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Hugo Mller1,
Wolfgang Mller2, Manfred Wehner3,Heike Liewald4 Print this page
1formerlyH. Schmincke & Co., GmbH & Co. KG, Feinste SEARCH THIS TITLE
Knstlerfarben, Erkrath, Germany
2H. Schmincke & Co., GmbH & Co. KG, Feinste Knstlerfarben,
Erkrath, Germany Advanced Product Search
3Gustav Grolman GmbH & Co. KG, Neuss, Germany
4Verband der Mineralfarbenindustrie e.V., Frankfurt/Main, Germany
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Copyright 2006 by Wiley-VCH Verlag GmbH & Co. KGaA. All rights
reserved.
DOI: 10.1002/14356007.a03_143.pub2
Article Online Posting Date: December 15, 2006

Abstract | Full Text: HTML

Abstract
The article contains sections titled:

1. Introduction
2. Organic Pigments
3. Inorganic Pigments
3.1. White Inorganic Pigments
3.2. Colored Inorganic Pigments
3.3. Black Pigments
3.4. Fillers
4. Dyes for Silk Painting
5. Binders
6. Quality Factors
7. Commercially Available Artists' Colors and Materials
7.1. Oil Colors
7.2. Acrylic Paints
7.3. Watercolor (Aquarell)
7.4. Pastels
7.5. Gouache and Distemper (Tempera)
7.6. Powdered Pigments
7.7. Silk Paints
7.8. Paints for Graphic Techniques
7.9. Other Artists' Materials

Artists'; colors represent just a small sector of the paint industry, the total invoiced sales in Europe were about 222.7 106
in 2004, the production of artists' colors in Germany amounted to about 4180 t with a value of 67.1 106 in 2004. Artists'
colors are mixtures of three major components: pigments, binders, and fillers.

Pigments determine the hue, hiding power, and tinting strength of artists' colors. Binders enable the pigments to adhere to
the substrate. Fillers can influence optical properties such as whiteness and hiding power, rheological behavior, mechanical
properties, and resistance to weathering and chemicals.

The commercially available artists' colors and materials are the following types: oil colors, acrylic paints, watercolors, pastels,
gouache and tempera, powdered pigments, silk paints, paints for graphic techniques, and others artists' materials such as
primers and varnishes.

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1. Introduction

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Artists' Colors : Ullmann's Encyclopedia of Industrial Chemistry : Wiley InterScience
Artists' colors represent just a small sector of the paint industry. In 2004 the production of artists' colors in Germany was
about 4180 t with a value of 67.1 106 and the total invoiced sales in Europe amounted to about 222.7 106 [1], [2].
Artists' colors are mixtures of three major components: pigments, binders, and fillers.

Pigments are defined as colored, black, white, or fluorescent particulate organic or inorganic solids which usually are
insoluble in, and essentially physically and chemically unaffected by, the vehicle or substrate in which they are incorporated.
They alter appearance by selective absorption and/or scattering of light. Pigments retain a crystal or particulate structure
throughout the coloration process [3], [4]. Pigments determine the hue, hiding power, and tinting strength of artists' colors.
Natural inorganic pigments have been known since prehistoric times. The principal pigments used were based mainly on iron
and manganese oxides, found in the soil as colored muds. Natural ocher was used in the Ice Age as a coloring material.
Around 2000 B.C., natural ocher was burnt, sometimes in mixtures with manganese ores, to produce red, violet, and black
pigments for pottery. Arsenic sulfide as the first clear yellow pigment, and ultramarine (lapis lazuli) and Egyptian blue cobalt
aluminum spinel were the first blue pigments. Terra verte and malachite were the first green pigments. The first modern
synthetic pigment was Prussian blue (1704), followed by the synthesis of cobalt blue (1777), Scheele's green, and chrome
yellow (1778) [5]. The synthetic materials provide the artist with colorants that are relatively pure and reproducible in color
and particle size.

A detailed description of the properties, production and uses of inorganic and organic pigments is given in Pigments,
Inorganic and Pigments, Organic.

Pigments and dyes are categorized according to their generic name and chemical constitution in the Colour Index [6].
Important pigment properties include tinting strength, light fastness, weather resistance, hiding power, transparency, shade,
dispersibility, and chroma ( Pigments, Inorganic).

In former times, whole egg, egg yolk, and egg white were used as binders. In the Middle Ages it was already known that egg
yolk act as emulsifier with oils or dissolved resins. Binders enable the pigments to adhere to the substrate.

Fillers can influence optical properties such as whiteness and hiding power (e.g., synthetic silicates and blanc fixe as partial
replacements for white pigments), rheological behavior, mechanical properties, and resistance to weathering and chemicals.

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2. Organic Pigments
Table 1 lists organic pigments used for artists' colors.

Table 1. Organic pigments used for artists' colors

C.I. name C.I. number Pigment type Lightfastness a

Pigment Yellow 1 11680 monoazo **

Pigment Yellow 3 11710 monoazo **
Pigment Yellow 65 11740 monoazo **
Pigment Yellow 74 11741 monoazo **
Pigment Yellow 83 21108 disazo **
Pigment Yellow 97 11767 monoazo **
Pigment Yellow 108 68420 anthrapyrimidine **
Pigment Yellow 150 12764 azo Ni-complex ***
Pigment Yellow 151 13980 benzimidazolone ***
Pigment Yellow 155 bisacetoacetarylide ***
Pigment Orange 5 12075 -naphthol **
Pigment Orange 34 21115 disazo *
Pigment Orange 43 71105 perinone ***
Pigment Orange 62 11775 benzimidazolone ***
Pigment Orange 67 12915 pyrazoloquinazolone ***
Pigment Orange 73 diketopyrrolopyrrole ***
Pigment Red 9 12460 naphthol AS **
Pigment Red 83 : 1 58000 : 1 alizarin crimson *
Pigment Red 112 12370 naphthol AS **
Pigment Red 122 73915 quinacridone ***
Pigment Red 144 20735 disazo condensation **
Pigment Red 170 12475 naphthol AS **
Pigment Red 176 12515 benzimidazolone **
Pigment Red 179 71130 perylene ***
Pigment Red 188 12467 naphthol AS **
Pigment Red 202 quinacridone **

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Pigment Red 253 12375 naphthol AS **
Pigment Red 254 56110 diketopyrrolopyrrole ***
Pigment Brown 25 12510 benzimidazolone ***
Pigment Brown 41 disazo condensation ***
Pigment Violet 19 73900 quinacridone ***
Pigment Violet 23 51319 dioxazine ***
Pigment Violet 29 71129 perylene **
Pigment Blue 15 : 3 74160 copper phthalocyanine ***
Pigment Blue 16 74100 phthalocyanine ***
Pigment Blue 60 69800 indanthrone ***
Pigment Green 7 74260 copper phthalocyanine ***
Pigment Green 36 74265 copper phthalocyanine ***

a see Table 5.

