Winsor & Newton original handbooks: a surface-enhanced Raman scattering (SERS) and Raman spectral database of dyes from modern watercolor pigments

Background: Winsor & Newton Ltd. has been one of the main fine art products providers since its establishment in 1832, being responsible for the manufacture of a wide assortment of materials ranging from oils and pigments to brushes and papers. All the items produced over the years have been indexed in a comprehensive historical archive. Original Winsor & Newton handbooks are a powerful resource which can offer insight into the world of artists' materials, and knowledge of artists' choices through the identification of substances employed to obtain particular colors. Scientific analyses of various kinds have been carried out on Winsor & Newton art materials over the years; however, a detailed study of the organic dyes contained in the watercolors manufactured by the company has never been performed thus far to our knowledge. Results: In the present study, we examined a number of color washes on drawing paper from two historical Winsor & Newton catalogues dating to the 19th and 20th century. An appropriate database was thus built, including surface-enhanced Raman scattering (SERS) and Raman spectra of organic colorants from a wide variety of shades. While the selection of colors offered by the company in the 19th century mostly included lakes prepared from plant and insect dyes, i.e. madder and cochineal, some tints based on synthetic dyes were also found in the 20th century handbook. Conclusions: The present article sheds new light on the chemical composition of a number of original Winsor & Newton color washes in terms of organic colorants contained in each shade. A special attention was dedicated to the analysis of those colors for which the formulation was ambiguous or not specified by the manufacturers, such as dragons' blood and most of the alizarin-based pigments. In addition, we were able to correct erroneous indications provided by Winsor & Newton on the composition of some tints, as in the case of violet carmine, and study how the formulation of certain pigments has been modified over the centuries.