非洲黄色蓝宝石的致色机理及改色研究
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摘要
利用激光剥蚀电感耦合等离子体质谱仪和紫外–可见–近红外分光光度计对产自非洲的铁含量较高而其它过渡金属元素含量较低的黄色蓝宝石的元素和光吸收谱进行测试。结果表明:非洲黄色蓝宝石的颜色是由Fe~(3+)外层d电子跃迁和O2-与Fe~(3+)的电荷转移两种呈色机制共同所致。利用还原退火的方法使黄色蓝宝石样品中新形成Fe~(2+)-Fe~(3+)同核异价离子对,同时其颜色由黄色变为深蓝色。Fe~(2+)-Fe~(3+)的形成及黄色蓝宝石样品颜色的改变,既证实了1993年Fritsch博士提出的"单独的Fe~(2+)-Fe~(3+)离子对可以使刚玉宝石呈现蓝色"的观点,也为天然黄色蓝宝石和山东昌乐深蓝色蓝宝石的改色提供了新的思路和理论依据。
The elements and optical absorption spectra of yellow sapphire with a high iron content and a low content of other transition metal elements from Africa were characterized by laser ablation inductively coupled plasma mass spectroscopy and ultraviolet visible near-infrared spectroscopy. The results show that the color of yellow sapphire is jointly contributed to outer d-electron of Fe~(3+) and charge transfer of O~(2–) and Fe~(3+). Fe~(2+)–Fe~(3+) is formed in the yellow sapphire by reduction annealing, and its color changes from yellow to dark blue. The formation of Fe~(2+)–Fe~(3+) and the change of the color of yellow sapphire support a previous conclusion that ‘Fe~(2+)–Fe~(3+) ion pair can make corundum blue' proposed by Dr. Fritsch in 1993. This work could provide some ideas and theoretical basis for color modification of natural yellow sapphire and dark blue sapphire from Changle, Shandong.
The elements and optical absorption spectra of yellow sapphire with a high iron content and a low content of other transition metal elements from Africa were characterized by laser ablation inductively coupled plasma mass spectroscopy and ultraviolet visible near-infrared spectroscopy. The results show that the color of yellow sapphire is jointly contributed to outer d-electron of Fe~(3+) and charge transfer of O~(2–) and Fe~(3+). Fe~(2+)–Fe~(3+) is formed in the yellow sapphire by reduction annealing, and its color changes from yellow to dark blue. The formation of Fe~(2+)–Fe~(3+) and the change of the color of yellow sapphire support a previous conclusion that ‘Fe~(2+)–Fe~(3+) ion pair can make corundum blue' proposed by Dr. Fritsch in 1993. This work could provide some ideas and theoretical basis for color modification of natural yellow sapphire and dark blue sapphire from Changle, Shandong.
引文
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[2]吴瑞华,刘琼林.Fe3+在蓝宝石中作用的研究[J].长春科技大学学报,2000,30(1):38?41.WU Ruihua,LIU Qionglin.J Changchun Univ Sci Technol(in Chinese),2000,30(1):38?41.
[3]KIEFERT L,SCHMETZER K.Blue and yellow sapphire from Kaduna Province,Nigeria[J].J Gemm,1987,20(7/8):427?442.
[4]SCHMETZER K,BOSSHART G,H?NNI H A.Natural coloured and treated yellow and orange-brown sapphires[J].J Gemm,1983,18(7):607?622.
[5]阮永丰,窦映平,李永庆,等.山东蓝宝石的色源和改色研究[J].硅酸盐学报,1996,24(2):203?208.RUAN Yongfeng,DOU Yingping,LI Yongqing,et al.J Chin Ceram Soc,1996,24(2):203?208.
[6]MARFUNIN A S.矿物物理学导论[M].李高山译.北京:地质出版社,1984:170?177.MARFUNIN A S.Physics of Minerals and Inorganic Materials:An Introduction(in Chinese).LI Gaoshan Trans.Beijing:Geological Publishing House,1984:170?177.
[7]陈道前.山东蓝宝石中Fe3+电子跃迁谱带的指派[J].西南工学院学报,1995,10(4):98?101.CHEN Daoqian.J Southwest Inst Technol(in Chinese),1995,10(4):98?101.
[8]FRITSCH E.Blue color in sapphire caused by Fe2+/Fe3+intervalence charge transfer[J].Gems Gemol,1993,29(3):151.
[9]KREBS J J,MAISCH W G.Exchange effects in the optical absorption spectrum of Fe3+in Al2O3[J].Phys Rev B,1971,4(3):757?767.
[10]FERGUSON J,FIELDING P E.The origins of the colours of yellow,green and blue sapphires[J].Chem Phys Lett,1971,10(3):262?265.
[11]LEHMANN G,HARDER H.Optical spectra of di-and trivalent iron in corundum[J].Am Miner,1970,55(1/2):98?105.
[12]TIPPINS H H.Charge-transfer spectra of transition-metal ions in corundum[J].Phys Rev B,1970,1(1):126?135.
[13]韩孝朕,郭守国,康燕,等.铁和钛在山东昌乐深蓝色蓝宝石中的致色作用[J].硅酸盐学报,2018,46(10):1483?1488.HAN Xiaozhen,GUO Shouguo,KANG Yan,et al.J Chin Ceram Soc,2018,46(10):1483?1488.
[14]MATTSON S M,ROSSMAN G R.Identifying characteristics of charge transfer transitions in minerals[J].Phys Chem Miner,1987,14(1):94?99.