蓝宝石的光致变色效应

Tenebrescence of Sapphire

  • 摘要: 针对近年来困扰市场的蓝宝石褪色、变色问题,以无优化处理天然蓝宝石、热处理天然蓝宝石以及合成蓝宝石作为研究对象,开展了多种光源的照射试验以及紫外-可见光谱、荧光光谱、电子顺磁共振谱和红外光谱测试分析,探究蓝宝石光致变色效应的行为与机制。测试结果表明,部分蓝宝石经长波紫外线、短波紫外线或X射线照射后,诱生出缺陷色心,形成以蓝区至绿区为中心、从紫外区延伸至红区约750 nm处的宽大吸收带,赋予蓝宝石褐(橙)色调,并降低蓝宝石明度;白光照射可使该吸收带缓慢漂白,从而使蓝宝石褪色。在此基础上,提出了蓝宝石光致变色效应的基本模型,指出蓝宝石所处光环境中白光与紫外线成分的比例决定了蓝宝石的颜色表现,地理位置改变和室内存放展示往往导致蓝宝石颜色发生变化。通过对几种光致变色光源进行对比分析,厘清了天然致色与人工辐照致色的划分界限,指出了天然致色的鉴别指征。此外,在合成蓝宝石中发现了罕见的红外波段"光致变色"现象。

     

    Abstract: The fading and discoloration of sapphires have emerged in recent years, bringing panics and confusions to the jewellers, consumers and gemmologists. To study the behavior and mechanism of tenebrescence in sapphire, multi light source irradiation tests and in situ photography were conducted on the collected specimens involving non-treated natural sapphire, heat treated natural sapphire and synthetic sapphire. Ultraviolet-visible (UV-Vis) spectra, fluorescence spectra, electron paramagnetic resonance (EPR) spectra and infrared spectra of the sapphire specimens were tested and analysed. With photography and UV-Vis spectroscopy, the photochromic impacts by various light sources were discussed, including 370 nm UV LED, DiamondViewTM, high pressure mercury lamp, low pressure mercury lamp, and Skyray EDX3600H EDXRF. The results showed that the tenebrescent effect is quite common in fancy colour sapphires from Sri Lanka and Madagascar with a light tone. After exposure to UVA, UVC or X-rays, new colour centers are induced within the sapphires and result in abroad, blue-green region centered absorption band which extends from the ultraviolet region to the red region around 750 nm, giving the sapphires an extra brown (orange) tone and lowering their brightness. Irradiation with white light can slowly bleach the broad absorption band and recover the initial colour. Hence a basic model of tenebrescent process in sapphire was proposed: UV/X-rays irradiation shifts sapphires from bleached (B) state to coloured (C) state, while white light irradiation reverses the reaction. When exposed to a mixture of both white light and UV/X-rays, an equilibrium position between B state and C state is to be achieved. Since the ratio of white light and ultraviolet light in the luminous environment dominates the colour performance of sapphire, geographical movement as well as indoor storage and display of sapphire often lead to alteration in the colour. In view of the predominant presence of UVA in the ultraviolet region of sunlight spectrum at earths surface, UVA-induced tenebrescent effect is suggested to be considered as a natural colouration, while UVC and X-rays should be classified as artificial irradiations. Gemmological indication of UVA tenebrescent coloration is found to be the yellow-orange fluorescence under UVA irradiation, which can be recognized by visual observation or fluorescence spectrum analysis. In addition, a rare infrared "tenebrescent" phenomenon is accidentally discovered in Verneuil synthetic light pink sapphires.

     

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