X射线衍射技术应用于宝石鉴定-合成及晶体结构研究进展

张妮; 林春明

doi:10.15898/j.cnki.11-2131/td.2016.03.002

X射线衍射技术应用于宝石鉴定-合成及晶体结构研究进展

张妮^1,,
林春明^2, ,

1.
金陵科技学院材料工程学院, 江苏南京 211169

2.
南京大学内生金属矿床成矿机制研究国家重点实验室, 江苏南京 210023

基金项目:
国家自然科学基金资助项目(41402073);金陵科技学院博士科研启动基金项目(jit-b-201329)

详细信息

作者简介: 张妮,博士,讲师,从事宝石矿床学、矿物学与沉积学研究。E-mail:znia@sina.com

通讯作者: 林春明,博士生导师,教授,从事沉积学与储层地质学研究。E-mail:cmlin@nju.edu.cn

中图分类号: P575.5

收稿日期: 2015-05-31

修回日期: 2016-05-05

录用日期: 2016-05-20

Review on the Application of X-ray Diffraction in Gem Identification, Synthesis and Crystal Structure Research

Ni ZHANG^1,,
Chun-ming LIN^2, ,

1.
College of Material Engineering, Jinling Institute of Technology, Nanjing 211169, China

2.
National Key Laboratory of Mineralizaiton Mechanism Research on Endogenous Metal Deposits, Nanjing University, Nanjing 210023, China

More Information

Corresponding author: Chun-ming LIN, cmlin@nju.edu.cn

Received Date: 31 May 2015

Revised Date: 05 May 2016

Accepted Date: 20 May 2016

摘要

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。
- X射线衍射法 /
- 宝石鉴定 /
- 宝石合成 /
- 宝石晶体结构 /
- 宝石研究技术
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.
- X-ray diffraction /
- gem identification /
- gem synthesis /
- crystal structure of gem mineral /
- technology of gemological research

HTML全文

图 1 富硅Anatolian蔷薇辉石的XRD图谱(Rod—蔷薇辉石；Qu—石英)

Figure 1.

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图 2 Moganite矿物(Mo)的晶体结构和蓝色玉髓的XRD图谱

Figure 2.

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图 3 氧参数u和尖晶石晶胞参数在热处理过程中随温度发生变化

Figure 3.

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图 4 尖晶石的热处理过程中温度与氧替换参数以及温度与M—O和T—O键长之间的关系

Figure 4.

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图 5 刚玉-石英-氟化铵以1∶1∶5的混合摩尔比在(a)770℃和(b)1000℃条件下合成氟托帕石的XRD图谱(T—托帕石，M—莫来石，Cr—刚玉，Q—石英)

Figure 5.

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参考文献(70)

