Molecular dynamics interpretation of structural changes in quartz

 Constant temperature and constant pressure molecular dynamics (MD) simulations were applied to quartz to calculate the structural details which are indeterminable in usual X-ray structure studies. The dynamics of the structural changes was analyzed by means of time-dependent atomic displacement parameters. The Si-O bonds expand with increasing temperatures through the α- and β-phases, and atoms vibrate around the α₁- (or α₂-) sites at lower temperatures in the α-phase, and over the energy barriers between the α₁- and the α₂-sites at higher temperatures in the α- and the β-phases. The ratios of time lengths spent by atoms in the α₁- and α₂-sites determine the apparent atomic positions as obtained in usual structure studies of α-quartz. More frequent transfer of atoms over the α₁- and the α₂-sites contributes positively to the thermal expansions, whereas larger amplitudes of vibrations, which carry atoms more distantly and more frequently from the β-sites, contribute negatively. The well-known steep thermal expansion in the α-phase is attributed to the additive contribution from the expansions of the Si-O bond lengths, the widening of Si-O-Si angles, and the increase of the atomic transfer-frequency between the α₁- and the α₂-sites. The nearly zero or negative expansion in the β-phase is caused by balancing the negative to the positive effects. The MD crystal transforms to the β-phase via a transitional state, where the α- and β-structures appear alternately with time, or coexist. The slight and continuous expansions observed right after the steep rise(s) of the volume or cell dimensions up to the nearly horizontal curve(s) are attributed to the continuous changes within the transitional state. Received: 17 July 2000 / Accepted: 13 January 2001     

Molecular dynamics study of structural changes in berlinite

Fractional coordinates and anisotropic temperature factors of atoms in berlinite, AlPO₄ with the quartz topology, were successfully simulated in a molecular dynamics simulation (MDS) at high temperatures. Time-dependent and time-averaged atomic order parameters were analyzed in detail with the aid of spectral densities calculated from trajectory data. These parameters show characteristic behavior of the order-disorder regime for a structure change, where atoms spend most of the time oscillating around the ₁-sites (or ₂-sites) in the low temperature α-phase, but oscillate over both sites in the higher temperature α-phase and the β-phase. In the spectral density functions calculated for atom order parameters, a nearly zero-frequency excitation, which is accompanied by the emergence of large-scale ₁ and ₂ clusters, appears at the Γ point of the Brillouin zone below the transition point T _o, and increases in intensity up to T _o. A low-lying optic branch along Γ-M, which is strongly temperature dependent in the small q-region, is another characteristic of the spectral density functions for the β phase. The spectrum at Γ continuously reduces its frequency from 0.6 THz at temperatures far above T _o to nearly 0 THz at temperatures approaching T _o from above. The dynamical behavior in β berlinite rapidly but continuously changes from that in less oscillatory clusters in the vicinity of T _o to that in the typical β phase at temperatures departing from T _o. Received: 10 August 1998 / Revised, accepted: 18 February 1999     

Molecular dynamics study of the crystal structure and phase relation of the GeO2 polymorphs

A two-body interatomic potential model for GeO₂ polymorphs has been determined to simulate the structure change of them by semi-empirical procedure, total lattice energy minimization of GeO₂ polymorphs. Based on this potential, two polymorphs of GeO₂; α-quartz-type and rutile-type, have been reproduced using the molecular dynamics (MD) simulation techniques. Crystal structures, bulk moduli, volume thermal expansion coefficients and enthalpies of these polymorphs of GeO₂ were simulated. In spite of the simple form of the potential, these simulated structural values, bulk moduli and thermal expansivities are in excellent agreement with the reliable experimental data in respect to both polymorphs. Using this potential, MD simulation was further used to study the structural changes of GeO₂ under high pressure. We have investigated the pressure-induced amorphization. As reported in previous experimental studies, quartz-type GeO₂ undergoes pressure-induced crystalline-to-amorphous transformation at room temperature, the same as other quartz compounds; SiO₂, AlPO₄. Under hydrostatic compression, in this study, α-quartz-type GeO₂ transformed to a denser amorphous state at 7.4 GPa with change of the packing of oxygen ions and increase of germanium coordination. At higher pressure still, rutile-type GeO₂ transformed to a new phase of CaCl₂-type structure as a post-rutile candidate. Received: 29 July 1996 / Revised, accepted: 30 April 1997     

