阳储岭钨钼矿床成岩成矿的热力学条件探讨及地质意义

在岩矿工作中主要是应用热力学的原理,以实验或计算的方法定量回答矿物(矿物组合)或岩石(矿石)形成的物理化学条件,从而达到解释有关地质现象的目的.在阳储岭斑岩钨钼矿床研究的基础上,笔者以热力学为工具,对有关成岩成矿的某些物化条件作了探讨,并介绍了有关计算方法. 成岩热力学条件(一)杂岩体的成岩温度1.斜长石地温计的应用M.Kodo(1970)提出应用斜长石斑晶与共存熔浆(基质)平衡的原     

基于3个不等粒径颗粒接触模型的土-水特征曲线

基于热力学原理及二维液桥计算模型,以3个不等径土颗粒为研究对象,推导出基质吸力与体积含水率之间的关系,得到微观模型下的土-水特征曲线。将3个不等粒径颗粒概化为限制粒径、中值粒径和有效粒径,研究了粒径大小、颗粒级配和土颗粒接触角的大小等因素对土-水特征曲线影响的规律。计算结果表明：体积含水率相同,颗粒粒径越大,相应的基质吸力越小;在同一基质吸力下,不均匀系数 越大即土颗粒越不均匀,其体积含水率就越低;接触角对土-水特征曲线的影响是明显的,即接触角越小土颗粒亲水性越好,同一基质吸力下的体积含水率也就越大,且曲线的进气值会随着接触角的减小而减小。     

炼锌固体废渣中重金属(Pb、Zn)的存在状态及环境影响

利用XRD、TEM/EDS和连续提取实验研究了土法炼锌固体废渣中重金属的矿物学特征及不同粒度中重金属的相态分布特征。与通常发现的重金属一般富集在小粒径废渣中的情况不同,本工作所研究的废渣样品中大粒径废渣与细粒径废渣相似,甚至有更高的金属含量。化学形态研究表明,冶炼过程形成的矿物(或玻璃质)集合体和堆积后的风化过程形成的次生矿物是废渣中重金属存在的主要化学相。同时发现Pb的残渣态很少(0.39%～15.75%),而Zn的残渣态较高(14.3%～46.2%),这可能与冶炼工艺所形成较多Zn的硅酸盐矿物有关。尽管可交换态Pb、Zn在不同相态中的相对比例非常小(Pb0.03%～1.30%;Zn0.03%～3.30%),但其绝对含量却比一般土壤或沉积物要高(Pb1.5～385μg/g;Zn3～590μg/g)。由于重金属可交换态有比其他化学相态更高的活动性和生物可利用性,因此,对环境有较大的潜在影响。废渣样品的微束分析表明,Pb在废渣中见有金属Pb存在形式或呈纳米金属Pb颗粒包裹于其他矿物或铁合金及熔球集合体中。同时不排除有Pb的碳酸盐矿物存在的可能。而以硅锌矿Zn2(SiO4)、锰硅锌矿(Zn,Mn)2犤SiO4犦和纤维状的丝锌铝石Zn8Al4犤(OH)8(SiO4)5犦·7H2O等矿物形式存在以及Fe、Mn等的铝硅酸盐形式存在的Zn,可能是导致Zn的残渣态较高的原因。与连续提     

青藏高原天然气水合物的形成与多年冻土的关系

天然气水合物是一种新型清洁能源,赋存在多年冻土区和海洋沉积物等低温高压环境中.青藏高原多年冻土面积占高原总面积的一半以上,是可能的天然气水合物赋存区.根据青藏高原多年冻土条件和天然气水合物形成的热力学条件,讨论了多年冻土地温梯度、冻土厚度与天然气水合物形成的热力学条件之间的关系和青藏高原存在天然气水合物的可能性.结果表明,青藏高原多年冻土区基本具备形成天然气水合物的热力学条件,最适宜的热力学条件是多年冻土地温梯度接近或略大于多年冻土底板附近融土的地温梯度,且融土地温梯度越小,越容易形成天然气水合物.估算得到天然气水合物最浅的顶界埋深为74 m左右,最深的底界埋深达上千米.     

