The world of inorganic pigment

➢ Introduction:
Inorganic pigments have been very important substances for human life
for thousands of years. They have contributed and continue to contribute
to the beautifcation of our daily life and habitat and to the accentuation
and diferentiation of objects, and infuence thoughts, moods, and feelings.
The industrial manufacture of inorganic pigments based on growing
chemical and physical knowledge started around 1800. Before that,
pigments based on natural materials or manufactured by mostly
empirical processes were used. Most of the technically relevant inorganic
pigments were developed and frst produced on an industrial scale in the
nineteenth and twentieth centuries. Ongoing developments are aiming to
improve existing conventional pigments as well as synthesize new,
innovative colorants, especially in the classes of efect pigments and
functional pigments. The objective of this text is to present
comprehensive knowledge about inorganic pigments, including
defnitions, types of pigments and their properties, historical pigments,
modern inorganic pigments, synthesis methods, and applications. It is also
intended to show the current status of new pigment developments
Defnitions Nowadays, pigments are defned as substances consisting of
small particles that are practically insoluble in their application system
and applied as colorants or because of their special corrosion-inhibiting
or magnetic properties [1]. They difer from dyes, which also belong to the
class of colorants, in that the latter are almost completely soluble in their
application medium. The most important application systems for
pigments are automotive and industrial coatings, paints, plastics, printing
inks, cosmetic formulations, and construction materials. Other
applications for pigments are found in paper, rubber, glass, porcelain,
glazes, and stains. The term “pigment” is derived from the Latin word
“pigmentum,”,which was originally used in the sense of a coloring
material. In the Middle Ages, the term “pigment” was also used for colored
plant extracts. In the terminology of biology, the term is still used today to
describe plant and animal colorants that are present in “dissolved” form
as extremely small particles in cells or cell membranes, as deposits in
tissue, or suspended in body fuids. In all these cases, the use of the term
“pigment” is misleading. In the interest of uniform terminology, it should
be replaced here by the more appropriate term “dye” [2]. The term
“colorant” covers all colored compounds regardless of their origin or use.
Some pigments and dyes exist in natural and synthetic variations.
Pigments are applied to surfaces (substrates), requiring binders in which
the particles are embedded (paints, coatings, printing inks, and cosmetic
formulations). When coloring plastics, the entire polymer material is
often pigmented. Dyes are applied to diferent surfaces during use.
Examples include textiles, leather, paper, and hair, to which the dyes are
applied in dissolved form. Unlike pigments, dyes must have an afnity for
the substrate to which they are to be fxed
 ➢ Classifcation of pigments
Pigments can be classifed according to either their chemical composition
or their optical and technical properties. The distinction between
inorganic and organic pigments is fundamental. Figure 1 shows a
classifcation of pigments and colorants within the category of “colorants”
(coloring materials). This fgure illustrates that dyes are, by nature,
organic compounds, and that white dyes do not exist. Fillers, as
substances closely related to pigments, are also included in Fig. 1. Like
pigments, these are solid materials that are added to application media to
improve the properties of the system or reduce the consumption of more
expensive

binder components. Fillers that are used mainly for cost reduction are
also called extenders. Like pigments, fllers are insoluble in the medium
used. They have the ability to improve coatings and other application
systems in terms of their density, porosity, and permeability to gases and
water. There is no clear diferentiation between fllers and pigments in
terms of their refractive index, but it is generally accepted that this index
is below 1.7 for fllers and above this value for pigments [2]. Figure 2
contains a detailed classifcation of inorganic pigments. White, colored,
and black pigments exist, as well as pigments with special properties. In
addition, the most important representatives of the various pigment
categories are listed. White pigments are represented by titanium dioxide
(rutile and anatase), zinc sulfde (including the lithopones), and zinc oxide.
Colored pigments show the widest variation, ranging from blue (complex
metal oxides, ultramarine, Prussian blue) through green (chromium(III)
oxide, complex metal oxides), and yellow (iron(III) oxide hydroxide,
complex metal oxides, lead chromate, bismuth vanadate, cadmium sulfde)
to red (iron(III) oxide, cadmium selenide, lead molybdate, cerium(III)
sulfde, calcium lanthanum oxonitride, lanthanum tantalum oxonitride).
The most important representative black pigment is carbon black. On the
basis of this variety of colored, white, and black pigments, it is possible to
obtain almost all conceivable colored and achromatic (white, black, and
gray) shades. Both single pigments and mixtures of two or more pigments
can be used to achieve a specifc shade. Special pigments are divided into
the classes: efect pigments (luster pigments) with two subclasses of
special efect pigments (pearlescent pigments, interference pigments) and
metal efect pigments, transparent pigments, luminescent
 ]