Modelling the formation of fission tracks in apatite minerals using molecular dynamics simulations

We introduce a simple method to simulate the “ion explosion spike” mechanism of fission track formation within the framework of classical molecular dynamics. The method is applied to six apatite compositions and the resulting tracks are compared with each other as well as with the damage produced by another mechanism—the “Displacement spike”. In contrast to experimentally observed tracks, the radii of simulated tracks are not dependent on their direction in the crystal. Since the simulations model accurately the elastic response of apatites, this suggests that the experimentally observed difference in track radii for tracks along different crystal directions is not entirely caused by anisotropy in the elasticity of apatite. We suggest that anisotropy in the interactions between the electric fields of fission fragments and the crystal ions is a major factor in the final radii of fission tracks. In fluorapatite, the simulations also reveal the formation of small clusters of fluorite-like material in the core of the fission track, a phenomenon which has yet to be confirmed experimentally.

Molecular orbital study on the onset of the pressure-induced transformations of the metastably compressed germanates

In order to elucidate the onset of the pressure-induced transformations of germanates consisting of GeO₄ tetrahedra at room temperature, we have investigated the stability of the crystal structures near the transition pressure in terms of the stability of the linkage of the tetrahedra. The stability of the linkage near the transition pressure is estimated from the results of the molecular orbital calculations for the model cluster H₆Ge₂O₇, which mimics the linkage of tetrahedra, as functions of the bond length d(Ge–O_br) with bridging oxygen and bond angles Ge–O_br–Ge. The calculation shows that the total energy of the linkage becomes minimum at d(Ge–O_br)=1.758 Å and br–Ge=130.4°, and that it increases with the deviation from the energy minimum geometry. From the compression behavior of framework and chain germanates, we find that the linkage of the tetrahedra becomes unstable with increasing pressure, and that these germanates commonly transform into their high-pressure phases when the linkage of the tetrahedra largely departs from the energy minimum geometry. This suggests that the high-pressure transformations of the metastably compressed germanates are induced by the instability of the linkage of tetrahedra.     

直至核幔边界的Mg2SiO4成分熔体剪切粘滞度的平衡分子动力学研究

熔体的粘滞度极大地影响熔体的各处动力学行为。虽然有一些有关酸碱生熔体粘滞度的数据但涉及地球更深部过程的基性和超基性熔体的粘滞度的数据很少。本项研究利用平衡分子动力学方法Ｍｇ２ＳｉＯ４成分熔体从２１６９Ｋ到５５９５Ｋ。压力从１０＾５Ｐａ到１３５ＧＰａ的粘滞度,所获得的粘滞度数据介于Ｕｒｂａｉｎｅｔ ａｌ,（１９８２）和Ｉｖａｎｏｖ ａｎｄ Ｓｔｅｎｇｅｌｍｅｙｅｒ（１９８２）的实验数据之间,比Ｓｈａ     

Molecular dynamics study of the α–β transition in quartz: elastic properties, finite size effects, and hysteresis in the local structure

The α–β transition in quartz is investigated by molecular dynamics simulations in the constant stress ensemble. Based on a frequently used two-body interaction potential for silica, it is found that anomalies in the elastic constants are at least in semiquantitative agreement with experiment despite the fact that no anomaly in the c/a ratio is observed in the simulations. A finite-size scaling analysis shows that first-order Landau theory is applicable to the employed model potential surface. This statement also applies to the susceptibility below the transition temperature T _tr, which has not yet been measured experimentally. Examination of the local order near T _tr reveals that the deformation of SiO₄ tetrahedral units is equally large in the β phase as in the α phase. However, large hysteresis effects can be observed in the local structure for distances r > 4 Å. The results are in agreement with the picture of a first-order displacive phase transformation which is driven by the motion of deformed tetrahedral SiO₄ units. Yet, the fast oscillations of oxygen atoms are around (time-dependent) positions that do not correspond to the ideal oxygen positions in β-quartz. The averaged configurations resemble the ideal structure only if averaged over at least a few nanoseconds.     