Azo pigments ( Pigments, Organic Azo Pigments) cover mainly the range of yellow, orange, red, violet, and brown
shades.

Examples for monoazo pigments are C.I. Pigment Yellow 1, Pigment Orange 5, Pigment Red 112, Pigment Red 176, and
disazo pigments include C.I. Pigment Yellow 83, Pigment Orange 34, and Pigment Red 144 (Table 1).

Polycyclic pigments used in artists' colors are:

Phthalocyanine pigments (e.g., Pigment Blue 15 : 3, Pigment Green 36)

Quinacridone pigments (e.g., Pigment Red 122, Pigment Violet 19)
Perylene and perinone pigments (e.g., Pigment Violet 29, Pigment Orange 43)
Isoindolinone and isoindoline pigments (e.g., Pigment Yellow 110)
Anthrapyrimidine pigments (e.g., Pigment Yellow 108) Diketopyrrolopyrrole pigments (e.g., Pigment Red 254).

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3. Inorganic Pigments
All inorganic pigments contain heavy metal constituents with the exception of titanium dioxide, carbon black, and ultramarine
pigments.

Table 2 lists inorganic pigments used for artists' colors.

Table 2. Inorganic pigments used for artists' colors a

C.I. name C.I. Common name Composition

number

Pigment White 1 77597 lead white 2PbCO3 Pb(OH)2

Pigment White 4 77947 zinc white ZnO
Pigment White 6 77811 rutile TiO2
Pigment White 18 77220 chalk CaCO3
Pigment White 19 77002 clay Al2O3 SiO2
Pigment White 22 77120 blanc fixe BaSO4
Pigment White 24 77002 alumina hydrate Al(OH)3
Pigment Yellow 35 77205 cadmium zinc sulfide (Cd,Zn)S
Pigment Yellow 42 77492 synthetic hydrated iron oxide FeOOH
Pigment Yellow 53 77788 nickel antimony titanium yellow (Ti,Ni,Sb)O2
(rutile)
Pigment Yellow - bismuth vanadate/molybdate 4BiVO4 3Bi2MoO6
184
Pigment Orange 77202 cadmium sulfide/selenide Cd(S,Se)
20
Pigment Red 101 77491 synthetic oxide Fe2O3
Pigment Red 108 77202 cadmium sulfide/selenide Cd(S,Se)
Pigment Brown 7 77491 sienna/umber Fe2O3

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Pigment Brown 24 77310 chromium antimony titanium (rutile) (Ti,Cr,Sb)O2
Pigment Brown 33 77503 zinc iron chromite brown (spinel) (Zn,Fe)(Fe,Cr)2O4
Pigment Violet 14 77360 cobalt violet phosphate CO3(PO4)2
Pigment Violet 15 77007 ultramarine red/violet Na,Si,Al,S
Pigment Violet 16 77742 manganese violet (NH4)Mn(P2O7)
Pigment Blue 27 77510 Prussian blue NH4[Fe(II)Fe(III)(CN)6] H
2O
Pigment Blue 28 77346 cobalt blue (spinel) CoAl2O4
Pigment Blue 29 77007 ultramarine blue Na,Si,Al,S
Pigment Blue 33 77112 manganese blue BaMnO4/BaSO4
Pigment Blue 35 77368 cerulean blue Co2SnO4
Pigment Blue 36 77343 cobalt chromite blue (spinel) Co(Al,Cr)2O4
Pigment Green 17 77288 chrome oxide green Cr2O3
Pigment Green 18 77289 viridian Cr2O3 2H2O
Pigment Green 19 77335 cobalt nickel zinc titanite green (Co,Ni,Zn)2TiO4
Pigment Green 23 77009 green earth iron(II) silicate with clay
Pigment Green 26 77344 cobalt chromite green (spinel) CoCr2O4
Pigment Green 50 77377 cobalt titanate green (spinel) Co2TiO4
Pigment Black 7 77266 carbon black almost pure C
Pigment Black 9 77267 bone black Ca3(PO4)2/C
Pigment Black 11 77499 black iron oxide Fe3O4

a All pigments have *** lightfastness (see Table 5).

3.1. White Inorganic Pigments

The largest group of the inorganic pigments are the white pigments, and they are among the most important in the artists'
palette. The four major white pigments in use today are titanium dioxide (TiO2, C.I. Pigment White 6), zinc white (ZnO, C.I.
Pigment White 4), blanc fixe (BaSO4, C.I. Pigment White 22), and white lead [Pb(OH)2 2 PbCO3, C.I. Pigment White 1].

White lead dates back to the early Greeks and was, until recently, the principal white oil-colors pigment because of its almost
ideal properties when mixed with oil. White lead may discolor on exposure to hydrogen sulfide. Nowadays, especially
because of the toxicity, the use of lead white is limited to restoration only.

Titanium dioxide ( Pigments, Inorganic Titanium Dioxide) occurs in nature in the modifications rutile, anatase, and
brookite. Rutile and anatase are produced industrially as the most important pigments in terms of quantity [7]. Titanium
dioxide (C.I. Pigment White 6) is of outstanding importance as a white pigment because of its scattering properties, its
chemical stability, its biological inertness, and its lack of toxicity. The pigment is frequently coated with colorless organic or
inorganic compounds of low solubility to improve its weather resistance, lightfastness, and dispersibility.

Zinc white is a fine white powder, which is amphoteric; it reacts with organic and inorganic acids, and also dissolves in alkalis
to form zincates [8]. Acute toxicity: rat, oral, LD50 > 15 000 mg/kg [9].