pigments (with two subclasses of fuorescent pigments and

phosphorescent pigments), and functional pigments [2]. The optical
behavior of efect pigments is based on the directional refection of visible
light from predominantly two-dimensional and aligned metallic (metal
efect pigments) or highly refractive transparent pigment particles
(pearlescent pigments), or on the phenomenon of interference
(interference pigments). Transparent pigments are characterized by
very small particles with size in the range below 100 nm and high specifc
surface area. Most of the technically relevant pigments consist of
particles that are even smaller than 30 nm. These are classifed as
nanomaterials. Pigmentation with these pigments leads to a transparent
appearance of the application systems. Luminescent pigments
(luminescent materials, luminophores, and phosphors) show optical
efects based on their ability to absorb radiation and emit it as light of
longer wavelength with a time delay (phosphorescence) or without a
time delay (fuorescence). Light emission often occurs in the visible
spectral range. External energy is necessary to enable luminescent
materials to generate light. The importance of functional pigments lies
not in their color but in various physical properties, which cannot be
derived from the original term “pigmentum.” Such materials, which
exhibit magnetic, anticorrosive, electrically conductive, infrared (IR)-
refective, ultraviolet (UV)-absorbing, and other physical properties, can
be appropriately described by the term “functional pigments.” Some of
the transparent pigments and the luminescent pigments can also be
classifed as functional pigments. The reason why functional pigments are
classifed as pigments is because of their similar morphological and
application–technical properties. Another classifcation of inorganic
pigments is based on their chemical composition (Table 1).

➢ General properties of pigments

In general, inorganic pigments are more stable against the infuence of
light, temperature, chemicals, and atmospheres than organic pigments.
Inorganic pigments also ofer the advantage of lower production costs.
Organic pigments usually require multistage syntheses and expensive
starting materials for their production. Both factors lead to comparatively
high market prices for organic pigments. However, compared with
inorganic colored pigments, organic pigments are often more color-intense
and thus more attractive.
for various applications. As also occurs with dyes, the aforementioned
lower stability of organic pigments often leads to their degradation over
time when interacting with UV radiation or atmospheric infuences. The
use of UV absorbers when applying organic colorants is an efective way of
extending their lifetime in application media. The choice of a pigment for
a specifc application can be based on several criteria (Table 2). A
pigmented system is described as a dispersion of pigment particles in a
translucent binding medium, which is initially liquid and after hardening
of the binder preferably solid. In most cases, a thin flm is formed, e.g., a
paint layer, with thickness of a few to hundreds of micrometers. In some
cases, such as in cosmetic formulations, the application takes the form of a
liquid dispersion. Incident light undergoes refection, refraction, and
absorption when interacting with the dispersion, resulting in the visual
appearance of the pigmented medium. The optical properties of a
pigmented system are mainly determined by the following factors: •
Pigment properties such as particle size, particle size distribution,
particle shape, refractive index, scattering coefcient, and absorption
coefcient • Properties of the application medium (binder) such as
refractive index and absorption • The pigment volume concentration in
the pigmented system Geometric parameters such as particle size
(diameter), size distribution, and shape are among the particularly
important properties of pigments. Particles are defned as the smallest
individual units of a pigment or powder in general. The structure, size,
and shape of particles can vary to a great extent. Typical units of particles
occurring in pigments are primary particles, agglomerates, and
aggregates (Fig. 3): • Primary particles (individual particles): particles
that are recognizable as individual units when using suitable imaging
methods (optical microscopy, electron microscopy); primary particles are
the optimum units for a pigment from the point of view of the application
Agglomerates: assemblages of primary particles and/or aggregates, where
contact between the particles typically occurs via corners and edges;
agglomerates can usually be easily destroyed by mechanical action and
converted into primary particles or smaller units. • Aggregates:
aggregations of primary particles, where contact between the particles
typically occurs via surfaces; this results in particles that adhere frmly to
one another and are difcult or impossible to separate from each other; they
often pose a problem in terms of application technology.

➢Interaction of pigments with light

The decisive factor regarding the optical appearance of a pigment is its
interaction with light in the spectral range visible to the human eye (about
400–750 nm). The following interactions are to be considered for the most
important pigment classes (Table 3). Figure 4 provides a comparative
illustration of this interaction using pigment particles embedded in an
application medium. The color that occurs in colored pigments due to the
absorption of light originates from the interaction of visible light with the
valence electrons of the pigments, which are to be regarded as solids. The
elements involved (cations and anions), their oxidation state or electron
confguration, and the respective crystal structure are decisive for a specifc
absorption. The special electronic structure of the pigments derived from
this is the basis for electronic transitions between diferent energy states
and thus for the absorption of certain wavelengths of light and the
formation of color [3, 4]. The fundamental relationships among the optical
characteristics of pigments can be comprehensively discussed on the basis
of four theoretical considerations [2]: • Lorenz–Mie theory • The theory of
multiple scattering • Kubelka–Munk theory • Colorimetry Mie or Lorenz–
Mie scattering refers to the elastic scattering of electromagnetic waves at
spherical objects, for example, pigment particles in an application medium,
whose diameter corresponds approximately to the wavelength of

the radiation. This scattering can be described physically with Lorenz–Mie

theory. Mie scattering produces the Tyndall efect [5, 6]. The theory of
multiple scattering is the mathematical formalism that is used to describe
the propagation of a wave through a collection of scatterers, for example,
a variety of pigment particles in an application system [7–10]. Kubelka–
Munk theory describes the light absorption and scattering properties of
pigmented systems, such as paint flms or coatings [11–13]. Colorimetry is
concerned with the quantifcation and physical description of human color
perception. It is similar to spectrophotometry, but has specifcally aims to
reduce spectra to the physical correlates of color perception, mostly to the
tristimulus values of the CIE 1931 XYZ color space and related parameters
[14, 15]. Figure 5 shows the relationship between the optical properties of
pigments and pigmented systems and their theoretical principles.
Refection spectra and spectral refection factor curves can be almost
entirely derived from physical parameters and relations by using these
four fundamental approaches [2].

