基于光谱分析的宋代建窑油滴釉组成特征与呈色研究

doi:10.3964/j.issn.1000-0593(2025)04-0986-08

摘要
参考文献
相关文章 (14)

全文: PDF (46522 KB)
输出: BibTeX | EndNote (RIS)

摘要：黑釉瓷在中国陶瓷史上占据重要地位，宋代建窑油滴釉瓷以其独特的釉色与斑纹备受推崇。为揭示油滴釉的组成特征及其呈色不同的内在原因，采用能量色散X射线荧光光谱仪（EDXRF）、色差计、扫描电子显微镜及其能谱仪（SEM-EDS）、显微聚焦拉曼光谱仪（Raman）、X射线光电子能谱仪（XPS）等测试手段对不同呈色油滴釉的组成、显微结构及烧制工艺进行分析。结果表明，宋代建窑油滴釉的硅铝比在6.77～11.15之间，与其他类型建盏瓷釉化学组成不同，油滴釉呈“高硅、高钾、低钙、低铁、低钛”的特征，暗示其配方独特。晶斑内外的元素分布存在明显差异，晶斑内富集的钙、铁、钛和磷等元素对晶斑的形成具有重要作用。不同呈色的油滴釉的化学组成未见明显区别，表明化学组成并非决定其呈色的主导因素，通过瓷釉中铁离子价态和胎色分析推断烧制气氛是影响析出晶体种类和尺寸的关键要素之一。当Fe²⁺/Fe³⁺比值较大时，胎色偏黑，以还原气氛为主，银白色晶斑是由聚集的ε-Fe₂O₃纳米晶或α-Fe₂O₃晶体薄膜对光产生强反射效应；当Fe²⁺/Fe³⁺比值较小时，胎色偏红，以氧化气氛为主，棕黄色和红棕色晶斑分别主要来源于5~10 μm雪花状ε-Fe₂O₃和α-Fe₂O₃晶体的化学色。化学色与结构色的耦合效应能调控呈色，黄绿泛蓝色晶斑则主要是由100~200 nm的ε-Fe₂O₃晶粒瑞利散射与化学色耦合产生，而银白泛红棕色则是由α-Fe₂O₃晶体薄膜对光产生的全反射与化学色的结果。该研究阐明了宋代建窑油滴釉的组成和结构特征，揭示了其多样化呈色机制，为深入挖掘建窑黑釉瓷的科技内涵提供了重要依据，对铁系析晶釉的创新与开发具有参考价值。

关键词：建窑；油滴釉；组成特征；呈色；氧化铁

Abstract：Black-glazed porcelain holds a significant place in the history of Chinese ceramics, with Song dynasty Jian kiln oil spot glazes being highly esteemed for their distinctive colors and patterns. To elucidate the compositional characteristics and underlying causes of the varying colors in oil spot glazes, we employed energy dispersive X-ray fluorescence (EDXRF), colorimetry, scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS), micro-focused Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS) to analyze the composition, microstructure, and firing processes of these glazes. The results indicate that the Si/Al ratio of Song dynasty Jian kiln oil spot glazes ranges from 6.77 to 11.15, distinct from other Jian ware glazes. These oil spot glazes are characterized by high silicon, high potassium, low calcium, low iron, and low titanium content, suggesting a unique formulation. There is a significant difference in elemental distribution inside and outside the crystalline spots, with calcium, iron, titanium, and phosphorus being enriched within them, playing a crucial role in their formation. No significant differences were observed in the chemical composition of oil spot glazes with different colors, indicating that composition is not the primary determinant of coloration. Instead, analysis of iron ion valence states in the glaze and body color suggests that the firing atmosphere is a key factor influencing the type and size of precipitated crystals. When the Fe²⁺/Fe³⁺ ratio is high, the body color tends to be darker, indicating a predominantly reducing atmosphere. The silver-white spots are caused by strong light reflection from aggregated ε-Fe₂O₃ nanocrystals or α-Fe₂O₃ crystalline films. Conversely, when the Fe²⁺/Fe³⁺ ratio is low, the body color tends to be reddish, indicating an oxidizing atmosphere. The brownish-yellow and reddish-brown spots primarily result from the chemical color of 5～10 μm snowflake-shaped ε-Fe₂O₃ and α-Fe₂O₃ crystals. The coupling effect between chemical and structural colors can modulate the glaze's coloration. Yellow-green spots with a blue tint arise mainly from Rayleigh scattering of 100～200 nm ε-Fe₂O₃ particles coupled with chemical color, while silver-white spots with a reddish-brown tint result from total reflection by α-Fe₂O₃ crystalline films coupled with chemical color. This study elucidates the composition and structural characteristics of Song dynasty Jian kiln oil spot glazes, revealing their diverse coloration mechanisms. These findings provide important insights into the technological aspects of Jian black-glazed porcelain and have implications for the innovation and development of iron-based crystalline glazes.

