working by the French method the following formula is suitable:—
Anhydrous kaolin 100
” soda 100
Sulphur 62
Coal 14
These formulæ are not to be regarded as unalterable. In the different
works such varied mixtures are used that it may be said with truth that
each works has its particular formula for the mixture, the composition
of which depends on the nature of the clay used in the works. The
composition of the mixtures used in works is kept secret as far as
possible. The formulæ given above refer to a clay approximating in
composition to the bisilicate of alumina.
It will appear from the description of the manufacture of ultramarine
that certain quantities of sodium sulphide are produced. The process
is, however, conducted so that sodium sulphide shall be formed; thus
the soda and Glauber’s salt used in the mixture may be replaced by the
sodium sulphide produced in previous operations. The liquors in which
the sodium sulphide is contained are evaporated to dryness, and as
much of the residue added to the clay as corresponds to the quantity
obtained from the usual amounts of soda and Glauber’s salt. Assuming
that these latter materials are pure, 80 parts of the sodium sulphide
residue correspond to 100 parts of soda, and 60 parts to 100 parts of
Glauber’s salt.
CHAPTER XXIV.
THE MANUFACTURE OF ULTRAMARINE.
We have thought it necessary to an understanding of the manufacture
of ultramarine to discuss the production of this important pigment in
some detail, for it is only possible to properly conduct an operation
regulated by chemical laws when the processes which take place are
accurately known.
The mixture of the materials used in making ultramarine must be most
intimate in order that the constituents may act chemically upon one
another. In some works the mixing is performed in a very laborious
manner—upon a heap of the dried, levigated clay the remaining materials
are thrown, and the whole shovelled about till it is completely
homogeneous. Naturally, instead of this primitive and costly operation,
mechanical mixers may be used, but the mixture can also be effected
in a simpler manner, which almost dispenses with the necessity for
a mechanical process. Of the substances to be mixed only kaolin and
sulphur are insoluble in water; the others and also the by-products
of previous processes are easily soluble. The soluble and insoluble
constituents of the charge may be mixed in a very simple way by
bringing the levigated kaolin in the form of paste, without drying,
into a pan, adding the solutions of the salts and the powdered sulphur.
The pans are most conveniently heated by the fire gases from the
ultramarine furnaces. After mixing the solutions with the clay to
a thick paste the heating is commenced, the solid substances are
prevented from sinking to the bottom by continual stirring, the
mixture is slowly evaporated, and an extremely intimate and complete
incorporation of the constituents occurs. The heating is continued
until a dry mass is obtained, which may be used for the second
operation without powdering.
The mixture of raw materials is heated for a long time at a clear red
heat, or, in some works, at a white heat. The operation demands some
care; air must be excluded and the whole mass must acquire a uniform
temperature. If both these conditions are not obtained in heating it is
very difficult to obtain a product of uniform colour.
In different works different arrangements are used for the calcining
process. In the older methods crucibles or dishes of fire-clay were
used, of such a shape that the bottom of one crucible formed the lid
of the crucible beneath, just as is the case with the saggers used in
porcelain kilns. The mixture is closely pressed into the crucibles, of
which piles are built in the furnaces. These must be so arranged that
each crucible is surrounded by the fire. The furnaces are very similar
to porcelain kilns.
This method of calcining is obviously attended with many drawbacks; a
large number of costly crucibles is required, a certain proportion of
which is lost at each burning, either by breakage in the fire or in
filling. The pressing of the charge into the small crucibles requires
much labour, as also the placing of the crucibles in the furnace and
their removal; at the end of the nine to ten hours’ calcining, it is
necessary to wait some time to take the crucibles out of the furnace,
or considerable loss will be caused by breakage of the crucibles due to
rapid cooling.
For these reasons in most works crucibles have been abandoned in favour
of muffles, a large number of which are built in one furnace. The
charge is placed in the muffles; after completion of the calcining it
is quickly raked out, and the still hot muffle at once recharged, thus
the losses of time and heat are reduced to a minimum. The muffles are
generally about 1 metre long, 1 metre wide and 30 to 40 centimetres
high. They are made of fire-clay, and, when kept in uninterrupted use,
last a long time. The muffles have a small opening at the back which
communicates with the furnace, so that the gases evolved have a free
outlet without reaching the working place. The front of the muffle is
closed by an iron plate in which are small openings, through which the
contents can be examined without the entry of much air.
Three muffles are generally built in a furnace, but, by suitable
alterations in the construction, a considerably larger number may be
heated in one furnace. Whatever the number of muffles, the furnace must
be so arranged that the fire can be controlled at will. This is best
done by a good damper; all the muffles must be uniformly heated.
J. Curtius recommends cast-iron cylinders, lined with a thin layer of
fire-clay. For this purpose a covering of fire-proof cement is used to
protect the retorts. This covering, as it is gradually destroyed, may
be renewed by smearing over the damaged places with fire-proof cement,
mixed with water or some binding material. Aluminium silicate, graphite
and coke may also be used. The retorts, _a_ (Fig. 28), project through
the wall of the furnace at one end. They rest on fire-proof stone
bridges, and can be put into communication with the air by the pipe,
_m_, which can be closed air-tight. Short pipes, _k_ and _d_, which
can be closed, connect the interior of the retort with the cooling and
collecting chambers, _P_ and _g_, the latter of which is connected by
_r_ with the vessel, _h_, where the gaseous products are absorbed. The
porous plate, _f_, prevents the charge in the hinder part of the retort
from becoming open and falling to pieces during stoking. In order to
obtain a regular heating of the retorts the fire gases passing through
the space, _q_, are led away at two opposite places by flues into the
main flue, _F_. The intimate mixture of finely-powdered materials
is introduced into the hinder part of the retort, the porous plate,
_f_, placed in position, the cover, _t_, closed up air-tight, and the
connection with the chamber, _P_, closed. On heating, the volatile
products pass through the porous plate and the pipe, _d_, into the
chamber, _g_, the more volatile portions, without mixing with the
furnace gases, passing direct to the absorption vessel, _h_, or to a
lead chamber, whilst the sulphur which distils over remains in _g_.
When the reaction is finished, by opening the cover, _t_, and the tube,
_m_, the crude green ultramarine in the retort can be rapidly oxidised
to blue by aspirating air at _m_, or after closing the opening, _d_,
and removing the plate, _f_, the green ultramarine can be raked into
the collecting chamber, _P_, and there oxidised. The retorts are then
immediately re-filled with the mixture and the temperature raised.
[Illustration: FIG. 28.]
The heating of a charge lasts nine to ten hours; the larger the
quantity of sodium sulphide in the mixture the shorter is the time
required. The mixture is spread out in the muffles in a layer 7 to
9 centimetres thick, and brought to a moderate red heat. When the
whole mass is uniformly hot it is more strongly heated; the change
of the constituents then becomes visible. The mixture takes at first
a brownish colour, and is somewhat similar in appearance to liver
of sulphur. The colour soon begins to incline to green, and finally
changes to a tolerably pure green, but always has a yellow tinge. Those
parts of the hot mass which come into contact with air are more blue,
and occasionally change to a pure blue. When crucibles are used the
upper layer of the contents is always bluer than the lower, and when
crucibles crack during the heating the portions near the cracks always
show distinctly a more or less blue colour.
When the calcination is finished the hot mass drawn out of the muffles
is at once brought into washing vessels, in which it is treated with
water so long as soluble materials are extracted. The compounds
dissolved in the water are chiefly sodium sulphide and sulphate and
a little alumina dissolved in caustic soda. The presence of a larger
quantity of caustic soda in the wash waters indicates too violent
heating. In this case the mass will not mix up easily in water; it
contains sintered lumps. The washed material is strained, spread out
on boards or linen stretched across frames, and completely dried by
artificial heat.
At this stage the product may be described as green ultramarine and
sold as such, or it may be converted into blue ultramarine. For the
latter purpose it is ground to a moderately fine meal, but green
ultramarine must be ground to a very fine powder; the finer the powder
the brighter the shade.
In order to obtain blue ultramarine from the washed and ground
substance, it is subjected for a short time to a moderate red heat
with unrestricted access of air. The heating by which the blue colour
is produced must be continued until the proper shade is obtained.
This operation is conducted in special muffles; in many works it is
customary to sprinkle powdered sulphur upon the heated mass during the
roasting. The sulphur burns, forming sulphur dioxide, which escapes
into the furnace through an opening at the back of the muffle. The
object of the addition of sulphur may be to keep the temperature from
rising beyond a certain point, or to prevent a possible reduction of
the sulphur compounds in the ultramarine.
The muffles used for finishing the ultramarine are similar to those
used in making green ultramarine; they are generally 50 centimetres
wide and 100 to 120 centimetres long. A muffle of this size will
contain 6 to 18 kilogrammes of green ultramarine. The temperature is
gradually raised to a gentle red heat, each muffle being provided in
front with an iron plate which prevents the cooling of the contents by
the external air. When the charge in the muffles is carefully observed,
it is noticed that the blue colour first appears at the surface and
the edges, _i.e._, at those places where the oxygen of the air has
unrestricted access. The mass is frequently turned over with an iron
rake, in order to expose all parts to the action of the air; samples
are frequently taken in order to observe the moment at which the
colour has reached its greatest intensity, when the heating is at once
stopped. By proper treatment about half an hour is required to convert
the charge of a muffle of the above dimensions into ultramarine of the
deepest blue. The hot mass is drawn out of the muffles and spread out
upon flags so that it may cool quickly. During the cooling the colour
is often observed to become considerably darker, which is a sign that
the ultramarine has not been heated for a sufficient length of time.
Mechanical arrangements are often used to continually turn over the
ultramarine in the muffles, which are then made in the form of
cylinders in which the ultramarine is continually turned by a stirrer
provided with wings. The whole arrangement is very similar to the
apparatus used for roasting coffee.
The ultramarine is then carefully ground to a very fine meal; it is
tolerably hard, and granite stones should be used, ordinary stones
would be too quickly worn down. It is not possible, by the most careful
grinding, to convert ultramarine into that condition of fine division
which is necessary if it is to be ground into paint; grinding must be
followed by levigation. The various qualities and shades brought into
the market differ only in regard to the fineness of their particles;
they do not vary in chemical nature, for the substance has always the
same composition.
It occasionally happens in ultramarine works that a charge does not
turn out a bright blue; the product is then sold as inferior quality
at a lower price, or is mixed with a larger quantity of good material.
In working by a settled process the different shades of ultramarine
vary in composition between narrow limits; the difference is caused by
variations in the raw materials.
It has been already remarked that there is no agreement as to the
composition of the colouring principle of ultramarine; some maintain
that it is an iron compound, whilst others regard the iron found in
ultramarine as an accidental impurity, which has no connection with
the colour. Recently this point appears to have been decided from the
results of many most accurate analyses of ultramarine. It has been
found that its chemical composition shows the greatest similarity with
the mineral nepheline.
Nepheline is a double silicate, its composition is expressed by the
following formula: Na₂O.SiO₂ + Al₂O₃.2SiO₂. By a comparison of the
analyses of green and blue ultramarine with that of nepheline, it is
seen that blue ultramarine may be regarded as nepheline combined with
sodium pentasulphide, whilst green ultramarine is nepheline combined
with sodium bisulphide. If this is the correct view, the two species of
ultramarine have the following formulæ:—
2{Na₂O.SiO₂ + Al₂O₃.2SiO₂} + Na₂S₅.
2{Na₂O.SiO₂ + Al₂O₃.2SiO₂} + Na₂S₂.
Ultramarine is one of the most permanent pigments. It is not altered by
the substances with which a pigment generally comes in contact. Being
a sulphur compound, it retains its colour completely in air containing
sulphuretted hydrogen. By acids, even weak organic acids such as malic,
citric or tartaric, it is rapidly decomposed, sulphuretted hydrogen
being evolved, and a greyish white residue left. It is sometimes found
that the sugar used in making lemonade produces a perceptible smell of
sulphuretted hydrogen. This is due to ultramarine, which has been added
to the sugar to hide its yellow colour.
From the preceding account of the manufacture of ultramarine it will be
understood that there exist only two species of ultramarine, green and
blue. In commerce a large number of different shades are found, which
are not to be regarded as pure ultramarine; they owe their particular
shade to additions. By mixing in a white pigment, such as barytes or
starch, the paler shades are obtained; by adding a small quantity of a
pure red pigment a colour with a violet tinge is produced. In a similar
manner any number of shades of ultramarine can be obtained.
The following account is taken from a new comprehensive work by J.
Wunder, on the different ultramarines.
=Preparation of Mixtures for Ultramarine.=—The following points are
to be observed: Chemically pure soda and ammonia soda react with
difficulty. The presence of caustic soda in the soda facilitates the
formation of sodium sulphide, and gives a finer product. It is also
of advantage to sprinkle the soda with a strong solution of sodium
sulphide. The more silica the mixture contains the more difficult is
the transformation into ultramarine, but the product is deeper and
better in shade, and has more resistance to alum and weak acids. The
sodium sulphide must react with silica and alumina. When oxygen enters
during the burning, silica is re-formed, which with soda and alumina
produces slags. In order to exclude oxygen many manufacturers burn
with restricted access of air; then the carbon bisulphide and sulphur
gases evolved are not burnt, but, together with tarry materials from
the coal, form an evil-smelling smoke, which renders the neighbourhood
objectionable. The coal consumption in burning is also greater. The
varieties rich in silica and stable towards alum are generally dark
reddish-blue. In order to obtain pure blue shades from mixtures rich in
silica they are burnt in closed crucibles to produce the green, which
is powdered and heated with restricted air supply, and the admission
of a little steam, to 160° to 180° C., when pure blue or greenish-blue
shades are obtained as required. In this way a mixture rich in silica
can be burnt to a good blue, containing 69·32 parts of silica to 30·67
parts of alumina, or 1 equivalent of Al₂O₃ to 3·84 equivalents of SiO₂;
whilst ultramarine rich in silica, made in the ordinary way, contains
at the most 66·7 parts of silica to 33·3 parts of alumina.
=Ultramarine Violet= was first introduced into commerce about the
year 1859 by the Nuremberg Ultramarine Works, under the direction of
Leykauf. By the reaction of moist calcium chloride on ultramarine
blue in the warm chambers above the furnaces the blue was changed to
violet. By the action of air a portion of the moist calcium chloride
is decomposed into lime and hydrochloric acid, the latter of which,
together with air, reacts on the blue. In 1872 Wunder, intending to
apply to the estimation of sulphur in ultramarine blue a method which
gives good results with metallic sulphides, passed chlorine over heated
ultramarine. The pigment was converted into a brownish-red substance,
which on washing combined with water and turned violet. The red
substance is not produced at every temperature; 300° C. is the most
favourable. On washing sodium chloride is dissolved; the washed violet
is free from chlorine, but has taken up water, which is expelled on
heating, when the violet turns to blue. A similar brownish-red body
is formed when sulphur trioxide is led over heated ultramarine blue,
and when sulphur chloride acts on warm ultramarine blue. When the
brownish-red chlorine compound is introduced into absolute alcohol, a
reddish-violet compound is produced, containing organic matter. Ethyl
chloride is formed at the same time. When ammonia gas is passed over
the heated chlorine compound it is absorbed; a violet ultramarine
is produced, from which the ammonia is not removed by washing with
water, but only by heating nearly to redness, or, better, by fusing
with caustic alkalis. Aniline combines in a similar manner. In order
to obtain a good violet the brownish-red chlorine compound must not
be formed; the violet is produced by leading chlorine and steam over
ultramarine blue at 160° to 200° C. Blue rich in silica is most
suitable for transformation into violet. The violet so obtained is not
decomposed by lime.
C. Mahla produced the chlorine in the blue itself by the reaction:
NH₄Cl + 2NH₄NO₃ = 6H₂O + 5N + Cl. By heating a mixture of ultramarine
blue with ammonium chloride and nitrate in crucibles at 200° C. a fine
violet is produced. It contains ammonia, which cannot be removed by
washing, but only by strongly heating or heating with concentrated
alkalis. This violet is decomposed by the prolonged action of lime,
in three days it is changed to a grey green. In the course of the
manufacture it was noticed that less nitrate was required in the
mixture according to the length of time it was exposed in porous
crucibles to the action of air and heat; by heating for a sufficient
length of time with access of air, a good violet is obtained with
ammonium chloride alone. In the manufacture of violet by means of moist
chlorine hydrochloric acid is formed, which is also the active material
in its formation by means of ammonium chloride. It was therefore to
be expected that chlorine gas might be replaced by hydrochloric acid,
if it were accompanied by sufficient air. This has been found to be
the case. The temperature must be maintained between 180° and 230° C.
Below 150° C. the blue is decomposed by moist hydrochloric acid gas; at
temperatures above 230° C. it is unchanged. Hydrochloric acid gas and
air, without steam, give with ultramarine blue on heating a brownish
red substance similar to that produced by dry chlorine; it also is
changed to violet by washing with water. The violet obtained by means
of moist chlorine differs from the blue from which it was formed, in
that the latter has lost one-sixth of its sodium and combined with
water and much oxygen. The following is the approximate formula for a
blue:—
Na₆Al₄Si₆S₄O₂₁,
and for the violet obtained from it
Na₅HAl₄Si₆S₄O₂₄ + H₂O.
The violet contains much thiosulphate. If it is decomposed by nitric
acid and silver nitrate added to the filtered solution a precipitate
is obtained which changes in colour from white to yellow, orange and
brown, just as the precipitate given by silver nitrate in solutions of
thiosulphates containing nitric acid.
=Chlorine and Steam Process.=—Chlorine does not attack iron at 150° to
250° C. The reaction is carried out in heated iron boxes 1 metre wide,
2 metres long and 65 centimetres high. The blue is spread out in a
layer 2 centimetres thick on earthenware plates, which stand one above
another at a distance of 5 centimetres, each supported on three feet.
The plates are introduced by means of iron tongs through large openings
in the top of the box; after filling iron plates are screwed on to the
openings, through them pass sheet-iron tubes reaching to the bottom,
in which thermometers can be lowered on wires. The iron boxes stand in
heated chambers, which have openings corresponding with the openings
in the boxes, and shut off from the interior of the furnace. Chlorine
and steam are led into the iron boxes at both ends through lead tubes
reaching to the bottom; the parts of these tubes in the furnace and the
iron boxes are protected by wide sheet-iron tubes, the space between
being filled with clay. The gases evolved, hydrochloric acid, sulphur
chloride and steam, pass from the covers through earthenware pipes into
boxes filled with limestone, upon which water drops, and thence to
the chimney. After filling, the boxes are heated to 280° C. and steam
introduced to remove sulphur; they are then allowed to cool to 160° C.,
when chlorine and steam are led in for three hours. The violet is then
finished, and the residual gases are blown out by a fan.
=Hydrochloric Acid and Air Process.=—The operation is conducted in
the same iron boxes, upon the bottoms of which, beneath the openings,
are earthenware dishes into which hydrochloric acid can be poured
through earthenware pipes. The chimney draught must be strong enough
to draw sufficient air through these pipes into the boxes. After the
temperature has been maintained for seven hours at 220° to 230° C.,
hydrochloric acid being poured in from time to time, the blue is
changed to a dull violet, which becomes brighter when hydrochloric acid
is repeatedly added at diminishing temperatures, 210°, 200°, 180° and
160° C. More recently the iron boxes have been replaced by stone chests
or by chambers above the ultramarine furnaces, the temperature in this
case being kept at about 200° C.
=Ammonium Chloride Process.=—A mixture of ultramarine blue with 5 per
cent. of ammonium chloride is heated during fourteen days in porous
crucibles placed in the upper chambers of the ultramarine furnaces,
when the contents of the crucibles become a handsome violet throughout.
If sodium nitrate is used together with ammonium chloride, the violet
is formed in a much shorter time. After washing, the violet still
contains nitrogen; on ignition or heating with strong alkalis it
loses ammonia. Unfortunately, this fine violet is decomposed by the
continued action of moist slaked lime. The violets made by the first
two processes absorb ammonia when this gas is led over them at 180° to
200° C., and it cannot be removed by washing.
=Pale Blue Ultramarine.=—If the violet is heated in hydrogen at 280° to
290° C., it is converted into a pure, bright, pale blue. This has an
absorption spectrum in which the red is not absorbed, but appears more
brilliant than in the spectrum of ultramarine rich in alumina. Pale
blue is turned violet blue by heating at 300° C., and at a red heat a
dull blue. It is not yet made on a commercial scale, but on account of
its great purity of shade it appears to be valuable for many purposes;
perhaps it may replace alumina cobalt blue. The composition of pale
blue is:—
Calculated for Found.
Na₅ 12·4 per cent. 11·9 per cent.
H₅ 0·54 ” 0·62 ”
Al₄ 11·7 ” 13·1 ”
Si₆ 18·2 ” 19·7 ”
S₄ 13·9 ” 12·7 ”
O₂₅ 43·3 ” 42·0 ” (by difference).
By a comparison of the composition of the violet and pale blue
ultramarines, it is seen that the chief difference is an increase of
hydrogen in the latter.
=Ultramarine Red.=—Since ultramarine violet increases in brightness
and redness of shade in the air, Wunder erroneously believed that
this was due to oxidation, and that, consequently, the violet could be
converted into a red by oxidising agents. Nitric acid vapours led over
ultramarine violet at 170° to 200° C. do not act upon it, but where
drops of nitric acid are spirted over, the violet is changed to red.
Wunder then reduced the temperature to 135° to 145° C. and obtained
the first ultramarine red. Iron is attacked by nitric acid at lower
temperatures, but not at 135° C.; the iron boxes previously described
could therefore be used. It was afterwards found that at a sufficiently
low temperature hydrochloric acid gas converts ultramarine violet into
red. The iron boxes cannot be used for this operation, as they are
attacked at the temperature; the stone chests are used instead. Other
acids also act on ultramarine violet; boric acid gives a reddish-violet.
The violet is spread out on the dishes standing on three feet mentioned
before, and heated to 128° to 132° C. At higher temperatures the violet
is unaltered, whilst below 100° C. it is decomposed. The hydrochloric
acid is poured in from time to time through earthenware tubes into
dishes in which it evaporates.
A mixture of red and blue would appear violet, but would behave
towards reagents in a different manner to real ultramarine violet.
Ultramarine blue is decomposed at 128° to 132° C. by hydrochloric acid
to a gelatinous mass, whilst at this temperature ultramarine violet is
changed into a bright red. From the blue no violet can be obtained by
nitric acid, but the violet gives a red at 135° to 145° C. Analysis
would also indicate the difference. Ultramarine red has the following
composition:—
Calculated for Found.
Na₃ 7·9 per cent. 8·1 per cent.
H₅ 0·57 ” 0·72 ”
Al₄ 12·3 ” 13·3 ”
Si₁₆ 19·1 ” 19·3 ”
S₄ 14·6 ” 15·2 ”
O₂₅ 45·6 ” 43·4 ” (by difference).
It appears that in the red two more equivalents of sodium have been
replaced by hydrogen. The violet is apparently a sodium salt of which
the red is the acid. The violet made by means of ammonium chloride
is also converted by hydrochloric acid gas at 128° to 132° C. into a
handsome red containing nitrogen, and the red is changed by hydrogen at
280° to 290° C. into a lighter pale blue.
CHAPTER XXV.
BLUE COPPER PIGMENTS.
=Bremen Blue and Green.=—The pigment known as Bremen blue or Bremen
green consists of copper hydroxide. It possesses all the disadvantages
of copper compounds; it is very sensitive towards sulphuretted hydrogen
and sulphur dioxide; in contact with air containing the former gas it
is quickly turned black. It has also other disadvantages; it cannot
be used in oil, for when ground in oil it is quickly discoloured, on
account of the formation of copper oleate. If a wall which has not
completely dried be covered with Bremen green, in a short time it will
be covered with spots. In spite of this small stability, Bremen green
is still largely used by artists on account of its low price, although
it could be replaced by other pigments almost as cheap and considerably
more durable.
Copper hydroxide comes into the market under many names. The pigments
known as blue verditer, lime blue and mountain blue contain essentially
copper hydroxide. The preparation of pure copper hydroxide on the
large scale will be first described. Copper sulphate is the usual raw
material. In order to obtain a colour of a pure blue shade it must be
free from iron, the presence of which would result in the production of
a discoloured precipitate.
A fairly concentrated solution of copper sulphate is warmed in a pan to
about 30° C.; weak caustic potash solution is added until the liquid
is slightly alkaline. A green precipitate separates, which consists of
copper sulphate and hydroxide. In order to remove the copper sulphate
from the precipitate, and impart to it the correct bluish-green colour,
it is left on a strainer until it has acquired a pasty consistency,
when it is brought into a tub and mixed with weak caustic potash
solution. Care must be taken that this potash solution is not too
concentrated, or it will withdraw water from the copper hydroxide and
produce black copper oxide. In order to prevent this result, which
would render the whole mass useless, a portion of the precipitate
is tested with the caustic potash solution. If it is blackened, the
solution must be diluted with the necessary quantity of water before it
is used. Instead of diluting with water, potassium carbonate solution
is often added. The addition of the caustic liquor is continued until
the colour of a test portion of the precipitate is not deepened by
further additions. When this point is reached the colour must be at
once withdrawn from the action of the alkali. It is brought into a
large tub filled with water, in which it is most carefully washed with
many waters.
Basic copper chloride may also be used as the raw material for this
pigment. It is obtained by treating scrap copper with 60 per cent. of
common salt and 30 per cent. of sulphuric acid. The pale green basic
chloride is then treated with caustic potash solution. This method
is now rarely used; copper sulphate is considerably lower in price
than formerly and copper hydroxide is prepared from it with the least
trouble.
=Neuberg Blue= is a mixture of copper blue with Chinese blue. The
larger the quantity of the latter component the deeper the colour.
Neuberg blue can be more easily ground with oil than pure copper blue.
It should not be used as a distemper colour, for the Chinese blue
is decomposed by the action of lime, and the colour will quickly be
spoiled by the separated ferric oxide.
=Lime Blue= is ordinary copper blue, mixed with varying quantities
of gypsum. It is paler than pure copper blue; different shades are
obtained by increasing the quantity of gypsum.
This pigment is made by dissolving 15 parts of copper sulphate in 1,300
parts of water, adding a strong solution of 121 parts of ammonium
chloride, and then milk of lime prepared from 30 parts of quicklime.
The precipitate is well washed, strained, ground, and finally dried.
Lime blue is brought into the market in several forms; in cubes
obtained by cutting up the stiff paste and then completely drying,
and in irregular lumps or a coarse powder. The pigments containing
copper hydroxide as their colouring principle are used less as artists’
colours than for distempering.
=Payen’s Mountain Blue= is a mixture of copper hydroxide with varying
quantities of calcium carbonate. It is prepared by adding calcium
chloride to a solution of copper sulphate and stirring in dilute milk
of lime. A green precipitate of basic copper chloride is formed;
potassium carbonate solution mixed with milk of lime is then added. The
latter mixture contains caustic potash, which decomposes the copper
chloride, copper hydroxide and calcium carbonate being simultaneously
precipitated. Different shades may be obtained; by increasing the
quantity of lime the product is paler. This pigment commonly comes
into the market in the paste form. When it is dried the operation must
be conducted at a low temperature; copper hydroxide is converted into
copper oxide at relatively low temperatures.
=Oil Blue.=—The pigment known under this name consists of copper
sulphide (CuS). It can be made in several ways. The simplest process,
which also gives a good product, is here described.
Sulphur is boiled in a glass flask with a long neck. When the heavy
reddish brown vapours begin to fill the neck, copper turnings or wire
free from oxide are thrown in. The copper burns in the sulphur vapour
with a red flame to cupric sulphide. When it has once commenced to
burn, the flask requires little heating, so much heat is produced
by the combustion of the copper that the sulphur continues to boil.
The introduction of copper is continued until only a small excess of
sulphur is left, the flask is then closed and allowed to cool. When the
contents have reached the temperature of the air the flask is broken,
and the mass boiled with caustic potash solution in order to remove
excess of sulphur.
The product obtained by this process has a handsome violet blue colour,
which must be shown by the whole mass. If portions taken out of the
flask are black, an excess of copper has been used. In order to improve
the colour of a faulty batch, it is mixed with sulphur and quickly
heated to the boiling point of sulphur, air being excluded. The excess
of sulphur is then removed by boiling with caustic potash solution.
Oil blue is a handsome but not very durable pigment. When used in
varnish, which protects it from the action of air, it is fairly
permanent.
=Copper Hydroxide.=—By precipitating carefully a solution of a copper
salt with caustic soda, a blue precipitate of copper hydroxide is
obtained, which, though not distinguished by any particular beauty, is
adapted for use as a distemper colour and for similar purposes. The
operation is conducted at ordinary temperatures; on account of its
voluminous nature the pale blue precipitate requires a long time for
washing. Hot solutions must not be used; at a temperature near the
boiling point of water copper hydroxide is completely decomposed into
black copper oxide.
CHAPTER XXVI.
BLUE COBALT PIGMENTS.
=Cobalt Blue, Thénard’s Blue, Cobalt Ultramarine, King’s Blue, Leyden
Blue.=—The pigment known under these names is a compound of cobalt
oxide with alumina, and is prepared in a similar manner to Rinmann’s
green. Of all the blue pigments used in painting, cobalt blue is the
most handsome and most durable. It is completely unaltered by the
atmosphere. The most powerful chemical reagents have but a slight
action upon it, and their action is less the higher the temperature
used in the manufacture. Cobalt blue is made by precipitating mixed
solutions of a cobalt salt and alum, washing, drying, and igniting the
precipitate. A product of pure blue colour is only obtained when alum
absolutely free from iron is used. If but very small quantities of iron
are present, the red ferric oxide has a very considerable influence on
the shade of the product.
The depth of colour varies according to the proportion of cobalt salt
used. The variation is not so considerable as in the case of cobalt
green; as a rule, 50 to 100 parts of cobalt sulphate or nitrate are
used to 100 parts of alum. The temperature at which the precipitate is
ignited must be much higher than that used for cobalt green; it should
be raised to a white heat. The crucible should be provided with a
well-fitting lid—the fire gases damage the shade of the colour.
When cobalt sulphate is ignited with ammonia alum, cobalt blue is
obtained; but this method is not to be recommended. The ignition must
be of long duration to completely drive off the sulphuric acid. The
author has made a cobalt blue of remarkable beauty in the following
manner: Alumina obtained by precipitating electrolytically an alum
solution (page 49) was mixed with a solution of pure cobalt chloride
to a thin pulp, which was quickly dried in a shallow porcelain dish.
The mixture, whilst still hot, was pressed into a crucible placed in
a larger one filled with magnesia; the crucible was heated to a good
white heat, at which it was maintained for an hour, when it was allowed
to cool. The cobalt blue made by this method has the purest blue
colour, being without that admixture of red which is not rarely to be
perceived in this pigment. To avoid the appearance of this red tint,
certain additions are made; a small quantity of a zinc salt is most
frequently employed, according to the quantity of which more or less
pale shades are produced.
=Cæruleum= is a pale blue pigment consisting of a compound of the
oxides of cobalt and tin. It is made by converting tin by the action
of nitric acid into white stannic oxide, adding a solution of cobalt
nitrate and evaporating to dryness in a porcelain dish whilst stirring;
whilst still warm the powder is strongly ignited. In cæruleum the
chemical combination is less firm than in the compounds of cobalt oxide
with zinc oxide or alumina, strong hydrochloric and dilute sulphuric
acids decompose it, continued treatment with nitric acid extracts all
the cobalt. Cæruleum resists completely all atmospheric influences.
The circumstance that all the cobalt in this compound may be removed by
treatment with nitric acid leads to the conclusion that the pigments
composed of cobalt oxide and another oxide are not chemical compounds
of the two oxides, but that the alumina, zinc oxide and tin oxide
serve simply as bases for the blue modification of cobalt oxide. That
a chemical compound cannot be present follows from the fact that the
quantities of the oxides uniting together may be very considerably
altered and a coloured product still obtained. The author has shown in
1868 that the blue modification of cobalt oxide is obtained by heating
the red. The change of the red colour of cobalt chloride into the blue
is not caused, as was formerly thought, by loss of water, but by the
transformation of the cobalt oxide contained in the compound from the
red into the blue modification. Strong bases are able to retain the
cobalt oxide in the blue form, and strongly basic oxides are therefore
used in the manufacture of this series of pigments.
=Cobalt Zinc Phosphate.=—This pigment is made by precipitating a
solution of zinc sulphate, free from iron, by sodium phosphate, adding
a solution of cobalt sulphate and again sodium phosphate so long as a
precipitate is produced. Excess of sodium phosphate is to be avoided,
otherwise a considerable quantity of cobalt remains unprecipitated. In
the directions given by Gentele it is stated that the sodium phosphate
must be in excess, and that the liquid above the precipitate must
possess a reddish colour. The author’s experiments have shown that a
pigment in every respect equal to that produced by Gentele’s process is
obtained when all the cobalt is precipitated. The precipitate, which
consists of variable quantities of zinc and cobalt phosphates, is dried
and ignited, when it acquires a very deep blue colour.
CHAPTER XXVII.
SMALTS.
This blue pigment is a very finely powdered glass, coloured by cobalt
oxide, according to the quantity of which products of very different
shades are obtained. If a very small amount of cobalt oxide is used
the smalts has a beautiful pale blue colour, but by the use of larger
quantities an almost black mass can be obtained.
Although the proportion of cobalt oxide contained in smalts is so
variable, yet it is probably present as a compound of constant
composition—the cobalt potassium double silicate of the formula CoO.
2SiO₂ + K₂O. 2SiO₂. The numerous published analyses of smalts lead to
this conclusion. The small quantities of other metallic oxides which
are found in smalts are to be regarded as chance impurities. Being a
glass free from lime smalts is easily decomposed; in this respect it
shows great similarity with water-glass, which is completely soluble in
boiling water.
Smalts comes into commerce in the form of powder. In the ”Blue Colour
Works” in which smalts is made a number of qualities are distinguished;
these are separated according to the fineness of the powder. Smalts of
good quality is composed of particles of the same size and has a pure
sky-blue colour. A shade inclining to red is generally to be ascribed
to the presence of iron; material of this nature is of little value.
Smalts is not easily attacked by chemical reagents. It has been above
stated to belong to the easily decomposed glasses, and it is attacked
by reagents which ordinary glass completely resists. Finely ground
smalts is strongly attacked by boiling sulphuric acid, and, after
fusion with soda, is soluble in acids. Water has some action upon
smalts; by the long continued action of a large quantity the shade is
injured, the colour acquires a greenish tinge.
In the manufacture of smalts there are three principal operations:—
1. Preparation of the charge.
2. Fusion of the charge.
3. Grinding the fused mass.
These processes are principally mechanical. Only as regards the
composition of the charge is chemical knowledge required.
=1. Preparation of the Charge.=—The cobalt is supplied by substances of
different origin—as a rule, roasted speiss cobalt and cobalt glance are
used; occasionally ores are employed without previous preparation. When
pure cobalt salts (sulphate and nitrate) are used, a product of very
fine shade is produced, but in practice these salts are not applicable
on account of their cost. There remain therefore only the compounds of
cobalt occurring in nature. On account of the foreign substances they
contain, these require a special treatment before they can be used in
the manufacture of smalts; the treatment varies according to the other
elements present in the cobalt ores. Ores containing bismuth are first
treated in order to obtain this valuable metal; ores containing arsenic
are roasted in furnaces of special construction, which are connected
with a series of stone or wooden passages in order to condense the
arsenic trioxide completely.
If ores are employed which contain only a small quantity of cobalt, the
same quantity of glass is melted time after time with fresh quantities
of the poor ore. At each operation cobalt is taken up. In place of
glass a mixture of potash and very fine quartz sand may be used with
advantage. It produces that species of glass which most easily takes
up cobalt oxide. The quartz sand is generally made by igniting flint
and quenching in water to facilitate the grinding; it is then powdered.
River sand is generally so impure that it would produce a brown or
green coloured glass, which, when fused with cobalt ores, would give
smalts of a bad shade.
=2. Fusion of the Charge.=—This process is very similar to the fusion
of ordinary glass. The materials, in very fine powder, are carefully
mixed and then ”fritted,” that is, heated until the mass sinters
together without melting. The real fusion is accomplished in glass
furnaces. The fritted mass is fused in small ”glass pots” made of
fire-clay, in a furnace similar in principle to the ordinary glass
furnace. The glass pots are made rather small, to hold about 50
kilogrammes, in order to obtain as homogeneous a product as possible.
They are placed to the number of six in a furnace heated by coal, in
which a very high temperature can be obtained. This is essential,
because the charge has a high melting point and must be made quite
fluid in order that impurities may settle.
The furnace must be slowly heated at first to prevent the pots from
cracking. When they are once heated the temperature is raised to
fuse the charge, which is repeatedly stirred so that the residues
may sink to the bottom. These residues consist chiefly of metallic
sulphides and arsenides. After six to seven hours’ fusion the stirring
is discontinued, and the temperature raised for a short time to the
highest it is possible to attain, so that the smalts may be as fluid
as possible. When this is the case it can be drawn out into long thin
threads. The melted glass is then taken out and poured into cold
water. The rapid cooling makes it extremely brittle, and considerably
facilitates the powdering.
When new pots are used for the fusion, their walls are considerably
attacked by the alkalis contained in the glass. In order to prevent
this a small quantity of common smalts is fused in them before the
introduction of the real charge; the inner surface then becomes covered
with a protective glaze.
=3. Grinding the Fused Mass.=—The smalts is next powdered under stamps.
These only differ from the ordinary construction in that both stamp and
trough are made of granite. The coarse powder from the stamps then goes
to mills of ordinary construction, in which it is ground as finely as
possible in a current of water. A blue liquid runs from the mills into
tubs. The coarser particles which settle in these vessels constitute
the article known commercially as strewing smalts, which is of small
value. The quantity of this quality is fairly considerable; it cannot
all be sold; part is fused in a later operation with a fresh quantity
of the fritted mixture. The liquid remaining in the tubs then gives
the different qualities of smalts. After having deposited the coarsest
particles in the first vessel it is brought into another, in which it
stays only a few minutes, when it is run off into another vessel, in
which also it remains but a short time. The liquid goes in this manner
through from three to five vessels, and in the process deposits all the
coarser particles. The oftener the liquid is brought into fresh vessels
the finer are the particles still suspended in it, and the longer it
should remain before being drawn off into another.
When the liquid has run through three or four vessels, as the case
may be, it still retains the finest particles in suspension. It is
now run into a tank, in which it remains until it is perfectly clear
and has deposited all the blue. The deposit in this tank has a dirty
bluish-grey colour; it is utilised by being added to a later fusion.
It would be expected that this last deposit would have the best shade,
since it consists of smalts in the finest state of division, which
would no doubt be the case if the smalts remained unchanged. Smalts
is, however, a glass which is rather easily decomposed. In grinding,
the smalts comes in contact with large quantities of water, and in the
succeeding levigation the water decomposes it; the final residue is
thus produced. In view of the easy decomposition of smalts by water, it
is necessary to carry out all processes in which it is in contact with
water as rapidly as possible, in order to obtain the largest yield of
smalts.
The smalts deposited in the successive vessels have a different
degree of fineness, and are sold under particular marks. The Saxony
works, which produce the greater part of the smalts used in Germany,
distinguish the qualities by letters. The better qualities are
distinguished by the same letter, the fineness of the quality being
indicated by the repetition of this letter. Thus FFFE, FFE, and FE
indicate qualities which are of lower value the less often the letter
F occurs in the mark. The qualities following those marked F are
distinguished by M; the lowest quality is marked OE. F indicates fine;
M, medium; and O, ordinary.
The qualities generally designated smalts are those deposited in the
third and fourth vessels; they are also known as king’s blue or azure
blue.
The processes used in different works apparently vary. The essentials
of the processes are, however, as they have just been described; the
time during which the liquid is left in the various depositing vessels
is different.
Smalts, being a glass, well resists the action of the weather, although
on account of the absence of lime it has not the great chemical
indifference of ordinary glass. Smalts is not altered by atmospheric
influences, but from analogy with the behaviour of water-glass, to
which smalts is closely related in chemical composition, we should
conclude that, although smalts resists the action of the air for a
tolerably long time, it cannot be regarded as absolutely permanent; in
the course of time potassium carbonate and silica will be formed.
Since the introduction of the manufacture of ultramarine, the use of
smalts has considerably decreased. Ultramarine is incomparably the
more handsome pigment, but it cannot be exposed to high temperatures
without undergoing change of shade. For purposes in which the pigment
is subjected to a high temperature, as in porcelain painting or
earthware glazing, smalts has maintained its position. Smalts is also
used in fresco painting, for colouring wax and tinting writing paper.
For the latter purpose it should be rejected. It has no influence on
the durability of the paper, but it spoils steel pens. Any one who
has written for a long time on paper coloured with smalts must have
observed this; the best steel pens are soon worn out by such paper. The
very fine splinters of glass present in large number in the paper act
upon the steel as a very fine but very hard file, and quickly wear it
down.
When smalts are used for painting earthenware, the outlines of the
design are quite obliterated, the cause of which is that smalts, being
itself a glass, fuses with the glaze (also a glass) of the vessel.
When clean outlines are required smalts should not be used; some other
cobalt pigment resisting heat should be substituted.
In addition to the above blue pigments which are in common use, there
are two others to be mentioned, rarely used and very costly—tungsten
blue and molybdenum blue.
=Tungsten Blue= is made by adding excess of ammonium chloride solution
to a hot solution of potassium tungstate, collecting the precipitate
resulting when the liquid has completely cooled, drying and heating
to redness in a crucible, through the cover of which a porcelain tube
reaches to the bottom. When the crucible begins to glow, hydrogen is
passed through the tube; the crucible is then heated to a full red
heat for fifteen minutes, the current of hydrogen being continued.
The pigment obtained in this way is a deep blue powder of velvety
appearance.
=Tessié du Motay’s Blue.=—The following is the method of preparation:
10 parts of sodium tungstate, 8 parts of tin crystals, 5 parts
of yellow prussiate, and 1 part of ferric chloride are dissolved
separately and the solutions mixed. The precipitate is washed and
exposed to light in thin layers. The blue colour develops in the course
of several days. According to the discoverer, this pigment consists of
a compound of tungsten oxide with a double cyanide of iron and tin;
in physical properties it is similar to good Prussian blue, but is
distinguished by greater durability on exposure to light and also by
a much higher cost. Up to the present this pigment has not been made
commercially.
=Molybdenum Blue.=—This fine but costly pigment is obtained by mixing
a solution of sodium molybdate with a solution of stannous chloride.
A blue precipitate is formed, which, after washing and drying, may be
used as an artists’ colour. It is distinguished by great durability. A
good shade of molybdenum blue can be obtained with greater certainty
by adding finely-powdered tin and a few drops of hydrochloric acid to
a solution of pure molybdic acid. In composition it is a mixture of
stannic molybdate and the blue modification of molybdenum oxide.
CHAPTER XXVIII.
GREEN MINERAL PIGMENTS—GREEN COPPER PIGMENTS.
=Copper Carbonate.=—In nature two salts occur containing copper,
carbonic acid, and water in different proportions—one, the mineral
malachite, has a fine emerald green colour; the other, azurite, is sky
blue. Both minerals are ground and levigated, and brought into commerce
as mountain green and mountain blue.
Compounds of copper with carbonic acid, made artificially, are
used under different names as pigments. The terms mountain blue
and mineral blue are applied indiscriminately to various copper
compounds; as mountain blue, or Brunswick green, pigments come into
commerce containing varying quantities of copper carbonate (made by
precipitating a copper salt with soda) mixed with barytes, zinc white,
or another white pigment, in order to obtain paler and deeper shades.
The poisonous Scheele’s green is also given the same name as that under
which copper carbonate is sold, _viz._, mineral green, so that the
composition of this colour can only be decided by analysis.
A green pigment, similar in composition to malachite, is obtained
by precipitating copper sulphate with soda in the cold and washing
quickly. If the precipitate is left in contact with the liquid,
its colour changes and it is converted into a blue mass similar in
properties to ground malachite. A green precipitate is obtained with
more certainty by precipitating a boiling solution of copper sulphate
with soda solution.
Both green and blue copper carbonate are pigments of little depth;
as a rule ground and levigated malachite and azurite have a greater
intensity of colour than the artificial pigments.
=Copper Arsenite.=—The compounds of arsenious acid with copper are
among the most handsome and bright colours which exist. It is thus
to be regretted that these pigments are disappearing more and more,
and indeed with every reason, from the pigments permitted by law.
In the end they must fall into complete disuse. It is a matter of
common report that these pigments, and particularly emerald green,
have frequently caused arsenical poisoning. Numbers of people have
been repeatedly made ill by the dust of emerald green fixed on light
fabrics, such as are used for ball dresses, simply by albumin or
dextrine, and brought into the air by the movements of the dancers.
It has been further shown that the air of rooms papered with hangings
coloured by emerald green contains small quantities of the most
poisonous of all arsenic compounds, arseniuretted hydrogen.
Although it is in the interest of colour makers to produce the
brightest possible colours, yet, on account of their dangerous
properties, pigments containing arsenic should be quite excluded.
In several countries their use is forbidden by law. Since there are
several pigments which can compete in brightness with the arsenic
colours, it is to be hoped that the latter will shortly disappear from
commerce.
=Scheele’s Green, Swedish Green.=—A solution of 32 parts of potash is
boiled with 11 parts of white arsenic (arsenious acid) until the latter
is completely dissolved. This solution of potassium arsenite is mixed
with a hot solution of 32 parts of copper sulphate free from iron. The
beautiful green precipitate is washed with hot water and dried. These
directions for the preparation of copper arsenite are due to Scheele,
the discoverer of the pigment. It can be prepared by several other
methods.
When white arsenic and copper sulphate are dissolved together, and
caustic soda added to the boiling solution, Scheele’s green is
precipitated. When made by this method the pigment must be very
carefully washed; if the excess of caustic soda is not completely
removed it is very hard when dry, and is difficult to powder. In order
to obtain darker greens the quantity of copper sulphate is increased.