➢ Historical pigments: from the beginning

of pigment use to the eighteenth century

The history of pigments is closely linked to the cultural history of mankind.

The beginning of the use of inorganic pigments goes back to the early
history of human society. Thousands of years ago, our ancestors were
already able to color textiles, skins, and utensils in a simple way using
naturally occurring substances. These were mostly of plant origin, but
could also come from animals [2, 16–18]. Cave paintings such as those at
Altamira and Lascaux date back to the Ice Age. They were almost certainly
made between 15,000 and 30,000 years ago. Natural manganese oxides
and charcoal were used for black tones, while yellow, orange, and red
tones were produced with the help of naturally occurring iron oxides.
Calcium carbonate was the basis for white and light shades. The earth
colors used were sometimes oxidized by fre and mixed with fats or resins.
Yellow ocher and red ocher (earths) were prepared from rocks by
crushing, slurrying, and grinding. Red ocher could be obtained by heating
yellow ocher. It can be assumed that, already in this period, natural
materials in powdered form were also used as pigments for body painting.
Thus, the use of pigments for the purpose of coloring surfaces can be
considered one of the oldest cultural activities of mankind. The artists of
the Ice Age used pigments mostly without a binder. The rock paintings
survived the millennia only because seepage water, which contained
colorless minerals, covered the pigments with protective transparent
mineral layers [19–21]. Methods for producing inorganic materials
suitable for use as pigments were further developed several millennia
later, especially in the ancient centers of Egypt and Babylon. The walls of
temples, burial chambers, and stone buildings, as well as wood and
ceramic surfaces, were used for color design. The pigments used were iron
oxide black, manganese oxide black, and lead sulfde (galena) for black
tones, iron oxide red and copper in colloidal form for red tones, and
calcium carbonate and kaolinite for white tones. Arsenic sulfde and Naples
yellow were the frst yellow pigments, while ultramarine in the form of
crushed lapis lazuli, Egyptian blue, cobalt aluminate, and ground glass
containing cobalt (smalt) were used for blue tones. The frst green pigments
were green earth and malachite. Some of these pigments were not of
natural origin. They were synthesized by empirical chemical methods. The
use of toxic substances such as arsenic and antimony compounds in
cosmetic formulations was widespread. Metals such as gold, silver, and
copper were also already used as colorants in the design of surfaces.
Egyptian blue was the most important pigment in Egypt, as blue was
considered a divine color. It was made from lime powder, quartz sand,
copper oxide, and soda (fux) [22, 23]. A thousand years later, another red
pigment was available in Ancient Greece in the form of cinnabar. This
naturally obtained pigment was also used in many ways during the Roman
Empire. The main source for this was the deposit in Almadén in Spain. With
white lead and red lead oxide, further pigments came into use in Ancient
Rome and were to play an important role in color design in the following
centuries. New trade routes to the Far East enabled the import of organic
and inorganic colorants, among which indigo and various colored minerals
were particularly important. Both Greeks and Romans decisively
developed the existing techniques in the application of pigments [24–27].
In the Middle Ages, book painting was initially of paramount importance.
Panel painting on an independent surface (initially a wooden panel but
subsequently canvas) developed only over the course of time. In the
twelfth century, Venice became the main hub for colorants in the world.
Various noble families from Venice and Florence began to promote art.
Painters and other artists came to the most important metropolises in Italy
at that time and took on commissions for their patrons. The church was
traditionally also an important client for painters and sculptors. Fresco
painting experienced its heyday in the early Renaissance with the painter
Giotto di Bondone . The Florentine painter Cennino Cennini (ca. 1370–
1440) was the frst to publish a handbook on painting with the title “Il libro
dell’arte o trattato di pittura” [28]. This book, written around the year
1400, was the most infuential textbook on painting of the Late Middle Ages.
It has remained of special cultural-historical and art-historical importance
until today because the author was the frst to disclose the secrets of
painting including all the relevant materials used [2, 18]. The compatibility
of the pigments used with the chalky substrate was a specifc problem in the
frescoes to be created. Blue hues were typically applied a secco because the
available blue pigments were attacked and thus altered by the lime. The
color palette ranged from earth colors (yellow ocher, Terra di Siena) to
mineral colors and synthetically produced pigment colors (lead tin yellow
and smalt). The colors were produced on the basis of recipes, some of
which were kept secret. Existing knowledge was passed on and used again
and again, but the basic colorants and binders were always further
developed and sensitively adapted to the diferentiated felds of application
[18, 28–31]. From the very beginning, artists’ colors were among the most
desirable colorants and thus contributed greatly to the development of
new pigments, dyes, and binders over the centuries [18, 32–35]. Painting
underwent a significant development in the Renaissance, with techniques
of oil painting reaching a completely new quality. The range of pigments
already used earlier was extended to include green earth (natural earth
pigment as a weathering product of ferrous silicates, purifed). Color-
intense varieties of this green pigment came from the Verona area
(Veronese green earth) and from Bohemia (Bohemian green earth). Other
important paint pigments were Naples yellow, auric pigment, lead tin
yellow, cinnabar, realgar, carmine (calcium and aluminum salts of carminic
acid), malachite, white lead, and painter’s charcoal [18, 36–38]. In the
eighteenth century, on the basis of the level of knowledge of chemistry
achieved at that time, which had increasingly developed from alchemy into
a science, the targeted synthesis of various inorganic pigments was
achieved for the frst time. Thus, in the course of this century, pigments
such as Prussian blue, Schweinfurt green, or cobalt blue became available.
In particular, the discovery of Prussian blue as a new blue pigment is well
known. The color maker Johann Jacob von Diesbach (who lived around
1700) and the alchemist Johann Conrad Dippel (1673–1734) were the frst
to succeed in synthesizing this pigment, in 1706 in Berlin. It took some
time until the preparation route was fully developed. The synthesis was
fnally made public by the chemist and pharmacist Caspar Neumann (1683–
1737) from Berlin, who provided the recipe for Prussian blue to the Royal
Society for anonymous publication [39, 40]. Today, Prussian blue is one of
the technically important blue pigments, mainly being used in paints and
printing inks. In technical applications, the pigment is usually referred to
as iron blue [2]. The pigment has even been used in the design of blue
postage stamps [41]. The production of Prussian blue and other newly
developed pigments initially took place in workshops and small
companies. These were to become the nuclei of the rapid upswing in color
chemistry that took place in the nineteenth century. A specialty among the
historical pigments is Maya blue. This pigment was rediscovered in 1931 at
the archaeological site of Chichén Itzá [42]. This intensely colored blue
pigment was widely used in wall painting, pottery, sculptures, and luxury
art in Mesoamerica and even as a therapeutic agent in pre-Columbian
times. It can be described as a hybrid organic–inorganic material resulting
from the attachment of indigo, a blue dye extracted from leaves of anil
(Indigofera sufruticosa and other plant species), to the clay matrix of
palygorskite, a fbrous phyllosilicate with an ideal composition of
(Mg,Al)4Si8(O,OH,H2O)24·nH2O [43, 44]. In this context, it is interesting to
refer to the preparation of indigo from Indigofera sufruticosa by
electrochemical monitoring using the voltammetry-of-microparticles
approach [45]. The chemical and physical–chemical analysis of inorganic
pigments used in art and on archeological objects is of great interest to
obtain knowledge about historical pigments. Today, a large number of
modern methods for the identifcation of pigments are available for such
analyses. The instrumental techniques most frequently used for such
analysis of cultural artifacts to obtain data on the chemical composition of
pigments contained are classical chemical analysis, activation methods,
faradaic electrochemical methods, spectroscopic methods, and
thermoanalytical methods. The instrumental techniques that can provide
data on the crystal and molecular structure of pigments include difraction
and spectroscopic methods as well as mass spectroscopy. Information on
the texture and strata structure can be obtained using light microscopy,
electron microscopy, and atomic force microscopy [46]. Table 4 presents
the most important representative historical pigments (in the period from
early human history until the eighteenth century), including both inorganic
and organic pigments.

