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A Study on the Changing Properties of Iron Oxides in Black Glazes using Raman Microscope -Focused on Black Glazes Excavated in Shinan Shipwreck-

라만분광현미경을 이용한 흑유자 유약 내 철산화물의 변화 양상 연구 -신안선 출수 흑유자를 중심으로-

  • Park, Jin Ho (Conservation Science Division, National Museum of Korea) ;
  • Yu, Heisun (Conservation Science Division, National Museum of Korea) ;
  • Chung, Yong Jae (Department of Heritage Conservation and Restoration, Graduate School of Cultural Heritage, Korea National University of Cultural Heritage)
  • 박진호 (국립중앙박물관 보존과학부) ;
  • 유혜선 (국립중앙박물관 보존과학부) ;
  • 정용재 (한국전통문화대학교 문화유산전문대학원 문화재수리기술학과)
  • Received : 2018.11.09
  • Accepted : 2019.04.09
  • Published : 2019.04.20

Abstract

In this study, black-glazed porcelain excavated from the Shinan shipwreck is analyzed to distinguish its characteristics. Glazes of Hong-Tang kiln are thin and exhibit little vitrification, whereas the Ci-Zhou-type and Cha-Yang kilns are similar in terms of their cross section. However, Raman mapping images reveal difference in the distribution area of magnetite. In this study, firing experiments are conducted to determine how iron oxides change properties in black glazes. The results show that when hematite is fired to a temperature greater than $1250^{\circ}C$, it becomes magnetite. Therefore, it is estimated that a firing temperature of approximately $1200^{\circ}C$ is suitable for the Hong-Tang kiln. In addition, glazes of the Ci-Zhou-type and Cha-Yang kilns are fired at approximately $1300^{\circ}C$. However, when the characteristics of firing in ancient kilns are considered, porcelain can be fired for a sufficiently long period to extend to glaze surfaces.

신안선에서 발견된 흑유자 중 자주요계, 차양요, 홍당요 등 3곳으로 분류된 6점의 유약에 대해 과학적 분석을 실시하였다. 홍당요는 유약 두께가 얇고 자화가 거의 이루어지지 않았다는 점에서 큰 차이를 보였다. 차양요와 자주요계 흑유자의 경우 단면상으로는 서로 공통점이 확인되었으나 라만 매핑 이미지를 통해 자철석의 분포 범위에서 차이가 있는 것으로 확인되었다. 이러한 차이가 나타나는 원인과 흑유자의 유약 형성 조건을 알아보고자 실시한 소성 실험 결과, 발색제로 사용된 적철석($Fe_2O_3$)은 $1250^{\circ}C$ 보다 높게 소성될 때 자철석($Fe_3O_4$)으로 변하여 흑색을 띠는 것으로 나타났다. 따라서 홍당요 흑유자는 약 $1200^{\circ}C$, 자주요계와 차양요 흑유자는 $1250{\sim}1300^{\circ}C$에서 소성하였을 것으로 추정하였다. 다만 고대 가마의 소성 특성을 고려할 때 자철석의 영역이 유약 표면까지 확장될 수 있을 정도로 오래 소성되었을 가능성도 배제할 수 없다. 향후 흑유자 유약에 대한 라만 스펙트럼 및 매핑 이미지의 데이터베이스 구축과 더불어 추가적인 실험이 이루어진다면 흑유자의 제작 조건을 규명하는 데 도움이 될 것으로 기대된다.

Keywords

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