A particularly bright green is obtained by dissolving copper sulphate
in water, with the addition of 12 to 15 per cent. of white arsenic, and
precipitating by a solution of potassium zincate, which is obtained
by boiling caustic potash solution with zinc filings, hydrogen being
evolved.
The shade of Scheele’s green depends on the relative quantities of
arsenious acid and copper sulphate employed. If the arsenious acid
predominates, a pale product is obtained; when excess of copper
sulphate is used, the colour is pure green. The pigment made according
to the foregoing directions possesses only small covering power. A
product better in this respect is obtained by precipitating a solution
of 100 parts of copper sulphate by a solution of 90 parts of potassium
carbonate, in which 66 parts of arsenious acid have been dissolved.
Scheele’s green is a bright green pigment, which resists the action
of the atmosphere tolerably well. It is easily decomposed by dilute
acids; when strongly heated arsenious acid is set free, and copper
arsenate and arsenide are produced. Copper arsenite is the essential
constituent of the pigments sold under the name of mineral green, which
is generally a mixture of copper arsenite with varying quantities of
mountain green.
=Brunswick Green, Green Verditer=, is a mixture of copper arsenite,
copper hydroxide and gypsum. It is prepared by dissolving 100 parts
of copper sulphate in water, adding a solution of ¼ part of arsenious
acid and 10 parts of anhydrous potassium carbonate, and finally
precipitating with milk of lime made from 20 parts of quicklime. The
pale to bluish-green precipitate is washed and pressed into flat cakes,
which are brought into the market and used as lime colours. This
pigment is not adapted for use in oil; when applied in that medium it
darkens considerably.
=Neuwied Green= is made in almost exactly the same manner as Brunswick
green, the chief difference being that a larger quantity of arsenic
is used, and thus a product obtained inclining more to green than to
blue. As a rule 2 to 2½ parts of arsenious acid are used to 100 parts
of copper sulphate. The colours found in commerce under this name very
often consist of mixtures of emerald green and finely ground barytes.
=Copper Oxychloride= was at one time largely used. At present it is
scarcely employed; it has been replaced by handsomer and cheaper
pigments. Copper oxychloride is made by exposing a wet mixture of
copper, copper sulphate and common salt to the action of the air.
To 111 parts of copper sulphate 112·5 parts of copper and the same
quantity of common salt are employed. The mixture is made into heaps,
which are wetted and from time to time shovelled about, so that the
air may come in contact with all portions of the mass, and the copper
chloride be converted into basic chloride. It is advisable to allow the
heaps to dry frequently after they have been turned over, so that the
air may more readily penetrate into the interior. Copper oxychloride
has a pale green colour of little brilliance. On this account it is
hardly ever used now; it forms the raw material for the preparation of
Bremen green.
CHAPTER XXIX.
EMERALD GREEN.
There are many versions as to the discovery of this pigment. According
to one it was first made in Schweinfurt by Russ and Sattler; another
version gives it that Mitis of Vienna first made it on the large scale.
It is possible, as has been the case with many chemical products, that
this pigment was simultaneously discovered by both. The method of
making the pigment was at first a secret possessed by few. Not until
the publication of a method by Liebig in 1822 was the preparation
of emerald green generally known. In recent times the industry has
supplied other colours which are less poisonous. The time should not be
far distant in which this handsome but highly poisonous pigment shall
no longer be found in commerce.
The circumstance that the poisonous nature of the pigment and cautions
as to its use were given great publicity, brought about the discovery
of the countless names under which it has been sold. It was endeavoured
by re-naming the pigment to pass it off as a different substance. All
the pigments which have been sold under the names of Mitis, moss,
patent, new, king’s green, etc., are either pure emerald green or
mixtures of it with barytes or gypsum, which additions were intended to
alter the shade of the green and make it appear to the buyer as a new
pigment.
In chemical composition emerald green is a compound of copper arsenite
and copper acetate. It has the following formula:—
3(CuO.As₂O₃) + Cu(C₂H₃O₂)₂.
This compound rarely comes into commerce in the pure state; it is
generally mixed with chrome yellow or lead sulphate, which are added
with the object of producing shades between yellowish-green and dark
green. Emerald green is a compound of constant composition. When made
by different processes it has the same properties. Under the microscope
it is seen to consist of crystals; when the pure substance is ground
it becomes paler, the intensity of the colour being diminished by the
breakage of the crystals. The colour of emerald green is not altered
by artificial light. This is a most valuable property; the majority of
green pigments appear yellowish-green in artificial light.
Emerald green can be made on the large scale by two processes; these
differ according to the copper salt used, which is either the acetate
(verdigris) or the sulphate. The latter is by far cheaper than
verdigris, which is now seldom used for this purpose.
=Manufacture of Emerald Green from Verdigris.=—By boiling for several
hours, 70 parts of ordinary verdigris are dissolved in water; in a
second vessel 100 parts of arsenious acid are dissolved in 1,500 parts
of hot water; the verdigris solution is filtered through a cloth into a
larger wooden vessel and mixed with two-thirds of the arsenic solution.
The mixture is well stirred and allowed to stand for some hours. A
precipitate of dull green colour is formed. This consists of copper
arsenite. After three to four hours the remaining one-third of the
arsenic solution is added; the precipitate then changes into the double
salt of which emerald green consists.
The use of such dilute solutions as are given in these directions is
essential when a product of particularly good colour is required.
Emerald green is a crystalline substance which is deeper in colour in
proportion to the size of its crystals. Large crystals can only be
formed from very dilute solutions; when strong solutions are used,
the emerald green has never the deep colour possessed by the product
of dilute solutions. In the place of ordinary (basic verdigris) the
so-called distilled verdigris (neutral copper acetate) can be used,
of which seventy-six parts are required for the quantity of arsenious
acid given. The emerald green made from ”distilled” verdigris is of
a yet deeper colour than that made from ordinary verdigris, but is
considerably dearer. Such emerald green is commercially described, very
incorrectly, as distilled emerald green.
The method given by Liebig is as follows: 4 parts of basic verdigris
and 3 parts of arsenious acid are separately dissolved in boiling
vinegar; the liquids are mixed and evaporated until a precipitate of
emerald green separates.
According to Ehrmann and Kastner, 70 parts of verdigris and 56 to 63
parts of arsenious acid are separately dissolved, the boiling solutions
mixed and boiled until the dirty green precipitate changes into a
bright green. In consequence of the rapid formation of the precipitate
due to the boiling, the colour is pale green; if a dark-coloured
product is required, the solutions are allowed to cool before mixing.
After several days a very dark-coloured precipitate separates from the
liquid; it consists of comparatively very large crystals of emerald
green.
=Manufacture of Emerald Green from Copper Sulphate.=—There are two
processes. Either the solution of copper sulphate is mixed with an
acetate, by which it is converted into copper acetate, and then with
arsenious acid, or copper arsenite is precipitated from the solution
of copper sulphate and then converted into emerald green by treatment
with acetic acid. If acetic acid can be cheaply obtained, the latter
process is to be recommended.
Braconnet gives the following directions: 3 parts of copper sulphate
are dissolved in a little boiling water, the hot solution is mixed with
a hot solution of 4 parts of arsenious acid and four parts of potassium
carbonate; the precipitate is then treated with 3 parts of pyroligneous
acid. The dull-coloured precipitate at first formed is changed by the
acetic acid to a bright green. The colour is more quickly produced
when the liquid is heated nearly to boiling for several hours. When
the desired shade appears the boiling is stopped and the precipitate
at once separated from the liquid, by long contact with which it would
give up arsenious acid and thus lose in shade.
According to Fuchs, 5 kilogrammes of lime and 25 kilogrammes of copper
sulphate are dissolved in acetic acid, then a boiling solution of 25
kilogrammes of arsenious acid is added. The precipitate is at once
formed; it is immediately separated from the liquid, washed, and dried;
the top liquor, with the addition of arsenious acid, can be again used
to precipitate the copper lime solution.
Emerald green has an extremely bright colour which surpasses other
green mineral pigments in beauty. The larger are the microscopic
crystals of which it consists the deeper is the colour. In order to
obtain the desired deep shade of emerald green it is necessary to
use very dilute solutions; from strong solutions the precipitate is
instantaneously produced, in which case it is impossible to obtain
large crystals. The covering power of emerald green, in consequence
of its crystalline nature, is less the deeper the shade. It cannot be
regarded as a permanent colour: very dilute alkalis and acids attack
it. By the action of sulphuretted hydrogen it is discoloured, owing to
the formation of black copper sulphide. It ought not to be used upon
lime, which withdraws acetic acid and produces yellowish-green copper
arsenite.
This pigment should not be used for distempering or for colouring wall
papers. By the action of the atmosphere on the arsenic it contains,
arseniuretted hydrogen is formed—an extremely poisonous gas, very small
quantities of which are sufficient to cause serious illness in the case
of susceptible people. In spite of its poisonous nature, emerald green
is still largely used. All possible shades of green can be produced
from it, yellowish-green or pale green, by admixtures of yellow
pigments, such as chrome yellow, or white pigments, such as barytes
or white lead. Many qualities of green known as palette green, Basle
green, etc., are generally composed of such mixtures.
=Mitis Green or Vienna Green= is obtained by dissolving verdigris in
acetic acid and adding a boiling solution of white arsenic in water;
acetic acid is then added until the precipitate dissolves. On boiling
the clear solution a green precipitate forms, which, when dry, is
a deep bluish-green of characteristic shade. This pigment is now
practically disused because of its poisonous nature, which is equal to
that of emerald green.
=Copper Stannate.=—This green pigment, also known as Gentele’s green,
can be made by two methods. Gentele gave the following process: 59
parts of tin are converted into stannic chloride by solution in _aqua
regia_; a solution of 125 parts of copper sulphate is added and copper
stannate is precipitated from the mixture by caustic soda, on washing
and igniting it acquires a pretty green colour. It may also be made by
fusing 59 parts of tin with saltpetre; the potassium stannate is then
dissolved in dilute caustic soda and copper sulphate solution added;
the precipitate is washed and ignited.
Copper stannate is tolerably durable, in this respect it considerably
surpasses emerald green. Only sulphuretted hydrogen has any
considerable action upon it, turning it to a dirty brownish-green hue.
=Kuhlmann’s Green= is a basic chloride of copper, obtained by heating
2 equivalents of lime with a solution of 3 equivalents of copper
chloride. It is important that the copper salt should be present in
excess. In shade Kuhlmann’s green is very similar to emerald green,
with which it agrees in retaining its colour by artificial light. It is
a somewhat less pure green than emerald green; the difference is only
perceived when the two pigments are directly compared. When, however,
it is considered that it is far more permanent than emerald green and
cheaper, a more extended use is indicated than is yet the case.
=Elsner’s Green= is a species of lake, made by mixing a solution of
copper sulphate with a decoction of fustic, adding a small quantity of
stannous chloride and precipitating with caustic soda. To 100 parts of
copper sulphate 10 to 14 parts of stannous chloride are used. According
as the copper salt or fustic extract predominates, the colour of the
precipitate inclines to blue or yellow.
Elsner’s green is also sold under the name of ”non-poisonous green”.
This description is incorrect; the pigment is indeed free from arsenic,
but is poisonous on account of the copper it contains.
=Casselmann’s Green= approaches emerald green in brightness. It
consists of a compound of copper sulphate with copper hydroxide
and water, CuSO₄.3Cu(OH)₂.½H₂O. This pigment is obtained by mixing
solutions of 4 equivalents of copper sulphate and 3 equivalents of
sodium acetate at a certain temperature. The author’s experiments
have shown that the best results are obtained when the solutions are
mixed at a temperature of about 100° C. With this object the solutions
are placed in vessels standing in a pan of boiling water; when their
temperatures have risen to about 100° C. they are quickly mixed, the
mixture stirred, and the precipitate allowed to settle. When the
precipitate is cautiously treated with very weak caustic soda solution
a rather deeper colour is obtained. This treatment should not be
continued too long, or the precipitate may acquire an ugly bluish shade.
=Lime Green= is a mixture of copper arsenite and calcium sulphate.
It is thus a pigment which ought no longer to be used, on account of
its poisonous properties. It is made by boiling milk of lime with
excess of arsenious acid so long as the latter is dissolved. To this
solution of calcium arsenite, copper sulphate solution is added so long
as a precipitate is formed. A mixture of copper arsenite and calcium
sulphate is precipitated.
=Patent Green= is similar in composition to lime green. A solution of
calcium acetate is made by adding quicklime or pure powdered limestone
to acetic acid; copper sulphate solution is then added, when gypsum is
precipitated and copper acetate remains in solution. A hot solution of
arsenious acid is next added, and the precipitated copper salt mixed
with the gypsum at the bottom of the vessel.
=Copper Borate.=—A pale green precipitate of copper borate is obtained
by adding a solution of 3 parts of borax to a solution of 2 parts of
copper sulphate. It must be dried at a very moderate temperature, or it
will decompose. When perfectly dry the precipitate can be heated to a
red heat without decomposition; according to the temperature employed
different shades are obtained. It is most convenient to take tests out
of the crucible from time to time during the ignition, and to quickly
cool the crucible when the desired shade is obtained. When levigated
this pigment may be used in oil, or as a porcelain colour.
=Copper Silicate (Egyptian Blue).=—When a solution of water-glass is
added to a solution of copper sulphate a pale green precipitate of
copper silicate is obtained, which can be heated to redness without
alteration. When 70 parts of white quartz sand, 15 parts of copper
oxide, 25 parts of chalk and 6 parts of soda are fused together a glass
is produced which, after pouring into water, grinding and levigating,
exhibits a pretty blue and very permanent colour. It appears from the
examination of the colours of the Egyptian mural paintings that this
pigment was already known to the ancient Egyptians.
CHAPTER XXX.
VERDIGRIS.
Verdigris is little used as a pigment, but is important to the colour
maker, because copper colours are made from it. In wine-growing
countries it is made from the marc at small expense and without much
labour.
In commerce several kinds of verdigris are distinguished; they differ
in physical and chemical properties. All verdigris consists of copper
acetate, either alone or combined with varying quantities of copper
hydroxide.
=Blue Verdigris= is made in large quantities in France and is commonly
known as French verdigris (_vert de gris naturel_). It has the
following formula:—
Cu(OH)(C₂H₃O₂).2½H₂O.
The process adopted in southern France, especially in the neighbourhood
of Montpellier, is as follows: copper plates are placed in layers in
heaps of the freshly pressed grape residues, which always contain
a certain quantity of must even when the most powerful presses are
used. The process is conducted either in large heaps or in pots; in
the first case care must be taken that the heaps are in a room whose
temperature does not lie below 15° C. It is important to maintain
this temperature, because the formation of acetic acid takes place
with sufficient rapidity only at temperatures not below 12° to 15° C.
Too high a rise of temperature in the heaps must also be avoided or a
considerable quantity of acetic acid will be volatilised. The heaps
should therefore not be made too large, otherwise the temperature
cannot be kept within the proper limits.
The residues contain a considerable quantity of sugar, which can be
transformed by fermentation into alcohol. If air has free access, the
alcohol is at once oxidised to acetic acid, which is recognised by
the acid smell given off. In order to make possible the entry of air
into the interior of the heaps, rectangular wooden bars are introduced
in piling up the heaps. These are carefully withdrawn when the heap
is finished, so that it is traversed by passages through which air
can enter. By the simultaneous action of air and acetic acid copper
acetate is formed, and since copper is always in excess, the acetate
produced is a basic salt. In consequence of the chemical processes, the
temperature of the heap rises to 35° to 40° C.; it is endeavoured to
attain this temperature by artificial heat. It has already been stated
that too great a rise of temperature is accompanied by a considerable
evaporation of acetic acid. The process is then finished in a short
time, but the loss of acetic acid is remarkable. When the temperature
is so regulated that it varies between 25° and 30° C. the process takes
a normal course—four to five days may be regarded as its duration.
The grape residues are effective on account of the sugar, which is
transformed into alcohol and then into acetic acid. Residues which
have been extracted with water after pressing should not be used in
the manufacture of verdigris; they contain but little sugar and hence
undergo a very feeble acetic fermentation. When such residues are used
the verdigris is often accompanied by black spots of copper sulphide
upon the plates; this is due to incipient decomposition of the residues.
As a practical test for the termination of the process a strip of
copper is plunged into the heap and left for some hours. It should
be covered by a uniform coating of verdigris; if it is covered with
small drops that is a sign that the process is not completed and the
heaps must be left some time longer. The course of the process can be
simply and safely followed by means of a thermometer. This is placed in
a perforated copper tube and plunged into the interior of the heap. A
continuous rise of temperature indicates a steady increase of chemical
action; the temperature of the room is regulated in accordance. When
the temperature in the interior of the mass begins to fall the process
is nearing the end. More heat is now supplied to assist the chemical
action. The process is at an end when, in spite of external heat, the
temperature of the heap decreases and approaches the temperature of the
air of the room.
Verdigris can also be made by placing sheet copper and grape residues
in layers in pots, which are deposited in a room of fairly uniform
temperature, such as a cellar. This method has the advantage that the
formation of the verdigris is finished in a shorter time, which is more
than counterbalanced by the labour and expense of filling the pots.
The copper plates, when removed from the heaps or pots, are covered by
a crust of thin needle-shaped crystals of a bright green colour. They
are shaken to free them from the adhering grape skins and seeds, and
then treated with weak vinegar, in which they are dipped; they are then
left standing on edge for several days. This treatment with vinegar has
the object of converting the neutral salt formed on the plates into
basic salt. The dipping into vinegar and exposure to air are repeated
six to eight times, when the originally pure green crust on the plates
is gradually changed into bluish-green verdigris. These processes
are continued until the plates are covered uniformly by a layer of
verdigris about 5 centimetres thick. The crust is then scraped off by
copper knives and stirred with water to a paste, which is pressed in
leather bags in rectangular moulds. The lumps are then slowly dried in
the air.
Plates which have been once used give a larger quantity of verdigris
in a second operation, which is to be ascribed to the fact that they
possess a larger surface than unused plates. New plates are made more
susceptible to the further action of the acid by dipping in strong
vinegar, by which they become covered with a layer of copper acetate.
The verdigris obtained by this method consists of crystalline scales of
a pale bluish-green colour, which produce a pale blue powder. In crude
verdigris grape seeds are often found, and occasionally stalks and
pieces of metallic copper. These admixtures are a consequence of the
method of manufacture and cannot be regarded as adulterants. Gypsum is
to be regarded as an adulterant. Verdigris often contains basic copper
carbonate.
Verdigris behaves in a peculiar manner with water. In contact
with a small quantity it swells to a bluish-green mass, which
becomes quite warm. Neutral copper acetate and the basic salts
2Cu(C₂H₃O₂)₂.Cu(OH)₂.5H₂O and Cu(C₂H₃O₂)₂.2CuO.1½H₂O are formed, the
latter of which is insoluble.
By the addition of a larger quantity of water the basic compounds are
decomposed, neutral copper acetate dissolves, and a mixture remains
of the compound Cu(C₂H₃O₂)₂.2CuO.1½H₂O and a brown basic acetate
containing still less acetic acid. On account of this peculiar
behaviour of verdigris towards water some care is required when it is
used as a water colour. A very dilute solution is not green, but has an
indefinite shade.
=Distilled or Crystallised Verdigris= consists of neutral copper
acetate, Cu(C₂H₃O₂)₂.H₂O. It can be made from blue verdigris by
treating with the amount of acetic acid required to completely
neutralise the copper oxide, or by decomposing copper sulphate with
the acetate of a metal which forms an insoluble or difficultly soluble
sulphate.
Crystallised verdigris is very simply made from ordinary verdigris;
the latter, whilst still moist, but containing only a small quantity
of water, or the acetic acid would be too largely diluted, is brought
into a pan and strong acetic acid poured over. Strong pyroligneous acid
may be used, its empyreumatic odour is without influence on the quality
of the product. The pan is heated until the contents almost, but not
quite, boil. They are frequently stirred so that the particles at the
bottom are brought in contact with the acid. A dark green solution is
formed; when its colour no longer increases in depth it is allowed to
stand until suspended solids sink to the bottom. The clear solution is
then drawn off and rapidly evaporated in shallow copper pans. It is
important that the liquid should not contain an appreciable quantity
of free acid. When a crystalline skin begins to form on the surface of
the solution it is drawn off into the crystallising vessels. These are
made of glazed earthenware; wooden rods are placed in them, on which
the crystallisation takes place. In order that large crystals shall
be obtained, it is necessary to maintain a regular temperature in the
room in which the crystallising vessels are placed. It is heated at the
commencement, and the temperature is allowed to sink a little towards
the end of the operation. From twelve to fourteen days are required to
obtain large crystals. The mass of verdigris crystals adhering to each
rod weighs 2·5 to 3 kilogrammes. The residual liquid is a saturated
solution of verdigris, and is used in the next operation. It is only
necessary to heat it with the residue from the first operation and some
acetic acid in order to obtain a crystallisable solution of verdigris.
The residue in the pan contains metallic copper, grape stems and
seeds, and basic copper acetate. The copper is extracted by moistening
with acetic acid and exposing to the air, when verdigris is formed,
which is added to a later batch.
It is often advisable to make verdigris from a soluble copper salt; the
process varies somewhat according to the salt employed. From copper
sulphate verdigris is obtained by the action of calcium acetate. When
solutions of these compounds are mixed, calcium sulphate separates
as a white precipitate, whilst a solution of the easily soluble
copper acetate is left. It is only necessary to mix the solutions in
equivalent proportions, separate the liquid from the precipitated
gypsum and evaporate. Gypsum is somewhat soluble in water, so that when
the solution is evaporated a double salt separates out first. This
consists of copper calcium acetate; it may be used as a pigment, but is
of less value than verdigris. It is advisable to prevent the formation
of this double salt, which is accomplished by adding copper sulphate
to a slightly acid solution of calcium acetate until a precipitate
is no longer produced. The solution of copper acetate is boiled for
several hours to effect the separation of the dissolved gypsum; at the
same time the iron contained as impurity in the copper sulphate is
also precipitated. The purified solution of verdigris is concentrated
and allowed to cool, when a further quantity of gypsum separates; the
solution is then evaporated to crystallisation.
If barium salts and lead acetate are cheap, barium acetate can be
obtained by double decomposition. When copper sulphate is added to
the solution of barium acetate so long as a precipitate is formed, a
solution of verdigris is produced, which only requires evaporation
to crystallise. The precipitate is barium sulphate, and can be used
as enamel white. It obstinately retains a quantity of copper, which,
though small, is sufficient to give it a greenish tint. By several
washings with acetic acid this copper is removed; the acid can be used
to obtain fresh quantities of verdigris, so that none is lost, and the
copper retained in the precipitate is regained. The precipitate, after
treatment with acetic acid, only requires thorough washing with water
to produce permanent white, satisfactory in every respect.
Ammonia may also be used in the manufacture of verdigris from copper
sulphate. Strong ammonia is left in contact with copper sulphate in
a covered vessel for several hours; gentle warming accelerates the
formation of copper ammonium sulphate. The liquid has then a fine blue
colour; it should not contain sufficient ammonia to be perceptible by
the smell. It is then gently warmed and acetic acid gradually added.
On continued heating small green crystals separate from the solution,
which is boiled with continual additions of acetic acid in small
quantities until small crystals appear on the surface, when it is
allowed to cool and the crystals are strained off.
”Distilled” verdigris forms deep bluish-green crystals, which
effloresce slightly in the air; they dissolve in 5 parts of boiling
water and in 13·4 parts at 20° C. When the solution is boiled for some
time the tribasic acetate separates; the liquid becomes brown and
acquires an acid reaction.
=German Verdigris= does not differ essentially from ordinary verdigris.
It is a compound of the following basic acetates: 2Cu(C₂H₃O₂)₂.CuO
and Cu(C₂H₃O₂)₂.2CuO. The method is similar to that in which grape
residues are used; where acetic acid is cheap the process is
especially appropriate. In Sweden, where pyroligneous acid is made
in large quantities and copper is also cheap, verdigris is made by
arranging copper plates and flannel in alternate layers. The plates
are frequently turned over and the flannel kept saturated with acetic
acid. The same chemical reactions occur as in the process in which
grape residues are used. When a layer of verdigris has formed on
the copper plates they are taken apart, exposed to the air, and
frequently wetted. The formation of the verdigris is thus completed.
The difference between this process and that adopted in wine-producing
countries lies simply in the use of pure acetic acid; the product is
free from the mechanical impurities introduced by the grape residues.
In properties German or Swedish verdigris is completely identical with
blue verdigris.
CHAPTER XXXI.
CHROMIUM OXIDE.
=Chrome Green.=—Although very different substances are commercially
known as chrome green, this name is usually applied to the very
valuable pigment which consists of pure chromium oxide. There is hardly
another pigment for the preparation of which such varied directions
have been given and whose shade varies so much according to the manner
of production.
The cheapest process is to ignite potassium bichromate with sulphur,
extract the mass with very dilute sulphuric acid and wash the residue.
The chromic acid is reduced by the sulphur; when the mass is treated
with sulphuric acid sulphur dioxide is evolved, potassium sulphide and
sulphate are dissolved, whilst pure chromium oxide remains. The larger
the quantity of sulphur used the paler is the chromium oxide. The
purity of the potassium bichromate has considerable influence on the
shade of the pigment; if iron is present in any quantity a discoloured
product always results. Convenient proportions are: 19 parts of
potassium bichromate and 4 parts of sulphur, which produce 9·33 parts
of chromium oxide. If potassium bichromate free from iron cannot be
obtained, the shade of the product is somewhat improved by treatment
with dilute hydrochloric acid, in which ferric oxide dissolves more
easily than chromium oxide. When the latter has been strongly ignited
it is soluble with very great difficulty.
There are many formulæ for the preparation of chromium oxide by means
of sulphur: in all the above statement holds good, that the more
sulphur the paler the product.
According to A. Casali, a chrome green which satisfies every
requirement is obtained by strongly igniting 1 part of potassium
bichromate with 3 parts of burnt gypsum. After ignition the mass is
boiled with very dilute hydrochloric acid. In this process the chromic
oxide is produced according to the following equation:—
2K₂C₂O₇ + CaSO₄ = 2Cr₂O₃ + 2K₂SO₄ + 2CaO + 3O₂.
On boiling with hydrochloric acid the lime is dissolved; when the
liquid remains distinctly acid after long boiling it is poured off and
the chromium oxide washed with hot water and dried.
In another method ammonium chromate is very gradually heated. At a
certain temperature the salt suddenly becomes incandescent and is
converted into a dark green, almost black, mass which has a very
similar appearance to dry tea-leaves. The green obtained after
washing and powdering is handsomer the lower the temperature of the
decomposition.
Chromium oxide may also be made in the wet way, but the product does
not compare in beauty with that obtained in the dry way. When soda
solution is added to a solution of chrome alum, a greyish green
precipitate of chromium hydroxide is formed; on ignition of the washed
precipitate pure chromium oxide remains.
In a similar manner chromium oxide is produced by precipitating with
soda solution the solution of chromium chloride obtained by adding
hydrochloric acid to a solution of potassium bichromate, and then
alcohol in small quantities, so long as a reaction occurs and the green
liquid becomes deeper in colour.
A handsome and bright chrome green is only obtained when the potassium
bichromate is quite free from iron, a very small quantity of which has
a very harmful effect upon the brightness of the pigment. The author
has found that there is no great difficulty in rendering commercial
potassium bichromate tolerably free from iron by recrystallisation. As
much of the salt is dissolved in boiling water as it will take up, the
boiling solution is quickly filtered and rapidly cooled with continual
stirring; the fine crystalline meal is left on a strainer until no more
liquid filters through, and then washed with a little cold water to
remove the mother liquor. The salt obtained by this simple operation is
of great purity and always produces chrome green of a good shade.
When chrome green contains ferric oxide it shows a blackish colour.
From such chrome green, which has little value, a product of more pure
colour can be obtained with a little care. By treatment with dilute
hydrochloric acid the ferric oxide dissolves, even when it has been
somewhat strongly ignited; chromium oxide loses almost all solubility
in dilute hydrochloric acid after heating at a relatively low
temperature. To facilitate the solution of the ferric oxide, the green
to be treated is finely powdered; it is then covered with a mixture
of equal parts of hydrochloric acid and water. After several days the
mass is strained and washed with pure water until the acid reaction
disappears. Comparative analyses have shown that almost the whole of
the ferric oxide can be removed from chrome green in this manner; the
brightness of the colour is considerably increased. It is, however,
advisable to employ materials free from iron in the manufacture of
chrome green.
Chromium oxide can be obtained as a colour of particular brightness,
according to the process of Leune, by precipitating it very slowly
from a solution in which it is contained in the green modification.
For this purpose a solution of chrome alum is boiled until the violet
colour has changed to green; the green modification of chromium oxide
is now contained in the solution. It is cooled to about 10° C., and
either freshly precipitated alumina or zinc carbonate added, very
gradually and in small quantities. A fine green shade of chromium oxide
separates; after washing and drying it is obtained in a condition in
which it can be used as a pigment.
Chromium oxide can indeed be obtained by this process, but it is not
distinguished by particular beauty; the author has never been able
to obtain, even by using the precipitant in very small quantities,
a chromium oxide surpassing in shade that obtained by the direct
precipitation of a chromium salt with an alkali.
The emerald green described in the following chapter is obtained in a
similar manner by precipitation with zinc oxide.
CHAPTER XXXII.
OTHER GREEN CHROMIUM PIGMENTS.
=Guignet’s Green= is a chromium oxide made in the dry way; it is
obtained by grinding 1 part of potassium bichromate with 3 parts of
pure boric acid and water, drying and heating to a dark red heat
with access of air. The hot mass is brought into water; by boiling
repeatedly with water it is freed from the boric acid which it
obstinately retains. In order to remove the last portions of boric acid
it is necessary to boil with sulphuric acid and then with caustic soda;
this treatment may be omitted for technical purposes, since the small
quantities of boric acid contained in the pigment are not harmful.
Guignet’s green is distinguished by the great resistance it offers to
chemical reagents; it is largely used in painting and calico printing.
Pale shades are obtained by additions of barytes.
=Emerald Green.=—This pigment must not be confounded with the more
important copper compound previously described, to which the name
emerald green is usually applied. It consists of chromium hydroxide
obtained by precipitating a solution of the green modification of a
chromium salt by zinc hydroxide. After careful washing it has a dull
green shade; it is a very durable pigment.
=Chrome Green Lake= is a mixture of chromium oxide with alumina; it
is obtained by precipitating a solution of alum and a chromium salt
by a soda solution. The precipitate, which contains aluminium and
chromium hydroxides, on ignition takes a paler shade in proportion to
the quantity of alumina it contains. For the chromium salt a solution
of potassium bichromate, which has been allowed to stand with sulphuric
acid and alcohol until if has acquired a pure green colour, may be used.
=Turkish Green.=—This pigment, which retains its fine green colour in
artificial light, is prepared in a peculiar manner: 40 parts of alumina
free from iron, 30 parts of cobalt carbonate and 20 parts of chromium
oxide are thoroughly ground in a mortar. The mixture is placed in a
porcelain tube, which is exposed to a strong white heat whilst pure
oxygen is led through. The oxygen may be replaced by air if it is
previously heated and under pressure.
Another recipe for Turkish green is to intimately mix 4 parts of
freshly precipitated alumina with 3 parts of cobalt carbonate and
2 parts of chromium oxide, heat the mixture in a crucible at a
white heat, powder and levigate. Turkish green has a characteristic
bluish-green colour; the shade is inclined to blue or green by
increasing the quantity of cobalt carbonate or chromium oxide.
=Leaf Green= is a pale green, very durable pigment similar to chrome
green lake. It is obtained by igniting mixtures of chromium oxide with
pure aluminium hydrate; the paleness of the shade is in proportion to
the amount of alumina.
=Chromium Phosphate Pigments.=—Several chromium phosphates are used as
pigments; the more important are described here.
=Arnaudan’s Green= is chromium metaphosphate; it is obtained by
intimately mixing 128 parts of neutral ammonium phosphate with 149
parts of potassium bichromate by long grinding, and carefully heating
the mixture at 170° to 180° C., but not higher, until the mass is pure
green. It is then brought into hot water and thoroughly washed; it has
a very handsome green colour, which is not altered in artificial light.
Ammonium arsenate may be used in the place of ammonium phosphate; a
handsomer green is then obtained, which is, however, very poisonous.
=Plessy’s Green= is essentially a chromium phosphate mixed with
variable amounts of chromium oxide and calcium phosphate. It is
obtained by boiling a solution of 1 part of potassium bichromate in 10
parts of water with 3 parts of a solution of acid calcium phosphate and
1 part of sugar, until the whole has become deep green. The chromic
acid is reduced by the sugar, so that the precipitate contains chromium
phosphate, chromium oxide and neutral calcium phosphate.
These two chromium phosphate greens are very stable towards chemical
reagents, and very durable towards atmospheric influences.
=Schnitzer’s Green.=—Thirty-six parts of sodium phosphate are melted
in its water of crystallisation, 15 parts of potassium bichromate
and 14 parts of Rochelle salt are then added. A large dish must be
used for the fusion, since the mass effervesces. The colour changes
gradually from yellow to green. When it is pure green the heating is
stopped, and, after cooling somewhat, as much hydrochloric acid is
added as the mass will absorb; then, after standing some time, it is
washed with cold and finally with boiling water. On account of their
great durability, the chromium phosphate pigments are well adapted for
paperhangings, calico printing and oil painting.
=Chromaventurine= is a glass coloured green by chromium oxide. It is
hardly used as a painters’ colour in the ordinary sense of the term;
it is applied in porcelain painting as an under-glaze colour, and is
largely used for colouring glass.
Chromaventurine is most simply made by the process of Pelouze: 250
parts of quartz sand, 100 parts of soda, 50 parts of calcium carbonate
and 40 parts of potassium bichromate are fused together. The presence
of iron would have a very harmful effect on the shade of the product.
Quartz sand generally contains a small quantity of ferric oxide, which
should be extracted by treatment with strong hydrochloric acid when a
product of the best colour is required. The calcium carbonate should
also, as far as possible, be free from ferric oxide.
=Chrome Blue= (Garnier).—A mixture of 48·62 parts of potassium chromate
with 65 parts of fluorspar and 157 parts of silica is fused in a
crucible lined with coal-dust.
CHAPTER XXXIII.
GREEN COBALT PIGMENTS.
From mixtures of chromium oxide, cobalt carbonate and alumina in
different proportions a series of pigments can be obtained varying
in shade between pale blue and bluish-green. On account of the great
stability of these colours at the highest temperatures they are of
great importance in porcelain painting, for which they are principally
used. It is necessary that the porcelain should be free from iron,
since ferric oxide forms a black compound with chromium oxide, very
small quantities of which would be sufficient to considerably damage
the fineness of the colour.
=Cobalt Green=, which is also known as Rinmann’s green or zinc green,
is a compound of the oxides of cobalt and zinc. It is always produced
when a cobalt compound is ignited with zinc oxide. Rinmann’s green
has not so deep a colour as the poisonous emerald green, but it is
distinguished by extraordinary durability, and deserves to be more
largely used than it is at present. This pigment is most simply made by
precipitating the mixed solutions of a zinc salt and a cobalt salt. It
is also formed by moistening pure zinc oxide with a cobalt solution and
igniting.
In precipitating the mixed solutions of zinc and cobalt salts products
of different shades are obtained, according to the proportions in
which the salts are used. If equivalent quantities are used, an almost
black product is obtained, quite useless as an artists’ colour. The
best result is obtained by mixing intimately pure precipitated cobalt
carbonate with zinc oxide and igniting the mixture; a mixture of 9 to
10 parts of zinc oxide with 1 to 1·5 part of cobalt carbonate gives
colours between pale green and dark green.
Especially fine Rinmann’s green is obtained by igniting cobalt arsenate
with zinc oxide and arsenious acid. The addition of the last-named
substance can only have the object of preventing the temperature from
rising too high, which might injure the beauty of the colour; arsenious
acid is volatile at a fairly low temperature.
Cobalt green is also obtained by evaporating a solution of cobalt
nitrate and zinc nitrate and igniting the residue, or by igniting
a mixture of the sulphates. In the latter case a tolerably high
temperature is necessary in order that the sulphates may be decomposed.
The author has found that a particularly handsome product is obtained
by mixing pure zinc oxide with a dilute solution of cobalt chloride,
drying and then slowly heating to redness in a crucible with a
well-fitting lid. Towards the end of the operation the heat is
considerably increased and maintained for a short time, after which the
mass is rapidly cooled.
CHAPTER XXXIV.
GREEN MANGANESE PIGMENTS.
=Manganese Green, Rosenstiehl’s Green.=—This pigment, which is handsome
but difficult to produce, consists of barium manganate. It can be
obtained by several methods, all of which produce a good green, but
with very unequal properties. Manganese green made from barium nitrate
has little durability; when made from barium hydrate it is more costly,
but very durable.
Barium manganate is most easily obtained by precipitating a boiling
solution of potassium manganate by barium chloride. The almost blue
precipitate becomes nearly white when washed and dried, but when it is
gradually heated on a porcelain plate to a dark red heat it acquires
a fine green colour. The heating must be carefully conducted; if the
temperature rises too high, the colour changes to a dirty greyish
brown, owing to the reduction of the manganic acid.
This pigment is also made by heating 14 parts of manganic oxide, 80
parts of barium nitrate and 6 parts of barytes with access of air until
the desired shade appears. The mass is then ground in a continuous
current of water until it is changed into a very fine powder and
nothing more is dissolved by the water. The best result is obtained
by Rosenstiehl’s process: 4 parts of barium hydrate, 2 parts of
finely-powdered barium nitrate and 0·5 part of artificial manganese
dioxide are rapidly mixed; the mixture is moistened and heated to a
dark red heat. The fused mass is boiled out with water and the residue
dried under a bell jar, under which are dishes of sulphuric acid and
caustic potash, the former of which absorbs the water, whilst the
latter keeps the air free from carbonic acid, which would injure the
shade of the moist substance.
Manganese green is amongst the pigments more recently discovered.
On account of its high price it has found but limited use up to the
present. It may be used in any vehicle, and is distinguished by great
permanence.
In regard to the preparation of this colour by Rosenstiehl’s method,
which of all gives the best results, it should be observed that the
shade largely depends on the quantity of barium hydrate used; the
greater this is the more the shade inclines to blue. If it is desired
to produce a colour of a greener tone than is produced by the fusion,
this can be accomplished by boiling for a very long time with very
weak hydrochloric acid, which extracts a portion of the base from the
compound and produces a deeper shade.
=Böttger’s Barium Green.=—A beautiful green is obtained by the process
given by Böttger, as the author has found. It consists of barium
manganate. The process is, however, somewhat costly, so that the
pigment would only be available for artists’ purposes.
A solution of potassium manganate is first made by gradually adding 2
parts of very pure pyrolusite, finely powdered, to a fused mixture of
2 parts of caustic potash and 1 part of potassium chlorate, bringing
the mass to a low red heat after the introduction of the whole of the
pyrolusite, and finally extracting with water, in which the potassium
manganate dissolves to a fine emerald green solution. This process
is unattended by difficulty if the pyrolusite contains a sufficient
quantity of manganese peroxide and is in a sufficiently fine powder,
which is most important. Potassium manganate is a very unstable
substance. Cold water must be used to dissolve it, and the solution
should not long stand exposed to the air, but should at once be used to
obtain barium manganate.
When the solution of potassium manganate is mixed with a solution of a
barium salt, a handsome violet precipitate immediately forms. This is
washed with water and quickly ground with ¾ to 1 part of its weight of
barium hydrate. The mixture is heated in a copper dish with constant
stirring to a low red heat; the colour changes gradually to a very fine
green. When the mass has reached the proper shade it is treated with
cold water to remove excess of barium hydrate, until the washings show
no trace of alkaline reaction.
=Manganous Oxide= is occasionally used as a green pigment, especially
for painting metal work; it is obtained in the following manner:
Manganese sulphate solution is precipitated by soda solution, and
the manganous carbonate obtained strongly ignited in a crucible. In
order to avoid oxidation of the manganous oxide, which would readily
occur in the process, it is necessary to prevent air from reaching
the substance. With this object the crucible in which the heating is
conducted is covered by another from which the bottom has been removed
and which is filled with coal. The air entering the crucible on cooling
must pass through the layer of glowing coals, by which it is deprived
of oxygen.
=Manganese Blue= is obtained, according to G. Bong, by igniting a
mixture of 3 parts of quartz, 6 parts of soda ash, 5 parts of limestone
and 3 parts of manganese oxide, or of 3 parts of quartz, 8 parts of
barium nitrate and 3 parts of manganese oxide, air being admitted and
reducing gases excluded. All materials must be free from iron. The
quantity of manganese oxide regulates the depth of the colour, but not
its shade; by increasing the soda a greener, by increasing the quartz a
more violet, shade is obtained.
CHAPTER XXXV.
COMPOUNDED GREEN PIGMENTS.
Mixtures of a yellow and a blue pigment produce a green; according as
one or the other predominates colours are obtained inclining to yellow
or blue.
In some cases the mixing can be accomplished in the actual production
of the pigments, so that a green precipitate is directly produced.
This is, however, rarely the case; generally the compound pigments
are obtained by simply mixing the two colours. The mixing can be done
either in the dry or the wet way; colours in the wet state are more
easily mixed than when dry, so that even when dry colours are employed
the mixing is done with the addition of water. Although the mixture
then requires a second drying, this method is still to be recommended,
in the first place, because the mixing can be more quickly done in
consequence of the greater mobility of the mass, and in the second,
because the formation of poisonous dust is completely avoided.
The mixing is generally accomplished by mechanical arrangements. If
dry colours are to be mixed, rotating cylinders may be used; these are
filled with the materials to be mixed, well closed and rotated about
the axis as long as may be necessary. It should be observed that when
colours which have a very different specific gravity, such as chrome
yellow and Prussian blue, are to be mixed, the cylinders must be
rotated for a much longer time than when colours of approximately equal
specific gravity are to be united.
In working in the wet way, which is to be preferred, sufficient water
is added to the colours to make a paste thin enough to be mixed by
spatulas; the mixture is thoroughly stirred and the pulp ground in
ordinary mills until the mixture is quite uniform. Already whilst on
the mills the pulp becomes thicker in consequence of evaporation; when
the grinding is finished it is spread out in thin layers so that it may
dry as quickly as possible. This is important in the case of mixtures
whose constituents have very different specific gravities, otherwise
the heavier pigment may sink to the bottom of the paste and the mass
thus lose its uniformity.
The compound green pigments come into the market under most varied
names, which are often entirely without connection with their chemical
composition. Such names are: mineral green, English green, oil green,
green vermilion; the most common are chrome green and Brunswick green.
It should be noted that these names are more strictly applied to simple
colours previously described.
=Chrome Green= is generally made by mixing deep chrome yellow and
Prussian blue; it can naturally be obtained in all possible shades.
The brightness of this already handsome pigment can be considerably
increased by the addition of a small quantity of indigo carmine. In
this case the mixing is best done by adding a solution of the indigo
carmine to the stiff paste and again sending the mixture through the
mill.
By additions of white substances paler shades of chrome green are
obtained; levigated terra alba or white pipe clay can be advantageously
employed.
=Elsner’s Chrome Green= is obtained by preparing a solution of yellow
prussiate of potash and potassium chromate and another solution of lead
acetate and ferric chloride. The two liquids are mixed with vigorous
stirring; according to the proportions of the materials a blue or a
yellow shade of green is produced.
=Silk Green.=—Forty-one parts of lead nitrate are dissolved in 20 to 30
times the weight of water, the solution is boiled in a copper pan, and,
according to the shade required, 10 to 30 parts of fine Chinese blue
are added. After well stirring, a solution of 10 parts of potassium
bichromate and 1 part of nitric acid is poured into the boiling liquid,
the mixture is again well stirred, the precipitate allowed to settle,
washed and dried. The green pigment obtained in this way has a peculiar
silky lustre, hence the name ”silk green”.
=Natural Green= is a mixture of Guignet’s green with picric acid; it is
used in making artificial flowers instead of emerald green.
=Non-arsenical Green= was proposed as a substitute for emerald green,
which, however, it does not equal in brilliance. It is obtained by
mixing copper blue (basic copper carbonate) with chrome yellow, chalk
and ferric oxide, in somewhat variable proportions. It usually contains
80 to 82 per cent. of the copper compound and 13 to 15 per cent. of
chrome yellow.
* * * * *
In making mixtures of pigments it is to be remembered that chemical
actions may occur in the mixture; colours which act upon one another
should not be mixed: the mixture would contain the cause of its own
destruction. For example, a lead pigment should not be mixed with one
containing sulphur in the form of a sulphide or sulphate. By following
this important rule the number of pigments which may be mixed together
is considerably diminished; the advantage is that durable colours are
produced, which do not change in a short time to an unrecognisable
shade.
CHAPTER XXXVI.
VIOLET MINERAL PIGMENTS.
=Chromic Chloride.=—The violet modification of chromic chloride is
a compound which is little used, but deserves the highest attention
on account of its durability and beauty of shade. Up to the present
chromic chloride has been almost exclusively used for colouring paper
hangings under the name of chrome bronze, which it has received in
consequence of its property of imparting a peculiar metallic lustre
to paper upon which it is rubbed. It is also possible to fix this
substance upon fabrics, which thus acquire a similar metallic lustre.
Pure chromic chloride forms beautiful peach-blossom coloured scales,
which can only be obtained by treating chromium oxide in a certain
manner with chlorine. The pure substance is practically insoluble in
water, but if the water contains but a trace of chromous chloride
the chromic chloride readily dissolves to a green solution. In the
preparation of this compound it is necessary to avoid the least trace
of chromous chloride, otherwise the product will begin to change when
it comes into contact with moist air.
Pure chromic chloride is obtained by proceeding according to the method
first given by Wöhler: the simple apparatus necessary is depicted in
Fig. 29. Pure chromic oxide is first made by any suitable process;
this is made into a paste with charcoal, starch paste and water, and
formed into small balls which are heated in a crucible to a white heat.