Molecular dynamics simulation of the effect of the Al-O-Al linkage on the P&1macr;-I&1macr; phase transition of anorthite

Molecular dynamics (MD) simulations of the influence of the Al-O-Al linkage on the P&1macr;-I&1macr; phase transition of pure anorthite (An) were carried out using two different types of structures with fully ordered (FO) and partially disordered (PD) arrangements of Al/Si in tetrahedral sites. Discontinuous changes in unit cell volumes and structure factors at the transition temperature were observed in FO-An but not in PD-An. These results show that the orders of the transitions of FO-An and PD-An are first and non-first, respectively. In both structures, the motions of the Ca atoms and the framework are strongly correlated with each other during the transition and Ca atoms dominate the system. Since high-temperature X-ray studies have shown that the transition of natural anorthite is non-first order, it is suggested that the natural anorthite has a partially disordered arrangement of Al and Si atoms. Received: 22 October 1998 / Revised, accepted: 12 March 1999     

NaAlSi3O8熔体粒子扩散行为压力效应的分子动力学研究

为了研究压力对钠长石成分熔体粒子微观扩散行为的影响,本文用分子动力学方法,探讨了2001．5K温度下,压力由50MPa上升到19862MPa的过程中,熔体的微观结构、粒子自扩散系数随压力的变化规律。研究表明,在升压过程中,低次配位体Al和Si向5次和6次配位体转变,Al的含量在15GPa达到极大值,而Si含量的极大值在20GPa仍未出现。Na的自扩散系数随压力升高单调下降,Al、Si和O的自扩散系数随压力升高先增后减,在8～10GPa左右达到极大值。网架形成粒子自扩散系数的极大值与Al和Si含量的极大值对应的压力点不一致。所有粒子的自扩散系数与它们与O之间键的寿命呈线性负相关。     

A computer simulation study of OH defects in Mg2SiO4 and Mg2GeO4 spinels

Classical atomistic simulation techniques have been used to investigate the energies of hydrogen defects in Mg₂SiO₄ and Mg₂GeO₄ spinels. Ringwoodite (γ-Mg₂SiO₄) is considered to be the most abundant mineral in the lower part of the transition zone and can incorporate large amounts of water in the form of hydroxyls, whereas the germanate spinel (γ-Mg₂GeO₄) corresponds to a low-pressure structural analogue for ringwoodite. The calculated defect energies indicate that the most favourable mechanisms for hydrogen incorporation are coupled either with the reduction of ferric iron or with the creation of tetrahedral vacancies. Hydrogen will go preferentially into tetrahedral vacancies, eventually leading to the formation of the hydrogarnet defect, before associating with other negatively charged point defects. The presence of isolated hydroxyls is not expected. The same trend is observed for germanate, and thus γ-Mg₂GeO₄ could be used as a low-pressure analogue for ringwoodite in studies of water-related defects and their effect on physical properties.     