青藏高原天然气水合物的形成与多年冻土的关系

天然气水合物是一种新型清洁能源,赋存在多年冻土区和海洋沉积物等低温高压环境中.青藏高原多年冻土面积占高原总面积的一半以上,是可能的天然气水合物赋存区.根据青藏高原多年冻土条件和天然气水合物形成的热力学条件,讨论了多年冻土地温梯度、冻土厚度与天然气水合物形成的热力学条件之间的关系和青藏高原存在天然气水合物的可能性.结果表明,青藏高原多年冻土区基本具备形成天然气水合物的热力学条件,最适宜的热力学条件是多年冻土地温梯度接近或略大于多年冻土底板附近融土的地温梯度,且融土地温梯度越小,越容易形成天然气水合物.估算得到天然气水合物最浅的顶界埋深为74 m左右,最深的底界埋深达上千米.     

热液条件下锐钛矿晶体生长的实验

为了解金属离子生长成为热液矿石矿物的过程和机理,使用氟钛酸钾稀溶液在100 MPa和200~400℃条件下开展了一系列等温不等时和等时变温实验.结果显示该热液条件下形成了不同形貌的锐钛矿.随着反应时间和温度的增加,锐钛矿由几十纳米生长至十几微米;10 h以内的晶体生长速度远高于10 h以后,相对高温下的晶体生长速度则高于低温,表明锐钛矿的热液生长与温度、过饱和程度密切相关.综合来看,粒子成核生长、定向附着和奥氏熟化先后控制了热液锐钛矿的生长,而金属在流体中的过饱和程度和溶解-沉淀过程则决定了其生长速度.因而锐钛矿的形态特征可用于指示其形成的温度、世代关系甚至含氟流体的演化历史.      

青藏高原天然气水合物的形成与多年冻土的关系

天然气水合物是一种新型清洁能源,赋存在多年冻土区和海洋沉积物等低温高压环境中。青藏高原多年冻土面积占高原总面积的一半以上,是可能的天然气水合物赋存区。根据青藏高原多年冻土条件和天然气水合物形成的热力学条件,讨论了多年冻土地温梯度、冻土厚度与天然气水合物形成的热力学条件之间的关系和青藏高原存在天然气水合物的可能性。结果表明,青藏高原多年冻土区基本具备形成天然气水合物的热力学条件,最适宜的热力学条件是多年冻土地温梯度接近或略大于多年冻土底板附近融土的地温梯度,且融土地温梯度越小,越容易形成天然气水合物。估算得到天然气水合物最浅的顶界埋深为74m左右,最深的底界埋深达上千米。     

中国地质大学(武汉)地球化学系建成热化学实验室

当前化学热力学理论引入地球化学领域中,对解决地球化学基础问题起了重要的作用,尤其在讨论地球化学过程自发进行的可能性、方向和限度以及定量计算地球化学过程进行的物理化学条件方面作用更为明显.但是,目前热力学应用受到热化学数据的限制;不少地球化学有意义物质的热力学资料尚缺乏足够的实验资科;同时,当前文献、手册上发表和引用的数据,多数是矿物和有关化合物的纯物质及标准状态下的热化学数据,而这些数据将随着矿物成分的稍有不同、矿物晶体结构的变化、有序—无序排布程度以及温度、压力条件的变更而有所差异.因而,必须针对研究的矿物实体进行热化学数据测定.     