The residual intimate mixture of chromic oxide and carbon is loosely
placed in a crucible which stands in a furnace; a porcelain tube is
cemented into the bottom of the crucible, it passes through the ashpit
to connect with a chlorine apparatus. Upon the crucible another larger
one is placed, which has a small opening in the bottom and serves as
a receiver for the sublimed chromic chloride. The heating and current
of chlorine are started at the same time, the fire is regulated so
that the lower crucible glows brightly. This is continued for an hour,
during which a rapid current of chlorine must pass into the crucible;
the fire is then removed and a slow current of chlorine passed through
the apparatus until it is quite cold.
[Illustration: FIG. 29.]
If the operation has succeeded the lower crucible is found empty and
the interior of the upper covered with the magnificent peach-blossom
crystals of chromic chloride. A small quantity of the chromic chloride
is tested as to its behaviour towards water; if it remains unaltered
the whole may be washed, but if it dissolves to a green solution
it must be again ignited in a current of chlorine. The washing is
necessary to remove small quantities of aluminium chloride formed by
the action of chlorine on the clay of the crucible.
=Manganese Violet, or Nuremberg Violet=, consists of manganic
phosphate. It is obtained by fusing glacial phosphoric acid with pure
pyrolusite, boiling the melt with ammonium carbonate, filtering the
solution, evaporating to dryness, and again fusing the residue. After
boiling with water this forms a handsome violet powder; it is suitable
for use as a very durable artists’ colour.
Shades of this pigment inclining to blue are obtained when a ferric
compound is added in the first fusion; the more iron ore is used the
more intense is the blue tone.
=Tin Violet or Mineral Lake= is obtained as a violet mass by igniting
an intimate mixture of 100 parts of tin dioxide with 2 parts of chromic
oxide. This pigment is completely permanent in air; it is suitable for
printing paper hangings and for colouring faience.
=Copper Violet, Guyard’s Violet.=—According to J. Depierre, this
pigment is obtained by precipitating a solution of copper ammonium
sulphate with potassium ferrocyanide, washing and drying the
precipitate and heating in a porcelain dish. At 170° C. cyanogen and
ammonia are evolved, the mass takes up oxygen and becomes violet; it
then resists the action of dilute acids and alkalis, and as a pigment
has great covering power. On heating to 200° C. it turns blue, and at
240° to 250° C. becomes greenish.
CHAPTER XXXVII.
BROWN MINERAL PIGMENTS.
=Lead Brown.=—When red lead is treated with nitric acid, lead monoxide
is dissolved, whilst deep brown lead peroxide remains. When the action
of the nitric acid is finished the residue is well washed and dried.
Lead peroxide is now extensively used for lucifer matches; it readily
gives up oxygen on heating, and thus accelerates the ignition of the
composition. Brown match-heads owe their colour to lead peroxide.
=Manganese Brown= consists of manganic oxide; it occurs in nature, but
seldom in a state of sufficient purity to be used as a pigment; it is,
therefore, generally made artificially. The process is very simple.
A solution of manganese sulphate is precipitated by caustic soda
solution, the manganous hydroxide produced is quickly changed by the
action of the air into manganic hydroxide. The colour is most rapidly
developed when the precipitate is spread out in thin layers; it is well
washed after it has changed to brown.
=Pyrolusite Brown= is manganese peroxide in a state of fine division.
It can be made from the residual liquors of the preparation of chlorine
by adding sodium hypochlorite. A brown precipitate results, which is
kept in contact with the liquid until it no longer changes in colour.
It is then washed with water slightly acidified with sulphuric acid,
and finally with pure water. When finely powdered, manganese peroxide
has a very fine brown colour. It is quite unaltered by the air and
thus, in consideration of its cheapness, deserves a much greater use
than it has yet found.
=Prussian Brown.=—When Prussian blue is heated in air it soon begins to
glow, and is converted into a brown mass, the shade of which depends
on the amount of impurity in the Prussian blue. It is desirable to use
Prussian blue quite free from impurities, so that a brown of the same
shade is always obtained. The brown obtained can be shaded by additions
of indifferent substances.
=Iron Brown.=—By igniting a mixture of 100 parts of finely levigated
natural yellow ochre with 5 parts of common salt a brown product is
obtained, which is pale or deep according to the temperature used. It
is a cheap and durable colour.
=Copper Brown.=—According to Cartheuser solutions of 2 parts of copper
sulphate and 1 part of Epsom salts are mixed, and a strong solution of
potassium carbonate gradually added so long as a precipitate forms. The
precipitate is washed, dried and ignited, when copper brown is obtained
as a brown powder of great permanence in air.
According to Schreger solutions of 2 parts of copper sulphate, 2 parts
of alum and 0·5 to 1 part of ferrous sulphate are mixed, potassium
carbonate solution added, the precipitate dried and ignited. The
redness of the shade is proportional to the quantity of ferrous
sulphate.
=Hatchett Brown= is copper potassium ferrocyanide. It is obtained by
precipitating a soluble copper salt with potassium ferrocyanide. Copper
salts behave towards potassium ferrocyanide in the same manner as iron
salts; different compounds result according as the ferrocyanide or the
copper salt is in excess. Hatchett brown is somewhat largely used for
painting wood.
=Chrome Brown.=—When solutions of potassium chromate and a copper
salt are mixed a precipitate of the composition CuCrO₄.2CuO.2H₂O is
obtained. On drying it acquires a fine brown colour; it forms a very
stable pigment.
Chrome brown can also be made by dissolving 10 parts of potassium
bichromate in 20 parts of water, heating to boiling, adding 13·5 parts
of solid copper chloride and then gradually a boiling solution of 10
parts of soda in 20 parts of water, until effervescence no longer takes
place. On cooling, chrome brown separates as a soft brown precipitate.
=Cobalt Brown= is a very durable compound pigment of a pleasing shade.
It is obtained in various hues by adding ferric oxide to the mixture
of alumina and a cobalt salt used for making cobalt blue. The process
may also be carried out by igniting ammonia alum with cobalt sulphate
and ferrous sulphate. The temperature required in this case to obtain a
bright colour is very high, and must be maintained for a long time to
decompose the whole of the ferrous sulphate.
The pigment can be obtained at a far lower temperature when ferric
chloride is used in place of ferrous sulphate. The mixture is made by
grinding together 5 parts of cobalt hydroxide and 25 parts of ammonia
alum, then adding a solution of ferric chloride, rapidly drying the
whole to a powder, and whilst still hot filling it into the crucible
in which the ignition is performed. When small quantities of ferric
chloride are used chocolate brown shades inclining to violet are
produced; the larger the quantity of the iron compound the more pure is
the brown.
It has been stated that it is important, in the preparation of cobalt
pigments, to prevent the entry of fire gases to the heated mixture;
the reducing action of the gases would materially damage the beauty
of the colour. It has been proposed to place a small quantity of
mercuric oxide at the bottom of the crucible. This would decompose
on heating, and create an atmosphere of pure oxygen in the crucible.
Apart from the cost of the mercuric oxide, which is considerable, it
would only be effective at the commencement of the operation, since it
is completely decomposed at a low red heat. The author has found an
addition of pyrolusite considerably more effective. This may be applied
by spreading a small quantity, about 5 per cent. of the mixture to be
heated, on the bottom of the crucible and covering it with powdered
glass, upon which the colour mixture is placed. An alternative course
is to place the crucible in a second, filling the space between the
crucibles with powdered pyrolusite. At a strong red heat oxygen is
slowly evolved from the pyrolusite; the entry of fire gases into the
crucible is thus prevented. In using the first method the crucible
is frequently spoilt, whilst in the second method the surrounding
pyrolusite protects it, so that it can be used again.
CHAPTER XXXVIII.
BROWN DECOMPOSITION PRODUCTS.
=Humins.=—Wood decomposes, like many other substances of organic
origin, to form compounds of a deep brown colour, which are known as
humins, on account of their occurrence in the humus of tilled soil. The
numerous compounds found in humus have all a deep brown colour, which,
together with their great stability, makes them very suitable for use
as pigments.
By various methods substances can be made so rich in humins that they
can be used as pigments. For this purpose sugar, starch, young plant
fibres and beet-sugar molasses may be used, which are converted into
humins with great rapidity when they are heated with water. In this
way the author has obtained handsome colours from sawdust. These
humins are most easily made by the following process: Thick beet-sugar
molasses are cautiously heated with 5 per cent. of caustic soda in
a very capacious iron pan. The already dark mass soon becomes quite
black when seen in thick layers, and evolves a considerable quantity
of gas; if the heating is too rapid the soft mass may boil over out
of a very large vessel. When the evolution of gas diminishes the heat
is increased and the mass frequently stirred. With some practice it
is possible to tell when the action is finished from the smell, which
is at first sweetish but later of a characteristic nature. At first
tests should be repeatedly taken from the mass; these are considerably
diluted with water until the liquid begins to be transparent. When two
tests taken at an interval show no difference of colour the heating is
stopped. The whole mass is then poured into water in order to dilute
the alkali, so that it will not destroy the strainer; the soft mass,
which in the wet state appears quite black, is washed with water until
the washings are neutral. The humin brown made in this way, when ground
with oil or gum solution, produces a very handsome brown of great
covering power and warmth of shade, also distinguished by complete
indifference towards chemical reagents.
The pigments we have designated humins contain a very large quantity
of carbon, to which they owe their dark colour. When peat or lignite
is treated with caustic soda in a similar manner, good shades of brown
are obtained; they are, however, surpassed in beauty by the brown
from molasses. A handsome but costly brown is obtained when crude
spirits of wine are heated with fuming sulphuric acid. Equal volumes
of alcohol and sulphuric acid are used; the mixture is heated in a
retort connected to a condenser, which is required on account of the
combustible vapours evolved from the mixture. When the mass is quite
black the heat is withdrawn; the residue is diluted with water, and
soda solution added so long as effervescence occurs. On filtering a
very soft brown powder is left, which forms a very handsome and durable
pigment.
=Bistre.=—When soot is produced at a very low temperature it is very
lustrous, and, in addition to carbon, contains a notable quantity
of the products of dry distillation. When this soot is powdered and
treated with water the latter substances are dissolved; boiling water
should be used. When water is no longer coloured the soot is suspended
in a large quantity of water and subjected to a process of levigation.
The fine powder obtained by repeated levigation has, when dry, an ugly
brown colour, but when ground it acquires an extremely warm shade.
CHAPTER XXXIX.
BLACK PIGMENTS.
Carbon occurs in nature in many different forms—the diamond, graphite
(black lead), and purified lamp black are, from the chemical point of
view, one and the same substance, namely, carbon. In colour making the
non-crystalline form of carbon, which is pure black, is alone used;
almost all black pigments used in painting are composed of tolerably
pure carbon. In whatever way and from whatever materials carbon is made
for use as a pigment, the manufacturer must always endeavour to obtain
it as pure as possible, and in a condition of the finest division; the
depth of colour and the covering power depend on these two conditions.
Carbon only shows a pure black colour when it is pure; if it contains
relatively small quantities of impurities, it has a more or less brown
shade.
At first sight it appears to be a very simple matter to obtain black
pigments from organic materials; it is simply necessary to expose them
in the absence of air to a temperature high enough to decompose them,
carbon is then left as a residue. In spite of the apparent simplicity
of this operation there are many difficulties. The preparation of good
black pigments demands considerable practice.
There are two methods by which carbon can be made for use as a pigment.
One has been indicated, the heating of organic materials in the absence
of air, _i.e._, their dry distillation; the second, which produces the
best qualities of black, consists in burning substances very rich in
carbon with a very small supply of air. The product of this process,
commonly known as soot, is very different in external appearance from
carbon made by dry distillation. The latter forms an easily powdered
mass, which only acquires lustre by grinding with oil, whilst soot
consists generally of very light flocks, which, in consequence of their
greasy nature, exhibit a peculiar velvety lustre.
In commerce there are many qualities of black, the names of which are
generally chosen quite arbitrarily. The so-called ivory black is an
example of this. At some period it was observed that ivory produced a
very fine black when carbonised; this black was made for a long time
from refuse ivory. When it was found that a similar black could be
made quite as well from much cheaper materials, it was no longer made
from ivory. The name, however, remains in trade to the present day: it
has come to be regarded as a description of quality. By the name of
ivory black a fine black pigment is understood; it is immaterial to the
consumer whether it is made from ivory or not: to him the quality of
the pigment, but not its source, is important.
According to the method of production, the black pigments can be
divided into charcoal blacks and soot blacks.
CHARCOAL BLACKS.
This term is applied to the pigments obtained by heating organic
substances in the absence of air. The charcoal blacks have two valuable
properties: they are easily made, and they exhibit a pure black shade
which it is far more difficult to obtain with the soot blacks. It is
very difficult to convert these pigments into the requisite state
of fine division. They cannot be levigated on account of their low
specific gravity, which causes them to settle very slowly in water.
It only remains to convert the charcoal into a very soft powder
by grinding, but even then the pigment has but little covering
power, because it is not possible to destroy the organic structure
of the substance carbonised. When the finest charcoal powder, made
by carbonising any organic substance, is examined under a powerful
microscope the structure of the particles is at once recognised, so
that it is almost always possible to decide whether the charcoal is
of plant or animal origin. A very careful examination may show what
particular part of the plant has been carbonised. If a manufacturer
succeeded in producing by direct carbonisation a black with the
covering power of a soot black, that black would soon be the only one
found in commerce.
The charcoal blacks come on the market under various names—ivory black,
bone black, vine black, Frankfort black, Paris black, etc. The ivory
blacks are the best quality, but recently true vine black, _i.e._, made
from grape residues, has come into use.
=True Charcoal Black.=—In charcoal-burning wood is burned in great
piles with restricted air supply; the greater part of the carbon
contained in the wood remains behind as charcoal, which is used for
fuel. The charcoal made from hard wood, such as maple or beech, is not
well suited for pigments; the lighter and more porous the wood, the
more pure is generally the shade of the charcoal, and the more easily
it can be ground. When, therefore, charcoal is to be used as a pigment
it should be made from wood of a porous nature; the wood of the lime,
black-alder and spindle tree is particularly adapted for this purpose.
Spent tan-bark is a very cheap, and at the same time suitable material
for this purpose. It generally consists of oak bark, and has lost the
greater part of the salts it contained by long contact with water;
also the woody substance of the bark has suffered a change which is
favourable to carbonisation. This is especially the case when the bark
has been stored for some time; a considerable quantity of the humins
previously mentioned has formed in it, and these are easily decomposed
at a low temperature.
The charcoal, however obtained, is ground to a soft powder. When it has
reached the proper degree of fineness it should be repeatedly washed
with water to remove the salts. When instead of pure water a very
dilute acid, such as hydrochloric, is used, practically all the salts
dissolve, and the residue consists of nearly pure carbon.
=Vine Black.=—In wine-producing countries a good and cheap black can be
made from the residues of the wine manufacture; this is the so-called
vine black. Either the pressed grapes or the lees separated in the
fermenting vessels may be used.
_Vine Black from Wine Lees._—The lees always contain a considerable
quantity of liquid, they must be thoroughly dried before they are
carbonised; this is most simply done by spreading out the pasty mass in
a thin layer, and exposing it to a temperature of about 100° to 120° C.
In drying the volume considerably diminishes. The lees are changed into
a brown mass which is easily powdered; it is packed into barrels while
still warm, and can be kept for a considerable time without alteration.
Fresh lees can be kept but a short time; they are quickly destroyed by
a rapid fermentation.
The dried lees are carbonised in iron tubes, protected from the
fire by a thin coating of clay mixed with chopped hair so that the
coat more readily adheres to the iron. Old stove pipes or cast-iron
gas or water pipes may be used. The tubes are about one metre long;
they are closed with well-fitting covers, in one of which is a small
opening through which the gases produced on heating can escape. These
covers are fastened on air-tight with clay. The process begins by
affixing the unperforated lid, and packing with a wooden rammer the
dry lees as tightly as possible into the tube; the second lid is then
luted in place. The tubes are placed near one another in a suitable
furnace and first slowly heated at the back, _i.e._, the end closed
by the unperforated cover. At the commencement of the operation heat
must be gradually applied. With too large a fire the products of
dry distillation might be evolved in sufficient quantity to force
the covers from the tube; air would then enter and the contents be
burnt. When the hinder part of the tube is red-hot, the heating is
conducted forward, and finally the whole length of the tube is brought
to a good red heat. The termination of the operation is shown by the
disappearance of the pointed flame of the products of distillation
which protrudes from the opening in the cover of the tube. When this
occurs, the fires are drawn; the tubes are left to cool in the furnace
until they can be taken out by the hands protected by wet cloths. The
covers are at once taken off and the hot contents emptied into a large
tub filled with water, which is thus soon raised almost to boiling
point. The time required for washing is thus considerably shortened.
The charcoal falls from the tubes in lumps, which soon fall to a fine
powder in the water. Wine lees consist of a mixture of yeast cells and
small crystals of tartar (a mixture of the tartrates of potassium and
calcium). On ignition these salts are converted into carbonates, by
which the particles of carbon are united. Potassium carbonate is very
readily soluble in water; in contact with the warm water it dissolves
in a very short time, the carbon particles then fall apart.
When the charcoal has settled to the bottom of the vessel the liquid
is drawn off. It can be utilised in a colour works, since it is a
fairly strong solution of potassium carbonate. The charcoal is mixed
with calcium carbonate, arising from the decomposition of the calcium
tartrate, and with the other insoluble salts which yeast ashes contain
in some quantity. These salts would prevent the proper grinding of the
charcoal; they are therefore removed by treatment with hydrochloric
acid after the water has been drawn off as completely as possible.
A small quantity of hydrochloric acid, diluted with an equal volume
of water, is poured over the charcoal, an effervescence of carbonic
acid follows, the easily soluble calcium chloride is formed and the
remaining salts are also dissolved.
The charcoal made in this way is very pure. After washing, grinding and
drying, it forms a pigment whose shade leaves nothing to be desired.
The drying must be conducted at a low temperature; charcoal in such a
fine state of division is very easily inflammable.
_Vine Black from Pressed Grapes._—The material contains the stems
and pressed remains of the grapes after the must has been expressed.
After-wine, spirits or vinegar can be obtained before it is used for
vine black. The process is exactly the same as for wine lees. The
charcoal taken from the tubes has rather more coherence than that made
from lees and must be ground. The black is a very useful pigment, but
is inferior to the black from lees. In regard to the latter, it should
be stated that it is a particularly good black pigment, and when finely
ground is as well suited for the preparation of the finest blacks, such
as are used in copper-plate printing, as the far more costly soot black.
The black from grape residues, or from grapes themselves (the poor
grapes removed in pruning the vine are used), can be employed with
advantage for many purposes for which the best black is not necessary.
The greater number of the pigments sold under the names of Frankfort
and Paris black consist of this substance.
=Bone Black or Ivory Black.=—Bone black, for of ivory black only the
name now exists, is distinguished by a peculiar quality which it owes
to the structure of the raw material from which it is made. This raw
material is animal bones, which largely consist of incombustible
materials (bone ash); these form a delicate framework whose interstices
are filled by organic matter. When bones are carbonised, the carbon
resulting from the decomposition of the organic matter is deposited on
the incombustible framework of bone ash and thus acquires a very great
surface.
Carbon is well known to possess very powerful absorptive properties,
which are especially developed in bone black, in consequence of its
fine division. The use of granular bone black (known as ”char”) in
sugar works, and generally for decolourising liquids, is due to the
peculiar state of division of the charcoal. For these purposes bone
black is used in enormous quantities; it is made in special works.
It does not fall within the scope of this work to give a detailed
description of the manufacture of bone black, and we must here restrict
ourselves to matters of special interest to the colour maker.
The bones are coarsely powdered and freed from fat by boiling; they are
then generally carbonised in iron retorts, a number of which are built
in a furnace in a vertical position; a valve at the bottom serves to
empty the retorts. In a well arranged apparatus the products of the dry
distillation of the bones, chiefly consisting of ammonium carbonate,
are collected. The retorts are carefully closed so that air cannot
enter, otherwise a portion of the carbon would burn and the black would
acquire a grey shade instead of the pure black which it should possess.
Bone black makers who work for sugar factories carbonise by preference
the densest bones; these produce a black of the most powerful
decolourising properties. This property is of no advantage to the
colour maker, who simply requires a very dense black. The bones
of young animals, and especially certain bones, contain a larger
proportion of cartilage than the hollow bones which produce the best
”char”. In making bone black to be used as a pigment just those bones
should be chosen which are of less value for ”char”.
On the small scale, bone black can be made by carbonising in crucibles;
these hold about 16 kilogrammes of bones, they have a projecting rim,
so that when one is placed upon the other it serves as a lid for the
first. Piles of these pots are formed, the top one being covered by a
well-fitting lid. The piles are heated in a furnace in such a manner
that the flames can freely circulate between them. At first a small
fire is applied; as soon as dry distillation of the bones begins, which
is recognised by pale white flames at the rims of the crucibles, the
fire is damped, because the burning products of distillation produce so
much heat that the crucibles are soon at a good red heat.
When the flames disappear the fire is maintained for about fifteen
minutes longer, and when the crucibles have cooled to some extent
they are taken out of the furnace and immediately emptied into a
sheet-iron cylinder, in which the charcoal remains until quite cold.
If the black comes in contact with air whilst still hot a portion of
the carbon burns and the product has little value either as a pigment
or for decolourising purposes. When quite cold the black is ground and
levigated. The bone ash it contains makes these operations easy. Bone
black contains at the most 12 to 13 per cent. of carbon; the remainder
consists of bone ash and water absorbed by the hygroscopic carbon from
the air.
Bone black which has been partially burnt in the process has a greyish
tinge; it may also have an ugly shade of brown: this is the case when
it has not been heated to a sufficiently high temperature, so that
it still contains some quantity of organic matter. Such black can be
made usable by again heating, but it would always be desirable to test
a small portion before the whole was ground and levigated; a uniform
heating of the finely-powdered black would be attended with difficulty.
Finely ground bone black has numerous uses as a pigment; by a simple
process it can be converted into almost pure carbon, which can be used
as an excellent black pigment for all purposes for which blacks are
employed. Bone black consists of bone ash upon which fine particles
of carbon are deposited. Bone ash is easily soluble in hydrochloric
acid; if finely ground bone black is treated with this acid and the
residue washed with water until the washings are neutral, a residue
of extremely soft and pure carbon is obtained, which has a deep black
colour and, in consequence of its fine division, very great covering
power.
CHAPTER XL.
MANUFACTURE OF SOOT PIGMENTS.
The soot which is formed in the incomplete combustion of organic
substances containing a large proportion of carbon is a mixture of
different substances, of which carbon is the chief; in addition to
this, we find in soot almost all the products which result by the
dry distillation of the substance from which it is formed. Soot from
hard wood contains different compounds to soot from soft wood; again,
rosin soot is of a different nature to that obtained in the incomplete
combustion of fats. We can thus define soot as very finely divided
carbon, mixed with the products of dry distillation.
The soot of hard woods, which contain little or no resin, has a deep
black, though dull hue; it is a gritty powder, and has little value as
a pigment. Wood containing much resin, such as the wood of the pine,
rosin, fish oil, asphaltum, in short, all bodies which are at the same
time easily combustible and rich in carbon, produce on the contrary a
handsome, glistening soot, which forms a valuable pigment.
In addition to this difference in composition, soot from different
sources differs also in the size of its particles. Soot forms light
flocks, which adhere to projections in the flues through which the
products of combustion pass; the larger the flocks the sooner they are
deposited, the smaller they are the longer they remain suspended. The
finest particles of soot are called ”flying soot,” which is very highly
prized on account of its fine division.
The manufacture of soot blacks is a very important industry: black
printing ink, which is used in such enormous quantities, is made from a
soot black; in addition, all the best black paints and lacquers. Soot
black was formerly made in the most primitive manner, and is still, to
some extent, as will be seen from the account of the manufacture of
rosin black. The process used for printing blacks is more rational, but
is still capable of great improvements. The principles of a rational
manufacture of soot blacks will be briefly indicated.
=The Manufacture of Soot Blacks on the Large Scale.=—The principle
of the arrangements necessary for making soot blacks is very simple.
An apparatus is required in which substances very rich in carbon can
be burnt at the lowest possible temperature; this apparatus must be
connected with suitable arrangements for retaining the soot carried
away with the products of combustion. The soot works as at present
arranged are developments of the crude arrangements still used in
districts in which there is an abundant supply of pine wood containing
much resin. The apparatus used in such localities consists of a low
masonry flue connected with a long pipe built of wooden boards. In
order to give this pipe a rough surface upon which the soot can
readily deposit, it is lined in several places with coarse linen, to
the projecting fibres of which the soot adheres. In the flue the very
resiniferous wood is burnt, especially the roots of pines, which are
very rich in resin; these burn with an unrestricted air supply with a
bright flame, but when the air is restricted, they give off a large
quantity of a very heavy smoke. The operation is commenced by first
making a good fire of dry split wood, the object of which is to heat
the flue and thus prevent the deposition of soot in it in the later
part of the process. If a deposit of soot formed in the flue it might
take fire, the fire would then spread further into the wooden flue and
a considerable loss of soot would occur. When the stonework has become
so hot that deposition of soot in it is no longer to be feared, the
materials are introduced from which the soot is to be made. As has been
said, pine roots are generally used, the chips of pine wood are also
used in some districts, and in general such combustible materials as
produce a large quantity of smoke.
The combustion in the flue must be conducted with care, it should
proceed at the lowest possible temperature, but this should not sink
below a certain minimum. If the fire is too strong the greater portion
of the carbon is burnt, which would otherwise be obtained as soot; the
yield of soot is very small, and generally only ”dust soot” would be
obtained, without any quantity of ”flying soot”. On the other hand, if
too little air enters, so that the combustion takes place at too low
a temperature, a large yield of soot is obtained, but it is of poor
quality. Soot obtained by combustion at too low temperatures has not a
pure black but a perceptibly brown colour; it has not the flocculent
nature of the best product, a small weight of which occupies a very
large volume, but is greasy and has a high specific gravity. The
lower the temperature used in producing soot black, the further is
the chemical change removed from that of ordinary combustion, and the
nearer to that of dry distillation. Soot produced with an insufficient
supply of air contains a considerable quantity of liquid and solid
products of dry distillation, which give it a brown colour and the
above-mentioned greasy nature.
In many soot works the air supply is regulated in a most primitive
manner: the workman places against the openings by which air is
admitted to the burning materials a larger or smaller number of bricks
according as the combustion appears to be too rapid or too slow.
Unfortunately there is no clear sign to indicate the temperature most
favourable for the production of the greatest quantity of soot, the
appearance of the flame alone can be taken as a guide. If the flame
appears pure white and very luminous and shows at its end no thick
black smoke the combustion is very complete, and but a very small yield
of soot is to be expected. On the other hand, if the flame continually
threatens to go out the air supply is too small and a liberal amount of
soot will be formed, but mixed with a large quantity of the products
of dry distillation. As far as it can be described in words the flame
should appear as follows: The colour should be a murky red, similar to
that of the flame of a bad tallow candle; in shape the flame should be
a long drawn out tongue, from the point of which a thick black smoke is
clearly seen. The soot deposits in the long board flues in the form of
flocks or dust. The properties of the soot which is deposited in the
different parts of the long flue vary according to the distance from
the place of combustion, near to which a good black soot is deposited,
requiring, however, long grinding with oil or gum solution to form a
good paint. At a greater distance the soft and very fine ”flying soot”
is deposited; it is the most pure black and is regarded as the best
quality. The soot deposited farther on is more and more brown, and
has a more greasy nature the greater the distance from the place of
combustion.
The flue for the reception of the soot must be made so long that hardly
any smoke is perceptible at the end, which it is convenient to connect
with a chimney with a good draught, regulated by a damper. In this case
the combustion and the speed at which the products enter the flues are
twice regulated.
The material of which the flues are constructed through which the
products of combustion are led influences the manner in which the soot
is deposited; the portions nearest to the grate must be of stonework,
but when the smoke has cooled to a certain extent different materials
can be used in addition to wood; flues made of sacking stretched over
laths are used. The fine flying soot adheres to the roughnesses of the
coarse sacking, and is easily loosened by striking the wall of the flue.
As we have said, the arrangements of most soot works are very
primitive; they obtain only a fraction of the quantity of soot which
they could produce by a proper regulation of the draught in the
combustion chamber and in the flue in which the soot deposits. We
shall now briefly describe the conditions which should be regarded in
constructing a soot works; these conditions have not been found to be
observed in any works we have seen, in this branch of chemical industry
so-called practical experience is alone regarded, and consequently the
”practical” soot burner loses large sums, literally up the chimney. A
black works can be properly designed by any one who knows sufficient
chemistry to understand the process of combustion. Of this most
educated men have some understanding, but the practical soot burner
appears to have but hazy ideas on the subject, for one occasionally
finds the arrangements for making soot in direct opposition to the
proper disposition.
For the sake of the uniformity of the product and of safety against
fire, the flues in which the soot is deposited should be entirely of
masonry; the joints of the bricks should be smoothly cemented over,
so that soot cannot collect in quantity in them. The end of this flue
should be connected with a high chimney provided at the top with a
well-fitting damper, so that the draught in flues and chimney can be
regulated at will or completely stopped. Such an arrangement, perhaps
somewhat costly, has many important advantages: it is fire-proof,
and when once warm remains so for a long time, since bricks are bad
conductors of heat. When the flue is hot no water condenses in it; all
the water formed in the combustion remains in the form of vapour, and
is carried away by the chimney. A further advantage is that it is not
often necessary to enter the flue to collect the soot; burning may be
continued for a long time, and a large quantity of soot taken at once
from the flues or soot chambers.
The soot collects on the walls of the chambers in flocks, which finally
become so heavy that they fall off and collect on the floor. The entry
to the soot chambers should be through a single iron door, tightly
closed whilst the chambers are in use, and cemented round. If this door
does not fit air-tight the combustion cannot be exactly regulated by
the damper on the chimney. The soot is removed from the chambers by a
workman, who sweeps off with a soft brush into a sheet-iron vessel the
soot adhering to the walls and lying on the ground. It is extremely
important that soot and nothing else should be collected; the brush
used for loosening the soot should be so soft that it does not rub off
mortar from the brickwork; the workman’s shoes should be provided with
felt soles, so that no particles are loosened from the floor of the
chamber and mixed with the soot. The admixture of the smallest quantity
of sand would be extremely harmful in the ensuing grinding of the soot;
the mills would be damaged.
The flues for collecting the soot in well arranged works are very
similar, but the apparatus used for burning the materials which produce
the soot varies greatly according to the nature of the material. Some
quantity of the soot black used in the arts is still made by burning
pine roots and chips, but for the finer qualities American rosin
is largely employed. Earth-wax or ozokerite and the hydrocarbons
obtained from petroleum and in the distillation of shale are materials
frequently used in making soot blacks of very good quality. For
the finest qualities, such as are used for fine printing inks,
copper-plate inks and black lacquers, soot obtained by burning fish
oils or cheap fatty oils is most commonly used. The great differences
in the physical nature of these materials demand the use of different
apparatus for their combustion. The space allotted to soot blacks in
this work would be far exceeded if the construction of all the forms of
apparatus were described; the most important only will be given.
[Illustration: FIG. 30.]
When rosin is the raw material, the combustion can be conducted in flat
spoon-shaped vessels placed before a narrow opening into the flue. Fig.
30 shows an arrangement very successful in practice. The spoon-shaped
iron vessel, G, stands in a second, G₁, which is filled with water:
this prevents the fused rosin from becoming too hot. If the temperature
in G rose too high, dry distillation would take place along with the
combustion of the rosin, and the soot would be largely contaminated
by the products of this distillation. This may proceed so far that in
place of the fine flocks of soot a greasy mass is deposited in the
flues, consisting of a mixture of soot with products of distillation,
from which the soot could be obtained only with great difficulty. The
soot and gaseous products of combustion pass through the opening, O,
into the flues, R R. This opening is only several centimetres wide,
but is nearly as long as the combustion vessel. Above the vessel,
G, is a movable iron cover, D, in which are slides by which the air
supply is regulated. The cover is only taken off when fresh material is
introduced.
The air supply cannot be sufficiently regulated by the slides in the
cover; these must be used in conjunction with the chimney damper. The
combustion is observed through a thick glass plate let into the cover.
At the commencement of the operation slides and damper are completely
opened. When the chimney is seen to emit a thick black smoke the flues
are filled with the products of combustion, and the speed with which
they pass through the flues must be regulated. The current of air is
decreased until only a little visible smoke escapes from the chimney,
and the flame is no longer white, but a murky red. It should be noted
that the first soot obtained from a new works is never of the best
quality, the production of this is only gradually attained. The cause
of this is that the new masonry is damp and gives up water to the hot
gases, so that they are cooled and their velocity disturbed; the soot
will also be damp. Thus a greasy soot is obtained. It is of very little
use to allow the installation to remain unused for some months after it
is completed; the brickwork would only dry superficially, and when it
was first heated the presence of the water would become evident.
In order to dry the whole erection to such an extent that the moisture
from the brickwork has no effect on the regular course of the
operation, it is advisable to commence with materials of little value
and to allow a portion of them to be lost by the use of a stronger
draught than is generally used, so that the flues can be freed from
all moisture as soon as possible. This applies equally to all kinds of
arrangements for this purpose.
[Illustration: FIG. 31.]
Lamps are used to burn liquid fats and mineral oils. These lamps
naturally have a different construction to those used for lighting,
which are constructed with the object of burning all the carbon in
the oil, so that the temperature may rise as high as possible and the
carbon burn at a high white heat. The lamps used in the soot black
manufacture are designed to burn only as much carbon as is absolutely
necessary to maintain the flame, at the same time the temperature of
the flame must be kept low, so that no portion of the soot is again
burnt. These lamps have flat burners and are enclosed in a sheet-iron
casing provided with an air regulator, which must work very accurately,
otherwise air will enter between the joints and the working of the
regulator will be deceptive. So that the material to be burnt shall
not be too strongly heated, which would be accompanied by great loss
when mineral oil is used, the reservoir should be placed outside the
iron casing which surrounds the burner.
Fig. 31 shows the construction of a soot lamp. The flat burner, B,
is placed in the cylindrical sheet-iron mantle, H, which is bent
above at not too sharp an angle. The products of combustion are led
into a chamber, K, from which they pass into the flues where the
soot is deposited. The form of the upper portion of the cylinder is
of importance; if this is bent at right angles, soot accumulates on
the angle, and when a mass has formed it falls off, and is partly
burned in the flame. If the cylinder is given a proper bend no soot is
deposited in it, but it is all carried away into the soot chambers.
The air regulator, S, is placed at the bottom of the cylinder; it must
turn easily. The larger the slits are made by the rotation of this
regulator, the more oxygen enters the flame, and the more vigorous
is the combustion. A small, well-fitting door is placed in the lower
part of the cylinder, through which the wick can be reached; opposite
to this a glass plate is inserted, so that the flame may be observed
without opening the door. The wick is raised or lowered by means of the
screw, R.
The oil reservoir, O, must be outside the cylinder: in the older
arrangements it is so placed that the wick sucks up the oil; the
workman who is in charge of the lamps must then take particular care
that the reservoirs always contain the proper quantity of oil, if he
neglects to keep the oil at the proper level the wick is charred; it
then sucks up too much oil, which cannot completely burn and is chiefly
distilled, so that the soot is oily and cannot easily be treated
afterwards. The most diligent and attentive workman who is in charge
of a large number of lamps may easily allow one of them to run short
of oil. With the oil reservoir above depicted, a new quantity of oil
flows only when the level of the liquid sinks below the line, U. As
soon as a small quantity is used air enters the reservoir, O, in place
of which oil runs out until the opening, U, is again closed by the
liquid. This construction of lamp only works well when thin oils are
burned, and great care must be taken that the lamps are kept constantly
clean.
Lamps of all constructions have some drawbacks, they must always be
cleaned, and losses of oil occur in filling. These defects are obviated
when, instead of providing each lamp with its own reservoir, a single
one is used for a large number of lamps, which are automatically fed
from it. In this case the attendant has only to regulate the air supply
to the lamps, and to see that the mechanical arrangement by which the
oil flows to the different lamps is working properly. When the lamps
are automatically fed, the burners must be firmly fixed, and all in
the same horizontal plane. A pipe connects each burner with a main
pipe running under the lamps, which latter pipe is connected with the
reservoir, and this in its turn is connected with another reservoir
placed a little higher. In the pipe connecting the two reservoirs is
a tap, which is opened by a float in the lower vessel as soon as the
level of the liquid in it sinks a little, and which remains open until
the level of the liquid has again risen to a certain height. The float
in the reservoir connected with the lamps is arranged so that the level
of the liquid is slightly higher than the burners. Under the slight
pressure oil continually flows to the burners, and it is not difficult
to regulate its flow so that all which reaches the burner is burned.
In using a new oil it is not easy at first to regulate the flow so
that absolutely all is burned without any dropping off the burner; to
prevent the loss of this portion, the lower end of the air regulator
is conical, at the apex of the cone is a small tube and under this
a vessel in which the unburnt oil is caught. In Fig. 32, S is the
air regulator, T the vessel to catch the unburnt oil, L the pipe
leading from each burner to the common pipe H, G the vessel in which a
float regulates the flow from a larger reservoir, so that the liquid
always remains at the same level. When tar oils are used, or thin
mineral oils, the pipes which convey the oil to the burners may be
made tolerably narrow, but when viscous oils or fish oils are burned,
narrow tubes would offer too great resistance to the flow, so that
it is always advisable to use fairly wide pipes. Viscous oils become
considerably more fluid at higher temperatures, it is therefore well
to place the reservoirs in the same room as the lamps; in winter the
temperature of this room is kept fairly high by the burning of the
lamps, and thus the oils remain fluid.
FIG. 32.
In recent years hydrocarbons of very low boiling point have been
placed on the market at low prices; these produce a black of very good
quality. On account of the low boiling point of these very inflammable
liquids, particular care is necessary in burning them; they are very
fluid and retain their fluidity at a low temperature. The reservoirs
for them should be placed for safety outside the lamp room, and
should be closed by an air-tight lid, with only one small opening
through which air can enter. When these low boiling liquids are used,
particular care must be taken to regulate the flow to the lamp, or
large quantities will evaporate without being burnt.
The materials used in the manufacture of soot black differ considerably
in chemical constitution. Rosin, animal and vegetable fats, distilled
oils and volatile hydrocarbons are used. Each of these substances gives
different decomposition products when heated, to which proper regard
must be had, since the quality of the black is dependent on them. The
more difficultly volatile are the products of distillation, the higher
must be the temperature at which the combustion is conducted, otherwise
the soot will contain a considerable quantity of these products of
distillation. In consideration of the great variety of materials used
for making soot black, it is impossible to say exactly in what manner
each should be treated: this must be left to the practical experience
of the manufacturer.
CHAPTER XLI.
MANUFACTURE OF LAMP BLACK.
The variety of soot black known as lamp black is the best; it is used
for making copper-plate inks and black coach paints. Its price is
much higher than that of ordinary soot black; for the best qualities,
twenty times the price of an ordinary black is paid. The materials
already mentioned are used for making lamp black, fish oils and rancid
vegetable oils, and in recent times mineral oil and tar oils. In regard
to vegetable oils it is to be observed that it is advisable to use
very rancid oil, which gives a larger yield of soot; experience has
shown that a very rancid oil requires a larger quantity of oxygen to
burn without a smoky flame than a sweet oil. This indicates that a
portion of the carbon in the rancid oil is present in such a form that
it requires a higher temperature to burn it than is required for the
carbon in sweet oils. The use of rancid oils for making soot blacks has
thus two advantages, it is much cheaper and produces a larger yield.
The only disadvantage, and not a very important one, attending the
use of rancid oil is that the free fatty acids in these oils strongly
attack the metallic parts of the lamps. This is especially the case
with copper and brass; only such portions of the lamps as is absolutely
necessary should be made of these metals; all other parts, and in
particular the oil reservoirs, should be made of tin plate.
Since the development of the coal-tar industry oils distilled from
coal tar have come into commerce at low prices. These oils consist of
carbon and hydrogen and are equally volatile with the essential oils,
to which class turpentine belongs. There are two kinds of these tar
oils, light and heavy; they differ both in specific gravity and in
the boiling temperature, which ranges between tolerably wide limits.
When the burning qualities of these oils are examined, they show a
great difference in the quantities of oxygen necessary for complete
combustion with a white flame without smoke. The more oxygen an oil
requires to burn with a non-smoky flame, the more suited it is for the
manufacture of blacks. Generally speaking, the difficulty of completely
burning these oils is in proportion to their specific gravity and the
height of their boiling point.
By the distillation of rosin, oils are obtained which also consist of
carbon and hydrogen and form a useful material for the manufacture of
soot blacks. The mineral known as earth-wax or ozokerite, a substance
intermediate between asphaltum and petroleum, can also be used, but
since it is a solid it must be burnt in troughs.
In burning light oils the arrangements can be very simply made; wicks
are not required and thus a considerable outlay is spared. In place
of the burner, shallow dishes are used into which the oil enters from
below, replacing that burnt away. It is necessary to cool these dishes
continuously from below, otherwise they would soon become so hot that
the greater part of the oil would evaporate without burning, and it
would also be very difficult to regulate the flame properly.
Black can be obtained from very resiniferous coal by burning in
furnaces with a regulated air supply. The product is, however,
generally largely contaminated by ash, and can only be used for common
purposes. Very resiniferous lignite gives a better product than coal;
the black can be partially separated from the ashes by shaking upon
water and then stirring, when the particles of ash sink to the bottom
and the light black floats on the top.
However carefully the manufacture of soot black is conducted, it
will always contain, in addition to carbon, varying quantities of
the products of distillation, partly solid and partly liquid. In
consequence of these admixtures the soot will not be pure black, but
will show a more or less brown tinge, which is clearly observed when
the black is smeared on white paper. At a certain thickness of the
layer of soot it will be seen that the colour is not black, but an
impure brown. When such soot, as it is taken from the chambers, is
chemically examined, it is found that it gives up a large quantity of
soluble matter to different chemical reagents. By proper treatment
it is possible to remove the admixtures almost completely, so that
nearly chemically pure carbon remains. Such pure carbon can be made by
boiling lamp black with strong caustic soda solution so long as the
liquid is coloured, and when caustic soda can dissolve nothing more,
the residue is boiled with _aqua regia_ until this no longer takes
up soluble matter. The black is then washed with water until free
from every trace of acid, and the residue dried. By this treatment
the soot is converted into a powder of the purest black hue which it
is possible to obtain. It is now no longer soot, but chemically pure
carbon in the non-crystalline form; heated upon platinum foil it burns
to pure carbonic acid without producing smoke or smell. In practice
the purification of the soot is not carried to the extent of producing
pure carbon; this would be accompanied by a diminished yield of the
pigment without increasing the commercial value of the product: the aim
of the manufacturer is simply to produce a substance of a pure black
appearance from the brown soot. To remove the brown substances present
in the crude soot the solvent action of caustic soda solution can be
used. The soot is several times boiled in iron pans with strong caustic
soda solution in order to dissolve the products of dry distillation.
It is superfluous to repeat this operation until fresh caustic soda
remains colourless. The treatment may be stopped when the solution
acquires a slight brownish colour. When the soot has been purified so
far it has lost its brown shade and now appears as a velvety black
powder, very soft and very light, and distinguished by extraordinary
covering power.
It is not so easy as it appears at first sight to judge of the quality
of a black pigment by its appearance. To the unaccustomed eye a pigment
may appear to be of an unexceptionable black, which to the expert
appears decidedly brown; only long practice can give the eye the
requisite keenness. In addition to the test already given—of smearing
on white paper—there is another especially to be recommended to the
inexperienced for discriminating between pigments. A small quantity of
the black under examination is intimately mixed with a white pigment;
white lead or zinc white is very suitable. If the mixture has a pure
grey shade, the black may be regarded as of good quality, but if it
contains brown substances the mixture has an indefinite, dirty shade
instead of a pure grey. This is a sure sign that the black requires
further purification.
Although caustic soda is now very cheap, its use for the purification
of soot black is tolerably costly, because it entails much labour. This
process is therefore only used for the finest qualities which are to be
employed for copper-plate inks and black coach colours. For inferior
qualities the method of calcination is used, which produces, when
properly carried out, a black of such purity that it can be used for
the preparation of even the finest black paints.
_Calcination of the Soot._—The substances which give the soot its brown
colour are products of dry distillation, and hence are all volatile at
a certain temperature; they can be separated from the soot by heating
it in the absence of air. The temperature necessary completely to
volatilise these compounds is fairly high. The soot must be heated to a
good red heat to obtain a safe result.
When the soot is heated too quickly or to too high a temperature it
undergoes an alteration which affects the quality of the product.
By too long or too vigorous ignition the soot changes its flocky
consistency to a sandy nature; it will then require much longer
grinding with oil to produce a uniform mixture than is the case with
the light flocculent soot, which very readily mixes with oil.
The soot is ignited in sheet-iron boxes with a coating to protect the
metal from burning. This coating is best made from clay and hair. A
very thin paste of clay and water is painted uniformly over the boxes
with a brush; when the first coat is dry a second and third are given.
When once the metal is completely covered with clay, several coats
are given of clay mixed with chopped tow until the layer is several
millimetres thick. The coating carefully made in this manner is very
durable, and the boxes can be used for a long time, whilst without
the coating they would very soon be burnt. Particular care must be
given to the manufacture of the boxes themselves; the bottoms must fit
very accurately, and should be coated with clay in order to ensure an
air-tight joint. The lids also must fit accurately, and when they are
closed must equally be made tight by clay.
The soot is at first loosely packed into the box and each portion then
pressed with a rammer so that it tightly fills the boxes. In the lid is
a very small opening, through which the volatile products can escape.
