Influence Mechanism of the Iron-Rich Raw Material on the Iron-Based Crystalline Glazes
SHI Pei1, JIN Zhi-wei1, WANG Fen1*, LUO Hong-jie1, 2, ZHU Jian-feng1, YE Guo-zhen3, ZHANG Yu-feng4
1. School of Material Science and Engineering, Shaanxi Key Laboratory of Green Preparation and Functionalization for Inorganic Materials, Shaanxi University of Science and Technology, Xi’an 710021, China
2. Research Institute of Cultural Relics, Shanghai University, Shanghai 200444, China
3. Zhejiang Xiaoshan Institute of Song Dynasty Porcelain, Hangzhou 311200, China
4. Henan Songgong Ru Porcelain Ltd., Ruzhou 467599, China
Abstract：Black glazed ware is one of the most common varieties in the colored glazed ware of ancient China. Due to the easy availability of raw materials, it is fired everywhere, especially in the Song Dynasty. At present, α-Fe2O3, ε-Fe2O3, Fe3O4 has been found in ancient black glazes, but there are few reports on the influence mechanism of iron-rich raw materials on crystal types. Therefore, the Qingshitou and Hongshitou from the Dayu Town of Ruzhou and the Zijintu from Hangzhou were chosen as the study subjects. They were studied comprehensively by an X-ray fluorescence spectrometer (XRF), X-ray diffractometer (XRD), confocal laser Raman spectrometer (Raman) and scanning electron microscope (SEM). Firstly, the iron-rich raw material’s chemical composition, phase and type of iron-containing phases were compared and analyzed by spectral information. And then, they were used alone as the raw material for glaze making to study the change mechanism of the iron phase after firing microstructure and spectral information. The results indicated that the contents of CaO, MgO and K2O in Qingshitou were high, which could reduce the high-temperature viscosity of glaze melt and increase its fluidity. It was conducive to particle migration and crystal nucleation and growth. The content of SiO2 in Hongshitou was only 61.36%, and it contained calcite crystal, so the melting temperature was low, and it was easy to form glass phase. At this time, iron existed in an ionic state. Besides, the contents of SiO2 and Al2O3 were high in the Zijintu, and the contents of CaO, MgO and K2O were low, so its melting temperature was high. Three kinds of iron-rich raw materials were melted into glazes. For the Qingshitou glaze, part of α-Fe2O3 had a decomposition reaction. The black magnetite (Fe3O4) was precipitated, as well as the concentration of α-Fe2O3 around the bubble increased continuously and escaped with the bubble rising to the glaze surface, resulting in the precipitation of brownish red crystal flowers. Based on this, Qingshitou was suitable as raw material for the black glaze. The Hongshitou glaze was mainly glass phase, and no obvious iron crystal was found. Hence, it was suitable as raw material for the celadon glaze. In the Zijintu glaze, the glass phase content was little, and the high content of SiO2 and large particle size of α-Fe2O3 were beneficial to the formation of rod-shaped ε-Fe2O3. Therefore, the glaze surface was dark brown with a metallic luster. It showed that Zijintu was suitable as raw material for the Zijin glaze. This study discussed the influence of iron-rich raw materials on the type of iron oxide crystallization, its glaze color and enamel, and revealed the physical and chemical process of iron oxide crystallization. It had important reference significance for studying ancient iron-based crystal glazes and the preparation of modern magnetic materials.
Key words：Crystalline glaze; Iron-rich raw material; Raman; α-Fe2O3; ε-Fe2O3
施 佩，金志伟，王 芬，罗宏杰，朱建锋，叶国珍，张玉凤. 富铁原料对铁系析晶釉的影响机制初探[J]. 光谱学与光谱分析, 2022, 42(05): 1628-1633.
SHI Pei, JIN Zhi-wei, WANG Fen, LUO Hong-jie, ZHU Jian-feng, YE Guo-zhen, ZHANG Yu-feng. Influence Mechanism of the Iron-Rich Raw Material on the Iron-Based Crystalline Glazes. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2022, 42(05): 1628-1633.
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