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Abstract This article describes a quantitative assessment method proposed to quickly identify the degree of deterioration of hardened leather artefacts. We used three techniques to artificially age samples, namely, dry-heat ageing (DH), UV-ageing (UV), and alkali-thermal ageing (AT). The deterioration mechanisms were studied via thermogravimetry/derivative thermogravimetry (TG/DTG) and attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR). Combined with amide III band deconvolution and second derivative fitting, we constructed a method for assessing the degree of deterioration by the relative content of random coils (referred to as R) in the secondary structure of the protein. The results show that with increasing ageing time, the macrostructures and microstructures of the leather changed to varying degrees. This study elucidates the differential behaviour of vegetable-tanned leather collagen under oxidative and hydrolytic mechanisms. Based on the deterioration characteristics and fitting results, we divided the hardened leather into the following three levels. Mild deterioration: 0 ≤ R ≤ 5%; leather with reduced pores and slight dryness and hardness but with a stable collagen structure; if the β-sheet content is ≥ 68% at this point, the leather may be recrosslinked by ultraviolet irradiation. Moderate deterioration: 6 ≤ R ≤ 25%; partial hydrogen bond breaking in leather, loosening of the collagen–tan matrix, dry and hard curling of the leather surface, and fibre cementation. Severe deterioration: R ≥ 40%, β-sheet ≤ 24%, and the α-helix is higher; surface reflection, severe macroscopic deformation and embrittlement, and the breakdown and gelatinization of the three-stranded helical structure of leather proteins. The quantitative analysis method was suitable for studying the deterioration mechanisms and assessing the degree of deterioration in Heishanling leather artefacts, which also provides a new practical scheme for assessing the degree of hardened leather. Graphical Abstract |
