天然硫化物矿物对地球深部热能的热电转化效应研究

金属硫化物半导体矿物在地壳中分布广泛,其中一些禁带宽度较窄的硫化物矿物,如黄铁矿、黄铜矿和斑铜矿等,在地热梯度下产生的天然热电势可将地球内部热能转化为电能。本文选取黄铁矿、磁黄铁矿、方铅矿、黄铜矿、斑铜矿以及斑铜矿-赤铁矿-辉铜矿集合体等天然硫化物矿物样品,研究了其热电特性。研究结果表明,300～700K下,除磁黄铁矿具有低塞贝克系数和超高电导率而表现出金属导体的电输运行为外,黄铁矿和黄铜矿为n型半导体,斑铜矿和斑铜矿-赤铁矿-辉铜矿集合体为p型半导体,具有150～500μV/K的显著塞贝克系数和5～95 S/cm的电导率,说明样品在地热梯度下具有产生显著热电效应的能力。根据激光闪射法测得的热扩散率以及样品的理论比热、密度计算热导率,斑铜矿及硫化物矿物集合体样品表现出小于1 W/(m·K)的低热导率,说明样品在局部热源影响下可形成较大温差。根据热电基本理论和地热梯度构建天然热电效应模型,对硫化物半导体矿物集合体产生的天然热电势、额外地表电流密度及热电转换效率进行了模拟计算得出经验公式,发现硫化物半导体矿物在300～650 K条件下能产生100 m V左右的天然热电势,产生的最大热电转化率可达4‰,且可以通过偶极电流源模型计算矿物体产生的额外地表电流密度。研究认为硫化物半导体矿物可能作为天然热电转换介质深刻影响地球内部能量的转化与传递过程。     

Mesoporous material Al-MCM-41 from natural halloysite

Aluminum-containing hexagonally ordered mesoporous silica (Al-MCM-41) with specific surface area of 509.4 m²/g was first synthesized using natural halloysite as source material by hydrothermal treatment, without addition of silica or aluminum regents. The samples were characterized by X-ray diffraction, transmission electron microscopy, N₂ adsorption–desorption measurements, and Fourier transform infrared spectra techniques. The results indicate that process parameters, including calcination temperature, pH value, n(SiO₂)/n(CTAB)/n(H₂O) ratio, and hydrothermal reaction time, show moderate effects on the preparation of Al-MCM-41. SiO₂/Al₂O₃ molar ratio could be effectively modulated by the calcination temperature for halloysite. Furthermore, we first clarified the structural evolution from natural halloysite to mesoporous material Al-MCM-41 at the atomic level.     

天然有机质与矿物间的吸附及其环境效应的研究进展

本文综述了天然有机质与矿物间吸附行为的研究进展.具体介绍了天然有机质与矿物间的吸附机理,包括配位交换、范德华力、静电引力、疏水作用、离子交换及阳离子桥;阐述了不同分子大小及亲疏水性组分的天然有机质在矿物上的吸附行为;讨论了影响吸附行为的环境条件（pH,离子强度）及天然有机-矿物体系对全球碳循环、重金属和有机污染物产生的环境效应,并提出了研究展望.     

含铀矿物对烃源岩生烃影响的热模拟研究

采用密闭容器加水的热模拟方法,从生烃组成特征、生烃量等方面,探讨了含铀矿物对烃岩热解生烃过程的影响.热模拟实验结果表明,在暗色泥岩和煤岩样品中加入含铀矿物后,气态烃和液态烃的生烃量都有比较明显的增加,其中煤岩的气态烃产量平均增加值为34%,而泥岩样品平均增加值也达到了30%以上.液态烃产率分析表明,含铀矿物也促进了泥岩和煤岩的液态烃产率.从泥岩氯仿沥青'A'族组成分析发现,加入催化剂后泥岩的饱和烃和芳烃在高温阶段具有规律性的明显增大的趋势,反映出非烃和沥青质甚至不溶有机质向相对稳定的饱和烃转化以及芳烃随演化程度增加的高聚合作用.综合以上分析,认为放射性铀对油气生成具有积极的意义.     

