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Pigment History

Artists' Pigments 1780-1880: History and Uses

The nineteenth century was more important than any other in the development of artists’ colors was. It was an outgrowth of the flourishing field of chemistry that began in the eighteenth century. Chemists and colormakers began working side by side to develop new formulas for pigment production. Totally synthetic pigments were produced for the first time. The discovery of previously unidentified minerals opened up a range of brilliant and permanent pigments the likes of which had never been known before.

The artists’ palette was lacking in yellows and greens more than any other hue by the end of the eighteenth century. A new hue was also needed to replace the costly ultramarine, genuine. The discovery of Cobalt, zinc, chrome and metallic cadmium early in the century made the necessary additions possible.
The later part of the century, improvements were made to some of the ancient dye colors and known minerals were developed for artists’ use. Zinc, for example, had been known since antiquity when it was melted with copper to form brass. Many pigments, including zinc, are found in the medical profession. It was employed then, as it is today, as a medicinal ointment (Paint and Painting [1982], 19).

The first part of this discussion of nineteenth century pigments will describe the most notable ones in the order that they were discovered. It will be concerned with the following issues:

1.The circumstances of their discovery and means of fabrication will be analyzed. Their method of manufacture falls into two groups. The ‘wet process,’ used for pigments such as Aureolin, chrome colors and emerald green, involves substances that are oxidized with water or mixed with chemicals and usually heated. Their pigment particles are generally crystalline in structure and tend to be less permanent than ‘dry process’ pigments. The latter, such as artificial ultramarine, cadmium and cobalt colors are generally made in a furnace with extreme heat (Blockx 1910, 53).

2. The characteristics of each pigment will be discussed. Pigments are inherently either opaque or transparent. The former would be more appropriate as a tinting or body color; the latter being better suited for a glaze color. Some pigments are lightfast and unchanged by impure air. In the nineteenth century there was a particularly high level of sulfur in the air that damages certain pigments. The cause of sulfur-bearing air was due to the use of coal and gas for heat and light in the artists’ studio as well as in the gallery. Sulfur is a by-product of the combustion of coal and gas (Field 1885, 88).

3.The opinions of important colormakers and writers will be mentioned. In particular, George Field (1777?-1854), British colormaker and Jacques Blockx (1844-1913), Belgian colormaker will be mentioned as they tested and sold the pigments under discussion.

4. The identification of the pigments, both microscopically and chemically will be analyzed. This information becomes important when the palettes of artists are not known and is useful for dating paintings on the basis of pigment availability. The process involves the removal of a very small fragment of dried paint from the painting. It is first examined under the microscope and then subjected to a variety of chemicals. By comparing the results to known pigment samples, identification can be made.

The latter part of this paper will analyze the palettes of some of the key nineteenth century painters. It will begin by discussing developments in the artists’ colorman’s trade, which were responsible for bringing the new pigments to the marketplace.

The middle of the century was marked by the publication of books on color theory and test results on the new pigments. The invention of the collapsible metal tube brought the artist out of the studio and into the landscape. The beginning of Impressionism was a result of these developments. Painting was revolutionized in the third quarter of the nineteenth century. It would have been quite a different story had the artists not capitalized on all that was happening.

The first modern, artificially manufactured color was Prussian blue. It was made by the colormaker Diesbach of Berlin in about 1704. Diesbach accidentally formed the blue pigment when experimenting with the oxidation of iron (Gettens and Stout 1966, 149-151). The pigment was available to artists by 1724 (Mayer 1970, 64).

Fifty years passed before the Swedish chemist Carl Wilhelm Scheele discovered the next new pigment in 1775. Scheele developed a green pigment while investigating the nature of arsenic. Scheele’s green, as it would be known, was the first to virtually replace the ancient copper carbonate greens by the end of the nineteenth century.

Scheele’s green was copper arsenate (CuHAs03); the first pigment to contain arsenic. Scheele mentioned it in 1777, in a letter to another scientist. In this letter Scheele discussed the highly toxic nature of the pigment. He also sought to protect himself from anyone else claiming the discovery. In 1778, the Stockholm Academy of Sciences published his detailed instructions for making it. First, potash and powdered arsenic sulfide (As203) were dissolved in water and heated. The alkaline solution that resulted was added, a little at a time because of foaming, to a warm solution of copper sulfate. When allowed to stand, the green pigment would settle out. The liquid was poured off and then the pigment was washed and dried on low heat (Harley 1970, 75-76).

The great exchange of scientific information at the end of the eighteenth century made Scheele’s green widely known. It was described in 1795 in the Practical Treatise on Painting in Oil, London. In 1812, its method of manufacture and range of variations were patented in England (Harley 1970, 76). Its yellowish-green color faded rapidly and sulfur-bearing air and sulfide blackened it pigments (Gettens and Stout 1966, 155). However, Field and Laurie considered it superior to other copper greens for its brilliance and durability, such as it was. Field also mentioned that an olive green could be made by burning either verdigris or Scheele’s green (Hartley 1970, 76).

Scheele’s green can be identified under the microscope as small and large irregular-shaped green flakes that are slightly transparent (Gettens and Stout 1966, 155). Laurie suggests that it can be identified by comparing it to copper carbonate greens under the microscope. He also discussed one method for chemically identifying arsenic compounds with a stannous chloride test. A sample of verditer (a copper green), a known sample of Scheele’s green and an unknown sample are placed on a glass slide. The samples are coated with collodion and immersed in a bath of stannous chloride dissolved in a strong hydrochloric acid. It is then heated to 60°C. The verditer will dissolve and the arsenic green will turn a brownish-black (Laurie 1914, 52).

A few years before he discovered his green, Scheele discovered a process for preparing compounds of sodium; lead oxychloride was a by-product. Although he published his findings for a new yellow pigment of lead oxychloride in 1775, he did not continue to develop it. Patent yellow, also known as Turner’s yellow (PbC12.5-7PbO) was patented by James Turner of England in February 1781, hence its name. Turner noted Scheele’s discovery as applicable for, "a method of producing a yellow colour for painting in oil or water, making white lead, and of separating the mineral alkali from common salt, all to be performed in one single process" (Harley 1970, 91-92). The yellow pigment was made by grinding together, in water, two parts of lead (either red lead or litharge) and one part of sea salt. The mixture was allowed to stand for twenty-four hours. A caustic soda solution was poured off and the remaining white substance was heated (and dried) until it reached the desired shade of yellow.

Turner’s patent did not prevent other manufacturers from copying his process. He sued one competitor and won the case on appeal in 1787. The case was published in books on patent law because it was won on a ruling that stated that if a patentee claimed to do several things by one process and one failed; the whole patent was void. In fact, Turner had listed several different names for lead and for the type of salt that could be used. Turner’s competitor could not prove definitively that variations in the raw materials would not produce the pigment and Turner retained his patent.

A statute ordered by an Act of Parliament extended the time allowed to Turner as the sole manufacturer because competitors had taken his rightful income. It went on to state that Turner’s yellow was superior and less costly than orpiment. It contributed to the National income of England and to the salt tax in that it was made from native raw materials.

Turner’s yellow was widely used in England and regarded as durable and bright. It was sold at one shilling per watercolor cake in spite of a known tendency to blacken. Field claimed that it worked well in both oil and watercolor but noted its impermanence in sunlight.

In spite of the introduction of more permanent yellows in the nineteenth century, it was produced on a large scale. C. T. Kingzett, author of The History, Products and Processes of the Alkali Trade, 1877, recorded its production at a soda factory at Walker-upon-Tyne, England, where it was sold as Turner’s Patent Yellow. At the Great Exhibition of 1851, an example of its use in oil was provided by the Washington Chemical Company of Washington, Durham, England (Harley 1970, 91-92).

