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摘要:
从古至今，由细微粒矿物(小于18μm)构成的无机矿物颜料被广泛应用于艺术品中，且艺术品的品质由矿物的粒径、种类等因素所决定，建立微区矿物颜料组成、分布的精准且无损的分析方法对于工艺开发、探究时代文化特征等具有重要意义。现有分析方法有颜色鉴定的色彩学分析，但受限于色差或色度而难以直接确定矿物的类别；此外，X射线衍射、扫描电镜-能谱等被应用于矿物成分鉴定，然而此类测试方法对样品有损伤风险、测试过程繁琐等不足，不利于文物保护或样品的再利用。本文基于激光拉曼光谱为微细粒矿物颜料提供无损分析方法，通过对25种常见无机矿物颜料进行532nm、638nm、785nm激光的拉曼光谱测试，建立了25种常见无机矿物颜料的拉曼光谱数据库。随后选用不同色系以及同色系的无机矿物颜料进行拉曼微区成像，在微区中能探测到1μm左右的细微粒矿物，且细微粒矿物颜料的拉曼指纹信息与建立的矿物颜料拉曼光谱数据库完全匹配，这为微细粒矿物颜料的组成和分布提供了精准分析的方法，适用多种微细粒矿物颜料的同时分析。
Abstract:Micro-fine pigment minerals have been widely used in artworks, and their particle size, types, etc. determine the quality. Accurate and non-destructive analysis of the composition and distribution of micro-mineral pigments is of great significance. The existing analytical methods include color analysis, but it is difficult to directly determine the minerals’ type by the chrominance values. X-ray diffraction, scanning electron microscopy and energy disperse spectroscopy have been applied to the identification of mineral components, but these methods carry the risk of damage to the sample and the process is complex. Here, a non-destructive analysis method for micro-fine minerals based on laser Raman spectroscopy is proposed. Firstly, 25 types of mineral pigments were tested by 532, 638 and 785nm lasers. Then, mineral pigments of different and similar colors were tested by Raman imaging, which detected about 1μm minerals in the microregion. This accurate analysis method achieved the composition and distribution of micro-fine mineral pigments, which is suitable for simultaneous analysis of various micro-fine mineral pigments. The BRIEF REPORT is available for this paper at
http://www.ykcs.ac.cn/en/article/doi/10.15898/j.ykcs.202403260068 .-
Key words:
- Raman spectroscopy /
- mineral pigments /
- micro-fine minerals /
- microanalysis
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表 1 本文所选用的25种无机矿物分类
Table 1. The categories of 25 types of inorganic minerals
矿物颜色 矿物名称 化学式 矿物别名 纯度 生产厂商 红色 氧化铁
四氧化三铅
硫化汞Fe2O3
Pb3O4
HgS赭石
铅丹
辰砂99.0%
95.0%
99.0%源叶生物科技有限公司
阿拉丁试剂有限公司
阿拉丁试剂有限公司黄色 铬酸铅
硫化镉
一水合氧化铁
铬酸钡
氧化铅PbCrO4
CdS
Fe2O3·H2O
BaCrO4
PbO铬黄
镉黄
赤铁矿
铬重晶石
密陀僧、黄丹98.0%
98.0%
99.9%
99.0%
99.9%艾览化工科技有限公司
麦克林生化科技有限公司
北京百灵威科技有限公司
艾览化工科技有限公司
阿拉丁试剂有限公司绿色 三氧化二铬 Cr2O3 铬绿 99.9% 阿拉丁试剂有限公司 蓝色 亚铁氰化铁 Fe4[Fe(CN)6]3 普鲁士蓝（中国蓝） BS(生物染色剂) 麦克林生化科技有限公司 白色 二氧化钛 TiO2 锐钛矿 99.8% 迈瑞尔生化科技有限公司 氧化锌 ZnO 锌白 99.6% 毕得医药科技有限公司 硫化锌 ZnS 闪锌矿 99.0% 艾览化工科技有限公司 三氧化二锑 Sb2O3 方锑石 99.5% 阿拉丁试剂有限公司 二氧化硅 SiO2 石英 AR(分析纯) 源叶生物科技有限公司 氧化铝 Al2O3 刚玉 200～300目 麦克林生化科技有限公司 二氧化锡 SnO2 锡石 99.0% 毕得医药科技有限公司 氢氧化铝 Al(OH)3 水铝石 99.5% 阿拉丁试剂有限公司 氢氧化钙 Ca(OH)2 羟钙石 95.0% 麦克林生化科技有限公司 硫酸钙 CaSO4 硬石膏 97.1% 毕得医药科技有限公司 硫酸钡 BaSO4 重晶石 AR(分析纯) 源叶生物科技有限公司 硫酸镁 MgSO4 硫苦 AR(分析纯) 科隆化学品有限公司 碳酸钡 BaCO3 碳酸矿 99.0% 阿拉丁试剂有限公司 碳酸铅 PbCO3 白铅矿 AR(分析纯) 源叶生物科技有限公司 灰黑色 石墨粉 C 炭精 99.9% 阿拉丁试剂有限公司 
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