Barium sulfate (blanc fixe) is of lower hiding power than white lead, but has resistance to hydrogen sulfide [10]. In artists'
colors barium sulfate is often used to adjust the consistency of the liquid paint.

3.2. Colored Inorganic Pigments

Natural Earth Pigments. Today natural earth pigments used as artists' pigments are green earth (ferrous silicate with clay,
C.I. Pigment Green 23) and natural iron oxides. Naturally occurring iron oxides and iron hydroxides have been used as
pigments since prehistoric times. They were also used as colorants by the Egyptians, Greeks, and ancient Romans. Of the
natural iron oxide pigments, hematite ( -Fe2O3) attained economic importance as a red pigment, goethite ( -FeOOH) as a
yellow pigment (C.I. Pigment Yellow 43), and the umbers and siennas as brown pigments (C.I. Pigment Brown 7). Their poor
tinting strength and less saturated color shade are due to their low purity and broader particle size distributions compared to
synthetic pigments. Frequently clays or silica are present in natural earth pigments.

Metal Oxides. Synthetic iron oxide pigments are by far the most important group of colored pigments. They include -
FeOOH (iron oxide yellow, C.I. Pigment Yellow 42), -Fe2O3 (iron oxide red, C.I. Pigment Red 101), and Fe3O4 (iron oxide
black, C.I. Pigment Black 11). Synthetic iron oxides are produced under controlled conditions by a number of manufacturing
processes. They are chemically purer and, because of their higher iron content, exhibit greater brightness than naturally
occurring oxides. Depending on their crystalline structure and other physical parameters, iron oxide pigments range in color
from various shades of red through ocher to black.

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Chromium(III) oxide, which forms the basis of chromium oxide pigments, crystallizes in a corundum lattice [11]. Chromium
oxide green pigments (Cr2O3, C.I. Pigment Green 17) contain only trivalent chrome. Acute toxicity: rat, oral, LD50 > 10 000
mg/kg [9]. Chromium oxide pigments yield a fairly dark olive-green shade. They are largely inert chemically and therefore
possess good resistance properties.

Complex Inorganic Color (CIC) Pigments. The term complex inorganic color pigment refers to the fact that such pigments
are a homogenous chemical phase and replaces the formerly used term mixed-phase metal oxide pigment, which gave the
false impression that they are mixtures.

Nickel antimony titanium yellow (Ti,Ni,Sb)O2 (C.I. Pigment Yellow 53, acute toxicity: rat, oral, LD50 > 5000 mg/kg [9]) and
chromium antimony titanium yellow (Ti,Cr,Sb)O2 (C.I. Pigment Brown 24, acute toxicity: rat, oral, LD50 > 5000 mg/kg [9]) are
rutile pigments. The rutile lattice of titanium dioxide absorbs nickel oxide or chromium(III) oxide as coloring components and
antimony(V) oxide to maintain an average cation valency of four.

The cobalt blue pigments are pigments with a spinel structure obtained by partial or complete replacement of metal ions of
the MgAl2O4 spinel by cobalt and chromium (e.g., CoAl2O4, C.I. Pigment Blue 28, acute toxicity: rat, oral, LD50 > 10 000
mg/kg [9]). Incorporation of cobalt and nickel in the inverse titanium spinels MgO2TiO4 and Zn2TiO4 produces cobalt green
pigments (e.g., Co2TiO4, C.I. Pigment Green 50, acute toxicity: rat, oral, LD50 > 10 000 mg/kg [9]).

All these pigments are chemically and thermally very stable and have outstanding lightfastness and resistance to
temperature, chemicals and weathering.

Cadmium Pigments. All cadmium pigments are based on cadmium sulfide (CdS, C.I. Pigment Yellow 37) and exist in a
highly stable hexagonal crystal form. Inclusion of zinc yields greenish yellow pigments [(Cd, Zn)S, C.I. Pigment Yellow 35]
and inclusion of selenium changes the shades to orange [Cd(S, Se), C.I. Pigment Orange 20], red [Cd(S, Se), C.I. Pigment
Red 108] and bordeaux. The terms cadmium yellow and cadmium red have become synonymous with brillant yellow and red
shades. Especially because of their excellent lightfastness, cadmium pigments are appreciated as artists' colors. Acute
toxicity: rat, oral, LD50 > 5000 mg/kg [9].

Ultramarine Pigments. Ultramarine blue is the synthetic equivalent of the naturally occurring semi-precious stone lapis
lazuli. The unique blue color is due to polysulfides within a sodium aluminum lattice, Na6Al6Si6O24(NaSn) (n = 2 4). Violet
(C.I. Pigment Violet 15) and pink (C.I. Pigment Red 259) ultramarines are derived from ultramarine blue (C.I. Pigment Blue
29) by further oxidation and ion exchange and have a very similar structure.

Ultramarines have excellent lightfastness and heat stability and, apart from their sensitivity to acid, good chemical resistance.

Manganese Violet Pigments. Manganese violet pigments are manganese ammonium pyrophosphates, and are red-shade,
bright, clean violets (NH4MnP2O7, C.I. Pigment Violet 16). Manganese violets have excellent lightfastness, good heat
stability and, apart from their sensitivity to alkalis, good chemical resistance.

The excellent lightfastness and purity of shade, both in mass tone and pale shades, makes manganese violet ideal for use in
artists' colors.

Iron Blue Pigments. The term iron blue pigment (C.I. Pigment Blue 27) has largely replaced a great number of older names
(e.g., Prussian blue, Berlin blue, Milori blue). These names usually denoted insoluble pigments based on microcrystalline Fe
(II)/Fe(III) cyano complexes with the formula MIFeIIFeIII(CN)6 H2O, where MI is potassium, ammonium, or sodium, of which
potassium is preferred because it produces excellent hues [11]. Acute toxicity: rat, oral, LD50 > 5000 mg/kg [9].

3.3. Black Pigments

Carbon black pigments (C.I. Pigment Blacks 6 and 7) are produced by thermal-oxidative dissociation of aromatic oils, e.g., by
the lamp black, furnace black, and gas black processes ( Carbon Production Processes). A further black pigment used
as an artists' color is bone black (C.I. Pigment Black 9), which essentially consists of carbon (10 20 %) and Ca3(PO4)2
(70 80 %) [12].