The heating begins quite gently at the back, and proceeds gradually to
the front; the boxes are finally brought to a good red heat, at which
they are maintained for about half an hour; at this temperature the
substances mixed with the carbon are almost entirely volatilised, and
the soot acquires its true black appearance. The soot itself attains
a red heat in the boxes and in consequence of its loose nature it
very readily burns. The precautions given above must be observed in
order to protect completely the soot against the action of the air. The
boxes should not have the smallest opening besides that in the cover
necessary for the escape of the volatile matters; through an opening
invisible to the naked eye so much oxygen may enter during the cooling
of the boxes that a considerable quantity of carbon will burn to
carbonic acid.
To avoid losses through the carbon burning precautions must equally be
taken in the cooling of the boxes. When the ignition is finished they
are drawn out of the furnace by tongs and placed upright on a stone
floor; as the cool air enters, and in contact with the red-hot carbon
would burn a portion of it. This can be prevented by a simple artifice:
a red-hot coal is placed on the small opening in the lid; this converts
the oxygen of the air which enters the boxes into carbonic acid. When
all the boxes are taken out of the furnace the doors of the room in
which they are placed are opened, so that they are cooled in the
draught. Finely divided carbon takes fire at a temperature far below a
red heat, so that the boxes should not be opened until their contents
are quite cold. If they were opened whilst hot the soot might take fire.
=Pine Black.=—Under this name a poor quality of black comes into the
market, which is much used for ordinary black paints, etc. The pine
black formerly brought into the market was what its name purported; it
was made from the roots of the pine in the primitive fashion already
described. The black was sold without further purification: it was a
soft light powder, very variable in shade on account of the absence of
control over the process: it varied from pure black to a dark brown.
At present, under the name of pine black many substances are sold,
generally without purification, made from the most different materials,
frequently from rosin, rosin residues, and other cheap materials.
CHAPTER XLII.
THE MANUFACTURE OF SOOT BLACK WITHOUT CHAMBERS.
A certain temperature is necessary for the combustion of every
substance; if a cold body is placed in the flame of a candle or an
oil lamp it becomes covered with soot, because it cools the flame to
such an extent that the carbon is no longer heated to the temperature
necessary for its combustion, and is, therefore, separated in a finely
divided condition. Use is made of this phenomenon in a method of making
soot black which has many advantages, of which the most important is
that expensive buildings are not required, and the manufacture can be
conducted in restricted space.
[Illustration: FIG. 33.]
A convenient arrangement for obtaining black by this process is
represented in Fig. 33. The thin-walled hollow cast-iron cylinder is
turned smooth on the outer surface, and is surrounded by a sheet-iron
cover at the distance of a few centimetres; it rotates in bearings,
which, like the spindles, are hollow; cold water is thus led through
the cylinder from a tank at a higher level. Below the cylinder are
placed, near to one another, smoking lamps, and at the side of the
cylinder is a broad brush of soft hair which continuously removes the
soot deposited on the surface, which then falls over an inclined plate
into the collecting vessel. The cylinder is kept in slow rotation by
any mechanical arrangement. The lamps are devised not to produce a
hot flame, but when this comes in contact with the cold surface of
the cylinder, it deposits a ring of soot on the rotating cylinder
which is then removed by the brush. The cylinder is kept cooled by
the water which runs through it. The soot which is collected shows a
tolerably strong brown shade in consequence of the rapid cooling of the
flame, which causes the formation of a large quantity of products of
distillation; the soot will always require ignition.
[Illustration: FIG. 34.]
It has been proposed further to simplify the manufacture of soot black
by this method, by burning coal gas under the cylinder from numerous
small openings in a pipe. Coal gas indeed gives a very fine deep black,
but the yield is so small that this process could never be adopted with
advantage.
The apparatus constructed by Thalwitzer for the manufacture of oil
black (Fig. 34) consists of a plate, _A_, with a rim, _a_, fastened to
a vertical axis, _b_. This is carried by bearings in _B_, and is kept
in rotation by the cog-wheels, _d_ and _f_, moved from the shafting,
_O_. The plate is cooled by water supplied by the pipe, _g_, it flows
away by _h_ and the annular vessel, _D_. The lamps, _e_, are connected
with the common oil reservoir by _n_. _H_ is a scraper fastened to _B_
by _x_.
CHAPTER XLIII.
INDIAN INK.
Indian ink consists of purified soot mixed with gum, as binding medium,
and a little camphor and musk. It is generally believed that Indian ink
is made in China by a process which is still a secret; this opinion
is supported by the fact that the ink made in Europe is almost always
inferior to the Chinese. It is quite possible that a substance which
produces a particularly fine black is used in China to prepare the soot
used for the ink, and which we do not yet know or do not use on account
of its high price. But it appears that the difficulty of producing an
ink equal in quality to the Chinese lies less in the quality of the
soot —for by the methods of purification already given we can make
almost chemically pure carbon—than in the extremely careful mechanical
treatment of the soot with the other constituents of the ink.
The genuine Chinese ink has a peculiar smell, which, when not hidden
by musk, distinctly recalls the smell of burning camphor; the camphor
tree is a native of China, so that it is not impossible that the soot
of the wood of this tree is used for the ink. The soot from camphor
alone would be too expensive, so that it is probable that camphor wood
is used from which camphor has been prepared, or that camphor soot is
mixed with the soot of a cheaper substance. In fact several varieties
of Chinese ink show distinctly the smell peculiar to soot produced by
fat. The binding material is animal glue, which is most thoroughly
ground with the carbon; the secret of making good Indian ink lies in
the careful grinding with the binding medium.
According to Piou, who lived for a long time in China and learned the
process there used, the black employed for the ink is made from the
resins of the pine and other trees. The soot is sieved through silk,
boiled with glue and water, and kneaded by hand with a little oil until
the mass has become completely homogeneous. It is then left for some
days, heated, and pressed into the moulds. This description is not very
satisfactory; the products obtained are far inferior to those made by
the ordinary European process.
The viscous mass obtained by long treatment of the black with the
binding medium is slowly dried, and again ground when it has become
thick. When a completely homogeneous paste has been obtained it is
made into sticks which are pressed into moulds, and then very slowly
dried so that they do not crack. Small cracks always occur; they are
filled in by a brush dipped in the thick paste, finally the sticks are
entirely or partially covered with gold leaf.
In order to impart to the ink the odour characteristic of the Chinese
ink, it is sufficient to use good lamp black, made odourless by
extraction with caustic soda, and to add a little solution of camphor
in turpentine during the grinding. If it is desired to impart the musk
smell which several Chinese varieties possess, a small quantity of a
spirit extract of genuine musk may be added.
The size solution is made by long boiling isinglass with water; it
must be so concentrated that it forms a strong jelly on cooling. A
small quantity of acetic acid is added, so that the grinding may not
be hindered by the viscous nature of the size, which the acid prevents
from gelatinising. When the mixture has been made by long grinding,
the mortar is warmed to 40° or 50° C., whereupon the acetic acid is
soon volatilised, and the mass rapidly becomes very thick.
=Neutral Tint Black.=—A mixture of Indian ink, Chinese blue, and a very
small quantity of madder lake forms the colour known as ”neutral tint,”
the shade of which is a peculiar greyish violet. By alterations in the
proportions of the constituents different shades of ”neutral tint” are
produced.
APPENDIX.—BLACK MINERAL PIGMENTS.
=Chrome Copper Black.=—When copper chromate is strongly ignited in air
and then treated with boiling nitric acid a glittering black compound
is obtained, which shows up well when printed on fabrics with albumin.
This and all similar pigments are distinguished by great durability.
=Chrome Black.=—When a mixture of chromium oxide with varying
quantities of ferric oxide is strongly heated, pigments are obtained
of all shades from dirty yellow and green to the deepest black. This
pigment is largely used in porcelain painting to produce a black, which
also can be obtained by other but much more costly methods. The best
mixture to produce a deep black contains one part of chromium oxide to
four parts of ferric oxide.
CHAPTER XLIV.
ENAMEL COLOURS.
An enamel is a glass distinguished from ordinary glazes by a much lower
melting point, and generally by opacity. Most enamels are coloured by
additions of metallic oxides.
Without going in detail into the art of enamelling, some observations
may here be given which appear indispensable for an understanding of
the manufacture of enamel colours. The enamels are glasses, but not
every glass can be used for an enamel, since the constituents of the
glass react with the substances by which the enamel is coloured, and
with certain colouring matters quite different shades to the intended
might be produced. Of equal importance with the composition of the
glass used in the preparation of the enamel is the temperature at which
the glass melts. Many colours bear but a low heat; they decompose at a
somewhat higher temperature and produce quite the wrong colour. This is
especially the case with the enamels coloured purple red by gold.
The enamel colours are fixed by mixing them with an easily fusible
glass (the flux), applying them to the object to be enamelled, whether
metal, glass, or porcelain, and heating the painted article in muffles
until the glass melts, and either dissolves the colouring matter or
encloses it unaltered. According as the enamel melts as a whole, or the
flux alone melts and encloses the colouring matter, so transparent or
opaque enamels are produced. The former are really coloured glasses,
the latter are glasses in which is enclosed the sintered colouring
substance.
Whilst enamels were formerly of importance only for artistic purposes,
they have recently attained great industrial employment; not only is
earthenware now covered with enamel, and thus made to resist the attack
of chemical reagents, but boiler tubes are lined with enamel to prevent
the formation of scale.
The colours used for enamels must in all cases be metallic oxides; for
yellow, silver and antimony oxides; for red, gold, copper oxide and
ferric oxide; for blue, cobalt compounds; for green, copper oxide or
chromium oxide. Two operations are required in the production of enamel
colours, the preparation of the flux and its fusion with the real
colouring substance. In most cases the latter operation takes place
simultaneously with the fixation on the enamelled article, but the
enamels may be melted and cast into lumps, which are then powdered.
=White Enamels.=—These are always ordinary crystal glass, to which tin
dioxide or potassium antimoniate has been added. Particular care must
be taken that only pure raw materials are used, for almost unweighable
quantities of iron compounds are sufficient to impart to the enamel a
yellow tinge. In almost all cases the glass must be decolourised by the
addition of pure pyrolusite (manganese dioxide), which at a red heat
gives up a portion of its oxygen to the ferrous oxide contained in the
glass, producing ferric oxide, which has much less colouring power. Too
large a quantity of pyrolusite imparts a blue tinge to the enamel.
The tin dioxide used in the glaze is made by direct oxidation of tin
in air. It has been found that tin burns much more easily in air when
it is mixed with lead; 20 to 40 parts of tin are melted with 100
parts of lead, and the alloy heated in shallow vessels in the air;
it takes fire at a certain temperature, and it is only necessary to
remove continually the layer of oxide in order to oxidise the whole
of the metal within a short space of time. The mixture of oxides
obtained in this manner is freed from particles of metal by grinding
and levigation; when it is fused with the glass, the lead oxide enters
into combination, whilst the tin oxide is embedded in the colourless
glass. When paste enamels are required the mass is melted in shallow
crucibles, poured into water and broken up to a coarse powder, which
is again fused. In some cases this operation must be repeated several
times to obtain a quite homogeneous product, for tin dioxide is very
heavy and sinks to the bottom of the fluid glass; this is readily
seen if the fused enamel is allowed to cool in the crucible. When the
crucible is broken the lower portions of the fused mass are dense
white, whilst the upper are merely milky white. By repeatedly fusing
the mass it is endeavoured to obtain it uniform. In fusing the enamel
care must be taken that it is heated in a vessel from which the fire
gases are completely excluded, since the smallest quantity of coal or
of ferruginous ashes coming into contact with the melted mass would
injure its colour. If the melting point of the enamel is too high it
can be lowered by the addition of a small quantity of pure quartz sand.
A fine white enamel is obtained by using litharge or red lead. The
mixture contains 60 parts of quartz sand, 30 of alum, 35 of common
salt and 100 of red lead. It is advisable to add a small quantity of
finely-powdered talc to the sand. In consequence of the considerable
proportion of alumina contained in this enamel it is difficult to melt,
and can be heated to very high temperatures without injury to the shade.
When antimony oxide is used a glass free from lead must be taken; lead
glass does not give a pure white with antimony oxide. A very good white
enamel is obtained by fusing 3 parts of crystal glass with 1 part of
sodium antimoniate.
=Coloured Enamels= owe their colour to metallic oxides. Enamels
coloured by metallic oxides, in which the oxygen is firmly united,
can be fired without great precaution, but if they contain oxides
easily decomposed, great care is required to obtain a fine colour. In
enamelling metals a white under-glaze is generally used beneath the
coloured enamel; it consists of a refractory white enamel. By this
means it is more easy to obtain pure colours.
=Yellow Enamels= are coloured by silver, antimony oxide combined with
litharge, or ferric oxide; from the latter a red can also be obtained.
To produce a yellow enamel by means of silver the article is first
enamelled white at a low temperature; silver oxide is then applied
where required, and the article again heated. It then frequently
happens that the surface has a metallic appearance owing to the
reduction of a part of the silver oxide to metallic silver. When this
coating is scraped off the enamel beneath is found to be coloured a
fine yellow.
The antimony yellow is obtained by mixing 1 part of antimony oxide, 1
part of alum and 1 to 3 parts of white lead, according to the depth of
colour required. These finely-powdered materials are intimately mixed
with 1 part of sal ammoniac, and heated in an open vessel with stirring
until the yellow colour appears. The vapours of the ammonium chloride
indicate the proper temperature for the operation. When this substance
is completely volatilised the temperature should not be further raised,
or the mixture would fuse.
By means of ferric oxide a fine and durable yellow is produced; the
quantity employed must not be too large, or a red colour will result. A
very high temperature is required for burning in this colour. The alum
used in making the yellow enamel colours serves to prevent the oxides
from fusing.
=Red Enamel.=—Ferric oxide is generally used. When a purple red is
required it is obtained either directly from metallic gold or from
purple of Cassius.
Red iron enamel is made by slowly heating 20 to 25 parts of pure
ferrous sulphate with 10 parts of aluminium sulphate until all the
water of crystallisation is expelled, when the temperature is gradually
raised to an intense heat. The shade depends upon the temperature: the
higher it is the darker is the colour. Tests are taken from time to
time of the mixture, and rapidly cooled. Hot ferric oxide is black,
consequently the shade can only be judged with complete certainty in a
cooled portion. Although the temperature required for the preparation
of this colour is very high, yet it ought not to rise so far that the
magnetic oxide is produced, a small quantity of which would cause the
enamel to appear dirty red, since it gives to the flux a blackish
green colour. The red ferric oxide colour should not be dissolved in
the glass of the enamel, but should be embedded in it. Thus, when the
enamel is burnt on, the temperature should not rise so high that ferric
silicate is formed, otherwise a yellow or even completely black enamel
results.
Purple red is obtained by means of gold; formerly purple of Cassius
was exclusively employed for this purpose, but an equally bright red
can be obtained from gold chloride. The colour obtained from gold will
bear only a very low heat; it must be mixed with a very fusible glass,
brought on to the article to be enamelled, and heated just sufficiently
to melt the mass. The following mixture is used for gold red and other
delicate colours: 3 parts of calcined borax, 3 parts of quartz sand and
1 part of chalk. A very small quantity of gold is sufficient to produce
a deep red, the amount of gold preparation used for a pale red or a
medium purple must be carefully weighed.
=Blue Enamels= are always coloured by cobalt oxide. Any cobalt
compound can be used, since at a red heat the silica of the glass
displaces other acids, and produces cobalt silicate. It is most simple
to take cobalt nitrate. This salt is readily obtained completely pure,
and absolute purity is of great importance, for only thus is a pure
blue produced.
Cobalt oxide produces a more or less deep blue when fused with varying
quantities of glass. In order to produce shades similar to turquoise
and forget-me-not, a white enamel must be used beneath the blue, or
bone ash must be mixed with the blue enamel; this produces a paler
colour, which is also opaque.
=Green Enamel= is coloured by copper oxide or chromium oxide. In the
former case 1 part of copper oxide is used to 30 to 50 parts of glass,
according to the depth of shade required. The enamel made with copper
oxide alone has never a pure green colour; it exhibits a blue tinge. A
pure green is obtained by adding a very small amount of ferric oxide,
which produces a yellow and compensates for the blue shade, so that a
pure green is formed.
Chromium oxide produces a beautiful emerald green without any addition.
The enamel may be exposed to very high temperatures without injury.
Green enamels may also be made by mixing blue cobalt enamel with a
yellow enamel: an unexceptional shade results, but this method is
seldom used, since green enamels are obtained in a simpler manner from
copper and chromium oxides.
=Violet Enamel.=—Manganese dioxide is used exclusively to produce
violet enamel; an extremely small quantity is sufficient to colour a
considerable quantity of glass. A pure violet shade is only obtained
when very pure manganese dioxide is used; the artificially prepared
substance should be used to produce the finest violet: the cost is
considerably greater than that of the mineral pyrolusite, but equally
good results can rarely be obtained from pyrolusite.
=Black Enamel.=—When a large quantity of ferric oxide, copper oxide or
cobalt oxide is fused with a glass, a deep black enamel is obtained.
Generally mixtures of these oxides are used; experience has shown that
a much deeper black is thus obtained than from any one alone.
Now that enamels are not used exclusively for artistic purposes, but in
considerable quantities for earthenware and other technical purposes,
the manufacture of enamel colours has attained considerable importance;
works already exist occupied almost exclusively with this special
branch of manufacture.
By Lacroix’ process enamel colours are made which can be applied to
porcelain without further admixture with a flux; for example, a very
fine blue is made by dissolving 300 parts of pure alumina and 100
parts of cobalt carbonate in nitric acid, evaporating the solution to
dryness, igniting the residue and fusing it with 300 parts of quartz
sand free from iron, 900 parts of crystallised boric acid and 1,800
parts of red lead. A blue glass is obtained which easily melts, but
is difficult to powder; but if poured when fluid in a thin stream
into cold water, it forms thin threads, which are very brittle in
consequence of the rapid cooling, and may be easily converted into a
soft powder.
CHAPTER XLV.
METALLIC PIGMENTS.
Metallic pigments do not always consist of metals; the name is also
applied to compounds which possess a pronounced metallic lustre; mosaic
gold, the preparation of which has been previously described, is an
example of such a pigment. Another variety of metallic pigment is made
by heating finely-powdered alloys; a layer of oxide is thus produced
upon the surface of the metallic particles, this layer produces a
shade of the colour of the metal or alloy. Metallic pigments are only
unalterable when they are composed of metals which are not changed
by the action of the air. As a matter of fact, this property is not
possessed by any of the metals used for this purpose; even gold and
silver are blackened by the action of the sulphuretted hydrogen in the
air. This alteration proceeds, however, very slowly when the metal is
enveloped by a layer of a binding medium, which is always the case when
the metallic powder is used for painting. There are many manuscripts,
the initial letters of which have been coloured by gold or silver,
in which the metals retain their peculiar lustre after the lapse of
centuries.
Metallic paints made from yellow alloys have never much durability:
they always contain copper, which readily alters; articles painted with
imitation gold soon lose their lustre, and in the course of time become
green.
=Shell-Gold.=—This very expensive artists’ paint is made by rubbing
gold-beaters’ refuse with gum solution upon a stone slab until a
completely homogeneous mixture results, which is then rapidly thickened
over the fire and generally allowed to dry in small shells. The
preparation so made is known as shell-gold: it is sold at very high
prices.
The operation of grinding the gold is very lengthy; it considerably
increases the cost of the already expensive material. The process may
be considerably shortened if the gold is obtained in a very finely
divided state by a chemical operation. For this process coins or broken
jewellery is heated in hydrochloric acid, and nitric acid gradually
added. The gold dissolves in the mixture. If it was alloyed with silver
a white precipitate of silver chloride is formed, which is filtered off
after largely diluting with distilled water. The solution is boiled
for some time to remove excess of nitric acid. A solution of ferrous
sulphate is then added; the liquid at once becomes bluish black, and
in a short time deposits a brown precipitate composed of chemically
pure gold, which is so finely divided that it is almost without the
characteristic glitter of gold. The precipitate is filtered off, dried
and preserved in stoppered bottles. In order to prepare shell-gold
from this gold powder it is simply necessary to grind it with thick
gum solution in a porcelain mortar; under the pressure of the pestle
the gold rapidly acquires its natural glitter. The grinding need only
be continued until the gold and gum solution are uniformly mixed.
The mixture so made should be at once filled into the shells, since
on standing the gold would soon separate from the gum solution in
consequence of its high specific gravity.
=Shell-Silver.=—Genuine shell-silver can be made by rubbing silver leaf
with gum solution upon a slab exactly as genuine shell-gold. In this
case also the labour may be considerably lessened by converting the
silver into a state of fine division by a chemical process. Silver is
dissolved in nitric acid, which must be quite free from hydrochloric
acid, or insoluble silver chloride would be formed. In the operation
brown suffocating fumes are evolved which attack the respiratory
organs; it should therefore be conducted in the open air or under a
flue with a good draught. The silver solution, which is generally
coloured blue by admixed copper, is diluted with a large quantity of
distilled water. A sheet of copper is then dipped into the liquid and
rapidly moved about in it. The silver then separates as a dark grey
powder; after washing it is chemically pure, and when ground with gum
solution it produces genuine shell-silver.
Shell-silver and shell-gold are rarely used in painting on account of
their cost; they are chiefly used for illuminated manuscripts. When
these metallic pigments are to be used in oil painting, in place of
gum they must be ground with a liquid which mixes with boiled oil or
essential oils. For this purpose copaiba balsam is to be recommended.
=Imitation Silver.=—The imitation silver pigments are made from an
alloy of tin and bismuth, or from a tin amalgam. The latter is most
easily made by melting tin in a porcelain dish and adding one quarter
of its weight of mercury; the mixture is then well stirred, and
allowed to cool. It quickly solidifies to a crystalline mass, which is
tolerably brittle and can be powdered without difficulty. To obtain a
substance of a true silvery appearance the amalgam must be converted to
a powder of a certain degree of fineness. If the powdering is carried
too far the product loses a great part of its metallic lustre, and
acquires a dull grey colour.
The bismuth alloy is made by fusing 100 parts of tin, adding 100
parts of bismuth, and then 10 parts of mercury. It is not absolutely
necessary to add mercury, but the addition has the advantage that the
solid alloy is far more easily powdered. The imitation silver made by
this process has a white metallic colour approaching that of genuine
silver, but not equal to it, especially in lustre. It is, however,
largely used in the industries on account of its low price; for
example, for paper hangings.
CHAPTER XLVI.
BRONZE PIGMENTS.
It would be anticipated from the name that bronze pigments were
composed of an alloy of copper and tin; in reality the alloy is
composed of copper and zinc, _i.e._, brass. The bronze pigments are
made by a similar process to that described for genuine gold and silver
pigments. The waste produced in the manufacture of imitation gold leaf
is ground with a solution of dextrine upon a slab until the mixture is
uniform and separate metallic particles can be perceived only through
a lens. Whilst genuine gold and silver paints are always made in small
quantities, on account of the expensive nature of the material, and
machinery is not employed, the bronze pigments are in different case;
the use of mechanical arrangements is necessary for producing the fine
subdivision, otherwise the bronze would be very dear on account of the
great cost of grinding. The mechanical arrangements required to divide
the alloy are of the ordinary nature, but special machines have been
constructed for the manufacture of bronze pigments, by which the metal
is far more quickly converted into powder than by means of grinding
machinery. These machines consist of metal drums studded on the
interior with a large number of fine needles and capable of very rapid
rotation. When a metal powder already tolerably fine is brought into
these drums, it is rapidly brought to such a condition of fine division
as would be attained by hand grinding only by prolonged and laborious
exertion.
The raw material for the manufacture of bronze powders is produced
in making imitation gold and silver leaf; the waste metal obtained
in beating the sheets is used. The employment of this waste has two
advantages: the metal is already in very thin sheets and is composed of
alloys varying in colour from silver white, through gold, to a bright
copper. In making leaf metal the waste of each colour is kept carefully
separate, so that it simply requires to be broken up to produce bronze
powders of different shades.
Before this waste is brought into the drums mentioned above it must be
subjected to a preliminary grinding in a mortar with a small quantity
of a fatty oil, which serves to bind together the mass. Sufficient oil
should be used to give the mass some degree of coherence; if too much
oil is added the space between the needles of the drum would be coated
with the mass and the process in the drum would require a much longer
time. The uniform mixture of oil and bronze waste is then brought
upon a wire sieve of the finest possible mesh, and the mass is rubbed
through by means of a fine metal brush into a vessel below; thus the
larger particles are retained by the sieve and only those which are
smaller than the mesh pass through. The product of this process is
then brought into the drums, which are rapidly revolved; the small
particles of metal are thrown with great force against the side and
are converted by the fine points with which it is studded into a very
fine powder. The time required for this process depends on the rate of
revolution and on the quantity of powder treated at once. The drums are
stopped from time to time and the contents examined. When the powder
is sufficiently fine it is taken out of the drum. This is most easily
accomplished if the drum is arranged to take apart into two halves.
In most works it is usual to free the bronze powder from the admixed
oil by subjecting the mass to the greatest pressure that can be
produced by a very powerful hydraulic press. The oil which flows
from the press is always green, which shows that chemical action has
taken place. In consequence of the large surface imparted to the oil
it becomes speedily rancid, and then contains free fatty acids which
attack copper very energetically.
[Illustration: FIG. 35.]
The use of hydraulic presses may be avoided by removing the oil
by means of a solvent. Fatty oils dissolve very readily in carbon
bisulphide, but this solvent cannot be used in this case, because
commercial carbon bisulphide always contains dissolved sulphur, which
would blacken the bronze powder. Petroleum ether and benzene are very
suitable solvents for this purpose. On account of the volatility of
these inflammable liquids lights must be absolutely excluded from the
room in which they are used, and in order to avoid loss of solvent
the bronze powder must be treated in closed vessels. The safest plan
is to use a special apparatus of simple construction to dissolve
the oil. Fig. 35 shows the construction of an arrangement suitable
for this purpose. It consists of a cylindrical vessel of tin plate
surrounded by a rim into which fits the edge of the cover. When the
lid is placed on and the rim filled with water, the contents of the
vessel are closed in air-tight and cannot evaporate. The lower portion
of the vessel is conical, and is joined to a pipe in which is a tap,
and which communicates at the side by a tube with the glass vessel in
which the solvent is contained; another tube connects the neck of this
vessel with the cover. When this apparatus is used for extracting the
oil from bronze powder, a filter of strong blotting paper is placed
in the conical portion of the vessel, care being taken that it fits
accurately so that it is not torn by the weight of the bronze. The oily
bronze powder is placed on this filter, the cover set on, and the rim
filled with water. By opening the tap attached to the solvent reservoir
the liquid is allowed to enter the cylinder from below, the air in the
latter passing through the tube in the cover to the reservoir. After
some hours the oil is dissolved, the tap in the cover is then opened
and the liquid run off by opening the lowest tap. If the bronze powder
is not quite free from oil after one treatment with the solvent, the
operation is repeated with a fresh quantity.
When free from oil the powder and filter are removed from the apparatus
and dried; the dry mass forms a solid cake, which is broken up in a
mortar and by a little grinding changed into a fine powder.
The colour of the bronze powder is the same as that of the alloy used,
but the shade is always rather paler than that of the coherent metal;
regard must be paid to this circumstance in making a bronze of a
determined colour: the alloy employed must have a rather deeper colour
than the shade the bronze is to possess.
The manufacture of leaf metal and bronze powder is frequently conducted
in the same works, which also often prepare the requisite alloys; we,
therefore, give a few examples of the composition of the alloys which
produce certain shades. The more zinc the alloys contain the lower is
their melting point, the greater their brittleness and hardness and
the paler their colour. An increase in the copper causes the colour
of the alloy to approach more nearly to that of gold, and increases
the malleability, a property useful in making leaf metal, but not
desirable in making metallic powder. A zinc copper alloy which contains
between 1 and 7 per cent. of zinc has an almost pure red, or even a
dark red colour; an alloy containing 7·4 to 13·8 per cent. of zinc has
a pure golden yellow colour, between 16·6 and 25 per cent. of zinc a
yellow appears. An increase of the percentage of zinc above this point
produces the colour of brass; it is noteworthy that an alloy containing
still more zinc, 33 to 41 per cent., again shows a reddish colour,
which is most developed when the alloy contains equal parts of zinc and
copper. If the zinc is increased still further the shade gradually goes
over to white; this change is already observed in an alloy containing
51 per cent. of zinc, which shows a pure golden yellow colour, and is
very brittle. When the zinc rises to 53 per cent. the colour is reddish
white; at 56 per cent. it is yellowish white, at 64 per cent. bluish
white, and between 75 and 90 per cent. the alloy is bluish-grey.
The alloys for bronze powders of different shades have the following
composition, according to R. Wagner:—
Copper, Zinc
per cent. per cent.
Pale yellow 83 17
Red 94-90 6-10
Deep red 100
Bronzes from English, French and Bavarian works contain the following
percentages of copper:—
ENGLISH BRONZES.
Orange 9·82 per cent.
Deep yellow 82·37 ”
Pale yellow 80·42 ”
FRENCH BRONZES.
Copper red 97·32 per cent.
Orange 94·44 ”
Pale yellow 81·29 ”
BAVARIAN BRONZES.
Copper red 98·92 per cent.
Violet 98·82 ”
Orange 95·30 ”
Straw yellow 81·55 ”
Speiss yellow 82·34 ”
In each case the remainder of the alloy consists entirely of zinc.
Alloys containing from 1 to 35 per cent. of zinc are only malleable
in the cold. The malleability is at the greatest with a content of
zinc between 15 and 20 per cent.; such alloys are the most suitable
for making leaf metal. Alloys containing between 36 and 40 per cent.
of zinc may be hammered either cold or hot, whilst the former alloys
become brittle on heating. When the percentage of zinc is still further
increased the malleability decreases. The most brittle alloys contain
60 to 67 per cent. of zinc.
The alloys are made in a furnace with a good draught, for copper
liquefies at a very high temperature. To prevent loss of copper by
oxidation the molten metal should not come in contact with air; it
should be covered by a layer of red·hot coal, which prevents oxygen
from reaching it. When the copper is completely melted, which is
ascertained by stirring with a piece of wood, the whole of the zinc
is added. Some skill is required in this operation, otherwise a large
proportion of the zinc will be volatilised, and the vapours will burn
when they come in contact with air, in which case dazzling bluish white
flames are seen over the crucible. The best method is to throw the zinc
into the crucible and immediately stir it into the molten metal with
a wooden rod. The products of the dry distillation of the wood, which
are given off in great quantity at this high temperature, keep the air
from the surface of the metal and prevent the oxidation of the zinc
vapours. The zinc is thoroughly mixed with the copper by stirring with
the wooden rod, the crucible is then slowly cooled, with the precaution
that the surface of the metal is kept covered by red-hot coals so long
as the metal is fluid. When sufficiently cool the metal is poured into
shallow iron moulds, in which it quickly solidifies; it is then rolled
into sheets, which may be converted into thin leaves by hammering in a
similar manner to that in which the gold-beater makes gold leaf.
To obtain bronze powders of different shades alloys of different
colours may be used; the bronze powders may also be shaded by two
methods—either by adding certain colouring matters of very great
colouring power or by partially oxidising the finely divided metallic
powder. In the first process the finely ground colouring matter is
mechanically mixed with the bronze powder. The use of manual labour
would involve a great loss of time; even when quite small quantities of
bronze and colouring matter are mixed in a mortar it is necessary to
grind diligently for a very long time before a mixture of homogeneous
appearance is obtained. In working on a somewhat larger scale it is
therefore advisable to adopt mechanical mixing arrangements. A very
simple apparatus suffices. A sheet-iron cylinder is used which can be
revolved, and provided with a well-fitting slide. In this cylinder are
placed the bronze powder and the colouring matter until it is about
half full; then, after tightly closing the slide, it is set in slow
rotation, which is continued until a test taken out shows a uniform
colour.
When bronze powder is slowly heated in a shallow vessel the colour
begins to darken at a temperature not much above the boiling point of
water. In consequence of the fineness of the particles of the metallic
powder the copper readily takes up oxygen, and is superficially
converted into copper oxide. This oxide is of a darker colour, and thus
by this method the shade of the bronze can be deepened as desired.
This simple operation requires a certain amount of practice to produce
a product of a determined shade. The desired result is most safely
attained when the bronze is spread out quite uniformly in a thin layer
upon a metal plate, which is gently heated from below. The powder soon
begins to darken; by cooling the plate the progress of the oxidation
may be arrested at any moment.
Recently bronze powders have come into the market showing all possible
colours in the deepest shades, by the aid of which very remarkable
colour effects can be produced. These bronzes are made by dissolving
an aniline dye in a little alcohol, pouring this solution over the
powder, and mixing the dye uniformly through the whole of the bronze by
working the mass for a sufficient length of time. In this way bronze
powders are produced which possess a green, red, blue or violet lustre,
according to the colour of the dye used. These colours with metallic
lustre can also be produced by bronzing the article with a white (zinc)
bronze, and then coating it with a varnish in which the required
aniline dye is dissolved. A bronze with a fine golden red glitter is
produced by applying a golden yellow bronze and then a varnish in
which a little aniline red is dissolved. It should be observed here
that these effects, produced by a coat of varnish in which an aniline
dye is dissolved, only turn out well when the dye is used in very
small quantity, for these colours are the strongest with which we are
acquainted, and in colouring power far surpass cochineal carmine, which
is renowned for this property.
When bronze is coloured by dyes the most varied shades can be obtained
with a metallic lustre. According to Conradty a very fine blue bronze
is obtained by boiling white bronze for some hours with a weak alum
solution, washing and drying, and then mixing in a mortar with a
strong solution of aniline blue in alcohol until the solvent has
evaporated. This operation is repeated until the desired depth of shade
is obtained. The bronze is then washed with pure water. Conradty also
recommends that the coloured bronze should be ground with a little
petroleum, and then exposed to the air to allow the petroleum to
evaporate. This operation, for which no chemical reason can be given,
is quite unnecessary. If other dyes or mixtures of them are used in
place of aniline blue, bronzes of corresponding colour are obtained.
However handsome are the bronzes coloured by this process, nearly all
have the disadvantage that the colours have little permanence, and
quickly fade when exposed to light. This is especially the case when
the bronzed article is coated with an oil varnish; if, however, a
spirit varnish is used, or indeed any varnish composed of a resin and a
volatile solvent, the colour of the bronze, protected by the layer of
resin, remains quite unaltered for a long time.
=Electrolytic Copper Bronze.=—Electrolytically precipitated copper may
be used as a bronze pigment; it is most simply made by adding pieces
of metallic zinc to a solution of copper sulphate free from iron and
violently shaking the flask for a long time. The liquid becomes warm,
and the copper separates in the form of a very fine precipitate, which
is collected on a filter and washed with air-free water (boiling water
is best) and then quickly dried. The upper portions of the precipitate
in the filter, which are exposed to the air, have generally a brownish
colour due to the incipient oxidation of the finely divided metal. They
are removed, and the lower portions show the characteristic colour of
pure copper.
In the same way silver can be precipitated from a solution of silver
nitrate in a finely divided state, but the particles of the silver
powder are so very small that they reflect very little light, and
consequently the powder has an unsightly grey colour. When a surface
painted with this silver is rubbed gently with a hard body, the
metallic lustre appears.
=Tungsten Bronze Pigments= are expensive and rarely employed. They
are obtained by fusing sodium or potassium tungstate in a porcelain
crucible and gradually adding tungstic acid until the mass has an
acid reaction. Tin dioxide is then added in quantity sufficient to
neutralise the tungstic acid; the mass is cooled and finely powdered.
According as potassium or sodium tungstate is used, a violet or reddish
pigment is obtained which exhibits the peculiar metallic lustre of a
bronze powder.
Still more costly is vanadium bronze, which is made by adding ammonium
vanadate to a solution of 2 parts of copper sulphate and 1 part of
ammonium chloride with continual stirring, until the precipitate no
longer re-dissolves on stirring. The liquid is then heated for several
hours to about 35° C., when vanadium bronze separates in golden yellow
scales. These are collected on a filter, washed and dried When ground
with oil or gum solution they can be used as a red gold bronze. The
colour is unaltered by the air.
CHAPTER XLVII.
VEGETABLE BRONZE PIGMENTS.
Under this apparently contradictory term, substances come into the
market which produce a peculiar metallic lustre. When applied under
certain conditions, the appearance is similar to that produced by real
bronze. The vegetable bronze pigments are lakes as pure and free from
foreign admixtures as possible. The lakes obtained from red wood or
logwood can be used for this purpose.
From the red woods (_see_ p. 384) a magnificent bronze pigment can be
obtained, which is either pure golden yellow or possesses a greenish
golden metallic lustre not unlike the colour of the wing cases of
the rose-bug. To obtain either shade a pure lake is first made by
extracting red wood with boiling water, adding a little carbolic
acid to the decoction (0·01 per cent. of the quantity of liquid) and
allowing to stand for several weeks. The liquid is syphoned off from
the deposit, heated, and alum added equal in quantity to 10 per cent.
of the wood used. The mixture is then allowed to stand for about a
week, the precipitate is filtered off, washed, and, if necessary,
dried. If the bronze is to be used in the form of water colour, the
precipitate is dried to a thick paste and mixed with about 10 per cent.
of its volume of thick gum solution, so that a viscid mass is obtained
which can just be applied with the brush. When the coating is made so
thick as to hide the surface of the bronzed article, it has when dry
the golden green colour.
In using this lake to prepare a pigment similar to gold bronze it must
be almost completely dried, and then mixed with the liquid obtained
in the following manner: White soap is melted on the water bath with
the smallest possible quantity of water, and when completely dissolved
the same quantity of white wax is stirred in, finally water is added,
so that the cooled liquid has the consistency of a moderately thick
varnish. When this liquid is ground with the requisite quantity of the
still damp lake and the mixture applied to paper, wood, or leather, and
after drying rubbed with a glass ball, it gradually acquires a very
fine golden bronze colour. This method of bronzing is largely used
in the manufacture of wall papers and for colouring fancy leather.
To protect this coating against the action of water, it should be
varnished when dry.
These bronze pigments may also be used in varnish. The lake is then
completely dried and ground with varnish in such quantity as to give a
thick mass which can just be brushed on.
The vegetable bronze is obtained from logwood in a similar manner, a
solution of stannic chloride being generally used to precipitate the
lake when a deep bronze is required, and alum for a pale gold shade.
By using mixtures of the two salts intermediate shades are produced.
The precipitate produced by alum may be shaded by means of potassium
bichromate. Hæmatoxylin forms with chromium oxide a deep bluish black
compound which has such intense colouring power that it is used to
colour writing ink. The ink is prepared by adding a little potassium
bichromate to a decoction of logwood. If a very small quantity of this
dark precipitate is mixed with the lake precipitated from logwood
extract by alum solution, colours are produced possessing the peculiar
metallic lustre and a shade depending upon the quantity of potassium
bichromate added. The addition of this salt must be very carefully
made, as a very small excess is sufficient to render the colour so dark
that it is useless as a bronze. The shade of the precipitate depends
upon the concentration of the liquid and other conditions, so that
it is impossible to give precise quantities. In practice, the safest
and most convenient method is to dissolve the bichromate in a large
quantity of water and add very small quantities of the dilute solution
to the logwood extract along with the alum. After each addition a
portion of the precipitate is rapidly mixed with the above-mentioned
solution of soap and wax, to which a little size has been added, and
then spread upon paper. If the desired shade has not yet appeared, a
little more bichromate is added and another test made, and the process
repeated until the proper shade is attained.
Pigments for colouring wall papers and fancy leather are not easily
made which produce such fine effects at so small a cost as the
vegetable bronze pigments, which deserve the greatest regard from the
colour maker and leather and paper manufacturers.
=Appendix—The Brocade Pigments (”Brocatfarben”).=—Under this
designation powders have been recently introduced characterised by
a strong metallic or glassy lustre, and very suitable for certain
purposes, such as the manufacture of wall papers, since they enable
remarkably fine effects to be produced. They consist of mica in a
tolerably fine state of division. Mica is a mineral which occurs
frequently in nature and which very readily splits into thin sheets;
it occurs in various colours. In thin sheets mica is colourless and
completely transparent; in somewhat thicker pieces it generally shows a
distinct metallic lustre similar either to that of gold or silver. When
ground to fairly fine powder, it has the same gold or silver lustre,
and gold or silver brocade colours are distinguished in commerce. They
are made by grinding mica which has been previously sorted according
to its appearance. The powdered mica can be sold as powder or may be
mixed with a binding substance in order to be ready for use. Gum Arabic
is generally used as the binding medium, but it can be replaced by the
cheaper dextrine. When printed upon paper the brocade pigments produce
the effect of a bronze, and in addition to their cheapness they have
the great advantage of being completely unaltered by the air.
PIGMENTS OF ORGANIC ORIGIN.
CHAPTER XLVIII.
LAKES.
The pigments commercially designated lakes generally consist of an
organic colouring matter united with a metallic oxide. In isolated
cases other compounds of colouring matters are included under the term,
such as indigo sulphonic acid, and yet more rarely pure colouring
matters are included, for example carthamine red. But the overwhelming
majority of lake pigments are compounds of a colouring matter with
the oxide of a metal. For this purpose the oxides of tin, lead and
aluminium are commonly used.
Lakes are generally made by mixing the solution of the colouring matter
with the solution of a salt of the metallic oxide, and precipitating
the oxide by an alkali. The colouring matter is separated along with
the oxide and forms with it a substance known as a lake. It has not
yet been decided whether the lakes are true chemical compounds of the
colouring matter with the metallic oxide, or whether the colouring
matter is simply held fast by the surface attraction of the finely
divided oxide. In favour of the latter view is the fact that a larger
or smaller quantity of the colouring matter can be united with a given
quantity of the oxide.
The lakes vary greatly in durability; some, such as the madder lakes,
can be counted among the most durable pigments, whilst others have very
little permanence, as for example, the logwood lakes.
The majority of the colouring matters used in the preparation of lakes
are of vegetable origin, but several are derived from animal sources.
The properties of the colouring matters used for this purpose vary
greatly; each material demands a special treatment for the production
of lakes. Therefore, in describing the methods by which lakes are made,
we shall give first the properties of the colouring matter in question,
and then proceed to the preparation of the lake. In the preceding
portion of the book the pigments have been arranged according to their
colour; the lakes will be described in the same order. The yellow, red
or green lakes of different origin will be treated in the same section
in order to facilitate reference to any particular pigment.
White lakes are not known, neither are there lakes which can be
described as black. With these exceptions lakes of all colours can be
made and also of all shades. As an example of this madder lake may be
given, which is found in commerce in a great variety of shades; it
can be made from the palest rose-red to the deepest purple red, or,
more properly, madder red, which is a characteristic shade. The shades
of any lake are obtained by mixing in a white pigment just as in the
manufacture of mineral pigments. Whilst, however, in the latter case
the white pigment must often be mechanically mixed with the colour, the
shading of the lakes is accomplished in their preparation. Generally
speaking, a pale shade of a lake is obtained by increasing the amount
of the salt, the oxide of which is used to precipitate the colouring
matter. The oxides in question are white (with the exception of lead
oxide); thus in the pale shades a small amount of colouring matter is
precipitated upon a large amount of oxide, whilst in the deep lakes
the reverse is the case, a large quantity of colouring matter is
precipitated upon a small quantity of oxide, and the shade thus appears
very deep.
Apart from the nature of the colouring matter contained in a lake,
and considering only the metallic oxide with which the colouring
matter is united, it appears that lakes containing lead oxide have
little durability. The combination between the colouring matter and
the metallic oxide in a lake is so loose that it is easily destroyed
by sulphuretted hydrogen; if a lake containing lead is exposed to the
action of air containing that gas the colour will, in the course of
time, inevitably blacken. The lakes containing tin are also susceptible
to sulphuretted hydrogen; in air containing but a trace of this gas
they quickly lose their brilliance and in time are quite discoloured.
Alumina is not affected by sulphuretted hydrogen, and must thus be
regarded as the most suitable oxide for the preparation of lakes. It
is generally applied in the form of alum, in the selection of which
great care is necessary if fine colours are to be produced. Commercial
alum frequently contains ferric oxide; when the alumina is precipitated
simultaneously with the colouring matter the ferric oxide is also
thrown down, and is mixed with the lake, its dark colour influencing
the shade of the lake greatly to its disadvantage. The effect of the
ferric oxide upon the colour of the lake is so important that it is
impossible, for example, to obtain a pale red lake with alum containing
iron. To avoid the bad results given by alum containing iron it should
be examined before it is used, and if it is found to contain any
considerable quantity of iron it should be rejected for this purpose.
After alum a solution of stannic chloride is most commonly used to
precipitate lakes, but it must be free from stannous chloride; it
produces as a rule darker lakes than alum. Care must be taken that the
stannic chloride solution is free from iron.
The ordinary process for making lakes is very simple: a clear
aqueous solution of the colouring matter is obtained; to this alum
or stannic chloride solution is added in proportion to the amount of
colouring matter dissolved by the water; the metallic oxide is then
precipitated by an alkali. Sodium or potassium carbonate or caustic
alkalis may be used; ammonia is very suitable for this purpose, since
it is free from iron. The precipitant must be cautiously added, it
is introduced in drops when the greater part of the colouring matter
has been precipitated; an excess of the alkaline solution would have
considerable effect on the shade of the precipitate. The precipitated
lake rapidly settles to the bottom of the almost colourless liquid; the
settling is particularly rapid when stannic chloride has been used. The
liquid is then drawn off, the pasty residue brought upon a strainer,
washed several times with water, and dried in the air or in stoves.
When dry, a properly prepared lake forms a mass of little coherence,
and can be readily ground to a soft powder, which may then be ground
with oil or gum solution to produce oil or water paints. At the same
time the materials are added to the pure lake which are used to shade
its colour; white pigments are generally employed for this purpose—the
paleness of the shade is proportional to the amount of white pigment
introduced. Certain lakes are shaded by small quantities of other
colouring matters; for example, the admixture of a small quantity of
a blue pigment with a pure red lake produces a much deeper colour
inclining to purple. If a small quantity of a red or blue colouring
matter is added to a yellow pigment there is produced a deeper yellow
inclining to orange, or a yellow inclining to green, in proportion to
the quantity of the added colouring matter.
