XIV | Table of contents for volume 1

1.7.2 Crystal structure and particle shape | 72

2 The chemistry of color | 77

2.1 Chemical absorption mechanisms | 77
2.2 SC: band gap transitions in semiconductors | 82
2.2.1 Valence and conduction band | 84
2.2.2 Color | 86
2.2.3 SC-based chromophores | 88
2.2.4 Influence of lattice width and crystal structure, thermochromism | 92
2.2.5 Alloys, solid solutions, and color | 95
2.2.6 Manufacture of semiconductor alloys | 100
2.2.7 Doping and blue diamonds | 101
2.3 LF: splitting d orbitals in a ligand field | 102
2.3.1 Crystal field theory and ligand field theory | 104
2.3.2 Splitting of degenerated d orbitals | 104
2.3.3 Spectroscopic selection rules | 111
2.3.4 Ligand-field splitting in octahedrally coordinated complexes | 113
2.3.5 Influence of ligand field strength | 121
2.3.6 Distortion of the octahedral field, Jahn–Teller effect | 125
2.3.7 Tetrahedral coordination | 127
2.3.8 LF-based chromophores | 130
2.4 CT: Charge transfer transitions | 131
2.4.1 Ligand-to-metal transition and oxygen-to-metal transition | 134
2.4.2 Metal-to-metal transition (MMCT), intervalence transition (IVCT) | 138
2.5 MO: molecular orbital transitions | 143
2.5.1 VB and MO model, resonance structures | 148
2.5.2 Chromophore enlargement, bathochromic shifts | 150
2.5.3 Donor–acceptor chromophores | 150
2.5.4 Polyene chromophore | 164
2.5.5 Polymethine chromophores | 183
2.5.6 Other chromophores: Sulfide radical ions | 189
2.6 Laking and colored lakes | 190
2.6.1 Structure of the color lakes | 194
2.6.2 Practical procedure | 197
2.6.3 Hue shift | 199

3 Inorganic pigments | 205

3.1 Carbon pigments | 207
3.2 Copper pigments | 217
3.3 Ultramarine pigments | 227
3.4 Oxide and sulfide pigments | 231
3.4.1 Classical heavy metal oxides and sulfides | 231
 Table of contents for volume 1 | XV

3.4.2 Iron oxide pigments, ocher | 238

3.4.3 Complex inorganic color pigments (CICP), mixed metal oxides
(MMO) | 254
3.4.4 Cerium sulfide pigments | 266
3.4.5 Chromium oxide pigments | 268
3.4.6 Titanium oxides and zinc oxides | 270
3.4.7 Cadmium sulfide pigments | 274
3.5 Bismuth pigments | 278
3.6 Chromium pigments | 280
3.6.1 Chromate and molybdate pigments | 280
3.6.2 Chrome green (PG15, CI 77510); fast chrome green (PG48, CI 77600);
zinc green | 284
3.7 Iron blue pigments (Prussian Blue, Berlin Blue, Milori Blue, Paris Blue,
iron blue, PB27, CI 77510, 77520) | 285
3.8 Various metal pigments | 288
3.8.1 Calcium carbonates | 288
3.8.2 Lead white, flake white, Kremser white, Cremnitz white (PW1) | 289
3.8.3 White sulfates | 290
3.8.4 Miscellaneous colored pigments | 291
3.9 Glasses | 293
3.9.1 Glass coloring | 298
3.9.2 “Decolorization” of glass, color compensation | 302
3.9.3 Ancient glass coloring | 303
3.9.4 Frit colors | 305
3.9.5 Opaque glass | 307
3.10 Enamel | 307

