高温高压下电解质溶液热力学性质的研究进展

高温高压下电解质溶液热力学性质的研究不仅对探讨地球内部流体的作用具有重要意义，而且在很多实际工业过程中也都有广泛应用。本综述了近10年来高温高压下电解质溶液热力学参数的实验测量和理论计算的进展，实验设备还有待进一步的改进和完善，以获得更高温度和压力下的数据，理论计算不仅有待于实验的发展，也与溶液的结构理论密切相关。     

常温高压条件天然水锰矿同步辐射X射线衍射实验

地球内部含水矿物的相关实验研究与名义上无水矿物的研究一样,对于正确理解地球内部水的分布与循环以及地球内部的物理化学性质和地球动力学性质具有同样重要的意义。同时,地球内部的水在地球演化中也起着非常重要的作用,它不仅会影响地球内部矿物岩石的物理化学性质,而且还对地球深部矿物岩石的电学性质,弹性性质等地球物理学性质以及板块运动,地幔对流及出现地震波不连续面等地球物理过程有着重要的影响。水锰矿,化学式为Mn O(OH),单斜晶系,为锰的氢氧化物矿物。到目前为止,对于水铝石(δ-Al OOH),纤铁矿(ε-FeO OH)等氢氧化物矿物在高压条件下的稳定性以及弹性性质的研究已较为广泛,但是对于与之具有相似拓扑结构的水锰矿(γ-Mn OOH)的高压弹性性质的相关研究却很少。同时,截至到目前,水锰矿的空间群结构也没有获得统一的认识。基于水锰矿高压下弹性性质以及晶体结构研究的重要性,本文利用金刚石压腔高压装置(DAC)和同步辐射角度色散X射线衍射技术,在室温、最高压力达12.74 GPa条件下,对天然的粉末水锰矿样品进行了原位高压X射线衍射研究。在0~12.74 GPa压力范围内未发现天然水锰矿发生相变。通过三阶Brich-Murnaghan状态方程对获得的不同实验压力条件下的晶胞参数和晶胞体积数据进行状态方程拟合,得到了空间群为P21/c的水锰矿的零压体积V0=135.46(4)3,零压下的等温体积模量K0=86(2)GPa,体积模量的压力导数K’0=6.8(6)。同时获得了天然水锰矿各个轴向的体积模量分别为:Kao=93(4)GPa,Kb0=62(5)GPa,Kc0=82(4)GPa,说明天然水锰矿为轴向压缩各向异性矿物,其中a轴最难压缩,c轴其次,b轴最易压缩。同时,通过与前人B21/d空间群水锰矿实验结果的对比,本文认为二者在各轴向上压缩性质的差异可能为氢键位置的不同所导致的。另外,将水锰矿的体积模量值分别与水锰矿脱水产物相-软锰矿(β-Mn O2)和与水锰矿具有相似拓扑结构的M3+OOH型氢氧化物进行了对比。我们认为氢键的存在以及水含量上的差异可能是造成水锰矿与软锰矿在体积模量上差异巨大的原因,而水锰矿与不同的M3+OOH型结构氢氧化物在压缩性质上的差别则可能由中心原子电负性的差异所导致。中心原子电负性的差异形成不同强度的化学键,进而造成它们压缩性质的差异。     

D-DIA装置与同步辐射源结合技术及其在矿物高温高压变形实验中的应用

高温高压变形实验是研究地球深部组成矿物流变学性质的重要技术手段之一.D-DIA(deformation-DIA)装置是最近10年来兴起的一种新的高温高压变形实验设备,通常可实现的最高压力为15 GPa和温度约为2 000 K;而同步辐射X射线衍射已经广泛地应用到物质结构科学的研究中,二者相结合,能够有效原位地研究材料物质在高温高压下的流变学性质.以美国布鲁克海文国家实验室配合有同步辐射源的D-DIA装置为例,介绍该装置的基本结构、工作原理及D-DIA装置与X射线结合技术如何实现矿物高温高压下变形过程的原位观测及相关定量力学数据的获取.这一技术突破了传统流变仪的压力局限,为在更高压力(P＞4 GPa)条件下研究地球深部组成物质的高温高压流变学性质提供了有效途径.      

