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The objective of this study was to evaluate the use of micro-Raman spectroscopy as a non-invasive vibrational spectroscopic technique applied to the examination of wool samples, which may be applied to textile materials of cultural heritage interest. In this work, a selection of wool materials were primarily investigated in their unaged states through the utility of a natural wool reference together with selected samples dyed with different natural colorants, namely woad, weld and madder. The identification of the main modes of vibration of the wool fibre keratin was assessed in all the samples, which aided the determination of the changes within the protein structure, in particular, through the cysteine and peptide cross-linkages brought about by the addition of the dyes that can produce effects similar to degradation. The dye too was assessed importantly to enable its identification through its characteristic scattering or fluorescence emissions on a woollen matrix, as well as to ascertain whether a uniform covering across the surface of the wool was achieved or not. Regarding the artificial degradation of the samples it was possible to observe numerous modifications within the molecular structure of the wool, in particular, within the amide I, C-H bending, amide III and S-S stretchings along with the physical photo-yellowing of fibres given by the presence of lipids dispersed across the surface of the wool. The effects of ageing on the dyed samples were also investigated, indicating that many of the bands relative to the colorants were still present, yet so too were numerous vibrations from the wool that also indicated a certain level of stress and degradation to the underlying wool.

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