[1]	Robert W. Gems, Their Sources, Descriptions and Iden-tification[M].London:Butterworths, 1983.
[2]	严俊,刘晓波,王巨安,等.应用FTIR-XRD-XRF分析测试技术研究新型仿制绿松石的矿物学特征[J].岩矿测试,2015,34(5):544-549. Yan J,Liu X B,Wang J A,et al.Determination of Mineral Compositions of New Imitated Turquoise by FTIR-XRD-XRF[J].Rock and Mineral Analysis,2015,34(5):544-549.
[3]	Harlow G E,Sorensen S S.Jade (Nephrite and Jadeitite) and Serpentinite:Metasomatic Connections[J].International Geology Review,2005,47:113-146.
[4]	Htipoglu M.Spectral,Electron Microscopical and Chem-ical Characteristics of the Gem-quality Silica-rich Rhodonite[J].Asian Journal of Chemistry,2012,24(2):733-741.
[5]	廖尚宜,李国武,彭明生.草莓红绿柱石(Pezzottaite)的晶体结构测定及其意义[J].矿物学报,2008,28(4):350-356. Liao S Y,Li G W,Peng M S.Crystal Structure Analysis of Pezzottaite and Its Implication[J].Acta Mnieralogica Sinaica,2008,28(4):350-356.
[6]	任伟,汪立今,李甲平.电子探针和X射线衍射仪测定新疆祖母绿宝石[J].岩矿测试,2010,29(2):179-181. Ren W,Wang L J,Li J P.Detection of Emerald from Xinjiang by Electron Probe Microanalyzer and X-ray Diffractameter[J].Rock and Mineral Analysis,2010,29(2):179-181.
[7]	孙访策,赵虹霞,干福熹.翡翠成分、结构和矿物组成的无损分析[J].光谱学与光谱分析,2011,31(11):3134-3139. Sun F C,Zhao H X,Gan F X.Nondestructive Analysis of Chemical Composition,Structure and Mineral Constitution of Jadeite Jade[J].Spectroscopy and Spectral Analysis,2011,31(11):3134-3139.
[8]	Kati M I,Turemis M,Keskin I C,et al.Luminescence Behavior of Beryl (Aquamarine Variety) from Turkey[J].Journal of Luminescence,2012,132:2599-2602.
[9]	Anghelina F L,Bratu V,Rusanescu C O,et al.Mathematical Model of Horizontal Divergence Contribution to the Integrated Intensity of Single Crystal Diffraction in XRD Analysis of Materials[J].Computational Materials Science,2014,94:142-149.
[10]	Fabisiak K,Piotrowska R T,Staryga E,et al.The Influence of Working Gas on CVD Diamond Quality[J].Materials Science and Engineering,2012,B177(15):1352-1357.
[11]	Abdel-Rehim A M.Thermal and XRD Analysis of Synthesis of Fluoro-Topaz[J].Thermochimica Acta,2012,538:29-35.
[12]	Noithong P,Pakkong P,Naemchanthara K.Color Change of Spodumene Gemstone by Electron Beam Irradiation[J].Advanced Materials Research,2013,770:370-373.
[13]	Lambruschi E,Gatta G D,Adamo D,et al.Raman and Structural Comparison between the New Gemstone Pezzottaite Cs (Be₂Li)Al₂Si₆O₁₈ and Cs-beryl[J].Journal of Raman Spectroscope,2014,45:993-999.
[14]	Widmer R,Malsy A K,Armbruster T.Effects of Heat Treatment on Red Gemstone Spinel:Single-crystal X-ray,Raman,and Photoluminescence Study[J].Physics and Chemistry of Minerals,2015,42(4):251-260.
[15]	Gatta G D,Adamo I,Meven M,et al.A Single-crystal Neutron and X-ray Diffraction Study of Pezzottaite,Cs (Be₂Li)Al₂Si₆O₁₈[J].Physics and Chemistry of Minerals,2012,39:829-840.
[16]	Venkateswara R R,Venkateswarulu P,Kasipathi C,et al. Trace Elemental Analysis of Indian Natural Moonstone Gems by PIXE and XRD Techniques[J].Applied Radiation and Isotopes,2013,82:211-222.
[17]	王永亚,干福熹.广西陆川蛇纹石玉的岩相结构及成矿机理[J].岩矿测试,2012,31(5):788-793. Wang Y Y,Gan F X.Mineral Structure and Mineralization Mechanism of Serpentine Jade from Luchuan,Guangxi Province[J].Rock and Mineral Analysis,2012,31(5):788-793.
[18]	Venkateswarulu P,Srinivasa R K,Kasipathi C,et al. Multielemental Analyses of Isomorphous Indian Garnet Gemstones by XRD and External PIXE Techniques[J].Applied Radiation and Isotopes,2012,70:2746-2754.
