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Effect to the Discoloration of Lead Based Pigments by the Factors of Air Environment

납(Pb) 계열 안료의 변색에 관한 대기환경인자의 영향 연구

  • Lee, Yu Jeong (Department of Cultural Heritage Conservation Science, Korea National University of Cultural Heritage) ;
  • Kim, Ji Won (Department of Heritage Conservation and Restoration, Graduate School of Cultural Heritage, Korea National University of Cultural Heritage) ;
  • Han, Min Su (Department of Heritage Conservation and Restoration, Graduate School of Cultural Heritage, Korea National University of Cultural Heritage) ;
  • Kang, Dai Ill (Department of Cultural Heritage Conservation Science, Korea National University of Cultural Heritage)
  • 이유정 (한국전통문화대학교 문화재보존과학과) ;
  • 김지원 (한국전통문화대학교 문화재수리기술학과) ;
  • 한민수 (한국전통문화대학교 문화재수리기술학과) ;
  • 강대일 (한국전통문화대학교 문화재보존과학과)
  • Received : 2017.02.28
  • Accepted : 2018.04.15
  • Published : 2018.04.20

Abstract

Lead-based pigments (Lead White, Massicot, and Red Lead) are known to cause discoloration easily in indoor air environments. This study was conducted to investigate the effect of representative indoor air environment factors ($O_2$, $CO_2$) on lead-based pigments. As a result of the experiment, almost all of the specimens showed changes of more than ${\Delta}E=5.0$ in their values of chromaticity under $O_2$ (99%, RH 99%) and $CO_2$ (36,000 ppm, RH 99%) environments. Scanning electron microscopy also showed that the pigment particles lose sharpness of the edge. Furthermore, under the degradation, the intensities of the characteristic peaks in the X-ray diffraction patterns were decreased, and Lead White, Massicot, and Red Lead exposed to $CO_2$ (36,000 ppm, RH 99%) were shown to include the new material cerussite ($PbCO_3$). In particular, Plattnerite ($PbO_2$) was identified on Massicot, and for white lead, the characteristic peaks disappeared and those of Cerussite were identified. It was confirmed that chemical change with discoloration can occur when these lead-based pigments are exposed to a high-humidity $CO_2$ environment.

납 계열 안료(연백, 밀타승, 연단)는 대기환경에서 변색이 쉽게 일어나는 것으로 알려져 있다. 본 연구는 산소($O_2$)와 이산화탄소($CO_2$)가 납 계열 안료인 연백, 밀타승 및 연단의 변색에 어떤 영향을 미치는지 관찰하였다. 실험 결과, $O_2$(99%, RH 99%)와 $CO_2$(36,000 ppm, RH 99%) 환경 하의 대부분의 안료 시편에서 ${\Delta}E=5.0$ 이상의 변색이 관찰되었다. 주사전자현미경 관찰에서는 안료입자의 모서리가 마모되는 현상을 관찰하였다. 또한 XRD 분석에서 열화 후 각 안료의 특징적 회절피크가 약해졌으며, $CO_2$(36,000 ppm, RH 99%)에 노출시킨 연백, 밀타승, 연단 시편은 탄산납의 주요 회절피크가 확인되었다. 특히 밀타승 시편은 Plattnerite($PbO_2$) 결정이 확인되었으며, 연백 시편은 기존의 XRD 피크들이 사라지고 Cerussite($PbCO_3$)가 동정되는 특징도 확인되었다. 이를 통해 고습의 $CO_2$ 환경에 납 계열 안료가 노출될 경우, 변색을 동반한 화학적 변화가 일어나는 것을 확인할 수 있었다.

Keywords

References

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