粒径及孔径分布对天然气水合物形成影响的研究进展

掌握影响天然气水合物(简称水合物)在海底沉积物中形成的因素对其能源和气候环境效应的评估有重要的意义。水合物的含量与沉积物颗粒的粒径紧密相关,水合物多产出于粗砂中。以人工样品为主的实验研究表明,由于孔隙半径产生的毛细管抑制压力,多孔介质的颗粒越细,孔隙越小,一定条件下稳定温度越低(或压力越高)。沉积物颗粒的比表面积与水合物饱和度呈现很高的相关性,比粒径更有优势。利用比表面积可以定量地表示粒径和孔隙大小之间的关系,量化分析孔隙大小对水合物形成的影响。此外,我国南海神狐海域水合物尽管赋存在细粒沉积物中,却具有较高的饱和度,这可能与南海沉积物中富含丰富的有孔虫壳体有关,通过微观层面的观察发现,这些古生物壳体不仅充当了沉积物中的粗砂部分,而且其多孔结构也使沉积孔隙空间增加,从而为水合物富集提供了有利的生长环境和便利的赋存空间。Klauda等的模型假定多孔介质孔径尺寸的概率密度分布函数为正态分布,新的相平衡模型包含了尺寸效应。颜荣涛等把有效孔隙半径和水合物饱和度联系起来,从而将水合物饱和度引入相平衡模型中。分形模型将分形参数与孔隙度建立了关系,但并没有与温压条件等进一步联系起来,对水合物形成和分解的影响还需做进一步的推导和实验。     

几个与温度有关的平衡关系式的简便推导

本文讨论了几个温度影响平衡的关系式，认为应用杂平衡常数的概念，可以把它们归结为温度对平衡常数的影响，从而使有关公式的推导更简捷明快。并从动力学和统计热力学的角度，推导出温度对平衡常数影响的关系式，指出上述影响的根源是温度影响粒子在能级中的玻兹曼分布     

The Surface Layer of a Crystal and Its Specific Role in the Process of Melt Formation

A crystal becomes melted in a few stages. The structure of the crystal surface differs from that of its interior. Therefore, as its interior is gradually involved in the melting process, the phase transition temperature becomes higher. The melting point becomes constant when all atoms have the same number of unsaturated bonds.     

A lunar core of Fe-Ni-S

Several workers have proposed that lunar samples were magnetized by a field created by a lunar core of molten Fe. Low abundances of siderophile elements in lunar rocks are compatible with formation of a metallic lunar core. A molten Fe core requires that the bulk of the Moon was above, or close to, the melting point, a requirement which disagrees with most models of the lunar thermal regime.A core (or perhaps a layer or pockets) of molten Fe-Ni-S, at or close to the eutectic composition would act as a lunar dynamo, and be at a temperature (approx. 1000°C) consistent with some reasonable models of lunar thermal history. The existence of a Fe-Ni-S core would also partly explain the depletion in volatile elements in lunar basalts. Such a core, occupying up to 20 per cent of the Moon's radius requires a bulk S content for the moon of only 0.3 wt per cent.     

Microstructure and Mechanical Properties of Mica Glass-Ceramics Prepared by Pressureless Sintering a Phlogopite and Various Additives

Mica glass-ceramics were prepared by pressureless sintering with a phlogopite and various additives as raw materials. The effects of CaF2 content, Li2O content, ZrO2 content, and sintering temperature on the microstructure and mechanical properties of the mica glass-ceramics were investigated by X-ray diffraction, scanning electron microscopy, and mechanical testing, respectively. The results show that the additive of ZrO2 has the best reinforcing effect on the flexural strength of the mica glass-ceramics. The smaller powder particles and the larger forming pressure result in the larger bulk density of the mica glass-ceramics samples. The main crystallite phases of samples with ZrO2 as additive were phlogopite and quartz with sintering temperature lower than 1120 ℃. The crystal phase of glass ceramics appeared fiberform and cross arranges with good lap. The highest value of flexural strength, 63.7 MPa, was shown on sample with 10wt% ZrO2 as additive and sintering temperature of 1120 ℃.     

