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上海大学学报(自然科学版) ›› 2025, Vol. 31 ›› Issue (1): 1-13.doi: 10.12066/j.issn.1007-2861.2648

• •    下一篇

长江口二号沉船出水绿釉瓷的腐蚀与脱落

赵萌1,2, 翟杨3,4, 赵静2, 赵荦4, 张可欣1,2, 葛彦4, 李强2, 褚晓波3, 岳学峥1, 罗宏杰2   

  1. 1. 上海理工大学材料与化学学院, 上海200093; 2. 中国科学院上海硅酸盐研究所, 上海200050;3. 上海博物馆, 上海200003; 4. 上海市文物保护研究中心, 上海200031
  • 收稿日期:2024-03-26 出版日期:2025-02-28 发布日期:2025-03-02
  • 通讯作者: 赵静(1981|), 女, 副研究员, 研究方向为脆弱硅酸盐质文化遗产保护. E-mail:zhaojing@mail.sic.ac.cn
  • 基金资助:
    上海市自然科学基金资助项目(23ZR1421000)

Corrosion and detachment of green-glazed ceramics salvaged from the Yangtze Estuary II shipwreck

ZHAO Meng1,2, ZHAI Yang3,4, ZHAO Jing2, ZHAO Luo4, ZHANG Kexin1,2,GE Yan4, LI Qiang2, CHU Xiaobo3, YUE Xuezheng1, LUO Hongjie2#br#   

  1. 1. School of Materials and Chemistry, University of Shanghai for Science and Technology, Shanghai 200093, China; 2. Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China; 3. Shanghai Museum, Shanghai 200003, China; 4. Shanghai Cultural Heritage Conservation and Research Centre, Shanghai 200031, China)
  • Received:2024-03-26 Online:2025-02-28 Published:2025-03-02

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摘要： 陶瓷器长期埋藏在水下环境会发生物理、化学及生物腐蚀. 采用X 射线荧光(X-ray fuorescence, XRF) 光谱、扫描电镜-能量色散X 射线(scanning electron microscope-energy dispersive X-ray, SEM-EDX) 能谱、X 射线衍射(X-ray diffraction, XRD)、傅里叶变换红 外(Fourier transform infrared, FTIR) 光谱和稳态荧光光致发光(photoluminescence, PL) 发射光谱分析等测试方法, 对长江口二号沉船出水的两件绿釉瓷样品的显微形貌与组成结构 等进行了分析. 结果表明: 绿釉瓷样品是在由高温烧制的, 以石英和莫来石为主的白胎和透 明瓷层表面施加低温绿色铅釉所制; 在长江口水下埋藏环境中, 绿釉层出现了主要由微生物 和化学变化导致的腐蚀凹坑、裂隙延伸, 并形成了Pb(OH)Cl 等腐蚀产物, 这些腐蚀质导致 釉层的裂纹扩展甚至贯通于绿釉层和透明瓷层的界面; 绿釉层裂纹区域以及瓷釉界面处含有 NaCl、CaCl2、Na2SO4 和CaSO4 等高吸湿性盐, 其渗透压和吸水作用加速了绿釉层的脱落; 微生物腐蚀、盐水溶液的渗透压等作用是加速绿釉层脱落的原因.

关键词: 出水陶瓷器, 微生物腐蚀, 釉层脱落, 高吸湿性盐, 渗透压作用

Abstract: Ceramics exposed to underwater environments for prolonged periods are vulnerable to physical, chemical, and biological corrosion. X-ray fuorescence（XRF）spectroscopy, scanning electron microscope-energy dispersive X-ray (SEM-EDX) spectrometry, X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, and steady-state fluorescence photoluminescence (PL) spectroscopy were used to analyze the microstructure and structural composition of the two green-glazed ceramic samples salvaged from the Yangtze Estuary II shipwreck. The results revealed that fabrication of the green-glazed ceramic samples involved applying a low-temperature green lead glaze on the surface of a combined white matrix and transparent ceramic layer mainly composed of quartz and mullite, which were ¯red at high temperatures. On the green-glazed ceramic samples recovered from sediments in the Yangtze Estuary, corrosive pits, crack extensions, and corrosive products were observed mainly comprising Pb(OH)Cl caused by microbial and chemical changes on the surface of the green-glazed layer. The corrosive substances were assumed to have contributed to the continuous expansion of cracks in the green-glazed layer, which had penetrated the interface between the green-glazed layer and the connecting transparent ceramic layer. Moreover, the cracked region of the green-glazed layer and the interface between the transparent ceramic layer and the green-glazed layer contained highly hygroscopic salts, including NaCl, CaCl2, Na2SO4 and CaSO4. The osmotic pressure of these salts and the swelling effect attributable to the absorption of water had accelerated the detachment of the green-glazed layer. These finndings will make a considerable contribution to furthering the understanding of the corrosion and glaze detachment of salvaged ceramics and provide scientific evidence for the protection of salvaged ceramics.

Key words: salvaged ceramics, microbial corrosion, glazed layer detachment, high hygroscopic salt, osmotic pressure effect

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