PIGMENTS - A Brief History of Color

compiled by
Pedro de la Montaña

Stone Age
‘The first period of cave painting knows only black and red outlines.

‘The third period uses solid black, red and brown for the surface and employs a pigment to get an effect of relief. Outlines black, body of animals modelled by smearing on it various tints obtained by mixing red and black. Introduction of red variations: tannish red, orange red, sepia. First traces of mixing color with white.
Stone Age graves in Europe indicate that numerous tribes, obviously in awe of amber’s unusual properties, wore pieces of it as amulets to ward off evil spirits.

Charcoal Black... the residue from the dry distillation of woods, is made by heating the wood in closed chambers or kilns. That which is produced from the willow, bass, beech, maple, or such other even textured wood is the best. For pigment purposes, the charcoal is ground and well washed to remove potash. It may be used in stick form for sketching purposes and for the preparation of cartoons. Charcoal is light and porous; in part, it retains the fine structure of the wood from which it was made and, for this reason, it is quite characteristic in appearance when viewed microscopically. It may be seen as small, opaque, elongated, and splintery particles. This form of carbon has been used as a pigment since very earliest times. It is found on the wall paintings at Bamiyan in Afghanistan. Laurie says that the cool grays of Frans Hals are a mixture of white lead and charcoal black.

8000 B.C.
Beads, pendants, and figurines carved from amber have turned up in graves dating from 8000 B.C. in northern Europe - placing amber among the early substances used by man for ornamentation.

Pre-dynastic Malachite (mountain green)
is perhaps the oldest known bright green pigment. ..It occurs in various parts of the world associated with secondary copper ore deposits. It is prepared as a pigment by careful selection, grinding, and sieving, but today it is seldom used, except perhaps to a small extent in the East.
In spite of its ready decomposition, it has remained unchanged in many paintings for centuries, just as it has in the earth. It is unaffected by light.
The history of malachite in painting runs closely parallel to that of azurite. It occurs on Sinai and in the eastern desert of Egypt, and was used there for eye paint as early as pre-dynastic times. It was found side by side with azurite in Chinese painting at Tun Huang and other temple sites, and it has perhaps been used in the East continuously to the present day. This copper green is found in all periods of European painting up to about 1800, but at the time it was nearly supplanted by artificial green pigments. It was used much in trees and foliage. Like azurite, it worked better in tempera than in oil. Thompson remarks that malachite, although widely used in the Middle Ages, is mentioned but little in contemporary literature on painting materials whereas azurite is spoken of repeatedly. This pigment is no doubt the verde azzurro of Cennino Cennini.
The history of malachite in painting runs closely parallel to that of azurite. It occurs on Sinai and in the eastern desert of Egypt, and was used there for eye paint as early as pre-dynastic times. It was found side by side with azurite in Chinese painting at Tun Huang and other temple sites, and it has perhaps been used in the East continuously to the present day. This copper green is found in all periods of European painting up to about 1800, but at the time it was nearly supplanted by artificial green pigments.

Mars Colors (Mars yellow, Mars orange, Mars red, Mars violet).
The Mars colors, so called, are artificial ochres which are made by precipitating (processes.) The (product) results in Mars yellow. When this Mars yellow is heated, various shades of orange, red, brown, and violet result, depending upon the degree and duration of the heat. The product must be thoroughly washed free from soluble salts to be useful as an artist’s pigment. The preparation of artificial iron oxide colors of this nature from iron vitriol was described in the middle XIX century. Although these Mars colors are very homogeneous and fine, they possess no advantage over the natural iron yellows and reds. They are sometimes sold for the natural iron oxides.
Painting Materials -Gettens and Stout pg 129

Massicot (litharge) are names which have long been used for the yellow monoxide of lead.
It is not an intense yellow but it has good hiding power and is similar to white lead in pigment properties. Chemically, it has properties like white lead... It is unaffected by strong light but may revert to white lead on ling exposure to damp air.
Litharge is more orange in color than massicot, caused by the presence of some red lead. It is not used as a pigment but is extensively employed as a drier in paints and varnished; it is important as an intermediate step in the preparation of red lead.
Yellow lead monoxide was known, certainly, as early as metallic lead, which has been found in sites that dates from pre-dynastic times in Egypt. Laurie found it on a scribe’s pallet dating 400 B.C. Davy identified as orange color on a piece of stucco in the ruins near the monument of Caius Cestius as a mixture of massicot and minium. Pliny described the preparation of both litharge and massicot.
Although De Wild list thirty nine Dutch and Flemish paintings of XV to XVII centuries in which he identified massicot, it is probable that the more stable double oxide of lead and tin which is called lead tin yellow was actually employed. In modern times, massicot is not used as a paint pigment.

5300 BC
Although proof of the existence of aluminum as a metal did not exist until the 1800's, clays containing the metallic element were used in Iraq as long ago as 5300 BC to manufacture high quality pottery. Certain other aluminum compounds such as the ‘alums’ were used widely by Egyptians and Babylonians as early as 2000 BC. Despite these early uses of the ‘metal of clays,’ however, it was almost 4,000 years before the metal was freed from its compounds, which made it a commercially usable metal.