Isomorphism of titanium in natural minerals

Spectra (electronic paramagnetic resonance) of 15 natural genetically different minerals (silicates, aluminosilicates, magnesiosilicates etc.) show Ti ³⁺ as the electronic center which determines the color and the thermolurninescence of several minerals. The energy of stabilization of this electronic center depends on its structural position, the cation replaced therein, and the surroundings. The temperature at which the EPR vanishes (150 to 5007deg;, depending on the mineral) may be taken here as a criterion of the energy of stabilization. The trivalent state of titanium, unusual as it is, may be due to the electronic capture by Ti⁴⁺, the well known electronic trap.     

Heterogeneous shock-induced thermal radiation in minerals

A 500 channel optical imaging intensifying and spectral digital recording system is used to record the shock-induced radiation emitted from 406 to 821 nm from transparent minerals during the time interval that a shock wave propagates through the sample. Initial results obtained for single crystals of gypsum, calcite and halite in the 30 to 40 GPa (300 to 400 kbar) pressure range demonstrate greybody emission spectra corresponding to temperatures in the 3,000 to 4,000 K range and emissivities ranging from 0.003 to 0.02. In the case of gypsum and calcite, distinctive line spectra, are superimposed on the thermal radiation. The observed color temperatures are a factor of 2 to 10 greater than the Hugoniot temperature, calculable on the basis of continuum thermodynamics and equation of state models for the shock states achieved in the three minerals. These observed high temperatures are believed to be real. We conclude that we are detecting a large number of closed spaced high temperature shear-band regions immediately behind the shock front. A shear instability model, such as proposed independently by Grady (1977, 1980), Ananin et al. (1974), and Horie (1980), in which small zones of highly deforming and melted material are produced which are the source of the detected thermal radiation and have a fractional effective area approximately numerically equal to the measured emissivity, can be used to predict an effective emissivity of 0.0065 directly behind the shock front. If shear band instability arises from viscous flow processes, Grady's model and mineral thermal properties yield for the shocked mineral viscosities values in the range of 10⁹ to 10¹⁵ P immediately behind the shock front.     

钨矿自然重砂矿物组合特征及其找矿意义

统计浙江、湖南、江西、湖北、新疆、青海、云南、广西、福建、河南、贵州、安徽、广东共计13个省(自治区)61个典型钨矿床(矿区)的自然重砂矿物报出情况,计算各重砂矿物的报出频率,分析得出矽卡岩型、热液型和斑岩型3种类型钨矿床所对应的自然重砂矿物组合及标型矿物组合。结果表明,不同类型的矿物组合既有相似处也有各自的代表标型。如此按照矿床类型建立的自然重砂矿物组合及其含量变化,对建立自然重砂找矿模型具有重要意义。     

锡矿自然重砂矿物组合规律及其找矿意义

为探究不同类型锡矿床所反映出的自然重砂矿物组合特征,统计了云南、福建、江西、浙江、湖南、青海和广西7省共35个典型锡矿床的自然重砂情况,通过计算和分析各自然重砂矿物在所对应类型矿床中的报出频率,得出矽卡岩型、热液脉型和斑岩型3种锡矿所对应的自然重砂矿物组合。所反映出的重砂矿物组合既有相似之处,如均出现锡石+白钨矿(或黑钨矿)的矿物组合,亦反映出不相同的地方,如矽卡岩型锡矿石榴子石报出率高,斑岩型锡矿锆石报出率高等。因此,按照矿床类型建立的自然重砂矿物组合对于建立自然重砂找矿模型具有重要意义。     