3.4. Fillers
Fillers are used to modify or influence certain physical properties of paints. Organic pigments with high tinting strength often
need a filler to adjust the consistency, hue, and hiding power.

Fillers of importance for artists' colors are natural barium sulfate (baryte), precipitated barium sulfate (blanc fixe), aluminum
hydroxide, calcite, precipitated calcium carbonate, and clays.

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4. Dyes for Silk Painting

Dyes as artists' colors are mainly used to color textiles, especially silk. Silk painting as a technique for producing exquisite
articles of clothing and works of art is a tradition that dates back thousands of years, particularly in Asia.

Table 3 gives a list of dyes that are used for silk painting.

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Table 3. Dyes for silk painting

C.I. C.I. number Chemical class Reactive System Lightfastness, 1/1

name a S.D. b

AY 61 azo 56
AO 95 disazo 45
ABr 413 azo metal complex 67
AB 83 42660 triphenylmethane 34
AG 81 anthraquinone 67
AB 222 azo (1 : 2 Cr complex) 7
BY 104 azo 67
RY 27 monoazo 6
RR 123 monoazo 4
RV 5 monoazo (metal vinylsulfonyl 67
complex)
RB 29 anthraquinone 56
RG 21 phthalocyanine 7
RB 113 azo (1 : 2 metal monochlorotriazinyl 6
complex)
DY 157 13965 monoazo 34
DB 199 sim. to phthalocyanine 7
74190
DE 1168 azo 5

a First letter: A = acid, B = basic, R = reactive, D = direct; second letter: B = blue, Bl = black, Br = brown, G = green,
O = orange, V = violet, Y = yellow.
b S.D. = standard depth (DIN 53235)

Reactive Dyes. Reactive dyes undergo true chemical bonding with the silk during fixing. Reactive dyes commonly used in
silk dyes either contain sulfatoethylsulfone (SES) groups or organo-halogen anchor groups (mono- and dichlorotriazine
groups, difluorchlorotriazine groups). With SES-type dyes, the reaction with the silk takes place with a vinylsulfone group that
is formed from the SES group during thermal or alkaline fixing and quickly reacts with the amino groups of the silk fiber.
Chloro-organic anchor groups react directly with the fiber, producing chloride as a reaction byproduct.

Acid Dyes. Acid dyes contain one or more anionic sulfonate and/or carboxylate groups and have high affinity towards wool
and silk. Fixing mainly results from ionic reactions which take place with the basic or cationized groups in the fibers. Acid
dyes can contain various classes of chromophores (azo, anthraquinone, triphenylmethane). Acid metal complex dyes are
used for darker shades or where particularly high wetfastness properties are required and for the manufacture of silk screen
dyes.

Direct Dyes. Direct (substantive) dyes are highly water soluble anionic dyes based on various classes of chromophores.
They are mainly used to color cellulose-based fibers. Direct dyes are fixed onto silk by ionic reaction and hydrogen bonding.

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5. Binders
For use as a paint or artists' colors pigments must be incorporated into a liquid or pastelike phase which allows it to adhere to
a surface.

Besides modern synthetic binders classical, natural binders are used for artists' colors. The thinning power and the
rheological characteristics of the paint are important for certain techniques like impasto or thin layer, and they depend on the
type of vehicle [13]. Binders which are transparent and colorless and impart high fastness to all physical properties are
preferred for artists' colors.

The binder incorporates the pigments and determines the physical and optical properties of the generated film. Physical
properties are film strength, elasticity, gloss, adhesion to the ground, and resistance to light, weather, alkali, acid, and heat.
Optical characteristics are transparency, hue, and refractive index, which determine the opacity of the pigment.

A paint generally consists of three components:

1. The film-former, a chemical that dries by polymerization, physically by evaporation of solvents, or by oxidation in air.
2. The solvent in which all other materials are dissolved or suspended if the binder is not liquid.
3. Small quantities of additives that perform special functions like accelerating or hindering functions, optimizing drying
processes, optimizing rheology and surface properties, and controlling the open time.

Combinations of film-formers are also used. For example, the type binder for tempera paints is a combination of oil and

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water-soluble gum arabic (or casein) emulsified with the aid of an emulsifying agent.

Table 4 lists types of binders which are used for artists' colors.

Table 4. Binders for artists' colors

Type of Film former Solvent Thinner Process

binder

Natural beeswax none physically

wax
turpentine turpentine evaporation
white spirit white spirit evaporation
Natural linseed, sunflower, oil oil of chemical reaction with oxygen
drying oil safflor oil turpentine,
white spirit
Natural dammar, mastic oil of oil of evaporation
resin turpentine, turpentine,
white spirit white spirit
shellac ethanol ethanol evaporation
Synthetic alkyd resins oil of oil of chemical reaction with oxygen
resin turpentine, turpentine,
white spirit white spirit
polymer dispersion water water polymerization
Natural animal-bone, skin, water water evaporation
glue and casein glue
plant gum arabic and water water evaporation
starch glue
Synthetic cellulose ether, water water evaporation
glue carboxymethyl
cellulose
Natural lime, gypsum water water chemical reaction with carbon
mineral dioxide (or physically with
water); no film is formed
Synthetic water glass water water chemical reaction with carbon
mineral dioxide to give silica; no film is
formed

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6. Quality Factors
The quality of artists' colors and the final fastness of the painting are determined jointly by the binders and pigments.

Pigments differ in their physicochemical and in their optical characteristics. Physically, pigments must withstand light,
weather, and heat. Chemically they must resist the action of alkali and acids. To prevent migration, the pigments must be
resistant to the binder, this mainly means insoluble in the binder.

Optical properties of pigments are shade, tinting strength, lightfastness, and hiding power. Pigments can fade or darken,
mainly under the action of UV radiation, which can break certain chemical bonds or change the molecular constitution. A
change in chemical structure means a change of absorption in the visible region of the spectrum and a subsequent loss of
tint or change of hue. However, if the pigment absorbs UV light without any change of molecule structure, decomposition of
the binder may be prevented [14], [15].

Three systems are used for defining lightfastness. The ASTM standard [16], defines five fastness classes, determined by
exposure to xenon lamps or sunlight and color matching. In the blue wool scale method (DIN 53952) a range of eight wool
strips are exposed to sunlight or a xenon lamp together with the paint, and after exposure the paint is evaluated according to
the change on the wool scale. Colormakers use a star system to indicate the lightfastness of paints to the artist [17].