[19]	兰延,陆太进,陈伟明,等.基于相对密度和X射线粉晶衍射技术测定硬玉岩中硬玉的含量,岩矿测试,2015,34(2):207-212. Lan Y,Lu T J,Chen W M,et al.A Non-destructive Measurement Method of Gem Jadeite Content in Jadeitite Based on Specific Gravity and X-ray Powder Diffraction[J].Rock and Mineral Analysis,2015,34(2):207-212.
[20]	Olabanji S O,Ige O A,Mazzoli C,et al.Accelerator-based Analytical Technique in the Evaluation of Some Nigeria's Natural Minerals:Fluorite,Tourmaline and Topaz[J].Nuclear Instruments and Methods in Physics Research Section B,2005,240:350-355.
[21]	于吉顺,雷新荣,张锦化编著.矿物X射线粉晶鉴定手册[M].武汉:华中科技大学出版社,2011. Yu J S,Lei X R,Zhang J H.X-ray Powder Identification Manual of Minerals[M].Wuhan:Huazhong University of Science and Technology Press,2011.
[22]	曹杰,李立平,王莎.翡翠仿制品——微晶玻璃的制备工艺初探[J].宝石和宝石学杂志,2008,11(1):46-49. Cao J,Li L P,Wang S.Preliminary Study on Process of Producing Jadeite Jade's Imitation-Glass-Ceramic[J].Journal of Gems and Gemmology,2008,11(1):46-49.
[23]	周川杰,胡瑶,郝爽,等.四川"雅翠"的宝石学特征及命名探讨[J].宝石和宝石学杂志,2013,15(3):43-49. Zhou C J,Hu Y,Hao S,et al.Gemmological Characteristics of ‘Yacui’ from Sichuan Province and Discussion of Nanjing[J].Journal of Gems and Gemmology,2013,15(3):43-49.
[24]	刘杰,李锐,谢敏,等.钙铝榴石玉仿翡翠的宝石学特征[J].宝石和宝石学杂志,2014,16(6):47-50. Liu J,Li R,Xie M,et al.Gemmological Characteristics of Grossular Jade as Jadeite Imitation[J].Journal of Gems and Gemmology,2014,16(6):47-50.
[25]	Hatipoglu M,Tuncer Y,Kibar R,et al.Thermal Properties of Gem-quality Moganite-rich Blue Chalcedony[J].Physica B,2010,405:4627-4633.
[26]	Hatipoglu M,Basevirgen Y,Chamberlain S C.Gem-quality Turkish Purple Jade:Geological and Mineralogical Characteristics[J].Journal of African Earth Sciences,2012,63:48-61.
[27]	韩辰婧,王雅玫,刘洋.翡翠中共生矿物含量对翡翠定名的影响[J].宝石和宝石学杂志,2013,15(1):28-36. Han C J,Wang Y M,Liu Y.Influence of Associated Minerals on Jadeite Naming[J].Journal of Gems and Gemmology,2013,15(1):28-36.
[28]	王铎,莫祖荣,李雪明,等.蓝色翡翠的呈色机制探讨[J].宝石和宝石学杂志,2013,15(2):14-17. Wang Y,Mo Z R,Li X M,et al.Study on Colouring Mechanisms of Blue Jadeite[J].Journal of Gems and Gemmology,2013,15(2):14-17.
[29]	徐泽彬,徐志,邓常劼,等."永楚料"翡翠的宝石学研究[J].宝石和宝石学杂志,2014,16(6):43-46. Xu Z B,Xu Z,Deng C J,et al.Gemmological Study on Jadeite Called ‘Yongchuliao’ in Jewelry Trade[J].Journal of Gems and Gemmology,2014,16(6):43-46.
[30]	王时麒,员雪梅,李世波.辽宁富铁蛇纹石玉的宝石学特征及开发利用[J].宝石和宝石学杂志,2007,9(4):1-6. Wang S Q,Yuan X M,Li S B.Gemmological Characteristics and Developing Prospect of Fe-rich Serpentine Jade from Liaoning Province[J].Journal of Gems and Gemmology,2007,9(4):1-6.
[31]	戴慧,刘瑱,张青,等.大别山区石英质玉宝石矿物学特征研究[J].宝石和宝石学杂志,2011,13(3):32-37. Dai H,Liu Z,Zhang Q,et al.Gemmological and Mineralogical Characteristics of Quartz Jade from Dabie Mountain[J].Journal of Gems and Gemmology,2011,13(3):32-37.
[32]	韩磊,洪汉烈.中国三地软玉的矿物组成和成矿地质背景研究[J].宝石和宝石学杂志,2009,11(3):6-10. Han L,Hong H L.Study on Mineral Components and Geological Background of Nephrites from Three Localities in China[J].Journal of Gems and Gemmology,2009,11(3):6-10.
[33]	周征宇,廖宗廷,廖冠琳.中国两个主要产地软玉的矿物学特征对比[J].矿物学报,2010(增刊):35-36. Zhou Z Y,Liao Z T,Liao G L.Comparison of Mineralogical Characteristics of Two Main Origin of Nephrite[J].Chinese Acta Mineralogica Sinica,2010(Supplement):35-36.
[34]	汤红云,钱伟吉,陆晓颖,等.青海软玉产出的地质特征及物质成分特征[J],宝石和宝石学杂志,2012,14(1):24-31. Tang H Y,Qian W J,Lu X Y,et al.Geological and Composition Features of Nephrite from Qinghai Province[J].Journal of Gems and Gemmology,2012,14(1):24-31.
