Analytical studies on commercial artists’ colour charts from Das Deutsche Farbenbuch (1925)—identification of synthetic and natural organic colourants by Raman microscopy, surface-enhanced Raman spectroscopy and metal underlayer ATR-FTIR spectroscopy

Historical colour charts provide a rich and often well-dated reference materials source for studying the chemical composition of all kinds of commercial brands of artists' paints. This article presents the results of an extensive analytical study of more than 80 paint hues from 11 colour charts that are included in the German standard book Das Deutsche Farbenbuch by H. Trillich (1925, Part II). Our research focused on the identification of synthetic organic pigments, whose quickly increasing significance for artists' paints in the early twentieth century is impossible to evaluate by documentary source research alone. A stepwise procedure combining different non- or minimally invasive vibrational spectroscopy techniques-Normal Raman and Surface-Enhanced Raman spectroscopy as well as Metal Underlayer Attenuated Total Reflection Fourier-transform Infrared Spectroscopy-allowed the identification of 18 different organic colourants in artists' watercolours, tempera and oil colours from six German manufacturers. In addition, micro-X-Ray Fluorescence spectroscopy was applied to determine the elemental pattern of substrates, fillers, and admixed inorganic pigments. In addition to a few traditional natural organic colourants (dark and rose madder lake, cochineal lake), most of the identified compounds comprised synthetic organic pigments or synthetic dyes from various chemical classes (indigo, anthraquinone, monoazo, ss-naphthol, xanthene, triarylcarbonium, nitroso, and azine compounds). Some of these have not or only rarely been reported in artists' paints so far. Since the identified organic colourants have mainly poor to fair (only sometimes good) fastness to light according to modern standards and partially also to solvents typically used in conservation treatments, it is evident that works of art from this period should be treated keeping in mind the possible presence of such colourants, when planning both interventive treatments and preventive measures.