Equations of state of CaSiO3 Perovskite: a molecular dynamics study

The molar volumes and bulk moduli of CaSiO₃ perovskite are calculated in the temperature range from 300 to 2,800 K and the pressure range from 0 to 143 GPa using molecular dynamics simulations that employ the breathing shell model for oxygen and the quantum correction in addition to the conventional pairwise interatomic potential models. The performance of five equations of state, i.e., the Keane, the generalized-Rydberg, the Holzapfel, the Stacey–Rydberg, and the third-order Birch–Murnaghan equations of state are examined using these data. The third-order Birch–Murnaghan equation of state is found to have a clear tendency to overestimate the bulk modulus at very high pressures. The Stacey–Rydberg equation of state degrades slightly at very high pressures along the low-temperature isotherms. In comparison, the Keane and the Holzapfel equations of state remain accurate in the whole temperature and pressure range considered in the present study. K ₀′ derived from the Holzapfel equation of state also agrees best with that calculated independently from molecular dynamics simulations. The adiabatic bulk moduli of CaSiO₃ perovskite along lower mantle geotherms are further calculated using the Keane and the Mie-Grüneisen–Debye equations of state. They are found to be constantly higher than those of the PREM by ~5%, and also very similar to those of the MgSiO₃ perovskite. Our results support the view that CaSiO₃ perovskite remains invisible in the Earth’s lower mantle.     

Molecular dynamics simulations of the phase transition between low-temperature and high-temperature clinoenstatites

 Phase transition between low-temperature clinoenstatite (LT-CEn) and high-temperature clinoenstatite (HT-CEn) was studied by using molecular dynamics (MD) simulations, based on empirical potential parameters. Starting from LT-CEn, the MD calculations were carried out at atmospheric pressure and at elevated pressures (1–6 GPa). At elevated temperatures the transformation from the starting LT-CEn to HT-CEn occurred at any pressure. It was confirmed that the HT-CEn has the same space group C2/c as diopside but the M2 site is six-coordinated, unlike diopside. A significant difference in the MD-simulated cell volumes between LT-CEn and HT-CEn was also observed, showing a first-order transition. In addition, there were some temperature ranges where LT-CEN and HT-CEn would be coexistent and very small thermal hystereses between increasing and decreasing temperatures during the transition. These behaviors are consistent with the characteristic of a thermoelastic-martensitic transformation. The phase boundary between LT-CEn and HT-CEn was determined for the first time. Its positive dT/dP slope strongly shows that the high-pressure clinoenstatite is a significantly distinct phase from HT-CEn although the both phases have the same space group, C2/c. Received: 8 November 2000 / Accepted: 28 April 2001     

钙长石成分熔体粘滞度和自扩散系数压力效应的分子动力学研究

用分子动力学方法,研究了1999 K下,压力由23 MPa上升到15183 MPa的过程中,CaAl_2Si_2O_8成分熔体的微观结构、剪切粘滞度和粒子自扩散系数的压力效应。在此基础上,探讨压力对剪切粘滞度与粒子自扩散系数之间关系的影响,并将它同微观结构的变化联系起来。结果表明,粒子自扩散系数的压力效应与熔体结构有很强的相关性;压力的挤压效应阻碍了粒子的扩散,而Si-O和Al-O 5次配位体的形成又加速了扩散过程,两种相反的作用相互抵消,造成的结果是在0～5 GPa范围内,Si~(4 ),O~(2-)和Al~(3 )等网架形成粒子的自扩散系数随压力变化不明显;当压力继续增大时,挤压效应占了主导,导致自扩散系数值快速减小。Ca~(2 )作为网架修饰粒子,自扩散系数随压力升高单调下降。压力小于5 GPa时,粒子自扩散系数的大小关系是:D_(Ca)>D_(Al)>D_O>D_(Si)。系统粘滞度随压力的变化与熔体中BO的含量密切相关:BO含量小于域值时,一定范围内BO含量的变化不会对粘滞度产生很大的影响,超过域值,BO含量的微小增加会导致粘滞度值迅速增大。有效应用Eyring方程的关键是方程中粒子跳跃距离的确定,本研究发现,Si~(4 )和O~(2-)的跳跃距离可以通过系统中非桥氧的百分含量来获得。这一发现使得我们能够利用系统中NBO的含量,结合Eyring方程有效进行不同压     

Interaction of calcium dioleate collector colloids with calcite and fluorite surfaces as revealed by AFM force measurements and molecular dynamics simulation