Effects of Sintering Temperature on Crystallization Behavior and Performance of Glass-Ceramics From Coal Fly Ash

The glass-ceramics was prepared from coal fly ash, limestone and Na2CO3 by sintering processes. Effects of the crystallization temperature (850–1100 ℃) on crystallization behavior, microstructure, sintering character and chemical stability of the glass-ceramics samples were analyzed by means of DTA, XRD, SEM and other analytical methods. The results show that the main crystalline phase of as-prepared glass-ceramics after crystallization treatment is gehlenite (Ca2Al2SiO7). The species of crystalline phases keep the same, however, the main crystalline intensity, line shrinkage rate and bulk density increase first then decrease with the increasing of heat treatment temperature. Water absorption of the samples was reduced as the heat treatment temperature rising. The glass-ceramics display high performance crystallization properties and chemical stability. The optimized glass-ceramics with desired sintering character and chemical stability was obtained by crystallized at 1050 ℃.     

Premelting at fusion of titanite CaTiSiO5: a calorimetric study

An extensive anomalously rapid increase of relative enthalpy H(T) ? H(298 K) of crystalline CaTiSiO₅ was observed by means of high-temperature drop calorimetry when melting point is approached. X-ray diffraction analysis of the quenched products after drop in calorimeter shows that this effect is related to premelting. The determined excess enthalpy of crystals near the melting point reaches up to 115 kJ mol^?1, that is about 82 % of the total enthalpy of melting, indicating that the premelting effect reflects configurational changes in the bulk of the crystals rather than a surface melting or any other type of partial melting. The obtained results support the presumption that calorimetrically measured premelting effect in titanite reflects the energy-consuming temperature-induced disordering of the framework elements, Si and Ti, which are strongly bonded to oxygen.     

煤层气吸附量动态变化模型研究

基于吸附势理论、气体状态方程,建立了煤储层压力与煤体吸附半径、孔隙半径与煤体吸附量、储层压力与煤体吸附量之间的关系模型,得出储层压力、吸附量、孔隙半径等多参数耦合的煤层气吸附量动态变化模型,利用潘庄区块煤体结构测试数据以及等温吸附试验结果对模型进行了验证。结果表明:潘庄区块以孔径小于7.7 nm的微孔为主,以孔径7.7 nm为临界点孔容呈先减小后增大趋势;模型计算的吸附量动态变化结果与煤体空气干燥基等温吸附变化结果在趋势上具有较高的一致性,模型的起始点为枯竭压力以及枯竭吸附量,得出潘庄区块枯竭吸附量为3 m3/t。模型不仅能够计算地层条件下不同温度和压力共同作用下煤体对甲烷气体的吸附量,且能够预测煤层气排采过程煤层气吸附量的动态变化,有助于确定煤层气排采工作制度以及提高煤层气采收率。      

高温实验研究火成岩成因的意义

通过对球粒陨石晚壳的分层及玻璃质的研究,探讨了类地行星的层圈构造划分及地球早期玄武岩与月岩形成的机理。论述了高温实验结果对火山岩、侵入岩、陨石及含水暗色矿物等有关成因研究的意义。根据酸性火山岩干熔与湿熔实验中矿物熔融顺序的不同,分析了花岗闻风而动 浆侵入酸度演经及浅色麻粒岩的 ,讨论了岩石熔点与酸度、结构的关系。根据玄武岩加花岗岩的熔融实验结果,排队了玄武岩浆同化花岗岩形成 白榴玄武岩的可能,并提出了高铝玄武岩浆与碱性苦橄岩浆分离结晶形成拉斑玄武系列岩石及出现跨越趋势的可能。通过不同酸度、不同温度熔体粘度的计算．阐述了同一温度下熔浆酸度愈大粘度增大率愈大的特点及其与火山相、喷发及火山类型的关系。通过轻度钠化、变质、风化的玄武岩熔融结晶实验与新鲜玄武岩的对比,指出具原岩显微结构的岩石．其化学成分仍可作为火山岩分类命名、系列划分的依据。通过玄武岩熔融结晶实验,研究了熔浆过冷度、成桉密度、晶体生长速度与矿物结晶程度的关系,并指出了白榴苦橄岩熔体在降温过程中,晶出矿物的共生组合、演化顺序及其意义。根据含水暗色矿物的升温研究,阐明了它们氧化、脱水与热光性的变化过程及其暗化、分解、熔融的变化阶段,阐述了它们在地质温度计、划分岩浆岩相等方面的作用,并由玄武岩的熔融结晶实验结果,研究了富钙单斜辉石在压力效应、淬火效应中Ti 与Al2含量的不同,还指出可能有“等温效应 的存在。     

