22 | 1 Introduction

Table 1.11: History of use of important red and purple painting pigments [16, 48, 49, 51, 52, 97, 99,
109, 116–121, 495] as well as sources from ▶Tables 1.2–1.7.

Name Composition Period of Use

Red
Red ocher, red earth, sinoper α-Fe2 O3 CT/EPT
PR102
Mars red, iron oxide red PR101 α-Fe2 O3 CT/EPT
Madder lake PR83 Anthraquinone Al lake MO
Alizarin crimson Alizarin Al lake MO
Kermes lake Kermesic acid Al lake MO
Carmine Carminic acid Al lake MO
Vermilion PR106 HgS SC
Red lead PR105 Pb3 O4 CT
Burnt sienna PR101, PR102, Fe2 O3 CT/EPT
PBr7
Burnt umber PR101, PR102, Fe2 O3 ⋅ zMnO2 CT/EPT
PBr7, PBr8
Chrome red PR103 PbO ⋅ PbCrO4 CT
Cadmium red PR108 Cd(S, Se) SC
Ultramarine pink PR259 Na3,6 (NH4 )0,25 (H3 O)1,94 ⋅ MO
[Al4,8 Si7,2 O24 ] ⋅ S3,01
Molybdate red PR104 Pb(Cr, S, Mo)O4 CT
Cerium sulfide red PR265, Ce2 S3 SC
PR275
Cadmium cinnabar PR113 (Cd, Hg)S SC
Organic pigments Miscellaneous MO
Purple
Purple C17 H8 Br2 N2 O2 MO
Han purple BaCu[Si2 O6 ] LF
Ultramarine violet PV15 Na6,08 (NH4 )0,17 (H3 O)1,28 ⋅ MO
[Al5,36 Si6,64 O24 ] ⋅ S3,83
Cobalt violet PV14 Co3 (PO4 )2 LF
Manganese violet PV16 (NH4 )MnP2 O7 LF
Ammonium cobalt phosphate NH4 CoPO4 ⋅ H2 O LF
PV49
Lithium cobalt phosphate PV47 CoLiPO4 LF
Organic pigments Miscellaneous MO

Yellow, orange, and dark red cadmium pigments, together with the cerium sulfides,
are creations of modern times, only made possible by advances in inorganic chemistry
in the nineteenth century, especially by discovering elements such as cadmium.

1.3.4 Color range blue

In the blue range of the spectrum, difficulties in pigment production occurred at all
times before the eighteenth century [429], ▶Table 1.12. Unfortunately, semiconductors
26 | 1 Introduction

The components could be mixed beforehand on the palette or directly on and in the
painting. The actual composition reflects the pigments commonly used in each epoch.
A change is noticeable across the seventeenth and eighteenth centuries. Painters re-
placed the expensive blue pigments azurite and ultramarine with new, more afford-
able ones such as Prussian blue and indigo. Similarly, lead-tin yellow recedes in fa-
vor of Naples yellow. As we will see, nature follows this path of color mixing in green
earths: a yellow FeII compound is mixed with a blue one, comprising FeII and FeIII and
colored blue by IVCT transitions.
With increasing mastery of oil painting techniques and the emergence of the Old
Master glazing technique, artists could achieve green hues by optical mixing, i. e., by
layering colored glazes, e. g., a blue and a yellow one. For this purpose, opaque colors
such as lead-tin yellow or Naples yellow were unsuitable, so yellow lakes or transpar-
ent ochers were used from the seventeenth century onward.
Though mixed greens provided quite lovely hues, still there remained problems:
– Copper pigments often darkened or affected other pigments by reacting with the
medium.
– Many of the pigments used were known to lose color more or less rapidly, predom-
inantly yellow and red lakes. Nevertheless, indigo, smalt, Prussian blue, and even
orpiment were also considered unsafe. Varnishes could provide protection.

The underlying difficulty is that pure green cannot be obtained by absorption of a

single complementary wavelength. The color closest to a pure green that we can
achieve by a single absorption band in the red spectral range is blueish green. Charge
transfer bands do not appear in this range for materials commonly used as colorants,
while semiconductors are principally not capable of inducing green color impres-
sions. The development of organic blue and green pigments requires a considerable
shift of an absorption band from the UV region into the yellow or red spectral range,
which only modern organic chemistry has achieved, tailoring electron donors and
acceptors.
An alternative to color mixing is the creation of two absorption bands around the
green spectral range, a task for a modern research chemist. Nature realizes this in
two green copper compounds, namely malachite and porphyrins (chlorophyll). Both
possess absorption bands in the blue and the yellow spectral range. However, green
copper compounds have the same disadvantages as blue ones in that they are unsta-
ble, of low intensity, and moderately toxic. Brilliant green copper pigments from the
industrial era were even highly toxic (though on behalf of their arsenic content). The
discovery of chrome in modern times made it possible to develop stable, brilliant green
chrome oxide hydrates.
However, even today, mixing green is the best way to achieve pure or intensive
neutral green colors.
 1.4 Paint systems, definitions | 27

1.4 Paint systems, definitions

Before we turn to details, some terms need to be clarified to facilitate understanding of
the following chapters. A paint system comprises all colored substances, binders, sol-
vents, auxiliaries, ground, and supports required for a particular painting technique,
e. g.:
– The paint system of oil painting includes colorants (pigments), binders (linseed,
poppy, or safflower oil), possibly resins, and a solvent (turpentine oil). Ground is,
e. g., a chalk ground or gesso, supports are, e. g., canvas or wooden panels.
– The paint system of writing or drawing ink comprises colorants (pigments or
dyes), a solvent (water), auxiliaries such as humectants, surfactants, and pH
buffers. A common support is a paper or board.