It should be observed that it is of great importance for the colour
maker to have a practised eye, sensitive to fine differences of
colour. He may then produce colours faultless in shade, for if by
chance a colour does not turn out well it may be improved by judicious
admixtures. It is quite impossible to give definite rules for the
mixing of colours; the estimation of a shade cannot be taught in words,
it demands long practice. By the use of a system, provided the user
has normal eyes, very slight differences of colour can be readily
estimated. A scale of colours should be made from pigments of pure
and definite shades, in which scale successful mixtures are gradually
inserted, so that a series is produced in which the separate pure
colours blend regularly into one another. Then, when it is required to
produce a pigment corresponding to a certain shade on the scale, with
a little practice the shade can be readily produced, for the scale
indicates which colour predominates.
The so-called sap colours are generally characterised by very pure
shades. They are produced by decomposing a lake by an acid or a strong
base, evaporating the solution of the colouring matter so obtained at
a gentle heat and mixing with gum, starch, or some other thickening
material to produce a mass of such consistency that it can be formed
into balls or sticks.
The decoctions of the dye-woods always contain other substances in
addition to the colouring matters, which are precipitated with the
colouring matter, and somewhat injure its shade. When such a lake
is decomposed the colouring matter is obtained in a purified form,
thus showing its full beauty. This solution of the purified colouring
matter might be again precipitated with a salt solution and lakes be
produced which would be much brighter than the original, but the losses
incidental to this double precipitation would be so great that the lake
would be made much too expensive.
CHAPTER XLIX.
YELLOW LAKES.
Yellow colouring matters are widespread in nature; from them are
obtained many yellow pigments used in dyeing and in the manufacture of
colours. The colours produced by the yellow vegetable colouring matters
are not particularly bright; thus the yellow lakes are used chiefly
to produce cheap pigments, whilst the inorganic pigments are used for
bright yellows.
=Dutch Pink.=—Several species of buckthorn (_Rhamnus_) contain a yellow
colouring matter—xanthorhamnin—which is obtained pure by extracting
the yellow berries with hot alcohol. On cooling, the impure colouring
matter separates; by repeated recrystallisation from alcohol it is
obtained in the form of crystalline needles, which are soluble in water
and alcohol.
The yellow lake known as Dutch pink is prepared from yellow (Persian)
berries, by boiling the crushed berries with water and mixing the
extract with a solution of alum. The lake is then precipitated by the
addition of powdered chalk. As a rule, 500 parts of water are used to
100 parts of berries, 20 parts of alum are added to the decoction, and
the mixture poured upon 75 parts of finely powdered chalk. The liquid
is decanted off, the residue filtered, washed and dried. Commercial
Dutch pink is made from a mixture of the decoctions of yellow berries,
quercitron bark and turmeric, to which the alum solution is added, and
then chalk. The precipitate is made into conical lumps, which are sold
as Dutch pink, and used for ordinary painting and for colouring leather.
=Weld Lake.=—The dyers’ weld (_Reseda luteola_) contains a yellow
colouring matter formerly much used in dyeing; a yellow lake can also
be obtained from it. When weld is boiled with water a deep yellowish
green decoction is obtained, from which yellowish-green flocks separate
on cooling. The lake can be obtained from all parts of the plant except
the root, the flowering shoots giving the largest yield of colour; the
lake is generally precipitated by alumina. Equal parts of weld and alum
are boiled with water until the latter is dissolved and the liquid is
coloured deep yellow; the hot solution is quickly filtered through a
thick linen cloth and soda solution gradually added in small quantities
with continual stirring so long as effervescence follows.
Alum entirely free from iron is required to produce a bright yellow
lake; a small quantity of iron has great influence on the shade. Weld
contains more or less tannin, which gives very dark blue or green
compounds with iron salts, the production of a very small quantity of
which suffices to convert the yellow shade into an ugly dirty colour.
Chalk may be used instead of soda to precipitate the alumina; in this
case the precipitate will contain calcium sulphate in addition to the
alumina compound of luteolin.
Weld lake may be used in oil, or size, or as a water colour.
=Gamboge Lake.=—Crude gamboge is the dried sap of certain East Indian
trees; it is used as an artists’ colour, but only in water; for use in
oil it is converted into a lake. A particular treatment is necessary
to obtain a handsome lake. Gamboge is treated for several days with
water and the soft mass ground on the slab or in a mill until it forms
a uniform paste, which is mixed with water to a thick liquid, which is
then put through a fine sieve. A hot solution of alum is then added
in the proportion of three parts of alum to one part of gamboge, the
mixture is boiled in a wooden vessel and two parts of nitric acid added
whilst well stirring; finally a dilute solution of potash is added
in small quantities until the liquid solidifies to a jelly, which is
spread out in thin layers on filter cloth, well washed with water and
dried at a gentle heat.
=Prepared Gamboge.=—Crude gamboge cannot be used in oil painting
because it never gives a uniform shade, but when the colouring matter
is freed from admixtures and ground with oil, it gives a deep durable
colour of great beauty.
The colouring constituent of gamboge is a resin which is fairly soluble
in strong alcohol, whilst the impurities are insoluble. The pure
colouring matter is obtained without great expense in the following
manner: Coarsely powdered gamboge is placed in a large flask with
strong alcohol; the flask is well closed, placed in a warm position
and repeatedly shaken; the deep yellow solution is carefully poured
off from the sediment, water is then added, when the colouring
matter separates in flocks. Only sufficient water should be added to
precipitate all the colouring matter; test portions of the liquid
should be examined from time to time, the alcohol can then be recovered
by distillation and used again. The colouring matter separated from the
alcoholic solution forms a hard mass on drying; it must be very finely
powdered before it is ground in oil.
There are many other yellow lakes which can be obtained by adding
alum to an aqueous decoction of the colour-bearing material and
neutralising the liquid. Such decoctions are obtained from fustic,
quercitron (_Quercus tinctoria_), young fustic (_Rhus cotinus_), the
root of barberry (_Berberis vulgaris_), annatto (the fruit of _Bixa
orrellana_), turmeric (the root of _Curcuma longa_), etc. The yellow
lakes obtained from these sources are seldom used in painting, the
mineral pigments are preferred on account of their finer appearance.
These colouring matters are largely used in dyeing to produce shades
varying from yellow to brown, the majority are also used in calico
printing.
=Fustic Lake.=—Of the colouring materials mentioned above fustic
produces a lake which is so handsome that it deserves larger use in
painting than it has yet found. ”Old fustic” is chipped immediately
before use and extracted with boiling water; whilst still hot the
extract is mixed with a hot solution of alum; on cooling a fine yellow
precipitate is formed, which when dry is frequently sold under the name
of Dutch pink. (Genuine Dutch pink is made from a decoction of yellow
berries; the majority of the pigments sold under this name are made
from decoctions of mixtures of the different yellow dye wares.)
To obtain the best lake from fustic the alum used must be completely
free from iron, otherwise only a dirty green lake is produced. Since
the least trace of iron damages the shade of the colour, fustic lake
is more frequently made by means of lead oxide. To obtain the lead
fustic lake the decoction is allowed to stand for several days, so that
the morin, which together with maclurin forms the colouring principle
of fustic, may separate; the liquid is filtered from the precipitate,
and lead acetate solution added which has been boiled with litharge to
saturation, so that the most basic acetate is produced. The lead fustic
lake has a deep yellow colour; it is well adapted for use in painting,
but, like all lead pigments, is not specially permanent in air. By
admixtures of levigated chalk or starch paler shades of the dull yellow
lake are obtained.
=Quercitron Lake.=—Lakes are seldom made from quercitron alone,
although they possess a deep yellow colour; they are more frequently
employed in dyeing when they are produced directly upon the fibre.
Quercitron lake can be made by treating the aqueous decoction of the
ground bark with tin crystals and a little alum solution. With tin
crystals alone a darker yellow lake is obtained than when alum is used
at the same time. Different shades may thus be produced.
Extract of quercitron bark comes into commerce as a greyish yellow
powder under the name of flavine, which has great colouring power, and
may be used with advantage in the place of aqueous extracts of the bark.
Since the discovery of the aniline dyes the applications of all lakes
have been largely extended, since the dyes enable brighter shades to be
obtained without the many processes necessary when natural colouring
matters are used, and do not require so much skill on the part of the
workman. This applies not only to yellow colouring matters, but to the
many other colouring matters formerly used by the dyer. The principal
reasons which have so quickly brought the new dyes to the front lie in
their greater beauty and in the diminished labour required in their use.
=Purree or Indian Yellow= must not be confounded with the yellow cobalt
pigment known also under the latter name. It is a compound of magnesia
with an organic acid—euxanthic acid. It is obtained from the urine of
cows fed upon mango leaves. It comes into commerce in lumps weighing
about 50 to 60 grammes, which are dark brown on the exterior, but on
fracture show a fine orange yellow colour. Indian yellow is little
used, and is not likely to attain importance. Many cheaper colouring
matters equal in shade are known.
=The Colouring Matter of Saffron.=—The dried stigma of the flowers of
the saffron, a species of _iris_, has been long used for colouring
foods. It contains a very handsome yellow colouring matter of a
characteristic shade; formerly this was largely used in silk-dyeing,
and especially for dyeing glove leather. It is practically now no
longer used; considerably cheaper aniline dyes produce an equally good
shade. On account of its high price (1 kilogramme of saffron contains
about 60,000 stigmata) this material cannot be used for lakes,
although they leave nothing to be desired in fineness of shade, but
they have no great permanence.
=The Colouring Matter of Gardenia Grandiflora.=—The fruits of this
plant, which are imported from Southern Asia, contain a beautiful dark
yellow colouring matter, which, according to Rochleder, is identical
with the colouring matter of saffron. It is readily soluble in water;
lakes of various shades can readily be obtained by the addition of
salts to the aqueous solution. Alum gives a pure yellow, lead acetate a
yellowish red, and stannous chloride a dark orange red lake.
CHAPTER L.
RED LAKES.
COCHINEAL AND CARMINE.
The purple of the ancients was obtained from the shellfish _purpura_;
it was so costly that it was regarded as an attribute of royalty.
According to history the Tyrians discovered this colour; at any rate
they were able to use it for dyeing. In the writings of the ancients
Tyrian purple garments were regarded as the greatest luxury. The art of
obtaining a purple from this source was lost; more recently it has been
re-discovered, but the colour is found in no way to correspond with
what we regard as a bright shade.
When the Spaniards conquered Mexico they found an insect cultivated
which produced a splendid red colouring matter. This insect, the
cochineal, is parasitic upon certain cacti, especially _Cactus
coccinellifer_ and _Cactus opuntia_. The females only are used as
colouring material; the males are very small, and much fewer in number.
The cultivation of the proper species of cactus and of the cochineal
has spread to most tropical countries. The females, which are attached
in enormous numbers, are brushed off and killed by heating upon hot
plates. They then appear as grains of the size of millet seeds, with
a wrinkled surface covered with a silvery grey dust. This variety of
cochineal is the best. Black cochineal also comes into commerce; it
has a brownish black colour. It is produced by killing the insects in
boiling water, by which the grey dust which covers the living insect is
removed. Cochineal produces when ground an ugly reddish brown powder.
The animal nature of cochineal cannot be recognised by the naked
eye, it is seen on examination under the microscope; this has given
opportunity for the most incredible adulterations of the costly
substance. Cases have been known in which a paste chiefly composed of
flour has been pressed into the form of cochineal, the grains coloured
by some cheap red colouring matter, powdered with the dust from boxes
in which cochineal has been packed, and placed upon the market as
cochineal. The expert would not be deceived by this gross fraud, but
another method of adulteration is far more difficult to recognise;
genuine cochineal is brought into commerce from which the greater part
of the colouring matter has been extracted, and which has been again
powdered with the grey cochineal dust. Such extracted cochineal does
not produce the same brownish-red powder as the fresh substance.
In the cochineal insect there is a very large quantity of colouring
matter: it may reach 50 per cent. of the weight of the dry insect. The
colouring matter, which is known as carmine (the same name is also
applied to its lake), is soluble in water with a fine red colour. When
cochineal is extracted with water the operation must be often repeated,
and each time fresh quantities of colouring matter are dissolved.
The cochineal may be exhausted by repeated boiling with water, but a
large quantity of liquid containing little colouring matter is then
produced. In order to obtain a strong solution of the colouring matter
the cochineal must be powdered; this is difficult on account of the
softness of the material, which does not give a fine powder, but a
pasty mass. The object is best attained by grinding the cochineal
through a mill similar to a coffee mill, but since the grooves of the
steel cone, which effects the crushing, may be easily clogged, the mill
must be arranged so that the cone can be taken out and cleaned.
The colouring principle of cochineal is an acid, carminic acid, which
was obtained by its discoverer, Warren de la Rue, in the following
manner: 1 part of powdered cochineal is boiled with 40 parts of
water for 20 minutes; after standing, the liquid is poured off from
the sediment, and mixed with a solution of 6 parts of lead acetate,
acidified by 1 part of acetic acid. The precipitate, which consists
of impure lead carminate, is filtered from the colourless liquid and
carefully washed; whilst still wet it is suspended in water, through
which sulphuretted hydrogen is passed; the lead carminate is decomposed
into lead sulphide and carminic acid, which dissolves in the water. The
colouring matter is not yet quite pure; the treatment with lead acetate
and sulphuretted hydrogen must be repeated, the solution then obtained
is evaporated at a low temperature, the residue dissolved in boiling
alcohol, phosphoric acid added to decompose traces of lead carminate
still present, then ether, finally the clear liquid is separated from
the precipitate and evaporated. By this process carminic acid is
obtained in a state of complete purity; unfortunately the process is
too complicated for practical application. Pure carminic acid is a
purple red mass, which transmits red light at the edges and forms a
pure scarlet red powder when ground. The aqueous solution gives, with
alum and ammonia, a characteristic precipitate, the colour of which
is the purest carmine-red; lead, zinc and copper salts produce purple
red precipitates. The composition of carminic acid is expressed by the
formula C₁₇H₁₈O₁₀.
CHAPTER LI.
THE MANUFACTURE OF CARMINE.
The colouring matter of cochineal is used in the form of a lake under
the name of carmine, the finest and most expensive colour used in
painting. However simple the preparation of carmine may appear, it
is not easy to obtain a product of great beauty; certain conditions,
still unexplained, play an important part in the process. Until not
long ago the manufacture of fine carmine was regarded as a secret; this
it is no longer, and with proper care any one may produce an entirely
satisfactory product. Many recipes have been given, some of the best
will be mentioned.
Whatever method is used to obtain carmine certain precautions must
be taken, without which it is impossible to obtain a bright colour.
Alkalis and alkaline earths in very small quantity affect the shade of
carmine, so that spring water should never be used in its preparation.
Pure rain water, or, still better, distilled water, should be employed.
The decoction of cochineal is difficult to filter. Paper cannot be
used, because the pores are so rapidly stopped up that new filters
would be continually required. Fine silk is the most serviceable; it
should not be washed with soap—the alkalinity of the small quantity of
soap the fabric would retain would affect the colour. The decoction is
made in a well-tinned copper pan, all other vessels should be of glass
or porcelain, which are most easily cleaned, and great cleanliness
is the prime essential to the success of the process. The greatest
care is required to prevent the contact of the liquid with iron during
the whole process, the smallest trace of this metal would result in a
discoloured product.
The essentials of the manufacture of carmine on the large scale are
that the colouring matter is dissolved in water, and precipitated by
the addition of an aluminium salt, generally alum, absolutely free from
iron. The more slowly the carmine separates the finer is its colour.
It is generally observed that the last portions to precipitate show
the brightest shade. This is because the foreign substances occurring
with the carminic acid in the decoction are thrown down with the first
portions of the precipitate. In the process of Frau Cenette, famous for
the beauty of the product, a solution is made from which the whole of
the carmine is separated in about three weeks. During this long time
the majority of the substances which have been dissolved in the water
together with the carminic acid are decomposed; the liquid acquires an
unpleasant smell, and is covered with mould. In the author’s opinion
so good a product is obtained by this process because the greater part
of the impurities is decomposed: the nearer the product approaches the
pure compound of carminic acid and alumina, the purer and brighter will
be the shade of the carmine.
It is known that light has considerable influence on the beauty of
carmine. During dull winter days it is quite impossible to produce so
fine a product as in summer. Instead of alum a tin solution may be
used to precipitate the colouring matter; the shade of the product is
different to that of alumina carmine.
CENETTE’S METHOD.—1 kilogramme of finely powdered cochineal is boiled
with 75 litres of water for two hours; 90 grammes of saltpetre are
added, the liquid boiled for three minutes, then 120 grammes of salt of
sorrel (acid potassium oxalate) are added and the liquid again boiled
for ten minutes. The liquid is then completely clarified by standing,
drawn off from the residue by a syphon, and brought into shallow glass
dishes which are placed, protected from dust, in a bright light in
a uniformly warm place. During several weeks the carmine separates,
the last portions being always brighter than the first. The addition
of potassium oxalate has the object of assisting the separation of
the carmine, for acid salts separate the carmine from solutions; the
saltpetre may reasonably be omitted.
The majority of the recipes for carmine, which are frequently sold at a
high price, differ but little from the above; acid potassium tartrate
is used instead of the oxalate, but the latter is to be preferred
because of the slight solubility of the tartrate. It is important
not to use too strong decoctions of cochineal, and to add only small
quantities of alum. The clear liquid is placed in shallow glass dishes.
After a few days the nature of the deposit should be examined: if a
considerable quantity of a red precipitate has formed, the liquid is
poured off into other dishes, in which carmine again separates during
the following days, and usually of a brighter colour than the first.
For example, 125 grammes of cochineal are boiled with 5 litres of water
during fifteen minutes, 30 grammes of very finely powdered alum are
added to the boiling liquid, which is again boiled for a few minutes,
allowed to clarify and cool. The greater part of the carmine is then
obtained in a few hours, but the liquid still separates carmine after
several days.
According to another formula 500 grammes of cochineal are boiled with
30 litres of water, 60 grammes of cream of tartar are added, then
30 grammes of alum, boiling is continued for several minutes, and
the liquid then allowed to cool. Carmine may be obtained in a very
short time by means of tin solution. The process is similar to that
just given. The liquid which would be set aside for the spontaneous
deposition of the carmine is, however, returned to the pan, and a
solution of pure stannous chloride added in drops, so long as the
solution is still clearly red. The carmine separates at the bottom of
the pan; the liquid drawn off, even when it appears almost colourless,
produces a further small quantity of carmine in a few days.
According to J. J. Hess, a brighter carmine is obtained when the fat of
the cochineal is previously extracted by ether or benzene.
Proposals have often been made to deepen the colour of prepared
carmine; this must be done with the greatest care, for it is very easy
to produce a less handsome instead of a finer pigment. The carmine is
moistened with distilled water containing about 5 per cent. of ammonia
solution.
Carmine readily dissolves in ammonia. This property may be applied to
test its purity, pure carmine should dissolve without residue in 5 to
6 times its quantity of ammonia. Any considerable residue denotes an
intentional addition of some adulterant. Starch, vermilion, and cheaper
lakes are used for this purpose. The red solution obtained by treating
carmine with the above quantity of ammonia may be used as a red ink.
This solution can also be used to purify carmine; when it is allowed to
stand in an uncorked bottle for some time the ammonia escapes, and the
greater part of the carmine is deposited as a very fine powder.
Carmine solution is made by dissolving carmine in the necessary
quantity of ammonia, adding glycerine equal in quantity to the ammonia,
driving off the latter by heat and diluting the liquid. This solution
is well adapted for colouring confectionery, but cannot be employed in
painting and writing, since the glycerine would prevent it from drying.
Carmine is extensively used in painting, and for many purposes cannot
be replaced by another pigment, _e.g._, the cosmetic known as vegetable
rouge can be made from no other pigment. Carmine may be used in all
methods of colouring; it is quite harmless for confectioners’ purposes.
=Munich, Vienna, Paris, or Florentine Lake.=—This fine deep red lake
differs from carmine in containing a much larger quantity of alumina,
thus possessing the character of an ordinary lake. Occasionally carmine
lake is intentionally mixed with light white substances, such as
magnesia, to obtain paler shades or cheaper pigments.
Whilst only the finest varieties of cochineal can be used to make
fine carmine, the cheaper sorts can be used for Florentine lake. The
cochineal used for carmine is boiled but a short time with water,
so that the residue contains considerable quantities of colouring
matter, which may amount to half of that originally present. The same
materials are used as in the preparation of carmine, and in this case,
too, stress should be laid upon their purity. The weight of the alum
is usually 10 to 15 times that of the cochineal; a little stannous
chloride and cream of tartar are also added to brighten the shade. All
these materials are boiled with the cochineal, soda is added to the
clear solution until effervescence no longer occurs, the separated lake
is then washed. The lake may be made with magnesia instead of alumina,
it is added in the form of magnesium sulphate; the more magnesia is
used the paler is the lake. The proportions in which the materials are
employed vary with each manufacturer. The following quantities have
always given the author a favourable result: Cochineal 10 parts, alum
150 parts, water 250 parts; or cochineal 10 parts, magnesium sulphate 5
parts, alum 0·5 part.
In making Florentine lake a fairly deep colour should be produced.
This may be mixed without difficulty in the wet or the dry state with
a white pigment, thus producing any desired shade, even to the most
delicate rose-red.
=Ammonia-Cochineal.=—This preparation, which is chiefly used by dyers,
is obtained by treating cochineal in a well-closed flask with strong
ammonia, which dissolves the colouring matter. After about a month alum
equal to about 3 per cent. of the amount of cochineal is added without
separating the undissolved residue from the solution, and the whole is
evaporated at a gentle heat in a tinned pan until it becomes a stiff
paste on cooling. The mass solidifies more readily if a small quantity
of starch paste is added. ”Cochineal paste” is cochineal which has been
treated in this manner; it is generally brought into the market in the
form of cakes or small slabs.
In addition to the true cochineal other species of the same insect
contain a red colouring matter and have a restricted use in dyeing. The
most important of these is the Polish cochineal (_Coccus polonicus_),
which lives on the roots of the _scleranthus_. It has not been proved
that these insects contain the same colouring matter as true cochineal,
but it is certain that the colouring matters of Polish and also of
Russian cochineal (_Coccus euvæ ursi_) are far inferior in beauty to
that of true cochineal.
CHAPTER LII.
THE COLOURING MATTER OF LAC.
From the punctures of the insect _Coccus lacca_ on certain East Indian
trees, especially those belonging to the genus _Ficus_, flow at the
same time resin and colouring matter in such quantities that the
insects are frequently enclosed and large red masses are formed on the
trees. The insects live in some measure in these masses, the females
lay their eggs in the spaces and the larvæ are said to feed on the red
sap contained in the mass. When the larvæ have left the incrustation,
generally in November, it is broken off from the branches and
collected. It is now known as stick-lac; it consists of large masses
of resin of a fine deep red colour. In the interior the cells of the
insects may still be perceived. On chewing, it becomes soft and colours
the saliva a deep violet. When stick-lac is boiled in water a portion
of the colouring matter dissolves. Good stick-lac contains 10 per cent.
of colouring matter and 80 per cent. of resin.
Seed-lac has the same origin as stick-lac, but frequently the greater
part of the colouring matter has been extracted; it rarely contains
more than 2·5 per cent., and is consequently of little value for
colouring purposes.
=Lac Dye.=—The colouring matter of stick-lac is generally separated
from the resin in India and comes into the market under the name of
lac dye. It is made by stirring coarsely powdered stick-lac in large
vessels for several hours with warm water. Almost the whole of the
colouring matter dissolves, whilst the resin remains as a ruby red mass
which is melted and brought into the market under the name of shellac.
The solution of the colouring matter is evaporated in shallow vessels
in the sun or boiled down in pans; the residue is made into cakes. At
present soda solution is used instead of pure water to extract the
colouring matter; a larger yield is obtained. Lac dye usually contains
45 to 50 per cent. of colouring matter, 25 per cent. of resin, and, in
addition, earthy substances which are to be regarded as intentional
admixtures.
In the preparation of lac dye by Stephen’s method coarsely powdered
stick-lac is boiled with soda, and the remainder of the colouring
matter contained in the resin extracted by repeated boiling with
water. All the extracts are then united and precipitated by alum. The
colouring matter separates as a lake which still contains a large
quantity of resin.
According to the patented process of Henley, the colouring matter of
seed-lac is extracted by hydraulic presses. The lac is filled into
press bags which are placed between iron boxes heated by steam. On
applying pressure the melted resin, shellac, comes through the bags,
whilst the colouring matter remains behind. If this method were
employed on the large scale, presses similar to those used in stearin
candle works would be suitable.
When lac dye is treated with hydrochloric acid the colouring matter
dissolves; the solution can be used to dye wool, which it colours a
beautiful red. The colouring matter is very similar in appearance to
that of cochineal, but has the appearance of much greater fastness. It
appears also to be similar in composition to carminic acid, but little
is known as to its chemical constitution.
When lac dye is to be used for painting it must be freed from resin;
this is accomplished by treating the finely powdered mass for a long
time with boiling alcohol and separating the solution of resin from
the undissolved colouring matter, which is then dried. In this way a
lake is produced known commercially as Vienna red and little inferior
to carmine lake. Unfortunately the price of lac dye, although it is
imported in large quantities from India to England, is so high that it
can only be used for artists’ colours.
CHAPTER LIII.
SAFFLOWER OR CARTHAMINE RED.
The safflower or bastard saffron (_Carthamus tinctoria_) grows wild
in Southern Europe, and is also cultivated. It contains two colouring
matters, yellow and red. The former is not used in dyeing, but is
employed for colouring liqueurs, since it is innocuous. The red
colouring matter is used for colouring artificial flowers and for fine
cosmetics; formerly it was employed in dyeing, but is now rarely used
for this purpose, since carthamine red has little permanence and can be
replaced by cheaper dyes.
The yellow colouring matter, which is not used, is generally removed
by treating the corolla of the safflower, which contains the colouring
matter, with water. After this treatment it is known as washed
safflower. In the dried corolla of the flower up to 36 per cent. of the
yellow colouring matter is found, whilst only 0·4 to 0·6 per cent. of
the red is contained.
It appears that the colouring matter of the safflower has been used
from the most ancient times. The Chinese employ it to obtain a handsome
cosmetic, the Tyrians are said to have used it in dyeing. In Europe it
was not cultivated before the seventeenth century, when it came into
use for dyeing.
In order to obtain pure carthamine red—and this is the form in which
it is generally used—safflower is treated for a long time with water
containing a little acetic acid until a yellow solution no longer
results. The residue is then treated with soda solution for several
hours, when the colouring matter dissolves; the solution is filtered
and neutralised with acetic acid. Cotton is then introduced. Carthamine
red is a colouring matter which at once dyes animal and vegetable
fibres when these are brought in contact with its solution. Thus the
whole of the colouring matter is precipitated on the cotton, which is
coloured a deep red. After twenty-four hours the cotton is taken out,
washed, and treated with soda solution, in which the colouring matter
dissolves. When this solution is carefully neutralised with citric acid
the colouring matter separates in the form of fine flocks. These are
collected, dissolved in strong alcohol, the solution evaporated to a
small volume, the colouring matter again precipitated by the addition
of a large quantity of water, and washed with pure water until the wash
waters begin to be coloured red. The pure carthamine thus obtained is
spread upon small cups, in which it dries to a beautiful red mass which
in somewhat thicker layers has a fine green lustre. It is brought into
commerce as ”cup red” or ”plate red”.
The small quantity of colouring matter contained in the safflower,
as well as the complicated process for obtaining it, make it evident
that this colouring matter will be among the most expensive found
in commerce. The high price is, however, neutralised by its great
colouring power, and by the fact that nothing can in all cases replace
it for colouring the best artificial flowers.
=Safflower Carmine.=—This substance, used by dyers, is a solution of
carthamine red in soda solution. It is only necessary to add an acid
after once introducing the fabric in order to fix the colouring matter
at once upon the fibre.
The shades produced by carthamine red are distinguished by a delicacy
of tint not produced by other dyes; all shades between the deepest red
and the palest rose-red may be obtained from it. Unfortunately it is
very susceptible to the action of alkalis; one careless washing of an
article dyed with carthamine is sufficient to remove the greater part
of the colour.
On account of its cost and little durability carthamine red is not
used in painting. It is principally employed in the artificial flower
industry for colouring flowers. Pure carthamine or a mixture with
finely powdered steatite is applied by rubbing.
=Alkanet.=—The roots of alkanet (_Alkanna tinctoria_) contain in the
bark a fine red colouring matter, from which also a violet lake can
be obtained, though this is rarely made. The plant is largely grown
in Southern Europe and also around Vienna. The colouring matter is
obtained pure by macerating the root for a long time with water and
then treating with strong alcohol, which dissolves the colouring
matter, together with a large quantity of resin. The alcohol is
distilled off, the residue extracted with ether, and the ethereal
extract treated with a large quantity of water, which extracts the
colouring matter. This is left in the pure state, when the solution is
slowly evaporated.
According to Carnelutti and R. Nasini alkannin is obtained by
extracting the root of _Anchusa tinctoria_ with petroleum ether,
evaporating, treating the residue with weak caustic potash, filtering,
and shaking the filtrate several times with ether. The solvent is
removed, the colouring matter precipitated by carbonic acid, dried over
sulphuric acid, and dissolved in ether. The filtered solution is then
allowed to evaporate. Alkannin is then obtained as a dark brownish-red
mass, which is easily powdered. It has a metallic lustre, and readily
dissolves in alcohol, glacial acetic acid and chloroform.
When alum is added to the aqueous solution of the colouring matter a
beautiful violet precipitate separates, which when dry is very suitable
for artistic purposes. Alkanet is little used. It is completely
replaced by much cheaper colouring matters.
CHAPTER LIV.
MADDER AND ITS COLOURING MATTERS.
The root of the madder (_Rubia tinctoria_) contains a red colouring
matter which is distinguished over all other colours of vegetable
origin by great fastness, on account of which it occupies a most
important position in dyeing and colour making. The use of madder in
dyeing has been much restricted by the discovery of artificial methods
of making alizarine, the most important colouring matter of madder.
Thus the following account of madder and its products is chiefly of
historical interest only.
Madder is cultivated in many countries. The roots, which vary from the
thickness of a quill to that of a finger, are cleansed from adherent
earth, carefully sorted according to size, and dried. In commerce a
distinction is made between stripped and unstripped madder. The cortex
of the root contains but little colouring matter and is generally
removed by mill-stones moving at some distance apart. The stripped
roots are finely ground, and are then known commercially as madder.
Merchants distinguish a large number of varieties, which are designated
according to the place of production. In addition to ground madder
there are a number of madder preparations which contain the colouring
matter in concentrated form, and are consequently used in smaller
quantity. The most important of these preparations are garancin,
garanceux, and the madder extracts.
”Refined madder” is made from the natural substance by subjecting it
to a process of fermentation, by which the substances accompanying
the colouring matters are largely decomposed, and the product becomes
relatively richer in colouring matter.
”Flowers of madder,” which have double the colouring power of madder,
are made by treatment with very dilute sulphuric acid. Madder is
stirred with five or six times its quantity of water to which about 1
per cent. of sulphuric acid has been added. After leaving the mixture
in a fairly warm place for five to six days alcoholic fermentation
takes place, and many substances which would be injurious in dyeing
are decomposed. The residue becomes in consequence richer in colouring
matter. When the fermentation is finished the residue is filtered
off, subjected to powerful hydraulic pressure, and the mass broken up
and very thoroughly dried at a temperature of 60° to 70° C. If it is
not thoroughly dried it soon becomes mouldy. This method of treating
madder, due to Julians, is simple, and has the advantage that from the
alcoholic liquid spirit may be obtained. In some respects this process
is more rational than the one immediately following: certain substances
which are destroyed in the manufacture of garancin are made useful, and
also the process requires little outlay.
=Garancin= is obtained from madder by treatment with sulphuric acid,
which decomposes the glucoside, and also sets free the colouring
matter united to lime and magnesia, which would otherwise be lost. In
addition, the warm acid radically attacks the nitrogenous compounds,
the greater portion of which is destroyed. Thus the residue contains
relatively more colouring matter, and the removal of substances which
accompany the colouring matter considerably facilitates the dyeing
process.
Although the preparation of garancin was recommended in 1828, it was
much later before the prejudice which prevented its general employment
was completely overcome, and garancin recognised as a very valuable
material for the dyer. The simplest process for preparing garancin is
as follows: Madder is several times washed with water, then pressed,
and the residue mixed with dilute sulphuric acid in a lead-lined
vessel. To 100 parts of madder 50 parts of sulphuric acid and 50
parts of water are taken, the mixture is heated by steam to 100° C.,
and maintained at this temperature for half an hour. By the action
of sulphuric acid of this strength considerable charring occurs, and
in particular the cell walls of the madder are attacked, so that in
the succeeding process the colouring matter is readily dissolved; in
consequence of the charring, the garancin acquires a deep brown to
black colour. When the action of the acid is finished, it is drawn off
and the residue washed with water until it is free from acid, when it
is dried. The process here described is the original method; it has
been much modified, hydrochloric acid, zinc chloride, alkalis, soap
solution, etc., being used in the manufacture of garancin. The colour
maker will rarely require to make garancin himself, so that it is
sufficient for our purpose to indicate what is understood by garancin,
and in what manner it is made.
=Garanceux.=—Madder which has been once used in dyeing still retains
some quantity of colouring matter; this is utilised by treating it by
the same process which is used to obtain garancin from fresh madder.
The treatment with sulphuric acid almost entirely destroys the cellular
structure, so that the residual colouring matter is made accessible to
solvents, and consequently the garanceux may be again used for dyeing.
=Madder Extract.=—The fixation of the colouring matter of madder upon
the fibre is attended with many difficulties; attempts were made to
present it in the purest form possible, or in such a condition that
the operation of dyeing was simplified. The commercial madder extracts
consist either of liquid extracts of madder, or of the more or less
pure colouring matter itself. Among the numerous solid or liquid madder
extracts, without doubt the most important is the crude alizarin (the
principal colouring matter of madder), made by the process discovered
almost simultaneously by Rochleder and Pernod. This is produced
by extracting either madder or garancin with hot water containing
sulphuric acid; about 5 grammes of acid are mixed with 1 kilogramme
of water and the madder boiled with this dilute acid in a lead-lined
vessel. The liquid separated from the solid residue becomes turbid on
cooling, and yellow flocks separate which consist of impure alizarin;
no further purification is required for practical purposes. Crude
alizarin is also obtained by treating madder with superheated steam.
These preparations are important, not only to the dyer and calico
printer, but also to the colour maker; from them the madder pigments
can be made in a very simple manner.
=The Constituents of Madder.=—Madder has been most thoroughly
investigated: its colouring matter, alizarin, is now made artificially.
In addition to woody fibre, madder contains sugar, mucilage, resin, a
glucoside (_i.e._, a substance which can be decomposed into a sugar and
another substance), and, in particular, two colouring matters known as
alizarin and purpurin.
Alizarin occurs ready formed in madder, and is also produced by the
decomposition of the madder glucoside into alizarin and sugar. To
obtain pure alizarin finely ground madder is extracted with boiling
water; on the addition of sulphuric acid to the decoction alizarin
separates together with other substances. The moist precipitate is
boiled with a solution of aluminium chloride, and, after filtering,
hydrochloric acid is added to the filtrate, when deep red flocks
separate, consisting of a mixture of alizarin and purpurin. The
colouring matters are further purified by dissolving in alcohol and
adding freshly precipitated alumina, which unites with them; the
alumina compounds are then boiled with strong soda solution, in which
the purpurin dissolves. The residue consists of aluminium alizarinate
mixed with resin, the latter is extracted with ether or benzene, and
the residue then decomposed with hydrochloric acid, when alizarin is
set free and is purified by recrystallisation.
Alizarin has the formula C₁₄H₆O₂(OH)₂. It forms fine red crystals
which are very little soluble in cold but more easily in hot water;
they dissolve readily in strong alcohol to a yellow solution. Alizarin
dissolves in alkaline liquids, the solution is dichroic; it appears
dark purple by transmitted light and pure blue by reflected light. When
the alkaline solution of alizarin is brought in contact with freshly
precipitated alumina the colouring matter is completely thrown down and
a beautiful red lake is formed.
The second madder colouring matter is purpurin. This is more soluble in
water than alizarin, it also dissolves in alum solutions; its alkaline
solutions are not dichroic. The formula of purpurin is C₁₄H₅O₂(OH)₃.
In addition to these two colouring matters, madder contains a third,
known as rubiacin, which also forms red compounds. It appears to be
fixed upon fabrics dyed with madder in company with the other colouring
matters.
Dyeing and printing with the colouring matters of madder are among the
most difficult processes in dyeing; a long series of operations is
required to fix the colour permanently on the fabric. The beautiful
deep red colour known as Turkey red is produced by madder; it is
distinguished from other vegetable colours by its great fastness. By
means of madder various other shades besides pure red may be produced.
This very valuable substance is largely used in dyeing and calico
printing to produce permanent colours.
CHAPTER LV.
MADDER LAKES.
The madder lakes are equally as permanent as the madder colouring
matters dyed upon fabrics. On this account and because of their
handsome colour they are highly prized by painters. The best qualities
of madder are necessary to produce fine lakes; it is more convenient
to use garancin or madder extract. Only when the colouring matter is
tolerably free from the foreign substances which accompany it can
a pure red madder lake be produced; the poorer qualities of madder
produce a lake which is not a pure red and is never bright. The good
repute of the madder lakes of certain makers is in great part due
to careful choice of the raw materials. This choice and care in the
process are the secrets of the manufacturers who produce good madder
lakes.
The author has found that the finest lakes can be obtained without
difficulty from the alizarin, separated in the before-mentioned manner
from madder by means of sulphuric acid. The small cost of obtaining
crude alizarin by this process enables it to be used on a commercial
scale. The labour involved in the process is far outweighed by the
excellent qualities of the lakes produced.
A very bright lake is obtained directly from madder by treating with
sulphuric acid (thus garancin is really used), digesting the mass
for several hours with a solution of alum absolutely free from iron,
filtering and adding at first a small quantity of soda solution; a
little madder lake is precipitated which is of the finest shade.
When this lake has settled the liquid is poured off and again mixed
with a little soda solution. The lake now precipitated is inferior
to the first, if the madder is not of specially fine quality. By
this fractional precipitation of the colouring matter, madder lakes
varying in beauty are produced; the separate fractions often differ
considerably in shade, this is because the later portions are more and
more contaminated by the foreign substances contained in the madder.
From inferior madder lake, which could only be sold at a low price,
a lake of the best quality can be produced in the following manner:
The lake is finely powdered, mixed with acetic acid and left to stand
twenty-four hours; the madder lake dissolves in the acid to a fine red
solution, whilst the impurities remain on the filter when the solution
is filtered. The clear solution is mixed with a large volume of water
free from lime, and the acetic acid neutralised by soda, when pure
madder lake separates. The addition of soda is not continued until all
the lake is precipitated, but only until the liquid is still slightly
red. Hydrochloric acid may be used instead of acetic; it is much
cheaper, but must be absolutely free from iron.
It has already been stated that the crude alizarin prepared as
described above is well suited as a source of madder lake, since it is
free from the majority of the substances which injure the purity of
the shade. It is treated with a boiling solution of alum and filtered
whilst hot; madder lake is then precipitated by cautious additions of
soda, the first portions precipitated being the best.
=Madder Carmine= is not often found in commerce; it consists of the
almost pure lakes of alizarin and purpurin. The process by which
this valuable pigment is produced is based upon the great stability
of the madder colouring matters. The following is the process on the
large scale: Good madder, very finely ground, is spread out in small
heaps in a room, the temperature of which is about 16° to 18° C.; the
heaps are moistened with water and left for several days. The mass
ferments and gives off a peculiar smell; in the fermentation not only
is the glucoside decomposed, but also many of the other compounds
contained in the madder, consequently the mass becomes dark and
considerably diminishes in weight. The end of the fermentation process
may be recognised by a little practice with tolerable certainty by
the disappearance of the peculiar smell; the mass is broken up and
transferred to a lead-lined vessel, in which it is mixed with three or
four times its weight of ordinary sulphuric acid. The acid is allowed
to act for several hours, the plant fibres are almost completely
charred, and the mixture becomes black. When the charred residue has
settled, the liquid is filtered through pure quartz sand or powdered
glass, and mixed with a large quantity of water. The carmine, which is
insoluble in water, separates as a red powder; it is then washed and
dried.
The colour of madder carmine is of such beauty that it can only be
compared with that of good cochineal carmine, but it is incomparably
more permanent than the latter and may be used in all varieties of
painting.
CHAPTER LVI.
MANJIT (INDIAN MADDER).
The roots of the East Indian _Rubia mungista_ contain purpurin and
another characteristic colouring matter, manjistin. This material is
a rarity in German commerce, but is imported into England from India
in tolerable amount and used in dyeing. Manjistin may be extracted
by boiling manjit repeatedly with a solution of aluminium sulphate,
uniting the liquids and acidifying strongly with hydrochloric acid. In
twenty-four hours a red precipitate forms in the liquid; it is dried
and treated with boiling carbon disulphide, which extracts purpurin
and manjistin and leaves undissolved a dark resin. The residue, after
distilling off the carbon bisulphide, gives up purpurin to dilute
acetic acid, manjistin remaining undissolved. When the purpurin has
been completely extracted, the residue is treated with a little boiling
alcohol and repeatedly recrystallised; manjistin is finally obtained in
golden yellow crystals of the composition C₁₄H₁₅O₂(OH)₂.CO₂H.
When a solution of manjistin in a little alcohol is mixed with water no
precipitate occurs; on then adding aluminium hydrate and long boiling
an orange red lake is produced. Lead acetate produces a deep orange red
lake when used in just sufficient quantity; with excess a fine scarlet
lake is obtained.
If manjit were a common article in the German market, it would be used
in the preparation of fine pigments with as much advantage as madder
and the various madder preparations.
=Chica Red, Curucuru, Carajuru.=—The colouring matter known under
these names rarely comes into commerce; it forms brownish-red masses
which acquire a peculiar golden glitter on rubbing. It is obtained
from the leaves of _Bignonia chica_, a native of tropical America. The
leaves are superficially dried and then covered with water; in the
warm climate the macerated leaves soon ferment, and a deep red powder
separates at the bottom of the vessel: this is the colouring matter; it
is dried, made into small cakes and brought into the market.
Chica red is only partially soluble in strong alcohol, the residue
chiefly consists of plant cells. Alum and stannous chloride precipitate
beautiful red lakes from the solution, which are distinguished by great
permanence when exposed to light. On account of the present high price,
this colouring matter has not yet obtained admission into the colour
industries, though it would be a valuable recruit.
Chica red has been little studied; an investigation would certainly
considerably increase our knowledge of the organic colouring matters.
Towards reducing agents it behaves in a similar manner to indigo; in
contact with caustic soda, grape sugar and water in closed flasks, a
violet liquid is produced; when exposed in an open vessel the violet at
once changes to brown, but if the liquid is syphoned off into dilute
hydrochloric acid a pure red precipitate separates, which is to be
regarded as the pure colouring matter.
CHAPTER LVII.
LICHEN COLOURING MATTERS.
Many lichens contain compounds from which colouring matters can be
obtained by appropriate treatment; the colouring matters known as
cudbear, archil and litmus were formerly much more extensively used in
dyeing than at present: like so many natural colouring matters they
have been replaced by coal-tar dyes.
The lichens which produce colouring matters live upon trees and rocks,
chiefly on the sea-shore; the colouring matters are thus generally
manufactured in places near the coast. The species principally used for
this purpose are _Lecanora_, _Rocella_ and _Usnea_.
The lichens contain colourless compounds, which by treatment with acid
or alkalis produce orcinol. In contact with moist air and ammonia,
orcinol is decomposed into water and orcein, which is the colouring
matter. The lichens are treated so as to produce the largest quantity
of orcinol, which is then converted into orcein. There is not space
here to enumerate and describe the many compounds obtained from
lichens, only the most important can be mentioned; these are erythric,
lecanoric and usnic acids. Lecanoric acid produces, under certain
conditions, orsellic acid, which is again changed to orcinol.
Pure orcinol, C₇H₈O₂. H₂O, is a crystalline substance of sweet taste;
it is soluble in ether, alcohol, water, etc. In damp air containing
ammonia, orcinol gradually acquires a fine red colour, being converted
into orcein, C₇H₇NO₃, according to the following reaction:—
C₇H₈O₂ + NH₃ + 3O = C₇H₇NO₃ + 2H₂O.
When pure, orcein is a brownish-red amorphous powder, soluble in
alcohol to a scarlet solution and in alkalis to a purple solution. On
the addition of water to the ammoniacal solution or of salt to the
alkaline solution, orcein is again separated; this procedure may be
used to completely purify the colouring matter.
=Archil= is principally obtained from the lichens _Lecanora_ and
_Rocella_. These lichens have a wide geographical distribution; archil
is made in Sweden, Italy and Spain. It is obtained in a simple manner:
the powdered lichen is mixed with decomposing urine to a paste, which
is allowed to lie in the air until the colour has changed through
red to violet; on the average fourteen days are required for the
transformation. More recently the process has been made less disgusting
by replacing urine by ammoniacal gas liquor. When the mixture is violet
all through the process is finished; the wet mass is packed into
barrels, which are well closed to prevent it from drying.
The presence of alkalis accelerates the formation of orcein; in many
districts it is customary to add a little lime to the mixture of lichen
and urine; alum is also added to retard putrefaction, which readily
occurs in warm climates.
Instead of using lichens to produce the colouring matter, they may be
extracted by boiling water, the solution considerably evaporated and
then exposed to the air with the addition of ammonia, until the violet
colouration appears. Slight additions of sulphuric acid give a more
purple tint; soda produces a deeper violet.
