不同色调红宝石的致色成因研究

doi:10.19657/j.geoscience.1000-8527.2025.004

摘要/Abstract

摘要：

红宝石作为重要的宝石材料,其颜色特征受到广泛关注,探索红宝石颜色与其化学成分之间的关系对于宝石学基础研究以及深入理解矿物生成机制都具有重要作用。本研究对30颗刻面红宝石(包括正红色、偏紫色和偏粉色)进行了紫外-可见光光谱、X射线荧光光谱及颜色特征分析。研究发现,红宝石颜色与其化学成分紧密相关,红宝石颜色的呈现主要受控于Cr含量,同时受到Fe、V和Ti等元素的影响。Cr³⁺的d-d电子跃迁⁴A₂→⁴T₂引起的吸收在偏紫色红宝石中最为显著;而Cr³⁺的d-d电子跃迁⁴A₂→⁴T₁和Cr³⁺的荧光发射峰引起的吸收在偏粉色红宝石中最为显著。紫外-可见光光谱中412 nm和548 nm处的吸收强度可有效指示红宝石中紫色调的浓淡,该两波长处的吸收强度越高,红宝石紫色调越浓。紫外-可见光光谱中的412 nm可作为红宝石颜色参数L和b的指示波长,该波长处的吸收强度与红宝石的明度L呈显著负相关关系,与红宝石的b值呈显著正相关关系。这一发现为红宝石颜色特征的定量分析提供了新的视角。

关键词: 红宝石, 致色成因, 颜色, 紫外-可见吸收光谱, X射线荧光光谱

Abstract:

Rubies, as significant gemstone materials, have garnered extensive attention for their color characteristics. Exploring the relationship between the color of rubies and their chemical composition is essential for foundational research in gemology and for a deeper understanding of mineral formation mechanisms. This study analyzed 30 faceted rubies (including vivid red, slight purple, and slight pink hues) using UV-Visible spectroscopy, X-ray fluorescence spectroscopy, and color characteristic analysis. The findings indicate that the color of rubies is closely related to their chemical composition, primarily controlled by the Cr content, along with influences from elements such as Fe, V, and Ti. The absorption due to the d-d electron transition (⁴A₂→⁴T₂) of Cr³⁺is most prominent in rubies with a slight purple hue, whereas the absorption related to the d-d electron transition (⁴A₂→⁴T₁) and the fluorescence emission peak of Cr³⁺ is most significant in rubies with a slight pink hue. Additionally, the absorption intensities at 412 nm and 548 nm in the UV-Visible spectrum effectively indicate the intensity of the purple tone in rubies; higher absorption intensities at these wavelengths correlate with a more pronounced purple hue. The 412 nm wavelength serves as an indicator wavelength for the color parameters L and b of rubies, demonstrating a significant negative correlation with the brightness parameter L and a significant positive correlation with the b value. This finding provides a new perspective for the quantitative analysis of ruby color characteristics.

Key words: ruby, chromogenic origin, color, UV-Visible spectroscopy, X-ray fluorescence spectroscopy

中图分类号:

刘富康, 郭颖, 赵贝, 刘美颖. 不同色调红宝石的致色成因研究[J]. 现代地质, 2025, 39(01): 158-166.

LIU Fukang, GUO Ying, ZHAO Bei, LIU Meiying. Chromogenic Mechanisms of Rubies with Varying Color Tones[J]. Geoscience, 2025, 39(01): 158-166.