➢Modern inorganic pigments: current status

and new developments
In the nineteenth century, the development of the synthesis of new
inorganic pigments, which had begun in the previous century, continued
steadily. Many of the chemical factories that were now being established
began to specialize in the industrial production of inorganic and organic
pigments and
in the technical synthesis of dyes. In addition to expanding the range of
colors, chemical processes provided easy and cost-efective access to
improved colorants with reproducible quality. In this way, numerous new
inorganic pigments expanded the range of technically useful colorants in
the nineteenth century, including chrome oxide green, cadmium yellow,
zinc white, ultramarine blue, iron oxide red, and metal bronzes (Cu/Zn).
Other synthetic inorganic pigments appeared on the market in the
twentieth century: titanium dioxide, cadmium red, iron oxide yellow, iron
oxide black, bismuth vanadate, and efect pigments based on mica. After
the frst synthetic organic pigments became available in the nineteenth
century, their range also expanded greatly in the twentieth century. The
application systems for pigments also changed and expanded greatly.
Automotive and industrial coatings, plastics, modern printing inks and
cosmetics, as well as building materials became the drivers for the
development of new color-imparting products. Today, a wide variety of
modern inorganic pigments are available for diferent applications
(Table 5). Figure 6 shows color charts of selected, technically signifcant
inorganic pigments. It should be borne in mind that the color impression
shown here can only be a color orientation. The color impression
achieved in a given application depends on various factors, above all on
the quality of the pigment (composition, impurities, and particle size
distribution), the application system, the concentration of the pigment in
the application system, and the type of application. Modern pigments are
produced on an industrial scale in batch processes on a ton scale. For the
production of inorganic pigments, precipitation and solid-state reactions
at high temperatures are the main options. For special pigments,
crystallization processes from molten salts, hydrothermal reactions, and
gas-phase processes are used. Technical pigment syntheses are based on
mature chemical processes that lead to reproducible pigment quality.
Users can thus be supplied with pigments ofering the same quality in
terms of color and other properties time and time again. Suppliers and
users, e.g., in the felds of coatings, paints, printing inks, plastics, and
cosmetics, are in close contact with each other to constantly harmonize
the requirements for pigments. Quality control is a crucial part of the
production process. Natural pigments now only play a role in iron oxide
pigments (for building materials). The global pigment market reached a
volume of around 12 million tons in 2020. It is dominated by the white
pigment