Schweinfurt green or emerald green was developed in an attempt to improve Scheele’s green. This copper aceto-arsenite (Cu(CH3COO)2.3Cu(AsO2)2) pigment was first produced commercially by the firm of Wilhelm Sattler at Schweinfurt, Germany in 1814 (Wehlte 1982, 131). Justus Von Liebig and Andre Bracconot separately published papers on its method of manufacture. Von Liebig’s paper "Sur une couleur verte" was published in 1823 in Annales de chimie XXIII (pp. 412-3). Verdigris (or acetic acid) was dissolved in vinegar and warmed. A watery solution of white arsenic was added to it so that a dirty green solution was formed. To correct the color, fresh vinegar was added to dissolve the solution. The solution was then boiled and bright blue-green sediment was obtained. It was then separated from the liquid, washed and dried on low heat and ground in thirty- percent linseed oil. The pigment was considered a good drier (Harley 1970, 77).

Schweinfurt green had brilliance unlike any other copper green. Field considered it a more durable pigment than Scheele’s green but it had the same tendency to blacken on exposure to sulfur-bearing air (Harley 1970, 77). Romanesque murals are known to contain the natural mineral emerald green and have held the color well. The old Masters, who used verdigris and copper greens due to a lack of more durable options, isolated the pigments in between coats of varnish that helped to alleviate changes. Schweinfurt green was also made more stable in a varnish medium (Doerner 1931, 83). It could not be mixed with sulfur-containing colors, such as cadmium yellow, vermilion or ultramarine blue because they acted chemically on it to produce a deep brown color (Laurie 1926, 93). Field considered its use to be limited as it was not a green that occurred in nature (Harley 1970, 77). The arsenic content made it extremely poisonous and it was blamed for deaths when employed as a wallpaper color (Pavey 1984, 24).

Microscopically, it appears as small rounded grains that are uniform in size making it readily distinguishable from Scheele’s green. At high magnification, the grains are radial in structure and a dark spot can be seen in the center (Gettens and Stout 1966, 113). It can be identified chemically by the stannous chloride test described for Scheele’s green and has the same reaction for arsenic. In potassium hydroxide, it turns into an ochre color and in weak sulfuric acid it dissolves and turns blue (Doerner 1934, 83).

Until the nineteenth century, the painter’s palette was lacking in a permanent, bright yellow more than any other primary hue. In painting and illumination of antiquity, gold leaf often served to balance the palette. Orpiment, a pale, lemon yellow was extensively employed as well. It lacked brilliance and was not mixable with most other pigments. Therefore, Turner’s yellow gained popularity very quickly. Another new yellow, Indian yellow, had the same rapid introduction. This research has not uncovered a known date of its introduction but Wehlte notes its appearance in the middle of the eighteenth century (Wehlte 1982, 95).

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The amateur painter, Roger Dewhurst, recorded the use of Indian yellow in 1786. He noted, in letters to friends, that it was an organic substance made from the urine of animals fed on turmeric and
suggested that it should be washed to prepare it for use as a pigment. Its
source remained a mystery for many years. Merimee in his book on painting of 1830, didn’t believe it was made from urine, in spite of its odor. George Field believed it was made from camel urine.


It was not until 1886 that the Journal of the Society of Arts in London embarked on a systematic inquiry of the
pigment known as purée of India. An investigator began his search at Calcutta.
He was sent to Monghyr, a city in Bengal. There, he found a small group of cattle
owners who fed their cows on mango leaves and water. The cows’ urine was a bright yellow.
They were extremely undernourished as they only received normal fodder occasionally.
Other Indian dairy cattle farmers of the same caste despised these ‘colormen’ and
limited their production. They were reportedly producing one thousand to fifteen
hundred pounds of the pigment per year but the investigator doubted the
production figures when he saw the small number of cows involved (Harley 1970,
105).

In order to prepare the urine as a pigment, this genuine magnesium euxanthate (Cl9H16OllMg5H20)
was heated until sediment was formed which was strained, pressed into lumps by
hand and dried. The extensive trade between India and England made it generally
available in England and was considered an English specialty (Harley 1970,
55-56). The rounded lumps were brown or dirty green on the outside and a
brilliant yellow-green on the inside. The cleaner, more golden yellow varieties
were greater in value (Doerner 1934, 66).

Indian yellow was used in both oil and watercolor painting. It was favored for its great body and depth of tone. It had a peculiar characteristic in watercolor for it faded in artificial light and in
the dark but was fairly stable in direct sunlight (Field 1885, 134). In 0il, it
dried slowly, as it required one hundred percent for grinding; the addition of
varnish improved its drying (Doerner 1934, 66). It could be mixed with all other
pigments but in oil its lightfastness was improved when isolated between layers
of varnish (Wehlte 1982, 95).

Under the microscope, Indian yellow appears as crystalline
(Gettens and Stout 1966, 119). It is decomposed by hydrochloric acid. When burned,
it should leave white ashes, as many organic substances do (Doerner 1934, 66).

Law prohibited the production of Indian yellow in the early years of the twentieth century. Wehlte adds that its
departure may have been due to the Indians for whom the torture of sacred
animals was against their religion. It also may have been due to British laws
that prohibited cruelty to animals (Wehlte 1982, 95).

Scheele’s green and Schweinfurt green would become virtually
obsolete by the end of the nineteenth century. The preparation of zinc oxide at
the end of the eighteenth century made the development of cobalt green, also
known as zinc green, possible. The Swedish chemist, Rinmann is credited with
developing a process for making a compound of cobalt and zinc in 1780 that he
published with the Stockholm Academy of Sciences. Arthur Herbert Church
published Rinmann’s process in his book, The Chemistry of Paints and
Painting London, 1901) (Gettens and Stout 1966, 109). According to Church,
cobalt green (CoO.nZnO) was made with the compounds of oxides of zinc and cobalt
by mixing them "with an alkaline carbonate" (Harley 1970, 77-78), and
then exposing the mixture to strong heat. After washing the sediment that
resulted, the pigment was ready to grind. The pigment was always bluish-green in
spite of the ability to widely vary the proportion of zinc to cobalt oxides in
production. The compound that is formed is chemically joined (Harley 1970,
77-78).

Cobalt green was a semi-transparent, moderately bright green. Most sources cited considered it to be absolutely
permanent as most pigments produced at high temperatures are (Gettens and Stout
1966, 109). However, tests made in 1847 and published in 1910 showed a browning
of the color in full-strength and a fading of it when mixed with lead white. The
colormaker, Blockx, added that the date of the tests bears certainty that the
green was made by Rinmann’s process (Blockx 1910, 72).

Cobalt green appears as fine, rounded and transparent particles under the microscope. It becomes reddish when mixed with hot acids or alkalis (Gettens and Stout 1966, 109).

Artists did not favor cobalt green although it could safely be mixed with all other pigments and
was a fast drier in oil. The poor tinting strength and high cost of cobalt green
kept it in limited use. Field called it, "chemically good and artistically bad"
(Field 1885, 141).

The next cobalt pigment to be introduced to the artists’ palette was cobalt blue. Although smalt, a pigment made from cobalt blue glass has been known at least since the Middle Ages, the cobalt blue
established in the nineteenth century was a greatly improved one (Mayer 1970,
67).

The isolation of the blue color of smalt wasdiscovered in the first half of the eighteenth century by the Swedish chemist Brandt. In 1777, Gahn and Wenzel found cobalt aluminate during research on
cobalt compounds (Harley 1970, 53). Their discovery was made during
experimentation with a soldering blowpipe (Wehlte 1982, 148). The color was not
manufactured commercially until late in 1803 or 1804.

