DOI QR코드

DOI QR Code

Study on Characteristics of Corrosion Products Generated in Iron Artifacts after Conservation Treatments

보존처리 후 철제유물에 생성된 부식물 특성 연구

  • Jeong, Ji-Hae (Division of Conservation Treatment, Yeongnam Institute of Cultual Properties) ;
  • Yang, Hee-Jae (Department of Cultural Properties, Gyeongju University) ;
  • Ha, Jin-Uk (Department of Energy & Environmental Engineering, Soonchunhyang University)
  • 정지해 (영남문화재연구원 보존처리팀) ;
  • 양희제 (경주대학교 문화재학과) ;
  • 하진욱 (순천향대학교 에너지환경공학과)
  • Received : 2013.05.16
  • Accepted : 2013.12.10
  • Published : 2013.12.20

Abstract

Iron objects become corroded at fast speed from the moment when they are excavated, so it is needed to control corrosion through processes of conservation treatment. However, re-corrosion mostly takes place in excavate iron objects, although they have already gone through the process of conservation treatment, and it is more difficult to carry out the second conservation treatment of re-corroded excavated iron objects than the first conservation treatment, and it requires a longer period of time to treat them as well. In this study, aims to discover factors of re-corrosion by scientifically analyzing corrosion products generated during the process of storage after the process of conservation treatment. The finished on conservation treatment of the iron artifacts, which were unearthed from three ancient site in Gyeongju by using the same conservation method between 2002 and 2009, re-corrosion condition observed on the packaging-iron artifacts. Focused on 9 target forged iron artifacts among them, this study analyzed the physical changes by mass measurement, naked-eye and microscopic observations and the chemical changes by SEM-EDS, XRD, IC and ICP analysis. The results show that the yellowish brown corrosion products formed on the facing surface of part dropped from the artifacts had different associated forms but acicular shape. In addition, the acicular shape became clearer as the color changed from red to yellowish brown. According to the process when the conservation treatment was completed, the mass of the artifacts increased in proportion to the corrosion products and the chloride ion ($Cl^-$) concentration had a tendency to increase relatively. ${\beta}$-FeOOH (akaganeite) was confirmed in the XRD analysis for the corrosion products of all the collected samples. As a result of ICP analysis, $Na^+$ and $Ca^{2+}$ components were confirmed.

철제유물은 출토되는 순간 급격한 환경변화로 인해 빠른 속도로 부식이 진행되므로 보존처리 과정을 거쳐 부식을 억제한다. 그러나 보존처리가 완료된 철제유물도 재부식이 발생하는 경우가 다수이며, 재부식된 유물의 보존처리는 1차 보존처리 시보다 그 처리가 어렵고 처리기간 또한 길어진다. 본 연구는 보존처리가 완료된 이후 보관과정에서 발생하는 부식생성물을 과학적으로 분석하여 재부식의 요인을 찾고자 하였다. 경주지역의 세 유적에서 출토된 철제유물을 동일한 약품과 방법으로 2002~2009년 동안 보존처리를 완료하였으나, 포장 보관 상태의 일부 철제유물에서 재부식 징후가 관찰되었다. 이중 재부식의 징후가 확인된 단조 철제유물 9점을 선별하여 질량측정, 육안관찰, 현미경을 통한 물리적 변화를 관찰하였고, SEM-EDS, XRD, IC, ICP분석을 통해 화학적 변화를 분석하였다. 그 결과, 유물에서 탈락된 부분의 접면에 형성된 황갈색 부식생성물은 군집한 형상만 다를 뿐 결정상은 공통적으로 침상형이 확인되었으며, 적색에서 황갈색으로 갈수록 침상의 형태가 뚜렷하였다. 보존처리가 완료된 시점의 경과에 따라 부식생성물이 증가할수록 유물의 질량이 증가하였고 염화이온의 농도가 상대적으로 높아지는 경향이 나타났다. 채집된 모든 시료의 부식생성물에 대한 XRD분석에서는 ${\beta}$-FeOOH(akaganeite)이 확인되었고, ICP분석 결과 $Na^+$, $Ca^{2+}$성분을 확인할 수 있었다.

