Monitoring UV-accelerated alteration processes of paintings by means of hyperspectral micro-FTIR imaging and chemometrics.

We explored the potential of infrared hyperspectral microimages to investigate the alteration of organic binders in pictorial layers after artificial UV light ageing. A set of paint mockups was prepared considering three different binders, namely, rabbit glue (a collagen-based proteinaceous binder), linseed oil (representative of drying oils) and egg tempera (a mixture of egg yolk and linseed oil). Four pigments (vermilion, orpiment, azurite and lead white) were considered in order to investigate the influence of pigment-binder interaction, following color changes by means of fiber optic reflectance spectroscopy (FORS). FTIR micro-images provided a representative picture of the complex and heterogeneous structure of paintings since each pixel contained the whole spectrum of the sample area from it was recorded. Principal component analysis (PCA) was used to analyze the FTIR images data in order to extract useful information about spectral changes taking place during UV induced ageing. Significant trends were observed, mainly depending on the binders and their degradation as a consequence of UV exposition in this pilot study on model samples. Several processes, such as the oxidation of proteins with the formation of carbonyl moieties and changes in amide band positions have been detected in the case of rabbit skin glue. The evaporation of linseed oil, probably due to the breakdown of the triacylglycerols, has been noticed for the binder alone but not when it was mixed with the pigments. In these cases, other spectral features depending on the pigment have been observed in the loading plots upon oxidation, namely the broadening of the carbonyl band, the appearance of carboxylic and dicarboxylic acids and the formation of metal carboxylates. For egg tempera, the main changes detected were related to the oxidation of lipidic components present in egg yolk fraction. Furthermore, in this case, the trend observed in the score graphs suggested that the presence of lead white accelerates its oxidation. It is interesting to note the major stability of the colored pigments when using this binder.