The Minister of the French government, Chaptal, appointed Louis Jaques Thenard and Merimee
to look into the improvement of artists’ colors. Thenard developed this new
cobalt blue by his observations at the Sevres porcelain factory. He experimented
with roasting cobalt arsenate and cobalt phosphate with alumina in a furnace
(Laurie 1926, 94). He published his results in late 1803-4 in the Journal des
mines, "Sur les couleurs, suives d’un procede pour; pour prparer
une couleur bleue aussi belle que l’outremer."

Thenard  tried the blue in oil and gum media and by the time his report was published,
the color had not changed after a two-month exposure test. Production began in
France in 1807 (Harley 1970, 53). Most sources cited regard Thnard
as the inventor of the blue. However, Leithner of Vienna is also mentioned as
one who developed cobalt arsenate as early as 1775 (Wehlte 1982, 148).

Cobalt blue (Co0.A1203) was generally regarded as durable in the nineteenth century. It requires one
hundred percent of oil to grind it as an oil paint otherwise its cool tone
can turn greenish due to the yellowing of linseed oil. To avoid the yellowing,
Laurie suggested that it be used as a glaze color or mixing it with white. It is
totally stable in watercolor and fresco techniques. Field called it a
"modern, improved blue" (Pavey 1984, 23). John J. Varley, author of List
of Colours (London, 1816), recommended it as a good substitution for
ultramarine blue for painting skies (Harley 1970, 54).

Cobalt blue has coarse particles, like azurite and ultramarine, genuine but is distinguished microscopically by their
non-crystalline appearance. It is chemically insoluble and unchanged, even in
strong hydrochloric acid (Laurie 1914, 49).

Forty years passed before another cobalt pigment was developed. Although
little is recorded on the history of cobalt yellow (or Aureolin), all sources
cited credit the discovery of this potassium and cobalt compound to N. W.
Fischer in Breslau in 1848. Gettens and Stout cite J. G. Bearn (The Chemistry
of Paints, Pigments and Varnishes, London, 1932) for the method of
manufacturing cobalt yellow. Mixing cobalt made potassium cobaltnitrite (CoK3
(NO2) 6.H20 salt with a concentrated solution of potassium nitrite. The sediment which results must be thoroughly washed or the pigment will not be stable (Gettens and Stout 1966, 109-110). It
was first introduced as a pigment for artists’ use by Saint-Evre, Paris in 1852 (Mayer 1970, 49)

Laurie and Blockx consider cobalt yellow chemically illogical for a permanent
pigment. Laurie, however, refers to tests made by Captain Abney and Professor
Russell who showed that it was reliable in watercolor (Laurie 1926, 89-90).
Blockx tested it in 1879 and by the time his book was published in 1910, he
found that it withstood strong sunlight. He added that it must be carefully
manufactured or it will brown in oil. He considered it the only color that could
reasonably replace Indian yellow (Blockx 1910, 66-67). It was known for its good
mixing quality with all other pigments and for particularly good tints in
watercolor. At high magnification, tiny crystals and crystalline clusters appear
(Gettens and Stout 1966, 110). It is unchanged in acids but will turn black in
sodium sulfide and brown in caustic soda (Laurie 1914, 54).

The remarkable range of pigments that could be produced with cobalt included cobalt violet, known since 1859. Salvetat firstdescribed the preparation of cobalt violet, dark in Comptes Rendus des
Seances de l’Academie des Sciences XLVIII in an article titled, "Matieres
minerales colorantes vertes et violettes." The dark variety is anhydrous
cobalt phosphate (CO3 (P04)2) which was made
by mixing soluble cobalt salt with disodium phosphate. It was washed and then
heated at a high temperature. The light variety, developed in Germany in the
early nineteenth century and is anhydrous cobalt arsenate (CO3
(ASO4) 2). The light variety was particularly poisonous
because of its arsenic content.

Both of the cobalt violets were considered to be very permanent but the light variety could change in oil due to the yellowing of linseed oil. They were both compatible with all painting media.
Their transparency, weak tinting strength and high cost limited their use but
their fastness to light made them more desirable than the older organic dye
violets.

Cobalt violets appear as irregular-shaped particles and particle clusters under the microscope and are largely unaffected by chemical tests (Gettens and Stout 1966, 109).

The last new pigment to be produced with cobalt in the nineteenth century was caeruleum blue. Although Höpfner introduced it as early as 1821, it was not widely available until its
reintroduction in 1860 by George Rowney in England (Wehlte 1982, 149). Its name
was derived from the Latin word caeruleum, meaning sky or heavens (Pavey 1984,
40). Caeruleum was used in classical times to describe various blue pigments
(Gettens and Stout 1966, 103).

Like cobalt green, blue and smalt, it was made by the action of heat on cobalt oxide with other metallic bases (Field 1885, 147). Caeruleum is cobaltous stannate (CoO.nSnO2)
and is made by mixing cobaltous chloride with potassium stannate. The mixture is
thoroughly washed, mixed with silica and calcium sulfate and heated
(Gettens and Stout 1966, 103).

This variety was a fairly true blue (not greenish or purplish) but it did not have the opacity or richness of cobalt blue (Field 1885, 147). It was not recommended for use in watercolor painting because
of chalkiness in washes. In oil, it kept its color better than any other blue
and was particularly valuable to landscape painters for skies (Doerner 1934,
81). Microscopically, its particles are fine, rounded and uniform. It is not affected by strong chemicals (Gettens and Stout 1966, 103).

After the new cobalt pigments, the next major group of pigments to be developed in the nineteenth century were derived from chrome. This orange-colored mineral was first observed, although not
identified, in 1770 in the Siberian Beresof gold mines (Paint and Painting [1982],
92]. In 1797 a Parisian chemist, Louis Nicholas Vauquelin isolated natural lead
chromate (chrocoite) and called it chrome because of the range of hues that
could be derived from it (Harley 1970, 92). He named it after the Greek word
xpwua, meaning color (Gettens and Stout 1966, 142).

The gold mine was not in continuous operation so that Vauquelin’s study was slow until a new source of the mineral was found in the Var region of France during the early years of the nineteenth
century.

The preparation of chromates of lead, specifically chrome yellow (2PbSO4.PbCrO4)
was published by Vauquelin in the Annales de Chimie IXX in 1809. A
solution of soluble lead salt (acetate or nitrate) was added to potassium
chromate. Varieties of yellow, orange and red could be produced with slight
adjustments of the solution (Harley 1970, 93). Orange required
that the solution be treated with a caustic soda (Laurie 1926, 89). Red
necessitated a strong solution of potassium chromate (Gettens and Stout 1966,
106).

Chrome yellow was greenish in hue and deep
chrome was a more brilliant, deeper yellow (Field 1885, 124). Chrome orange was
extremely bright and Field described it as "rank" (Harley 1970, 118).
Chrome red was also known as scarlet chrome and was a cold, red hue. It was the
least popular of the new chrome pigments due to a tendency towards dullness when
mixed with lead white (Doerner 1934, 75). It was not listed in the color
catalogues of Winsor and Newton after 1842 (Harley 1970, 119).

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The chrome colors were in use by 1816 but on a limited basis. In 1820, a substantial source of chrome ore was found in North America and large scale production began, j. J. White of Rutherglen,
Scotland is known to have produced chrome colors that year. Their excellent
hiding power and low cost made them a welcomed alternative to Turner’s Patent
yellow and orpiment. Chrome yellow cost one shilling per watercolor cake
in 1835 (Harley 1970, 93). Although less poisonous than orpiment, they were
toxic as well, due to their lead content. They were fast drying in oil and more
permanent in oil than in watercolor. The darker shades were more permanent than
the lighter ones that tended to fade when exposed to sunlight. The darker shades
were known to brown over time (Doerner 1934, 62-63). All chrome colors were
blackened by sulfur-bearing air and the yellow variety sometimes would turn
green when mixed with organic pigments.

