Review on the Application of X-ray Diffraction in Gem Identification, Synthesis and Crystal Structure Research
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摘要: 因宝石检测常附带无损要求、宝石评价具科学性和不确定性等特点,X射线衍射(XRD)在宝石学这门矿物学的分支学科中的应用具有特殊性,其应用领域主要集中在三个方面。①宝石鉴定领域:对单晶宝石和多晶宝石进行物相鉴定、宝石产地特征研究以及宝石矿物多型的种类划分等。例如根据XRD图谱,可将品种繁多的微晶石英隐晶质变种玉髓中不同的SiO2质矿物相精确区分;通过黏土矿物成分及其含量可将鸡血石中"地"的种类进行划分。②宝石矿物的晶体结构研究:对成分复杂的单晶宝石进行晶体化学分析、获取矿物类质同象替代情况、利用结晶度划分宝石品质。例如晶格参数中的c/a比值可将绿柱石的Al八面体类质同象替代和Be四面体类质同象替代进行区分;软玉中通过XRD数据计算出的结晶度与软玉的品质关系密切。③宝石学研究技术的开发:对宝石的优化处理过程进行监测,在宝石合成过程中检验矿物晶形大小、结晶质量及内应力等,以有机宝石的晶体结构为基础的人工养殖技术研究。例如尖晶石在热处理过程中,Mg离子由四面体中的T位迁移至八面体中的M位,导致M-O和T-O键长随温度变化,并反映在尖晶石的色调中;在托帕石合成过程中,XRD数据显示770~800℃时形成含氟托帕石(与天然托帕石结构相同),而在950℃和1000℃出现含氟托帕石离解成刚玉和莫来石。目前,我国在宝石学的XRD应用方面起步较晚,国外在宝石鉴定、优化与合成方面的应用相对成熟。本文认为,该技术与扫描电镜、质子探针等分析技术的联用仍有很大发展空间。Abstract: Due to the nondestructive requirements of gem testing, evaluation of precious stones shows characteristics of science and uncertainty. Gemological application of X-ray Diffraction (XRD) is specialized, with its application mainly concentrated in three aspects:① Gemstone identification:phase identification of the monocrystalline gemstones and polycrystalline gemstones; origin of the gemstones; classification of the pleomorphic gem minerals. For example, according to the XRD patterns of microcrystalline cryptocrystalline quartz variants, different silica mineral phases of the chalcedony can be distinguished accurately; types of Di in bloodstone can be distinguished through the composition and content of clay mineral. ② Research on crystal structure of the gem minerals:analysis of crystal chemistry of the monocrystalline gems with complex composition; situation of the substitution of mineral isomorphism; quality of the gem by using the degree of crystallinity. For example, through the c/a ratio in lattice parameters of beryl, aluminium octahedral isomorphism and the beryllium tetrahedral isomorphism can be distinguished. The relationship between the crystallinity calculated from XRD data and the quality of nephrite is close. ③ Development of gemological research technology:to monitor the process of gemstone optimization; to inspect the mineral crystal size, crystalline quality and internal stress during the synthetic process of gemstones; to research the artificial breeding technology based on the crystal structure of organic gemstones. Take the heat treatment process of spinel as example:magnesium irons moved from octahedral M-O to tetrahedral T-O, resulting in the bond length of M-O and T-O changing upon temperature and being reflected in the spinel color. During the synthesis process of topaz, XRD data shows that the structure of the formed fluorine topaz is similar to natural topaz at 770-800℃. At 950℃ and 1000℃, the fluorine topaz is decomposed to corundum and mullite. XRD research in the gemological application began relatively recently in China. In other countries, application in gem identification, optimization and synthesis are relatively mature. There is still much room for the development of XRD when combined with other technologies such as the Scanning Electron Microscope and Proton Microprobe.
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