=French Purple= is a compound of the archil colouring matter with
lime, _i.e._, a lime lake. This beautiful substance is obtained by
treating the lichen for some minutes with ammonia, pressing out
the liquid and neutralising it exactly with hydrochloric acid. The
precipitate obtained consists of the lichen acids; it is again
dissolved in ammonia and the solution exposed to the air until it has
become cherry red. When this is the case the liquid is quickly boiled
and placed in large shallow dishes, which are kept at a temperature
of 75° C. until the colour is purple-violet. Calcium chloride is then
added; a garnet red precipitate is produced, which, when washed and
dried, constitutes French purple.
Archil and French purple produce shades of great beauty and purity,
but they have little durability and are quickly altered by exposure to
light. They are, therefore, seldom used as pigments. The same is the
case with cudbear and litmus.
=Cudbear= is a dirty purple powder with an ammoniacal odour and salt
taste. It is made on a large scale in Holland. It differs from archil
only in containing the colouring matter in the solid form.
=Litmus= is generally made from lichens of the genus _Variolaria_,
though varieties of _Rocella_ and _Lecanora_ are often used. It is not
made in quite the same manner as archil and cudbear. Together with the
ammonia, potash is added to the powdered lichen. The mixture is left
until it has become violet, when urine, potash and lime are added at
intervals to continue the decomposition until the colour is changed to
blue and the whole mass has become a paste. Gypsum and lime are then
added, the mixture formed into rectangular plates, and brought into the
market, described by a number, according to the amount of gypsum added.
Pure litmus should leave little solid residue when dissolved in water,
the solution should be a fine violet. On account of its want of
stability this colouring matter is not used in dyeing. It can be used
for colouring foods since it is innocuous; but indigo carmine has much
greater colouring power and at the same time gives fine shades.
The only use of litmus at the present time is as an indicator to decide
whether a solution is acid, neutral or alkaline. In a quite neutral
solution litmus is violet. Acids turn the solution to red and alkalis
to pure blue. In preparing litmus tincture regard must be given to
the fact that the aqueous solution of the colouring matter is always
alkaline; acid must be cautiously added until the colour is violet, and
the least addition of acid or alkali suffices to change it to red or
blue.
CHAPTER LVIII.
RED WOOD LAKES.
Red wood is obtained from species of _Cæsalpinia_ growing in South
America. The following varieties are distinguished: Fernambuco or
Brazil wood, Bahia wood, St. Martha wood, Lima wood and Sapan wood,
all of which contain the same colouring matter, but in different
quantities. Red wood comes into commerce either as thick logs of a fine
red colour or as finely-rasped chips. Fernambuco and Sapan woods are
accounted the best varieties. Although the colouring matters contained
in these woods have been investigated for a long time, an accurate
knowledge of them has only recently been obtained. The pure colouring
matter of red wood, brasilin, forms orange-coloured needle-shaped
crystals, soluble in water, alcohol and ether. On careful heating it
partially sublimes undecomposed. Brasilin most probably results from
the alteration of a substance contained in the inner less coloured
portion of the wood; this compound, brasileïn, has been obtained in
colourless needles; its solution acquires a red colour on boiling, and
produces the pure colouring matter.
Brasilin is a weak acid of the composition C₁₆H₁₄O₅. It forms
handsomely coloured compounds with most metallic oxides, which are
much used in dyeing. A decoction of red wood gives with alum and
soda solution a handsome lake of a pure red colour. With a solution
of stannic chloride it at once produces a red precipitate. When a
solution of potassium chromate is added to a decoction of redwood, a
dark brown precipitate separates, which is a compound of chromium oxide
with the partially altered colouring matter. The decoction produces a
brownish red compound with ferric oxide.
The decoctions of red wood contain, in addition to the colouring
matter, a number of other substances which would injure the shade of
the lake obtained from the decoction. The greater portion of these
substances may be separated by allowing the decoction to stand for
several days, when a dirty reddish brown mud forms at the bottom of
the vessel. This simple method of purification is attended with the
disadvantage that, especially in summer, the decoction rapidly becomes
mouldy. This may be prevented by the addition of a little carbolic
acid; not more than 0·01 per cent. of the quantity of liquid is
required. The foreign matters may also be separated by adding milk or a
solution of glue to the decoction, but the simpler process of allowing
it to stand gives the best result.
From the behaviour of brasilin towards the metallic oxides, as given
above, it follows that compounds of different colours can be made from
red wood. These are utilised in dyeing, but in colour works red wood
is only used for the preparation of red lakes. The lakes are found in
commerce under numerous names, the most common of which are Venetian
lake, Vienna lake, Florentine lake, Berlin lake, etc. According as
the colouring matter is combined with alumina alone or with stannic
chloride in addition, pale or deep lakes are obtained. The different
shades of red wood lakes found in commerce are obtained by additions of
a white pigment. For this purpose levigated chalk, gypsum, lycopodium
powder, and other white pigments light in weight are used.
In preparing red wood lakes the decoction should always be purified by
the process mentioned above; there is then more certainty of obtaining
a bright lake. It is advisable to dilute the decoction considerably
with pure water before precipitating the lake; experience has shown
that brighter colours are thus obtained. To 100 parts of wood 130 to
150 parts of alum are used. The latter is dissolved alone and mixed
with the decoction, the lake is then precipitated by soda solution. As
the lake separates the liquid becomes lighter; portions should be taken
out of the vessel in order to see when all the colouring matter is
thrown down. If too much soda solution is added the lake takes a violet
shade.
A particularly fine lake is obtained from Fernambuco wood when the
extract is acidified with a weak acid, such as acetic, and stannic
chloride used together with alum in precipitating the lake. One hundred
parts of rasped wood are boiled with 300 parts of water to which acetic
acid has been added; the extract is then boiled with 130 parts of alum
until the latter is dissolved. To the filtered liquid 20 to 25 parts
of stannic chloride are added whilst stirring well, and the lake is at
once precipitated by soda solution.
If the lake from Fernambuco wood does not turn out well, a better
product may be obtained by treating the lake with such a quantity of
hydrochloric acid that a small portion remains undecomposed. This is
filtered off, and the colouring matter reprecipitated in combination
with alumina by neutralising with soda solution.
By adding a little Dutch pink more orange shades of the Fernambuco lake
are obtained. In this manner any intermediate shade between pure red
and pure yellow can be produced. It is important to lay down a standard
series of shades, and always to make pigments which exactly correspond
with one of them. It is not possible to make a determined shade of
red wood lake or any other lake obtained from a decoction by working
with accurately weighed quantities. In general the result will be near
the desired shade, but only by chance will it be hit exactly. This is
because different samples of the dye-wood do not always contain the
same quantity of colouring matter. It is indeed possible with practice
to estimate approximately from the colour of the decoction the shade
of the lake which will be obtained from it; but this can only be done
exactly by comparing the shade of a small batch of the lake with the
standard shades. Thus in the case of a Fernambuco lake it will be seen
by comparison with the standard shades whether the colour of the small
batch is too deep, too violet, etc.; then by using more alum or more
tin solution the defects can be removed.
CHAPTER LIX.
THE COLOURING MATTERS OF SANDALWOOD AND OTHER DYE-WOODS.
In addition to the dye-woods in more common use, the tropics furnish
a number of woods which contain fine colouring matters, but which are
only in restricted use, either on account of their cost or because they
are not always to be bought. To these belong the camwood or barwood of
Madagascar, the East Indian sandalwood, and other woods which have not
yet been used for colouring purposes even in the tropics.
The most commonly used of the rarer dye-woods is sandalwood, obtained
from _Pterocarpus santalinus_. It is garnet red in colour, sinks in
water, and produces a fine red meal, which rapidly becomes brown in
air owing to oxidation of the colouring matter. According to recent
researches, sandalwood contains two colouring matters, one obtained
from the other by oxidation. Only one of these, santalin, is known
with certainty. Sandalwood contains about 16 per cent. of santalin,
which when pure forms a crystalline powder, differing from other
wood colouring matters in being almost insoluble in water. Up to the
present it has only been used in dyeing to obtain handsome and fast red
colours. From it very bright lakes may be obtained, which may be used
equally as well as the red wood lakes. The aluminium and tin lakes are
especially fine. The extract of sandalwood is obtained by boiling very
fine chips with water, then adding alcohol and leaving the mixture.
When stannic chloride or alum, or a mixture of the two, is added to the
solution of the colouring matter a red precipitate is produced which,
after washing and drying, furnishes a bright red lake.
CHAPTER LX.
BLUE LAKES.
=Indigo.=—The colouring matter of the indigo plant is distinguished by
great resistance to the action of light, air, and chemical reagents.
It is thus often cited as a particular example of a fast and durable
colour. It is very largely used in dyeing, and in certain combinations
is important as a painters’ colour.
Indigo comes into commerce in a great variety of qualities, all
imported from the tropics, in which alone the plant grows. The
principal varieties are Indian, Java, Egyptian, American and African,
but in these merchants make numerous subdivisions which are often to
be distinguished from one another only by very small differences. Good
indigo, whatever its source, has the following characteristics: It
appears in almost cubical lumps, but may also form irregular masses.
The lumps must show a small specific gravity, a higher might be caused
by intentional additions of sand or earth. It is without taste and
smell, and the colour of the finest varieties is not particularly
bright, but when rubbed with a hard substance, or even by the pressure
of the finger nail, it acquires a peculiar coppery lustre, which is the
more intense the purer the indigo, and is thus regarded as a common
test of quality. Indigo is completely insoluble in almost all solvents;
in hot oils a small quantity dissolves, which again separates on
cooling. The following are the principal signs by which the quality
of indigo is recognised in commerce: It forms a dull-coloured, loose,
light mass of earthy nature, a fresh fracture of which has a completely
uniform appearance. It must be so porous that it at once adheres to the
tongue. Uniformity of colour, light weight and fine fracture are the
most important of the practical tests for good indigo. The composition
of indigo is well known; we shall glance rapidly over the most
important substances which occur in indigo in varying quantity.
=The Constituents of Indigo.=—Indigo contains the following compounds:
Indigo blue, indigo red, indigo brown, indigo gluten, water and salts.
The single important constituent for the purposes of the colour maker
is indigo blue, or indigotin.
Pure indigo blue can be obtained from indigo only by a lengthy
process. The indigo is boiled in turn with dilute sulphuric acid,
caustic potash, and strong alcohol. The gluten dissolves in the acid,
the indigo brown in the potash solution, and the indigo red in the
alcohol. By these operations indigo blue is finally obtained in a state
of almost complete purity, it now contains only a small quantity of
inorganic substances. The quantity of pure indigo blue obtained in this
manner varies, according to the purity of the indigo employed, from 20
to 75 per cent. Indigo blue can also be obtained by direct sublimation
from indigo, but the yield is very small, since a large proportion is
decomposed by dry distillation.
The most important constituent of indigo, indigo blue, can be obtained
in quite pure form by a peculiar chemical process. When finely powdered
indigo is brought in contact with a reducing agent in the presence
of a strong alkali, the indigo blue is converted into indigo white,
which forms a soluble compound with the alkali, which compound is
stable only so long as it is protected from the action of the air. In
contact with air indigo white is at once oxidised, and is reconverted
into indigo blue, which separates from the liquid as a soft deep blue
powder; after washing and drying it is quite pure. Whilst sublimed
indigo blue forms needles with a splendid coppery lustre, when
precipitated from a solution of indigo white by the action of oxygen it
is obtained as an amorphous powder, which acquires the coppery lustre
only when rubbed.
The process of the reduction of indigo blue by a reducing agent in the
presence of a strong base is not only of theoretical interest, but is
largely used in practice. Fabrics are generally dyed with indigo by
immersing them in a solution of indigo white (known as the indigo vat),
and then exposing them to the air. The oxidation of the indigo white
then takes place on the fibre, upon which the indigo is deposited in a
very finely divided form; the blue colour is not immediately formed,
there is an intermediate green stage.
Indigo is used principally in dyeing. Certain of its compounds are
used as pigments; the starting point in the preparation of these is a
compound of indigo blue with sulphuric acid. When indigo is treated
with sulphuric acid, according to the duration of the reaction and the
temperature at which it is performed, either the monosulphonic acid
or disulphonic acid is formed. The reactions proceed according to the
following equations:—
C₁₆H₁₀N₂O₂ + H₂SO₄ = H₂O + C₁₆H₉N₂O₂.HSO₃
C₁₆H₁₀N₂O₂ + 2H₂SO₄ = 2H₂O + C₁₆H₈N₂O₂.(HSO₃)₂
When indigo is treated with eight times its weight of strong sulphuric
acid, and the solution considerably diluted, indigotin monosulphonic
acid separates as a fine blue precipitate, which dissolves with
difficulty in water and alcohol, and is insoluble in dilute acids. In
order to obtain the disulphonic acid 1 part of indigo is digested with
15 partsof sulphuric acid at 50° to 60° C. for several days. If fuming
sulphuric acid be used the solution is effected in a shorter time.
The solution is diluted with a large quantity of water, when a little
monosulphonic acid separates; the clear solution is drawn off and a
piece of wool immersed in it. The sulphonic acid is soon fixed by the
animal fibre; the wool is washed with water and then treated with a
solution of ammonium carbonate, when a deep blue solution of ammonium
indigotin disulphonate is produced. This solution is evaporated at a
low temperature and treated with strong alcohol, which leaves a residue
of the pure disulphonate, which is dissolved in water, the solution
precipitated with lead acetate and the lead indigotin disulphonate
treated with sulphuretted hydrogen. The colourless solution becomes
blue on evaporation; finally pure indigotin disulphonic acid is left as
an amorphous deliquescent mass. The solution became colourless owing to
the reducing action of the sulphuretted hydrogen; when this was driven
off by heating the blue colour reappeared.
CHAPTER LXI.
INDIGO CARMINE.
Indigo carmine is used in the laundry, for blue inks and as an artists’
pigment; in chemical composition it is a mixture of the sodium salts
of the two indigotin sulphonic acids described in the last chapter.
In working on the large scale it is particularly important that the
indigo should be finely powdered and completely free from moisture. It
is a laborious process to powder indigo in mortars, and loss always
occurs through the formation of dust. Thus when large quantities of
indigo are to be powdered it is advisable to use rotating cylinders.
These are strong casks bound with iron hoops and provided with a
well-fitting slide, through which the indigo and a number of iron balls
are introduced. When these casks are rotated for a sufficient length of
time the indigo is converted into the finest powder without any loss.
=Indigo Mills.=—Special mills have been designed for powdering indigo.
They may be advantageously employed for other materials also. The
construction of a well-designed colour mill is represented in Fig. 36,
in which indigo may be very finely powdered without loss. It consists
of a cast-iron pan, which can be closed by a well-fitting cover.
Through the cover passes the axis of the rotating part, which is moved
by the bevel cog-wheels and the handle. Above the cog-wheel fastened
to the axis is a cross piece carrying heavy balls at the ends, which
serve to keep the motion regular. In the interior of the pan four
vertical rods are attached to the axis; these are placed at such a
distance that they drive before them the heavy balls in the circular
depression of the pan. The action of this apparatus is very simple.
After the introduction of the indigo through an opening in the cover
the axis is put in rotation, the vertical rods attached to the axis
roll the balls before them, and thus break up the lumps of indigo. The
larger pieces of indigo oppose considerable resistance to the rotation,
which should at first be slow. When the lumps have been broken down the
speed of rotation can be considerably increased. After the operation
has been continued for a sufficient length of time the indigo is
converted into an impalpable powder.
[Illustration: FIG. 36.]
To facilitate the removal of the ground indigo, an arm carrying a brush
of fine hair should be attached to the horizontal arm of the axis.
If this brush is placed so that it sweeps the bottom of the circular
depression in which the balls move, all the indigo powder in this
depression will be carried in one direction. In the depression is an
opening closed by a slide during the grinding. The brush expels the
ground indigo through this opening when the axis is slowly rotated;
it is collected in a vessel below. The larger and heavier are the
balls in this mill, the more rapidly will a given quantity of indigo
be powdered, and the greater will be the power required to drive the
machine. By means of a pulley on the axis of the cog-wheel the mill can
be driven by mechanical power.
The powdered indigo is exposed for a long time to a temperature of 120°
C., to completely dry it. For this purpose it is spread out on sheets
of tin plate in a thin layer and heated so long as a test portion
decreases in weight. The powder whilst still warm is at once mixed with
the sulphuric acid; 4·5 kilogrammes of fuming sulphuric acid and 1
kilogramme of ordinary sulphuric acid (66° Bé) are used to 1 kilogramme
of indigo. Heat is developed in the operation, and in order to prevent
the indigo from being charred the vessel in which the mixture is made
is placed in a larger vessel filled with cold water. The mixture is
stirred with a glass spatula until it is quite uniform. The vessel
is then maintained at a temperature of about 50° C. (not more than
60° C.) for 7 to 8 days. After the lapse of this time the indigo is
completely dissolved, and the vessel is found to contain two distinct
layers, the upper fluid and the lower a paste. The contents are mixed
with cold water, about 10 kilogrammes of water to 1 kilogramme of
indigo. A solution of 10 kilogrammes of common salt is then added in
small quantities at a time. Indigo carmine is insoluble in strong salt
solutions; it separates as a deep blue precipitate, which is allowed
to settle and then filtered. If it were attempted to wash out the
remainder of the salt solution retained by the carmine, a considerable
quantity of the latter would dissolve as soon as the salt solution
became diluted to a certain extent. To avoid such loss the precipitate
is allowed to drain completely on the filter, and then spread out upon
bricks, which absorb the water, so that the carmine forms a stiff
paste.
Indigo carmine, from which the salt has not been completely washed out,
dries completely when exposed to the air. This may be prevented by the
addition of glycerine, which is a very hygroscopic substance, and so
keeps the carmine always moist, thus preventing the crystallisation of
the salt.
Indigo carmine easily dissolves in water to a deep blue liquid. It
has tremendous colouring power, in which respect it is only equalled
by genuine cochineal carmine. As mentioned above, indigo carmine is
extensively employed in the manufacture of ink. The so-called alizarin
inks show a very pale colour as they flow from the pen, and only become
deep black after some time. To make these inks equally visible at the
first indigo carmine is added, by which they acquire a handsome blue
colour.
Indigo carmine may also be made by digesting 1 part of dry powdered
indigo for 24 to 36 hours with 4 parts of strong sulphuric acid,
diluting with water, quickly filtering through a linen cloth, and
adding 4 parts of common salt. The precipitate is then collected and
dried on gypsum or clay plates.
=Blue Lake.=—When alum is added to a solution of indigo sulphonic acid,
and then soda solution, a blue precipitate is formed, which, when dry,
resembles Chinese blue in appearance. It is used in painting. This
indigo blue lake is superior to other blue lakes by reason of its
fastness to light. It is rather dear, and is mixed with starch, so that
it may be sold at low prices; the mixture is formed into slabs and sold
as ”new blue,” ”indigo extract,” etc. It is chiefly used in the laundry.
Under various names a number of blue pigments are sold consisting of
ordinary qualities of indigo mixed with Prussian blue, smalts, chalk,
etc. These are used in the laundry, and also for distempering.
CHAPTER LXII.
THE COLOURING MATTER OF LOGWOOD.
The wood of _Hæmatoxylon campechianum_ (logwood), a native of South
America, comes into the market in small logs of a red colour; it
contains a colouring matter whose properties are fairly well known.
Before the discovery of the coal-tar dyes logwood was a most important
colouring material; by means of it red, blue, violet and black colours
can be obtained. At present it still plays an important part in dyeing.
Many varieties of logwood come into commerce. The most important are
Campeachy wood, Honduras, Jamaica and St. Domingo logwood; the first
named is the best, and the last the poorest quality. To facilitate
the extraction of the colouring matter by water logwood is frequently
sold in chips. Many dye-wood grinders moisten logwood with lime water;
this gives the powder a better colour, but diminishes the yield of
colouring matter. Since the only useful constituent of logwood can be
extracted by treatment with water, and the wood is only a carrier of
the colouring matter, which is only useful for fuel when exhausted,
logwood extracts are largely used in place of the wood. The extracts
are black resin-like masses, which easily dissolve in water; they are
very hygroscopic, and should therefore be kept in closed vessels.
=Logwood Extract.=—Solid extracts can be obtained from the majority of
dye-woods. The use of these is a great convenience to the dyer and
the colour maker; the method by which extracts are made is therefore
briefly described.
Dye-wood extracts can be made on the small scale, by washing out the
finely divided wood until soluble matters are no longer taken up by
the water, and cautiously evaporating the united extracts. When the
extract becomes concentrated the greatest care must be taken to prevent
burning on the bottom of the vessel; a burnt extract is always darkened
by the presence of products of decomposition, and its solution has a
brown colour. Apart from this, the complete extraction of the colouring
matter requires much time, and such dilute solutions are produced that
they cannot be evaporated, but at the best can be used in the place of
water to extract fresh quantities of wood.
When steam is utilised to extract dye-woods these defects are
removed. A burnt extract is not to be feared, and a small quantity of
water is sufficient to extract the colouring matter completely. The
apparatus illustrated in Fig. 37 is very suitable for the extraction
of dye-woods, and in general for obtaining vegetable extracts. The
extraction vessel is pear-shaped, its two hollow axes move in hollow
bearings. Thus it may be turned upside down, and steam and water can be
introduced into the interior through the axes, which are connected with
the pipes, E, W, and R. The opening at the pointed end of the pear is
closed by the screw, S; through it the substances to be extracted are
introduced. In the lower portion of the vessel is a sieve upon which
the materials are spread out. The opening of the pipe connected with E
and W is below the sieve.
[Illustration: FIG. 37.]
The process is commenced by introducing the materials through the
upper opening, fastening the cover down steam-tight by the lever,
B, and the screw, S, and then running in water through W until it
flows out through the lower of the two narrow pipes which are shown
somewhat paler in the shaded portion of the drawing. All the taps are
then closed with the exception of that on the upper of the two small
pipes. By opening the cock on R steam is led in. As a rule, steam at a
low pressure is used, not more than half an atmosphere. The contents
begin to boil in 15 to 30 minutes, steam then issues from the open
tap. According to the nature of the material to be extracted, boiling
is continued from 40 to 60 minutes. The side tap is then closed, and
the tap on the pipe E opened. The pressure of the steam now forces the
liquid up the pipe E; the pressure of half an atmosphere is sufficient
to raise it about 4 metres. In this way it can be forced into a tank
above. The rest of the liquid can be run off through the cock, _h_,
at the bottom of the vessel. When quite empty the cover is taken off,
the vessel turned over, and the solid residue removed. One extraction
of dye-woods is not sufficient to remove the whole of the colouring
matter; in most cases the wood is treated a second time before the
apparatus is emptied. Even then some quantity of colouring matter
remains in the wood. The twice extracted wood is brought into a tub
filled with water, and the solution resulting from the long contact
of the water with the wood is used in the next operation to extract
new quantities of wood instead of fresh water. The dimensions of the
extraction vessel vary according to the size of the works. A large
apparatus costs not much more than a smaller, since in both cases the
labour is the same, so that it is advisable to use a large apparatus.
When the copper extraction vessel is made to have its greatest diameter
about 1 metre, it can be charged with about 50 kilogrammes of rasped
wood at once.
[Illustration: FIG. 38.]
The extraction apparatus of Hänig and O. Reinhard is shown in Fig. 38.
It can be turned over by means of cog-wheels. In the cover are an air
valve, _e_, and safety valve, _f_; below the cover is a coil, _k_,
fed with cold water from _c_. In the extraction, by opening the valve
_v_, steam enters through _a_ at _l_; it is condensed by the cooled
cover, the condensed water flows through the material on the sieve,
and collects in the space B. After some time _v_ and _z_ are opened,
the liquid is then boiled by the steam in the coil, _s_. Steam rises
through the material, is condensed on the cover, and again drops down.
At the end of the operation the solution is drawn off through the cock,
_h_.
[Illustration: FIG. 39.]
=Kohlrausch’s Process for Obtaining Concentrated Extracts of Colouring
Matters and Tannins.=—When dye-wood or tan-bark is continually brought
in contact with fresh quantities of water, after some time it is
exhausted; if the solution containing a certain quantity of the soluble
matters is brought in contact with fresh material not yet extracted,
it takes up more soluble matter, and thus becomes more concentrated.
The substances contained in tan-bark are very soluble in water, so that
by the appropriate treatment of a certain quantity of bark, divided
amongst different vessels, with a certain quantity of water, on the
one hand the bark can be exhausted completely, and on the other very
concentrated solutions (”bark extracts”) obtained. The process patented
by Kohlrausch is based upon the principles just stated; it can be
used to obtain tannin extracts from tan-bark and colour extracts from
dye-wood. In this process the raw materials need not be finely ground
in order to be completely extracted; they may be used in large pieces.
It will be understood from the following description that fine bark
meal or finely-rasped dye-wood could not be worked.
[Illustration: FIG. 40.]
The apparatus consists of a number of 10 to 20 extractors connected
together, also with a water tank above, and with a boiler. A single
extractor is represented in section in Fig. 39, together with
the necessary pipes and valves by which it is connected with the
neighbouring extractors, the water tank and the boiler. Fig. 40 is a
plan of three extractors connected together.
The extractors consist of wooden or copper vessels, slightly conical
in shape, and of sufficient strength to resist the pressure of one
atmosphere. On the top is a copper dome closed by a lid, through which
the raw material is introduced, and also steam and water. Immediately
above the bottom is an opening, also closed by a screw, which serves
to remove the exhausted materials. An inclined sieve is placed at some
distance above the bottom; upon this the material rests. The extract
collects below the sieve, and may be run off by the pipe or brought
into another extractor. All the metallic portions of the apparatus
which come in contact with the liquid must be made of a metal such as
copper, which does not act upon tannic acid. Iron cannot be used; it
forms deep bluish or greenish black compounds with tannic acid, which
would cause the extract, instead of being pale and clear, to resemble
ordinary writing ink.
In a range of 10 extractors the process is carried out in the following
manner: The extractors numbered 1 to 10 are filled with bark or
dye-wood and closed; 1 is then filled with water from the tank, and
heated by steam to 50° to 70° C. After some time the contents of 1 are
forced into 2, and 1 is again filled with water, so that the material
in 2 is in contact with the solution from 1, whilst the material in 1
is warmed with a fresh quantity of water under pressure; the extract
in 2 is transferred to 3, that in 1 to 2, and 1 is again filled with
water, and so on. Finally from 10 a very strong extract of tannin
or colouring matter is obtained. The quantity of water required to
fill one extractor has come ten times in contact with fresh bark
or dye-wood. The material in 1 has been treated with ten times the
quantity of water; it is now exhausted, and is replaced by fresh
material. The sequence of the vessels is now changed. The original
extractor 2 is to be regarded as 1, and 1 as 10. After ten repetitions
the original order of the extractors re-obtains. Ninety-nine per cent.
of the tannic acid of bark is extracted in this way.
The concentrated extracts obtained in this apparatus should be mixed
with a little carbolic acid to prevent decomposition; they may then
be filled into barrels. The extracts may also be so far concentrated
by evaporation that they become syrupy. The tannins are readily
decomposed; they would be considerably altered if their solutions were
evaporated in open vessels. The extracts are therefore evaporated at a
very low temperature under diminished pressure in vacuum pans, which
are now much used for the concentration of solutions of substances,
such as sugar, which would be injured by heating above a certain
temperature. Essentially, a vacuum pan is a thick-walled copper vessel,
in which the liquid is warmed by a steam coil. It is connected with an
air pump, which exhausts the air at the commencement of an operation,
and afterwards steam. The liquid is thus constantly evaporated under
a low pressure. Extracts of tan-bark and dye-woods boil briskly
under these conditions at temperatures below 60° C., at which no
decomposition of the tannin or the colouring matter is to be feared.
When the solutions have been evaporated to the proper strength they are
run off directly into the packages in which they are to be despatched,
and in which they become syrupy or even solid masses, according to the
extent to which the evaporation has been driven.
The packages should be at once closed; the thick extract is thereby
most simply and safely prevented from decomposing, to which risk it
would be exposed by the access of mould spores. If these were already
present in the barrels or were communicated to the extract by the air,
they would either be killed by the hot liquid or would be prevented
from developing for a long time. In the closed vessels the extracts
remain completely unaltered.
The concentrated solution of colouring matter obtained by extracting
dye-woods in the above apparatus can be at once used, after dilution,
in the preparation of lakes and in dyeing, but it is not an extract in
the ordinary commercial sense of the term, _i.e._, it does not solidify
on cooling. To obtain solid extracts the concentrated solutions must
be evaporated; concentration with fire heat would be attended with
danger to the quality of the extract, steam heat is therefore used.
The liquid to be evaporated is brought into shallow steam-jacketed
pans, in which the operation is continued until the liquid solidifies
into a resin-like mass when dropped on cold stone. When sufficiently
evaporated the extract is allowed to solidify, broken into lumps,
and these packed whilst still warm into barrels lined with paper.
The lining is necessary on account of the hygroscopic nature of the
extracts; when they are exposed to the air they absorb water and form a
viscous fluid which soon becomes mouldy.
A properly prepared dye-wood extract should dissolve in water without
residue, and the solution when largely diluted should show the
characteristic colour of the wood with no brownish shade, and when the
colouring matter is precipitated from such a solution by a metallic
salt the residual solution should be almost colourless. If the extract
dissolves incompletely in water and the solution is brown after
precipitation of the colouring matter, the extract has been burnt in
the evaporation.
* * * * *
Logwood and logwood extract contain two substances of importance
in dyeing and colour making. These are hæmatoxylin and hæmateïn.
Hæmatoxylin is found in logwood in greatest amount shortly before the
wood is cut. When pure it forms colourless crystals of a peculiar sweet
taste, which are soluble in cold water with difficulty, more easily
in hot, and readily soluble in alcohol or ether. The composition of
hæmatoxylin is expressed by the formula C₁₆H₁₄O₆.
Hæmatoxylin is not a colouring matter. It is important because from it
is obtained the essential colouring matter of logwood—hæmateïn. When a
trace of ammonia is added to the colourless solution of hæmatoxylin,
the liquid at once becomes dark red owing to the formation of hæmateïn.
When a larger quantity of ammonia is added the liquid acquires a deep
red colour, and then contains only hæmateïn (its ammonia compound),
which is formed according to the following equation:—
C₁₆H₁₄O₆ + NH₃ + O = C₁₆H₉O₅.NH₄ + 2H₂O.
To obtain hæmateïn in the pure state it is then only necessary to add
sufficient acetic acid to decompose the hæmateïn ammonia compound.
Hæmateïn separates as dark violet crystals, which readily dissolve in
water and alcohol; its aqueous solution gives blue precipitates with
the majority of the metallic salts. This behaviour of hæmatoxylin
towards ammonia explains the increase in colouring power of logwood,
which has been exposed for a long time to the action of the air in the
rasped state. Through the action of the ammonia in the air a larger
quantity of the hæmateïn ammonia compound has been formed. It has
been proposed to facilitate the formation of this ammonia compound
by moistening rasped logwood with a very dilute glue solution and
allowing it to lie in the air. This process can only have the object
of utilising in the formation of hæmateïn the ammonia resulting from
the decomposition of the glue, but in this decomposition deep-seated
reactions occur, which might affect the hæmateïn itself. It thus
appears more suitable to effect the formation of hæmateïn by the direct
use of ammonia. This can be done with little cost by watering heaps of
rasped logwood with ammonia and repeatedly shovelling about the wood
so that it comes into contact with the air. The author has found that
the conversion of hæmatoxylin to hæmateïn is very complete in this
process; care should be taken not to make the layer of rasped wood too
deep, and to take its temperature frequently. In the transformation
of hæmatoxylin to hæmateïn the temperature rises, the rise might be
injurious if it proceeded too far. Thus if the temperature of the
interior of the heap is found to be high the wood should be turned over.
The solution of the logwood colouring matter produces handsome lakes,
all of which have, however, the inconvenient property of acquiring
an ugly grey colour on long standing. The finest and most durable of
the logwood lakes is known as violet lake, which is made with alumina
salts. The best result is obtained when a solution of aluminium
acetate, obtained by precipitating alum with lead acetate, is mixed
with a logwood decoction or a solution of logwood extract. The
precipitate is pale or deep violet according to the amount of aluminium
salt added. After drying to a certain point at a gentle heat it can be
mixed with gum solution to a paste, which is then completely dried.
Logwood is most valuable in dyeing and calico printing, in which it
serves to produce a fine and durable black. When potassium chromate is
added to a decoction of logwood a deep black liquid results, which can
be used as a good and cheap writing ink. If somewhat stronger solutions
are used a greenish precipitate first separates, which soon acquires a
pure black hue; it is the chromium lake of hæmateïn. This compound is
very durable and is largely used in dyeing to produce fast blacks. The
black precipitate might be dried and used as an artists’ black pigment
if the carbon blacks were not cheaper and more durable.
CHAPTER LXIII.
GREEN LAKES.
The yellow colouring matters produce green compounds with copper salts.
These are important because they can be produced without great cost,
and are not as poisonous as the arsenic pigments, although copper
compounds are far more poisonous substances than should be used for
certain purposes. Their employment might be attended with danger if
used to colour children’s toys and pictures.
These green copper lakes are simply made by adding copper sulphate
solution, free from iron, to a hot decoction of yellow berries or
weld until the liquid is emerald green, and then adding caustic soda
solution in small quantities to precipitate the lake. The temperature
of the liquid should not be more than 50° to 60° C. when the caustic
soda is added. It has been maintained that these lakes turn out well
only when the precipitation is so conducted that the residual liquid is
quite colourless. The author has, however, found it more satisfactory
to discontinue the addition of caustic soda when the liquid is somewhat
coloured, since when the precipitation is complete other substances
besides colouring matter may be precipitated.
=Chlorophyll.=—All the higher plants contain the same green colouring
matter—chlorophyll. It has a very fine shade, is fairly fast, and the
raw material from which it is produced is to be obtained at nominal
cost. Special attention should, therefore, be paid to this colouring
matter.
Chlorophyll is very easily obtained. Grass of a good green, green
leaves, or any green portion of a plant is allowed to stand with weak
caustic soda solution in a large vessel for twenty-four to thirty
hours. The liquid is poured off, brought to the boil for a moment, at
once filtered and neutralised with hydrochloric acid. The chlorophyll,
which has been dissolved by the caustic soda, is then thrown down as a
grass green precipitate; after washing and drying it can be used as a
pigment. A chlorophyll lake can be obtained by dissolving the colouring
matter in caustic soda and adding alum solution. The green precipitate
is a compound of chlorophyll and alumina.
Tschirch gives the following method for obtaining chlorophyll: Green
leaves (grass), not containing tannin, are extracted with boiling
alcohol, the extract cooled, filtered and evaporated until a sticky
mass remains. This is washed with hot water until the washings are
colourless, and the residue extracted with cold alcohol. The solution
is evaporated to half its volume, the separated crystals are dissolved
in alcohol, and the solution heated on the water bath with zinc dust.
A deep emerald green solution with a red fluorescence is obtained; it
can be preserved unaltered for a long time in blue glass bottles. It
retains its colour in diffused daylight also for a lengthy period. A
beautiful green chlorophyll lake is obtained by boiling this solution
with the solution of an aluminium salt and precipitating with soda.
Unfortunately, the lake is not fast. The chlorophyll solution obtained
by this process is quite innocuous, and is well adapted for colouring
liqueurs and confectionery.
=Sap Green.=—This lake, also known as bladder green, is obtained from
unripe yellow (Persian) berries. It can be used as a water colour, but
not in oil painting. This pigment differs from the ordinary yellow
berry lake in colour and chemical composition; the yellow lake is a
compound of xanthorhamnin with the metallic oxide, whilst sap green
contains an uncrystallisable bitter substance, rhamnocathartin.
The lake is obtained from yellow berries which are not quite ripe.
They are broken up and left in a warm place. The mass soon ferments;
after about ten days it is pressed. Four parts of the liquid are then
mixed with 0·5 part of alum and 0·5 part of potassium carbonate. The
salts are dissolved in boiling water, and the solutions added to the
hot sap. The mixture is then evaporated to the consistency of a thick
syrup, which is generally packed in animal bladders, hence the name of
”bladder green”. Some care is necessary in the evaporation to prevent
the burning of the soft mass on the bottom of the vessel. If the
evaporation is carried somewhat further the mass solidifies on cooling;
it is then black, and only transmits green light at the edges. The use
of potash in preparing sap green is attended with the disadvantage that
the hygroscopic nature of the salt prevents the colour from drying. If
magnesia is used instead of potash the lake dries far more rapidly,
but has much less covering power. Sap green is principally used for
colouring paper and leather.
Orange-coloured lakes also can be obtained from yellow berries by
precipitating the decoction with stannic chloride. These lakes are not
directly employed, but are produced immediately upon the fabric in
dyeing.
=Chinese Green, Lokao.=—Under this description a green lake has
recently been imported from China. It is a valuable pigment. Chinese
green is sold in flat cakes, which are blue, with a green or violet
lustre. The powdered lake is pure green and partially soluble in
water; it contains colouring matter, water and inorganic matter
consisting chiefly of clay and lime.
Chinese green is made in China in a peculiar manner from the twigs
of certain species of _Rhamnus_. According to report, the bark is
boiled with water and a cotton cloth immersed in the decoction. The
fibre fixes a colourless substance which becomes green on exposure to
air. The cotton is repeatedly dipped into the decoction until it has
absorbed a large quantity of colouring matter. It is then washed with
cold water and boiled with water upon which cotton yarn is laid. The
colouring matter suspended in the liquid adheres to the yarn, which
is washed with a little cold water, and the colouring matter then
collected upon paper and dried.
If Chinese green is really made by this process, it is not a lake but
a vegetable colouring matter, to which clay has been added to increase
its weight or to make it plastic. Very fine lakes can be obtained from
Chinese green by dissolving it in a solution of alum, and adding soda
solution. When Chinese green is dissolved in acetic acid and ammonium
chloride and a zinc salt added, a blue lake is produced on the further
addition of sodium acetate. A bluish violet lake is obtained by
treating Chinese green with a strong reducing agent and adding calcium
acetate.
=Charvin’s Green.=—The very high price at which genuine Chinese green
was sold whilst it was still a novelty, gave rise to attempts at
imitation. Charvin, of Lyons, succeeded in producing a pigment from
_Rhamnus_ which has the characteristic property of Chinese green of
retaining its colour in artificial light. He plunged the bark of common
buckthorn into boiling water, boiled for a few minutes, and allowed
the whole to stand for twenty-four hours. Lime water was added to the
brown liquid, which was then exposed to the action of the air in
shallow vessels, when it gradually turned green and deposited a green
precipitate. When this appeared, the liquid was brought into glass
vessels and potassium carbonate solution added so long as a precipitate
resulted, which after drying had all the properties of genuine Chinese
green.
Although for some time Chinese green was a very fashionable colour, its
use is now almost discontinued, although it can be used with advantage
as an artists’ pigment, and its preparation by Charvin’s method is
neither difficult nor specially costly.
CHAPTER LXIV.
BROWN ORGANIC PIGMENTS.
=Asphaltum= is found in large deposits in several regions of the earth.
It is a compound of carbon and hydrogen, and varies in appearance from
cobblers’ wax to tar. Asphaltum is of organic origin and is closely
related to the mineral oils. Among the pigments usually employed by
artists asphaltum plays an important part; it produces very warm
shades between brown and deep black. The preparation of asphaltum for
artists’ use is very simple. Good uniform lumps, free from sand and
other impurities, are coarsely powdered and mixed with a solvent in a
well-stoppered flask. Asphaltum readily dissolves in essential oils,
and also, though with more difficulty, in fatty oils. It dissolves
slowly at the ordinary temperature, but quickly on warming. On account
of the inflammability of the essential oils generally used, certain
precautions must be taken. The asphaltum is mixed with turpentine
in a large flask which is well closed and heated by hot water. In a
short time a viscous mass is formed which is mixed with the solvent by
shaking.
Asphaltum may also be prepared, without dissolving, by powdering and
grinding with oil exactly as a mineral pigment.
=Sepia.=—This brown pigment has a warm hue which is not readily
surpassed. It is an animal product; the cuttle-fish, a species of
cephalopod which abounds in all warm seas, produces a peculiar
colouring matter which is stored in a sac, commonly called the ink-bag.
It is used by the animal for protection, when pursued it ejects the
contents of the bag, and thus makes the surrounding water so dark that
it is enabled to escape.
Sepia is made almost exclusively in Italy. The contents of the ink-bag
are quickly dried, and then rubbed with strong caustic lye to a thick
pulp. More caustic lye is then added, and the mixture heated almost to
boiling; from the filtered solution sulphuric acid precipitates the
pure colouring matter.
As one of the most handsome brown pigments, sepia is largely used, but
unfortunately it can only be used as a water colour. On account of its
cost, sepia is frequently imitated. Vegetable substances are charred,
extracted, and the extract concentrated until it solidifies on cooling;
it is then finely powdered, made into a paste with gum Arabic or
tragacanth, and formed into cakes. All such imitations are, however, so
imperfect that they are at once recognised. On comparison with genuine
sepia, none of them is found to possess the warm shade peculiar to
sepia.
Brown colouring matters can be obtained by heating all soft portions of
plants. The products have a deep brown shade in consequence of the high
proportion of carbon they contain. When the young twigs of soft woods
are exposed in closed cylinders to a temperature of about 300° to 400°
C., and the residue powdered, colours ranging from a dark rust brown to
almost pure black are produced. The higher the temperature employed the
more nearly the shade approaches to black.
Parts of plants which contain sugar or similar compounds become deep
brown at comparatively a low temperature. The colour, which varies from
brown to hyacinth red, is due to caramel. This substance is produced
when coffee, beetroot, or chicory root, all of which contain a large
proportion of sugar, are heated. Such pigments are little used; they
cannot be ground with oil, and in water can rarely be mixed with other
colours.
CHAPTER LXV.
SAP COLOURS.
Under the designation of ”sap colours” several pigments are brought
into the market in the condition in which they are ready for immediate
use in printing. The term is practically restricted to lake pigments
which form a transparent layer when dry, thus the sap colours may be
defined as dissolved lakes mixed in a viscous medium, such as thick
gum solution. In general the sap colours are not much used, since when
wetted with water they again dissolve, which is not the case with
pigments ground in oil. Yet for certain purposes they are commonly
used, as in the manufacture of playing cards.
In the manufacture of these pigments only colouring matters soluble
in water can be used, the number of which is restricted. According to
a particular method a tin lake is first made, which is decomposed by
a strong base, such as ammonia, so that the colouring matter again
goes into solution. The very deep coloured liquid is then mixed with a
thickener and an indifferent white substance such as flour or starch,
formed into thin sticks, and sent into the market.
A decoction of buckthorn berries is used for the yellow sap colours.
It is considerably evaporated, and then mixed with 2 to 3 per cent. of
alum, after which starch paste or gum Arabic and sugar are added in
proper quantity, and the mixture evaporated at a low temperature so
that it is not browned by over-heating.
When a tin lake is employed in the preparation of a sap colour, the
precipitate obtained by adding stannic chloride to the solution of
the colouring matter is washed, and, without drying, treated with a
small quantity of strong ammonia; generally about 10 per cent. of
the volume of the precipitate is sufficient to dissolve the lake. It
is always better to leave a portion of the precipitate undissolved
than to modify the colour by the addition of too much ammonia. The
precipitate should be dissolved in a glass vessel; the liquid is well
stirred, covered over, and allowed to stand until the undissolved
portion of the precipitate has settled. The ammoniacal solution of the
colouring matter cannot be concentrated by evaporation. Thus, before
the precipitate is dissolved it must be well freed from water by long
draining. To give the solution the proper consistency about an equal
quantity of thick gum solution is added, and then sufficient starch
to form a paste which can be rolled into thin sticks, which are then
dried upon boards at a gentle heat. Sap colours are made in exactly the
same way from any other colouring matter adapted to the purpose. In
using these colours it is simply necessary to bring them into water;
if they contain only gum and sugar in addition to colouring matter
they completely dissolve, but if they contain starch the solution is
incomplete. As a rule starch is only added to give the colour the
consistency requisite for printing.
Red sap colours can be made either from red wood lake or from cochineal
carmine; the former is used in ammoniacal solution, the latter as a
solution of the pure carmine in ammonia. The colour is prepared from
red wood by allowing a decoction to stand for several days, adding 2
to 3 per cent. of alum, evaporating and thickening with gum solution.
This colour is cheap, but cannot compare in beauty with that obtained
by treating red wood tin lake with ammonia. The solution of genuine
carmine in ammonia produces a sap colour which leaves nothing to be
desired in regard to shade, but on account of the cost of carmine
it can but rarely be used. A solution of pure indigo carmine mixed
with gum solution is used as a blue sap colour; it can be shaded by
additions of red or yellow colours. Chinese blue may be used instead
of indigo carmine; it dissolves in a solution of oxalic acid. When
Chinese blue, which has been thoroughly washed, is mixed whilst still
moist with a little saturated oxalic acid solution, the blue dissolves,
and the solution may then be made into a paste by the addition of
thickening materials.
Green sap colours are made, as a rule, by mixing yellow and blue. All
shades can be thus obtained. A green colour of different composition
is obtained by boiling the violet solution of chrome alum with gum
solution until the colour changes to green. Violet colours are obtained
by mixing red and blue. Sepia produces a brown sap colour.
It has been proposed to use glucose in place of the much dearer gum
Arabic, and also to use malt extract as thickener. These substances
absorb water from the air, and thus the colours prepared with them
never become quite hard, but always remain pasty. For some purposes
this is a decided advantage, since such colours can be readily taken up
by the brush and easily rubbed up with water, but they cannot be formed
into cakes as is usually done with water colours. When the colours are
to be made into cakes they must be thickened with gum Arabic alone,
without glucose or malt extract. The cakes must be dried with great
care; if they are dried too quickly they will crack or even fall to
pieces.
CHAPTER LXVI.
WATER COLOURS.
