矿物材料现代测试技术1绪论

1、武汉理工大学资环学院 管俊芳,1,Modern Testing Technique（Mainly in mineral material analysis) 矿物材料现代测试技术资环学院管俊芳,武汉理工大学资环学院 管俊芳,2,Purpose: Learn how to measure or determine (1) the chemical composition, (2) the structure, (3) the surface morphology, and (4) the physical and chemical properties of the material,武汉理工大

2、学资环学院 管俊芳,3,Main References1 X射线结构分析 ，祁景玉主编， 同济大学出版社20032 材料分析测试技术， 哈工大出版社，20033 X射线分析简明教程，地质出版社，彭志忠主编4 无机非金属材料测试方法，杨南如主编，武汉理 工大学出版社 ，1990 5 X射线衍射与电子显微分析，漆雍、戎咏华编，上海交通大学，1992 6 材料分析测试方法，上海交通大学出版社 王成果7 表面分析方法，国防工业出版社 美A.W.赞德纳,武汉理工大学资环学院 管俊芳,4,现代测试技术有别于传统的化学分析及光学显微镜鉴定方法，它是在19世纪末20世纪初物理学多项重大发现（电子、X射线、放射

3、性等）及相关应用研究的基础上发展起来的，世界各主要国家的分析仪器行业于20世纪40年代末、50年代初逐步形成(日本、美国、德国等)。70年代以后，由于真空技术、计算机信息处理技术、自动化控制技术等的飞速发展及新能源、新材料、新元器件的不断引入，一些基础理论问题的突破，生产和应用研究范围的不断扩大，使得各种测试分析仪器逐渐完善，新的测试仪器不断涌现，从而极大地推动了各学科研究及生产技术的发展。 现代测试技术具有如下六大特征：,现代测试技术特点:,武汉理工大学资环学院 管俊芳,5, 以“三微”技术为主流：“三微”指微量、微束、微区。微量：指极少的分析样品用量及对微量元素的较低检测 极限(10-9)

4、；微束：指极细的激发束（如电子束、离子束、激光束等）， 通常1nm。微区：指极小的分析区域， 如微米纳米范围 以电子探针为例，其检测极限为100ppm，分析区域为几个nm3， 所以其绝对感应量为10-1410-16g，这比以往任何分析手段的灵敏度都高。,武汉理工大学资环学院 管俊芳,6, 以高度自动化控制为主要趋势: 自动化程度的提高可以最大程度地减少人为分析的误差，如X射线结构分析中衍射强度数据的获得，最早是采用多重胶片照相方法，对衍射点强度进行目估，而现在则采用计数器直接自动探测，极大地提高了精度及效率。 分析数据处理的高度计算机化 计算机对大批量数据的复杂运算具有绝对的优势。 分析手段综

5、合化 如电子探针配合扫描电镜、电子能谱、图形分析系统等，不但可以进行微区成分分析，还可进行微形貌及元素分布等的综合研究；扫描电镜和透射电镜中也不仅可分析物质的微观形貌，同时也可进行对观察对象的实时成分测定。,武汉理工大学资环学院 管俊芳,7, 分析功能多样化 在常规分析设备中增加其它附件，可以进行特殊条件下的测试分析。如在四园单晶衍射仪中增加高压附件，就可进行高压物相研究；在透射电镜中装上冷热台，则可进行生物或无机相变研究；扫描电镜与一动态拉伸系统连接，便可观察到材料在应力作用过程中的结构变化。 测试分析网络化 许多大型测试分析仪器由于造价高昂，为达到资源共享的目的，将分析过程网络化已成为必然

6、的趋势。如美国国防部MMC项目（材料显微表征中心），把分布在美国各地的多个实验室的数台电镜进行联网，从而实现异地操作。,武汉理工大学资环学院 管俊芳,8,本课程的教学目的 1了解现代测试技术的主要研究内容； 2了解主要分析仪器的基本理论、基本概念、主要技术 原理及应用特征； 3 通过本课程的系统学习，能根据一定的研究方向和课题，提出合理的测试项目设计；,武汉理工大学资环学院 管俊芳,9,Preface 序论,武汉理工大学资环学院 管俊芳,10,1.Outline 1.1 Chemical composition analysis 1.2 Structural analysis 1.3 Morp

7、hological properties 1.4 Analysis of physical and chemical properties 2. Analyzing Methods 2.1 Chemical Composition 2.1.1 Wet chemical analysis 2.1.2 Adsorption spectroscope 2.1.3 Radiating spectroscope 2.1.4 Other methods,2.2 Structural Analysis 2.2.1 X ray diffraction 2.2.2 Transparent Electron Mi

8、croscope 2.2.3 Infrared spectroscope 2.2.4 Laser Raman spectroscope 2.3 Surface morphological observation 2.4 Physical and chemical properties,武汉理工大学资环学院 管俊芳,11,Outline1.1 Chemical composition analysis: to determine the kinds and the contents of the elements in a material. Qualitative and Quantitati

