云南红宝石的宝石学特征及改善工艺研究
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摘要
红宝石是世界上最珍贵的宝石品种之一,目前市场上优质红宝石极其稀缺,且价格一路走高。云南元江红宝石矿发现于20世纪80年代末,是目前国内最好的红宝石矿,储量大,基本上处于未开采状态,国内外有关它的报道和研究较少。通过对云南红宝石矿床的实地考察并结合地质资料分析,得出了云南红宝石的矿床特征,并探讨和分析了云南红宝石矿的特点及矿床成因；
本文运用EPMA、XRF、SEM等现代测试技术对各种类型的云南红宝石的物化性质进行测试和分析,从化学成分、晶体结构、晶体形态及微形貌、粒度、颜色、透明度、密度、裂理、发光性等方面得出了云南红宝石的宝石学特征；采用拉曼光谱、红外光谱、紫外-可见光吸收光谱、激发光谱等光谱分析技术对云南红宝石进行测试和分析,并与其它产地的红宝石及合成红宝石进行了对比分析,结合晶体场和量子学理论进一步分析和探讨了云南红宝石的致色元素和致色机理,分析了杂质元素的位置与赋存状态、聚片双晶、裂隙及孔洞等因素与红宝石质地的关系。结果表明,云南元江红宝石颜色丰富,粒度大小不一,裂理发育,存在大量包裹体,透明度低。主要致色离子为Cr、Fe、Ti等,其中Cr2O3的平均含量为0.45%(含量范围为0.03-2.22%),颜色的深浅跟Cr3+的含量直接相关,而Fe、Ti等杂质离子影响云南红宝石颜色的色调,使云南红宝石偏粉红至紫色调。云南红宝石中以375、414、640cm-1拉曼位移为典型特征；红外光谱除了与Al-O振动相关的吸收峰以外,还显示出硬水铝石的吸收峰；吸收光谱中表现出Cr3+、Fe3+等杂质离子引起的吸收,吸收位置为407、550nm和378nm处；激发光谱项处于248、415和580nm处,分别与A2→4T1(P)的跃迁、4A2→4T1(F)的跃迁和4A2→4T2(F)的跃迁相对应,荧光光谱也与杂质元素有关。
有针对性的拟定优化改善方案,通过选用合适的助剂、合理的工艺流程和温度制度,针对云南红宝石的颜色或质地进行热处理,在氧化气氛中采用Al(OH)3或Al(OH)3和CaCO3为助剂在1480℃下恒温24小时的热处理条件下,Fe、Ti等杂质元素的析出或发生价态变化,使云南红宝石的颜色和透明度得到很好的改善。使用Bi203和Al(OH)3助剂和充填剂,在1480℃、开放条件下对红宝石进行裂隙充填实验能有效改善红宝石的品质,并能达到有效充填开放裂隙和孔洞的目的,从而提高云南红宝石的观赏性和市场价值。
Rubies are one of the most precious gems in the world. High-quality rubies is extremely rare on the market and the price is going up.
Ruby deposit in Yuanjiang, Yunnan province which was found in the late 1980s, is the best ruby mines in China. It is abundant in reserve and is in non-mining state. The research on this deposit or rubies is not much. In this paper, the characteristics of the ruby deposit and rubies are researched by exploring and studying some geological data, and the genesis of rubies deposits is analyzed.
Physical-chemical characteristics were tested and analyzed by EPMA, XRF, SEM and other modern test technology to different types rubies from Yunnan province, such as chemical composition, crystal structure, crystal morphology and micro-morphology, color, transparency, density, cleavage, luminosity and so on. Raman spectroscopy, infrared spectroscopy, and UV-visible absorption spectroscopy were tested and analyzed to rubies from Yunnan province. At the same time, spectra were compared with rubies from different origin. Color-causing elements and coloration mechanism of rubies were discussed by theory of crystal field and quantum theory. Impurity component, polysynthetic twinning, fracture and hole are main factors influencing the transparence of rubies. The results showed that Rubies from Yuanjiang, Yunnan province contain a large quantity of inclusions and low transparency. Main color-causing element is Cr, Fe, Ti, etc. Among these elements, average content of is 0.45%(concentration range 0.03-2.22%). Color shade is directly related to the content of Cr3+, including energy level transitions of 4A2→4T1、4A2→4T2 and 2E→4A2, which cause strong broad absorption band at 407,551nm and 694 nm fluorescence peak. The content of Fe, Ti ions in rubies influences color tones and makes rubies pink or purplish.375,414 and 640cm-1 raman shifts are related to Al-O vibrations, and 1080cm-1 raman shift is related to calcite inclusions. and IR spectra showed 381cm-1、420cm-1 and 647cm-1 characteristic bands of Al2O3.
Based on gemmology and coloration mechanism, enhancement process is especial to rubies from Yunnan province, including useful assistant reagents, reasonable experiment process and temperature system for improving color and transparence of rubies. Impurity elements such as Fe, Ti precipitated or changed in valen treated in oxidizing atmosphere at 1480℃and for 24hours at constant temperature and used Al(OH)3 or Al(OH)3 and CaCO3 reagants. After the heat treatment, color and transparence of rubies improved. Filling experiments under open atmosphere at 1480℃and used Bi2O3 and Al(OH)3 reagants can fill the fracture and hole of rubies effectively.