萤石矿自然重砂矿物组合规律及其找矿意义

为探究不同类型的萤石矿所反映的自然重砂矿物组合所携带的对各类型萤石矿的指示特征,统计了浙江、湖南、湖北、青海、广西、福建、安徽、新疆、甘肃、河北共计10个地区23个典型萤石矿床的自然重砂矿物报出情况,计算各重砂矿物报出率,分析得出热液型矿、后期热液型及热液充填型3种类型萤石矿床各自对应的自然重砂矿物组合和标型矿物组合。结果显示,各类型矿床自然重砂矿物组合既有相同之处也有显示各自的特点。因此,按照矿床类型建立的自然重砂矿物组合及其含量变化,对于新一轮的矿产资源勘查具有重要的意义。     

银矿自然重砂矿物组合规律及其找矿意义

根据20世纪60年代全国范围内展开的自然重砂测量工作所累积的自然重砂数据资料,统计了全国各省72个典型银矿床的自然重砂情况,通过计算和分析各自然重砂矿物在所对应的类型的矿床中的报出频率,得出火山沉积型、沉积型、变质型、侵入岩型4种类型的银矿所对应的自然重砂矿物组合。展现这4种类型矿床的重砂矿物组合的相似之处及不同之处。按照这种方式建立的不同矿床类型的自然重砂矿物组合,对于建立自然重砂找矿模型具有重要的意义。     

无机界矿物天然自净化功能之矿物光催化作用

在简述半导体光催化理论及TiO2多相光催化作用近30年研究现状的基础上，重点对国内外一直处于空白状态的天然含钒金红石光催化性能进行研究。天然含钒金红石中部分Ti^4 被V^5 包括Fe^3 、Cu^2 和Zn^2 等杂质离子替代可引起其晶格畸变与缺陷。机械粉碎到70～80μm后可使其晶胞膨胀0.33％，原位加热700～1100℃其晶胞可膨胀0．93％～2．13％，淬火改性其晶胞收缩0．01％～0．07％。受热改性其体相中V^5 向表面偏析。对晶格畸变的修复可表现为晶面重构和再结晶作用及微应力释放作用。粉碎的金红石对卤代烃三氯乙烯和四氯乙烯具有一定的降解效果而表现出良好的光催化活性。加热1000℃，金红石对卤代烃的降解率明显提高。淬火1000℃和1100℃，金红石对卤代烃的降解速度大大加快。而电子辐射金红石对三氯乙烯的降解率则明显降低。通过52种金属氧化物和金属硫化物半导体矿物的初步研究，发现大多数金属氧化物矿物产生光电子的波长范围是249～777nm，吸收光主要是可见光。而大多数金属硫化物矿物产生光电子的最大波长大于921nm，吸收光主要是红外光，充分表明无机界具有光催化功能的半导体在可见光条件下就可以产生光电子与空穴。系统开展无机界矿物光催化作用研究，对揭示地球生命过程和环境演化有着不可替代的作用，对氧化降解地球表层系统中有机污染物尤其是不能自行降解的持久性有机污染物有着至关重要的作用。     

In situ strength measurements on natural upper-mantle minerals

Using in situ strength measurements at pressures up to 10 GPa and at room temperature, 400, 600, and 700°C, we examined rheological properties of olivine, orthopyroxene, and chromian-spinel contained in a mantle-derived xenolith. Mineral strengths were estimated using widths of X-ray diffraction peaks as a function of pressure, temperature, and time. Differential stresses of all minerals increase with increasing pressure, but they decrease with increasing temperature because of elastic strain on compression and stress relaxation during heating. During compression at room temperature, all minerals deform plastically at differential stress of 4–6 GPa. During subsequent heating, thermally induced yielding is observed in olivine at 600°C. Neither orthopyroxene nor spinel shows complete stress relaxation, but both retain some stress even at 700°C. The strength of the minerals decreases in the order of chromian-spinel ≈ orthopyroxene > olivine for these conditions. This order of strength is consistent with the residual pressure of fluid inclusions in mantle xenoliths.     

