Short History of the Pigments

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The oldest known pigments

At the beginning — before 30,000 B.C.¹, the only known pigments were white (chalk), black (burnt wood or carbon black, i.e. soot) and various colored earths. These pigments were absolutely permanent and lightfast. It means that you can leave them under the light of the sun during centuries: their color won’t fade at all.

But there is a little problem with this sort of pigments: their colors are rather drab; none of them has a bright color.

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Oldest known and absolutely permanent pigments *) **)

Chalk White
Yellow Earth No.1
Yellow Earth No.2
Yellow Earth No.3
Yellow Earth No.4
Yellow Earth No.5
Brown Earth No.1
Brown Earth No.2
Brown Earth No.3
Red Earth No.1
Red Earth No.2
Black (burnt wood)

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The first bright color

Probably the brilliant shades of some flowers, berries, roots and other vegetables colors were known very early. But these fugitive pigments fade when exposed to sunlight. Already in prehistoric times, more than 3000 years B.C., the Chinese had discovered the first bright permanent red: a mineral called Cinnabar (natural mercury sulfide). When ground, it’s known under the name of Vermilion. This pigment has a rather capricious permanence: sometimes, when exposed to light, it can become black, but this process is unpredictable.

Vermilion (Cinnabar Red)

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The colors of the Egyptians

The Egyptians knew eight colors:

Calcium Sulfate (= plaster)
Carbon Black
Yellow Ochre
Red Ochre
Cinnabar
Egyptian blue (Blue Frit)
Malachite
Orpiment (King’s Yellow)

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The pigments of the Roman Antiquity

In addition to all the preceding ones, the Ancients knew the following pigments:

White Lead
Realgar
Verdigris
Malachite
Azurite
Indigo
Tyrian Purple

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The pigments of the Old Masters

In the course of the centuries, brighter pigments were discovered. Some of them were lightfast, others fugitive. For example, the Old Masters of the Middle Ages and the Renaissance knew no permanent bright green. That’s why so many trees in their paintings have turned brown with the time. Another example: like the Chinese, they knew Vermilion but we’ve already said that this bright red pigment has a strong tendency to turn black when exposed to light.

They knew another red pigment: Lead Red (tetroxide of lead = Minium) which had a bad reputation (because it can turn brown when exposed to light) but which has now proved to be more permanent than Vermilion in the Italian paintings of the 14th century! Compared with Vermilion, this pigment has an more orange shade.

Another of their bright red pigments, Madder (prepared from the root of an Old World hairy herbaceous plant named Rubia Tinctorum), fades easily under the light of the sun. (Its juice however was one of the most permanent dyes of the Roman Antiquity.)

They knew a superb permanent blue, that was absolutely lightfast, but more expensive than pure gold (!), Ultramarine, which was a grinded semi-precious stone: lapis lazuli. However, this splendid blue fades immediatly when exposed to acids.

The Masters of the Middle Ages had a marvellous yellow: Lead-Tin Yellow Type II. This pigment, which is extraordinary permanent (one can verify it in the museums), was widely used in Italy in the 14th an 15th centuries under the name of “giallorino”. But, strangely enough, it soon disappeared — replaced by “Naples Yellow” (lead antimoniate). It’s now impossible to find it in the stores. As for Naples Yellow (PY41), this pigment is so toxic that it has now been replaced by most manufacturers by various mixtures, the best of which could be non toxic (and absolutely permanent) mixtures of natural earths (or synthetic iron oxides) and Titanium (or Zinc) White.

Giallorino (Lead-Tin Yellow Type II)
Red Lead (Minium)
Vermilion (Cinnabar Red)
Madder, sort No.1
Madder, sort No.2
Lapis Lazuli (= Genuine Ultramarine)

A special mention must be made of a pigment widely used by the Old Masters, particularly the Italians: Terre Verte (Green Earth), a natural greenish earth pigment of which the composition varies enormously according with the area where it is found, so that the shade ranges from a pale grayish to a dull yellowish green (it’s a complicated compound made up of various aluminium, iron, magnesium and potassium silicates). In addition, the lightfastness changes with the different sorts, the best ones being absolutely permanent.

Terre Verte, sort No. 1
Terre Verte, sort No. 2
Terre Verte, sort No. 3

It’s no use talking a long time about other pigments of the Middle Ages and the Renaissance, because nearly all of them have completely disappeared nowadays.

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The colors of Cennino Cennini

However, I want to pay tribute to one of the most important books of the history of painting, Cennino Cennini’s Libro dell’arte (1437), in which the author explains which colors the Italian painters of the 14th and 15th centuries actually used. These were:

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What about browns and violets?

You will immediatly remark that there are neither browns nor violets in this palette.

Browns

It’s well established now that the Medieval painters didn’t love the brown colors. Their browns were mixtures of sinopia and black, sometimes with a little yellow ochre. Further in his book, Cennino explains us the manner of painting flesh and hair colors: the basic color is always a mixture he calls “verdaccio”, containing black, white, yellow ochre and a red pigment (Cinnabar or Sinopia) in various proportions. Try it and you will obtain a great variety of flesh colors and browns.