含铁闪锌矿热力学性质的推导

热容是矿物热力学性质的基础,通过热容测定,可以推导出矿物的其他热力学性质,本文在对３个含铁闪锌矿样品的热容进行实验测定的基础上,推导出它们的热力学性质,本文的研究结果为系统地研究闪锌矿及其成矿物理化学条件参考数据。     

基于假三元模型的透辉石-硬玉固溶体热力学性质计算

自然界中矿物多以固溶体形式存在,据其晶体化学特征计算热力学性质是开展矿物成因理论研究的基础。本文引入描述二元矿物固溶体热力学性质的假三元模型,计算得到了透辉石-硬玉固溶体系列的热力学性质。该模型通过构造一种高度有序的中间相,同时考虑长程和短程有序效应,基于热力学平衡态矿物固溶体自由能最低的规律,可以计算特定组分下矿物的平衡自由能、焓和熵等热力学参数。本文针对透辉石-硬玉固溶体体系,取绿辉石为其中间有序态,计算了其活度-成分关系和温度-组分相图等,发现绿辉石随温度升高的有序无序相变为一级相变,相变温度为1 148±25 K,与实验研究结果一致。本文获得的透辉石-绿辉石-硬玉体系的热力学参数可用于视剖面图方法研究MORB成分的岩石的榴辉岩相变质作用过程。     

CaSiO_3-钙钛矿的热力学状态方程

<正>地震学观测对了解地球深内部的结构、物质组成具有重要意义。高温高压矿物学实验为理解地震学观测,确定地球内部的物质组成提供重要的实验依据。我们的研究集中在利用高温高压实验手段,为描绘下地幔的密度和速度结构提供更为准确的实验数据。该项研究的对象是下地幔最为重要的矿物之一——CaSiO3-钙钛矿。CaSiO3-钙钛矿在下地幔的体积分数约为8%。因高温高压原位实验研究的缺乏,致使我们无法准确获取温度对热力学状态方程影响的信息     

机器学习在矿物结构搜索及性质预测方面的应用

研究矿物在高温高压下的结构及其物理、化学性质是了解地球内部物质组成及动力学演化的基础。实验观测和理论计算是目前最主要的两种方法，前者受技术的局限，高温高压下的数据点比较匮乏；后者容易实现高温高压，但计算精度和效率往往难以两全。基于上述问题，机器学习作为一种很有前景的工具，与第一性原理计算相结合，能够精确、高效地预测矿物结构及各种性质。本文首先介绍了构建机器学习势的一般流程，对目前应用广泛的深度势能方法进行详细阐述。然后探讨了机器学习方法在计算矿物物理领域中的应用，如矿物新相结构搜索、热力学性质和输运性质预测、元素配分及同位素分馏等，并分析了机器学习方法相比于传统方法的优势。最后对机器学习方法目前存在的不足进行了简单总结并对其应用前景提出展望。     

交代作用体系的一些热力学性质研究

近年来,作者对水热交代形成的岩石及其铁、金和银矿床进行了一系列的高温高压实验和相平衡的热力学性质的研究。实验过程中交代反应的热力学计算是应用经典和经验公式进行。对实验矿物稳定性和相关系,根据吉布斯f=C+2-P的相律公式,利用Schreine-makas方法作拓扑学图,从而获得了交代岩及其铁、金和银矿床形成的物理化学条件,揭示了交代作用体系的一些热力学性质、特征和成岩成矿的机理。     

高温高压下元素配分的原位实验与计算模拟研究进展

地球内部元素的配分行为具有重要意义,有助于揭示地球内部物质循环、元素成矿、超临界流体性质等基础地质问题。同步辐射微聚焦X射线荧光光谱(SR-μXRF)结合金刚石压腔(DAC)技术,可以在高温高压条件下实现高准确度和高分辨率的原位(in situ)测试元素在不同物相间的浓度,并获取配分系数。而基于地球化学热力学的理论计算模拟,可以获得元素在不同物相间的赋存形式,有助于揭示元素配分机制。本文综述了SR-μXRF结合DAC技术和地球化学热力学计算模拟原位测定高温高压下元素配分的研究方法,及其在地球内部元素迁移、成矿作用和地球早期形成过程等领域中的应用进展,认为利用该套方法研究高温高压下元素配分行为的体系将变得更加复杂,对温度、压力条件则要求更高。本文旨在更新和丰富高温高压下元素配分系数数据,深化对地球内部物质循环等问题的认知。     

硬主石的高温高压实验研究进展

高温高压实验研究是国际地球科学研究的前沿领域和重要方向之一,模拟地球深部的温度和压力环境,研究地球内部物质的物理和化学性质,是解释地震波数据、了解地球内部结构和动力学过程的重要途径.硬柱石是大洋冷俯冲带中的一种重要变质矿物,国内外学者开展了大量的硬柱石高温高压物理化学性质的实验研究,并取得一系列重要成果.本文对硬柱石的高温高压实验研究成果进行了梳理和总结,包括硬柱石的热稳定性、压缩性、振动光谱性质以及物性参数等,指出前人研究中存在的不足,提出未来研究中需要加强的方向.本文旨在让更多的学者对硬柱石的高温高压物理化学性质具有更加全面的认识.     