They are microscopically identified by their crystalline particles, the deeper shades having a more rectangular shape (Gettens and Stout 1966, 106). The lighter, more yellow shades have finer
particles (Doerner 1934, 75). They are identified chemically by a change to
black in sodium sulfide. In nitric acid, the orange turn’s bright yellow and
the yellow is only slightly affected. In other acids, the yellow turns red
(Laurie 1914, 54).

Chrome green was developed sometime in the
first quarter of the nineteenth century. Its discovery was possible because of
Vauquelin’s research. It was a homogeneous mixture of chrome yellow and
Prussian blue. Chrome green was made by thoroughly mixing Prussian blue with a
paste of barytes, china clay and chrome yellow. It is so chemically united that
its separate parts cannot be distinguished microscopically, unlike a color that
is mixed on the artists’ palette. It had excellent hiding power and was
inexpensive but was not lightfast due to the darkening of its chrome yellow
component (Gettens and Stout 1966, 105). It is identified chemically by the
disappearance of the Prussian blue upon treatment with caustic soda (Laurie 1914, 55).

Three more yellows were developed from Vauquelin’s element. They were all sold under the name Lemon yellow and were introduced to the artists’ palette around 1830 (Paint and Painting (1982, 17). The most permanent of these was strontian yellow (SrCr04). Mixing solutions of strontian chloride to neutral potassium chromate (Gettens and Stout 1966,159) made it. Barium yellow (BaCrO4) was made much the same way as
yellow except barium chloride replaces the strontian. The third was
zinc yellow (3ZcCrO4.K2Cr207), a double salt solution with potassium chromate (Wehlte 1982, 87).

Strontian yellow was a cool, light yellow but richer in tone than barium yellow (Doerner 1934, 64). All three were
semi-transparent; strontian yellow was the most opaque. They were used in both
oil and watercolor. Like all chrome colors, they tended to turn greenish in oil.
Zinc yellow was the only non-toxic chrome color. Field is said to have
introduced barium yellow in England as a less costly alternative to Platina
yellow that was made from platinum (Harley 1970, 95). Blockx preferred barium yellow also.
He found its permanence to be outstanding after thirty years
and that it had an additional advantage of being mixable with all other pigments
(Blockx 1910, 77).

Barium yellow is observed as lozenge-shaped extremely fine particles; less fine are the crystalline particles of strontian yellow (Gettens and Stout 1966, 159), distinguished chemically because it is the
only one which does not turn black in hydrochloric acid (Wehlte 1982, 87).

By 1885, an imitation strontian yellow was invented. It resembled the original but contained no strontium. It was said to have been more durable than the original (Field 1885, 126).

Two other green pigments also resulted from the development of chromium. Their excellent permanence and lack of toxicity could replace all other greens, both ancient and modern. A color maker in Paris,
Pannetier, first sold opaque oxide of chromium, as an artist’s pigment in
1838. Viridian or transparent oxide of chromium followed in 1859.

Oxide of chromium, opaque (Cr203) was made by heating potassium bichromate with boric acid or sulfur until its
water was lost and a powder was formed (Gettens and Stout 1966, 107). It was
prepared for both oil and watercolor but its extreme opacity made it a poor
watercolor. Its color tone was cool and dull (Field 1885, 136).

The transparent variety, viridian (Cr203.2H20) began its production in
the same way as the opaque variety but the hot powder was put into vats of cold
water until it acquired two water molecules. A bright, bluish green resulted
which had excellent tinting strength. Guignet of Paris patented the process for
manufacturing viridian in 1859 (Gettens and Stout 1966, 173).

Although viridian required much more oil to grind it as an oil paint (fifty to one hundred percent) compared to thirty percent in the opaque variety, both were good driers. Viridian, however, is
prone to cracking if one misuses this transparent pigment too thickly (Wehlte
1982, 125-128).

They are distinguished microscopically by their large particle sizes (Gettens and Stout 1966, 173). They differ in that viridian’s particles are slightly rounded and the opaque variety has coarse
particles. They are insoluble and unchanged in chemical tests (Laurie 1914, 55).

Viridian was known as Permanent green when sold as a mixed green with zinc or cadmium yellows in the second half of the nineteenth century (Doerner 1934, 84).

Vauquelin is sometimes also credited with the development of Iodine Scarlet (also known as Pure Scarlet). In about 1811 or 1812, iodine was discovered by a French manufacturer of saltpeter. In 1814, Sir
Humphrey Davy brought some iodine back home with him to England and published
proof that it was an element. Vauquelin published the preparation of Iodine
Scarlet and other iodine compounds in 1814 in Annales de Chimie XC. His
article "Des experiences sur l’iode" described a simple recipe
involving the grounding with a stone mortar iodine and mercury which quickly
united to form an intense red hue. More detailed instructions for its
preparation were published by Merimee in 1830. He also mentioned that in England the pigment is sometimes sold as scarlet lake (Harley 1970, 118).

Iodine scarlet (HgI2) was known to have great body and opacity and more brilliance than vermilion. It was,
however, a very fugitive color that could only be mixed on the palette with an
ivory knife as metal knives turned it black. Iodine scarlet could not be mixed
with other metallic pigments. Field said that "_certainly nothing can
approach it as a colour for scarlet geraniums; but its beauty is almost as
fleeting as the flowers" (Field 1885, 107-108).

Zinc has been known as a mineral since antiquity when it was melted with copper to form brass. It was also known then, as it is today, as a medicinal ointment. Sources differ on who first isolated
the element. Harley and Wehlte claim it was Henkel in 1421 who first produced
metallic zinc. Gettens and Stout maintain it was the German chemist, Margraaf in
1746. Historians agree, however, that in 1782, zinc oxide was suggested
as a white pigment. Guyton de Morveau at L’Academie
de Dijon, France, reported on white pigments and the raw materials which might
serve as white pigments, including zinc oxide in that year. He suggested zinc
oxide as a substitute for white lead. Although the pigment became very important
to nineteenth century painters, it never replaced the ancient lead White.

Metallic zinc had originally come from China and the East Indies. When zinc ore was found in Europe, large-scale
production of the extracted metallic zinc began. In 1794 and 1796 patents were
issued for the manufacture of zinc oxide to the English colormaker John Atkinson
of Harrington Near Liverpool (Harley 1970, 166).

The French method of manufacturing, known as the ‘indirect process’ used the zinc smoke derived from molten zinc, which was heated to 150°C and collected in a series of chambers. This early
form of zinc white was not accepted by artists because of its slow drying time
in oil and poor covering power (Gettens and Stout 1966, 177). In 1803, Julius
Caesar Ibbetson wrote <u>An Accidence or Gamut of Painting in Oil and
Watercolors, </u>London, and said, "White lead is the only white we have of
sufficient body to use in oil. White has been made from zinc, but it has not
sufficient substance." A zinc white watercolor was available at that time
which was made with liquid silver (Harley 1970,167).

Zinc white was accepted as a watercolor by
1834 but it was some years later before its difficulties in oil were overcome.
In 1834, Winsor and Newton, Limited, of London, introduced a particularly dense
form of zinc oxide which was sold as Chinese white. It was different from former
zinc white in that the zinc was heated at much higher temperatures than the late
eighteenth century variety (Paint and Painting [1982], 18). The name ‘Chinese
white’ is said to have come from the oriental porcelain that was very popular
in Europe in the eighteenth and nineteenth centuries (Pavey 1984, 30). George H.
Backhoffner of London disputed Winsor and Newton’s claim of their superior
white watercolor in his book Chemistry as Applied to the Fine Arts, London,
1837. Backhoffner recommended Flemish white as superior-white lead. Winsor
and Newton believed that although scientists would ignore Backhoffner, artists
would not use the Chinese white because Backhoffner lectured widely in the Art
Academies and his opinion would be well known to them. In 1837, Winsor and
Newton published a response to Backhoffner in Remarks on White Pigments used
by WaterColour Painters and distributed copies to the artists. They were
successful in convincing artists of the superiority of Chinese white because the
name is still synonymous today for all zinc white in watercolor (Harley 1970,
168).