Table 5 compares the three scales.

Table 5. Comparison of lightfastness scales

ASTM class (D4303/93a) Star scale Blue wool scale (DIN 53952)

I *** highest lightfastness 8 very excellent

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7 excellent
II ** very good lightfastness 7 excellent
6 very good
III * sufficient lightfastness 6 very good
5 good
IV o little lightfastness 4 quite good
3 moderate
V 2 little
1 very little

Opacity depends on the ability of a pigment to scatter light in a paint film. If the pigment does not scatter light, the layer is
transparent. If light is strongly scattered, the film is opaque [13].

The light-scattering power of a pigment depends on its particle size and its refractive index relative to that of the medium in
which it is dispersed.

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7. Commercially Available Artists' Colors and Materials

7.1. Oil Colors
Paints made from vegetable oils (drying oils) have been known since the Middle Ages. In the mid-1500s, oil painting on
canvas was the standard technique for artists' easel painting. Advantages of these paints include ease of manipulation due to
the long open time, the ability to correct the painting after a couple of days, and the wide range of effects that can be
produced (transparent to opaque in full range). Colors do not change to any great extent on drying, which takes place by
reaction with atmospheric oxygen [15]. Then, the film becomes insoluble in white spirit or turpentine. The drying oil
incorporates the pigment particles and forms a rigid and flexible film. The oil also acts as an adhesive, fixing the pigments on
the ground. The optical efficacy is shown by the brillancy and the color of the pigments.

The best consistency for oil colors is a smooth, short and buttery paste which does not flow of its own accord and is without
tacky, stringy, or long characteristics. The brush strokes must be visible in the applied paste.

The drying process of artists' oil colors is influenced by the type of oil and the pigment properties. The proportion of
unsaturated fatty acids determines the drying properties. The drying properties increase with increasing content of linoleic
and linolenic acids.

Properties of the dried oil color, which are also influenced by the pigment to some degree, include consistency, extent of
oxidation, flexibility and hardness, which finally result in durability and stability to the environment and physical or chemical
treatment.

Table 6 lists the most common drying oils for oil colors.

Table 6. Percentage fatty acid composition of drying/semi-drying oils used in artist's oil colors

Drying oil Palmitic/stearic acid Oleic acid Linoleic acid Linolenic acid

Linseed 9 22 17 52
Walnut 8 17 61 14
Soya 14 21 56 8
Safflower 10 13 77
Poppy seed 10 16 75
Sunflower 10 28 61

Dryers influence the drying times of paints by compensating for the varying effects of the pigments. One of the most common
dryer is cobalt naphthenate [17]. This dryer is a skin sensitizer, and the presence of more than 1 % of it in oil colors requires
health-warning labeling.

Presently, two main types of oil colors are available commercially: traditional colors with drying oils as binders, and resin oil
colors containing dammar, mastic or acrylic resin. Some brands contain beeswax as a stabilizer for increased shelf life, film-
forming properties, or consistency.

For further information on the composition of oil colors, see [18].

A new generation of water-miscible oil colors is now on the market. These oil colors can be diluted with water and are

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suitable for persons sensitive to solvents. Instead of normal linseed oil, modified oils are commonly used, together with
emulsifying agents.

7.2. Acrylic Paints

Artists' colors based on acrylic dispersions were first produced in the 1950s in the United States [20]. They are highly
expressive and favored by many contemporary artists. Acrylics are used for impasto and flowing techniques like aquarelle,
airbrush, fabric painting, mural painting, silkscreen painting, print making, sculpture, photo retouching, and hard-edge
painting. They can be applied to paper, paperboard, canvas, wood, murals, leather, and textiles, which are usually treated
with gesso, mediums, or additives. Acrylic paints are produced in various qualities and viscosities in dissolvers, roll mills, or
ball mills and available in tubes or jars.

The paints consist of pigments (see Tables 1 and 2), fillers, acrylic dispersions, wetting agents, defoamers, coalescence
additives, preservatives, and water [19]. For further specifications of acrylic paints, see [21], [22].

Acrylic dispersions are based on acrylic acid, methacrylic acid and their methyl, ethyl and butyl esters. The most frequently
used dispersions for artists' paints contain mainly ethyl and methyl acrylate resins. They can be diluted with water and dry
rapidly to a permanent water-insoluble film, which is soluble in certain organic solvents (e.g., dichloromethane).

During the drying process water evaporates and the dispersed acrylic particles coagulate.

This process depends on the minimum film forming temperature, a typical physical property of the resins. Drying
temperatures of acrylic paints should not be lower than 8 C and not exceed 15 30 C [20]. Another important physical
property for producers is the glass transition temperature. For mechanism of the coalescence process of acrylic dispersions,
see [21].

Acrylic films are durable, flexible, do not discolor, and are easily overpainted. They can be of any thickness and have no
tendency to crack. Like water colors, the appearance of the dry film differs from that of the freshly applied paint. Because of
the quick drying process all brushes and tools have to be cleaned immediately after use.

An environmental risk of dispersions is posed by their content of emulsifiers. They are classified as slightly water polluting.
Liquid paint has to be disposed of as hazardous waste. Preservatives are a human health risk if undiluted, but due to the
concentration of 0.2 0.3 % in normal use, no health labeling is required.

A special line of acrylic colors is airbrush paint, which is liquid, also based on water, containing either acrylic dispersions or
water-soluble acrylic resins and highly dispersed pigments.

7.3. Watercolor (Aquarelle)

Transparent watercolor painting is not associated with any particular period. KOLLER suggested that watercolor painting
started in the 1400s [23].

Watercolor is a translucent paint which utilizes the brilliant white of the paper for its whites and pale tints. This definition is not
absolutely correct, because the pigments and their typical characteristics influence the properties of the color. The pigments
are not normally transparent but are applied in such thinned-out consistency that their effects are nearly as brilliant as those
of the naturally transparent pigments. The ability of the paper to absorb and fix pigment particles in its interstices is equally
important as the ability of the binder to bind the color to the ground; thus, watercolor is more like a stain [14].

Pigments for watercolors require the highest lightfastness, because there is no other light-absorbing medium on the surface
of the paper. Pigments containing lead are not used for the production of watercolors.