Phase relations of osumilite and dehydration melting in pelitic rocks: a simple thermodynamic model for the KFMASH system

 Thermodynamic modelling of (1) osumilite solid solutions and (2) dehydration melting in pelitic compositions within the KFMASH system is quite successful in reproducing the invariant and univariant reactions determined in experimental studies. Even though rather preliminary, such melt thermodynamic models may be very useful in interpolating and extrapolating the limited information available from a small number of experimental runs. These methods allow the compositions of all phases to be monitored as a function of pressure, temperature and equilibrium phase assemblage for any desired bulk composition. Locating the higher variance phase fields (e.g. quadrivariant, quinivariant) is often difficult or impossible by inspection, but is made relatively easy using thermodynamic software such as thermocalc. In the KFMASH system the calculated partition of Fe and Mg between osumilite, garnet, cordierite, orthopyroxene and biotite are shown to be in good agreement with experimental and natural data and allow reliable calculation of mineral compositions coexisting with quartz-saturated and H₂O-undersaturated melts for a variety of bulk compositions. These phase diagram calculations allow quite tight limits to be placed on the pressure, temperature and water activity conditions which accompanied metamorphism of natural osumilite occurrences in Nain, Namaqualand, and Rogaland. At fixed bulk composition, the initial melting of pelites by dehydration of biotite can occur via univariant, divariant or trivariant equilibria depending upon pressure of metamorphism. Of particular interest is that, for low pressures or more magnesian bulk compositions, fluid-absent melting begins by generating liquid from the high-variance assemblage biotite+cordierite+K-feldspar+ quartz. This type of modelling allows investigation, at least qualitatively, of the fine scale details of melt production as a function of changes in pressure, temperature and bulk composition. Received: 29 November 1995 / Accepted: 22 April 1996     

硅酸盐体系的化学平衡:(2)反应热力学

通过具体的应用实例,系统介绍了在矿物材料学研究中硅酸盐体系的多相平衡反应热力学的基本原理。对硅酸盐体系的典型多相平衡反应进行了热力学计算,包括:(1)微晶玻璃制备过程中的硅酸盐熔融反应;(2)霞石正长岩和高铝粉煤灰利用技术中的硅酸盐烧结反应;(3)S iO2-CaO-H2O体系和KA lS i3O8-CaO-H2O体系雪硅钙石、硬硅钙石的水热晶化反应;(4)高铝粉煤灰和霞石正长岩烧结产物的溶解反应;(5)Na[A l(OH)4]-A l(OH)3-H2O体系和Na2SO4-Ca(OH)2-H2O体系中α-A l(OH)3和CaSO4.2H2O的析晶反应。研究成果可望对矿物材料制备实验方案设计、工业生产过程优化及改进产品性能提供理论指导,同时为同类材料学研究提供借鉴。     

TYPES OF FOLDING OBSERVED IN COAL DEPOSITS OF THE SOUTH URALIAN BASIN

If temperature and composition dependencies of partitioning are taken into account in modeling equilibrium processes, unexpected chemical trends are derived. Failure to consider variations in partition coefficients with temperature and composition in modeling equilibrium melting or crystallization processes leads to wildly erroneous results. Because of changes in partition coefficients with temperature and composition, incompatible elements can exhibit apparently compatible behavior, complex parallel or perpendicular trends can develop from a single process and bulk composition, and trends that appear to require several controlling phases can be explained with only one phase of variable composition. The exercises illustrated here demonstrate that complex trends can be misinterpreted if the variations in partition coefficients are not taken into account, and the “average” phase proportions and compositions controlling an evolutionary trend can be erroneously estimated. Complex trends, such as those in Apollo 15 green glass beads, can possibly be understood in terms of simple partial equilibrium melting of one or two phases.