Economic and Environmental Geology (자원환경지질)

The Korean Society of Economic and Environmental Geology (대한자원환경지질학회)
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Degradation of Lead-based Pigments by Atmospheric Environment

납계열 안료의 대기환경에 따른 열화특성

  • Park, Ju Hyun (National Research Institute of Cultural Heritage, Restoration Technology Division) ;
  • Lee, Sun Myung (National Research Institute of Cultural Heritage, Restoration Technology Division) ;
  • Kim, Myoung Nam (National Research Institute of Cultural Heritage, Restoration Technology Division)
  • 박주현 (국립문화재연구소, 복원기술연구실) ;
  • 이선명 (국립문화재연구소, 복원기술연구실) ;
  • 김명남 (국립문화재연구소, 복원기술연구실)
  • Received : 2022.05.23
  • Accepted : 2022.06.24
  • Published : 2022.06.28
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Abstract

We examined degradation characteristics of lead based pigments(white lead, Red lead, Litharge) according to atmospheric environmet condition, for example atmospheric gas(CO2, NO2) and soluble salt. Painted samples not changed material compositions but were occured the color change(𝚫E 4~31) after exposed UV irradiation. All sample were not affected by CO2 gas not only color but chemical composition. However, samples were remakably changed color exposed NO2 gas and it was formed secondary product like as lead nitrate. Such as red lead and white lead samples' color difference were 𝚫E 2 and 𝚫 10 respectively and became dark, along with litharge became bright and color difference was 𝚫E 5 after react with NO2 gas. It confirm that NO2 was influential factor than CO2 in the case of same concentration. Furthermore salt spray test was taken to figure out soluble salt influence in fine dust. The result showed noticeable color change and secondary product was formed on samples' surface. The glue film peeled off or hole, and color changed around the secondary products. After salt spray, XRD pattern showed decrease peak intensity and lower crystalinity. As a result of salt spray test, white lead was formed new product litharge and litharge was formed litharge and minium. According to the results, influential atmospheric factors for conservation of paint pigments were UV, NO2, soluble salt, and litharge was most weakness throughout lead base pigments.

연백, 연단, 밀타승으로 대표되는 납계열 안료의 대기환경에 따른 열화특성을 규명하였다. 자외선에 노출된 채색시편들은 모두 색차가 4~31로 어두워졌으나 성분에 변화는 없었다. CO2는 시편의 색상 뿐 아니라 성분 변화에 큰 영향을 주지 못하였다. 반면 NO2에 노출된 시편들은 색변화가 크게 나타나고 Lead nitrate(Pb(NO3)2)와 같은 2차 생성물이 확인되었다. 연백과 연단은 NO2에 의한 색차가 각각 2와 10으로 시험 전에 비해 어두워졌으나 밀타승은 색차가 5이고 시험 전에 비해 밝게 변했다. 이를 통해 CO2와 NO2가 동일한 농도일 경우 CO2에 비해 NO2가 안료 보존에 영향력 있는 대기환경 인자임을 확인할 수 있다. 미세먼지에 존재하는 염의 영향을 보기 위해 5% NaCl(in distilled water)를 제조하여 염수 분무 시험을 실시하였다. 그 결과 연백, 연단, 밀타승 모두 시편 색변화와 함께 표면에 2차 생성물이 형성되었다. 이로 인해 아교도막이 박락되거나 hole이 형성되었으며, 생성물을 중심으로 색상이 변하였다. 또한 염수분무 후 XRD 피크 강도와 결정도가 함께 낮아진 것을 볼 수 있다. 염수분무 후 시료의 성분분석 결과 연백의 경우 Litharge가, 밀타승의 경우 Litharge와 Minium이 새로 형성되었다. 이를 통해 채색안료의 보존에 영향력 있는 대기환경 인자는 자외선, NO2, 수용성 염임을 확인하였고 특히 납계열 안료 중 밀타승의 안정성이 다른 안료에 비해 낮은 것을 알 수 있었다.

Keywords

Acknowledgement

본 연구는 문화재청 국립문화재연구원 문화유산 조사연구(R&D)사업의 지원을 받아 수행되었습니다.

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