5000 BC
‘In Egypt the oldest class of painting is vase painting. It shows white lines on hand burnished red. The combination of a rich red with highly reflecting black is the first satisfying use of a color scheme in Egypt.


3400 BC
‘Dynastic times. Started flat painting on walls with a color scheme of black, red, yellow, green white.

3000 BC
Indigo is documented to have been used at this time.

2000 BC.
Certain aluminum compounds such as the ‘alums’ were used widely by Egyptians and Babylonians as early as 2000 BC. Despite these early uses of the ‘metal of clays,’ however, it was almost 4,000 years before the metal was freed from its compounds, which made it a commercially usable metal.

Inks are paint like fluids and pastes used for writing and printing. The use of colored fluids for drawing characters on parchment, hide, or cloth was common in ancient Egypt and China at least as early as 2000 BC. Ancient writings that are still preserved often used inks based on lampblack (carbon black), a finely ground pigment dispersed in water or oil, and sometimes stabilized with a vegetable gum or glue.

1500 BC
Tyrian purple, used by the Phoenicians in the 15th century BC, was produced from certain varieties of crushed sea snails. Another snail variety, the banded dye-murex, was discovered in the 1980s to be the source of hyacinthine purple, a blue-purple dye known in biblical Hebrew as tekhelet and employed up to 3,600 years ago for dyeing ritual prayer shawls. The use of indigo as long ago as 3000 BC has been documented; synthetic indigo is still an important dye because it is exceptionally fast.


IV Dynasty of Egypt
Egyptian Blue (blue frit, Pompeian blue)
The inorganic blue color most commonly found on wall paintings of Egyptian, Mesopotamia, and Roman times is an artificially made pigment which contains as its essential constituents copper, calcium, and silica. Lucas, who gives a very good summary of the history and occurrence of this blue, says it was made by heating a mixture containing silica, a copper compound, calcium carbonate, and natron.
Chaptal appears to have been the first to call this material a ‘frit’ but, although it does contain some glass as impurity, the blue is definitely a crystalline compound. Laurie and co-workers point out that the Egyptian ceramics; that glaze was applied to a base of carved sandstone at a temperature somewhat lower than that required to form the crystalline blue. There is contemporary mention of this artificial blue which includes descriptions of its method of preparation. It is no doubt the Egyptian caeruleum of Pliny.
Vitruvius describes its manufacture but erroneously states that the method for making it was first discovered in Alexandria.
Egyptian blue which is coarsely crystalline and pure blue in color is similar, in appearance, to finely ground azurite. Unlike azurite, however, it is insoluble in acids, is not affected by light or heat (except at very high temperatures), and by alkalis only on fusion. Many specimens, well over 3000 years old, appear to be little changed by time or environment.
This history of Egyptian blue is largely ancient. Spurrell states that it was found as early as the IV Dynasty in Egypt. Laurie observed it on paintings from the palace at Knossos. Raehlman, Chaptal and others have found it on Pompeian and other Roman wall paintings. It has further been identified as the dark blue material of a mace head from Nuzi, Iraq; as the material of the blue inlay in ivories from Samaria; and as a blue pigment on Roman wall painting from Dura Europos in Syria. Partington has reviewed the history and occurrence of Egyptian blue and he says; ‘No ancient European people could successfully imitate Egyptian blue and the secret of its manufacture was lost between A.D. 200 and 700.’
A modern blue pigment called ‘Pompeian blue,’ which is entirely similar in chemical composition and optical properties to the ancient copper-lime silicate blue but which is purer and finer, is now available form a French source.

‘The fifth Dynasty introduced blue and gray (ca. 2000 b.c.)

‘The twelfth Dynasty introduced violet.

“The eighteenth and nineteenth Dynasty, the last great period, uses as main colors terra cotta red, black, white, dark brown, (Nile) green, blue, yellow. New is the dotting of blue with black, green with yellow and the iridescent shades.

‘In Crete the early Minoan period (3400-2100 b.c.) Shows only red wash.

‘The First Middle Minoan period (2100-1900 b.c.) red, black, white.

‘The Second Middle Minoan period (1900-1700 b.c. red, blue, black, white.
“The Third Minoan period added gray.

‘The late Minoan period (1500-1300 b.c.) Shows rose, gray-blue, red-brown, creamy white, and the use of transparence for women’s garments. Through all Crete periods red and black are predominant.

‘The frescoes in the palace of Menelaus in Tyrrhene 2000-1000 b.c. show the first use of pink.

‘Early Mycenae frescoes show the repetition of the color scheme red, black, later white.

‘On the Greek Mainland down to the 6th century the main colors are black, white, red and yellow.

‘Demokritos described in his two treatises: ‘On color and On Painting’ the work of the 5th century painting as consisting of four colors from which the others were obtained: red, yellow, black, white. Gold is derived by mixing white and red with a touch of yellow, purple is made from red, black and white (3 parts of red, 1 part of black, 2 parts of white); indigo by mixing black and yellow; green from yellow and purple, etc, The old Greeks knew 819 shades mixed of these four basic colors.