9、ve Analysis.,武汉理工大学资环学院 管俊芳,12,describing the chemical composition:Weight concentration: for solid, liquidGeneral element %wt Micro Element: ug/g (g/t) (stands for ppm) 10-6Super-micro : ng/g (ppb) 10-9Hint Element: pg/g (ppt) 10-12Volume concentration: for liquid, gasGeneral: mol/LMicro: mmol/L,武汉理

10、工大学资环学院 管俊芳,13,Two kinds of composition expression:a) For metal, single element material, sulfide, and some other materials that their ions are not oxygen. Expressing as Element content.For example:Iron(钢材): Fe: 99.00%wt, C: 1.00%wtPyrrhotite(磁黄铁矿) (Fe1-xS): Fe: 63.00%wt S: 36.00%wt Ni: 0.50%wt,武汉理工

11、大学资环学院 管俊芳,14,For oxide(氧化物), Silicate(硅酸盐), and some other materials that their ion is oxygen (carbonate碳酸盐, sulfate硫酸盐). When expressing their compositions, generally as oxide types,武汉理工大学资环学院 管俊芳,15,For example:Orthoclass 钾长石(KAlSi3O8): K2O15.13%wt SiO2 63.51%wt Al2O318.99%wt Na2O1.34%wt CaO0.13%

12、wt Fe2O3 0.09%wtCalcite 方解石(CaCO3): CaO 55.03%wt FeO 0.12%wt MgO 0.22%wt CO2 43.97%wt,武汉理工大学资环学院 管俊芳,16,validating digits and their round35.01452 validating digits after point: 35.01 3 digits: 35.0144 no, 6 yes, 5 odd yes even no2 digits: 35.045 -35.04 35.035-35.04 35.0451 -35.05,武汉理工大学资环学院 管俊芳,17,1

13、.2 structural Analysis:To determine the arrangement of the elements in a material: Crystal system, Cell parameters, atom coordinates in the unit cell, and also to determine the mineral phase(s),武汉理工大学资环学院 管俊芳,18,C (Carbon): can be graphite(石墨) or be diamond(金刚石), because they have different structur

14、e (atom arrangement is different)SiO2： -Quartz, -quartz,Al2SiO4O: Andalusite (红柱石) Kyanite (蓝晶石),武汉理工大学资环学院 管俊芳,19,Describing the crystal: Crystal system: cubic, tetragonal, orthorhombic, monoclinic, triclinic, hexagonal, triogonal, Symmetry: plane (m), Center(c), Axles(1,2,3,4,6,3-,6-), Cell Parame

15、ters: a, b, c, , ， Atomic coordinates: halite (NaCl) (石盐): Cl: 0,0,0; ,0, ; 0, ; ,0; Na:0,0,; 0,0; ,0,0; ,.,武汉理工大学资环学院 管俊芳,20,1.3 Morphological properties (Surface observation) To observe the surface characteristic of the material.Macro Micro Super Micro: Macro - by naked eyes. Micro - by microscope

16、 , electron microscope Super Micro -Scanning tunneling microscopy Atomic force microscopy,武汉理工大学资环学院 管俊芳,21,To observe the shape of the particles, their boundary characteristic , in some cases, to observe atom arrangement directly.Generally, the morphological analysis is combined with chemical analy

17、sis. It is called micro-region analysis ( both chemical and morphological analysis),武汉理工大学资环学院 管俊芳,22,1.4 Analysis of physical and chemical properties Including Thermal, Light, electricity, mechanics, etc.,武汉理工大学资环学院 管俊芳,23,2. Analyzing Methods,武汉理工大学资环学院 管俊芳,24,2.1 Chemical Composition2.1.1 Wet Che

18、mical Analysis: (solid, liquid, gas)- liquid - chemical reaction- calculating chemical analyzing result,武汉理工大学资环学院 管俊芳,25,Silicate analysis (including oxides) used for most of the material: (It is called 13 items analysis)SiO2, Al2O3, MgO, FeO, Fe2O3, CaO, K2O, Na2O, MnO, TiO2, P2O5, (H2O)+, (H2O)-p

19、ercent (%wt), Bulk sample (2.0g), long period (2 weeks)Generally 2 validating digits after point.,武汉理工大学资环学院 管俊芳,26,2.1.2 Adsorption spectroscope (Instrument analysis)(solid, liquid, gas)- liquid - adsorption spectroscopy measuring (different cation adsorbs different wavelength of light) General con

20、centration (%wt) to micro (ug/g) and also to hint concentration (ng/g),武汉理工大学资环学院 管俊芳,27,a) AADS (Atom Adsorption Spectroscope) Mainly used to determine micro elements (about all elements in the Element Table) From general concentration to micro- concentration ( %wt to ug/g) b) ICP( Plasma) Mainly u

21、sed to determine micro to hint elements (most of the elements in the Table can be determined) (ug/g -ng/g),武汉理工大学资环学院 管俊芳,28,2.1.3 Radiating Spectroscope light source - solid sample- second light (the wavelength of the 2nd light changes according to the kind of the elements in the solid sample) - me

22、asuring the 2nd light wavelength, so the kinds and the contents of the elements in the material can be determined.,武汉理工大学资环学院 管俊芳,29,a) x ray Fluorescence Spectroscope (XRF) X射线荧光光谱仪General to micro concentration (%wtug/g).Light source : x ray with continues wave length.Sample: solid.the elements fr