First-principles study of high-pressure stability,structure, and elasticity of FeS2 polymorphs

The pressure-dependent elastic properties of the Fe–S system are important to understand the dynamic properties of the Earth’s interior. We have therefore undertaken a first-principles study of the structural and elastic properties of FeS₂ polymorphs under high pressure using a method based on plane-wave pseudopotential density function theory. The lattice constants, elastic constants, zero-pressure bulk modulus, and its pressure derivative of pyrite are in good agreement with the previous experiments and theoretical approaches; the lattice constants of marcasite are also consistent with the available experimental data. Calculations of the elastic constants of pyrite and marcasite have been determined from 0 to 200 GPa. Based on the relationship between the calculated elastic constants and the pressure, which can provide the stability of mineral, it would appear that pyrite is stable, whereas marcasite is unstable when the pressure rises above 130 GPa. Static lattice energy calculations predict the marcasite-to-pyrite phase transition to occur at 5.4 GPa at 0 K.     

The electronic structures of the pyrite-type disulphides (MS2, where M = Mn,Fe, Co,Ni, Cu,Zn) and the bulk properties of pyrite from local density approximation (LDA) band structure calculations

A local density approximation (LDA) band structure method, the Linear Muffin-Tin Orbital Atomic Sphere Approximation (LMTO-ASA) method has been used to calculate the electronic structures of the pyrite-type disulphides (MS₂, where M = Mn, Fe, Co, Ni, Cu, Zn). The total density of states has been calculated for 10 eV above and below the Fermi Level, along with the separate contributions from metal and sulphur and shows that the metal d band occurs above the sulphur p bands in MnS₂, FeS₂, CoS₂ and NiS₂, whereas in CuS₂, the d band passes through the sulphur p band and in ZnS₂, it lies below the sulphur p band. Substantial hybridization of the metal d states with the sulphur states occurs. FeS₂ is calculated to be a semiconductor with a direct band gap of 0.64 eV in good agreement with experiment. The calculated local densities of states have been used in turn to calculate X-ray photoelectron spectra and Bremsstrahlung Isochromat spectra for this series of compounds, and these also show reasonable agreement with experimental data. A particular strength of the LMTO-ASA method is the ability to calculate and predict certain bulk properties of solids of interest in mineral physics. This has enabled the first reasonably accurate calculations of the total energy of the valence electrons of the system for pyrite (FeS₂), given as — 345.885 rydbergs per unit cell, and the equilibrium unit cell volume which is within 3.3% of that determined experimentally. A theoretical pressure vs. volume curve for pyrite was also calculated along with values for the bulk modulus. However, our calculations predict a bulk modulus of 6.75 Mbar which is too high by a factor of 4.6 due to the simplifying assumption of a uniform scaling of interatomic distances on compression.     

Atomistic simulation of the structure and elastic properties of pyrite (FeS2) as a function of pressure

Interatomic potential parameters have been derived at simulated temperatures of 0 K and 300 K to model pyrite FeS₂. The predicted pyrite structures are within 1% of those determined experimentally, while the calculated bulk modulus is within 7%. The model is also able to simulate the properties of marcasite, even though no data for this phase were included in the fitting procedure. There is almost no difference in results obtained for pyrite using the two potential sets; however, when used to model FeS₂ marcasite, the potential fitted at 0 K performs better. The potentials have also been used to study the high-pressure behaviour of pyrite up to 44 GPa. The calculated equation of state gives good agreement with experiment and shows that the Fe–S bonds shorten more rapidly that the S–S dimer bonds. The behaviour of marcasite at high pressure is found to be similar to that of pyrite.     

Thermodynamic properties of San Carlos olivine at high temperature and high pressure

In this study, the thermal expansion and heat capacity of San Carlos olivine under high temperature and high pressure are reported. Combining accurate sound velocity data under different P–T conditions with density and heat capacity data at ambient pressure, the density, adiabatic bulk modulus, shear modulus, and most importantly, thermal expansion and heat capacity, of San Carlos are extracted to 14 GPa by a numerical procedure using classic thermodynamic relationships. These data are in agreement with published findings. To estimate the temperature gradient in the upper mantle, we also report the fitting equations of thermal expansion and heat capacity of San Carlos olivine as a function of both temperature and pressure to the P–T condition of the 410 km discontinuity, which provide the thermodynamic properties with increasing depth in the Earth’s interior.     