Colormakers refer to the transparency and lightfastness of each shade in their product information sheets. For determination
and definition of lightfastness, see [24].

SCHINK [25] classified the watercolors as staining and nonstaining colors. Staining colors are pigments of high adhesive
power or of extremely fine grain size which stick to the paper or stain it strongly after application. Nonstaining colors can be
washed off with a moist brush, cloth, or other tools. These pigments have weak adhesive power and good mixing properties
with other pigments on the paper. Watercolors consist of finely dispersed pigments in a watery solution of gum arabic and/or
dextrin, wetting agents (e.g., oxgall), and fillers. Sugar, glycerol, glucose syrup or different types of nontoxic glycols are used
as softeners.

The combination of natural gum and softener determines the solubility of solid watercolors in pans. This system, especially
the binder and fillers, guarantees the free flow of the paint, good wetting properties, and a stable pigment dispersion at high
dilution [14]. Preservatives are added to prevent the growth of microorganisms.

The dispersing process is normally carried out in roll mills, which allow a high degree of dispersion of the pigment.

Solid watercolors in pans are manufactured by pouring the liquid mass into pans followed by drying or by extrusion of a high-
viscosity paste, which is cut to shape.

7.4. Pastels
Compared to other painting mediums, pastels allow very pure and simple paintings very similar to painting with pure
pigments on a rough ground. The pigments adhere solely by adhesion without a binder.

Pastels are made from a colored watery paste, which is kneaded and then molded into a crayon shape. Only a weak binding

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medium is used. To obtain a moldable paste, the pigments are ground together with clay or light spar and a solution of the
binder.

Pastels are defined as soft or hard. Commonly gum tragacanth, gum arabic, sugar, gelatin, casein, aqueous oat extracts, and
wax emulsions are used as binders.

Lead and cadmium pigments should not be used in pastel sticks due to the dust that can be generated during application and
to avoid skin contact when artists blend the colors with their fingers.

The range of a complete pastel series starts with pure colors, followed by lighter and darker shades. FLATTMANN [26] gives an
example of such a series of shades:

M: 80 % white added
K: 60 % white added
H: 40 % white added
F: 15 % white added
D: the pure color
C: 15 % black added
A: 40 % black added

The effect of pastel painting is achieved by diffusion of the light scattered from the surface. This results in an optical problem
on fixation of the painting. Fixation reduces the opacity and diffusion of the surface-scattered light and so the painting
becomes darker. The use of titanium white or zinc white in combination with the colored pigments, however, compensates for
this process and allows easier formulation of the paint [26].

Fixatives for pastels, as described in [14], are ca. 1 2 % solutions of a natural resin, like mastic, dammar, Venetian
turpentine, or shellac in highly volatile solvent such as diethyl ether, ethanol, or white spirit. Commercially available fixatives
are solutions of yellowing-resistant ketones or acrylic resin in alcohol for spray application. In some cases, aqueous fixatives
such as gelatin or casein can also be used.

7.5. Gouache and Distemper (Tempera)

Gouache and distemper are described together here because of their similar applications and compositions. The term
tempera (from the Italian temperare = mixing) refers to thin, watery colors based on egg white or gum arabic, as well as for
colors with egg yolk as binder [27]. Depending on the nature of the emulsion of aqueous binders and vegetable oils, tempera
varies from opaque to transparent. The use and formulation of tempera in the early 1900s is referred to in [28], [29].

Tempera colors are insoluble, but this does not mean that they are absolutely waterproof. This permits overpainting without
changing the underlying layers. Under completely dry conditions tempera colors are water-resistant. In contrast to oil
paintings, which may become yellow or darken in course of time, tempera paintings remain unchanged. Properly painted
tempera pictures are less likely to crack with age than oil paintings, but there are some other restrictions due to the
inflexibility of the film of a tempera painting [13].

Tempera binders consist of linseed, sunflower, poppy, or other vegetable oils and/or solutions of dammar, mastic, or Venice
turpentine emulsified in watery solutions of gum arabic, casein, or simply egg yolk or whole egg. Oil in water emulsions are
also used.

Casein/oil tempera emulsions tend to turn yellow quickly; this can be avoided by adding saponified wax or Venice turpentine
instead of oil [13]. Beeswax can also be used as a paste in white spirit (hydrophobic phase) or as emulsifying agent in
saponified form [30]. Typical additives in tempera paints are further spikenard, clove oil, nontoxic glycols, emulsifying agents
and preservatives. Glycerol and castor oil act as plasticizers. Tempera paints are produced in ball mills, dissolvers, or roll
mills.

Tempera paints are applied to paper, paperboard, canvas, and wood which has been pretreated with a primer. Tempera
painting is still often combined with oil painting, most like a preliminary coating (imprimatura) [14], [27]. The grounds are
based on chalk, marble, or light spar as well as pure glue or half-oil grounds [30]. Tempera painting can be with or without
varnish.

Gouache (from the Italian guazzo = puddle) paints consist of glue binder, pigment, opaque fillers, and water. They are
opaque watercolors with the same basic binding medium and mainly the same pigments as aquarelles. Opacity is obtained
by adding white pigments or calcium carbonate [31].

In the late 1700s in England, aquarelles was called watercolor and clear gouache was called body color [32]. In the 1700s
and 1800s gouache painting played an important role in European art, especially in Italy and France [33]. Gouache paint is
applied in thicker layers than aquarelles. The binding medium contains softeners, but the risk of cracking of the painting
cannot be avoided, neither with synthetic resins (polyvinyl compounds) nor with gum arabic and dextrin.

Finger paints for children are water-miscible and nonwaterproof-drying colors which can be easily removed from paper and
other grounds with water and tissues. Finger paints are subject to government regulations and must not contain toxic
substances. A positive list of applicable binders, fillers, organic solvents, detergents, and embittering agents is part of
European standards. Pigments and preservatives must be permitted for use in food or cosmetics. The migration of certain
elements (Sb, As, Ba, Cd, Cr, Pb, Hg, and Se) is also restricted [34].

7.6. Powdered Pigments

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The use of pure powdered pigments is one of the oldest methods of artwork. All pigments used in artists' colors are
commercially available and can be used with different binders for self-made artists' colors.

