闪锌矿中结构铁的X射线衍射定量分析

闪锌矿中的铁包括结构铁和以六配位形式存在的出溶铁,本文提出了应用Ｘ射线衍射测定闪锌矿中结构铁质量分数的新方法。通过对一系列不同结构铁质量分数闪锌矿的主要衍射线强度的理论计算发现,随着闪锌矿中结构铁质量分数的增加,其主要衍射线强度比值Ｉ（００２）／Ｉ（１１１）,Ｉ（１３３）／Ｉ（１１１）,Ｉ（１３３）／Ｉ（１１３）和Ｉ（００２）／Ｉ（１１３）逐渐递减,尤以Ｉ（００２）／Ｉ（１１３）比值递减最为明显,两者几乎呈线性负相关。利用该原理对国内典型铅锌矿床中闪锌矿的结构铁质量分数进行了测定,并与化学分析结果进行对比。     

茂名山阁高岭土中铁赋存状态的EPR研究

ＥＰＲ研究结果表明,茂名山阁高岭土中铁的赋存状态有两种,即结构铁和游离铁。结构铁存在于高岭石晶格中,以Ｆｅ３＋置换八面体中的Ａｌ３＋,分为处于斜方晶场对称的结构铁Ｉ和处于更高晶场对称的结构铁Ｅ。结构铁含量（Ｆｅ２Ｏ３）００８１％～０１２２％,其中,Ｉ铁含量００３１％～００５５％,Ｅ铁含量００５０％～００６７％。Ｉ铁和Ｅ铁含量均与高岭石结晶度指数呈密切负相关,而Ｅ铁和Ｉ铁含量比值与高岭石结晶度指数呈正相关。游离铁以杂质形式存在,含量（Ｆｅ２Ｏ３）０４６７％～０６４８％,主要为赤铁矿、褐铁矿和针铁矿。化学除铁处理对结构铁不产生影响,而可去除绝大部分游离铁。     

黄铁矿的x射线衍射谱及其找矿意义

本文的特色在于不仅研究了黄铁矿的ｘ衍射特征，同时还详细探讨和挖掘了黄铁矿ｘ衍射特征与其含金性之间的关系。研究表明，黄铁矿的ａ０值和某些特定面网的ｘ衍射强度比值对金矿的找矿评价具有标型意义。越是偏离（大于或小于）标准ａ０值的黄铁矿，其含金性越好。Ｉ３１１／Ｉ２１１、Ｉ２００／Ｉ２１０、Ｉ２００／Ｉ１１１的大小变化与含金性变化具有良好的一致性。其中尤以Ｉ３１１／Ｉ２１１反应最为灵敏。     

谱学研究在印章石中的应用:以昌化石为例

在野外地质工作、显微镜下观察、电子探针分析和差热分析的基础上,运用X射线衍射分析、红外光谱分析对印章石(以著名的昌化石为例)进行了谱学分析。昌化石主要矿物成分为高岭石族矿物,主要为迪开石及高岭石-迪开石过渡矿物。通过X射线衍射图谱分析计算其结晶度指数(HI)表明,高岭石族矿物的结晶有序度存在明显的高低变化。红外光谱特征显示,其中属于外部羟基振动的3 697cm-1谱峰强度(A)与属于内部羟基振动的3 620cm-1谱峰强度(B)的比值随着结晶度指数的降低有逐渐升高的趋势,且比值A/B的大小可以大致用来区分高岭石和迪开石:一般高岭石比值大于1,而迪开石小于1。差热分析的结果也印证了高岭石族矿物有序度高低变化的现象,如:高岭石族矿物在加热到400℃～700℃时会出现一个强烈尖锐的吸热峰,吸热峰的强度及温度与其有序度的高低存在正相关性。当主要组成矿物成分为较纯净的迪开石时,其有序度相对较高,透明度也较好;当主要矿物成分为高岭石-迪开石过渡矿物时,其有序度较低,透明度也较差。X射线衍射分析和红外光谱都是研究分析印章石的有效方法,但X射线分析通常为有损分析,且仪器使用条件相对较高;而红外光谱则可以无损且具有扫描时间短等...     