titanium dioxide (rutile and anatase). Indeed, TiO2 pigments account for
around 60% of global pigment production. In terms of the quantities
produced, iron oxide and carbon black pigments lie in second and third
place, respectively. Well over 90% of all colorants used today are
inorganic pigments. Nevertheless, with an annual production of less than
1 million tons, organic pigments are also an attractive class of colorants
with a wide range of applications [47]. The complexity of the industrial
production of inorganic pigments is briefy outlined below using three
examples.

➢Technical synthesis of titanium dioxide and iron oxide

pigments
The following condensed descriptions of the production of titanium
dioxide and iron oxide pigments are a selection intended to demonstrate
important processes used in the production of inorganic pigments, such as
precipitation and solid-state reactions, in general. An additional reason
for choosing titanium dioxide and iron oxide pigments is the great
economic importance of these products.

➢ Titanium dioxide pigments

Two processes are available for the industrial production of high-quality
titanium dioxide white pigments: the sulfate process, frst used in 1916,
and the chloride process, which reached production maturity in 1960 [2,
48–50]. The task in both processes is to produce pure white TiO2 pigment
starting from mostly black or gray titanium-containing raw materials
(ilmenite or titanium slag in the sulfate process; natural or synthetic
rutile in the chloride process). Specifed parameters such as average
particle size, particle size distribution, particle shape, and crystal
structure (rutile, anatase) must be achieved, dependent on the intended
application. In the sulfate process, ilmenite or titanium slag is dissolved in
hot concentrated sulfuric acid: During subsequent cooling, iron(II) sulfate
(green salt) crystallizes out and can be separated from the resulting
sulfuric acid solution. After separation of various transitionmetal ions, the
colorless titanyl sulfate solution now present is subjected to hydrolysis by
addition of water: A titanium dioxide hydrate precipitate is formed,
which, after fltration, washing, and drying, is fed to calcination at 800–
1000 °C: After this step, the granulometric properties of the obtained
coarse titanium dioxide particles are adjusted by a grinding process. TiO2
pigments synthesized in this way are often stabilized against UV radiation
using a specifc surface treatment (aftertreatment). Rutile is the more
stable TiO2 modifcation compared with anatase, but is also UV active to a
lesser extent. An additional aspect of such a treatment is the improvement
of the application properties of the pigments, especially with regard to
their compatibility with the binder system. The surface treatment is
carried FeTiO3 + 2H2SO4 → TiOSO4 + FeSO4 + 2H2O. (1) TiOSO4 + (x +
1)H2O → TiO2 ⋅ xH2O + H2SO4. (2) TiO2 ⋅ xH2O → TiO2 + xH2O. (3)
out mostly using a thin colorless layer (often consisting of SiO2, Al2O3,
and/or ZrO2, but also organic components), which is applied to the TiO2
particles by wet chemical means to completely coat them on the surface.
Furthermore, it is possible to perform intrinsic stabilization by
incorporating suitable ions into the crystal lattice of the TiO2 already
during its synthesis. TiO2 pigments produced by the sulfate process often
consist of rutile/anatase mixtures. Pure rutile or anatase pigments can be
obtained by a suitable choice of reaction parameters (calcination
temperature and dopants). In the chloride process, natural or synthetic
heavily contaminated rutile reacts at 800–1200 °C with chlorine gas and
coke (summary equation without partial reactions): The resulting
titanium tetrachloride is separated from solid chlorides by distillation.
Subsequently, the very pure TiCl4 thus obtained reacts with oxygen at
more than 1000 °C, producing TiO2 in the form of a pigmentary powder:
TiO2 pigments produced by the chloride process are also partially
stabilized intrinsically or by means of surface treatment. Similarly to the
sulfate process, the ratio of rutile to anatase can be infuenced by the
choice of suitable reaction parameters. For exterior applications of TiO2
pigments, which are of great practical importance especially in the feld of
automotive coatings, stabilized rutile pigments are almost exclusively
used. The additional use of UV-absorbing substances in the pigmented
paint helps to ensure that TiO2-containing coatings easily achieve the
required long lifetimes. Titanium dioxide pigments are the best-known
white pigments in terms of optical properties, because of the high
refractive indices of 2.7 for rutile and 2.5 for anatase. The refractive
index as is optical material property that is defned as the ratio of the
speed of light in vacuum and the phase velocity of light in a medium into
which the light enters. High values, as in the case of titanium dioxide,
indicate high refection and strong hiding power and explain the
exceptional properties of titanium dioxide as a white pigment. The wide
use of TiO2 pigments is also due to the fact that they are very suitable for
brightening any other color shade. The chemical classifcation of titanium
dioxide, which for many years was considered unproblematic from a
regulatory point of view, has been the subject of intense discussion in the
last few years. In 2021, the responsible EU authority changed the
classifcation in such a way that several titanium dioxide powder qualities
(depending on the particle size) are to be classifed as carcinogenic.
Mixtures containing titanium dioxide in powder form with 1% or more of
TiO2 + 2 Cl2 + 2 C → TiCl4 + 2 CO (4) TiCl4 + O2 → TiO2 + 2Cl2. (5) the
particles with aerodynamic diameter ≤10 μm are consequently also
classifed as dangerous [51].
 ➢ Iron oxide pigments
Several processes are used today for the production of highquality iron
oxide color and black pigments [2, 52, 53]: • Solid state reactions (roasting
process) for red, black, and brown pigments • Precipitation reactions
(Penniman–Zoph process, scrap process) for yellow, red, orange, and
black pigments • Aniline process (Laux process) for yellow, red, and black
pigments In all cases, iron(II) sulfate heptahydrate (FeSO4·7H2O, green
salt) is used as the starting material. In the roasting process, oxidative
calcination produces α-Fe2O3 (summary equation without partial
reactions): The so-produced iron(III) oxide is used as a red pigment or can
be converted into black Fe3O4 by additional thermal treatment under
reducing conditions. The Penniman–Zoph process starts with an FeSO4
solution that, in the presence of an α-FeOOH seed suspension, reacts with
iron scrap to form pigmentary α-FeOOH (summary equation without
partial reactions): The iron oxide yellow obtained in this way can be
converted into iron oxide red by calcination in air at temperatures above
500 °C: Thermal treatment of α-Fe2O3 in reducing atmosphere, e.g., under
hydrogen or hydrogen-containing gases, can be used for the production of
black Fe3O4 pigments: In the Laux process, aromatic nitro compounds
react with iron flings in the presence of AlCl3 to form α-FeOOH and
aniline: The synthesis of α-FeOOH can also in this case be followed by a
further reaction to obtain α-Fe2O3 and Fe3O4. The latter is the most
important black pigment besides carbon black, but is also used as a
magnetic pigment.
The use (6) 6 FeSO4 ⋅ H2O + 11∕2O2 → 3α - Fe2O3 + 6SO3 + 6H2O. (7)
FeSO4 + Fe + 1∕2O2 + 3H2O → 2α - FeOOH + H2SO4 + 2
of iron(II) chloride instead of aluminum chloride in the Laux process leads
directly to Fe3O4 pigments with very high tinting strength.