Selective destruction and differentiation of clay minerals from natural diaspore admixture by mortar grinding

A dry grinding process at several periods has been used successfully in order to differentiate among the different minerals forming a natural diaspore clay. This is achieved by selective and incongruent destruction of the clay minerals of this admixture, on the basis of their disparate structural stability, hardness and relative amount present. Kaolin clays (represented mainly by kaolinite + halloysite) are destroyed after >3 hr grinding, anatase after ～40 hr, whereas the structure of α-AlOOH is still preserved after >250 hr, as ascertained from XRD. From IR spectroscopy analysis it is inferred that as a consequence of grinding prototropy takes place in some of the clay hydroxyls. This is supported by water losses results at 600°C.     

The heat capacity of two natural chlorite group minerals derived from differential scanning calorimetry

The heat capacity of natural chamosite (X_Fe=0.889) and clinochlore (X_Fe=0.116) were measured by differential scanning calorimetry (DSC). The samples were characterised by X-ray diffraction, microprobe analysis and Mössbauer spectroscopy. DSC measurements between 143 and 623?K were made following the procedure of Bosenick et?al. (1996). The fitted data for natural chamosite (CA) in J?mol^?1?K^?1 give: C _p,CA = 1224.3–10.685?×?10³?×?T ^??0.5???6.4389?× 10⁶?×T ^??2?+?8.0279?×?10⁸?×?T ^??3 and for the natural clinochlore (CE): C _p,CE = 1200.5–10.908?×?10³?×T ^??0.5?? 5.6941?×?10⁶?×?T ^??2?+?7.1166?×?10⁸?×?T ^??3. The corrected C _p-polynomial for pure end-member chamosite (Fe₅Al)[Si₃AlO₁₀](OH)₈ is C _p,CAcor = 1248.3–11.116?× 10³?×?T ^??0.5???5.1623?×?10⁶?×?T ^??2?+?7.1867?×?10⁸×T ^??3 and the corrected C _p-polynomial for pure end-member clinochlore (Mg₅Al)[Si₃AlO₁₀](OH)₈ is C _p,CEcor = 1191.3–10.665?×?10³?×?T ^??0.5???6.5136?×?10⁶?×?T ^??2?+ 7.7206?×?10⁸?×?T ^??3. The corrected C _p-polynomial for clinochlore is in excellent agreement with that in the internally consistent data sets of Berman (1988) and Holland and Powell (1998). The derived C _p-polynomial for chamosite (C _p,CAcor) leads to a 4.4% higher heat capacity, at 300?K, compared to that estimated by Holland and Powell (1998) based on a summation method. The corrected C _p-polynomial (C _p,CAcor) is, however, in excellent agreement with the computed C _p-polynomial given by Saccocia and Seyfried (1993), thus supporting the reliability of Berman and Brown's (1985) estimation method of heat capacities.     

A novel technique for characterizing thermal expansion in minerals

When a crystalline solid is subjected to a temperature increase, its constituent polyhedra may change in size and shape and rotate relative to one another. If the deformation can be approximated by a linear transformation of atomic coordinates, these changes can be quantitatively described in terms of second rank tensors. An iterative least-squares method is used to calculate strain and rotation tensors given the positions of the coordinating atoms of a polyhedron at two temperatures. The method is applied to polyhedral thermal expansions in silicate and oxide minerals.     

Volatile components of natural fluids: Evidence from inclusions in minerals: Methods and results

A database compiled by the author on volatile components in fluid inclusions (5300 analyses compiled from 300 publications) was used to compare destructive and nondestructive analytical techniques and thermal and mechanical methods for the extraction of volatiles in destructive techniques. Possible explanations are proposed for opposite conclusions published by various researchers. The paper summarizes the principal outcomes of the long-lasting discussion on the optimal methods able to provide the most reliable results. No unambiguous answer is provided. Analysis of extensive literature data indicates that each of the techniques is characterized by its own advantages and disadvantages, and an optimal solution should be selected with regard for the materials to be analyzed and formulated tasks. In any event, the results require careful interpretation. The average composition of natural fluids calculated from extensive statistical material is as follows (mol %): 70.3 H₂O, 21.4 CO₂, 6.3 CH₄, 2.0 N₂, and 0.07 H₂S. The distribution of volatile components was examined in minerals from hydrothermal ore deposits of various types (gold, tungsten, tin, and base-metal) and metamorphic rocks     