[35]	金晓婷,丘志力,戴苏兰,等.四川雅安绿色软玉的宝石矿物学特征[J].宝石和宝石学杂志,2014,16(5):1-8. Jin X T,Qiu Z L,Dai S L,et al.Gemmological and Mineralogical Characteristics of Nephrite from Ya'an,Sichuan Province[J].Journal of Gems and Gemmology,2014,16(5):1-8.
[36]	侯弘,王轶,刘亚非.韩国软玉的宝石学特征研究[J].西北地质,2010,43(3):147-153. Hou H,Wang Y,Liu Y F.Study of Gemological Characteristics of Korea Nephrite Jade[J].Northwestern Geology,2010,43(3):147-153.
[37]	廖冠琳,周征宇,廖宗廷.台湾碧玉的X射线粉末衍射和红外吸收光谱特征[J].宝石和宝石学杂志,2012,14(4):23-29. Liao G L,Zhou Z Y,Liao Z T.XRD and IR Spectra Study on Green Nephrite from Taiwan[J].Journal of Gems and Gemmology,2012,14(4):23-29.
[38]	杨林.贵州罗甸玉矿物岩石学特征及成因机理研究[D].成都:成都理工大学,2013. Yang L.Study on Petro-mineral Features and Genetic Mechanism of Luodian Jade,Guizhou Province[D].Chengdu:Chengdu University of Technology,2013.
[39]	陈呈,於晓晋,王时麒.河北唐河透闪石玉的宝石学特征及矿床成因[J].宝石和宝石学杂志,2014,16(3):1-11. Chen C,Yu X J,Wang S Q.Study on Gemmological Characteristics and Ore Genesis of Nephrite from Tanghe,Hebei Province[J].Journal of Gems and Gemmology,2014,16(3):1-11.
[40]	赵茸珊编著.结晶学及矿物学[M].北京:高等教育出版社,2012. Zhao R S.Crystallography and Mineralogy[M].Beijing:Higher Education Press,2012.
[41]	Gatta G D,Nénert G,Guastella G,et al.A Single-crystal Neutron and X-ray Diffraction Study of a Li,Be-bearing Brittle Mica[J].Mineralogical Magazine,2014,78(1):55-72.
[42]	Hatipoglu M.Spectral Electron Microscopical and Chemical Characteristics of the Gem-quality Silica-rich Rhodonite[J].Asian Journal of Chemistry,2012,24(2):733-741.
[43]	Zbik M S,Raftery N A,Smart R,et al.Kaolinite Platelet Orientation for XRD and AFM Applications[J].Applied Clay Science,2010,50(3):299-304.
[44]	Ehrich S N,Hanson J C,Camara A L,et al.Nuclear Instruments and Methods in Physics Research Section A:Accelerators,Spectrometers,Detectors and Associated Equipment[J].National Synchrotron Radiation Instrumentation Conference,2011,649(1):213-215.
[45]	王轶,常娜,刘亚非,等.应用X射线衍射-激光拉曼光谱-电子探针等分析测试技术研究旬阳朱砂玉的矿物学特征[J].岩矿测试,2014,33(6):802-807. Wang Y,Chang N,Liu Y F,et al.Study on the Mineralogical Characteristics of Cinnabar Jade by X-ray Power Diffraction-Laser Raman Spectroscopy-Electron Probe from Xunyang,Shanxi Province[J].Rock and Mineral Analysis,2014,33(6):802-807.
[46]	陈涛,严雪俊,鲁纬,等.昌化鸡血石的宝石学研究[J].宝石和宝石学杂志,2009,11(2):7-10. Chen T,Yan X J,Lu W,et al.Gemmological Study on Chicken-blood Stone from Changhua[J].Journal of Gems and Gemmology,2009,11(2):7-10.
[47]	周丹怡,陈华,陆太进,等.基于拉曼光谱-红外光谱-X射线衍射技术研究斜硅石的相对含量与石英质玉石结晶度的关系[J].岩矿测试,2015,34(6):652-658. Zhou D Y,Chen H,Lu T J,et al.Study on the Relationship between the Relative Content of Moganite and the Crystallinity of Quartzite Jade by Raman Scattering Spectroscopy,Infrared Absorption Spectroscopy and X-ray Diffraction Techniques[J].Rock and Mineral Analysis,2015,34(6):652-658.
[48]	Moxon T,Carpenter M A.Crystallite Growth Kinetics in Nanocrystalline Quartz (Agate and Chalcedony)[J].Mineralogical Magazine,2009,73(4):551-568.
[49]	Ralph,Jolyon,Ida Ralph.Moganite:Moganite Mineral Information and Data[M].London:MinDat, 2007.
[50]	Sen S K,Chakraborty K R.Magnesium-Iron Exchange Equilibrium in Garnet-biotite and Metamorphic Grade[J].Neues Jahrbuch fuer Mineralogie Abhandlungen,1968,108:181-207.