By 1844, a better zinc white for oil was developed by LeClaire in Paris. He ground the zinc oxide (ZnO) with poppy oil that had been made fast drying by boiling it with pyrolusite (Mn02).
In 1845, he was producing the oil paint on a large scale (Harley 1970, 168). By
1850, zinc white was being manufactured throughout Europe.

Zinc white was still a slow drying white requiring twenty-three parts of oil to one hundred parts of pigment whereas lead white requires fifteen parts of oil. Zinc is essentially permanent in sunlight
although the yellowing in oil affects its brightness (Laurie 1926, 83). It had
advantages over white lead because it was not blackened by sulphur-bearing air
or other pigments containing sulphur, as lead is (Blockx 1910, 59-60). It is
non-toxic and more economical than white lead. Unlike lead white, it was prone
to become brittle and crack over time. The general consensus was that both
whites should be employed in oil painting because each had advantages over the
other. Mixtures of both were common.

Since zinc oxide is derived from smoke fumes, its particles are very fine and are difficult to observe except at very high magnification. It readily dissolves in alkaline solutions, acids and
ammonia without foaming (Gettens and Stout 1966, 177).

Stromeyer discovered metallic cadmium in 1817 but production of the cadmium pigments was delayed until about 1840 because of the scarcity of the metal (Harley 1970, 95). A natural mineral, green
ochite, is known in nature but was not used for pigments (Paint and Painting [1982],
18). Cadmium Sulfide (CdS) was prepared with an acid solution of cadmium salt
(either chloride or sulfate) which was heated with hydrogen sulfide gas until a
powder was formed. Hues ranging from a lemon yellow to a deep orange were made
in this way (Gettens and Stout 1966, 101-2). Cadmium red was not made until
about 1910 (Paint and Painting </u>[1982], 18).

The deeper varieties of cadmium yellow and orange were the most permanent (Laurie 1926, 88). The paler varieties were known to fade on exposure to sunlight (Laurie 1926, 88). All of the cadmiums were
brilliant and the deeper shades had the greatest tinting strength. Field claimed
that the best cadmiums were those produced without an excess of sulfur and that
the permanence of a carefullyy made cadmium was improved when mixed with lead
white using only an ivory knife (Field 1885, 123). They were used in both oil
and watercolor but could not be mixed with copper-based pigments (Doerner 1934,
65).

The particle sizes of the deeper cadmiums are about fifty times larger than the paler varieties (Gettens and Stout 1966, 102). They are transparent particles that appear in clusters, microscopically.
Cadmium pigments are dissolved in hydrochloric acid and nitric acids and are
unchanged by sodium sulfide (Laurie 1914,51).

Ultramarine blue, artificial is one of the best-documented pigments of the nineteenth century probably because its invention was requested of chemists and not the result of their independent
research. Ultramarine, genuine made from the semi-precious gem lapis lazuli was
so costly in the nineteenth century that artists infrequently used it. The hue
is a necessary component in a balanced palette of warm and cool colors; without
it a cool, deep blue is lacking.

The beginning of the development of ultramarine blue, artificial was known from Goethe. In about 1787, he observed the blue deposits on the walls of lime kilns near Palermo in Italy. He was aware
of the use of these glassy deposits as a substitute for lapis lazuli in
decorative applications. He did not, however, mention if it was suitable to
grind for a pigment (Plesters 1966, 76). The blue deposits were also taken from
the Saint Gobain glassworks by M. Tess&auml;ert who found them in a soda furnace
(Gettens and Stout 1966, 163). Tess&auml;ert was reportedly the first to suggest to
the Societé d’Encouragement pour L’Industrie Nationale that a method for
making a synthetic ultramarine should be investigated. He gave his blue samples
to Vauquelin. In 1814, Vauquelin published his findings that the blue masses
were similar in composition to the costly lapis lazuli in the Annales de
Chimie LXXXIX , "Note sur une couleur bleue artificiale analogue a l’outremer"
(Gettens and Stout 1966, 163). In 1824, the Societ&eacute;
d’Encouragement offered a prize of six thousand francs to anyone who could
produce a synthetic variety not to exceed three hundred francs per kilo. The
prize was not awarded for four years because all that was submitted to them were
imitations based on cobalt or Prussian blue without regard for the analysis of
the gem which was published in 1806 by Desormes
and Clement.