23、om Na11-U92. but can not distinguish the different charges of the same element: Fe2+ and Fe3+b) X ray Photoelectron Spectroscope (XPS) X射线光电子（能）谱仪Mainly to identify the elements (qualitative).it can distinguish different environments of the same element. O in CO3 and in SiO4 and in H2O.Source light:

24、 x ray with certain wave length.Sample: solid.,武汉理工大学资环学院 管俊芳,30,c) Isotope Analysis: To determine the ratio of the different isotopes of the same element. Mainly use to determine the age of the sample.Source light: Proton H100y 14C 50,000 32Si *00,000 36Cl *,000,000 129I*,000,000 K/Ar*,000,000 Rb/S

25、r,Sm/Nd, U/Pb*00,000,000,) Stable isotope,) Radiating Isotope,武汉理工大学资环学院 管俊芳,31,2.1.4 other methodsa)Electron Probe Microscopic analysis 电子探针（显微分析仪） Similar to XRF. But the light source is electron beam, and the analysis only be in a very small region. So it is called micro-region chemical analyzing

26、 method).Two kinds of result: Wave disperse Spectroscopy Energy Disperse SpectroscopyElement range: Na11 - U92Concentration range: %wt ug/g( It also can not distinguish the different charges of the same element, for example: Fe2+ and Fe3+).,武汉理工大学资环学院 管俊芳,32,b) AES（Auger electron spectroscopy） 俄歇电子谱

27、仪 light source: electron beam condition: vacuum Similar to EPMA. Using special detector determine the energy of the Auger electron. It can only determine the chemical composition of the very surface layer. (5-20A)c) Element Analyzer: 元素分析仪 Organic analysis Five elements Quantitative analysis: C, H,

28、O, N, S:,武汉理工大学资环学院 管俊芳,33,c)Chromatogram (色谱分析) Two kinds: gas, liquid: （气相色谱仪、液相色谱仪） C,H,O,N,S Qualitative. Mainly to determine the structure of the organic. For example, the length of the carbon chain.d)Mossbuare Spectroscope: 穆氏保尔谱仪 （穆谱） To determine the ratio of the different charges of the sam

29、e element. For example, Fe2+/Fe3+e)Backscattering Spectroscope: 背散射电子谱仪 To determine the depth of the elements in the plate sample.,武汉理工大学资环学院 管俊芳,34,Composition analysis: Bulk analysis, micro-region analysis, surface analysis, Isotope ratio analysis, organic analysis general micro hint analysis. Ch

30、arge analysis circumstance of elements analysis,武汉理工大学资环学院 管俊芳,35,2.2 Structure Analysis2.2.1 X ray diffraction (XRD) X射线衍射a)single crystal method: single crystal: 50um - 0.5 mm. Light source: characteristic X ray instrument: four-circle single crystal x ray diffract-meter. 四园单晶x射线衍射仪 Mainly to dete

31、rmine the structure of the new material. In some cases, to determine the crystal parameters,武汉理工大学资环学院 管俊芳,36,b)Powder crystal method: Sample: powder(200 mesh) Light source: characteristic x ray Instrument: powder x ray diffract-meter Mainly to determine the mineral phase, qualitative or quantitativ

32、e. In some cases, to determine the structure of the new material Only valid to the crystal.,武汉理工大学资环学院 管俊芳,37,2.2.2 Transparent Electron Microscope (TEM) Light source: electron beamSample: very very thin (0-10nm) To determine the structure of the sample in a very small region. (nm region)It can dire

33、ctly observe the distribution of the crystal lattice,武汉理工大学资环学院 管俊芳,38,2.2.3 Infrared Spectroscope (IR): Light source: Infra-red lightSample: solid(powder), liquid, gas.Check the adsorption of the sample to the light from light source.Different chemical bonds can adsorb different wavelength of the l

34、ight. To determine the existence of the chemical bonds in the sample (material), also can be used to determine the mineral phase (different mineral has different chemical bonds: their kinds and strength).Adsorption spectroscope.,武汉理工大学资环学院 管俊芳,39,2.2.4 Laser Raman Spectroscope (RAMAN): Light source:

35、 laser with a certain wavelength.Sample: solid, liquid, gas.When excited by laser, the chemical bonds in the material can radiate a certain wavelength of light.similar with IR. But IR is a kind of adsorption spectroscope.Radiation spectroscope. To determine the existence of the chemical bonds in the

36、 sample (material).,武汉理工大学资环学院 管俊芳,40,2.3 Surface Morphological ObservationNaked eyes: 1*Microscope: 40-400, (1,000 max)Scanning Electron Microscope (SEM) 10,000 sample should be conductive or be made to be conductive.Environment SEM(ESEM) : similar with SEM. But the sample can be conductive or not.Field Emitted SEM (FSEM): 1,000,000 conductive.Transparent Electron Microscope (TEM): 1,000,000 similar with FSEM, but TEM can also do structural analysis.Scanning tunneling micro