还原性热处理条件下锆石的宝石学特征及颜色

Yan Xiaoxu, Yue Suwei, LI Suitian, Wang Peilian
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摘要

锆石中由放射性衰变引起的色心可以通过热处理去除。这种行为也可以改变它们的颜色和透明度,以提高观赏和商业价值。市场上绝大多数蓝色锆石是由红褐色锆石经高温热处理而成。然而,其颜色机制长期以来一直存在争议。采用红棕色和黄褐色的锆石,在还原气氛中加热,以确定蓝色改性的最佳温度。通过对其标准宝石学性质、红外吸收光谱(IR)和紫外可见分光光度(UV-Vis)分析,探讨了热处理中变色的机理。热处理结果表明,在950 ~ 1 000℃还原气氛下热处理,红棕色锆石可转变为浅蓝色锆石。热处理前样品在434 cm-1和610 cm-1处的红外光谱显示其变质作用较弱。热处理后,438/436 cm-1(峰)的吸收增强,1 100 ~ 900 cm-1(带)的吸收变窄,表明样品的晶态恢复。样品的紫外可见光谱表明,Y3+被Zr4+取代,产生510 nm左右的吸收带,导致辐射,使无色结晶锆石变成红棕色的变质锆石。热处理后,510 nm波段的消失是由于Y3+取代产生的色心分解引起的。800 nm波段强度较弱,在640 nm左右出现吸收。U4+产生653 nm和690 nm的强吸收峰和一系列弱吸收峰。640nm波段被认为是处理样品呈现蓝色的主要原因,而653nm波段及其周围的吸收可能与此有关。
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Gemmological Characteristic and Colour of Zircon under Heat Treatment in Reducing Condition
The colour center caused by radioactive decay in zircons can be removed by heat treatment. This behavior also may modify their colour and transparency to improve the ornamental and commercial value. A large majority of blue zircons in the market are obtained from reddish-brown zircon by heat treatment under high temperature. However, the colour mechanism of which have long been controversial.Reddish-brown and yellowish-brown zircons were applied in this study, and heated in reducing atmosphere in order to confirm the optimum temperature of blue colour modification. The mechanism of altering colour in heat treatment was also investigated in this study by analyzing their standard gemmological properties, infrared absorption spectroscopy (IR) and ultraviolet-visible spectrophotometry (UV-Vis). The results of heat treatment showed that reddish-brown zircons could be changed into light blue zircons by heat treatment under 950-1 000 ℃ in reducing atmosphere.The IR spectra of the samples at 434 cm-1 and 610 cm-1 before heat treatment show their low metamictization.After heat treatment, the absorption of 438/436 cm-1 (peak) get strengthened and the 1 100-900 cm-1 (band) narrowed down, which indicates that the crystalline state of the samples restored. The UV-Vis spectra of the samples showed that the absorption band around 510 nm was generated by Y3+substituting with Zr4+, leading to radiation and turned colourless crystalline zircons into reddish-brown metamict ones. After heat treatment, the vanishment of 510 nm band was caused by the breaking down of colour center generated by Y3+substitution. The 800 nm band showed weak intensity, with the emergence of absorption around 640 nm. The strong absorption peak of 653 nm and 690 nm and a series of weak absorption peaks were caused by U4+. The 640 nm band was presumed to be the main cause of the blue colour of the treated samples, and the 653 nm with its surrounding absorptions might relevant to it.
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