PAGE 4

On February 4, 1828, the prize was awarded to Jean Baptiste Guimet who submitted a process he had secretly developed in 1826. Guimet’s ultramarine was sold for four hundred francs per pound. In Paris a short while later, lapis lazuli cost between three to five thousand francs per pound at that time. Independent of Guimet, Christian Gottlob Gmelin, a professor of chemistry at the University of Tubingen discovered a slightly different method based on the analytical results of Désormes and Clément which he published only one month after Guimet. Gmelin claimed that he beat Guimet and a rivalry ensued for years but France upheld Guimet’s right to the prize. By about 1830, Guimet’s ultramarine was being produced at a factory that he opened in Fleurieu-sur-Sâone, France. F. A. Köttig at the Meissen porcelain works in Germany was producing Gmelin’s method by 1830 as well (Plesters 1966, 76).
Artificial ultramarine, also known as French ultramarine is Na8-10A16Si6024S2-4. It was made by heating, in a closed-fire clay furnace, a finely ground mixture of China clay, soda ash, coal or wood, charcoal, silica and sulfur. The mixture was maintained at red heat for one hour and then allowed to cool. It was then washed to remove excess sodium sulfate, dried and ground until the proper degree of fineness was obtained (Harley 1970, 55). It could be ground to larger particles to obtain a deeper color or finer for a pigment with better tinting strength. This process, known as the indirect process, was also used to produce a green color (Plester 1966, 77). Heating the blue pigment with sal ammoniac or any hydrochloric acid, respectively (Gettens and Stout 1966, 167) made violet and red varieties that were developed in Germany between 1870 and 1880. The red and violet varieties, however, had poor tinting strength (Plesters 1966, 76).
French ultramarine blue was non-toxic and as permanent as the natural variety but darker and less azure. It was prepared in both oil and watercolor. In oil it dried well despite a high percentage of oil needed for grinding and in watercolor produced clean washes (Field 1885, 145).
The artificial variety is distinguished microscopically from the natural by its more rounded finer particles (Field 1885, 164). They react the same chemically by being bleached in acetic acid (Laurie 1914, 55).
Madder red was another important synthetic pigment produced in the early years of the nineteenth century. This time, cost was not a factor in its development, but the need for a more permanent version of its ancient precursor. Dyes derived from the extract of the madder plant’s root (rubia) were in use by the ancient Egyptians for coloring textiles (Plesters 1966, 28). Bleached areas of natural madder can frequently be seen on fifteenth and sixteenth century paintings (Wehlte 1982, 92).
In the early nineteenth century, the natural madder dyestuff was developed as a pigment. Later in the century, a synthetic version was produced. In the mid-eighteenth century, most natural madder (Rubia tinctorum) was grown in Holland. England was importing all of the madder used in their textile production from Holland at a cost of three hundred thousand pounds per year (Laurie 1966, 28).
In 1804, the Societé d’Encouragement des Artes awarded a medal to Sir Henry Englefield of England for a method of the preparation of madder lakes, dyestuffs that are attached to an inert substrate. This is a necessary process in order to grind such a pigment in oil. George Field had developed a press for extracting the dye that would filter and powder it. In an 1806 notebook, he noted his anger upon learning about the award because he had already been producing madder lake. He recorded his madder lake preparation in a notebook dated November 1808. One-half pound of alum (the inert substrate) was added to one-half pint of hot water and heated. He then added three-quarters of a pound of washed madder and heated the mixture for almost one hour. He strained the mixture, dried it on heat and let it set until it crystallized. He noted that it was "beautifully purple" (Richter and Härlin 1974, 81).
The madder lakes, which were prepared in a variety of shades from brownish to purplish to bluish reds were known to have superior permanence than the unlaked madders. It was a good glazing color that spread well in oil and was also prepared as a watercolor (Richter and Härlin 1974, 80).
In 1826, the French chemists Colin and Robiquet first isolated the coloring principle from the madder plant and published their findings in Annales de Chimie XXXIV, "Recherches sur la matière colorante de la garance" in 1827. In the madder root, there are two coloring agents. One is the permanent alizarin and the other rapidly fading purpurin. It was the alizarin component (C14H804) that was made synthetically by the German chemists C. Graebe and C. Lieberman in 1868 and patented in England the same year (Gettens and Stout 1966, 91). The synthesis caused the rapid decline and almost total disappearance of the madder-growing industry. As in the natural madder lake aluminum hydrate (alum) is used as a substrate for the synthetic variety, most commonly known as alizarin crimson.
Although alizarin crimson had superior permanence over the madder lake because of the absence of purpurin, both madder lakes were used in oil and watercolor painting. Some painters complained that the synthetic variety was less saturated and brilliant than madder (Gettens and Stout 1966, 91). Both varieties were non-toxic, slow drying in oil and the deeper shades were more lightfast than the lighter ones. Both were compatible with all other pigments (Wehlte 1982, 111-112).
The base on which both varieties are substrated is indistinguishable under the microscope. Nor can the natural and artificial be identified even at high magnification. They are both soluble in hydrochloric acid (Gettens and Stout 1966, 91).
Crimson, a natural dyestuff made from the bodies of the insect, cochineal was also prepared on a lake base. Although known since at least the sixteenth century, Crimson lake was a more permanent version developed in the nineteenth century.
William Henry Perkin (1838-1907), while a student at the Royal College of Chemistry in England, founded the organic color industry of coal tar dyes. He was researching the synthesis of quinine when he accidentally came upon an extract of purplish hue when oxidizing impure aniline with potassium bichromate (Pavey 1984, 39). The term aniline dyes are applied to all chemicals derived from the distillation of coal tars. Coal tar, a by-product of coke and gas manufacturing, is a compound consisting mainly of carbon, hydrogen, nitrogen and sometimes sulfur (C27H25N4 (SO4) ½).
Since Perkin’s discovery, many thousands of coal tar dyes have been prepared. Some are used in the preparation of lake pigments such as crimson. They were hastily introduced into painting because of their richness and brilliance but serious damage resulted as many of them are quite fugitive (Gettens and Stout 1966, 108). Mauve, a reddish violet, was one of the first coal tar pigments which was prepared as a lake by substration on clay, tannin and mineral colors. It required a large proportion of filler to gain any body. Since coal tar pigments tended to be transparent, they were mainly employed in watercolor (Doerner 1934, 90). In the second half of the nineteenth century, a standard for the permanence of artists’ pigments was established that required coal tar colors to be at least as permanent as alizarin madder lake (Gettens and Stout 1966, 108).
Magenta, a brilliant, red-purple aniline dye was produced in 1858 by Natanson. It was named after the site of a battle in Italy that took place the same year (Pavey 1984, 39).
C. Himly of Kiel invented antimony vermilion or orange antimony sulfide in 1842. The high cost of cadmiums and vermilions may have prompted its manufacture from antimony sulfide (Sb2S3). Antimony vermilion ranged in hue from orange to deep red. Its use was known in the adulteration of real mercury vermilion, but it was rarely employed by artists due to its fugitive nature. Its main application was as a pigment in the rubber industry (Gettens and Stout 1966, 94). Murdock Scotland patented it in 1847 (Mayer 1970, 40).
The high cost of cobalt violet prompted the development of the permanent pigment manganese violet. Manganese ammonium phosphate ( (NH4) Mn2 (P207)2) was first prepared by E. Leykauf in Nurnberg in 1868 by melting together manganese dioxide and ammonium phosphate. The resulting violet mass was added to phosphoric acid and heated until the correct color was obtained. Although it was a truer violet hue than cobalt violet, dark (which is redder and brighter) it was not used very much by artists because of its dull tone and poor hiding power (Doerner 1934, 81).
The nineteenth century painter had no real gap in his palette with regard to browns, blacks and earth colors. Pigments such as the umbers and siennas were in use since antiquity and their stability (with few exceptions) was well known. However, by the nineteenth century, cracks had developed in the paintings of the seventeenth and eighteenth centuries where bitumen (also known as asphaltum) was used as an underpainting color. Rembrandt and other seventeenth century painters as a final glaze color also used it and its cracking was evident (Wehlte 1982, 119). One of the more popular browns developed in the nineteenth century was Egyptian Mummy. Although it is unknown who first thought of grinding it into a fine powder and, without disguising its name, using it as a pigment; it was known as an internally taken drug in sixteenth and seventeenth century Europe. It was not uncommon for a drug to be tried out as a pigment and its introduction into the artists’ palette is believed to be in the early nineteenth century (Harley 1970, 142).
The raw material came from the large communal tombs near the Pyramids in Egypt. The ancient Egyptians used large quantities of liquid asphaltum to embalm the bodies of humans as well as sacred animals along with aromatic herbs and resins. Asphaltum is a complex natural mixture of hydrocarbons that are the residue of the natural evaporation of petroleum. When the bodies were excavated, they were found to be wrapped in bandages that were somewhat decayed. When Wehlte visited von Moeve’s color factory in Berlin, he obtained a sample of the raw material for the pigment that contained decayed bandages, thick arteries and hollow bones (Wehlte 1982, 120).
The first known recipe for the preparation of Egyptian Mummy as a pigment was in 1797. It was anonymously listed in A Compendium of Colours, and other Materials used in the Arts dependant on Design, published in London. The instructions for its preparation were:
The finest brown used by Mr. West [presumably the American painter, Benjamin West] in glazing is the flesh of mummy, the most fleshy are the best parts; ... it must be ground up with nut oil very fine, and may be mixed for glazing with ultramarine, lake, blue, or any other glazing colours; when it is used, a little drying oil must be mixed with the varnish, without which it will be longer in drying, which is the only defect it has, as it may be used in any part of a picture without fear of changing (Harley 1970, 142-143).
Until 1925, genuine Mummy was a common shade listed in the range of artists’ colors.
Sepia has been known since classical times as writing ink. It was available in stick form from which artists could prepare liquid ink with gum arabic. Its method of preparation was improved in the late eighteenth century and was prepared as a watercolor and oil pigment.
The exact chemical composition of sepia is unknown but it is a complex nitrogenous organic compound with a characteristically fishy odor (Gettens and Stout 1966, 155). It is derived from the secretion and glands of the cuttlefish (sepia officinalis), mainly found in the Adriatic Sea. When the cuttlefish is threatened or attacked, it releases a dark brown liquid as a disguise. Suspending them in the air-dried the ink bags (glands). Andrew Ure, writing in London in 1843 (A Dictionary of Arts, Manufacturers and Mines, p.1098) added that the ink sac must be removed and dried as soon as possible after the fish was caught because it putrefied quickly (Harley 1970, 145).
Due to the pale nature of the dye, Professor Seydelmann (1750-1829) of Dresden developed a method of achieving a more concentrated variety in the 1770s by extracting the dye with potassium hydroxide (Wehlte 1982, 118). The dried extract was first ground alone and then ground and boiled with an alkaline lye solution. It was then filtered and neutralized with hydrochloric acid. The resultant brown coloring matter was separated, washed in water and dried at a low temperature. The very fine grain powder was ground with gum arabic and made into cakes or prepared in tubes for watercolor (Harley 1970, 145).
A sepia cake from the colorman Rudolph Ackerman was found at a pharmacy near Darmstadt, Germany. It was stamped, as was the practice of colormen at the time, with " ’Printseller and colourman’ Rudolph Ackerman." His watercolors were well known and references to them can be found in many nineteenth century books on painting. In 1801, he published A Treatise on Ackerman’s Superfine Water Colours in London (Richter and Härlin 1974, 80). Sepia was also produced in Italy and known as Roman Sepia.
PAGE 5