‘Greece in the age of the Tyrants (600 b.c.) Used red for bodies, blue for hair. The 5th century started attempts in shading.

‘The 4th century started the struggle with the third dimension.

‘The 3rd and 2nd century knew all about space, color and light, and no landscaping.
‘Roman painting followed the Greek tradition.

‘Pompeian wall painters first used superimposition of color to get a multicolour effect. Over a layer of black they laid a red layer and obtained by this method a rather deep, brownish red, effect.
‘Known colors up to the end of the Roman empire were the earth colors: red ochre, terra verte, umber; Lead colors: white lead, red lead, yellow oxide of lead, copper applied with vinegar; lampblack, burnt ivory and charcoal; blue was carbonate of copper; vegetable and animal dyes: purple, madder (red and yellow) indigo, kermes (scarlet), woad (blue).

‘The only important colors modern times added to the classic color scheme were ultramarine and lapis lazuli.’

Indigo was known and used as a dye in early Egypt. It was mentioned by Pliny, who called it ‘indicum’. It has been identified as one of the pigments used for decorating Roman parade shields of c 200 A.D. found at Dura Europos in Syria, was mentioned as early as the XIII century in European commercial transactions and was used in Italian painting certainly as early as the XV century and probably even much earlier.
A coloring material much like indigo has been observed in the blue layer beneath an azurite film in a Sienese painting. De Wild lists four paintings, three by Frans Hals and all of the XVII century, in which he found indigo.

Classical Times
Madder, Madder Lake (see also Alizarin)
is a natural dyestuff from the root of the herbaceous perennial, Rubia tinctorium, which formerly was cultivated extensively in Europe and in Asia Minor. The color matter, which is chiefly alizarin, is extracted from the ground root by fermentation and hydrolysis with dilute sulphuric acid. The madder plant is native to Greece and was used as a source of dye perhaps as early as classical times. It has been identified as the source of a pink color on a gypsum base from an Egyptian tomb painting of the Graeco Roman period.

77 A.D.
The Roman author Pliny make public his Historia Naturalis, in which amber is scientifically described as a product of the plant world.

Pliny reports that a small carved figure of amber was worth more in the marketplace than a slave.

Chrysocolla was a classical name to indicate various compounds that were useful in the hard soldering of gold. (Greek: gold glue) and among these were certain green copper minerals, Pliny may have meant malachite by it. The name is now used by mineralogist, specifically, for natural copper silicate. In the natural state, its appearance is similar to malachite, except that the color is somewhat more blue. When ground to a fine powder, it retains its green color quite satisfactorily and may serve for a pigment in a water soluble medium. ...The pigment is stable to light and to ordinary environments but is decomposed by acids and is turned black by hear and warm alkalis. This mineral has had little mention as a painting material. Gettens identified it on wall paintings at Kizil in Chinese Turkestan and described some of its properties. It occurs in Egypt and the Sinai peninsula and has been identified by Spurrell as a pigment on certain Twelfth Dynasty tombs at El-Bersha.

500 A.D -1500 A.D. middle ages
Bole is the name frequently given in the arts to clay, either white or colored. White bole is about identical with kaolin. Red bole is a natural, ferruginous aluminum silicate which was originally found in Armenia but now elsewhere in Europe. It is similar to ochre in composition but is softer and more unctous, and because it is capable of receiving a high polish, it has served since early mediaeval times as a ground for gilding. It is obtainable today under various names such as ‘gilders red clay’ ‘red burnish gold size.’

Bone White (bone ash) is made by calcining animal bones... Ash from the bones of different animals varies little in composition. Bone white is a grayish white and slightly gritty powder. In mediaeval times, it was used on paper or parchment to give it tooth or abrasive quality to receive the streak of silver point.

Brazil Wood is a natural red dye. ...that used in the Middle Ages came from Ceylon. It was known and called ‘brazil’ many centuries before the discovery of the country, Brazil.
Brazil wood lakes, which are prepared with different mordants, vary in color from bright cherry to deep red and are sold under a variety of names.... These lakes are insoluble in water and in alcohol but are partially soluble in alkalis, giving them a brownish red color. Mineral acids decompose them with a yellow to orange red solution. They are not stable in string light. Brazil wood dyes are said to have been used in great quantities in mediaeval times in dyeing, in painting, and in inks, perhaps more than madder at an early date, bur were later replaced by more brilliant colors.

700's (Eighth c. Tempo period)
There are many other natural forms of calcium carbonate, some of which are useful in painting. One of them, marble, is a familiar crystalline variety of calcium carbonate or limestone. Marble dust has been mixed with lime for the plaster ground of fresco painting and of line wax painting. Another, oyster shell white, can be made from the shells of almost any mollusk. It was perhaps usual to burn the shells before powdering them. This white was a pigment in Chinese and Japanese painting, and as Thompson says that it appeared also in mediaeval England, chiefly mixed with orpiment. Even calcined egg shells were used as the source of a fine lime white. Coral, the calcareous remains of various marine animals, yields, when ground up, a pale pink powder that the Chinese and Japanese made into paint for certain purposes. Uyemura says it was used as early as the Tempo period (VIII century) in Japan. Lime white, derived from line putty, or water slaked lime, went into Italian fresco painting under the name, bianco sangiovanni. On exposure to air, this was slowly reconverted to calcium carbonate or chalk.