Powdered pigments are mainly used in mural painting (fresco) and encaustic painting. There are three different mural-
painting techniques [13]. The traditional fresco buon process involves painting on a wet, freshly prepared lime-plaster wall,
with pigments dispersed in water only. The pigment particles are cemented on the lime surface in the same manner as the
lime particles bond with each other and with sand. When the plaster dries, the calcium hydroxide reacts with atmospheric
carbon dioxide to form insoluble calcium carbonate. Therefore, only lime-resistant pigments can be used for this technique,
mainly inorganic pigments.

Fresco secco painting is performed on a finished, dried lime-plaster wall with pigments in an aqueous binding medium. The
wall is impregnated with limewater, and the pigments are dispersed in water and a solution of casein. Secco painting must be
applied in a thin layer, and the pigments must be resistant to lime.

The silicate technique eliminates the disadvantage of traditional fresco painting, that is, its sensitivity to atmospheric
pollutants such as sulfuric acid. Potassium water glass is used as the binder. Only alkali-resistant pigments and water glass
are used. Water glass reacts with the atmospheric carbon dioxide to give silica and calcium silicate, which form a water-
permeable layer. The technique was discovered by KEIM in Munich, and Keim's silicate paint is still available today.

In the encaustic technique, the powdered pigments are mixed with beeswax and a small amount of dammar and melted to a
pasty waxy paint. This is applied to canvas with special heated tools or to plaster-walls and results in a painting of high tinting
strength and high fastness to humidity and air pollution.

7.7. Silk Paints

Paints Fixed by Ironing. Once the paint has dried, it is fixed to the silk with a hot iron at ca. 150 C. The main advantage of
these widely used iron-on paints is the simple method of fixing, which can be carried out at home, and the higher
lightfastness of the pigments used in this type of silk paints. The disadvantages are limited flow behavior, poor solubility, and
a somewhat stiffer texture of the silk afterwards.

Commercial iron-on paints consist mainly of aqueous pigment dispersions finished with dispersants and binders based on
polyacrylics or polyurethane.

Dyes Fixed by Steam. After drying, these dyes are fixed in special steaming equipment. Those involved in silk screening as
a hobby without access to such equipment can use a domestic steam pressure cooker as an alternative.

The main disadvantage associated with steaming lies in the method of fixing itself. The advantages of steam-fixed dyes are
very good flow behavior, good solubility, high brilliance, good fastness, and the very soft texture of the painted silk. Silk dyes
for steam fixing mainly consist of aqueous solutions of reactive or acid dye.

7.8. Paints for Graphic Techniques

Less common in the field of artistic techniques but nevertheless of importance are printed graphics.

Copperplate engraving is rarely used today, but wood- and linocut, etching, and lithography are still employed. For most of
these applications the paint is based on oleic binders, and only for linocut is an aqueous paint used. Linoleum does not
permit very delicate cutting, and it is characterized by blocky or posterlike forms. The technique has a certain popularity
among artists and in schools for the production of more casual work. Many artists of the 1900s like Matisse, Picasso,
Vlaminck and Rholfs preferred it to the more gnarled woodcut. Waterbased linocut paints are preferred for this application.
The use of commercial printing inks is not recommended [13]. These waterbased paints are similar in composition to
aquarelle and gouache paints, and certain properties are intermediate between the two, but the drying time of this type of
paint is considerable longer than that of aquarelle or gouache. It contains organic and inorganic pigments, gum arabic, fillers,
wetting agents, preservatives, glycerol, and nontoxic glycols. The characteristic effect of the colors is mainly semiopaque or
semitransparent.

Lithography ( Imaging Technology Lithography (Planographic Printing, Offset)) requires various artists' materials: gum
arabic, oil of turpentine, shellac, asphalt, rosin, talc, and others. Drawing materials are crayons, watercolor crayons,
waxchalk, chalk, and India ink. India inks contain shellac (solved with borax in water), carbon black, and water. Others
additionally contain beeswax, paraffin, or soap [35].

The printing ink was based on boiled linseed oil, linseed stand oil, and/or alkyd resins. Formerly artists produced the paint
themselves from pigment and linseed oil. Today, offset printing oil is generally used.

7.9. Other Artists' Materials

Primers are used to seal porous surfaces before applying colors. Priming provides a smooth surface, which ensures that the
subsequent paint layers adhere firmly. Primers are based on alkyd resins, acrylic emulsions, or linseed oil. They are
pigmented with titanium dioxide or chalk. In oil painting, canvas, hardboard, bare wood, and other grounds are glue-sized
before the primer is applied.

Solvents are used to dilute colors and clean up tools and materials. Solvents normally evaporate completely after application.
The most widely used are white spirit, freshly distilled oil of turpentine, petroleum distillates, as well as brush cleaners and
paint removers created as different mixtures by paint makers.

Mediums are used to improve the physical properties and behavior of a color. They are essential for certain techniques and
are mixed in certain proportions with the paint. Mediums contain the same binder as the paint system or a compatible binder:

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alkyd resins, dammar, acrylic resins or ketone resins for oil colors; acrylic emulsions for acrylic paints; gum arabic, starch,
dextrin, and others for watercolors and gouaches. Some additionally contain thickening agents or other additives.

Varnishes provide a clear, transparent coat which gives substantial protection against environmental influence, but especially
against dirt. The optical properties strongly influence the final appearance of a picture. Modern synthetic varnishes do not
produce the same amount of gloss and color saturation as traditional varnishes. Molecular mass and refractive index are
factors determining the optical properties of varnishes [36]. Changes in solubility, brittleness, crosslinking, and others result
from unavoidable ageing. Resins for varnishes are mastic, dammar, acrylic, and ketone resins, and in some cases poly(vinyl
acetate) and low molecular mass hydrocarbon resins. They are dissolved in white spirit, oil of turpentine, or ethanol.

Modern commercial varnishes contain UV-absorbing substances.

Retouching varnish can be applied after drying of oil paintings to give a temporary protection, but mainly for making a uniform
surface between several layers of oil paint. After 10 or 12 months a normal picture or final varnish can be used to give the
intended final protection. Beeswax or synthetic waxes and inorganic matting agents are added to varnishes for matte effects.