In the last quarter of the eighteenth century, sepia drawings became very popular. Sepia virtually replaced bistre and Indian ink because of its richer tone. Sepia drawing was included in art schools and during Goethe’s time was used to record travel scenes, as snapshots are used today. The Romantics of the nineteenth century used sepia in sketches for paintings.
Sepia is fairly permanent to light but in thin washes it will fade upon exposure to sunlight. It appears microscopically as irregular, fairly coarse particles most of which are opaque, with some being a semi-transparent yellow mauve (Gettens and Stout 1966, 155).
Many varieties of blacks have also been known since antiquity such as charcoal, ivory and lamp blacks. The name carbon black is generally used as a generic name for those blacks that are made from the partial burning or carbonizing of natural gas, oil, wood, vegetables and other organic matter. In 1864, a process was developed in America for a black more suitable for watercolor. It was widely employed in 1884 (Mayer 1970, 46). The American process used natural gas as the raw material. The smoky flame resulting from the burning of natural gas was first directed to cool revolving metal drums. The black deposits were automatically removed from the sides of the drums with scrapers. The resultant powder was of a finer grain than other blacks allowing it to spread better in watercolor. It was a stable pigment, unaffected by light and air (Gettens and Stout 1966, 103).
Two of the later known manganese pigments were manganese black and brown. Field listed them as black oxide of manganese. Ralph Mayer mentioned that they were patented in England by Rowan in 1871 but not widely used (Mayer 1970, 58). Both he and Field indicate that they were extremely permanent and fast driers in oil (Field 1885, 88).
The last noteworthy pigment to be developed in the period 1780 to 1880 was synthetic Indigo. Indigo is a natural vegetable; whose coloring matter is indigotin (C16H10N202) from the plant indigofera tinctoria. The natural dyestuff was used in the Far East for coloring cloth and has been known since the fifteenth century in painting (Wehlte 1982, 153).
To prepare the dye, freshly cut plants were soaked until soft, packed into vats and left to ferment. It was then pressed into cakes for use as a watercolor or dried and ground into a fine powder for use as an oil paint.
In 1880, A. Baeyer synthesized indigotin and by 1900 the synthetic all but replaced the natural variety. Indigo was known to fade in thin washes upon exposure to sunlight; with the synthetic version more resistant. Wehlte (1982, 153) and Laurie (1926, 96) do not support its use in the artists’ palette.
In addition to zinc white, two other whites were developed in the nineteenth century. Barium sulfate (BaSO4), also known as Barium white, Blanc Fixe, Permanent white and Constant white were made from the natural mineral and also artificially prepared. The natural mineral was known from the fifteenth to the seventeenth centuries as ceruse, an extender for white lead.
The artificial variety of barium sulfate was developed in the early nineteenth century and sold as Blanc Fixe. Both Blanc Fixe and natural barium sulphate were too transparent to be accepted as an oil white. Their transparency, however, made them good extenders for oil colors and as inert substrates for lake pigments (Harley 1970, 164). They were more widely accepted in watercolor for their transparency but had the defect of being lower in tone when wet than when dry (Field 1885, 103).
Lithopone was the last white developed in the nineteenth century. It was a combination of zinc sulfide and artificial barium sulphate (ZnS and BaSO4). In this case, artificial barium sulphate was not a filler but a necessary component in the manufacture of lithopone. In the early years of its manufacture (the mid-nineteenth century), lithopone was used as a ground for oil painting but was prone to darkening and cracking (Laurie 1926, 58). Although its defect was corrected by the end of the century, its early reputation kept artists from using it until about 1930 (Wehlte 1982, 75).
The artists’ colorman’s trade had much to do with the rapid introduction of new pigments into the artists’ palette. Before the mid-eighteenth century, virtually all artists’ materials were prepared in the studio, especially pigments, which were purchased in the form of a powder and ground into oil or gum by the artist or his/ her assistants. Colormen saw the increasing interest of amateurs in painting and set up production on a large scale. They were also supplying house painters with inexpensive color ground with a horse-drawn mill. Many artists, though, were justifiably suspicious that their pigments were being adulterated with filler and were reluctant to purchase ready-to-use colors.
Technological advances, however, continued unabated. In 1976 a mill was developed in France which was specifically designed to reduce the risk to colormen of the inhalation of toxic pigments, especially lead white. Above the grinding slab, an umbrella-shaped opening was connected to a long pipe that was attached to a furnace. The heat from the furnace drew loose particles and fumes up and away from the colorman. Although this process was effective in terms of safety, it was used strictly for hand grinding (Harley 1970, 58). A different mill was developed in 1804 for large-scale grinding. The Rawlinson’s hand-operated single-roll grinding mill was designed especially for the colormen and recommended by the Royal Society of Arts, London. It had no apparatus for drawing away dangerous substances but it was a fast, economical way to prepare pigments (Paint and Painting [1982], 39).
By the end of the nineteenth century, technology had greatly improved the materials of painters. The color range was substantially increased and the need for costly, impermanent pigments was largely eliminated. Painters varied considerably, however, in their use and exploitation of the new pigments.
Francisco Goya’s (1746-1828) bold moody paintings and dark palette were not created from the new pigments that were available in his lifetime. He did not avail himself of Scheele’s or Schweinfurt green, or cobalt green. He was, however, using cobalt blue that he could mix with Naples yellow or yellow ochre to make a rather dull green (Lane and Steinitz 1942, 23)
The neoclassicist Jacques Louis David (1748-1825) subordinated color to line and preferred a palette of primary colors. His strict academic methodology precluded the need for any pigments that the Old Masters did not have. With the exception of Prussian blue and Cassel earth, available since the early eighteenth century, David’s palette was composed primarily of red and yellow earths, blacks and greys. He was using vermilion and ultramarine blue, presumably the genuine variety. The Old Masters had used those pigments. At the end of David’s life, he added chrome yellow that would have balanced a primary range of hues (Birren 1965), 55).
Although the Romantic painter Theodore Géricault (1791-1824) was one of the first artists of the nineteenth century to revolt against the neoclassicism of David and the French Academy, his palette remained virtually the same as theirs (Birren 1965, 57). One can only speculate as to the potential he would have had with the new, brilliant pigments that were introduced shortly after his death in 1824.
During the 1830s and 1840s numerous advances occurred in painting technology and theory. Of the many books on color theory published in the first half of the nineteenth century, the most notable was Michel Eugene Chevreul’s work of 1839. George Field published his most complete book on colors for the artist in 1835. The invention of the collapsible metal tube in 1841 made this decade one that would change painting, forever.
George Field (1777? -1854) was both an author and color manufacturer in England. He had been testing pigments for lightfastness and durability for at least thirty years when his book Chromatography: A Treatise on Colours and Pigments for the use of Artists was published for the first time in 1835 (Taylor 1885).
Field was awarded a gold medal from the Royal Society of Arts in 1815 for his improvements in the method of filtering lake pigments. In 1818, he published Chromatics: An Essay on the Analoqy and Harmony of Colours that was a short book on ideas about primary, secondary and tertiary colors. Chromatography outlined the properties of pigments. It was written especially for artists and gave practical advice on the advantages and disadvantages of pigments, both old and new (Harley 1979, 75-84).
Michel Eugene Chevreul’s (1786-1889) book The Principles of Harmony and Contrast of Colors and their Application to the Arts, was well known to the Impressionists and Neo-Impressionists. The background that Chevreul had for writing his book was ideal. He was the son of a physician and by age twenty was working in a laboratory and writing scientific papers. In 1816, he was appointed the Professor of Chemistry and the director of the dye houses at the famous Gobelin tapestry house. The experience he gained from working at Gobelin led to his theories on optical color mixing which was central to the methodology of the Impressionists and Neo-Impressionists.
