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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.

We have established optimal methods for terahertz time-domain spectroscopic analysis of highly absorbing pigments in powder form based on our investigation of representative traditional Chinese pigments, such as azurite [blue-based color pigment], Chinese vermilion [red-based color pigment], and arsenic yellow [yellow-based color pigment]. To accurately extract the optical constants in the terahertz region of 0.1 - 3 THz, we carried out transmission measurements in such a way that intense absorption peaks did not completely suppress the transmission level. This required preparation of pellet samples with optimized thicknesses and material densities. In some cases, mixing the pigments with polyethylene powder was required to minimize absorption due to certain peak features. The resulting distortion-free terahertz spectra of the investigated set of pigment species exhibited well-defined unique spectral fingerprints. Our study will be useful to future efforts to establish non-destructive analysis methods of traditional pigments, to construct their spectral databases, and to apply these tools to restoration of cultural heritage materials.

회화문화재의 손상상태를 진단하기 위하여 현재까지 국내에서는 육안관찰, 적외선 촬영, X선 촬영 등이 활용되고 있으나 표면에서 확인되지 않는 하부층의 손상상태에 대한 3차원적 정보획득에는 한계점이 있었다. 본 연구에서는 최근 우리나라에서 문화재 분야에 막 응용되기 시작한 테라헤르츠 분광분석기술을 회화문화재 상태진단에 적용하는 연구를 수행하였다. 먼저 우리나라 회화문화재의 손상양상을 고려한 의사시편을 제작하고 테라헤르츠 반사펄스 이미징기술을 적용하여 채색층 하부의 바탕층 및 배접층의 손상에 대한 정보 획득을 시도하였다. 그 결과 바탕층과 배접층의 균열, 층위 간 이격, 이격의 범위와 정도에 대한 정보획득이 가능함을 확인할 수 있었다. 또한 의사시편에서 얻어진 결과를 바탕으로 실제 회화문화재인 보물 제1792호 남양주 봉선사 비로자나삼신괘불도에 대하여 테라헤르츠 이미징기술을 적용한 결과, 유물의 3차원적 손상 형태와 손상 정도에 대한 정보를 획득할 수 있었다. 이는 비파괴, 비접촉식의 테라헤르츠 이미징기술이 우리나라 회화문화재의 3차원 손상상태 진단에 활용될 수 있음을 확인시켜 주는 결과이다.