Fixatives are dilute solutions of acrylic and ketone resins in white spirit or of shellac in ethanol for fixation of drawings made
with pencil, charcoal, chalk, pastel, and aquarell and gouache paintings.

Canvas is a flexible support woven from cotton, linen, or polyester yarn. The durability and stability of canvas depend on the
type of yarn and the compactness and grain (texture) of the fabric. Normal canvas is already treated with an acrylic primer,
but it can also be prepared in the traditional way with aqueous glue (size) followed by a stiff gesso which consists of chalk or
light spar, linseed oil, and some aqueous glue.

Good quality watercolor paper is manufactured from cotton fibers, which impart strength and durability. It must be acid-free.
Gelatin sizing gives a strong paper which is recommended for a wide range of water-based media (also gouache and
acrylic).

Other types of papers of different weight and thickness, different sizing, grain, texture, as well as vellum and parchment, are
available for gouache, acrylic, and oil techniques. Normally they should be prepared with gesso; oil paint in particular needs
an isolating ground to avoid absorption of oil by the paper.

There is a wide range of artists' brushes for all painting techniques and materials, even for pastels. Most brushes are made
from natural bristle, natural hair, or synthetic fibers intended to simulate the characteristics of the natural fibers. Aquarelle and
wash brushes are maufactured from finest pure red sable, but ox, pony, and goat hair are also used. For oil, acrylic, or
gouache painting the artist can use stroke brushes of different types of hair and a range of hog brushes.

Other accessories for artists are easels, palettes, palette knives, tiles, saucers, dippers, charcoal, rubbers, pencils, cutters,
and tools for calligraphy, etching, lithography, and linocut.

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References
1. Statistisches Bundesamt.
2. CEPE European Council of the Paint, Printing Ink and Artists' Colours Industry 7, 2004
3. DCMA, American Inkmaker, June 1989.
4. ETAD/BCMA/VdMI/EPSOM Safe Handling of Pigments, European Edition 1995.
5. G. Buxbaum, Industrial Inorganic Pigments, VCH Verlagsgesellschaft, Weinheim, Germany 1993.
6. Colour Index, 3rd ed., vol. 3, The Society of Dyers and Colorists, Bradford, The American Association of Textile
Chemists and Colorists, 1982, p. 3318.
7. Titandioxid, Rmpps Chemie-Lexikon, 9th ed., Thieme, Stuttgart 1992.
8. ISO 275; RAL 844: C 2, C 3 1974; ISO-DP 9238 1992.
9. Data from relevant safety data sheets.
10. Bariumsulfat, Rmpps Chemie-Lexikon, 9th ed., Thieme, Stuttgart 1992.
11. G. Benzing et al.: Pigmente und Farbstoffe fr die Lackindustrie, Expert Verlag, Ehningen 1992.
12. Knochenkohle, Rmpps Chemie-Lexikon, 9th ed., Thieme, Stuttgart 1992.
13. R. Mayer: The Artist's Handbook of Materials and Techniques, 4th ed., R. Mayer Publications, New York 1985.
14. M. Doerner: Malmaterial und seine Verwendung im Bilde, Ferdinand Enke Verlag, Stuttgart 1994.
15. G. P. A. Turner: Introduction to Paint Chemistry and Principles of Paint Technology, 3rd ed., Chapman & Hall, London
New York 1988.
16. ASTM D 4303 /93a Standard Test Methods for Lightfastness of Pigments Used in Artists' Paints.
17. K. Wehlte: Werkstoffe und Techniken der Malerei, Otto Maier Verlag Ravensburg 1997.
18. ASTM D 4302 96a, Standard for Artist's Oil Paints.
19. H. Kittel: Lehrbuch der Lacke und Beschichtungen, vol. IV, Verlag W. A. Colomb in der H. Heenemann GmbH, Berlin-
Oberschwandorf 1976.
20. D. Simmert: Acrylharzknstlerfarben, Kunsttechnologie und Konservierung, "Heft 1", Wernersche Verlagsgesellschaft,
Worms 1995.
21. H. Kittel: Lehrbuch der Lacke und Beschichtungen, vol. I/3, Verlag W. A. Colomb in der H. Heenemann GmbH, Berlin-

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Artists' Colors : Ullmann's Encyclopedia of Industrial Chemistry : Wiley InterScience

Oberschwandorf 1974.
22. ASTM D 5098, Standard Specification for Artists' Acrylic Emulsion Paints.
23. Reclams Handbuch der knstlerischen Techniken, vol. 1, Phillip Reclam jun., Stuttgart 1998, p. 270.
24. ASTM D 5067, Standard Specification for Artists' Watercolor Paints.
25. C. Schink: Mastering Colour and Design in Watercolour, Watson-Guptill Publications, New York 1989.
26. A. Flattmann: The Art of Pastel Painting, Watson-Guphill Publications, New York 1987.
27. E. Reinkowski-Hfner: Tempera, Kunsttechnologie und Konservierung, "Heft 2", Wernersche Verlagsgesellschaft,
Worms 1994.
28. R. H. Wackernagel: Neues zur Maltechnik Wassily Kandinskys, Kunsttechnologie und Konservierung, "Heft 2", 1997.
29. A. Hoffmeister-zur Nedden: Zur Maltechnik von Paula Modersohn-Becker, Kunsttechnologie und Konservierung, "Heft
2", 1997.
30. K. Wehlte: Temperamalerei, Otto-Maier-Verlag, Ravensburg 1961.
31. E. Berger: Quellen und Technik der Fresko-, Oel- und Temperamalerei des Mittelalters, Reprint Verlag, Vaduz 1982.
32. B. Cohn: Wash and Gouache, The Center for Conservation and Technical Studies, Fogg Art Museum and The
Foundation of the American Institute for Conservation, Havard College, Cambridge, Mass. 1977.
33. C. Ehrenfort: Aquarell- und Gouachefarben, Diplomarbeit, Institut fr Museumskunde an der Staatlichen Akademie der
Bildenden Knste, Stuttgart 1993.
34. No. prEN 71-7: 1997 E, Safety of Toys Part 7: Finger Paints Requirements and test methods.
35. W. Dohmen: Die Lithographie, DuMont Buchverlag, Kln 1982.
36. E. Rene de la Rie, The Influence of Varnishes on the Appearance of Paintings, Studies in Conservation 32 (1987) 1
13.
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