本文运用EPMA、XRF、SEM等现代测试技术对各种类型的云南红宝石的物化性质进行测试和分析,从化学成分、晶体结构、晶体形态及微形貌、粒度、颜色、透明度、密度、裂理、发光性等方面得出了云南红宝石的宝石学特征；采用拉曼光谱、红外光谱、紫外-可见光吸收光谱、激发光谱等光谱分析技术对云南红宝石进行测试和分析,并与其它产地的红宝石及合成红宝石进行了对比分析,结合晶体场和量子学理论进一步分析和探讨了云南红宝石的致色元素和致色机理,分析了杂质元素的位置与赋存状态、聚片双晶、裂隙及孔洞等因素与红宝石质地的关系。结果表明,云南元江红宝石颜色丰富,粒度大小不一,裂理发育,存在大量包裹体,透明度低。主要致色离子为Cr、Fe、Ti等,其中Cr2O3的平均含量为0.45%(含量范围为0.03-2.22%),颜色的深浅跟Cr3+的含量直接相关,而Fe、Ti等杂质离子影响云南红宝石颜色的色调,使云南红宝石偏粉红至紫色调。云南红宝石中以375、414、640cm-1拉曼位移为典型特征；红外光谱除了与Al-O振动相关的吸收峰以外,还显示出硬水铝石的吸收峰；吸收光谱中表现出Cr3+、Fe3+等杂质离子引起的吸收,吸收位置为407、550nm和378nm处；激发光谱项处于248、415和580nm处,分别与A2→4T1(P)的跃迁、4A2→4T1(F)的跃迁和4A2→4T2(F)的跃迁相对应,荧光光谱也与杂质元素有关。
有针对性的拟定优化改善方案,通过选用合适的助剂、合理的工艺流程和温度制度,针对云南红宝石的颜色或质地进行热处理,在氧化气氛中采用Al(OH)3或Al(OH)3和CaCO3为助剂在1480℃下恒温24小时的热处理条件下,Fe、Ti等杂质元素的析出或发生价态变化,使云南红宝石的颜色和透明度得到很好的改善。使用Bi203和Al(OH)3助剂和充填剂,在1480℃、开放条件下对红宝石进行裂隙充填实验能有效改善红宝石的品质,并能达到有效充填开放裂隙和孔洞的目的,从而提高云南红宝石的观赏性和市场价值。
Rubies are one of the most precious gems in the world. High-quality rubies is extremely rare on the market and the price is going up.
Ruby deposit in Yuanjiang, Yunnan province which was found in the late 1980s, is the best ruby mines in China. It is abundant in reserve and is in non-mining state. The research on this deposit or rubies is not much. In this paper, the characteristics of the ruby deposit and rubies are researched by exploring and studying some geological data, and the genesis of rubies deposits is analyzed.
Physical-chemical characteristics were tested and analyzed by EPMA, XRF, SEM and other modern test technology to different types rubies from Yunnan province, such as chemical composition, crystal structure, crystal morphology and micro-morphology, color, transparency, density, cleavage, luminosity and so on. Raman spectroscopy, infrared spectroscopy, and UV-visible absorption spectroscopy were tested and analyzed to rubies from Yunnan province. At the same time, spectra were compared with rubies from different origin. Color-causing elements and coloration mechanism of rubies were discussed by theory of crystal field and quantum theory. Impurity component, polysynthetic twinning, fracture and hole are main factors influencing the transparence of rubies. The results showed that Rubies from Yuanjiang, Yunnan province contain a large quantity of inclusions and low transparency. Main color-causing element is Cr, Fe, Ti, etc. Among these elements, average content of is 0.45%(concentration range 0.03-2.22%). Color shade is directly related to the content of Cr3+, including energy level transitions of 4A2→4T1、4A2→4T2 and 2E→4A2, which cause strong broad absorption band at 407,551nm and 694 nm fluorescence peak. The content of Fe, Ti ions in rubies influences color tones and makes rubies pink or purplish.375,414 and 640cm-1 raman shifts are related to Al-O vibrations, and 1080cm-1 raman shift is related to calcite inclusions. and IR spectra showed 381cm-1、420cm-1 and 647cm-1 characteristic bands of Al2O3.
Based on gemmology and coloration mechanism, enhancement process is especial to rubies from Yunnan province, including useful assistant reagents, reasonable experiment process and temperature system for improving color and transparence of rubies. Impurity elements such as Fe, Ti precipitated or changed in valen treated in oxidizing atmosphere at 1480℃and for 24hours at constant temperature and used Al(OH)3 or Al(OH)3 and CaCO3 reagants. After the heat treatment, color and transparence of rubies improved. Filling experiments under open atmosphere at 1480℃and used Bi2O3 and Al(OH)3 reagants can fill the fracture and hole of rubies effectively.
引文
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