➢ Attempts to develop new inorganic

pigments:
In the feld of inorganic pigments, great eforts have been made in recent
decades to develop new products and introduce them to the market.
These eforts have been successful above all in the area of efect pigments,
and to some extent also in functional pigments. In the case of white,
colored, and black pigments, however, no new representatives have been
added since the market launch of the yellow pigment bismuth vanadate in
the mid-1970s [2]. At least, since the beginning of the use of bismuth
vanadate, it has been possible to reduce the use of cadmium sulfde and
chromate pigments, which are classifed as toxic or carcinogenic [54]. In
the 1990s, a new red pigment, γ-Ce2S3, was developed and launched on
the market [55, 56]. One of several processes for producing this pigment
involves the reaction of Ce(OH)3 with H2S at temperatures ranging from
700 to 1000 °C. Attempts to use γ-Ce2S3 to displace red pigments
containing cadmium, lead, and chromate failed because it is not sufciently
stable in the presence of moisture and changes with the release of
hydrogen sulfde. Another attempt to develop and market new color-
intense yellow, orange, and red pigments was made around the year 2000
on the basis of oxonitrides (LaTaON2, CaTaO2N, SrTaO2N) [57]. The
production of such pigments involves a complicated solid-state reaction,
the transfer of which from laboratory to production scale has failed so far.
In addition, the high manufacturing costs prevented the further pursuit of
this development that is interesting from a coloristic point of view.
Oxonitride pigments are therefore not important from an industrial point
of view for future developments. A few years later, yttrium-indium-
manganese oxides with composition YIn1−xMnxO3 were reported to be
suitable as high-color blue pigments [58]. The production of such
pigments proceeds via the solid-state reaction route. The probability of
technical applications of such pigments can be considered low, since both
the availability of the raw materials and the production costs are
problematic. Basically, three challenges have to be overcome in all new
pigment developments: Effectiveness = technical performance (higher
color strength, better dispersibility in the application medium, and
increased hiding power) Economy = customer benefts (improved utility
value through lower pigment consumption and lower price per kg of
pigment) Ecology = environmental and toxicological safety (low content
or complete absence of critical heavy metals and low CO2 footprint in
pigment production). Only if these three criteria can be evaluated
positively can it be assumed that a pigment idea will be pursued to market
maturity [59]
 ➢ Efect pigments