Sound velocities and elasticity of cordierite and implications for deep crustal seismic anisotropy

The elastic properties of cordierite, a common volatile-bearing metamorphic mineral, were measured using Brillouin spectroscopy under ambient conditions. We obtain a bulk modulus of K_S =129(1) GPa, and a shear modulus of G=54.0(4) GPa. The bulk modulus of cordierite is much larger than those of other crustal framework silicates (e.g., quartz and feldspars), but is similar to K_S for denser upper mantle phases such as olivine. This is likely a result of the cordierite crystal structure, as suggested by a similarly high value of K_S for minerals with closely related structures. Cordierite has an unusually high K/G ratio of about 2.4, and a Poisson’s ratio of 0.31,which may be a diagnostic seismic properties of areas in which cordierite-rich metamorphic rocks occur. The overall velocity anisotropy of cordierite is relatively low (<14%) in comparison with many other metamorphic minerals. Calculated velocities for a representative lower crustal rock suggest that cordierite is not likely to explain the high seismic anisotropy observed in some lower crustal sections. Cordierite would have a strong influence on the bulk seismic anisotropy only in rocks where it is present in large concentrations and has a strong preferred orientation. Although such rocks are known to occur, they are uncommon. Received: 23 Deceber 1997/ Revised, accepted: 12 October 1998     

Evaluation of the impact of pyrite oxidation on rock characteristics and environment by laboratory tests

Pyrite is a common and abundant sulfidic mineral subject to oxidation. The weathering characteristics of rock-bearing pyrite sometimes impose serious influences on the surrounding environment as the oxidation of pyrite (FeS₂) generates acid drainage that results in the acceleration of rock weathering and the discharge of heavy metals into the environment. Such an accelerated weathering of rocks can reduce its mechanical properties and therefore menace the stability of rock structures, such as excavated slopes and tunnels. The evolution of physical properties of rocks and the chemical composition of drainage were evaluated in this study by a weathering test using a double Soxhlet extractor for 1 month in a laboratory setting. Three groups of biotite gneiss classified according to their pyrite content were used for the Soxhlet extraction experiment (group A with less than 0.1 wt% of pyrite; group B with about 3.3 wt% of disseminated pyrite; group C with about 5.65 wt% of vein type pyrite). The massive groups A and B had limited weathering on the surface; however, group C with the pyrite vein experienced weathering on the surface as well as along the pyrite vein. The weathering type regulated by the occurrence of pyrite apparently controlled the mechanical properties of the rock samples and the chemistry of the drainage. Groups A and B showed no significant quick absorption ratio after the 1-month experiment; however, group C had about 10 % increase in value. The uniaxial compressive strength of the three groups decreased about 20, 10 and 45 % for groups A, B and C, respectively. The mechanical properties of the samples and the chemical compositions of the drainage indicate that the oxidation of pyrite contained in the samples accelerated weathering, resulting in deterioration of mechanical properties of the rocks, and could result in the discharge of heavy metals and acid into the environment with the drainage.     

An integrated thermodynamic mixing model for sphalerite geobarometry from 300 to 850°C and up to 1 GPa

An asymmetric, Margules-type, solid solution model was used to model the mixing behavior of Fe-Zn sphalerites. The model is based on an analysis of experimental results from fifteen independent data sources. After a careful, stepwise, analysis of the available runs, the solid solution model was constrained using a refined experimental database of 279 experiments which were simultaneously regressed to obtain the excess parameters and a general geobarometric equation. The model indicates that, when pressures are low, the value of γ_FeS^Sph, which is always greater than one, is higher at low FeS contents and an increase in temperature causes it to decline. However, for certain compositions γ_FeS^Sph values might be slightly less at low T than at high T. This behavior is corrected when pressure increases, regardless of the composition. The excess Gibbs free energy has positive values at any P&T while it is asymmetric. Pressure increases the value of the excess free energy. On the other hand, the Gibbs free energy of mixing is always negative, with a single minimum that tends to move towards Fe-poorer compositions as the pressure goes up. An increase in temperature leads to a more negative Gibbs free energy mixing function suggesting that increasingly Fe-poorer sphalerite would be expected at high temperatures and pressures. The application of the solid solution model to a selection of case-studies provided results which are consistent with independent pressure estimates. However, the pressure determinations for sphalerite + pyrite + pyrrhotite and sphalerite + pyrrhotite assemblages are very sensitive to uncertainties in the composition of the phases involved and, to a lesser extent, to temperature. The results of the application of the model to a field case (scheelite-mineralized Hercynian veins from the Central Pyrenees) were also consistent when compared with independent pressure-constraining silicate assemblages. Thus, the solid solution model described in this paper provides a workable framework with which to compute the pressures of the formation of rocks over a wide range of geological conditions.     