巴林石、寿山石透明度研究

通过分析巴林石、寿山石样品的FTIR与XRD光谱特征,指出有序度指数（OI）、结晶度指数（HI,DHI）及半高宽（FWHM（00l））在用于研究高岭石与地开石混合相样品的组分时具有局限性;计算了样品的有序度指数和结晶度指数并研究了各自与透明度之间的关系,结果证实,寿山石样品的透明度随其有序度与结晶度的增加而增大,但没有发现巴林石样品存在类似规律。     

关于伊利石结晶度诸指数的评价

本文根据结晶学原理、Ｓｃｈｅｒｒｅｒ定律、Ｗａｒｒｅｎ－Ａｖｅｒｂａｃｈ理论和Ｘ射线衍射峰形态学原理提出任何衍射峰都是由五个基本要素组成的,即：衍射峰位置;最大衍射强度;半高宽;衍射峰形态和对称性。各衍射峰要素都具有其自身的物理学意义,其中,只有半高宽和衍射峰形态是与晶体内部结构和大小即结晶度相联系的。据此,分析评价了与Ｘ射线衍射相关的Ｋüｂｌｅｒ指数、Ｗｅｂｅｒ－ＤｕｎｏｙｅｒｄｅＳｅｇｏｎｚａｃ－Ｅｃｏｎｏｍｏｕ指数、Ｗｅａｖｅｒ指数、Ｍｉｌｉｅｒｓ指数、Ｗｅｂｅｒ指数、分解ＨＷ及纯Ｃ轴厚度等伊利石结晶度指数的理论基础、使用前提和条件、特点及误差源。指出Ｋüｂｌｅｒ指数、Ｗｅｂｅｒ－ＤｕｎｏｙｅｒｄｅＳｅｇｏｎｚａｃ－Ｅｃｏｎｏｍｏｕ指数和分解ＨＷ为非条件性单一结晶度指数;Ｗｅａｖｅｒ指数、Ｗｅｂｅｒ指数和高宽比为条件性单一结晶度指数;消除晶体内部微应变影响的ｃ轴厚度为全面描述伊利石结晶度指数;而Ｍｉｌｉｅｒｓ指数不可描述伊利石结晶度。     

基于X射线衍射评价高岭石结构有序度

对采自江苏、福建、江西、云南、广西等地7个高岭石样品进行X射线衍射分析，并利用Hinckley指数(HI)、随机缺陷密度(R₂)、八面体C位空隙含量(W_C)、Aparicio-Galan-Ferrell指数(AGFI)对高岭石样品的结构有序度进行综合评价。HI是经验参数，仅能定性的反映高岭石的结构有序度，且不适用低结构有序度高岭石。AGFI容易受到杂质矿物的影响，且分峰处理过程容易引进操作者主观误差，最终影响高岭石结构有序度的准确判断。R₂和W_C是从晶体结构上反应高岭石的结构有序度，且在计算上受杂质矿物和操作者主观影响较小。R₂指数仅适用于结构有序度较高的高岭石，而八面体C位空隙含量对于高结构有序度和低结构有序度的高岭石均适用，是一种准确性高且操作简单的评判高岭石结构有序度的方法。     

高岭石矿物缺陷结构研究——以晋北晚古生代煤系地层高岭岩为例

本文主要根据ＸＲＤ分析和ＩＲ光谱分析的有关参数，对山西境内产部晚古生代煤系夹矸高岭岩的矿物结构特征进行了详细研究，认为高岭石矿物结晶度与其显微结构有关，隐晶质高岭岩比碎屑团粒状和蠕虫状高岭岩结晶指数高。高岭石的无序度主要反映于（ａ，ｂ）面上的随机层错，同时与样品中低缺陷相的比率有关。动荡的水介质环境可能导致其无序度的增加。     

石英的结晶度指数及其标型意义

用Ｘ射线粉晶衍射方法测量石英的衍射峰，计算得到几种结晶并指数，这些指数定量地反映了石英矿物的内部结构完整性─结晶度。石英的结晶度可以作为估计矿床形成深度的标志。石英的结晶度随其形成世代从早到晚而增大，随形成方式不同而具较大差别。结晶度还可以指示矿化作用特征，并作为找矿标型特征；不同产状和成因类型的石英具有不同的结晶度指数。变质作用和重结晶作用能提高石英的结晶度。石英的结晶度还可以用于构造应力的分析。     