The colours thus called are so prepared that they easily mix with water
to such a condition that they can be applied with the brush. Special
pigments are not required for this purpose, ordinary dry colours are
simply mixed with a binding medium soluble in water, and the paste is
generally pressed into cakes. In commerce very different qualities
of water colours are found, ranging from cheap children’s playthings
to the most costly colours used by painters in water colour. Those
pigments which are not already in very fine powder, in consequence
of the process by which they are made, such as chrome yellow, must
be subjected to a very careful process of levigation. To simplify as
far as possible this laborious process, it should be conducted by
grinding the pigment as finely as possible, well stirring it in a tub
with water, allowing to rest for several minutes, and then running off
the liquid into a second tub, from which it is again drawn off into a
third after several, minutes. The liquid remains in the last vessel
until it is quite clear, when the deposit is collected. This is now so
fine a powder that a powerful microscope is required to distinguish
the separate particles. The residue in the first and second vessels
consists of the coarser particles; it is again ground with fresh
material. In this process regard must be given to the specific gravity
of the material: the higher it is the shorter is the time during
which the liquid is allowed to remain in the tubs, since the coarser
particles of heavy substances settle very rapidly. In dealing with the
light lakes, such as the alumina lakes, the liquid in which the lake
is suspended must remain much longer at rest. Two vessels may be used
instead of three, without danger of the precipitate containing coarse
particles.
Gum Arabic and tragacanth are used as binding materials for the
pigments. Dextrine is also much used in place of the expensive gums;
for this purpose only pure white dextrine should be used, since the
brown colour of ordinary dextrine would injure the shade of the
colours, especially of pale colours. Gum Arabic and dextrine, which
are readily soluble in water, require no special preparation before
their solutions are mixed with the pigments. The solutions are made by
treating with water; they are then allowed to stand for several days in
a tall vessel so that impurities may settle. If the solutions are very
turbid, they are filtered through closely woven linen.
Gum tragacanth requires rather different treatment. It is not
completely soluble in water, in which it only swells up to a great
extent. It is prepared by leaving it for several days in water, and
when it has swollen, rubbing the slimy mass in a mortar until it is
completely uniform.
The levigated pigments are allowed to dry in the air to a soft paste,
which is mixed with the proper quantity of gum Arabic and tragacanth
solutions. As a rule the two gums are used together. The colouring
matter and binding medium may simply be ground together, but long
grinding would be required to produce a completely homogeneous mixture.
The costly manual labour is therefore as far as possible replaced by
machinery, by which means a cheaper and also more uniform product is
obtained. The machines by which the pigment is ground with the binding
material are of simple construction. They consist of rollers placed in
pairs one above the other and moving in opposite directions. The two
rollers of each pair are connected by cog-wheels, in such a way that
the lower moves more slowly than the upper. In consequence of this
arrangement, the rollers, in addition to crushing, exert a grinding
action upon the viscous mass passing between them. As a rule, after the
colour has passed through one pair of rollers, it goes through a second
and third, from the last of which it is taken off by a scraper. It is
now completely uniform.
The binding medium must be of such consistency that, after grinding
with the pigment, a fairly stiff paste results which is suitable for
pressing. The cakes of colour are pressed out in an ordinary spindle
press, which should be so constructed that the stamp in the down stroke
comes upon the paste beneath it and stamps out cakes upon which the
engraving of the die is clearly shown. If the cakes crack when slowly
dried, the medium contains too much gum Arabic. If the impression
of the die upon the cakes is not sharp, and if they remain rather
elastic when completely dry, too much tragacanth has been used. It is
rather difficult to grind a stiff paste, many manufacturers prefer to
grind the colour in a rather more fluid condition, and then to allow
the paste to thicken by drying to the consistency necessary for the
production of good cakes.
The moulds in which the cakes are made must be very carefully worked in
metal, so that the description and trade mark print clearly upon the
cakes. The cakes should be dried at the ordinary temperature or but
little higher. They are placed upon smooth boards, and care is taken
that the temperature of the drying room remains uniform, which is the
condition requisite for the production of the fewest cracks. When it is
intended to place on the market only faultless and well-stamped cakes
they must be sorted when dry, and the cracked ones rejected; these can
be worked up in the next operation.
The dry cakes are given a good appearance by coating them with a weak
solution of gum, and then drying. According to the price at which these
colours are to be sold the cakes are given a different character. The
finest colours are generally made into larger cakes and packed in
handsome boxes, whilst ordinary cheap colours are made into small lumps
or circular plates, flat on one side and somewhat convex on the other,
and packed in boxes of soft wood.
=Moist Water Colours.=—Instead of grinding water colours with gum
Arabic or tragacanth and bringing them on the market in the dry state,
they may also be sold in a condition resembling that of oil paints.
This may be accomplished by using very viscid glucose syrup instead
of gum Arabic, and grinding the pigments in this exactly as in oil.
Glucose is very hygroscopic, the colours prepared with it remain moist,
and may be spread out upon the palette like oil colours. It is then
only necessary to wet the brush in water and mix the mass with it in
order to obtain colour of the proper consistency.
Moist water colours have also been known as ”honey colours,” since this
mixture of sugars was formerly used for their preparation; it also is
hygroscopic. Honey is no longer used; the much cheaper glucose answers
the same purpose. On account of their semi-fluid nature, moist water
colours are put up in tubes just as oil colours. They are thus rather
dear, but are little used.
CHAPTER LXVII.
CRAYONS.
Crayons are coloured pencils by which pictures may be, so to speak,
”dry painted”. At present this method of painting is little used,
though it was in vogue in the last century, but coloured pencils,
especially blue and red, are much used for writing. Crayons are now
used in a very convenient form, being generally made in the same manner
as lead pencils. The coloured mixture from which the crayon is made
is produced in the form of a paste containing a soft, finely ground
mineral, well mixed with the colouring matter and an amount of binding
medium just sufficient to hold the powders together.
Gypsum is generally used as the soft white mineral forming the base
of the coloured mass. It is much better to use steatite (soap-stone),
which is not much dearer, and has many advantages over gypsum. The
preference given to steatite is based upon a comparison of the
properties of the two minerals; gypsum is crystalline, steatite is
non-crystalline. Powdered gypsum has essentially a dry character,
whilst powdered soap-stone is of a peculiar greasy nature, and
consequently can be readily smeared upon a flat surface; it also
imparts a pleasing lustre to the colours with which it is mixed.
The manufacture of crayons consists in preparing and moulding the
coloured mass. The process is commenced by mixing the powdered colour
and soap-stone in a closed rotating cylinder. The rotation is continued
until the mixture is uniform in colour. The quantity of colour to
be mixed with the soap-stone depends upon the shade to be produced.
Manufacturers who make a speciality of crayons prepare a number of
shades of each colour. The artists who use crayons, however, usually
require only those of a pure shade, since they themselves can produce
the intermediate shades from the essential colours. On this account it
is advisable to make crayons of distinct and deep colours. The mineral
pigments are the most suitable: for yellow, deep chrome yellow; for
red, vermilion or deep madder lake; for green, one of the pure green
pigments, such as chrome green; for blue, Chinese blue or ultramarine;
for brown, burnt sienna or manganese bistre. For white and black
crayons levigated chalk is used, alone or mixed with a sufficient
quantity of fine vine black or some other good black. Either gum Arabic
or size may be used as binding material. When the former is employed
the crayon becomes so brittle when dry that it breaks when pointed with
the knife, in spite of the greatest care. Size produces a less brittle
crayon, and is also much cheaper, so that it is preferred.
The paste from which the crayons are to be formed is made by mixing
thin size with the colouring matter and steatite to a soft pulp, which
is then kneaded to secure uniformity. The process then proceeds in a
different manner according as the crayon is to be pressed or sawn out.
For producing the crayons by pressing, a simple apparatus is required.
It consists of a horizontal metal cylinder with a well-fitting piston.
The front of the cylinder is closed by a metal plate in which is an
orifice of rather greater diameter than the crayons to be made. In
front of the cylinder is an endless band which moves away from it. In
using this apparatus to shape the crayons, the paste is made of such
consistency that a slight pressure forces it out of the orifice in the
front of the cylinder in a coherent rod. When the cylinder is filled
with the paste, care must be taken that it includes no air bubbles,
for these would cause the rod to break. The piston is then put in
position and the mass forced by uniform gentle pressure out of the
narrow opening. The endless band must move away at the same rate as
the rod proceeds from the cylinder, so that a long stick of the crayon
mass rests upon it. This stick is cut up by a blunt knife into uniform
lengths, which are dried upon boards covered with blotting paper, and
are then enclosed in casings similar to those of the ordinary lead
pencil. The rods must be given a rather greater diameter than they are
to possess when dry, since they shrink somewhat in drying.
The second method consists in producing a thick paste which is moulded
into blocks of the length of the crayons. These blocks are very slowly
dried at a uniform temperature, and when completely dry, are cut by a
fine saw into thin rods, which are then enclosed in a wooden case. The
powder produced in sawing is used in the next operation. This simple
process has many drawbacks. In the first place it is difficult in
drying large blocks of the crayon mass to avoid cracks, which must be
carefully filled with thin paste. Also in sawing up the blocks a large
number of rods will be broken, even with the most careful treatment
(these are again worked up with the powder produced in sawing). Thus,
generally, the formation of crayons by pressure is preferred.
It is important to dry the crayon rods so far that they do not shrink
further after they are placed in the case; otherwise they would break
up when sharpened. At times it is quite impossible to make a usable
point on such a faulty crayon.
=Crayons for Earthenware.=—Crayons for this purpose are made, according
to M. Rösler, by finely powdering colours suitable for glass and
earthenware, and mixing them to a paste with a solution of 2 parts of
gum Arabic and 1 part of Marseilles soap. Pencils are then moulded from
the paste and wrapped in a strip of paper just previously dipped in a
paste of gypsum. Upon unglazed articles or ground glass these crayons
can be used like a lead pencil. The colour is fixed by burning in the
usual manner.
CHAPTER LXVIII.
CONFECTIONERY COLOURS.
Confectioners employ several colours. Yellow, brown and black are
usually obtained by means of caramel; the other colours, red, green
and blue, which are also largely used, must be made from harmless
compounds. Unfortunately, colour makers have been known to offer the
consumer for this purpose colours which by no means correspond to this
requirement; even the poisonous arsenic pigments have been used for
colouring sweets. In such a case the user of the colours is less to be
blamed than the manufacturer, who should sell for this purpose only
colours in no way injurious to health. Fortunately we possess among
the pigments of organic origin a sufficient number to satisfy these
requirements: for green, either sap green or leaf green may be used
without hesitation; for red, cochineal carmine is well suited, and for
blue, indigo carmine. The two pigments last named are indeed expensive,
but since they possess great colouring power they can still be used for
colouring cheap sweets.
For colouring liqueurs equal care must be taken to choose non-injurious
colours. Those mentioned above may also be used for this purpose.
Recently these colours have been largely displaced by the aniline dyes,
which are particularly adapted by their beauty and great colouring
power for the colouring of confectionery or liqueurs. There should
be some hesitation in using these dyes for colouring articles of
food. Some of them are made by means of arsenic compounds, and it is
very difficult to free them absolutely from every trace of arsenic.
But supposing the dye to be free from arsenic, there may still be
objections to its use, for the pure dyes themselves may possess
poisonous properties, and thus ought not to be used for colouring
articles of food.
For colouring foods the colours above mentioned are sufficient. Orange
is obtained by mixing caramel with red, violet by mixing red and blue,
and the shades thus produced are quite sufficient for the purpose in
question. The colour maker should sell the colours in such a condition
that they can be used without further preparation. The colours for
confectioners and liqueur makers should be put on the market in a
semi-fluid or pasty condition. For this purpose carmine should be
ground with a very thick sugar syrup. Leaf green and indigo carmine
require no further preparation; they are already semi-fluid, they
readily diffuse, and are also soluble in alcoholic liquids.
CHAPTER LXIX.
THE PREPARATION OF PIGMENTS FOR PAINTING.
According to the purpose for which they are to be used pigments require
a different method of preparation. The preparation of pigments for
certain special purposes, such as sap colours, cake colours and water
colours, has been already described. The present chapter deals with the
preparation of those pigments which are used in large quantities by
artists and for ordinary painting.
Colours for artistic purposes require different treatment to those
used for ordinary painting. It is important that both should be ground
to a completely homogeneous mixture with the binding medium. At first
sight this appears to be a simple operation, but in practice there
are difficulties which are not too easily overcome. Artists’ colours
are generally ground with a drying oil. The drying oils are vegetable
oils which, when exposed to the air in a thin layer, in a short time
become very viscous, and finally completely resinify; linseed, poppy,
and nut oils possess this property. As a rule, artists’ oil paints are
ground with poppy oil. To prevent the paint from drying to a solid
mass by exposure to air it is enclosed in protecting vessels. Formerly
the ground paint was sold in small bags of bladder. These are now no
longer used; instead, collapsible tubes made of a soft tin alloy are
employed. They are closed at one end; the other has a neck upon which
a metal cap screws down. Pigments ground with just sufficient oil to
form a thick paste may be preserved in these air-tight tubes without
altering in consistency.
Cheaper pigments, such as white lead, white zinc, chrome yellow, etc.,
which are principally used in ordinary painting, are ground with raw or
boiled linseed oil. Ordinary boiled oil is made by boiling linseed oil
with litharge; it contains a certain quantity of lead in solution. It
has been repeatedly stated in this work that lead compounds are very
sensitive to sulphuretted hydrogen. Pigments which are not themselves
altered by sulphuretted hydrogen acquire a dark shade when they are
ground with ordinary lead-boiled oil, because the lead is slowly but
certainly converted into black lead sulphide on exposure to air. Thus,
in order to retain the original beauty of colour, lead-boiled oil
should be replaced by oil boiled with manganese borate, which is at
least as cheap and has the advantage that the oil does not darken in
air. Now that zinc oxide is so cheap it is more and more used in place
of white lead, it is not sensitive to sulphuretted hydrogen, and does
not even change its colour in an atmosphere of the pure gas. It seems
to be quite illogical to use this pigment with a lead-boiled oil. A
coating would be quite discoloured in the course of time, whilst,
if used with manganese-boiled oil, it would retain its white shade
unaltered.
The dry pigment was formerly mixed with the oil by manual labour. The
pigment was spread out upon a smooth stone slab, the oil poured over,
and the two substances rubbed to a uniform paste by means of a glass or
stone rubber known as a muller.
=Paint Mills= are constructed in various ways. The mixture of colour
and oil is ground either between two metal plates or between two
rollers pressed close together.
[Illustration: FIG. 41.]
Fig. 41 represents the construction of a paint mill in which the
grinding is accomplished by a rotating disc. The mixture of pigment
and oil stirred together is brought into the hopper, T, from which it
must pass between the rotating grinding disc, M, and the lower surface
of the hopper. The two substances are thus mixed together. The ground
paint flows out of the ring-shaped vessel surrounding M into a receiver
below. The grinding disc is driven by means of horizontal and vertical
toothed wheels, the latter of which is connected with a pulley driven
by power. By means of a screw on the lower part of the plate in which
is the bearing of the axle of the grinding disc, the distance of the
latter from the lower surface of the hopper can be adjusted. The
process begins by adjusting the disc at a considerable distance from
the hopper. When the paint has once gone through the apparatus the
disc is raised so that the colour is more finely ground. The ground
paint is returned to the hopper until it is quite uniform.
This form of mill can be made in different sizes. Fig. 42 shows the
construction of a form for grinding by hand. The actual grinding
arrangements are exactly the same as those previously described; the
difference lies simply in the use of a fly-wheel turned by a handle.
The illustrations are due to the kindness of W. Sattler of Schweinfurt,
who makes paint mills as a speciality in different sizes and of
excellent quality.
[Illustration: FIG. 42.]
In the second form of paint mill the paint is passed between smooth
rollers moving in opposite directions with different speeds, which thus
exert a grinding action in addition to the crushing effect. The two
rollers are provided with cog-wheels with a different number of cogs in
order to give the different speeds.
In order that the paint may be sufficiently ground in one operation,
roller mills are made with several pairs of rollers, one above the
other, the lower rollers being somewhat nearer together than the
upper. The paint is fed on to the top pair of rollers, and, after
going through these, passes to the next, and finally, after going
between all the pairs of rollers, collects in a receiver below in a
finished condition. By the use of such mills the paints can be ground
sufficiently fine in one operation, if a proper number of rollers is
used. When only two or three pairs are used and the paint is to be very
finely ground, it must be passed through the whole mill two or three
times.
CHAPTER LXX.
THE EXAMINATION OF PIGMENTS.
When an accurate examination of a pigment is required, the only course
is to conduct an exact chemical analysis, which can only be done by an
expert chemist in a well-equipped laboratory. But often it is necessary
in the course of trade to decide rapidly the nature of a pigment or to
detect the adulteration of a dear pigment with a cheaper, and for this
purpose it is important to have a method of examination which can be
conducted without much apparatus, and which requires no great chemical
knowledge. It is quite possible to test the majority of pigments in a
simple manner. Few reagents are necessary. For an examination of the
mineral pigments the following are generally sufficient: hydrochloric,
nitric and sulphuric acids, caustic soda solution and ammonium sulphide.
The examination of a pigment containing organic compounds is somewhat
more difficult, especially when it is necessary to ascertain the
nature of the colouring matter. In this case additional reagents are
required—stannous chloride, alum solution, etc.
Since the present work is intended to meet the requirements of the
practical man, the behaviour of the different pigments towards
ordinary reagents is given in tabular form, the pigments of the same
colour being taken together. Since the colouring matters of organic
origin, as they occur in the lakes, require a rather more detailed
examination, the testing of pigments composed of inorganic materials
only is first given, afterwards the properties of the organic colouring
matters, so far as is necessary, will be added.
=Mineral Pigments.=—If the substance to be examined is in the form of a
dry powder, it may at once be tested with the reagents mentioned, but
if it is a paint or water colour, the oil or gum must be first removed,
otherwise it would not be possible to recognise with certainty the
action of the reagents.
From water colours, which are ground with gum Arabic or tragacanth
solution, it is easy to separate the pigment from the binding medium.
The colour is allowed to stand in a tall narrow beaker with a somewhat
large quantity of water. After some time the lumps become soft, they
are then repeatedly stirred up, the pigment allowed to deposit, and the
water, which now contains the binding medium, poured off.
The removal of oil from a paint is somewhat more difficult. A quantity
of the paint is placed in a flask with a mixture of equal parts of
strong alcohol and ether, or with benzine. The flask is lightly corked,
and, after frequent shaking, allowed to stand. The liquids mentioned
are good solvents for oils. After a day or two the pigment will
generally have deposited at the bottom of the flask. The solution is
then poured off, the residue mixed with a small quantity of the solvent
and transferred to a filter, where another small quantity of solvent is
poured over it. The solvent is allowed to drain off, and the residue is
dried. A powder without coherence should be left; this is the pigment
free from oil. It can be treated like an originally dry colour.
The pigments are most conveniently examined in test tubes. If these are
not at hand the reactions may be carried out on a plate of glass lying
on white paper. The powder is placed on the glass and the reagent
dropped on to it from a glass rod dipped in the liquid.
=Examination with the Blowpipe.=—From the behaviour of pigments at high
temperatures important conclusions may be drawn as to their nature.
For this purpose small porcelain crucibles are used; broken pieces of
porcelain or an iron spoon may also be employed. An ordinary spirit
lamp is generally sufficient as a source of heat. In some cases a
higher temperature is required, which is obtained by means of the
blowpipe.
The blowpipe is an invaluable instrument in the examination of mineral
pigments. By means of it, almost without reagents, the nature of the
pigment can generally be ascertained. The reagents necessary in using
the blowpipe are soda, borax, and the solution of a cobalt salt.
The following method should be observed in examining pigments by means
of the blowpipe. A quantity of the substance, about equal in volume to
two grains of rice, is placed in a small hole cut by a knife in a piece
of charcoal, where it is heated by the blowpipe flame. The behaviour
of substances is different in the oxidising and reducing flames of the
blowpipe. When a flame is blown out to a point by means of the blowpipe
it may be seen that the flame consists of two conical portions, one
inside the other. The inner is known as the reducing flame, because
metallic oxides heated in it produce a bead of metal, or, as the change
is chemically expressed, are reduced to metal. The outer cone has the
opposite properties; metals melted in it are quickly changed into
oxides by the action of the oxygen of the air, which has unrestricted
access. In examining a pigment with the blowpipe the reducing flame
is first used. The nature of the bead of metal, such as is readily
obtained from lead pigments, often allows the composition of the
substance to be recognised with certainty. If the behaviour of the bead
of metal is not conclusive it is further heated in the oxidising flame.
The metal is thus converted into oxide, which deposits on the charcoal,
and by its colour and volatility or want of volatility enables the
metal contained in the pigment to be determined.
A solution of cobalt nitrate or chloride is used in testing for certain
metallic oxides. The substances are moistened with a very dilute
solution of one of these substances before heating. After they have
been heated they show characteristic colours if certain oxides are
present.
Several metallic oxides give a characteristic colour when fused with
borax. For this purpose a small loop is made at the end of a thin
platinum wire; this is moistened and dipped in powdered anhydrous
borax. On heating in the blowpipe flame the borax adhering to the wire
melts to a colourless glass. In testing a pigment the transparent
bead of borax is then dipped into the powder, and again fused in the
blowpipe flame. It is of great importance in this test to fuse but a
very small quantity of material in the borax bead; some metallic oxides
have such great colouring power that, when too much is used, the bead
appears quite black, so that its colour cannot be recognised.
REACTIONS OF THE WHITE PIGMENTS.
_On Heating on Charcoal_:—Lead pigments give a lead bead in the
reducing flame, which is converted in the oxidising flame to lead
oxide, forming a deposit on the charcoal surrounding the hole.
Antimony white gives a brittle metallic bead in the reducing flame.
This burns in the oxidising flame with the evolution of white vapours,
and is at the same time covered by small shining crystals.
Bismuth white in the oxidising flame gives a rainbow-coloured
incrustation spreading far over the charcoal.
Tin white gives a malleable metallic bead, converted by nitric acid
into a white powder.
Zinc white is converted into a green mass when moistened with cobalt
solution and heated in the oxidising flame.
The more expensive white pigments are frequently mixed with cheaper
substances, _e.g._, white lead with finely powdered barytes, chalk or
gypsum. Such admixture is distinctly to be regarded as adulteration,
since the added substances have not the covering power of white lead.
In the case of coloured pigments an addition of a white material is not
to be regarded as adulteration, since the addition is made in order to
impart a paler shade to the colour.
+---------------+--------------+-----------+----------+-------------+
| Pigment. | Hydrochloric | Caustic | Ammonium | On Heating. |
| | Acid. | Soda. | Sulphide.| |
+---------------+--------------+-----------+----------+-------------+
|Antimony white |Dissolves, |Dissolves. |Turns |Turns yellow |
| |solution | | reddish |and melts. |
| |on turbid | | yellow. | |
| |adding water. | | | |
| | | | | |
|White lead |Dissolves with|Dissolves. |Turns |Becomes |
| |effervescence,| | black. |permanently |
| |solution gives| | |yellow. |
| |crystalline | | | |
| |lead chloride.| | | |
| | | | | |
|Lead |Dissolves |Dissolves |Turns |Turns yellow.|
| oxychloride |without |on boiling.| black. | |
| |effervescence.| | | |
| | | | | |
|Lead sulphate |Insoluble. |Dissolves |Turns |Unaltered. |
| | |on boiling.| black. | |
| | | | | |
|Permanent white|Insoluble. |Insoluble. |Unaltered.|Unaltered. |
|(barium | | | | |
| sulphate) | | | | |
| | | | | |
|Bismuth white |Insoluble. |Insoluble. |Turns |Evolves |
| | | | black. |reddish |
| | | | |brown fumes, |
| | | | |which redden |
| | | | |litmus paper.|
| | | | | |
|Zinc white |Dissolves |Dissolves. |Unaltered.|Turns yellow,|
| |without | | |becomes white|
| |effervescence.| | |again on |
| | | | |cooling. |
| | | | | |
|Tin white |Dissolves. |Dissolves. |Turns |Unaltered. |
| | | | yellow. | |
+---------------+--------------+-----------+----------+-------------+
REACTIONS OF THE YELLOW PIGMENTS.
+-----------+---------------+-------------+----------+-------------+
| Pigment. | Hydrochloric |Caustic Soda.| Ammonium | On Heating. |
| | Acid. | | Sulphide.| |
+-----------+---------------+-------------+----------+-------------+
|Chrome |Green solution |Becomes |Blackened.|Fuses to a |
| yellow |above a white |orange on | |yellow mass. |
| and |residue, which |boiling and | | |
| chrome red|is soluble on |dissolves. | | |
| |largely | | | |
| |diluting. | | | |
| | | | | |
|Cassel |Unaltered, |Becomes paler|Blackened.|Melts. |
| yellow |becomes white |on boiling, | | |
| |on boiling. |liquid | | |
| | |yellow. | | |
| | | | | |
|Naples |On boiling |Reddish |Turns |Melts at |
| yellow |orange, then |yellow. | brownish |a high |
| |white. | | black. |temperature. |
| | | | | |
|Massicot |Turns white. |Partially |Blackened.|Melts |
| | |soluble on | |with some |
| | |boiling. | |difficulty. |
| | | | | |
|Lead iodide|Turns white. |Dissolves. |Blackened.|Melts. |
| | | | | |
|Barium |Yellow solution|Unaltered. |Unaltered.|Unaltered. |
| yellow | which | | | |
|(chromate) |gives white | | | |
| |precipitate | | | |
| |with sulphuric | | | |
| |acid. | | | |
| | | | | |
|Cadmium |Dissolves with |Unaltered. |Unaltered.|Melts with |
| yellow | evolution of | | |difficulty. |
| | sulphuretted | | | |
| | hydrogen. | | | |
| | | | | |
|Zinc |Yellow |Yellow |Unaltered.|Melts with |
| yellow |solution. |solution, | |difficulty. |
| | |white | | |
| | |residue. | | |
| | | | | |
|Cobalt |Red solution. |Colourless |Unaltered.|Becomes |
| yellow | |solution, | blackish |
| | |greyish blue | |at high |
| | |precipitate. | |temperatures.|
| | | | | |
|Orpiment |Unaltered. |Colourless |Yellow |Volatilises. |
| | |solution. | solution.| |
| | | | | |
|Turpeth |Dissolves. |Unaltered. |Blackened.|Turns red. |
| mineral | | | | |
+-----------+---------------+-------------+----------+-------------+
_On Heating on Charcoal_:—Chrome yellow, chrome red, Cassel yellow,
massicot and lead iodide give lead beads in the reducing flame. Chrome
yellow and red when fused with soda give red masses soluble in water.
Naples yellow gives a lead bead and white fumes without smell.
Orpiment gives an odour of garlic.
Cobalt yellow, when heated with alumina, is turned blue.
Cadmium yellow produces a brown incrustation on the charcoal.
The examination before the blowpipe serves especially for the
recognition of lead, chromium, antimony and arsenic. If a pigment
blackens on heating, the presence of an organic colouring matter is
indicated, such as Dutch pink, weld lake, etc.
The adulteration of pigments free from lead by colours containing that
metal is recognised by the blackening produced by ammonium sulphide.
REACTIONS OF THE RED PIGMENTS.
+---------+-------------------+------------+----------+------------+
| Pigment.| Hydrochloric Acid.| Caustic | Ammonium | On Heating.|
| | | Soda. | Sulphide.| |
+---------+-------------------+------------+----------+------------+
|Chrome |Green solution, |Yellow |Turns |Fuses. |
|red | white residue |solution |greenish | |
| | soluble on |and white |black. | |
| | largely diluting.|residue. | | |
| | | | | |
|Red lead |Chlorine is |Almost |Turns |Turns yellow|
| | evolved, white |unchanged. |black. |and finally |
| | residue. | | |melts. |
| | | | | |
|Ferric |Slowly dissolve to |Unaltered. |Slowly |Become dark |
|oxide | yellow solution. | |blackened.|blackish |
|pigments | | | |brown. |
| | | | | |
|Antimony |Dissolves with |Dissolves to|Becomes |Melts. |
|vermilion| evolution of |colourless |darker, | |
| | sulphuretted |solution. |partially | |
| | hydrogen. | |soluble. | |
| | | | | |
|Mercury |Unaltered. |Turns |Unaltered.|Volatilises,|
|vermilion| |yellowish. | |sulphur |
| | | | |dioxide |
| | | | |evolved. |
| | | | | |
|Mercuric |Dissolves to |Dissolves to|Blackened.|Fuses and |
|iodide | colourless |yellowish | | then |
| | solution. |solution. | |volatilises.|
| | | | | |
|Realgar |Unaltered. |Dissolves to|Dissolves |Volatilises.|
| | |colourless |to yellow | |
| | |solution. |solution. | |
+---------+-------------------+------------+----------+------------+
_On Heating on Charcoal_:—Chrome red and red lead give lead beads in
the reducing flame. The former gives a red mass when fused with soda,
which dissolves to a yellow solution.
Ferric oxide pigments become darker, but give no incrustation.
Antimony vermilion burns with production of sulphur dioxide and white
fumes without smell when heated in the oxidising flame; when fused with
soda before the blowpipe, it gives a white brittle bead of metallic
antimony.
Vermilion volatilises in the oxidising flame and gives a smell of
sulphur dioxide.
Mercuric iodide readily fuses and volatilises.
Realgar volatilises. When heated with soda in the reducing flame, white
fumes with an odour of garlic are produced.
REACTIONS OF THE BLUE PIGMENTS.
+---------------+---------------+----------+----------+------------+
| Pigment. | Hydrochloric | Caustic | Ammonium | On Heating.|
| | Acid. | Soda. | Sulphide.| |
+---------------+---------------+----------+----------+------------+
|Prussian, |Dissolve to |Decolour- |Liquid |Blackened. |
|Chinese, |green solution,| ised, |yellowish | |
|Paris, |then yellow. |brown |green. | |
|Turnbull’s, | |residue. | | |
|and Brunswick | | | | |
|blue | | | | |
| | | | | |
|Mountain blue |Dissolves to |Blackened.|Blackened.|Blackened. |
| |yellowish-green| | | |
| |solution. | | | |
| | | | | |
|Ultramarine |Rapidly |Unchanged.|Unchanged.|Unchanged. |
| |decomposed | | | |
| |with evolution | | | |
| |of sulphuretted| | | |
| |hydrogen. | | | |
| | | | | |
|Smalts |Almost |Unchanged.|Blackened.|Fuses at |
| |unaltered, | | |a high |
| |greenish | | |temperature.|
| |solution on | | | |
| |long boiling. | | | |
| | | | | |
|Cobalt blue |Unchanged. |Unchanged.|Unchanged.|Infusible |
| | | | |and |
| | | | |unchanged. |
+---------------+---------------+----------+----------+------------+
_On Heating on Charcoal_:—Prussian, Chinese, Paris, Turnbull’s and
Brunswick blue are turned black, the residue colours the borax bead
pale brown in the oxidising flame, and pale green in the reducing
flame.
Ultramarine is unaltered at a high temperature.
Smalts, on long heating in the reducing flame with borax, gives a dark
blue bead.
Cobalt blue is infusible; it colours the borax bead blue. The bead
loses its fine colour on long heating in the reducing flame.
Mountain blue is blackened before the blowpipe. When the residue
is moistened with hydrochloric acid and again heated, the flame is
coloured bright green. When fused with borax in the oxidising flame, an
emerald green bead is formed.
REACTIONS OF THE GREEN PIGMENTS.
+---------------+---------------+----------+------------+-----------+
| Pigment. | Hydrochloric | Caustic | Ammonium |On Heating.|
| | Acid. | Soda. | Sulphide. | |
+---------------+---------------+----------+------------+-----------+
|Verdigris |Dissolves |Unaltered.|Blackened. |Blackened |
|(all varieties)|to green | | |with |
| |solution, | | |evolution |
| |smell of | | |of peculiar|
| |acetic acid. | | |odour. |
| | | | | |
|Bremen green, |Green |Unaltered.|Blackened. |Blackened. |
|Brunswick green|solution and | | | |
| |white residue. | | | |
| | | | | |
| | | | | |
|Emerald green, |Dissolve to |Gradually |Become |Blackened |
|Scheele’s green|greenish |coloured |brownish |and evolve |
| |solution. |brownish |black. |garliclike |
| | |yellow. | |odour. |
| | | | | |
|Copper borate |Dissolves to |Black |Becomes |Fuses. |
| |greenish |residue. |brownish | |
| |solution. | |black. | |
| | | | | |
|Rinmann’s green|Dissolves to |Unaltered.|Blackened. |Unaltered. |
| |rose-red | | | |
| |solution. | | | |
| | | | | |
|Chromium oxide |Almost |Unaltered.|Becomes dark|Unaltered. |
| |unaltered. | |dirty green.| |
| | | | | |
|Chrome green |Becomes deeper |Unaltered.|Becomes dark|Unaltered. |
| lake |in colour. | |dirty green.| |
| | | | | |
|Manganese green|Dissolves to |Dissolves |Discoloured.|Unaltered. |
| |green |to green | | |
| |solution. |solution. | | |
| | | | | |
|Green |Is decolourised|Unaltered.|Unaltered. |Unaltered. |
| ultramarine |with evolution | | | |
| |of sulphuretted| | | |
| |hydrogen. | | | |
+---------------+---------------+----------+------------+-----------+
_On Heating on Charcoal_:—Verdigris, Bremen and Brunswick greens give
black residues on charcoal, which produce a bluish-green bead when
fused with borax in the oxidising flame.
Emerald green and Scheele’s green behave in a similar manner, but on
heating evolve an odour of garlic.
Rinmann’s green gives a blue borax bead.
Manganese green is discoloured in the reducing flame.
REACTIONS OF THE BROWN PIGMENTS.
+----------------+------------+-----------+----------+-----------+
| Pigment. |Hydrochloric| Caustic | Ammonium |On Heating.|
| | Acid. | Soda. | Sulphide.| |
+----------------+------------+-----------+----------+-----------+
|Lead brown |White |Dissolves. |Blackened.|Turns |
| |residue, | | |yellow |
| |chlorine | | |and fuses. |
| |evolved. | | | |
| | | | | |
|Manganese brown |Dissolves |Unaltered. |Becomes |Unaltered. |
| |to yellow | |flesh | |
| |solution. | |coloured. | |
| | | | | |
|Pyrolusite brown|Dissolves |Unaltered. |Becomes |Unaltered. |
| |to yellow | |flesh | |
| |solution, | |coloured. | |
| |chlorine | | | |
| |evolved. | | | |
| | | | | |
|Prussian brown |Dissolves |Unaltered. |Blackened.|Turns to |
| |to yellow | | |reddish |
| |solution. | | |brown. |
| | | | | |
|Iron brown |Dissolves |Unaltered. |Blackened.|Unaltered. |
| |to yellow | | | |
| |solution. | | | |
| | | | | |
|Chrome brown |Dissolves |Yellow |Blackened.|Blackened. |
| |to greenish |solution, | | |
| |yellow |black | | |
| |solution. |residue. | | |
| | | | | |
|Cobalt brown |Dissolves |Unaltered |Blackened.|Unaltered. |
| |to reddish | or | | |
| |yellow |blackened. | | |
| |solution. | | | |
| | | | | |
|Hatchett brown |Unaltered. |Becomes |Blackened.|Blackened. |
| | |greenish | | |
| | | blue. | | |
| | | | | |
|Humins, Bistre |Unaltered, |Give yellow|Unaltered.|Burn. |
| |yellow |liquid. | | |
| |liquid. | | | |
+----------------+------------+-----------+----------+-----------+
_On Heating on Charcoal_:—Lead brown gives a lead bead in the reducing
flame.
Manganese brown and pyrolusite brown, when fused with saltpetre on
platinum foil at a high temperature, give a bluish-green mass.
Prussian brown and iron brown give a pale green borax bead in the
reducing flame, which turns yellowish brown in the oxidising flame.
Chrome brown heated, moistened with hydrochloric acid, and again
heated, colours the flame green. It also gives a green borax bead.
Cobalt brown produces a blue borax bead.
Humin substances burn when heated on charcoal.
REACTIONS OF THE BLACK PIGMENTS.
Almost all black pigments consist of carbon, upon which reagents have
no action. They should be at once heated on charcoal. If they burn
away completely in the oxidising flame they consist of lamp black or
carbon obtained by some process of incomplete combustion; if a white,
infusible residue is left, the pigment is bone (ivory) black; if the
residue is black the substance under examination must be ”neutral
tint,” chrome black, or chrome-copper black. The two former give a pale
green borax bead, whilst chrome-copper black gives a deep green bead,
and when heated, moistened with hydrochloric acid, and again heated, it
colours the flame green.
CHAPTER LXXI.
EXAMINATION OF LAKES.
In examining lakes it is necessary to ascertain the nature of the
organic colouring matter, the base with which this is united, and
also the nature of the substances mechanically mixed with the lake to
lighten its shade.
It is most convenient to examine the pigment first for mechanical
admixtures. If an effervescence follows the addition of hydrochloric
acid, denoting the presence of a carbonate, this is generally calcium
carbonate. White lead is rarely used, since it is very heavy and is
more expensive. Gypsum and magnesia are occasionally added to lakes;
they are recognised by examining the residue left on ignition.
In testing for the metallic oxide which is united with the colouring
matter a small quantity of the lake is heated in a little porcelain
crucible until all organic substances are completely destroyed. The
residue is then examined for aluminium and tin oxides, by means of
which lakes are most frequently prepared.
REACTIONS OF THE ORGANIC COLOURING MATTERS.
+----------+----------+----------+--------+---------+--------+
|Colouring | Dilute | Caustic | Lime | Strong | Alum. |
| Matter. | Acids. | Soda. | Water. | Nitric | |
| | | | | Acid. | |
+----------+----------+----------+--------+---------+--------+
| YELLOW.| | | | | |
|Buckthorn |Slight |Yellowish |Slight |Reddish |Pale |
| berry |turbidity.| red. |greenish|brown. |yellow. |
| extract | | |precipi-| | |
| | | | tate. | | |
| | | | | | |
|Dutch pink|Yellow |Brown. |Brownish|Reddish | —— |
| |solution. | | |brown. | |
| | | | | | |
|Weld |Slight |Golden |Greenish|Golden |Slight |
| extract |turbidity.| yellow. |yellow. |yellow. |yellow |
| | | | | |precipi-|
| | | | | | tate.|
| | | | | | |
|Weld lake |Yellow |Unaltered.|Greenish|Golden | —— |
| |solution. | |yellow. |yellow | |
| | | | |solution.| |
| | | | | | |
|Gamboge |Unaltered.|Deep |Deeper |Deep | —— |
| | |reddish |yellow. |yellow. | |
| | |yellow. | | | |
| | | | | | |
|Gamboge |Yellow |Deep |Deeper |Deep |Yellow |
| lake |solution. |reddish |yellow. |yellow. |precipi-|
| | |yellow. | | | tate.|
| | | | | | |
|Fustic |Becomes |Dirty |Deeper. |Slight |Pale |
| |paler. |brownish | |precipi- |yellow |
| | | red. | | tate. |precipi-|
| | | | | | tate.|
| | | | | | |
|Quercitron|Becomes |Deeper. |Deeper. |Paler. |Paler, |
| |paler. | | | |slight |
| | | | | |precipi-|
| | | | | | tate.|
| | | | | | |
|Young |Slight |Purple |Reddish.|Greenish.|Slight |
| fustic |greenish | red. | | |greenish|
| |precipi- | | | |precipi-|
| | tate. | | | | tate.|
| | | | | | |
|Turmeric |Carmine |Brown. |Brown. |Carmine |Yellow. |
| | red. | | |red. | |
| | | | | | |
| BLUE. | | | | | |
|Indigotin |Unaltered.|Yellowish | —— |Yellow. | —— |
| | |brown | | | |
| | |solution. | | | |
| | | | | | |
|Indigo |Unaltered.|Yellowish | —— |Yellow. | —— |
| carmine | |brown | | | |
| blue lake| |solution. | | | |
| | | | | | |
|Litmus |Turns red.|Unaltered.| —— | —— | —— |
| | | | | | |
|Logwood |Red. |Violet. |Blue. |Yellow. |Dirty |
| | | | | |violet. |
| | | | | | |
| RED. | | | | | |
|Cochineal |Becomes |Violet. |Becomes |Yellow. |Red |
| decoction| paler. | |darker. | |flocks. |
| | | | | | |
|Carmine |Red |Violet |Becomes |Yellow. | —— |
| | solution.|solution. |darker. | | |
| | | | | | |
|Lac, |Yellowish |Violet | —— |Yellow. |Red |
| lac dye | red. | solution.| | |precipi-|
| | | | | | tate.|
| | | | | | |
|Safflower |Unaltered.|Red | —— | —— | —— |
| red | |solution. | | | |
| | | | | | |
|Madder |Red |Red | —— |Yellow. |Red |
| lake | solution.|precipi- | | |precipi-|
| | | tate. | | | tate.|
| | | | | | |
|Red wood |Pale red. |Violet. |Carmine |Yellow. |Red |
| | | |red | |precipi-|
| | | |precipi-| | tate.|
| | | | tate. | | |
| | | | | | |
|Red wood |Red |Violet | —— |Yellow. | —— |
| lake | solution.|solution. | | | |
_The remaining red colouring matters give such uncertain
reactions that it is almost impossible to distinguish
between them by ordinary means; they are therefore not
included here._
| GREEN. | | | | | |
|Sap green |Reddish |Brownish |Becomes |Reddish | —— |
| | brown. | green. |deeper. |yellow. | |
| | | | | | |
|Leaf green|Green |Green | —— |Reddish | —— |
| |solution. |solution. | |yellow. | |
| | | | | | |
| BROWN. | | | | | |
|Sepia |Unaltered.|Brown | —— | —— | —— |
| | |solution. | | | |
| | | | | | |
|Catechu |Paler. |Reddish |Reddish |Yellowish|Reddish |
| solution| | brown. |brown. |brown. |yellow |
| | | | | |color- |
| | | | | | ation.|
+----------+----------+----------+--------+---------+--------+
+----------+---------+---------+----------+---------+--------------+
|Colouring |Stannous | Ferric | Copper |Gelatine | |
| Matter. |Chloride.|Chloride.| Acetate. |Solution.| Remarks. |
| | | | | | |
+----------+---------+---------+----------+---------+--------------+
| YELLOW.| | | | | |
|Buckthorn |Slight |Olive |Dirty |Slight | —— |
| berry |greenish |green. |yellow. |precipi- | |
| extract |yellow | | | tate. | |
| |precipi- | | | | |
| | tate. | | | | |
| | | | | | |
|Dutch pink| —— | —— | —— | —— |Chars when |
| | | | | |heated on |
| | | | | |platinum foil.|
| | | | | | |
|Weld |Consider-|Greenish.|Reddish |Slight |Gives yellow |
| extract | able | |yellow |turbid- |scales |
| |yellow | |precipi- | ity. |some time |
| |precipi- | | tate. | |after adding |
| | tate. | | | |potassium |
| | | | | |bichromate. |
| | | | | | |
|Weld lake | —— | —— | —— | —— | —— |
| | | | | | |
|Gamboge | —— | —— | —— | —— |Readily melts |
| | | | | |and burns. |
| | | | | | |
|Gamboge |Yellow | —— | —— | —— | —— |
| lake |precipi- | | | | |
| | tate. | | | | |
| | | | | | |
|Fustic |Yellow |Blackish |Brownish |Consider-|Lead acetate |
| |precipi- |green |yellow | able |gives an |
| | tate. |precipi- |precipi- |precipi- |orange red |
| | | tate. | tate. | tate. |precipitate. |
| | | | | | |
|Quercitron|Yellowish|Becomes |Yellowish |Reddish | —— |
| |red |green, |green |precipi- | |
| |precipi- |green |precipi- | tate. | |
| | tate. |precipi- | tate. | | |
| | | tate. | | | |
| | | | | | |
|Young |Orange |Brownish |Brown |Yellowish|Ammonia |
| fustic |red |green |flocculent|red |gives red |
| |precipi- |precipi- |precipi- |precipi- |coloration. |
| | tate. | tate. | tate. | tate. | |
| | | | | | |
|Turmeric |Yellow. |Brown. | —— |Fairly |Very |
| | | | |large |sensitive |
| | | | |precipi- |to alkalis. |
| BLUE. | | | | tate. | |
| | | | | | |
|Indigotin | —— | —— | —— | —— |On heating |
| | | | | |gives |
| | | | | |peculiar |
| | | | | |odour and |
| | | | | |purple red |
| | | | | |vapours. |
| | | | | | |
|Indigo | —— | —— | —— | —— |On heating |
| carmine | | | | |gives |
| blue lake| | | | |peculiar |
| | | | | |odour |
| | | | | |and purple |
| | | | | |vapours. |
| | | | | | |
|Litmus | —— | —— | —— | —— |Unpleasant |
| | | | | |smell on |
| | | | | |heating, |
| | | | | |white ash. |
| | | | | | |
|Logwood |Dirty |Dark | —— |Very |Black with |
| |violet. |coloured | |turbid. |potassium |
| | |solution.| | |bichromate. |
| | | | | | |
| RED. | | | | | |
|Cochineal |Reddish | —— | —— | —— |Completely |
| decoction|violet | | | |soluble |
| |flocks. | | | |in ammonia. |
| | | | | | |
|Carmine | —— | —— | —— | —— | —— |
| | | | | | |
|Lac, |Red | —— | —— | —— | —— |
| lac dye |precipi- | | | | |
| | tate. | | | | |
| | | | | | |
|Safflower | —— | —— | —— | —— |Rapidly |
| red | | | | |decomposed |
| | | | | |by boiling |
| | | | | |with alkalis. |
| | | | | | |
|Madder |Red | —— | —— | —— | —— |
| lake |precipi- | | | | |
| | tate. | | | | |
| | | | | | |
|Red wood |Deep |Violet |Violet | —— | —— |
| |red |precipi- |red | | |
| |precipi- | tate. |precipi- | | |
| | tate. | | tate. | | |
| | | | | | |
|Red wood | —— | —— | —— | —— |Much ash |
| lake | | | |on ignition. |
_The remaining red colouring matters give such uncertain
reactions that it is almost impossible to distinguish
between them by ordinary means; they are therefore not
included here._
| GREEN. | | | | | |
|Sap green | —— | —— | —— | —— |White ash |
| | | | | |on ignition. |
| | | | | | |
|Leaf green| —— | —— | —— | —— |White ash |
| | | | | |on ignition. |
| | | | | | |
| BROWN. | | | | | |
|Sepia | —— | —— | —— | —— |Burns with |
| | | | | |peculiar |
| | | | | |smell. |
| | | | | | |
|Catechu |Brownish |Brownish |Brown |Consider-| —— |
| solution|precipi- |green |precipi- | able | |
| | tate. |precipi- | tate. |precipi- | |
| | | tate. | | tate. | |
+----------+---------+---------+----------+---------+--------------+
It is not easy to decide which colouring matter is united with the
metallic oxide, because the organic colouring matters do not give,
as a rule, decided reactions. In examining pigments of this kind
it is always advisable to test at the same time a pigment of known
composition, and to compare the reactions of the two. The colouring
matter of the lake is first brought into solution. This is accomplished
by the action of dilute hydrochloric acid, which decomposes the
compound of metallic oxide and colouring matter, the latter dissolving.
