ABSTRACT
Terahertz spectroscopy has been increasingly utilized as an effective nondestructive tool for the diagnosis, analysis, and restoration of artworks. In particular, in the case of artist's pigments, the terahertz probe reveals the vibrational modes that are unique to a given pigment species under study, motivating the ongoing efforts to establish a comprehensive terahertz spectral database of representative pigments. Standard archived spectra are typically acquired at room temperature and susceptible to spectral broadening, which often renders pigment identification difficult, if not impossible. In this paper, we report the frequencies of the vibrational modes of minium (Pb3O4, red lead) by performing terahertz time-domain spectroscopy at room temperature and also at low temperatures. Clear absorption peaks appear at 54.9, 62.1, 71.3, and 83.9 cm-1 at room temperature and blue-shift as the temperature decreases. In addition, new absorption peaks of 59.8 and 66.4 cm-1 are observed below 150 K, which signify a structural phase transition occurring at 170 K in minium. Our results are expected to enhance our understanding of the vibrational activity of minium and suggest a future direction for how to improve and refine the existing terahertz spectral databases for pigment analysis.
ABSTRACT
Terahertz spectroscopy can be utilized as an effective nondestructive identification tool for the study of artist's pigments. Consequently, extensive measurements have been conducted on representative pigment species, and a few terahertz spectral databases have been constructed. However, the reported spectra were often acquired from pigment samples mixed with polyethylene at room temperature with low resolution, which often led to low-quality spectra with unresolved overlapping lines further broadened due to thermal effects. Here, we present our study of vermilion (HgS, mercury sulfide) as an illustration of how we can overcome such difficulties by studying free-standing oil-paint samples at room temperature and then by performing low-temperature measurements on polyethylene-mixed samples to minimize line broadening due to thermal effects. Our results identify clearly resolved absorption peaks due to lattice vibrations of vermilion at 40.4, 44.5, and 89.9 cm-1 at 2 K. The temperature dependence of the peak shift and line broadening reveals anharmonic characteristics of these lattice vibrational modes. Our approach will definitely suggest new ways to improve and enhance existing terahertz spectral databases of ancient and modern pigments toward actual analysis, diagnosis, and conservation of heritage artworks.