高岭石/乙酰胺插层复合物的制备及结构表征

乙酰胺在熔融状态下直接插层高岭石，产物经无水乙醇洗涤，得到纯净的高岭石／乙酰胺插层复合物。XRD结果显示高岭石层间距从0．721nm膨胀到1．102nm。插层作用使得高岭石内表面羟基伸缩振动峰由3651cm^-1。移动至3647cm^-1。处，变形振动峰由911cm^-1移动至907cm^-1处；乙酰胺3211cm^-1和3390cm^-1处NH2基伸缩振动峰消失，并在3478cm^-1处产生一新的振动峰，这些表明原高岭石层问氢键的损失及与乙酰胺分子之间氢键的形成。高岭石内羟基的吸收峰由3616cm^-1移动至3611cm^-1处，以及其硅氧面的骨架振动峰变化表明乙酰胺的甲基中CH嵌入到高岭石的复三方空穴中。进而构建高岭石／乙酰胺插层复合物的结构模型，结果表明该模型的理论计算值与实际测量结果具有很好的一致性。     

Distribution and Influence of Iron Phases the Physico—Chemical Properties of Phyllosilicates

Clay minerals from different Cretaceous stratigraphic successions of Egypt were investigated using XRD,DTA,dissolution analysis(DCB),IR,Moessbauer and X-ray Electron Spin Resonance(ESR) spectroscopes.The purity of the samples and the degree of their structural order were determined by XRD.The location of Fe in the octahedral sheet is characterized by absorption bands at-875cm^-1 assigned as Al-OH-Fe which persist after chemical dissolution of free iron.The Moessbauer spectra of these clays show two doublets with isomer shift and quadrupole splitting typical of octahedrally coordinated Fe^3 ,in addition to third doublet with hyperfine parameter typical of Fe^2 in the spectra of Abu-Had kaolinite (H) sample.Six-lines magnetic hyperfine components which are consistent with those of hematite are confirmed in the spectra of both Isel and Rish kaolinite samples.Goethite was confirmed by both IR and DTA.Multiple nature of ESR of these clays suggested structural Fe in distorted octahedral symmetry as well as non-structural Fe.Little dispersion and low swelling indices as well as incomplete activation of the investigated montmorillonite samplas by NaCO3 appear to be due to incomplete disaggregation of montmorillonite particles.This can be explained by the ability of Fe-gel to aggregate the montmorillonite into pseudo-particles and retard the rigid-gel structure.However,extraction of this ferric amorphous compound by dithonite treatment recovers the surface properties of the montmorillonite samples.On the other hand,the amount and site occupation of Fe associated with kaolinite samples show an inverse correlation with the parameters used to describe the degree of crystallinity perfection,color,brightness and vitrification range of these kaolinite samples.     

高岭石的结晶度和精泥流变性能的关系

造纸涂料分气刀和刮刀涂料两种,它们的主要区别在于固含量高低和流变性能的好坏。刮刀涂料要求固含量高,流变性能好,即粘度低,一般小于500mpa.s。实践证明,流变性能的好坏,与高岭石的结晶度密切有关。结晶度高,则流变性能好。因此,可以用“x衍射”法测定高岭石的d(001)半高宽(w)代入公式c=100(1/w)计算高岭石的结晶度(c),进而判断精泥的硫变性能及其用途。     

EPR Parameter of Order Degree in Natural Kaolinite and Its Relation to Weathering

Conclusions In studying the degree of order (or disorder) in kaolinite, X-ray diffraction and DTA are commonly used, but spectroscopic method (as EPR, IR)has become a useful and additional tool now. The total iron content and the intensity of Fe³⁺(I) line are not always correlated negatively with order degree in natural kaolinite. But in the present case, they show direct correlations. So it appears that they cannot be used as an ideal parameter for measuring the order degree in kaolinite. The ratio of Fe³⁺(E)line and Fe³⁺(I)line intensities obtained directly from EPR spectrum of Fe³⁺at g_eff=4 appears to be a better EPR parameter for measuring the magnitude of order degree in kaolinite and for determining the intensity of some geological processes (such as weathering, hydrothermal alteration and so on) with aid of kaolinite. However, EPR data can only be used to qualitatively estimate the degree of order in kaolinite and related geological process for the present. There is still much work to be done in order to make EPR a method of quantitative estimation in the field.     