1431
Bistre is a brown water color pigment which is derived from the tarry soot of burned, resinous wood and beechwood. It is similar to asphaltum in color and composition. The color varies from saffron yellow to brown black, depending upon the source and treatment of the raw material. It was sometimes mixed with red ochre to give it a warmer tone. Church says that the ground raw product is washed with hot water before it is mixed with gun and glycerine in the preparation of water color. The tarry nature of bistre (as with asphaltum) makes it an unsuitable pigment, except perhaps in very thin washes. He also says that exposure to strong sunlight oxidizes the tarry materials of wood origin have probably been used for centuries. Meder says that first literary mention of bistre was by Jehan le Begue in 1431; it had been used extensively, however, it Italian book illustrations in the XIV century. It was used by Rembrandt for wash drawings. It is still listed by artists’ supply dealers, but is little used since it is admitted by them not to be permanent.


1500's
Azurite - This natural copper carbonate was no doubt the most important blue pigment in European paintings from the XV to the middle of the XVII century and in paintings of that period it is found more frequently than ultramarine.
De Wild lists nineteen early Dutch and Flemish paintings on which he identified azurite. Europe had various sources of the mineral. There is evidence that Hungary was the principle source in the middle XVII century when Hungary was overrun by the Turks. One of the early names for azurite was azure d’Alemagna, indicating that it came from Germany. It is the azurro della magna of Cennino Cennini, and was known by numerous other names in mediaeval times.

Chalk, black or red has a more emphatic effect and also an indication of color. Chalk drawing first came into wide use in sixteenth century Italy. The many Italian masters who employed black or red chalk or the two in combination include Carpaccio at Venice, Andrea del Sarto at Florence, Correggio at Parma and the Carracci at Bologna. The suggestion of flesh color given by red as a reinforcement of black has attracted portrait painters. The Clouets in sixteenth century France used sanguine with a simplicity that also gave a remarkable lifelike effect, the great collection in the Musee Conde, Chantilly, showing their unique quality. They may be compared with Holbein whose drawings of members of the Tudor court include such variations of the medium as black chalk on a flesh colored ground.
The supreme example of the mediums capacity is given by Watteau in his studies of figures and figure details for his paintings in red or red, black and white on a toned ground. ... A modern example of the depth of light and shade obtainable on a grained paper is provided by the drawings of Seurat.

The textile dyeing industry in Europe originated in the 16th century, when the Portuguese, Dutch, and English introduced indigo.

Madder Lake - Perkins and Everest say: “About the time of the Crusades the cultivation of madder was introduced into Italy and probably also into France. The Moors cultivated it in Spain, and during the sixteenth century it was brought to Holland. Colbert introduced it into Avignon in 1666, Frantzen into Alsace in 1729, but only toward 1760-1790 did it become important. During the wars of the Republic, its cultivation was largely abandoned, and only after 1815 did this again become regular.”

Mummy
A brown, bituminous pigment was once actually prepared from the bones and bodily remains of Egyptian mummies which had been embalmed with asphaltum. It was claimed that, though time, the asphaltum had lost some of its volatile hydro carbons, and the powder from the ground up, embalmed remains was more solid than recent asphaltum and was better suited for a pigment. Apparently, it was once a favourite with some artists. Church says that it was certainly used as an oil paint at least as early as the close of the XVI century. Little is known about its history; it has not been mentioned in reports on the identification of materials in paintings. It is now perhaps unobtainable and is no longer desired in the arts. Some oil paints sold under that name are substitutes which contain bituminous earths like Van Dyke brown. The microscopic character of true mummy has not been described, but its properties and behaviour are much like those of asphaltum.

1516
Indigo ‘It employment in Europe was very limited until in 1516 when it began to be imported from India by way of the Cape of Good Hope, but its introduction in large quantity did not occur until about 1602. Owing chiefly to the opposition of the growers of woad, its European rival as a dyeware, it met with much opposition, and various laws were enacted both on the continent and in England prohibiting its use. It was called a ‘devilish drug’ and was said to be injurious to fabrics. In 1737 its employment was legally permitted France, and from this period its valuable properties appear to have become gradually recognized through Europe.

1523
Cochineal (carmine lake, crimson lake) is a natural organic dyestuff that is made from the dried bodies of the female insect, coccus cacti, which lives on various cactus plants in Mexico and in Central and South America. It was first brought to Europe shortly after the discovery of those countries. Eibner says that it came in after the conquest of Mexico in 1523 and was first described by Mathioli in 1549. The coloring principle of cochineal extract is carminic acid.
The cochineal lakes are not permanent to light. They turn brownish and then fade rapidly in strong sunlight, particularly when used in water color. In oil, however, they are fairly stable and were used formerly in the preparation of fine coach colors.