The challenges regarding the development of new pigments have been

fulflled for many modern efect pigments, which have been the front-
runners in the feld of inorganic pigments since the 1980s. This applies in
particular to special efect pigments (transparent efect pigments,
pearlescent pigments, and interference pigments), but also to a lesser
extent to metallic efect pigments. Especially with special efect pigments,
unique gloss and color efects, e.g., iridescent, glittering, and iridescent
colors, can be achieved in the application. It is important that the platelet-
shaped pigment particles are oriented parallel to the substrate or surface
and parallel to each other in their application system. This is the only way
to achieve the desired optical efects in coatings, printing inks, plastics, or
cosmetic formulations. Typical metal efect pigments consist of thin metal
platelets with diameter of up to 100 µm and thickness of less than 1 µm.
Suitable metals for such pigments are aluminum and copper, but also
zinc/copper alloys [60]. The starting materials for metal efect pigments
are the corresponding metals in the form of ingots. These are usually
melted and then sprayed in liquid form. The resulting metal grit is then
mechanically formed into thin platelets in ball mills in the presence of
mineral oils, oleic and stearic acids. Dry grinding is out of the question for
safety reasons, as the fresh metal surfaces produced during the grinding
process are extremely reactive. In the case of aluminum pigments, which
are of greatest technical importance, a diferentiation is made today
between the following three types in the order of their time of origin:
“cornfake type,” “silver dollar type,” and “VMP type” (vacuum metallized
pigment). While the cornfake and silver dollar type are produced by the
process described above, the VMP type, developed only in recent years, is
produced by vacuum evaporation of metallic aluminum and deposition of
the vapor onto a polymer foil. The thin aluminum layer formed on the foil
after cooling is detached and ground into pigment particles. The pigment
particles obtained in this way are very thin. Their thickness is usually well
below 50 nm. Figure 7 shows electron micrographs of the three types of
aluminum pigment. The metallic gloss efects to be achieved are stronger
when the pigment surfaces are smoother and fewer scattering centers are
present at the edges and surfaces. Thus, from an optical point of view, the
silver dollar type and above all the VMP type
represent further developments of the traditional cornfake type [61].
Typical special effect pigments are based on the layer–substrate principle.
Thin platelets consisting of natural or synthetic mica, silicon dioxide,
aluminum oxide, or glass take over the function of a substrate. All these
substrate materials are optically low-refractive. The dimensions are on
the order of magnitude mentioned for metal efect pigments. Titanium
dioxide, α-iron(III) oxide, and other optically highly refractive metal
oxides form thin layers on the substrate platelets. The thickness of the
metal oxide layer is mostly in the range of 40–250 nm [62, 63]. In the
interaction with light, refection, refraction, and interference play the most
important role for these pigments. Depending on the coating material,
absorption also comes into play, e.g., in the presence of iron oxide layers.
Gloss and color efects are determined by the choice of substrate and
coating. Multiple layers can also be deposited on the substrate platelets. In
such cases, an alternating arrangement of high- and lowrefractive-index
layers is usually considered. Interference colors are produced by the
superposition of wavelengths of incident light refected at the interfaces.
The color efect thus produced depends on the layer thickness of one metal
oxide or more than one metal oxide (if several metal oxide layers are
used). Figure 8 shows the typical structure of a layer–substrate pigment.
As an example of such a pigment, a cross-section through a TiO2–mica
pigment is included (scanning electron micrograph). The layer–substrate
principle was frst used for efect pigments based on platelets of natural
mica. To date, mica platelets coated with TiO2 or α-Fe2O3 are among the
most important pigments in this class [2]. The production of such
pigments starts with the grinding of natural muscovite mica. The platelets
produced during the milling process are classifed to produce several grain
fractions. The fractions play a decisive role in determining the optical
properties of the pigment particles produced in the further manufacturing
process, since their size and shape are derived from the mica platelets
used. In the next step, the mica particles of a fraction are suspended in
water. A titanium salt solution (TiOCl2, TiOSO4) or iron salt solution
(FeSO4, FeCl3) is dropped into the suspension at elevated temperature
and defned pH with stirring. Under these conditions, titanium dioxide
hydrate or iron oxide hydrate nuclei are formed, which are deposited on