According to DIN, the german industry standard, the term colorant applies to all sub-
stances with inherent coloring properties, whether pigments or dyes.

Pigments
Colorants that are insoluble in the binders and solvents of a paint system are called
pigments. The painter fixes them to the ground or support by employing the binder.
The actual artists’ color or paint is a dispersion of pigments in the binder and solvent. It
can be fluid (e. g., an ink), semi-viscous (e. g., watercolor pigments in a gum solution)
or viscous and pasty (e. g., oil paint). The binder can also act as a solvent, such as oil in
oil paints. All artists’ pigments are insoluble in linseed oil and water and are suitable
for producing oil, acrylic, watercolor paints, and printing inks. (When discussing in-
dustrial printing inks, we must take care since some industrial printing techniques use
strong or aromatic solvents capable of dissolving some classes of organic pigments.)
Pigmented paintings tend to be opaque. Artists can apply bodily paints (in more
or less viscous masses such as oil paint) using an impasto technique, lending visi-
ble texture to the painting. Due to their thickness, impasto layers are opaque. If the
artist decides to apply paint thinner or dilute it with a solvent, the paint layer may
be thin but still opaque. The transparency of a pigment depends on its refractive in-
dex and its particle size. Some pigments such as titanium white, vermilion or ocher are
highly opaque. An artist must select pigments with a low refractive index or particular
grades to obtain glazes. Manufacturers can grind some pigments to a grade at which
their scattering power is minimal so that they appear transparent, ▶Section 1.6.6. Usu-
ally, manufacturers indicate these grades in the trade name, e. g., “transparent yellow
ocher” in contrast to (opaque) “yellow ocher.” Today, it is often possible to adjust the
opacity of a pigment smoothly from glazing or transparent to opaque: yellow ocher,
e. g., is a superior opaque pigment but can be transparent in specific particle sizes.
Applications such as pigmented inkjet inks also require pigments with small particle
sizes.
 1.5 Basic physical processes, spectra | 29

Figure 1.3: Basic principle of absorption. As an example, a material (possessing two energy levels
EGS and EES ) is irradiated with white light. EGS is called ground state and EES is called excited state.
Here, ΔE = EES − EGS = hν applies. In spectroscopy, ground and excited states are often called initial
and final states, ΔE = Eif = Ef − Ei .

1.5.1 Emission colors

The first primary type of a spectrum comprises a single, more or less sharp peak, ▶Fig-
ure 1.4. Such a spectrum is created by a self-luminous body emitting light of a specific
wavelength, which is not the case in painting, but very much so in a video installa-
tion. The color perceived corresponds to the wavelength of the peak’s maximum and
its “width.” The peak’s maxima would be located in the blue and yellow spectral range
in the example. The width of a peak can be defined as its full width at half-maximum,
called FWHM or bandwidth, if a normal distribution describes the peak. The sharper
the peak is, the purer is the color, visualized by the distinct “narrow” yellow peak in
contrast to the “broad” blue one in ▶Figure 1.4. If the peak broadens in the visible
range, it resembles more and more the regular white light, and the perceived color is
pale, not very distinct, and vanishes more and more.
A compound showing such a spectrum can exhibit all rainbow colors, as the figure
shows, especially the distinct shades purple (420 nm), blue (460 nm), green (525 nm),
yellow (575 nm), orange (600 nm), and red (650 nm). The specified wavelengths are to
be taken as typical values since the exact color impression depends strongly on the
precise shape of the spectrum.

1.5.2 Absorption color

The counterpart to the spectrum just discussed is one in which only light of a particu-
lar wavelength is absorbed. When we irradiate a body with white light, and the body
is capable of absorbing the energy of a specific wavelength through an electronic tran-
sition, as shown in ▶Figure 1.3, we get an idealized reflectance spectrum containing a
30 | 1 Introduction

Figure 1.4: The ideal emission spectrum of a self-luminous compound. Depicted is the intensity I.
The perceived color corresponds to the wavelength λ of the peak’s maximum and its “width,” e. g.,
the full width at half-maximum (FWHM) or bandwidth. The smaller the bandwidth of the peak, the
purer the hue (yellow in this case). The reciprocal relationship between energy hν of the radiation
and wavelength λ can also be seen. Color perceptions and wavelength ranges are typical values.

“hole” or “absorption band” at this wavelength, ▶Figure 1.5(a). This scenario is typ-
ical for artists’ pigments. Also typical is that absorption bands, in reality, are by no
means sharp, ▶Figure 1.5(b).
The mixture of the residual light determines the color impression of such a spec-
trum. As a rule of thumb, we perceive the complementary color to the color corre-
sponding to the wavelength of the peak. If a body absorbs light of 590 nm, this corre-
sponds to yellow light, so the complementary color and the color impression of this
body is blue, ▶Table 1.14. Note that this situation is the reverse of that in ▶Figure 1.4:
The color of light emitted at 580 nm is yellow, but the color of a body absorbing at
580 nm is blue.

Table 1.14: Correlation between absorbed wavelength λmax , the color of the corresponding emission,
and the perceived color [205, Chapter 34]. A pure green color impression can hardly be created.

Color of λmax λmax /nm Color perception Energy/eV

Purple 380–430 Yellow-green 3.26

Blue 430–480 Yellow 2.75
Cyan blue 480–490 Orange 2.57
Blue-green 490–500 Red 2.52
Green 500–560 Magenta 2.33
Yellow-green 560–580 Purple 2.17
Yellow 580–595 Blue 2.13
Orange 595–605 Cyan blue 2.11
Red 605–750 Blue-green 2.04
Magenta 750–770 Green 1.65

Compounds exhibiting an absorption peak can take on all colors from yellow-green
to purple to blue-green except for pure medium green. ▶Figure 1.5(b) illustrates re-