成岩带、近变质带与一维纳米级层状硅酸盐

运用X射线衍射分析技术，计算了成岩带、近变质带粘土矿物C^*方向的粒度。根据阿尔卑斯造山带前陆碎屑岩粘土矿物粒度与伊利石结晶指数的关系，推导出了伊利石、绿泥石、蒙脱石、伊蒙混层、高岭石和叶蜡石的c^*方向粒度变化趋势曲线。结果表明，大多数产于成岩带和近变质带的粘矿物其c6*方向粒工为几至几十纳米。成岩带和近为质带是一维天然纳为级土帮物的产地。     

Distribution and Influence of Iron Phases on the Physico—Chemical Properties of Phyllosilicates

Clay minerals from different Cretaceous stratigraphic successions of Egypt were investigated using XRD,DTA,dissolution analysis(DCB),IR,Moessbauer and X-band Electron Spin Resonance(ESR) spectroscopies.The purity of the samples and the degree of structural order were determined by XRD.The location of Fe in the octahedral sheet is characterized by absorption bands at-875cm^-1 assigned as Al-OH-Fe which is present after chemical dissolution of free iron.The Moessbauer spectra of these clays sow two doublets with isomer shift and quadrupole splitting typical of octahedral coordinated Fe^3 ,in addition to third doubler with hyperfine parameter typical of Fe^2 in the spectra of Abu-Had kaolinite (H)sample.6-lines magnetic hyperfine components which are consistent with those of hematite are confirmed in the spectra of both Isel and Rish kaolinite samples.Goethite was confirmed by both IR and DTA.Multiple nature of ESR of these clays suggested structural Fe in distorted octaedral symmetry and as non-structural Fe.Little dispersion and low swelling indices as well as incomplete activaiton of investigated montmorillonite samples by NaCO3 appear to be due to incomplete disaggregation of montmorillonite particles.This can be explained by the ability of Fe-gel to aggregate the montmorillonite into pseudo-particles and retard the rigid-gel structure.However,extraction of this ferric amorphous compound by dithonite treatment recovers the surface properties of the montmorillonite samples.On the other hand,amounts and site occupation of Fe associated with kaolinite samples show a negative correlation with the parameters used to describe the degree of crystalline perfection,color,brightness and vitrification range of these kaolinite samples.     

青海省河南县三叠系伊利石结晶度与极低级变质作用

在开展“青海省河南县托叶玛地区I47E007023、I47E008023、I47E009023、1I47E009024四幅1:5万区域地质矿产调查”时,为验证该地区三叠系变质情况,针对三叠系中泥岩(页岩)的伊利石结晶度做了分析测试。30件样品的实验结果表明: 北部宗务隆—泽库地层分区三叠系泥岩(页岩)伊利石Kübler结晶度指数为0.312~0.537,晶胞参数b₀为0.898 0~0.903 2 nm,判断其变质温度小于350 ℃,具葡萄石-绿纤石和沸石相; 南部西倾山地层分区三叠系泥岩(页岩)的伊利石Kübler结晶度指数为0.21~0.318,b₀为0.898 1~0.901 4 nm,变质温度主要分布在200~350 ℃,局部>350 ℃,具葡萄石-绿纤石和绿片岩相。研究认为青海省河南县地区区域变质程度较低,为极低级变质作用或者未发生区域变质作用,且南部西倾山地层分区的变质程度略高于北部宗务隆—泽库地层分区变质程度。这一变质相带研究结论与前人认为的“区域低温动力变质作用及低绿片岩相变质带”不一致,变质程度相对更低。该研究证实了在青海省河南县地区三叠系地层中不存在大面积区域变质作用,仅存在极低级区域变质作用。     

Crystallinity and metamorphism of illite from Triassic strata in Henan County of Qinghai Province

