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, 16,17,18].

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 fire 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 [19,20,21].

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 sulfide (galena) for black tones, iron oxide red and copper in colloidal form for red tones, and calcium carbonate and kaolinite for white tones. Arsenic sulfide and Naples yellow were the first 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 first 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 (flux) [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 [24,25,26,27].

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 (ca. 1270–1337). The Florentine painter Cennino Cennini (ca. 1370–1440) was the first 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 influential 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 first 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 specific 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 differentiated fields of application [18, 28,29,30,31]. 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, 32,33,34,35].

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, purified). 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, 36,37,38].

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 first 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 first to succeed in synthesizing this pigment, in 1706 in Berlin. It took some time until the preparation route was fully developed. The synthesis was finally 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 suffruticosa and other plant species), to the clay matrix of palygorskite, a fibrous 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 suffruticosa 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 identification 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 diffraction 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.