Key words：Jian kiln; Oil spot glaze; Compositional characteristics; Coloration; Iron oxide

收稿日期: 2024-05-21 修订日期: 2024-09-05

中图分类号:

O657.3

基金资助: 国家重点研发计划项目（2023YFF0905800），景德镇市重点科技项目（2023SF001）资助

通讯作者: 吴军明 E-mail: woshiwxb@126.com

作者简介: 江财水，1995年生，景德镇陶瓷大学考古文博学院博士研究生 e-mail: 2020094019@stu.jci.edu.cn

引用本文:

江财水，吴军明，周健儿，包启富，刘昆，郑乃章. 基于光谱分析的宋代建窑油滴釉组成特征与呈色研究[J]. 光谱学与光谱分析, 2025, 45(04): 986-993.
JIANG Cai-shui, WU Jun-ming, ZHOU Jian-er, BAO Qi-fu, LIU Kun, ZHENG Nai-zhang. Study on the Compositional Characteristics and Colour of Oil Spot Glaze of Jian Kiln in the Song Dynasty Based on Spectral Analysis. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2025, 45(04): 986-993.

链接本文:

https://www.gpxygpfx.com/CN/10.3964/j.issn.1000-0593(2025)04-0986-08 或 https://www.gpxygpfx.com/CN/Y2025/V45/I04/986

[1] YE Wen-cheng(叶文程). Archaeology(考古), 1964, (4): 191.
[2] LI De-jin（李德金）. Archaeology（考古）, 1990, (12): 1095.
[3] LI Jian-an(栗建安). Archaeology（考古）, 1995, (2): 148.
[4] LI Kai(李凯). Palace Museum Journal(故宫博物院院刊), 2022, (4): 92.
[5] LI Jia-zhi(李家治). Chinese History of Sci-Tech: Volume of Ceramics(中国科学技术史: 陶瓷卷). Beijing: Science Press(北京: 科学出版社), 1998. 206.
[6] CHEN Xian-qiu, HUANG Rui-fu, ZHOU Xue-lin, et al(陈显求, 黄瑞福, 周学林, 等). Journal of Jingdezhen Ceramics Institute(景德镇陶瓷学院学报), 1995, (1): 26.
[7] Dejoie C, Sciau P, Li W D, et al. Scientific Reports, 2014, 4: 4941.
[8] JIANG Cai-shui, FANG Yuan, BAO Qi-fu, et al(江财水, 方圆, 包启富, 等). Chinese Ceramics(中国陶瓷), 2023, 59(4): 68.
[9] SHI Pei, JIN Zhi-wei, WANG Fen, et al（施佩, 金志伟, 王芬, 等）. Spectroscopy and Spectral Analysis(光谱学与光谱分析), 2022, 42(5): 1628.
[10] LI Mei, LI Wei-dong, LU Xiao-ke, et al(李玫, 李伟东, 鲁晓珂, 等). Journal of the Chinese Ceramic Society(硅酸盐学报), 2020, 48(7): 1134.
[11] Shi X, Yu Y, Sun Q, et al. RSC Advances, 2019, 9(71): 41927.
[12] LIU Han, ZHOU Jian-er, BAO Qi-fu, et al(刘韩, 周健儿, 包启富, 等). Journal of the Chinese Ceramic Society(硅酸盐学报), 2018, 46(9): 1287.
[13] Shi P, Wang F, Zhu J, et al. Ceramics International, 2018, 44(14): 16407.
[14] Holé C, Ren Z, Wang F, et al. Materials Today Communications, 2022, 33: 104329.
[15] LI Ji-yuan, LIU Chen, ZHANG Hong(李计元, 刘晨, 张虹). China Ceramic Industry(中国陶瓷工业), 2023, 30(3): 18.
[16] YANG Zhong-tang, LI Yue-qin, WANG Zhi-hai, et al(杨钟堂, 李月琴, 王志海, 等). Northwestern Geology（西北地质）, 1996, (2): 49.
[17] Stoch P, Goj P, Ciecińska M, et al. Ceramics International, 2020, 46(11): 19146.
[18] Lopez-Sanchez J, Serrano A, Del Campo A, et al. Chemistry of Materials, 2015, 28(2): 511.