泥页岩储层岩石力学特性及脆性评价

泥页岩储层的岩石力学特性对油气开发影响极大,进行泥页岩力学特性和脆性评价方面的研究,可以为泥页岩油钻井和压裂设计工作提供技术支撑。实验研究表明,泥页岩抗压强度与围压、杨氏模量成正相关;体积应变量随杨氏模量减小而增大,随泊松比增加而增加;泥页岩破坏在低围压下以劈裂式破坏为主,高围压时多出现剪切式破坏。泥页岩的脆性与其弹性参数和矿物组成关系密切,通过数值模拟和实验测量,综合弹性参数和矿物组分两种方法提出了一种新的脆性评价方法-弹性参数与矿物成分组合法(EP&MC Method),并实现了单井脆性评价,效果较好。脆性评价既是储层岩石力学特性分析的重要内容,也是压裂选层的重要依据。     

Energetics of multiple oxides with spinel structure

A thermodynamic model for multiple oxides with spinel structure based on the atomistic approach (lattice energy, enthalpy, bulk modulus) and semiempirical estimates (heat capacity functions, entropy, thermal expansion) is presented. The model fits the experimental high temperature free energy values of the reference compounds, with a mean absolute error of 0.65 percent (19 values). The standard state stable configuration of most reference compounds is shown to be achieved at a local minimum in the free energy vs. degree of inversion function. This is interpreted as evidence of internal consistency of the model.     

Dualistic distribution coefficients of trace elements in the system mineral–hydrothermal solution. IV. Platinum and silver in pyrite

The FeS₂–Ag–Pt–As system was studied using hydrothermal thermogradient synthesis (with internal sampling) of pyrite crystals at a temperature of 500°C and pressure of 1 kbar in ammonium chloridebased solutions. The modes of occurrence of precious metals (PM) were determined using atomic absorption spectrometry (AAS) in its version of statistical selections of analytical data on single crystals (SSADSC), electron microprobe analysis (EMPA), scanning electron microscopy with energy-dispersive spectrometry (SEM-EDS), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). The concentration of Pt in its structural mode in pyrite is as high as 10–11 ppm and is practically not correlated with the As concentration. The dualistic distribution coefficient of Pt between pyrite and hydrothermal solution is 21 ± 7 for the structural mode and 210 ± 80 for the surface-related mode of this element. No inclusions of either any Pt-bearing minerals or Pt itself was detected. Platinum is an element highly compatible with hydrothermal pyrite and is different in this sense from gold, and pyrite is underestimated as a potential concentrator of platinumgroup elements (PGE). The distribution of Ag in pyrite is highly heterogeneous. The likely reason for this is that the Ag solid solution cannot be quenched, and hence, the Ag concentrations broadly vary and are very unsystematically distributed in natural pyrite crystals. Assuming this hypothesis, the limit for Ag accommodation in FeS₂ can be estimated using SSADSC at 0.09 ± 0.06 wt % under the experimental parameters, and the distribution coefficient of the structural Ag mode is thereby evaluated at 1400 ± 700. When crystallizing together with FeS₂ proustite (Ag₃AsS₃) near its melting point, forms mixtures with dervillite (Ag₂AsS₂), in which Ag deficit is counterbalanced by excess divalent As. The limit of As incorporation into pyrite under these conditions is ≤0.1 wt %. SEM-EDS and XPS data indicate that the surface phases are of three types. In the course of crystal growth, practically two-dimensional nonautonomous phases (NP) are aggregated into submicroscopic and micrometer-sized crystalline bodies (mesocrystals) that largely inherit their unusual minor-element composition from NP and are enriched in Ag, Pt, As, and other minor elements. NP and mesocrystals are enriched in Al, which was transferred into them from the Al-bearing Ti alloy of the reaction containers. Silver occur in the volume of the crystals and on their surface as monovalent silver sulfide. Arsenic was detected mostly in the form of di- and trivalent arsenic sulfides. Pentavalent arsenic oxide was identified only on the surface of the crystals and can be easily eliminated by ion milling.