Keywords

References

  1. Antunes, R.A., Costa, I. and de Faria, D.L.A., 2003, Characterization of corrosion products formed on steels in the first months of atmospheric exposure. Materials Research, 6, 403-408. https://doi.org/10.1590/S1516-14392003000300015
  2. Jeong, J.H., Kim, D.Y., Kim, N.Y. and Kim, G.H., 2011, A Study of Conservation Treatment and Characteristic Analysis on the Bronze artifacts from the Sindae-ri Relics, Gyeongsan. Science and Engineering of Cultural Heritage, 10, 6. (in Korean with English abstract)
  3. Jeong, J.H., 2012, Studies on Characteristics of Re-corrosion Products Generated in Iron Artifacts. Master's Thesis, Gyeongju University. (in Korean with English abstract)
  4. McNeil, M. and Selwyn, L.S., 2001, Electrochemical Processes in Metallic Corrosion. Handbook of Archaeological Sciences, John Wiley & Sons, Ltd., 611.
  5. Min, S.K., Lee, J.H., Lee, J.B. and An, B.C., 2007, A Study on Desalization and Corrosion Products Formed on Salinized Archaeological Iron Artifacts. Journal of the Korean Institute of Surface Engineering, 40, 44-56. (in Korean with English abstract) https://doi.org/10.5695/JKISE.2007.40.1.044
  6. Moon, W.S., Kim, B,G., Wi, K.C. and Hwang, J.J., 1993, The Study of Environment Change for Iron Antiquities after Excavation. Conservation Studies, 14, 45-58. (in Korean with English abstract)
  7. National Research Institute of Cultural Heritage., 2009, Conservation of Metal Objects. Yemack, 180-181. (in Korean)
  8. North, N.A., 1982, Corrosion products on marine iron. Studies in Conservation, 27, 75. https://doi.org/10.1179/sic.1982.27.2.75
  9. Refait, P.H., 1997, The mechanisms of oxidation of ferrous hydroxychloride ${\beta}-Fe_2(OH)_3Cl$ in aqueous solution : the formation of akaganeite vs goethite. Corrosion Science, 39, 539-553. https://doi.org/10.1016/S0010-938X(97)86102-1
  10. Selwyn, L.S., Sirois, P.J. and Argyropoulos, V., 1999, The corrosion of excavated archaeological iron with details on weeping and akaganeite. Studies in Conservation, 44, 217-232. https://doi.org/10.1179/sic.1999.44.4.217
  11. Selwyn, L.S., McKinnon, W.R. and Argyropoulos, V., 2001, Models for chloride ion diffusion in archaeological iron. Studies in Conservation, 44, 109-120.
  12. Turgoose, S., 1982, Post-Excavation Changes in Iron Antiquities. Studies in Conservation, 27, 97-101. https://doi.org/10.1179/sic.1982.27.3.97
  13. Xie, X., Yang, H., Zhang, F., Li, L., Ma, J., Jiao, H. and Zhang, J., 2009, Synthesis of hollow microspheres constructed with ${\alpha}-Fe_2O_3$ nanorods and their photocatalytic and magnetic properties. Journal of Alloys and Compounds, 477(1-2), 90-99. https://doi.org/10.1016/j.jallcom.2008.10.161
  14. Yeongnam Institute of Cultural Properties, 2009, The Ancient Site at Deokcheon-ri, Gyeongju. Research Report of Antiquities, 171. (in Korean)
  15. Yeongnam Institute of Cultural Properties, 2010, The Ancient Tombs Site at Hwangseong-dong, Gyeongju. Research Report of Antiquities, 174. (in Korean)
  16. Yeongnam Institute of Cultural Properties, 2011, The Ancient Tombs Site at Gueo-ri, Gyeongju. Research Report of Antiquities, 182. (in Korean)

Cited by

  1. Corrosion Stability of Iron Artifacts after Treating with Water Treatment vol.33, pp.5, 2017, https://doi.org/10.12654/JCS.2017.33.5.07