Assessment of Raman microscopy coupled with principal component analysis to examine egg yolk–pigment interaction based on the protein CH stretching region (3100–2800 cm −1 )

This work seeks to identify the slight changes in the characteristic CH stretching region (3100–2800 cm −1 ) of a protein‐based binder and fatty acid esters from egg yolk, which may occur in complex paint samples due to the presence of particular pigments. To date, this protein region—where historic pigments do not show characteristic Raman bands—has not been used to identify possible interactions between painting materials, in spite of its potential due to the mentioned feature. This study is based on the investigation of pure egg yolk model samples and tempera model samples prepared by mixing this binder with some historic pigments (cinnabar, raw Sienna, lead white, gypsum, calcite, azurite, lapis lazuli and smalt) as binary samples. All samples were analyzed in this region by Raman microscopy (RM) coupled with principal component analysis (PCA) for three color groups (red, white and blue) separately. The results show relevant spectral changes in the CH stretching region of amino acids and polyunsaturated fatty acids esters of the egg yolk binder, particularly in the azurite, lead white and gypsum‐based tempera samples. Lesser interactions were discerned in the tempera samples made with smalt, as well as shift in the region of polyunsaturated fatty acid esters of the egg yolk binder in the cinnabar and raw Sienna‐based tempera paintings. No interactions were recognized between the egg yolk and the pigments calcite and lapis lazuli. The effectiveness of applying RM combined with PCA for identifying interaction processes between binders and pigments is demonstrated. Copyright © 2011 John Wiley & Sons, Ltd.