基于光谱技术的建窑宋代黑釉瓷物化组成及制备工艺研究

doi:10.3964/j.issn.1000-0593(2025)02-0448-08

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摘要：建窑，位于今福建省南平市，是宋时烧造黑釉茶盏的著名窑场之一。建窑创烧于晚唐五代，历经宋、元、明、清代，烧瓷历史近千年。建窑黑釉瓷品种丰富，釉色多变，主要为黑釉、兔毫釉和柿红釉色居多。建窑黑釉瓷在中国陶瓷历史上占据重要地位，并深刻影响了亚洲陶瓷历史，尤其是日本陶瓷。对于建窑黑釉瓷的科学研究，国内外学者主要致力于分析建盏胎釉的化学组成、微观结构，揭示建窑釉瓷的成瓷机理及制备工艺。然而，作为建窑黑釉瓷的代表品种，黑釉、兔毫釉和柿红釉，三者的原料组成、制备工艺及呈色机理的异同仍然不明晰。因此，采用超景深光学显微镜(OM)、X射线荧光光谱仪(XRF)、显微共聚焦拉曼光谱仪(μ-RS)、X射线衍射仪(XRD)和分光光度计等多种光谱技术，通过对建窑大路后门和芦花坪窑址出土的宋代黑釉、兔毫釉以及柿红釉的微观形貌、化学组成、物相组成以及釉外观呈色进行比较研究，解析黑釉、兔毫釉和柿红釉在原料组成、烧成工艺及呈色机理方面的异同。结果表明：黑釉、兔毫与柿红釉瓷胎中大部分主量元素含量无明显差异。三者着色元素均为Fe₂O₃，黑釉与兔毫釉的Fe₂O₃含量接近(6.0~7.0 wt%)，而柿红釉铁含量最高(~10.5 wt%)。较高的Fe₂O₃含量使得柿红釉面呈现红棕色。在所有样品的断面釉中、兔毫釉表面的毫纹中以及柿红釉面均发现有微米级枝状亚稳相ε-Fe₂O₃晶体。且ε-Fe₂O₃晶体的分布与兔毫釉面毫纹分布及柿红整体釉色一致。同时，在兔毫毫纹中及柿红釉面均发现赤铁矿晶体(α-Fe₂O₃)。由此可知，棕色兔毫与柿红釉呈色均来自于ε-Fe₂O₃与赤铁矿的共同着色。此外，在釉中发现石英、锆英石、铁板钛矿及金红石晶体。而三者胎的化学元素组成相似，物相主要为石英、方石英与莫来石，部分样品中发现少量赤铁矿。采用X射线荧光光谱(XRF)、显微共聚焦拉曼光谱(μ-RS)、X射线衍射仪(XRD)、分光光度计等多种光谱技术结合超景深光学显微镜(OM)，能够高效精准解析建窑黑釉瓷的微观结构与物相组成，为揭示黑釉、兔毫釉和柿红釉的原料及制备工艺异同提供了理论依据，并为类似古瓷的研究提供了一定的借鉴意义。

关键词：建窑；黑釉瓷；XRF；XRD；显微共聚焦拉曼光谱；制备工艺

Abstract：Jian kilns in Nanping City, Fujian Province, were famous during the Song Dynasty (CE 960-1276), producing black glazed tea-bowls. Jian kilns were created during the late Tang and Five Dynastiesand lasted through the Song, Jin, Yuan, Ming, and Qing dynasties. Jian wares havenumerous varieties and various glaze colors, mainly including pure black glaze, hare's fur (HF) glaze, and persimmon red (PR) glaze. These types not only occupied an important position in the history of ancient Chinese ceramics but also profoundly influenced the history of ancient Asian ceramics, especially the history of ancient Japanese ceramics. Much research was devoted to analyzing Jian wares' chemical composition and microstructure to understand color generation and manufacturingtechnology. However, the differences betweenthese representative types (black glaze, HF glaze, and PR glaze) concerning the raw materials and preparation process are still unclear. In this work, various spectroscopic techniques such as X-ray fluorescence spectrometer (XRF), micro confocal Raman spectrometer (μ-RS), X-ray diffraction (XRD), and spectrophotometer combing optical microscope (OM) were applied to study the microstructure, chemical and mineral composition, and glaze appearance of black glaze, HF glaze, and PR glaze of Jian kilns. The results showed no significant difference in the content of most major elements, except for the CaO content in black glaze, which was ~1 wt% higher than that in HF glaze and PR glaze. The coloring elements are Fe₂O₃. The Fe₂O₃ content of black glaze and HF glaze is similar (6.0~7.0 wt%), while the iron content of PR glaze is the highest (10.5 wt%). The high content of Fe₂O₃ results in a reddish-brown color on the PR glaze surface. Many micro-scale branched metastable phase ε-Fe₂O₃ crystals were detected in the glaze cross-sections of all samples, the brown stripes on the HF glaze surface, and the PR glaze surface. Meanwhile, several hematite crystals (α-Fe₂O₃) were found in both brown stripes of HF glaze and PR glaze surfaces. From this, it can be inferred that -the combined coloring of ε-Fe₂O₃ and hematite colors is brown HF and PR glaze. In addition, quartz, zircon, pseudobrookite, and rutile crystals were detected in the Jian glazes. The chemical composition of the three bodies is similar, with the main phases being quartz, quartz, and mullite. A small amount of hematite was also found in some HF samples. This article uses various spectroscopic techniques such as X-ray fluorescence spectroscopy (XRF), micro confocal Raman spectroscopy (μ-RS), X-ray diffraction (XRD), and spectrophotometer combined with an ultra depth of field microscope (OM) to efficiently and accurately analyze the microstructure, chemical and mineral composition of Jian wares. This work also provides a theoretical basis for revealing the differences in raw materials and preparation processes of Jian black glaze, HF glaze, and PR glaze and provides certain reference significance for the study of similar ancient ceramics.

Key words：Jian kilns; Black glazed wares; XRF; XRD; Microscopic confocal Raman spectroscopy; Manufacture technology

收稿日期: 2024-07-23 修订日期: 2024-11-11

中图分类号:

K876.3

基金资助: 国家自然科学基金项目(62205191, 52272019, 52272020)，硅酸盐质文物保护教育部重点试验室(上海大学)开放课题(SCRC2024KF02ZD, SCRC2024KF04TS)资助

作者简介: 王甜，女，1988年生，陕西科技大学副教授 e-mail: wangtian@sust.edu.cn

引用本文:

王甜，杨少雄，夏森伟，王芬，王莹，孙建兴，孙莉，李强，罗宏杰，朱建锋. 基于光谱技术的建窑宋代黑釉瓷物化组成及制备工艺研究[J]. 光谱学与光谱分析, 2025, 45(02): 448-455.
WANG Tian, YANG Shao-xiong, XIA Sen-wei, WANG Fen, WANG Ying, SUN Jian-xing, SUN Li, LI Qiang, LUO Hong-jie, ZHU Jian-feng. Research on the Chemical and Mineral Composition of Jian Wares in the Song Dynasty Using Multiple Spectroscopic Techniques. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2025, 45(02): 448-455.

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