1600's
Bistre (Fr.) A Brown pigment, made from charred wood, used as ink, or chalk, or - principally in the 17th c. - as a wash. Rembrandt’s drawings are mostly in bistre.
The pen line in Old Master drawings is often reinforced by washes of bistre, a dilution of wood soot, which has a later equivalent in the sepia originally derived from the ink of the cuttle fish.

Blue Verditer is a name now given to an artificial basic copper carbonate. The pale greenish blue pigment is little used today, but can still be obtained from some artist’ colormen. ... The artificial copper blues have not been credited with great permanence, and Thompson says that they had a tendency to revert to green through the loss of their ammonia content. According to Laurie..the manufacture of blue verditer seems to have been carried on in England in large quantities at one time. Thompson states that ‘the artificial blues from copper are probably more significant in medieval painting than all the rest (of the blue pigments) put together.’ They were the best cheap substitutes for the more expensive azurite and ultramarine. Laurie identified this pigment in various English illuminated manuscripts of the early XVII century. He records, in another place that it was used throughout the XVIII century and the ‘Madame de Pompadour’ by Boucher, the National Gallery, Edinburgh, is painted with it.

1700-1800
Bitumen - A rich brown pigment made from asphaltum. Its use through pleasant is very dangerous, since it never dries completely. It was popular during the 18th and 19th c. and has been the cause of severe damage in many paintings of those periods.

1761
Aluminum is the third most abundant element (8%) in the earth’s crust, exceeded by oxygen (45%) and silicon (28%).
The metal’s name is derived from ‘alumen’, the Latin name for alum. In 1761 the french chemist Guyton de Morveau proposed the name ‘alumine’ for the base in Alum.

1780
Cobalt Green is similar to cobalt blue, except that zinc oxide replaces wholly or partly the aluminum oxide in the latter. Cobalt Green is semi transparent and does not have great hiding power. It is fine and regular in particle size; the grains are rounded and transparent, bright green in transmitted light, and they are highly refracting and birefracting. It is a stable and inert pigment and can be used im mixtures and in different techniques.
Church says: ‘Cobalt green is, in fact, one of the too rare pigments which is at once chemically and artistically perfect.’ It has not had, however, great favour with artists because it covers only moderately well, is costly and because its color can so easily be imitated by mixtures. Although it was discovered by Rinmann in 1780, it was not until after the middle XIX century, when zinc oxide became available in large quantities, that cobalt green in turn became commercially possible. Laurie gives 1835 as the date of the first literary mention of cobalt green as a pigment.

1787
Antoine Lavoisier identified alumine as the oxide of a then-undiscovered metal.

1797
L.N. Vauquelin, the discoverer of chromium (1797) described the preparation and properties of lead chromate in his 1809 ‘Memoir’.

1800's
Cerulean blue - It is a stable and inert pigment and is not affected by light or by strong chemical agents. ..It has limited tinting strength, but is the only colbalt blue pigment without violet tint. It was known at the beginning of the XIX century as a blue compound that could be made by heating tine oxide with a cobalt solution, but not until the year 1860 was it introduced under the name, ‘coeruleum,’ by Messrs G. Rowney and Co., who suggested its use for aquarelle and for oil painting. (The word , caeruleum, was used in classical times rather loosely to indicate various blue pigments.

Chrome Red - a brick red, crystalline powder, is basic lead chromate. It is stable under ordinary conditions, but is not widely used as an artist’s pigment because it lacks brilliancy and is readily affected by sulphur gasses. Little is known about its history as a pigment, but it probably came into use in the early part of the XIX century.

1802
Cobalt Blue is now the most important of the cobalt pigments. The color varies slightly with different methods of manufacture and with the amount of impurities present, but it is usually a pure shade of blue, especially in natural light.
Chemically, cobalt blue is very stable; it is insoluble in strong acids and alkalis and is unaffected by sunlight; it can be used in all painting techniques, even for the blue coloring of ceramic glazes, in much the same way as cobalt oxide is used.
Cobalt blue was discovered by Thenard in 1802. De Wild gives a brief account of its history and says: ‘since the new pigment satisfied a recognized demand, it was employed everywhere relatively soon after its discovery especially in France, as was natural.’ The earliest picture painted in Holland on which it was identified by De Wild was 1840 and he adds, ‘hence its use did not penetrate into Holland directly after its discovery.’ It has been identified on a water color painting by R.P. Bonington, 1801-1828. Since it is one of the most costly of artists’ colors, it is liable to adulteration and to substitution by ultramarine and even blue lakes.

1807
In 1807, Sir Humphry Davy assigned the name ‘aluminium to the metal and later agreed to change it to ‘aluminum’. Shortly thereafter, the name ‘aluminium was adopted to conform with the ‘-ium’ ending of most elements, and this spelling is now in general use through out the world, except in the United states (where the second ‘i’ was dropped in 1955) and Italy (where ‘alluminio’ is used).