图/表 7

图1 红宝石样品的图片 (a)偏粉色红宝石(PP);(b)偏紫色红宝石(PR);(c)正红色红宝石(R)

Fig.1 Photographs of ruby samples

图2 红宝石的显微特征 (a)正红色红宝石中的针状包裹体;(b)偏紫色红宝石中的针状包裹体;(c)偏紫色红宝石中的愈合裂隙;(d)偏粉色红宝石中的愈合裂隙

Fig.2 Microscopic characteristics of rubies

图3 红宝石的紫外-可见光吸收光谱(共30颗)

Fig.3 UV-Visible absorption spectra of rubies (30 particles)

图4 不同种类红宝石的紫外-可见吸收光谱中特征波长吸收值热图 (a)偏粉色红宝石(PP)的紫外-可见吸收光谱中特征波长吸收值热图;(b)偏紫色红宝石(PR)的紫外-可见吸收光谱中特征波长吸收值热图;(c)正红色红宝石(R)的紫外-可见吸收光谱中特征波长吸收值热图;(d)所有红宝石的紫外-可见吸收光谱中特征波长吸收值热图

Fig.4 Heat maps of characteristic wavelength absorption values in UV-Visible absorption spectra of different types of rubies

表1 红宝石化学元素含量(%)

Table 1 Chemical element content of rubies (%)

光谱	Al₂O₃	SiO₂	Cr₂O₃	BaO	V₂O₅	Ga₂O₃	Fe₂O₃	TiO₂	ZnO	CuO
PP1	98.072	1.227	0.418	0.200	0.065	0.009	0.009	-	-	-
PP2	97.483	1.468	0.646	-	0.082	-	-	0.295	0.025	-
PP3	99.205	-	0.51	0.219	0.059	-	-	-	-	0.001
PP4	97.388	1.361	1.026	-	0.047	-	-	0.177	-	-
PP5	98.32	0.983	0.381	0.259	0.056	-	-	-	-	-
PP6	97.843	1.442	0.446	0.180	0.090	-	-	-	-	-
PP7	97.993	1.250	0.524	0.179	0.054	-	-	-	-	-
PP8	99.296	-	0.439	0.207	0.058	-	-	-	-	-
PP9	97.857	1.227	0.535	-	0.067	-	-	0.314	-	-
PP10	99.308	-	0.581	0.061	0.05	-	-	-	-	-
PR2	99.019	-	0.636	0.257	0.087	-	-	-	-	-
PR3	99.224	-	0.626	0.108	0.041	-	-	-	-	-
PR4	99.099	-	0.691	0.157	0.053	-	-	-	-	-
PR5	98.422	-	1.217	0.183	0.163	0.014	-	-	-	-
PR6	98.228	0.983	0.497	-	0.068	0.014	-	0.211	-	-
PR7	99.221	-	0.537	0.203	0.039	-	-	-	-	-
PR8	99.029	-	0.559	0.309	0.103	-	-	-	-	-
PR9	98.114	1.129	0.387	-	0.066	-	-	0.303	-	-
PR10	97.468	1.335	1.151	-	0.046	-	-	-	-	-
R1	97.383	1.286	0.531	-	-	-	0.794	-	-	0.007
R2	98.984	-	0.397	-	-	-	0.619	-	-	-
R3	98.755	-	0.569	-	-	-	0.675	-	-	-
R4	98.939	-	0.344	-	-	-	0.716	-	-	-
R5	97.585	1.205	0.531	-	-	-	0.678	-	-	-
R6	98.113	1.107	0.498	-	-	-	0.281	-	-	-
R7	98.752	-	0.466	-	-	-	0.783	-	-	-
R8	97.632	1.118	0.471	-	-	-	0.778	-	-	-
R9	98.902	-	0.422	-	-	-	0.633	-	-	0.043
R10	97.345	1.168	0.702	-	-	-	0.786	-	-	-

图5 不同种类红宝石的颜色参数 (a)红宝石的明度;(b)红宝石的a值;(c)红宝石的b值;(d)红宝石的彩度

Fig.5 Color parameters of different types of rubies

图6 红宝石紫外-可见吸收光谱中412 nm处的吸收强度分别与红宝石明度(a)和参数b(b)的关系

Fig.6 Relationships between the absorption intensity at 412 nm in the UV-Visible absorption spectrum of rubies and the brightness (a) and parameter b (b) of rubies, respectively

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