An analytical study on the nave mural paintings of the church "The Nativity of the Virgin" of Rila monastery, Bulgaria, painted by Zahari Zograph was carried out. Vibrational spectroscopy was applied to identify the pigments and organic materials used in the mural paintings. To complement the spectral information, elemental composition of the samples was determined by SEM-EDX. The data showed that smalt with carbohydrate binder was applied for the blue background, green colour was executed by green earths and red-orange colourby red lead. Azurite is the pigment used to paint the blue colour of the saints' hoods. The mordant for gilding was prepared of drying oil, resin and siccative metal oxides as evidenced by SEM-EDX, ATR-FTIR and pyrolysis GC-MS analysis. The use of azurite is related to Zahari Zograph's works as it was not found in any of the previously studied murals in the church painted by other artists.
For the first time, wall paintings of 20th century Russian artists in Bulgaria were analysed by means of complementary analytical methods. Representative samples collected from the Russian church St. Nicholas in Sofia, decorated by the famous Russian artists Vasily Perminov, Michail Maletski and Nikolay Shelehov during different periods of time, were examined by means of micro-Raman spectroscopy, attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy and X-Ray fluorescence (XRF). The results of the study reveal that colourful palette was achieved by using various pigment mixtures of traditional and modern synthetic pigment as titanium white, barium white, calcite, chrome green, green earth, hematite, ultramarine, madder lake, carbon black, vermilion, Naples yellow. The analysis of the paint binders allow to conclude that Maletski and Shelehov have used egg tempera as painting technique, while Perminov has worked in two painting techniques - oil and egg tempera.
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