A portion of the lake should remain undecomposed, so that the solution
has no strong acid reaction by which the action of the reagents to be
used would be modified. When the lake has been treated for some time
with dilute hydrochloric acid, water is added and the solution of the
colouring matter filtered from the residue. Small quantities of this
solution are then treated with the different reagents. By a comparison
of the reactions given by the solution and by a solution of the pure
colouring matter, the nature of the colouring matter under examination
may be decided.
In deciding in the first place if a colour is of organic origin, it
is treated with hydrochloric acid in the above manner. If a coloured
solution results, an organic colour is probably present. Chlorine water
is then added to a portion of the solution; if the latter is quickly
decolourised an organic colouring matter is certainly present, for they
are all decomposed by the continued action of chlorine.
The following reagents are used in testing organic colouring matters:
dilute sulphuric or hydrochloric acid, caustic soda solution or lime
water, strong nitric acid, which, in consequence of its oxidising
properties, gives different reactions to the other acids. Of the
metallic salts, alum, stannous chloride and ferric chloride are used,
and occasionally copper acetate. Glue solution is also used in the pure
form of isinglass or gelatine solution, with which several colouring
matters give characteristic precipitates. The foregoing tables give the
behaviour of the colouring matters contained in the organic pigments
towards the reagents mentioned above.
CHAPTER LXXII.
THE TESTING OF DYE-WOODS.
In the manufacture of pigments from dye-woods or other organic
substances, the value of the raw material is in proportion to the
amount of colouring matter it contains, other things being equal. It
is specially desirable to estimate accurately the colouring matter in
expensive materials such as indigo and cochineal.
There are a number of methods which permit an accurate estimation
of the indigo blue in indigo. One good process is founded upon the
decomposition of indigo blue by chlorine, when the colour of the
solution changes from blue to yellow. Since a definite amount of
chlorine is required to decompose indigo blue, from the quantity of
chlorine required by a sample of indigo, its content in indigo blue can
be ascertained.
Whilst the percentage of indigo blue contained in indigo can be
found with tolerable accuracy, though by a rather elaborate process
requiring special apparatus, there is no convenient method for
examining the other organic colour materials by which their content
in active constituents can be readily found. In practice a process is
particularly valuable which requires little time and no complicated
apparatus. Colouring materials can be rapidly tested by a physical
process which requires little time and an inexpensive apparatus. Under
similar conditions the extract of a dye-wood is deeper in colour in
proportion to the colouring matter it contains. If therefore the
intensity of the colour of the extract can be accurately measured,
there is no difficulty in drawing a certain conclusion as to the amount
of colouring matter in the raw material.
[Illustration: FIG. 43.]
=The Colorimeter= is the apparatus adapted for the purpose in question.
There are many forms of colorimeter. The instrument devised by Dubosq
is distinguished by simplicity and accuracy of results before other
apparatus of similar construction. Dubosq’s colorimeter consists of the
following parts (Fig. 43): two glass cylinders, C and C₁, the bottoms
of which must be perfectly plane both inside and outside (the accuracy
of the results depends upon this), stand upon a sheet of plate glass.
Two glass cylinders of smaller diameter, T and T₁, are suspended in C
and C₁. The bottoms of these cylinders must also be quite plane. It
would be very expensive to make glass cylinders of this kind in one
piece. The same result is obtained by providing each cylinder with
a metal ring upon which screws another ring in which is cemented a
circular piece of plate glass.
Light should only reach the eye of the observer in a direction parallel
with the axis of the cylinders. C and C₁ are therefore blackened on
the outside. The inner cylinders, T and T₁, are fastened to racks
moving vertically. The distance through which the cylinder is moved
is measured by a scale on one of the racks. Above the cylinders T and
T₁ are Fresnel’s prisms. Below C and C₁ is a mirror, S, which can be
adjusted to throw light vertically upwards. Beams of light pass through
the plate glass and the bottoms of the cylinders C and T, C₁ and T₁,
unrefracted, they are then deviated by the Fresnel’s prisms so that the
observer looking down through the telescope, F, has a circular field of
view, one half of which is illuminated by the light passing through the
cylinder C, and the other by the beam passing through C₁. The intensity
of the light which has passed through the two cylinders can thus be
accurately compared.
In order to use this apparatus to compare the intensity of colour of
two liquids, the following process is performed: A liquid is made,
the colour intensity of which is taken as 100. The colour intensity
of the liquid under examination will then be represented by a number
indicating the relation between its intensity and that of the standard
liquid. A solution of caramel in water is generally used as the
standard, since this substance has very great intensity of colour.
The preparation of absolutely pure caramel is difficult, and it is
therefore advisable, in order always to have the standard solution of
the same intensity, to prepare a large quantity of caramel solution at
once, to add carbolic acid to prevent it from decomposing, and to keep
it in well-closed bottles. When the standard solution is almost used
up the colorimeter is employed to prepare a fresh quantity of equal
intensity.
To render possible an exact comparison of two substances they
must be tested under the same conditions, that is, the solutions
of the colouring matters must be made in exactly the same manner.
Finely-powdered materials dissolve more readily than coarse powders. In
making the solutions which are to be examined for intensity of colour,
the raw materials must be brought into a condition of fine division
by the same instrument, for example, a rasp. The colour solution is
made by boiling 100 grammes of the dye-wood with exactly a litre of
distilled water for precisely thirty minutes. The liquid is then
filtered into a 1-litre flask. The dye-wood absorbs water, and some is
lost by evaporation, so that considerably less than 1 litre of liquid
is collected in the flask. Distilled water is added to make up the
volume to 1 litre.
If two samples of logwood are treated in this manner, solutions are
obtained which contain the colouring matter in the same proportions
in which it exists in the two samples. The intensity of colour of the
solutions is then estimated in the following manner: The cylinder C is
filled with the standard caramel solution up to a mark on the outside
of the cylinder. The cylinder C₁ is filled with the decoction to the
same height. The distance between the bottoms of the cylinders, R and
T, R₁ and T₁, must be made smaller in proportion to the intensity of
colour of the liquid between them. If now the amount of light which
penetrates a layer of caramel solution of a certain thickness be taken
as unity, the depth of a layer of the decoction must be greater, the
smaller the quantity of colouring matter it contains, in order that
the two halves of the field of view may be equally illuminated. The
cylinder T₁ must be raised to a greater height the smaller the quantity
of colouring matter in the liquid, in order that the two halves of
the field may be illuminated to the same extent. If the colouring
power of the caramel solution is taken as 100, the colouring power of
the decoction can be readily calculated from the height to which the
cylinder, T₁, is raised. The heights of the layers of liquid between
the bottoms of the cylinders C and T, C₁ and T₁, are inversely as the
quantities of colouring matter contained in the respective cylinders.
When caramel solution is used as the standard the intensity of the
light in the two halves of the field can be judged, but not the
intensity of colour. In order to estimate the latter a solution of that
colouring matter must be used as a standard which is the principal
constituent of the decoction under examination. Thus, in a careful
examination of logwood a solution of hæmatoxylin would be used, and
in the examination of red wood a solution of pure brasilin, as the
standard. In this case a saturated solution of the colouring matter
would be taken as the standard. If the intensity of its colour were
represented by 100, the colour intensity of the wood under examination
would always be less than 100, and would, with tolerable accuracy,
represent the percentage of colouring matter in the wood. The result
would not be quite accurate, because the dye-wood contains other
substances which dissolve in water on boiling and affect the colour of
the decoction, but the results are of such accuracy that for practical
purposes no material mistake will be made by taking them as percentages
of colouring matter.
Although at first sight the estimation of the colouring matter in a
dye-wood by means of the colorimeter appears somewhat complicated,
yet it yields the most accurate results with the smallest expenditure
of labour and time. The value of a colouring material may also be
estimated by preparing the pure colouring matter from a weighed
quantity. This process is lengthy, demands considerable practice, and
only gives good results when it is carried out with the most painful
accuracy. The colouring matters in question are precipitated by lead
salts. If the dye-wood extract contained colouring matter alone its
amount could be found by observing the volume of a lead solution of
known strength required to precipitate the colouring matter completely.
The decoctions, however, contain other substances which form lead
compounds, and are precipitated together with the colouring matter, so
that if the precipitate were regarded as the pure lead compound of the
colouring matter a very inaccurate result would be obtained. In order
to obtain results with some pretensions to accuracy the lead compound
of the colouring matter must be purified. The impure precipitate is
washed and suspended in water, through which sulphuretted hydrogen is
passed until all the lead is precipitated as lead sulphide, which is
filtered off, excess of sulphuretted hydrogen expelled by boiling,
and the solution again precipitated by a lead salt. This precipitate
may be regarded without considerable error as the lead compound of
the colouring matter. The weight of colouring matter contained in the
quantity of wood used can be calculated from the weight of the dry
precipitate. This method is somewhat complicated and tedious; the
results are inferior in accuracy to those obtained by means of the
colorimeter, which instrument furnishes the most suitable method for
testing dye-woods for practical purposes.
A thorough knowledge of chemistry is indispensable to the colour
manufacturer who wishes to carry on his business on any extensive
scale. It enables him to match any sample of colour submitted to him
and to test his raw materials with ease. We have indeed given in a
section of this book simple methods by which the majority of commercial
pigments can be tested with tolerable accuracy by means of a few
reagents, and for ordinary purposes these methods are sufficient. But
when an accurate examination of a pigment is required, it must be
conducted by the ordinary processes of analytical chemistry. The colour
manufacturer has not only to carry out these occasional examinations,
but has frequently to test certain raw materials which he uses in
large quantities. Soda may be taken as an example. An estimation of
the percentage of sodium carbonate in this substance is an exceedingly
simple matter to the chemist, but can hardly be carried out without a
knowledge of chemistry.
A manufacturer without chemical knowledge, who is carrying on an
industry which, like the manufacture of colours, rests entirely upon a
chemical foundation, will constantly be compelled to seek advice from
a scientific chemist. Many pigments can be made according to a settled
formula, but the results of working strictly according to the formula,
without a knowledge of the reasons for the operations, can only be
satisfactory whilst no irregularity occurs. The least irregularity
places those who work blindly in a completely helpless position, for
they do not know what is wrong and cannot remove the hindrance.
In the manufacture of pigments certain by-products are produced. These
can be utilised by a manufacturer possessed of chemical knowledge,
whilst they are simply thrown away by many, thus making the manufacture
of the particular pigment far more expensive than when the by-product
is also made valuable. Strictly speaking, there are no worthless
by-products in making pigments, every liquid obtained in precipitating
a colour might be further utilised. Salt solutions can only be
regarded as worthless by-products when the cost of separating the salt
from the solution would be greater than the value of the product. Thus
we cannot conclude this section of the work without again insisting
that the study of chemistry is indispensable to the colour maker, since
his industry is chemical from beginning to end. The colour maker who
works simply by recipes will never raise himself above the position of
an ordinary workman, who does what he is told without thinking of what
he is doing. The smallest mistake in carrying out the process generally
results in the complete failure of the whole operation and thus causes
the manufacturer material loss.
CHAPTER LXXIII.
THE DESIGN OF A COLOUR WORKS.
In the establishment of a colour works several conditions are
necessary. The most important is the supply of water in sufficient
quantity and purity. It has already been stated that many pigments
cannot be made with water containing much organic matter or salts,
since the dissolved substances affect the shade. This action not only
takes place in the formation of the colour, but is also unpleasantly
manifest when it is washed. The delicate lakes are discoloured by
organic matter in the water, and are so changed by any considerable
quantity of lime that the alteration in shade is clearly perceptible
after continued treatment. If the water contains but a very small
quantity of iron, the preparation of some pigments is made quite
impossible, since—and this is especially the case with the lakes—the
ferric oxide is precipitated together with the pigment, and in
consequence of its characteristic colour imparts to it an ugly shade.
Thus in choosing a site for a colour works the available water supply
must be carefully examined. If it is not sufficiently pure or in
sufficient quantity, the position must be regarded as unsuitable.
No colour maker, although working on the largest scale, is in a
position to make all the materials he requires. With the continual
development of the chemical industries, the number of these substances
which can be made economically in the colour works continually
diminishes. It is far more advantageous to obtain them from works
in which they are made on the large scale. Many of these substances
are required in large quantity, so that a site should be chosen in
direct communication with the railway, so that the cost of carriage
is diminished, and also the cost of distributing the manufactured
materials. This is especially necessary for materials which have a low
value and consequently can bear no high cost of carriage.
In regard to the space required by a colour works, no actual dimensions
can be given, since these vary with the extent of the business, and
with the pigments produced. In the price lists of large colour works
all the commercial pigments are generally quoted, but they are rarely
if ever actually made in one works, but are obtained at a lower price
from other establishments, which make a speciality of certain pigments,
and by working on a large scale can produce them at such a cost that
the smaller manufacturer is not in a position to compete with them.
Thus there are works in which only white lead or ultramarine is made.
If a colour manufacturer is in the fortunate position of placing his
works on a river, he has not only an unrestricted water supply, but may
also be able to use water power, the cheapest of all powers. When water
power is available, it will be used to raise the large volumes of water
required and to move the machinery for grinding the raw materials,
rasping dye-woods, etc. In a colour works of any size a boiler is
required; if water power is not used, it must be of sufficient power to
give steam for driving the engine, for boiling liquids and for heating
the drying stoves. The boiler is of great advantage in providing steam
for dissolving salts, extracting dye-woods and boiling liquids. When
liquids are boiled by steam there is considerable economy in that the
majority of the boiling tubs can be of wood, which is provided with
a protective coating for liquids which attack wood. Thus there is
economy in dispensing with large metal pans and with the fireplaces
in which they would be built, and also in the course of time there is
considerable saving in fuel.
For a well-equipped colour works a drying stove, in which the pigments
can be thoroughly dried, is important. It is most convenient to heat
drying stoves with steam. The temperature can be easily regulated by
increasing or diminishing the supply of steam. For drying pigments
which would not be injured by considerable increase of temperature, the
drying stove may be heated by a fire.
In a colour works in which many pigments are made sulphuretted hydrogen
is frequently required. Since all lead pigments are blackened by this
gas, the greatest care is required in using it. Also the poisonous
nature of sulphuretted hydrogen is generally under-estimated. In
working with sulphuretted hydrogen, the apparatus depicted in Fig. 3
should be used. It should be placed in a position, such as a closed
yard, in which escaping gas will be harmless. If this cannot be done
the precipitation should be accomplished in closed vessels, from which
a pipe should carry the gas to a fire, where it will be burnt to
sulphur dioxide and water.
In most cases the manufacturer of colours makes but a certain number
of pigments and rarely or never all which are mentioned in his price
lists. The dimensions of the establishment will be in accordance. In
commencing a new colour works it is advisable from purely financial
reasons to produce at first a limited number of colours, but these
in perfection. By many experiments and diligent study of chemistry a
colour manufacturer may hope to compete successfully in so difficult a
branch of chemical technology as the manufacture of colours.
CHAPTER LXXIV.
COMMERCIAL NAMES OF PIGMENTS.
In commerce the pigments are found under the most different names, the
most common of which have been given together with the description
of the pigment. No regularity can be found in the names chosen for
the different pigments; quite arbitrary designations have been taken.
Pigments are most commonly named after places—for example, Prussian
blue, Paris blue, Bremen green; also after the discoverer—Turnbull’s
blue, Hatchett brown. Whilst these names give the place of production
or the name of the discoverer, and thus have some foundation, there are
many others for which no reason can be assigned, _e.g._, King’s yellow.
Certain names are based upon the chemical composition of the pigment.
These should be used by preference, but now that the expressions white
lead, chrome yellow and Chinese blue have become common no one would
think of speaking of basic lead carbonate, lead chromate or ferric
ferrocyanide. The confusion in the nomenclature of colours is increased
by placing pigments which possess English names upon the market under
French, German or Latin names, which are often sadly mutilated. This is
more the case in Germany than in England.
It may easily happen that a reader of a work on colour making might
search in vain for a pigment whose name he had somewhere heard, whilst
the book contained a description of the colour and its properties,
but under another name. To remove this difficulty it has been thought
necessary to collect the names of the different pigments, which are
contained in the following table. The French and German names are also
given. The most usual names are printed in italics.
WHITE PIGMENTS.
=Basic Lead Carbonate.=—_White lead, flake white._
_Céruse_, _blanc de plomb_, blanc d’argent,
blanc de neige, fleur de neige, blanc de Venise.
_Bleiweiss, Schieferweiss_, Schneeweiss, Silberweiss,
Kremserweiss, Kremnitzerweiss, Berlinerweiss,
Venetianerweiss, Hollanderweiss, Hamburgerweiss.
=Lead Oxychloride.=—_Pattison’s white lead_.
Blanc de Pattison, blanc d’Angleterre.
_Bleiweiss_, Pattisonweiss, englisches Patentweiss.
=Lead Sulphate.=—Lead bottoms.
Céruse de Mulhouse.
_Bleiweiss_, Vitriolweiss.
=Barium Sulphate.=—_Enamel white_, permanent white, blanc fixe,
baryta white.
_Blanc fixe_, blanc permanent.
_Permanentweiss_, _Barytweiss_, Schneeweiss, Mineralweiss,
Neuweiss.
=Zinc Oxide.=—_Zinc white_, permanent white, flowers of zinc.
_Blanc de zinc_, oxyde de zinc, fleur de zinc.
_Zinkweiss_, Zinkblumen, weisses Nichts, Ewigweiss.
=Basic Bismuth Nitrate.=—_Pearl white_, bismuth white,
Spanish white.
_Blanc d’Espagne_, blanc de bismuth, blanc de fard.
_Wismuthweiss_, _Spanischweiss_, Perlweiss, Schminkweiss.
YELLOW PIGMENTS.
=Lead Chromate.=—_Chrome, Chrome yellow._
_Jaune de chrome_, jaune d’or.
_Chromgelb, Königsgelb, Citronengelb_, Neugelb, Parisergelb,
Leipzigergelb, Kölnergelb, Zwickauergelb, amerikanisches Gelb.
=Lead Oxide.=—_Litharge, massicot_.
_Bleiglätte_, Glätte, Massicot.
=Lead Oxychloride.=—Patent yellow.
_Jaune minéral,_jaune breveté_, jaune de Montpellier.
_Casselergelb, Veronesergelb,
_Mineralgelb_, Patentgelb, Englischgelb, Parisergelb,
Montpelliergelb.
=Lead Antimoniate.=—_Naples yellow._
_Jaune de Naples_, jaune d’antimoine.
_Neapelgelb_, _Antimongelb_.
_Giallolino_, Giallo di Napoli.
=Barium Chromate.=—_Lemon yellow_, baryta yellow, yellow
ultramarine, permanent yellow.
_Barytgelb_, _gelbes Ultramarin_, Chromgelb.
=Zinc Chromate.=—_Zinc yellow_, zinc chrome.
_Jaune de zinc_, jaune permanent, jaune bouton d’or,
jaune de chrome inaltérable, jaune d’outremer.
Zinkgelb, Chromgelb.
=Cadmium Sulphide.=—_Cadmium yellow_, aurora yellow.
Jaune brillant.
_Cadmiumgelb._
=Basic Mercuric Sulphate.=—_Turpeth mineral_, mercury yellow.
Jaune de mercure.
_Mercurgelb, Königsgelb_, mineralischer Turpeth.
=Cobalt Potassium Nitrite.=—_Aureolin_, cobalt yellow.
_Jaune indien._
Kobaltgelb.
=Arsenic Disulphide and Trisulphide.=—_Realgar_, orpiment,
_King’s yellow_.
Orpiment, jaune royal.
_Realgar, Auripigment_, Rauschgelb, Rauschroth, Königsgelb,
Chinagelb, Persischgelb, Spanischgelb.
=Stannic Sulphide.=—Mosaic gold.
_Musivgold._
YELLOW LAKES.
_Dutch pink_, French yellow, _stil de grain_, jaune d’Avignon,
jaune français, _Schüttgelb_.
_Yellow lake_, jaune de gauche, _Waulack_.
_Indian yellow_, jaune indien, _Purre_, _Indischgelb_.
_Gamboge_, gomme-goutti, _Gummigutt_, _Gummigutti_.
RED PIGMENTS.
=Basic Lead Chromate.=—_Chrome red, orange chrome, Persian red_,
Derby red, Chinese red.
Jaune d’or, _jaune orange_, pâte orange. _Chromroth_,
_Chromorange_.
=Mercuric Sulphide.=—_Vermilion_, cinnabar.
_Vermillion_, cinabre.
_Zinnober_, Vermillon, Chinesischroth, Patentroth.
=Mercuric Iodide.=—_Scarlet._
Ecarlate.
_Jodinroth_, Scharlachroth.
=Ferric Oxide.=—_Rouge, colcothar, Indian red, Venetian red_,
crocus, caput mortuum, Mars red.
Rouge des Indes, rouge de Mars, rouge d’Angleterre.
_Englischroth_, Engelroth, Berlinerroth, Königsroth,
Kaiserroth, Neapelroth, _Indischroth_, Persischroth,
Eisensafran, Todtenkopfroth, _Marsroth_.
=Cobalt Phosphate or Arsenate.=
Chaux métallique.
Kobaltrosa.
RED LAKES.
=Cochineal Lakes.=—_Carmine_, _crimson lake_.
Laque carminée.
_Carmin_, Cochenilleroth, Münchenerlack, Wienerlack,
Florentinerlack, Pariserlack.
=Lac Dye.=
_Lack-lack, Lack-dye_.
=Madder Lakes.=—_Rose madder_, purple madder, madder carmine.
Laque de garance.
_Krapplack_, Wienerlack, _Krappcarmin_, Garancincarmin.
=Red Wood Lakes.=—Rose pink, Florentine lake.
Laque en boules, laque de Vienne, laque de Venise,
laque de Florence.
Kugellack, Münchenerlack, _Wienerlack, Berlinerlack,
Florentinerlack_, Venezianerlack, Neulack.
=Carthamine.=—Safflower, Spanish red.
_Rouge de carthame_, rouge de Chine, rouge d’or,
rouge en écailles, rouge végétal, rouge de Portugal.
_Safflorcarmine_, Safflorroth, Tassenroth, _Tellerroth_,
Vegetalroth.
BLUE PIGMENTS.
=Ferric Ferrocyanide.=—_Prussian blue_, _Chinese blue_, Paris blue,
Berlin blue, _Brunswick blue_.
_Bleu de Prusse_, bleu de Paris, _bleu de Berlin_, bleu
d’Anvers.
_Pariserblau_, _Berlinerblau_, Preussischblau, Sächsischblau,
Neublau, Oelblau, Wasserblau, Mineralblau, Erlangerblau,
Zwickauerblau, Waschblau, Louisenblau, Raymondblau.
=Ferrous Ferricyanide.=—Turnbull’s blue.
Bleu de Turnbull.
Turnbull’s Blau.
(The names given under ferric ferrocyanide are also used.)
=Ultramarine.=—Lime blue, Royal blue.
_Outremer_, bleu d’azur.
_Ultramarin_, Azurblau, Lazurblau, Lapis lazuli-Blau.
=Copper Hydroxide or Carbonate= (singly or together).
—_Blue verditer_, lime blue, mountain blue.
_Bleu de montagne, bleu de chaux, bleu de cuivre_,
cendres bleues, bleu de Payen.
_Bergblau_, _Mineralblau_, _Oelblau_, _Kalkblau, Neubergblau,
Kupferblau_, Bremerblau, Steinblau, Hamburgerblau,
Neuwiederblau, Casselerblau.
=Cobalt Oxide Alumina Compound.=—_Cobalt blue_,
Thénard’s blue.
_Bleu de Thénard_, bleu de cobalt.
_Kobaltblau_, Thénard’sches Blau, Kobalt-ultramarin,
Königsblau, Leydenerblau, Leithnerblau, Wienerblau, Cæruleum.
=Cobalt Potassium Silicate.=—_Smalts._
Bleu de smalt, bleu d’azur, _bleu de Saxe_.
_Smalte_, _Schmalte_, Blaufarbenglas, Sächsischblau,
_Streublau_, Königsblau, Kaiserblau, Azurblau, _Eschel_.
BLUE ORGANIC PIGMENTS.
=Indigo Sulphonates.=—_Indigo carmine_, soluble indigo.
_Bleu de Saxe._
_Indigocarmin_, Carminblau, präcipitirter Indigo,
_Carminblau_.
=Indigo Lake.=—Bleu d’Angleterre, bleu de Hollande.
Neublau, Waschblau, Holländerblau, Englischblau,
Tafelindigo.
GREEN PIGMENTS.
=Copper Carbonate.=—_Mountain green_, Hungarian green, lime green.
_Vert de montagne_, vert minéral, vert de cuivre,
vert de Hongrie.
_Berggrün_, Kupfergrün, ungarisches Grün, Tirolergrün,
Malachitgrün, Mineralgrün, Schiefergrün, Glanzgrün, Staubgrün,
Wiesengrün, Apollogrün, Wassergrün, Oelgrün, Alexandergrün.
=Copper Arsenite.=—_Scheele’s green, verditer_, lime green,
_mineral green_.
_Vert de Suède_, vert de Scheele.
Scheel’sches Grün, _Schwedisches Grün_, Mineralgrün,
Braunschweigergrün, Neuwiedergrün, Erdgrün, Aschengrün.
=Copper Aceto-Arsenite.=—_Emerald green._
_Vert de Vienne_, vert de Mitis, vert breveté.
_Schweinfurter Grün, Mitisgrün, Wiesengrün, Englischgrün,
Patentgrün_, Hörmann’s Grün, Papageigrün, Kaisergrün,
Königsgrün, Wienergrün, Kirchbergergrün, Leipzigergrün,
Zwickauergrün, Baslergrün, Parisergrün, Neuwiedergrün,
Würzburgergrün, Originalgrün, Jasnügergrün.
=Copper Stannate.=
_Gentele’s Grün_, Zinngrün.
=Copper Oxychloride.=—
Kuhlmann’s Grün, Elsner’s Grün, giftfreies Grün.
=Copper Borate.=
Borgrün, Kupfergrün, giftfreies Kupfergrün.
=Copper Acetate.=—_Verdigris_, distilled or crystallised verdigris.
_Vert de gris_, vert de gris naturel, vert de gris distillé,
vert de gris en grappes.
_Grünspan_, destillirter, französischer, deutscher,
präcipitirter or krystallisirter Grünspan.
=Chromium Oxide and Hydroxide.=—_Guignet’s green_, chrome green,
lime green, _viridian_.
_Vert de chrome_, vert Pannetier, vert Guignet,
vert de soie, vert émeraude, vert naturel, vert virginal.
_Chromgrün_, grüner Zinnober, Laubgrün, Smaragdgrün,
Deckgrün, Myrthengrün, Permanentgrün, Amerikanergrün,
Neapelgrün, Gothaergrün, Guignet’s Grün, Mittler’s Grün,
Pannetier’s Grün, Chromgrün in Lack, Tükisgrün,
Seidengrün, Naturgrün.
[The green produced by mixing chrome yellow with
Prussian blue is known in England as chrome green,
Brunswick green, oil green, etc., and on the continent
by the names given above for chromium oxide.]
=Chromium Phosphate.=—Arnaudan’s green.
Vert Arnaudan, vert de Plessy.
Arnaudan’s, Plessy’s, Schnitzer’s Grün.
=Cobalt Oxide-Zinc Oxide.=—_Cobalt green_, Rinmann’s green.
_Vert de Rinmann_, vert de cobalt.
_Kobaltgrün_, Rinmann’s Grün, Zinkgrün, permanenter
grüner Zinnober.
=Barium Manganate.=—Rosenstiehl’s green.
Vert tiges de roses.
Mangangrün, _Rosenstiehl’s Grün_, Böttger’s Grün.
VIOLET PIGMENTS.
=Chromic Chloride.=
Chrombronze, Permanentbronze, Tapetenbronze.
=Manganese Phosphate.=—Nuremberg violet.
Manganviolett, Nürnberger Violett.
BROWN PIGMENTS.
=Lead Peroxide.=
Bleibraun, Flohbraun.
=Manganic Oxide and Peroxide.=—Manganese brown.
Brun de Mangane, bistre minéral.
_Manganbraun_, Bisterbraun, _Mineralbister_, Kastanienbraun,
_Braunsteinbraun_.
=Copper Potassium Ferrocyanide.=—Hatchett brown.
Brun de Prusse.
Hatchett’s Braun, Kupferbraun, Chemischbraun, Breslauerbraun.
=Ferric Oxide.=—Brown ochre, Mars brown.
Eisenbraun, Van Dyck Braun, Ockerbraun, Sienabraun.
Prussian brown is Prussian blue decomposed by heat
(see page 280).
Chrome brown and cobalt brown (see pages 280, 281).
BLACK PIGMENTS.
=Carbon.=—_Ivory black_, bone black, Frankfort black, vine black,
_vegetable black, drop black_, carbon black, lamp black_.
Noir d’ivoire, noir de Frankfort, noir de Cologne,
noir d’Allemagne.
Kienruss, Flatterruss, Russschwarz, Rebenschwarz,
Hefeschwarz, Beinschwarz, Spodium, Elfenbeinschwarz,
Frankfurterschwarz, Pariserschwarz, Wienerschwarz,
Lampenschwarz, Oelschwarz, Spanischschwarz, Drusenschwarz.
=Carbon mixed with Other Substances.=
Neutral tint, composition black, neutral black.
Teint neutre, noir de composition.
Compositionsschwarz, Neutraltinte, Naturaltinte.
Indian ink.
Encre de Chine.
Tusche.
APPENDIX.
THE CONVERSION OF METRIC INTO ENGLISH WEIGHTS AND MEASURES.
The conversion of metric into English weights and measures can be
readily accomplished by means of the following relationships:—
MEASURES OF LENGTH.
1 metre = 100 centimetres = 39·37 inches.
1 foot = O·3381 metre.
MEASURES OF CAPACITY.
1 litre = 1,000 cubic centimetres = ·2209 gall.
1 gall. = 4·5436 litres.
MEASURES OF WEIGHT.
1 kilogramme = 1,000 grammes = 2·205 lb.
1 gramme = 15·443 grains.
1 cwt. = 50·802 kilogrammes.
CENTIGRADE AND FAHRENHEIT THERMOMETER SCALES.
To convert temperatures expressed in Centigrade degrees to Fahrenheit
degrees multiply by 9, divide by 5, and add 32.
To convert temperatures expressed in Fahrenheit degrees to Centigrade
degrees subtract 32, multiply by 5, and divide by 9.
INDEX.
Acid, acetic, 30.
— carbonic, 30.
— hydrochloric, 25.
— nitric, 28.
— oxalic, 31.
— sulphuric, 27.
— tartaric, 31.
Acids, 25.
Alizarin, 372.
Alkalis, 32.
Alkanet, 368.
Alum, ammonia, 48.
— Roman, 46.
— soda, 47.
Alumina, 49.
— gold purple, 193.
Aluminium compounds, 42.
— sulphate, 43.
Alums, 44.
Ammonia, 23.
— cochineal, 362.
Ammonium chloride, 25.
— sulphide, 25.
Annaline, 131.
Antimony blue, 179.
— compounds, 59.
— oxychloride, 129.
— trioxide, 129.
— vermilion, 178.
— yellow, 151.
Antwerp blue, 203.
Apparatus, washing, 120.
Appendix, 469.
Aqua regia, 29.
Archil, 381.
Arsenic compounds, 59.
Asphaltum, 414.
Aureolin, 156.
Barium carbonate, 42.
— chloride, 41.
— compounds, 41.
— green, Böttger’s, 271.
— sulphate, 116.
— yellow, 152.
Barytes, 116.
Bismuth compounds, 59.
— white, 130.
Bistre, 284.
Black, bone, 290.
— charcoal, 286.
— chrome, 318.
— chrome-copper, 318.
— enamel, 325.
— ivory, 290.
— lamp, 307.
— neutral tint, 318.
— pigments, 285, 444.
— pine, 312.
— soot, 294, 313.
— vine, 288.
Blowpipe, 436.
Blue, antimony, 179.
— Antwerp, 203.
— Bremen, 226.
— Brunswick, 200.
— Chinese, 196, 201.
— chrome, 267.
— cobalt, 230.
— copper pigments, 226.
— Egyptian, 250.
— enamels, 323.
— lakes, 390, 397.
— lime, 228.
— manganese, 272.
— mineral, 200.
— mineral pigments, 194.
— molybdenum, 239.
— Neuberg, 227.
— oil, 228.
— Payen’s, 228.
— pigments, examination of, 441.
— Prussian, 199.
— Soluble Prussian, 200.
— Tessié du Motay’s, 293.
— tungsten, 238.
— Turnbull’s, 203.
— ultramarine, 204.
— — pale, 223.
— verdigris, 252.
Bone black, 290.
Böttger’s barium green, 271.
Brasileïn, 384.
Brasilin, 384.
Brazil wood, 384.
Bremen blue, 226.
— green, 226.
Brocade pigments, 341.
Bronze, electrolytic copper, 337.
— pigments, 329.
— pigments, tungsten, 338.
Brown, chrome, 280.
— cobalt, 281.
— copper, 280.
— decomposition products, 283.
— Hachett’s, 280.
— iron, 280.
— lead, 279.
— manganese, 279.
— mineral pigments, 279.
— organic pigments, 414.
— pigments, examination of, 443.
— Prussian, 280.
— pyrolusite, 279.
Brunswick green, 243.
Cadmium compounds, 53.
— yellow, 153.
Cæruleum, 231.
Calcium carbonate, 40.
— compounds, 39.
— hydroxide, 39.
— oxide, 39.
— phosphate, 40.
— sulphate, 40.
Carajuru, 379.
Carbon, 30.
Carmine, 354, 357.
— indigo, 394.
— madder, 376.
— safflower, 367.
Carthamine red, 366.
Casselmann’s green, 249.
Cassel yellow, 148.
Cassius, purple of, 190.
Caustic potash, 33.
Caustic soda, 37.
Charcoal blacks, 286.
Charvin’s green, 412.
Chica red, 379.
Chinese blue, 196, 201.
— green, 411.
— vermilion, 170.
Chlorine, 20.
Chlorophyll, 409.
Chromaventurine, 266.
Chrome alum, 35.
— black, 318.
— blue, 267.
— brown, 280.
— copper black, 318.
— green, 260, 274.
— — Elsner’s, 274.
— — lake, 264.
— red, 186.
— yellow, 134.
— — cadmium, 153.
— — calcium, 151.
— — pale, 139.
— — zinc, 152.
Chromic chloride, 276.
Chromium compounds, 58.
— oxide, 260.
— stannate, 189.
Chrysean, 162.
Cobalt arsenate, 189.
— blue, 230.
— brown, 280.
— compounds, 56.
— green, 268.
— magnesia red, 188.
— red, 188.
— ultramarine, 230.
— zinc phosphate, 232.
Cochineal, 354.
Colorimeter, 450.
Colours, simple and mixed, 71.
Colour works, design of, 457.
Commercial names of pigments, 460.
Confectionery colours, 427.
Copper acetate, 65.
— arsenite, 241.
— borate, 250.
— brown, 280.
— carbonate, 240.
— compounds, 65.
— hydroxide, 229.
— nitrate, 65.
— oxychloride, 243.
— silicate, 250.
— stannate, 248.
— sulphate, 65.
— violet, 278.
Covering power, 10.
Crayons, 423.
Cream of tartar, 34.
Cudbear, 382.
Curucuru, 379.
Design of a colour works, 457.
Dextrine, 420.
Drying oils, 429.
— stove, 459.
Dutch pink, 348.
Dye-woods, 449.
Egyptian blue, 250.
Elsner’s chrome green, 274.
— green, 249.
Emerald green, 244, 264.
Enamel colours, 319.
Enamel white, 116.
Enamels, black, 325.
— blue, 323.
— green, 324.
— red, 322.
— violet, 324.
— white, 320.
— yellow, 322.
Examination of pigments, 434.
Extracts, 398, 402.
Fernambuco wood, 384, 386.
Ferric oxide pigments, 180.
Ferrous chloride, 54.
— sulphate, 54.
Filter press, 124, 125.
Florentine lake, 361.
French purple, 38.
Fustic lake, 351.
Gamboge lake, 349.
— prepared, 350.
Garanceux, 372.
Garancin, 371.
Gardinia grandiflora, colouring matter of, 353.
Glucose, 422.
Gold, compounds of, 69.
Green, Arnaudan’s, 265.
— Bremen, 226.
— Brunswick, 243.
— Casselmann’s, 249.
— Charvin’s, 412.
— Chinese, 411.
— chrome, 260, 274.
— cobalt, 268.
— Elsner’s, 249.
— emerald, 244, 264.
— enamel, 324.
— Guignet’s, 264.
— Kuhlmann’s, 249.
— lakes, 409.
— leaf, 265.
— lime, 250.
— manganese, 270.
— mineral pigments, 240.
— natural, 275.
— Neuwied, 243.
— non-arsenical, 275.
— patent, 250.
— pigments, compounded, 273.
— pigments, examination of, 442.
— Plessy’s, 266.
— Rosenstiehl’s, 270.
— sap, 410.
— Scheele’s, 241.
— Schnitzer’s, 266.
— silk, 275.
— Turkish, 265.
— verditer, 243.
— Vienna, 248.
Guignet’s green, 264.
Gum Arabic, 420.
Guyard’s violet, 278.
Gypsum, 40.
Hachett’s brown, 280.
Hæmateïn, 406.
Hæmatoxylin, 406.
Humins, 283.
Hydrometer, 24.
Indian ink, 316.
— madder, 378.
— red, 185.
— yellow, 352.
Indigo, 390.
— carmine, 394.
Introduction, 1.
Iron brown, 280.
— compounds, 54.
— red, 182.
Ivory black, 290.
Kuhlmann’s green, 294.
Lac, 363.
— dye, 363.
Lake, blue, 390, 397.
— Florentine, 361.
— fustic, 351.
— gamboge, 349.
— green, 409.
— quercitron, 351.
— weld, 349.
Lakes, 6, 9, 343.
— examination of, 445.
— madder, 375.
— red, 354.
— yellow, 348.
Lamp black, 307.
Lead acetate, 62.
— antimonate, 115.
— antimonite, 115.
— arsenite, 159.
— brown, 279.
— chloride, 64.
— chromate, 134.
— compounds, 60.
— iodide, 154.
— monoxide, 143.
— nitrate, 61.
— orange, 146.
— oxychloride, 113.
— red, 144.
— sulphate, 61, 112.
— sulphite, 114.
— tungstate, 128.
— white, 73, 74, 75, 77.
— white, hard and soft, 191.
Leaf green, 265.
Lichens, 380.
Lime, 39.
— blue, 228.
— green, 250.
Litharge, 143.
Lithophone, 119.
Litmus, 382.
Logwood, 398.
Lokao, 44.
Madder, 370.
— carmine, 376.
— extract, 372.
— Indian, 378.
— lakes, 375.
Magnesia, gold purple, 192.
— white, 130.
Magnesium carbonate, 41.
Manganese blue, 272.
— brown, 279.
— compounds, 59.
— green, 270.
— sulphate, 56.
— violet, 278.
— white, 130.
Manganous oxide, 272.
Mangit, 378.
Mars yellow, 155.
Massicot, 143.
Mercuric ammonium chloride, 175.
— chloride, 68.
— iodide, 176.
— nitrate, 68.
— sulphite, 163.
Mercurous chloride, 68.
— nitrate, 67.
Mercury compounds, 67.
— yellow, 158.
Metallic pigments, 326.
Metals, heavy, 51.
Mills, paint, 430.
— white lead, 86.
Mineral lake, 278.
Molybdenum blue, 239.
— compounds, 59.
Montpellier yellow, 148.
Mosaic gold, 160.
Naples yellow, 149.
Natural green, 275.
Neuberg blue, 227.
Neutral tint black, 318.
Neuwied green, 243.
Nickel compounds, 56.
— yellow, 157.
Non-arsenical green, 275.
Oil blue, 228.
Orange lead, 146.
— Mars, 155.
Orceïn, 300.
Orcinol, 380.
Orpiment, 159.
Paint mills, 430.
Patent green, 250.
Payen’s mountain blue, 228.
Permanent yellow, 152.
Pigments, artificial mineral, 6.
— commercial names of, 460.
— earth, 6.
Pine black, 312.
Pink, Dutch, 348.
Plessy’s green, 266.
Poisonous pigments, 13.
Potassium alum, 45.
— bichromate, 35.
— bitartrate, 34.
— carbonate, 32.
— compounds, 32.
— ferricyanide, 35.
— ferrocyanide, 35.
— hydroxide, 33.
— nitrate, 34.
— sodium chromate, 35.
Precipitation, 7.
Preparation of pigments, 429.
Prepared gamboge, 350.
Prussian blue, 199.
— brown, 280.
Purple, alumina gold, 193.
— French, 381.
— magnesia gold, 192.
— of Cassius, 190.
— red, 189.
Purpurin, 373.
Purree, 352.
Pyrolusite brown, 280.
Quercitron lake, 351.
Quicklime, 39.
Realgar, 159.
Red, carthamine, 366.
— chica, 379.
— chrome, 186.
— cobalt, 188.
— — magnesia, 188.
— enamels, 322.
— hæmatite, 180.
— Indian, 185.
— iron, 182.
— lakes, 354.
— lead, 144.
— Mars, 155.
— mineral pigments, 163.
— pigments, examination of, 440.
— purple, 189.
Red wood lakes, 384.
Rosenstiehl’s green, 270.
Safflower, 366.
— carmine, 367.
Saffron, 352.
Sal ammoniac, 25.
Salt, common, 38.
Sandalwood, 388.
Sap colours, 416.
— green, 410.
Scheele’s green, 241.
Schnitzer’s green, 266.
Sepia, 414.
Shell-gold, 326.
Shell-silver, 327.
Siderin yellow, 156.
Silk green, 275.
Silver chromate, 189.
— compounds, 69.
— imitation, 328.
Smalts, 233.
Sodium chloride, 38.
— hydroxide, 37.
— salts, 37.
— thiosulphate, 38.
Soluble Prussian blue, 200.
Soot black, 313.
— pigments, 294.
Stannic chloride, 59.
Stannous chloride, 59.
Stove, drying, 459.
Sulphuretted hydrogen, 26.
Swedish green, 241.
Tessié du Motay’s blue, 239.
Thallium pigments, 159.
Thénard’s blue, 230.
Tin compounds, 59.
— violet, 278.
— white, 130.
Tragacanth, 420.
Tungsten blue, 238.
— bronze pigments, 338.
— compounds, 59.
— yellow, 157.
Turkish green, 265.
Turnbull’s blue, 203.
Turner’s yellow, 149.
Turpeth mineral, 158.
Ultramarine, 3, 204, 211.
— artificial, 206.
— cobalt, 230.
— natural, 205.
— violet, 219.
— yellow, 152.
Vanadium compounds, 59.
Vegetable bronze pigments, 339.
Verdigris, 252.
— blue, 252.
— distilled, 255.
— German, 258.
Verditer, green, 243.
Vermilion, 3, 163, 166.
— antimony, 178.
— Chinese, 170.
— chrome, 186.
Vienna green, 248.
Vine black, 288.
Violet copper, 278.
— enamel, 324.
— Guyard’s, 278.
— manganese, 278.
— mineral pigments, 276.
— Nuremberg, 278.
— tin, 278.
— ultramarine, 219.
Vitriol, blue, 65.
— green, 54.
— oil of, 27.
Washing apparatus, 120.
Water, 16.
— colours, 419.
— — moist, 422.
— examination of, 20.
— hard, 17.
— iron in, 18.
— organic matter in, 18.
Weld lake, 349.
White, bismuth, 130.
— enamel, 116, 121, 320.
— lead, 73, 74, 75.
— lead mills, 86.
— magnesia, 131.
— manganese, 130.
— mineral pigments, 72.
— patent, 73.
— permanent, 116, 121.
— pigments, examination of, 437.
— tin, 130.
— tungsten, 128.
— zinc, 126.
Witherite, 42, 117.
Yellow, antimony, 151.
— barium, 152.
— cadmium chrome, 153.
— calcium chrome, 151.
— Cassel, 148.
— chrome, 134.
— enamels, 322.
— English, 149.
— Indian, 352.
— lakes, 348.
— Mars, 155.
— Mercury, 158.
— mineral pigments, 133.
— Montpellier, 148.
— Naples, 149.
— nickel, 157.
— pale chrome, 139.
— pigments, examination of, 439.
— Siderin, 156.
— tungsten, 157.
— Turner’s, 149.
— zinc chrome, 152.
Zinc chrome yellow, 152.
— oxide, 53.
— sulphate, 53.
— sulphide, 119.
— white, 126.
— — Griffith’s, 128.
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