Before the early nineteenth century, paint that was not sold in powder form was sold packaged in a pig’s bladder. It was bound at the top with a cord to keep air out. This was particularly important for the marketing of lead colors as they were sold in the form of a partially ground paste, so as not to have inhalable dust in the air. The paint was released by puncturing the bladder with a tack and then closing the hole off with the tack. Their apparent convenience was overshadowed by the tendency of the bladders to leak. James Hams devised a metal syringe tube in 1822. A screw at one end was turned to force the paint out of a hole at the other end. A cap was put over the open end when not in use. They worked well but their high cost made them only usable by established professionals. Sir Thomas Lawrence used them and a set was given to Queen Victoria by her mother (Paint and Painting [1982, 57). When, in 1830 Mérimée wrote, "It is hardly probable that many English painters have adopted this expedient," he must have been referring to such a metal syringe tube (Birren 1965, 61). Winsor and Newton developed a less costly glass syringe tube in 1840 but it was not until 1841 that the American portrait painter, John G. Rand, invented the collapsible metal tube. Flattening metal and cutting it into the desired shape made it. The earliest tubes had a metal stopper to close off the open end. The earliest tubes were produced in England because of especially large tin deposits there.
The opposite styles of J.M.W. Turner (1775-1851) and Ingres (1780-1867) were paralleled by very different uses of the new pigments. Turner experimented with many new pigments, including some of the most fugitive ones. Ingres´ palette, however, was very much the same as David’s with the addition of cobalt blue and the new artificial ultramarine, very soon after its introduction. Mérimée, upon reporting in 1828 about the success of Guimet’s artificial variety, added that Ingres´ had used it on the drapery of a principle figure in the Apotheosis of Homer (Musée Charles X, the Louvre) of 1827 (Plesters 1966, 77).
A scientific examination of Turner’s paint box, preserved in the Tate Gallery Archives, was done in 1954. It revealed an eclectic variety of old and new, conventional and unconventional pigments (Hanson 1954, 162-173). Many historians have discussed Turner as an artist of great imagination and have also emphasized his total lack of concern for craftsmanship or the preservation of his finished works. Damage had occurred to his work in his own lifetime, particularly the problem of fading. Winsor and Newton recorded a conversation that Turner had with them. Winsor had noticed that Turner was frequently purchasing fugitive colors from him and one day he reproved Turner about this practice. Turner replied, "Your business is to make colours...mine is to use them" (Pavey 1984, 19). Turner’s palette included the new pigments chrome yellow and orange, cobalt blue, iodine scarlet, barium yellow, carbon black and Turner’s yellow. Many red lake colors were also found including one that was made in an unconventional way and was extremely fugitive (Hanson 1954, 162-173). Turner was apparently as unconcerned about the permanence of his palette as he was about the protection of his finished works.
The palette of Eugène Delacroix (1798-1863) was more complex than those already described. His romantic style was exemplified by a preponderance of warm colors, both old and new, in his palette. Delacroix was generally influenced by the style of Baroque art. Birren indicated that Delacroix’s color range was derived from Van Dyke as suggested to Delacroix by the Baroness de Meyendorf in 1845. The palette appropriately included all pigments that were available in the seventeenth century, with the exception of emerald green that was first known in 1614. By at least 1861, however, Delacroix had considerably added to Van Dyke’s palette. It was at this time that Delacroix’s style had shifted towards the romantic. He stressed color over line and drawing and was becoming an important color theorist. The new pigments he added included cobalt (probably blue), Egyptian brown (also known as Egyptian Mummy), cadmium (yellow), Indian yellow, light chrome yellow and zinc yellow (Birren 1965, 58). Delacroix was also known to mix, on his palette, at least twenty-five other colors. These he used on murals. Since cobalt violet was not introduced until shortly before his death, all the violet colors were mixed on his palette by combining, for example, cobalt blue, red lake and vermilion. Baudelaire said, "I have never seen a palette so meticulously prepared as Delacroix’s...like a carefully chosen bunch of flowers" (Lane and Steinitz 1942, 23). Unlike Turner, his choices of new pigments were mainly reserved for those regarded as permanent in his lifetime.
The revolutionary new style of Impressionism was disencumbered by nineteenth century developments in pigment technology. Bythe third quarter of the nineteenth century the break from the French Academy was complete, photography was changing the reasons for painting, the art of Japan provided new options and a whole new palette was now possible. The formulation of new theories about color could not have been fully explored without the kind of saturated hues that chemistry had provided. The alla prima method of painting would have had a palette of pastel shades. If the Impressionists had had to mix most of their colors with white to achieve hues with the body and opacity they needed, the movement would have been short lived. Without the development of tubes with which they could transport their palette into the landscape and make use of generously loaded brushstrokes, only the very most determined painter would have survived.
One can realize the influence of the new pigment technology by looking at the palettes of such painters as Pissarro, Signac and Bonnard. They eliminated blacks and browns (including related reddish and yellowish earth browns) and their palettes were almost totally comprised of new pigments. Their color ranges were small in relation to earlier nineteenth century painters with Signac employing the widest range of eleven hues. These painters and their contemporaries were influenced by the color theories of Chevreul. They used small brushstrokes of unmixed color placed close together that were optically blended when viewed at a distance. This method created the brilliant, shimmering effect of light that characterizes late nineteenth century art.
Camille Pissarro (1830-1903) once said to Cézanne, "Never paint except with the three primary colors and their derivatives." Pissarro followed such a practice. His typical palette was: (1) white lead, (2) chrome yellow, (3) vermilion, (4) rose madder, (5) ultramarine, artificial, (6) cobalt blue, and (7) cobalt violet (Lane and Steinitz 1942, 24). As colorists know, a warm and coo1 version of each primary color is advisable for mixing pure secondary colors. Pissarro made such choices with the exceptions of yellow and violet.
The Neo-Impressionist Paul Signac (1863-1935) had a palette that was more balanced because of the color theories that he followed. He and Seurat followed color theory strictly to build color relationships on their paintings. Signac chose cadmium yellow and cadmium yellow pale, the former being warmer than the latter. He did the same with reds choosing vermilion (warm) and rose madder (cool). His blues ranged from the very warm coeruleum to the relatively neutral cobalt blue to the cool ultramarine, artificial. He also added emerald green for a brilliant shade one would be unable to mix. He used both the new zinc white and the ancient white lead, each possessing advantages and disadvantages (Birren 1965, 66).
Pierre Bonnard’s (1867-1947) palette was just as individualistic as his work was in relation to those already described. He chose two greens, cobalt green and emerald green. Like Pissarro, he used both cobalt blue and ultramarine, artificial. Bonnard selected strontian yellow and cadmium yellow, the former being cooler than the latter. He only opted for one red that was carmine lake. This left a curious gap in the cooler red end of the spectrum. Perhaps to balance this gap, cobalt violet served its purpose as a very cool color. The nature of his white is unknown (Birren 1965, 67).
The palettes of these artists are serviceable to any painter working today, just as the palette of the Old Masters sufficed for the Neo-Classicist, The new brighter colors available to late nineteenth century artists aided in their break from classical art. Their palettes were in direct opposition to accepted styles of painting. The chiaroscuro that characterized classical art was replaced by the luminosity of bright sunlight. Thus is the importance of nineteenth century pigment technology as it helped the revolution of Impressionism and all that came after.
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