天然矿物材料在复合材料中的应用价值

本文介绍了复合材料的特殊工业意义、发展前景及天然矿物在复合材料中的利用价值。天然矿物和复合材料的关系及应注意的问题。     

几种天然半导体矿物热电特性对地震电场变化的 启示意义

采用BHTE 06型热电测量仪,选择磁铁矿、毒砂、黄铁矿、黄铜矿4种代表性天然半导体矿物进行了不同活化温度下热电势的测量。测试结果显示:几种矿物均有“热电势绝对值随活化温度增加而增加”的规律。根据半导体矿物热电特性的基本理论和天然矿物形成条件的分析,笔者认为:地壳内广泛存在天然半导体矿物,绝大多数半导体矿物具有热电特性。由于“孕震发震过程中存在同源电磁场和热场相互作用”,所以伴随孕震发震过程的热场变化可能激发半导体矿物产生热电效应,进而产生新的附加热电势场。这种附加热电势场可能是映震前兆信息源。这说明,广泛存在的天然半导体矿物极有可能是孕震发震过程大地电场异常变化的重要影响因素之一。因此,深入探讨天然半导体矿物的热电效应,对全面理解震前电场前兆异常变化的机理具有启示意义。     

Sorption isotherms and kinetics of chromium uptake from wastewater using natural sorbent material

Chromium (VI) which exists in many industrial wastewater is considered highly toxic. The aim of the present investigation was to study the reduction of chromium (VI) to chromium (III) and then removing it with the help of weathered basalt andesite products. Reduction of the chromium (VI) to chromium (III) by hydrazinium sulfate was investigated. The influence of hydronium ion concentration, contact time, hydrazinium sulphate dosage and temperature has been tested in batch runs. The process was found to be acid, temperature and concentration dependent. The suitability of weathered basalt andesite products as a potential sorbent was assessed for the removal of chromium (III) following batch mode of operation. The effect of various parameters such as hydronium ion concentration, shaking time, sorbent dose, initial metal ion concentration and temperature on the removal of chromium (III) from aqueous solution was studied. Thermodynamic parameters (?H°, ?S° and ?G°) for the sorption process were evaluated. Analysis of sorption obtained results showed that the sorption pattern followed the Freundlich, Langmuir and Dubinin-Kaganer-Radushkevich isotherms. The process follows pseudo second order rate and surface diffusion is identified as the predominating mechanism. The sorption process was shown to be reversible by the recovery of sorbed chromium (III) upon extraction with 0.5 M nitric acid. The sorbent, before and after sorption, was characterized by fourier transform infrared spectrometer, X-ray diffraction, scanning electron microscope, transmision electron microscope and thermogravimetric analyse methodes. An increase in crystallanity after sorption of chromium was observed. An industrial effluent was successfully treated with the same sorbent with convincing results.     

天然矿物低温催化脂肪酸酯生烃反应动力学研究

选择十八烷酸甲酯为模型化合物,以 10种天然矿物为载体,通过动力学方法考察了天然矿物对脂肪酸酯生烃反应的催化作用.结果表明,地质低温条件下天然矿物对脂肪酸酯生烃反应具有催化作用.矿物的催化作用主要体现在对反应活化能和指前因子的影响上.粘土、碳酸盐和金属元素对于脂肪酸酯生烃反应具有不同的催化作用,碳酸盐矿物相对于粘土矿物使生烃反应的活化能降低,过渡金属化合物矿物存在时,催化反应活化能介于碳酸盐和粘土矿物之间.天然矿物的存在能够升高或降低反应指前因子.