Microstructure Characterization and Mineral Morphology of Tea-Dust Glaze Made in the Ding Kiln of the Northern Song Dynasty
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摘要:
茶叶末釉古瓷作为最早出现的结晶釉之一，开展深入研究可明确其矿物晶体特征、呈色机理以及古代烧制工艺，丰富古陶瓷数据库。目前相关研究多来源于二十世纪末，样本稀少且囊括的年代和窑口严重不足，所用科学仪器多已淘汰，亟需更多实验分析与数据支撑。本文采用光学显微镜(OM)、激光剥蚀电感耦合等离子体质谱(LA-ICP-MS)、扫描电镜-能谱(SEM-EDS)、激光共聚焦拉曼光谱(LRS)、飞行时间二次离子质谱(ToF-SIMS)等现代科学仪器对北宋定窑茶叶末釉样本中矿物晶体开展了分析和表征。结果表明，釉中主晶相与辽金龙泉务窑一致，为钙长石和辉石；釉面整体表现为酱-黑色釉基质富铁(Fe2O3含量均值9.73%)和矿物结晶富铁(Fe2O3含量均值11.33%)，除α-Fe2O3和Fe3O4晶体等熔后重结晶矿物，还有铁镁尖晶石、残余高岭石等未融熔矿物，反演出制釉原料中有镁的加入以及烧成温度可能低于1200℃，异于前人高温烧制的观点。SIMS离子成像揭示了胎釉交界处为厚约20～80μm的钙长石晶体层，而非化妆土或玻璃态的致密反应层。研究揭示了茶叶末古瓷中Fe元素不均匀富集，部分区域过饱和而析出含铁矿物晶体，釉面颜色则主要由黄褐色的矿物晶体斑点和酱-黑色玻璃基质共同组成，同时ToF-SIMS在古瓷微区原位的形貌结构和元素分析上效果显著，能够辨别钙长石、碱性长石等微米级矿物。
Abstract:The tea-dust glaze ancient porcelain is one of the earliest crystalline glazes, which is rarely studied deeply because of its rarity. In this study, the mineral crystals in tea-dust glaze made in the Ding Kiln of the Northern Song Dynasty were analyzed by optical microscope (OM), laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), scanning electron microscopy coupled with an X-ray energy dispersive spectrometer (SEM-EDS), laser confocal Raman spectrometer (LRS), and high-resolution time of flight-secondary ion mass spectrometry (ToF-SIMS). The results show that the main crystal phase in the glaze is the same as that of the Longquanwu Kiln in the Liao and Jin Dynasty, which is anorthite and augite. The overall performance of the glaze is that the sauce-black glaze matrix is rich in iron (Fe2O3 mean 9.73%) and the mineral crystal is rich in iron (Fe2O3 mean 11.33%). In addition to α-Fe2O3 crystals, Fe3O4 crystals and other recrystallized minerals after melting, the glaze also has pleonaste, residual kaolinite and other unmelted minerals from raw glaze materials. The residual kaolinite shows that the firing temperature of the samples in this study was most likely below 1200℃. The BRIEF REPORT is available for this paper at
http://www.ykcs.ac.cn/en/article/doi/10.15898/j.ykcs.202401290011 .-
Key words:
- tea-dust glaze /
- minerals /
- element imaging /
- ToF-SIMS /
- LA-ICP-MS
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表 1 茶叶末釉表面不同颜色斑点元素分析结果
Table 1. Analytical results of elements in different color spots of the tea-dust glaze
不同颜色斑点 元素含量(%) Na2O MgO Al2O3 SiO2 K2O CaO TiO2 Fe2O3 P2O5 MnO 黄褐色斑点 0.93 1.74 13.99 53.94 3.25 12.09 1.65 11.33 0.88 0.20 酱-黑色基质 0.96 1.58 12.44 58.96 4.03 10.32 1.28 9.73 0.53 0.17 整体 0.94 1.66 13.22 56.43 3.64 11.21 1.47 10.54 0.71 0.18 
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表 2 茶叶末瓷釉层中元素分析结果
Table 2. Analytical results of elements in glaze layer of tea-dust porcelain
釉面至釉底
行号元素含量(%) Na2O MgO Al2O3 SiO2 K2O CaO TiO2 Fe2O3 P2O5 MnO 第1行 0.87 1.28 18.36 57.44 3.62 10.29 0.94 6.92 0.16 0.11 第2行 0.84 1.68 13.36 59.79 3.84 9.94 1.16 9.05 0.19 0.16 第3行 0.87 1.55 13.13 61.50 4.37 9.34 0.92 8.03 0.12 0.15 第4行 0.84 1.65 12.59 61.53 4.42 9.18 0.88 8.60 0.14 0.16 第5行 0.86 1.65 13.51 60.63 3.88 9.66 0.93 8.60 0.12 0.16
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表 3 EDS下矿物晶体元素组成
Table 3. Elemental composition of mineral crystals under EDS
EDS所取点位 元素原子占比(at%) Si Al Ca Fe Mg K Na Cr Ti Mn 1 63.67 13.8 8.14 3.97 3.61 4.85 1.96 / / / 2 60.59 21.39 7.99 2.08 2.48 1.07 4.22 / / 0.18 3 51.53 25.74 13.82 3.83 1.6 1.13 2.35 / / / 4 5.61 2.18 1.26 89.71 / 0.98 / / / / 5 41.2 34.14 3.26 4.79 4.37 2.78 3.03 / 5.87 / 6 1.85 / 0.43 65.59 29.93 0.23 / 1.96 / / 7 11.78 6.5 / 77.79 / / / / 3.92 / 注：元素原子占比低于0.10at%以“/”表示。
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