1814
Emerald Green is an artificial pigment which was first made at Schweinfurt, Germany, in 1814. It is copper aceto-arsenite and can be prepared in several ways, in all of which the important raw materials are copper, acetic acid (or verdigris), white arsenic, and sodium carbonate.
Emerald green, as the pigment is now called, is bright blue green in color, is one of the most brilliant of the inorganic colors, and is quite unlike any other green pigment. It has fair hiding power. Some specimens of emerald green are quite characteristic... It does not enjoy popularity as an artist’s pigment because it is poisonous and dangerous to handle. Ia Paris green, it has long been used as an insecticide.) It is readily decomposed by acids and by warm alkalis, and it is blackened by heat. It is fairly permanent, however, in an oil or varnish medium.
Emerald green has not been identified frequently on paintings. De Wild found it on only one (dating 1860). Occasionally it is seen as the green pigment used for making an imitation patina over repairs on ancient Chinese bronzes.

1818
Chrome Yellow the most important of the commercial yellow pigments, is lead chromate. (It) can vary in shade from lemon yellow to orange, depending upon the particle size, which, in turn, depends upon the conditions of precipitation. Lighter shades usually contain lead sulphate, or other insoluble lead salts. The middle hues are neutral lead chromate, and the orange leads are basic lead chromate.
When chemically pure, chrome yellow is fairly permanent to light, but it is frequently observed to darken and become brown on aging. Sometimes, especially when mixed with colors of organic origin, it takes on a green tone. It is most satisfactory when used in oil. In fresco painting, only a basic lead chromate (chrome orange or red) can be used, for yellow chromes are turned by alkali. Much chrome yellow is used with Prussian blue to make chrome green. As a pigment, it dates from the beginning of the XIX century. L.N. Vauquelin, the discoverer of chromium (1797) described the preparation and properties of lead chromate in his 1809 ‘Memoir’. He mentioned that it could be prepared in different shades, depending on the conditions of precipitation. Chrome yellow did not come into commercial production, however, before 1818. One finds it occasionally on XIX century paintings. Laurie says that Turner used chrome yellow and chrome orange. It is not much used now in painting because more permanent yellows are available.

1826
Alizarin (alizarin crimson) is the coloring principle of the madder root and it was first isolated from that source in 1826 by Colin and Robiquet.

1835
Laurie gives 1835 as the date of the first literary mention of cobalt green as a pigment.

1842
Antimony Vermilion is antimony sulphide.. it may be had in hues varying from orange to deep red... It was first made by C. Himly in Kiel in 1842. Although antimony sulphide figures as a pigment in the rubber industry, it is little used in paint because it is fugitive and not very stable chemically.

mid-19th century
Until the mid-19th century, all dyes were derived from the leaves, twigs, roots, berries, or flowers of various plants or from animal substances.

1851
Cadmium Red Lithopone It is stable under ordinary conditions and is light fast. It is a strictly modern pigment, having been in use only since 1926.
Cadmium Yellow the color of the pure cadmium sulphide ranges in hue from lemon yellow to deep orange, depending upon the conditions of precipitation. Cadmium sulphide is found in nature as the mineral, greenockite, but the use of the mineral as a pigment has not been mentioned.
It is permanent and fast to light. The modern product, because of freedom from excess, free sulphur, is competitive with most other pigments. Laurie says that the cadmium yellows were first shown in the 1851 Exhibition. It is now perhaps the most important yellow pigment on the artist’s palette and is widely available in numerous shades.

1856
Coal Tar Colors are made from the distillation products of coal tar, a by product of coke and coal gas manufacture, and are compounds which contain chiefly carbon, hydrogen, nitrogen, and sometimes sulphur. Benzene, toluene, anthracene, naphthalene, phenol, and pyridine are all direct coal tar distillation products. By processes of synthetic organic chemistry, these distillation products may be changed to dye intermediates like aniline, phthalic acid, etc., which, in turn , may be synthesized to color products which are dyes. Since the discovery of the first aniline dyestuff, mauve (see Mauve), by William Perkin in England in 1856, many thousands of coal tar dyes have been prepared. Some have become important in the preparation of lake pigments, being values for their richness and brilliance in color. Many coal tar lakes lack permanence and have rightly caused the whole range of lake pigments to be looked upon with suspicion by the artist. In recent decades, however, there had been a very decided improvement in the permanence of coal tar dyestuffs; like the dyes of natural origin, those in the red region of the spectrum are the more permanent, but there has been a great improvement in the stability of lake pigments for other regions of the spectrum, examples of which are the Hansa yellows and the phthalocyanine blues. For the future, there may be developed organic colors which will rival the inorganic colors in light stability and general permanence.

Magenta is a brilliant red purple organic dye. It was first prepared by Natanson in 1856. It is soluble in alcohol, acetone, and aqueous solutions. Although a fugitive dye, it has been used for water colors and is still listed among them by artists’ colormen.

