明代永宣时期景德镇御窑青花瓷“铁锈斑”的显微结构研究  

The Microstructure of“Iron Spot”on Blue-and-White Porcelain From Jingdezhen Imperial Kiln in Yongle and Xuande Period of Ming Dynasty

作　　者：王文轩 温睿[1] 张悦 江建新 WANG Wen-xuan;WEN Rui;ZHANG Yue;JIANG Jian-xin(Key Laboratory of Cultural Heritage Research and Conservation(Northwest University)and School of Cultural Heritage(Northwest University),Xi’an 710127,China;Shaanxi History Museum,Xi’an 710061,China;Jingdezhen Institute of Ceramic Archaeology,Jingdezhen 333001,China)

机构地区：[1]西北大学文化遗产研究与保护技术教育部重点实验室,西北大学文化遗产学院,陕西西安710127 [2]陕西历史博物馆,陕西西安710061 [3]景德镇考古陶瓷研究所,江西景德镇333001

出　　处：《光谱学与光谱分析》2023年第1期190-197,共8页Spectroscopy and Spectral Analysis

基　　金：国家自然科学基金项目(11575142);陕西省教育厅科研计划项目(20JS147);中国博士后科学基金面上项目(2020M673619XB)资助。

摘　　要：“铁锈斑”,是青花瓷线条色彩浓重处凝聚成的黑色、褐色或带有金属锡光的斑点。作为早期青花瓷器一种典型的鉴定特征,长久以来被认为与使用高铁低锰的进口钴料有关。多年来虽有零星报道,但受到亚微级晶体尺寸、釉熔体不均一性以及元素掺杂、晶体偏析等因素影响,其形态及结构并未得到充分研究,从而导致“铁锈斑”呈色机理不明,其作为进口钴料鉴定标准的观点也遭到质疑。结合前人研究,发现拉曼光谱与扫描电镜能谱仪在古陶瓷微晶结构解析方面极具优势,为系统阐明“铁锈斑”成分结构特征与呈色机理,使用超景深三维视频显微镜、扫描电镜与能谱仪(SEM-EDS)、拉曼光谱仪(Raman)对五件景德镇御窑永宣时期青花瓷器样品中“铁锈斑”处晶体的显微形貌与结构进行解析,并利用激光剥蚀电感耦合等离子体发射光谱(LA-ICP-AES)分别测试样品白釉区域、蓝彩区域与“铁锈斑”区域的成分。显微观察结果表明,不同样品“铁锈斑”区域析晶形态及分布的多样性是造成“铁锈斑”呈现众多视感的主要原因,且同一斑点的析晶区域内伴生有多种形态的晶体。显微结构表明,永乐时期“铁锈斑”枝晶主要以CoFe_(2)O_(4)-Fe_(3)O_(4)固溶体为主,宣德时期“铁锈斑”的晶体则以掺杂了Mg^(2+)和Co^(2+)的MnFe_(2)O_(4)-Mn_(3)O_(4)固溶体为主,并伴生有网状钙长石析晶。结果表明,使用进口钴料或国产钴料烧制的青花瓷器上均可形成“铁锈斑”,由于其形成的主要晶体均属于立方晶系反尖晶石结构,在宏观形态上具有一定相似性,因而造成了以往对“铁锈斑”认知的误解。该研究实现了对明代永宣时期御窑青花瓷“铁锈斑”显微结构与成分特征的解析,凸显了拉曼光谱与扫描电镜能谱联用在古陶瓷复杂微晶结构解析方面的应用前景,首次揭示了“锡光”物理结构色呈色机理,为�“Iron spot”refers to the black,cyan and brown spots with metallic tin light condensed from the drawing lines on the blue and white porcelain.As a typical identification feature of blue-and-white porcelain of the early Ming dynasty,it has long been considered related to the use of imported cobalt with high-Fe and low-Mn.Although there have been sporadic reports over the years,due to factors such as submicron crystal size,glaze in homogeneity,element doping,and crystal segregation,its morphology and structure have not been fully studied,resulting in the color mechanism of“iron spot”unclear,and the view that“iron spot”as an identification standard for imported cobalt pigment being questioned.Combined with previous research,we found that Raman spectroscopy and scanning electron microscope equipped with energy dispersive spectrometer have great advantages in analysing ancient ceramic microcrystal structures.In order to further explore the composition and structure characteristics of“iron spot”,the ultra-depth three-dimensional video microscope,scanning electron microscope with energy dispersive spectrometer,and Raman spectrometer was used to analyze the crystal microstructure of“iron spot”in five blue-and-white porcelain samples of Jingdezhen imperial kiln in the Yongle and Xuande period of Ming dynasty.The composition of the samples’white glaze area,blue color area and“iron spot”area was tested by laser ablation inductively coupled plasma emission spectroscopy.The microscopic observation results show that the diversity of crystallographic morphology and distribution in the“iron spot”area of different samples is the main reason for many visual perceptions:the octahedron and its massive aggregate crystals precipitated on the glaze surface present a point-like flashing visual perception;the dendrites that are oriented in parallel and well-developed are prone to the phenomenon of“tin light”;the frosted visual perception is caused by the close arrangement of dendritic and snowflake-like c

关 键 词：铁锈斑 青花瓷器 拉曼光谱 显微结构 

分 类 号：O657.37[理学—分析化学]