4 Organic colorants | 309

4.1 Natural organic colorants | 310
4.2 Synthetic organic colorants | 312
4.2.1 Meaning of molecular structure | 315
4.3 Carotenoids | 317
4.3.1 Xanthophylls | 317
4.4 Flavanoids | 319
4.4.1 Origin in metabolism | 319
4.4.2 Classification | 320
4.4.3 Flavan-3-ols (catechins), flavan-3,4-diols, and flavanones | 321
4.4.4 Flavones | 322
4.4.5 Anthocyanins | 327
4.4.6 Neoflavones | 334
4.4.7 Quinone methides | 336
4.4.8 Chalcones and quinochalcones | 337
1 Introduction
Why write a book on such a particular topic as the chemistry of painting? Since I paint
myself, the question of the nature of the materials used was evident to me, and it was
with enthusiasm that I began my research. However, I quickly discovered that most of
the known books dealt more with the technique of painting and less with the nature of
the materials, mentioned only in passing. The question “What is in the tube of yellow
oil paint?” was replaced by “What causes yellow ocher or chrome yellow to appear
yellow?” And more questions followed: “Why does the linseed oil in the tube form a
clear film? And why is the chrome yellow purer and more intensive than the yellow
ocher? What happens when paintings are damaged by age?”
What I imagined was a book not about painting but the chemistry of painting; to
write it, I had not only to work through a whole physical-chemical library but also
unexpected sections such as dairy farming, adhesives, professional cake baking, and
the art of restoration.
It was fascinating not only to gain deeper insight into the nature of my painting
materials but also to experience the great wealth of subject areas that are necessary
to explain the basic materials and principles of painting, encompassing quantum me-
chanics, solid-state and semiconductor physics, inorganics and organics, biochem-
istry, and the chemistry of natural products and colloids. I had to read books on the
technology of dairy products as well as technical articles on frying oil used for fast
food or the problem of discoloration of olives and apples when cut with iron knives.
I became knowledgeable about the Kamares style of Minoan vases and the pressure
dependence of the s orbitals of lead in certain minerals in the depths of the earth.
Some books took me back to 1831 or even into the Middle Ages. Some research results
were only obtained in papers as late as 2010; many questions are still open or wait-
ing for a conclusive clarification. Several research projects aim to answer them in the
future. Some results were only possible with the most modern methods of analysis. Us-
ing the latest high-tech analytics in museum laboratories has significantly expanded
our knowledge in recent years by gaining deeper insights; so far, seemingly proven
facts may even need to be adapted.
There were some surprising discoveries. After reviewing some medieval paint
recipes, I learned how I could obtain basilisks if I were in need of them—astonishing
was also the high number of articles revolving around modern methods to analyze the
composition of contemporary artists’ materials whose origins lie not precisely in the
dark past. For example, in the case of acrylic paints or modern inks, the accompany-
ing information contains surprisingly vague statements such as “an anionic acrylate”
or “linseed oil-based.” These are products guarded by company or production secrets.
Even conservators then have to go to an analytical laboratory to find out how they best
treat their treasures.

https://doi.org/10.1515/9783110777116-001
2 | 1 Introduction

My intention with this book is to summarize the widely scattered knowledge to

provide comprehensive information about the nature of painting materials to natural
scientists interested in art and art lovers curious about the nature of materials.
Dear reader, whatever your interests are, let me show you the path leading along
the boundary between painting and science. Accompany me on tour through both
fields using ▶Figure 1.1 as our map that illustrates the sights along our way. Let us
divide our route into several stages:
– First, we will become acquainted with the basic physical process of light-matter
interaction (from ▶Section 1.5 on), followed by the chemical principles of color
(▶Chapter 2). To do so, we will look into four fundamental mechanisms of chem-
ically induced color impressions.
– Next, we look at the colorants as the actual means of artistic expression. Based
on the knowledge gained so far, we discuss inorganic (▶Chapter 3) and organic
(▶Chapter 4) pigments relevant to art and their causes of color. Likewise, we give
an overview of dyes suitable for graphics and drawing (▶Chapter 5).
– Painters do not use only colorants but, in fact, whole paint systems. For colorants
to be applicable as expected by a particular technique and to form durable layers
of paint, they must integrate into complex systems, e. g., oil or acrylic paints. We
will first learn about the components of such systems, their functions, and modes
of action (▶Chapter 6) and then proceed to examine actual paint systems in detail,
including painting such as oil, acrylic, and watercolor, as well as drawing, e. g.,
pastels or pencils (▶Chapter 7).
– Finally, we conclude with an examination of materials and paint systems of ink-
based graphics, such as writing, drawing and printing, and modern media such
as inkjet printers or color laser printers (▶Chapter 8).

What makes the field of painting chemistry very exciting is the interaction of chemical
and physical factors to induce the final visible color of a pigment.
– Chemical causes. The molecular structure is primarily responsible for the color
of a pigment or a dye. Type, oxidation state, and linkage of atoms determine if,
at which wavelengths, and how intensively an atom or molecule absorbs visible
light, and thus appears colored.
– In pigments, several physical phenomena join this primary cause. Large, spatially
extended objects are subject to scattering, favoring specific wavelengths and emis-
sion geometries. Other processes such as developing surface plasmons can add
new absorption bands. These phenomena usually depend on the pigment parti-
cles’ size, morphology, and shape.
– In addition, supramolecular phenomena participate in creating a final color im-
pression. Individual molecules or ions can mutually interact in solid or crystal-
lized pigment particles, changing or amplifying absorption bands, or creating
new ones. Uniform crystalline structures facilitate such interactions, while dis-
turbances of a regular structure, in contrast, suppress them. Also, broad distribu-