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Violets

For making violet, Cennino recommands to mix Ultramarine and Red Lake. But one knows now that the Middle Ages painters often get violets by glazing a transparent red lake over a blue underpaint (made with Azurite or Ultramarine), or conversely by glazing a blue transparent pigment over a pink or red underpaint. Sometimes too, the underpaint was already a violet or lilac mixture of red, blue and white.

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The colors of the 16th century

It can seem strange that the Tuscan Cennino didn’t say a word about the Siennas and the Umbers, which are Tuscan and Umbrian (i.e. Italian) natural earths though. It was in the 16th century only that the painters began to use brown pigments widely, among others, Burnt Sienna, Raw Umber and Burnt Umber.

Burnt Sienna
Raw Umber
Burnt Umber

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The pigments of the last centuries

In the course of the centuries, the chemistry discovered new pigments. Here are the most important ones. (The first column gives the dates of commercial availability of each color, which can vary among countries).

1724 1750 Prussian Blue ferric ferrocyanide, discovered in 1704 by Diesbach (Berlin, Germany) about 1750 Mars Pigments artificial iron oxides, discovered round the middle of the 18th century 1818 Chrome Yellow lead chromate, discovered in 1809 by Vauquelin (France) 1820 1830 Cobalt Blue cobalt aluminate, discovered in 1802 by Thénard (France) 1828 French Ultramarine = artificial ultramarine, complex compound of alumina, silica, soda and sulfur, discovered in 1824 or 1826 by Guimet (France) 1829 1846 Cadmium Yellow cadmium sulfide, discovered in 1817 1834 1850 Zinc White zinc oxide, known since the discovery of zinc (the element) in 1746 by Margraaf (Germany), but only proposed as a pigment in 1782 by Courtois (Dijon, France) 1835 Cobalt Green complex mixture of cobalt and zinc oxide, discovered in 1780 by Rinmann (Sweden) 1838 1862 Viridian = Vert Émeraude, transparent hydrated oxide of chromium, secretely discovered by Pannetier and Binet (Paris, year unknown) but the manufacturing process was published and patented in 1859 by Guignet (France) 1856 (William Perkin’s) Mauve First aniline dyestuff to be made synthetically about 1860 Cobalt Violet cobalt phosphate, discovered in 1859 by Salvétat (France) 1860 1861 Cobalt Yellow = Aureolin, potassium cobaltonitrite, discovered in 1848 by Fischer (Breslau, Germany) 1860 1870 Cerulean Blue cobaltous stannate, discovered in 1805 1862 Chromoxide Green opaque oxide of chromium, discovered in 1809 about 1868 Alizarine Alizarin Crimson, 1,2-dihydroxy-anthraquinone, the first natural dyestuff made synthetically in 1868 by Graebe and Lieberman (Germany) 1870 1880 Ultramarine Violet variety of French Ultramarine 1890 1900 Manganese Violet manganese ammonium phosphate, discovered in 1868 by Leykauf (Nurnberg, Germany) about 1910 first Azo Yellows PY1, PY3 synthetic organic yellow pigments 1910 1919 Cadmium Red sulfo-selenide of cadmium, discovered in 1892 1916 1919 Titanium White titanium dioxide, known since 1870 or earlier 1936 Phthalocyanine Blue copper phthalocyanine, discovered in 1935 by ICI (Imperial Chemical Industries, Ltd) 1938 Phthalocyanine Green chlorinated copper phthalocyanine about 1950 Nickel Titanium Yellow oxides of nickel, antimony and titanium

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Recently appeared pigments

Dioxazine Purple PV23 = Carbazole Violet Indanthrene Blue PB60 = Anthraquinone Blue Mars Black PBk11 synthetic iron oxide Permanent Magenta PV19 quinacridone Permanent Rose PV19 quinacridone

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Very recently discovered pigments (end of the 20th century)

Chromophytal Yellow PR128 = Transparent Yellow Anthraquinoid Red PR177 Diketo-Pyrrole Red PR284 = (new) “Permanent” Alizarines

As you can see in the tables above, in general, the first pigments to have been discovered were inorganic ones (i.e. pigments containing only minerals and no organic carbon). Later on, with the enormous development of the organic chemistry, synthetic organic pigments were made too. At first (1856) they were derivated from aniline (synthetized from distillation products of coal tar) and had extraordinary bright — but unfortunately often very fugitive — colors. The first synthetic organic pigment that was relatively permanent (compared with the preceding ones) was Alizarin (PR83), discovered in 1868.

All these new synthetic colors were generally sold in tubes with fantasy names, so that the painter had no possibility to control the composition of the materials he was working with, and couldn’t know if it was a permanent or a fugitive color. In 1892, Winsor & Newton was the first manufacturer to publish the chemical composition of its colors, with details on their permanence. Gradually, all the other brands followed. At the end of the 20th century, the color makers began to use the Color Index System.

In the middle of the 20th century, as a generel rule, the anorganic pigments were more lightfast than the organic ones. But like to any rule, there were exceptions.

Now, at the beginning of the 21th century, there is no general rule about the permanence and lightfastness of pigments any longer. For more details see “Lightfastness of the pigments of the 21th century”.

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