In order to verify the Triassic stratum metamorphism in this area, the crystallinity of illite in mudstone (shale) of Triassic stratum was analyzed and tested during the 1:50 000 regional mineral geological survey (I47E007023, I47E008023, I47E009023,1I47E009024)in Tuoyema area of Henan Mongolian Autonomous County in Qinghai Province. According to the experimental results of 30 samples, the crystallinity index of Triassic mudstone (shale) illite Kübler in Zongwulong-Zeku stratigraphic division in the north is 0.312-0.537, and the cell parameter b₀ is 0.898-0.903 2 nm. The metamorphic temperature is less than 350 ℃, with the grape-chlorite and zeolite facies. The crystallinity index of Triassic mudstone (shale) illite Kübler in the western inclined mountain stratigraphic division in the south is 0.21-0.318, and the b₀ value is 0.898 1-0.901 4 nm. The metamorphic temperature is mainly between 200 and 350 ℃, with the local temperature above 350 ℃ and grape-chlorite and greenschist facies. It is considered that the regional metamorphism grade in this area is very low or has no regional metamorphism. The metamorphism degree of the western dipping mountain stratum in the south is slightly higher than that of Zongwulong-Zeku stratum in the north. The measured metamorphic facies belts are not consistent with the previous thought, that is "regional low temperature dynamic metamorphism and low greenschist facies metamorphic belts", and the degree of metamorphism is relatively lower. It is confirmed that there is no large area regional metamorphism in the Triassic strata of Henan County in Qinghai Province, but only very low-level regional metamorphism.     

应用国际标样对伊利石结晶度测定值的校正及其意义

伊利石的结晶度(IC),又称Kbler指数(K.I.),是指粘土矿物伊利石10×10-8cmXRD峰的半高宽。作为一个变质程度的指标,结晶度广泛用于研究高级成岩—极低级变质—低级变质作用的演变过程,随着变质程度的提高,伊利石结晶度逐渐增大。根据Kbler的建议,近变质带(极低级变质带)上、下边界的伊利石结晶度分别为0.42(°Δ2θ)和0.25(°Δ2θ)。然而,测定伊利石结晶度时,由于缺少国际标样,且各实验室间的样品制备、仪器条件、测试方法也不相同,因而导致获得的数据有较大差别,缺少可比性;因此,使用国际标样对数据进行校正,使各实验室获得的数据都能直接地进行对比,是非常必要的。利用X射线衍射方法测定了由L.N.Warr提供的5个伊利石结晶度的国际标样(其中,4个为岩石碎屑样品,采自英格兰西南部的极低级变质带;1个为单矿物样品,采自印度的花岗岩),获得了校正方程,ICCIS=0.977IC测定值+0.0336(°Δ2θ),R2=0.9835。在实验室内对213件采自国内的样品进行测定,测试条件与国际标样的测试条件相同,利用此方程对测得的伊利石结晶度数值进行校正,证实本实验室对伊利石结晶度的测定具有较高的可信度和国际可比性。     

Aluminium X-ray absorption Near Edge Structure in model compounds and Earth’s surface minerals

Aluminium K-edge X-ray absorption near edge spectra (XANES) of a suite of silicate and oxides minerals consist of electronic excitations occurring in the edge region, and multiple scattering resonances at higher energies. The main XANES feature for four-fold Al is at around 2 eV lower energy than the main XANES feature for six-fold Al. This provides a useful probe for coordination numbers in clay minerals, gels, glasses or material with unknown Al-coordination number. Six-fold aluminium yields a large variety of XANES features which can be correlated with octahedral point symmetry, number of aluminium sites and distribution of Al-O distances. These three parameters may act together, and the quantitative interpretation of XANES spectra is difficult. For a low point symmetry (1), variations are mainly related to the number of Al sites and distribution of Al-O distances: pyrophyllite, one Al site, is clearly distinguished from kaolinite and gibbsite presenting two Al sites. For a given number of Al-site (1), variations are controlled by changes in point symmetry, the number of XANES features being increased as point symmetry decreases. For a given point symmetry (1) and a given number of Al site (1), variations are related to second nearest neighbours (gibbsite versus kaolinite). The amplitude of the XANES feature at about 1566 eV is a useful probe for the assessment of Al^IV/Al^total ratios in 2/1 phyllosilicates. Al-K XANES has been performed on synthetic Al-bearing goethites which cannot be studied by ²⁷Al NMR. At low Al content, Al-K XANES is very different from that of α-AlOOH but at the highest level, XANES spectrum tends to that of diaspore. Al-K XAS is thus a promising tool for the structural study of poorly ordered materials such as clay minerals and natural alumino-silicate gels together with Al-subsituted Fe-oxyhydroxides. Received: 18 December 1996 / Revised, accepted: 2 June 1997