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Experimental study for removing silver sulfide from silver objects by Nd:YAG laser cleaning

은제품의 황화은 부식층 제거를 위한 Nd:YAG 레이저클리닝 실험 연구

  • Lee, Hyeyoun (Division of Restoration Technology, National Research Institute of Cultural Heritage) ;
  • Cho, Namchul (Department of Cultural Heritage Conservation Science, Kongju National University)
  • 이혜연 (국립문화재연구소 복원기술연구실) ;
  • 조남철 (국립공주대학교 문화재보존과학과)
  • Received : 2014.01.24
  • Accepted : 2014.03.04
  • Published : 2014.03.20

Abstract

Silver objects tarnish with black from reaction with sulfurous acid or hydrogen sulfide of atmospheric. Blackening of silver objects results from formation of silver sulfide($Ag_2O$) on the surface. Silver sulfide usually is usually removed by conservation treatment. There are several cleaning methods such as chemical, electrochemical and micro-abrasion cleaning, but all of them consume silver. This study investigated the safe and effective parameter of laser cleaning by test on silver coupons. Laser cleaning is a selective process for the removal of specific substances. At first, laser cleaning applied to plain silver coupons, which were not corroded, to find out the safe range of laser energy density. From results, plain silver coupons were not changed at 1064nm below $4.00J/cm^2$ and at 532nm below $2.39J/cm^2$. The corrosion layer(silver sulfide) of artifical corroded silver coupons was removed at 1064nm with $2.39J/cm^2$ by 5~10 pulses and at 532nm with $1.19J/cm^2$ by 5~10 pulses. The removal thickness of corrosion layer was about 13-25nm per a laser pulse using AES analysis. In addition, laser cleaning tested the tarnish silver rings based on the results of silver coupons. As a result of test, the black surface were clean successfully and gave luster of silver, which showed the application possibility of laser cleaning for silver objects.

은제품은 대기의 아황산가스나 황화수소 등과 반응하여 검게 변색된다. 검은 변색은 표면에 황화은이 형성되는 것으로 보존처리시 제거하는 것이 일반적이다. 황화은을 제거하는 방법은 화학적, 전기화학적, 미세마모법 등을 사용하지만 모두 은의 손실을 초래한다. 따라서 본 연구는 표면 오염물만을 선택적으로 제거할 수 있는 레이저클리닝을 은시편에 실험하여 안전하고 효율적인 레이저 조건을 알아보고자 하였다. 먼저 부식되지 않은 순수한 은에 레이저를 조사하여 안전한 레이저에너지밀도 범위를 확인하였다. 실험 결과 은은 1064nm $4.00J/cm^2$ 이하, 532nm $2.39J/cm^2$ 이하 레이저에너지밀도 범위에서 안전하였다. 인공적으로 부식시킨 은판의 부식층(황화은)은 레이저조건 1064nm $2.39J/cm^2$로 약 5~10회, 532nm $1.19J/cm^2$로 5~10회 조사하였을 때 제거되었다. AES를 이용하여 레이저 펄스당 제거되는 부식층 두께를 확인한 결과 약 13 ~ 25nm이다. 은 시편의 레이저클리닝 조건을 은제품에 적용한 결과 표면의 검은 부식층이 제거되었으며 은 광택도 유지되었다. 이를 통해 은제품의 레이저클리닝 적용 가능성을 확인하였다.

Keywords

References

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