Mauve
is an artificial organic dyestuff belonging to the azine group of dyes. This was the first dyestuff ever to be made synthetically, It was discovered n England in 1856 by Sir William Perkins, who prepared it by the oxidation of crude aniline with chromic acid. Because aniline was the starting point for this as well as for several other which followed, the term, ‘aniline dyes’ came to indicate all those made synthetically, particularly those from chemicals derived from the distillation of coal tar. The term has been carelessly applied to dyes not derived from aniline or related to it. Pure mauve dye comes in the form of reddish violet crystals. When applied, the color is dull violet. It was patented in England where it was widely used for a time in dyeing cloth. Although it is fugitive, it has been used as an artists water color to a small extent, and today is still listed by some colormen among water color paints.

1859
Cobalt Violet The color is reddish violet; it is transparent and weak in tinting strength, and this fact, in addition to its high cost, seems to be the reason why it is not more generally used as a pigment. It is stable and unaffected by most chemical reagents and can be used in all techniques. They are still listed by artists colormen. The preparation of cobalt phosphate as a pigment was first described by Salvetat in 1859.

1860
Cerulean blue introduced under the name, ‘coeruleum

1861
Cobalt Yellow The pigment has a very pure yellow color and a fair hiding power. It is fast to light and air and is stable with other inorganic pigments, but it may accelerate the fading of some organic colors and itself turn grown. It is decomposed by hear, by strong acids and alkalis, and is slightly soluble in cold water. The pigment has been used perhaps more in water color than in oil. It was first introduced as an artist’s pigment in 1861 (Laurie) Messrs. Winsor and Newton, Ltd, say (1930 catalogue, p. 14 and in a private communication) that it was first introduced by them and was popularized by Aaron Penley, a celebrated water color painter. They also say that they introduced primrose aureolin in 1889. Although available today in water color medium, cobalt yellow does not appear to be widely used as an artist’s color, one reason being that it is expensive.


1862
Chromium Oxide Green, opaque It is permanent in all painting techniques. The opaque oxide is not so much in use by artists as the transparent oxide (1797) suggested its use for coloring ceramic glazes in 1809, but it evidently did not appear as an artist’s pigment until about 1862.

1868
Alizarin (alizarin crimson) First synthesized by two German chemists, C. Graebe and C. Lieberman, who reported their discovery in 1868. This is important in the history of organic chemistry, for alizarin was the first of the natural dyestuffs to be made synthetically. Its discovery caused the rapid decline and the almost complete disappearance of the large madder-growing industry in France.

The ‘alizarin crimson’ lake used so extensively in artists’ paints is nearly all from this source. Some painters have said, however, that synthetic alizarin does not give the pleasing, saturated, and fiery tone that madder alizarin gives.
Alizarin was the first natural dye to be produced synthetically (1868), and by 1880 indigo had been synthesized. By 1916, an extensive technology had developed, most of it concentrated within a German cartel that held a virtual monopoly over dye production. Only with the onset of World War II did German lose its position as the world’s principal suppliers of dyes. Today the U.S. dye industry, aided by the post-World II acquisition of German technology, has become a major exporter of dyes.

Madder was the source of the dye, Turkey red, formerly used in large quantities in textiles and is still the color for French military cloth. The cultivation of the madder root and its employment for dyeing and pigment purposes almost ceased shortly after a synthetic method for making alizarin was discovered by the German chemists, Graebe and Lieberman, 1n 1868.

1869
In 1869 Sir William Perkin developed a practical process for manufacturing synthetic alizarin that proved to be less expensive and more consistent in color than the natural material. Today natural alizarin has little importance as a dyestuff, although it is used as a chemical intermediate in the production of more sophisticated dyes and as a coloring material for artists’ pigment.

Manganese Violet
Church says that it has a truer hue than cobalt violet (cobalt phosphate) which is redder as well as brighter. The pigment is permanent to light and is unaffected by hear, but it is decomposed by strong acids and by alkalis, which makes it unsuited for fresco. It is not much used by artist because it is dull in tone and has poor hiding power. Little is known apparently about the history of this pigment, except for a statement by Messrs Winsor and Newton in their catalogue (1930) that it was first introduced by them in 1890. It is understood, however, to have been first prepared by E.Leyhauf in 1869, and named by him ‘Nurnberg violet’.

1870's
Cezanne was using the prismatic color palette of the impressionist, but he soon discovered the expressive limitations of the theory.

1871
Eosine is the potassium salt of tetrabromofluorescein and was first made by Caro in 1871. It was formerly used for preparing red inks of a very fine scarlet hue, but is not a fast color; it fades rapidly in sunlight. ‘Geranium lake’ is the name sometimes given to a brilliant bluish red lake made by precipitating eosine on an aluminum hydrate base.

1874
Lithopone
It has about the same whiteness but has greater hiding power than zinc white. This pigment, in the early days of its manufacture, had one serious defect, a tendency to darken (gray or blacken( in strong light but to turn white again in the dark. The trouble was traced to various causes, among which were the presence of foreign metallic impurities, but, after years of research, a lithopone is now produced which does not suffer charge in light. The so called ‘titanated lithopones,’ which contain about 15 per cent titanium oxide, have hiding power superior to that of straight lithopone.
Lithopone was apparently first produced and patented by John Orr in England about 1874. It is now industrially important and widely used in interior paints, lacquers, and enamels, for it has a combination of exceptional whiteness, brightness, and low cost. It has not been much used as an artist’s pigment because, perhaps, of its unfortunate early history. It is used for poster colors and for cheap water colors. One may expect to find it in the priming coats of modern, prepared artist’s canvas.

