中国内蒙古巴林左旗棕红色石榴石的宝石学特征及晕彩成因研究

Gemmological Characteristic and Cause of Iridescence of Garnet from Balin Left Banner, Inner Mongolia, China

  • 摘要: 我国内蒙古赤峰市巴林左旗白音诺尔铅锌矿床产出一种晶体颗粒硕大、晶面发育完整、颜色为棕褐色调、晕彩效应强烈的晕彩石榴石。本研究以7颗白音诺尔的晕彩石榴石为研究对象,采用傅里叶变换红外光谱仪、紫外-可见分光光度计、激光显微共聚焦拉曼光谱仪、电子探针以及扫描电子显微镜测试分析,旨在厘清其宝石学特征以及晕彩效应机制。结果表明,该产地晕彩石榴石的指纹区红外光谱主要由Si-O四面体的振动所致,其中位于435 cm-1处吸收峰归属为ν2对称弯曲振动,位于470~590 cm-1的吸收峰归属为ν4不对称弯曲振动,而位于810~935 cm-1的吸收峰归属为ν3不对称伸缩振动;拉曼光谱测试结果表明800~1 200 cm-1的拉曼谱峰归属于(Si-O)str振动,400~600 cm-1的拉曼谱峰归属于(Si-O)bend振动所致,300~400 cm-1的拉曼谱峰归属于R(Si-O)4,150~300 cm-1的拉曼谱峰与T(Ca)有关,其他的拉曼谱峰则是T(SiO4)导致的;紫外-可见光谱仅显示2个吸收峰,位于408 nm与438 nm处,分别与Mn2+向第一个场独立状态4A14E跃迁以及八面体场中Fe3+的d-d电子跃迁6A14A14E(G)有关;电子探针分析表明,样品化学式计算结果为(Ca3.011Mn0.035Mg0.006) (Fe1.796Al0.188) Si2.977O43,属于钙铁-铝固溶体系列;背散射电子图像显示薄片样品中存在与Fe3+与Al3+有关明暗相间的分区,且明亮区域比暗色区域Fe3+的平均质量分数高2%±,而Al3+质量分数则低2%±;扫描电子显微镜下发现薄片(211)以及薄片(110)层状结构厚度不同,前者厚度平均为400~600 nm,而后者厚度不均匀,最厚可达约24 μm,表明其晕彩效应是薄膜干涉导致形成的。使用光程差公式结合晕彩石榴石的折射率,计算出晕彩石榴石可以产生薄膜干涉效应的理论层状厚度范围为438.08~766.65 nm。

     

    Abstract: The Baiyinnuoer lead-zinc deposit of Balin Left Banner, Inner Mongolia, China, produces a kind of large garnet crystal with well-developed crystal surface and strong iridescent effect. It is favored by gem and mineral collectors. Seven iridescent garnets from Baiyinnuoer were selected as the research objects for clarifying the gemmological characteristics and iridescent effect mechanism of the mineral. Fourier transform infrared spectroscopy, ultraviolet-visible spectrscopy, laser microscope confocal Raman spectroscopy, electron probes and scanning electron microscope were used in this study. The infrared spectra showed that the absorption of iridescent garnet is mainly caused by the vibration Si-O tetrahedrons and in the fingerprint area absorption peak at 435 cm-1 belongs to ν2 symmetric bending vibration, and the absorption peak at 470~590 cm-1 are assigned to ν4 asymmetric bending vibration, while the absorption peak at 810~935 cm-1 is caused by ν3 asymmetric stretching vibration. Raman spectra showed that the Raman shifts of 700~1 000 cm-1 are classified as (Si-O)str vibration, 400~600 cm-1 are classified as (Si-O)bend, 300~400 cm-1 are caused by R(Si-O)4, 150~300 cm-1 is related to T(Ca), and the remaining Raman shifts are caused by T(SiO4). The UV-Visible spectra only showed two absorption peaks, located at 408 nm and 438 nm, respectively, related to the transition of Mn2+ to the first field independent state 4A14E and the d-d electron transition of Fe3+ in the octahedral field 6A14A14E(G). The electron probe testing results showed that the chemical formula calculation result of garnet is (Ca3.011Mn0.035Mg0.006)(Fe1.796Al0.188)Si2.977O43, which belongs to the series of calcium iron garnet to calcium aluminum garnet. Under the backscattered electron, there are stripes intersecting light and dark related to Fe3+ and Al3+, and the average content of Fe3+ in the light area is about 2% higher than that in the dark area, while Al3+ is correspondingly about 2% lower. Under scanning electron microscopy, it was found that the thickness of layered structure of the sheet (211) and sheet (110) were different. The the former was 400~600 nm on average, while the latter was uneven, with the maximum thickness of about 24 μm. This indicates that the iridescence effect of the iridescent garnets from Baiyinnuoer is caused by thin-film interference. According to the optical path difference formula combined and the refractive index of iridescent garnet, it was calculated that the theoretical layer thickness range of iridescent garnet that can produce thin film interference effects is between 438.08 nm and 766.65 nm.

     

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