粉色—紫色缅甸尖晶石热处理前后紫外-可见光谱分析

Analysis of UV-Vis Spectrum on Pink-Purple Spinel from Burma before and after Heat Treatment

  • 摘要: 选取5颗粉色—紫色缅甸尖晶石原石为实验样品,分别在1 200℃和1 600℃下进行恒温10 h的热处理实验。通过分析样品成分及热处理前后紫外-可见光谱,发现粉色—紫色尖晶石样品均为含微量Fe元素的镁铝尖晶石,且在350~600 nm范围内出现吸收带的位置基本相同,其致色原因与八面体中Fe3+和四面体中Fe2+的自旋禁阻跃迁及二者间电荷耦合作用有关。对比样品的两次热处理后紫外-可见光谱结果发现,热处理过程促进350~430 nm及500~600 nm范围内吸收强度增加,前者与高温下尖晶石内部结构无序引起近紫外区O2-→Fe2+、Fe3+离子间电荷转移作用增加有关,后者由进入四面体内部Fe3+同相邻位置内Fe2+共同作用产生。在经1 600℃热处理后,近紫外区吸收边强度再次增加使样品光谱发生明显改变,色调偏红,部分样品因热处理诱发内部裂隙、透明度降低,热处理效果不明显。

     

    Abstract: In this paper, 5 pieces of pink-purple spinels from Burma were selected as experimental samples and heated at 1 200℃ and 1 600℃ for 10 hours respectively.Through laser induced breakdown spectroscopy (LIBS) analysis for the chemical compositions and UV-Vis spectroscopy, it was found that all samples were MgAl2O4 with trace amount of element Fe and the UV-Vis absorption bands were basically the same in the range 350-600 nm.The causes for their colours may be related to spin-forbidden transition of Fe3+ in octahedral site and Fe2+ in tetrahedral site and charge transfer between these pairs.Comparing UV-Vis spectra before and after heat treatment, it was found that the absorption intensity of all samples were enhaced dramatically in 350-430 nm and 500-600 nm areas.The absorption band at 350-430 nm is believed to be caused by increasing intervalence charge transfer between O2-→Fe2+、Fe3+ after the disorder structural transition.The absorption band at 500-600 nm is believed to be caused by Fe3+ in tetrahedral site effected by Fe2+ in adjacent site.After the heat treatment at temperature of 1 600℃, the absorption intensity in near ultraviolet region increased again and led to a clear change in UV-Vis spectrum, which making the apparent colour of samples become redder, however, some samples fail to follow this result due to internal fissures and lower transparency.

     

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