New methods for the identification of malachite pigments with varying particle sizes used in ancient Chinese murals by spectroscopic techniques

Abstract

This study attempts to propose a simple, low-interventive and higher accuracy identification method for malachite pigments with varying particle sizes based on attenuated total reflection-Fourier transform infrared (ATR-FTIR), and evaluate the accuracy of ATR-FTIR and ultraviolet–visible near-infrared (UV-VIS-NIR) spectroscopy for identifying particle sizes. The micro-morphology, particle size, colour difference, and spectral characteristics of the malachite samples were determined using scanning electron microscopy (SEM), laser particle size analysis, colourimetry, UV-VIS-NIR and ATR-FTIR spectrometry. The principal component analysis (PCA) and mathematical models based on nonlinear curve fitting using UV-VIS-NIR and FTIR spectral data were developed and evaluated for the particle size identification of various malachite samples (pure malachite samples, fresh and aged malachite-rabbit glue samples). SEM morphological results showed that the malachite pigments with smaller particle sizes appear to have irregular flakes with a few loose agglomerated granules attached to the surface. The weight-specific surface area also increased gradually as the pigment particle size decreased. The colour difference results revealed that smaller malachite particle size gradually shifted toward the red–blue regions in CIE L*a*b* colour space. In addition, more intense reflectance and IR spectral absorbance peaks were observed in the case of the smaller particle size. The above proposed methods of particle size identification proved to be highly feasible and effective in predicting pigment particle size, which were confirmed by the PCA identification results and the mathematical model. Also, ATR-FTIR spectroscopy could provide more accurate predictions than UV-VIS-NIR spectroscopy, by keeping prediction errors below 5.5 μm.