[51]	张蓓莉编著.系统宝石学(第二版)[M].北京:地质出版社,2006. Zhang B L.Systematic Gemmology (The Second Edition)[M].Beijing:Geological Publishing House,2006.
[52]	Groat L A,Giuliani G,Marshall D D,et al.Emerald Deposits and Occurrences:A Review[J].Ore Geology Reviews,2008,34:87-112.
[53]	Viana R R,Evangelista H J, da Costa G M,et al.Characterization of Beryl (Aquamarine Variety) from Pegmatites of Minas Gerais,Brazil[J].Physics and Chemistry of Minerals,2002,29(10):668-679.
[54]	Yakubovich O V,Pekov I V,Steele I M,et al.Alkali Metals in Beryl and Their Role in the Formation of Derivative Structural Motifs:Comparative Crystal Chemistry of Vorobyevite and Pezzottaite[J].Crystallography Reports,2009,54:399-412.
[55]	Chanda S C,Manna A,Vijayan V,et al.PIXE & XRD Analysis of Nanocrystals of Fe,Ni and Fe₂O₃[J]. Materials Letters,2007,61:5059-5062.
[56]	Hinckley D N.Variability in ‘Crystallinity’ Values among the Kaolin Deposits of the Coastal Plain of Georgia and South Carolina[J].Clays and Clay Minerals,1963,11:229-235.
[57]	王妍.巴林石透明度的影响因素及颜色成因探讨[D].北京:中国地质大学(北京),2012. Wang Y.Study on the Influencing Factors of Transparence and Color Gensis of Balin Stone[D].Beijing:China University of Geosciences (Beijing),2012.
[58]	Arasuna A,Okuno M,Okudera H,et al.Structural Changes of Synthetic Opal by Heat Treatment[J].Physics and Chemistry of Minerals,2012,40(9):747-755.
[59]	陈全莉,周冠敏,尹作为.珊瑚化石的红外光谱及XRD研究[J].光谱学与光谱分析,2012,32(8):2246-2249. Chen Q L,Zhou G M,Yin Z W.Infrared Spectroscopy and XRD Studies of Coral Fossils[J].Spectroscopy and Spectral Analysis,2012,32(8):2246-2249.
[60]	Rahman M A,Oomori T.Structure,Crystallization and Mineral Composition of Sclerites in the Alcyonarian Coral[J].Journal of Crystal Growth,2008,310(15):3528-3534.
[61]	谢先德,张刚生.珍珠层中文石晶体择优取向的XRD极图分析[J].矿物学报,2001,21(3):299-302. Xie X D,Zhang G S.XRD Pole Figure Analysis of the Preferential Orientations of Aragonite in Nacre[J].Acta Mineralogica Sinica,2001,21(3):299-302.
[62]	Ma Y F,Gao Y H,Feng Q L.Characterization of Organic Matrix Extracted from Fresh Water Pearls[J].Materials Science and Engineering C,2011,31(7):1338-1342.
[63]	Inoue M,Yokoyama Y,Harada M,et al.Trace Element Variations in Fossil Corals from Tahiti Collected by IODP Expedition 310:Reconstruction of Marine Environments during the Last Deglaciation (15 to 9ka)[J].Marine Geology,2010,271(15):303-306.
[64]	Gothmann A N,Stolarskib J,Adkinsc J F,et al.Fossil Corals as an Archive of Secular Variations in Seawater Chemistry Since the Mesozoic[J].Geochimica et Cosmochimica Acta,2015,160(1):188-208.
[65]	Suzuki M,Kim H,Mukai H,et al.Quantitative XRD Analysis of {110} Twin Density in Biotic Aragonites[J].Journal of Structural Biology,2012,180(3):458-468.
[66]	Pandey M,Cunha R D,Tyagi A K.Defects in CVD Diamond:Raman and XRD Studies[J].Journal of Alloys and Compounds,2002,333(1-2):260-265.
[67]	Heiman A,Lakin E,Zolotoyabko E,et al.Microstructure and Stress in Nano-crystalline Diamond Films Deposited by DC Glow Discharge CVD[J].Diamond and Related Materials,2002,11(3-6):601-607.
[68]	Fishers D.Brown Diamond and High Pressure High Tem-perature Treatment[J].Lithos,2009,112(12):619-624.
[69]	Phillips W R,Griffen D T.Optical Mineralogy,the Nono-paque Minerals[J].Geojournal,1981(6):595-596.
[70]	陆太进.钻石鉴定和研究的进展[J].宝石和宝石学杂志,2010,12(4):1-6. Lu T J.Development on Identification and Research of Diamond[J].Journal of Gems and Gemmology,2010,12(4):1-6.