the mica platelets if the reaction is carried out appropriately. In the

course of the reaction, an oxide hydrate layer grows on the platelets, the
thickness of which is determined and adjusted by the amount of titanium
or iron salt solution added. After the precipitation reaction is complete,
the next steps are fltration, washing, drying, and calcination (700–950 °C).
Only after thermal treatment is titanium dioxide or iron(III) oxide formed
from the oxide hydrate on the surface of the mica platelets. This
simultaneously achieves the high refractive indices that are so important
for the refection of light at the pigment surface. In addition, the layers
adhere frmly to the substrate surface after calcination. In the case of
titanium dioxide, the anatase modifcation is always formed after thermal
treatment. To obtain rutile layers, thin tin dioxide layers are frst
deposited on the mica platelets. The structural relationship between SnO2
and TiO2 (rutile) causes the titanium dioxide formed during calcination to
crystallize in the rutile modifcation. As with the titanium dioxide white
pigments, surface coatings are also used for the metal oxide mica
pigments for reasons of increased stability and improved compatibility
with the application medium [2, 64]. More recent developments in special
efect pigments include pigments based on platelet-shaped silica
(goniochromatic color efects, i.e., strongly dependent on the viewing
angle), aluminum oxide (extremely sparkling color efects, especially in
paints, e.g., in automotive coatings), and borosilicate glass (particularly
intense and pure interference colors). For some years now, platelets made
of synthetic mica have also been available as substrates. A special
production process has been developed for each of these substrate
materials. The technology ranges from web coating (silicon dioxide) to
crystal growth from molten salt (aluminum oxide, synthetic mica) to
spraying of liquid glass drops from a glass melt onto a smooth substrate
New developments also include various efect pigments in which iron
oxide layers are deposited on aluminum platelets. Such pigments
combine the high hiding power of metal efect pigments with strong red,
orange, and gold tones resulting from the absorption of the iron oxide in
combination with interference phenomena [2]. Inorganic pigments with
functional properties such as anticorrosive and magnetic pigments have
been available for a long time. However, there is still a need for the
development of improved but also completely new products in this
segment. This involves functions such as corrosion protection, electrical
conductivity, IR refection, UV absorption, or laser markability. In all
functional applications, pigment and application medium must be well
matched to achieve the desired property of a surface, e.g., a paint flm
[65–68]. Some newer functional pigments are based on the layer–
substrate principle already presented for special efect pigments. This
principle can also be used in a suitable way for electrically conductive,
IR-refective, and laser-markable pigments [64, 65, 68]. Table 6 contains a
list of such pigments with compositions and applications. Electrically
conductive pigments based on mica platelets coated with a conductive
(Sn,Sb)O2 layer exhibit conductivity sufcient for antistatic fooring and
electrostatic wet painting. Their advantage over conductive carbon black
pigments is the light-gray color of the mica pigments, which ofers the
user extended coloristic possibilities. Certain infrared-reflective
pigments based on the layer–substrate principle are attracting growing
interest for various applications. The main focus is on the range of solar
thermal radiation (near infrared, 750–1400 nm). Mica pigments with
TiO2 layers of suitable thickness refect a large part of solar thermal
radiation from their surface while at the same time
allowing through the main part of the light visible to the human eye and
important for photosynthesis in plants (photosynthetic active radiation
(PAR), 400–750 nm). Thus, such pigments, embedded in polymers, can be
used in a favorable way for greenhouses and agricultural flms, but also
for transparent roof elements and exterior parts of buildings, where the
aim is to avoid temperature rises under solar infuence while maintaining
the transmission of visible light [64, 65]. Functional pigments based on
the layer–substrate principle are also suitable for laser marking of
polymers. Layers consisting of TiO2 or (Sn,Sb)O2 deposited on mica
platelets are particularly suitable for this purpose. When focused
 ➢ Uses of Pigments:

▪ Use in natural, synthetic and glass fiber dyeing.

▪ It is mostly use for printing
▪ Use for blended fabric dyeing
▪ Use in dope dyeing
▪ It also used for the coloration of metal, wood, stone, soap,
▪ detergent, colored pencil, PVC, rubber, paper and other
surfaces as paint.

➢ Advantages of Using Pigments

▪ Applicable to all kinds of fibers and fiber blends

▪ Compound shades are produced with ease
▪ . Easy and cheap process
▪ Easy shade matching Environment friendl
▪ The full-color range is available
 ➢Disadvantages of Using Pigments .

▪ Depth of shade usually limited to light to medium

▪ Make the fabric stiffer and so uncomfortable
▪ Sometimes fastness
▪ . Rubbing is not good

➢ Summary
The history of inorganic pigments began thousands of years ago. From the
use of natural pigments in cave and wall painting to the synthetic
pigments most commonly used today, it has been a long road marked both
by man’s search for ever new color design possibilities and by the use of
empirically gained knowledge and later systematic, scientifcally based
chemical research. Today, a wide range of inorganic white, colored, black,
and efect pigments are available, which when supplemented by organic
pigments, can comprehensively serve all relevant applications in color
design. However, there is great interest in replacing pigments containing
cadmium, lead, and chromate with pigments of the same color quality.
Little progress has been made in this respect in recent decades (the
exception being the yellow pigment bismuth vanadate, launched in 1975).
Many inorganic compounds would be well suited as pigments in terms of
their color but are not considered due to their toxic or carcinogenic
properties. Many developments in recent decades have been directed
primarily at optimizing the properties of existing pigments in terms of
grain size, crystal structure, purity, stabilization (UV radiation), and good
compatibility with the application medium. Innovations that have led and
continue to lead to a large number of new products are to be found in
efect pigments and functional pigments. Innovative new developments
can also be expected in this feld in the coming years. Funding Open Access
funding enabled and organized by Projekt DEAL. Open Access This article
is licensed under a Creative Commons Attribution 4.0 International
License, which permits use, sharing, adaptation, distribution and
reproduction in any medium or format, as long as you give appropriate
credit to the original author(s) and the source, provide a link to the
Creative Commons licence, and indicate if changes were made. The images
or other third party material in this article are included in the article's
Creative Commons licence, unless indicated otherwise in a credit line to
the material. If material is not included in the article's Creative Commons
licence and your intended use is not permitted by statutory regulation or
exceeds the permitted use, you will need to obtain permission directly
from the copyright holder. To view a copy of this licence,
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