1880
Indigo dye synthesized.
Indigo
is a blue vegetable coloring matter which seems to have been used in the Far East very early for dyeing cloth and for painting. The dye is yielded by different plants of the genus Indigofera, among which I. Tinctoria, probably of Indian origin, was the chief source of the indigo of commerce until the time of the discovery of the process for making synthetic indigo by Baeyer in 1880.
Indigo was formerly grown all over the world, particularly in India and china, but since 1900 the synthetic product has almost entirely replaced the natural.

1886
Although aluminum powder as probably available as early as the middle XIX century, it was not until a decade or so after 1886, when aluminum began to be produced in large commercial quantities by the Hall process that the powders became readily available. It was first used for coating picture frames and radiators. Aluminum powder did not become important as a pigment for commercial paints until after 1920.

1889
Messrs. Winsor and Newton, Ltd, say (1930 catalogue, p. 14 and in a private communicatio) say that they introduced primrose aureolin in 1889.

1890's
Camouflage...The word “camouflage” probably comes from the French camouflet, the term for a small exploding mine that throws up gas and smoke to conceal troop movement. ...
It was Thayer who, in the early 1890's began creating a wholly formed doctrine of concealing coloration, worked out through observation and experiment and his nature studies.

1892
Cadmium Red By adjusting the proportion of sulphur to selenium and by regulating the conditions of precipitation, shades varying from vermilion to deep maroon may be obtained. Cadmium red is now a popular and favourite pigment, and today it has, to a great extent, replace vermilion on the artist’s palette... The various cadmium sulpho-selenides are stable and light resistant under ordinary conditions. Their history is more recent that of the straight cadmium sulphides. Although a red orange cadmium pigment containing selenium was mentioned in a German patent in 1892, it seems that the commercial production of cadmium reds did not begin until about 1910.

1899
Lithol Red or Lithol Toner
is one of the most important and widely used of the synthetic red dyestuffs of the modern lake pigment industry. Lithol red is bluish red with a deep blue red undertone. It does not bleed in oil and has good stability to light and hear. It has not been offered to the artists’ trade under this name, but no doubt is found in some cheap red paints as a substitute. It was first made by Julius in 1899.

1910
Commercial production of cadmium reds begins about 1910.

1916
By 1916, an extensive technology had developed, most of it concentrated within a German cartel that held a virtual monopoly over dye production. Only with the onset of World War II did German lose its position as the world’s principal suppliers of dyes. Today the U.S. dye industry, aided by the post-World II acquisition of German technology, has become a major exporter of dyes.

1920
Aluminum powder did not become important as a pigment for commercial paints until after 1920.

Antimony Oxide was introduced to the paint trade as a pigment under the trade name, ‘Timonox’, in 1920 by the Cookson Lead and Antimony Co., Ltd, of England. It has good hiding power. ...Since it is darkened by hydrogen sulphide, it is usually mixed with zinc oxide, which has preferential absorption for that gas. Antimony oxide has not been mentioned specifically as an artist’s pigment, and it has no advantage over other white pigments.

1926
Cadmium Red Lithopone It is stable under ordinary conditions and is light fast. It is a strictly modern pigment, having been in use only since 1926.

1927
Cadmium Yellow Lithopone...can be produced in a variety of shades ranging from lemon yellow to orange and at a cost considerable less than that for pure cadmium sulphide. It is a very finely divided pigment and its properties are similar to the straight sulphide. When this pigment was first introduced, H.W. Ward reported that cadmium yellow lithopone had all the fastness to light and hear of the pure sulphide but did not quite equal it in covering power. At the time of his report (January 1927), he said that his pigment had been on the market three or four months. Until very recently the cadmium lithopones were the only cadmium yellows manufactured in the United States.

1935
Manganese Blue
is a comparatively new pigment which seems to have been first mentioned in the patent literature about 1935. This green blue pigment is essentially barium manganate fixed on a barium sulphate base. Although weak in tinctorial and in hiding power, this pigment may have special uses because of its chemical stability. So far, it has been used almost exclusively for coloring cement; it should be of interest to fresco painters.


Molybdate Orange
a pigment of recent origin, is a mixed crystal compound of lead chromate, (et c.) As pigment, it has high covering power and tinting strength. First described in the German patent in 1930. Although Molybdate orange went into production soon after 1935 for use in printing inks and paints, it is not known that it has been used, as yet, in artists paints. Because of its brilliant color and other desirable properties, however, it may be expected soon to find use for that purpose.

1940's
Metal-complex dyes, used primarily on wool, are combinations of a dyestuff and a metal, usually chrome. In use since the 1940s, they were developed from the older mordant dyes and are highly light- and wash-fast.

1955
in the United states the second ‘i’ in Aluminum is dropped.

1960
The Young-Helmholtz theory received empirical support from the discovery in the 1960's of three types of cones sensitive to red, green and blue, respectively.