Spherical calcium dioleate particles (∼ 10 μm in diameter) were used as AFM (atomic force microscope) probes to measure interaction forces of the collector colloid with calcite and fluorite surfaces. The attractive AFM force between the calcium dioleate sphere and the fluorite surface is strong and has a longer range than the DLVO (Derjaguin–Landau–Verwey–Overbeek) prediction. The repulsive AFM force between the calcium dioleate sphere and the fluorite surface does not agree with the DLVO prediction. Consideration of non-DLVO forces, including the attractive hydrophobic force, was necessary to explain the experimental results. The non-DLVO interactions considered were justified by the different interfacial water structures at fluorite– and calcite–water interfaces as revealed by the numerical computation experiments using molecular dynamics simulation. The density of interfacial water at the fluorite surface is low and the fluorite surface is not strongly wetted by water molecules. In contrast to the water at the fluorite surface, water molecules at the calcite surface form tightly packed monolayer structures and the calcite surface is extensively hydrated by water molecules. The interfacial water structure agrees with the AFM force measurements and the flotation recovery data. The strong attraction between the calcium dioleate colloid and the fluorite surface, and the moderately wetted fluorite surface by water molecules explain the better flotation response of fluorite with the oleate collector colloid.     

二氧化碳注入下岩层变形和流体运移分析:(Ⅱ)实例分析

第I部分[1]提出了一个两相流-岩层流固耦合模型,为了应用该模型对超临界二氧化碳注入过程中岩层力学响应和流体运移进行评估,采用Comsol商业程序,提出了相应的数值分析方法。给出了模型参数的确定方法,并采用室内试验数据对模型进行了验证;通过现场的温度和压力条件以及岩层的Van Genuchten参数,确定了二氧化碳的密度和黏度。基于三轴压缩试验、有效应力系数试验和渗透性试验,对力学模型及耦合关系中的参数进行了验证。最后给出一个应用实例,该岩层位于地下680⁷00 m深度,宽度为100 m,分析了不同二氧化碳注入速率下注入压力的演化规律,得到了岩层中孔隙压力、竖向应变和损伤变量的分布,并对二氧化碳的运移规律也进行了分析。研究结果为超临界二氧化碳注入过程中岩层力学响应和流体运移的评估提供了理论基础。     

高温下TiO2的相转变动力学及后期颗粒生长研究

利用原位高温XRD方法测量了锐钛矿相TiO2在不同温度下(850、863、875、888、900℃)时间与转化率之间的关系,证实锐钛矿-金红石相转变为一级反应。计算的相转变活化能为432.788±25.657 kJ/mol,指前因子为4.847 454×1015 s-1。利用ESEM观察了样品在相转变完成后,经历不同温度(888、900、930、960、1 000℃)相同烧结时间(10 h),和相同温度(1 000℃)不同烧结时间(0、5、10、15、20 h)下颗粒晶型变化和颗粒长大情况。在1 000℃以下时,温度对颗粒粒度的影响并不明显,并且不出现完好的晶型。1 000℃时,随着时间的延长,颗粒粒度不断增大,并在10 h以后出现完好晶型。根据lnDt(Dt为t时间下颗粒的平均粒度)和lnt的关系图,认为颗粒生长应经过两个不同时期。     

深部咸含水层CO2注入的流体迁移模拟研究 ——以松辽盆地三肇凹陷为例

CO2地质封存是减少温室气体向大气排放的有效措施之一,而深部咸含水层CO2地质封存是目前可行的最有潜力的封存技术。先前研究表明,松辽盆地是一个潜在的封存场地。基于对松辽盆地地质资料的初步分析,选取三肇凹陷的姚家组1段和青山口组2、3段地层作为CO2的注入层,建立一个典型二维模型,研究CO2注入后的迁移规律。结果表明,CO2注入后会向上和侧向迁移,后期可能出现的对流作用能促进CO2的溶解。残留气体饱和度、注入层水平和垂直渗透率的比值对模拟结果影响最大。此外,储层中的薄页岩夹层有利于CO2的溶解,因此,在保证注入性和封存量的情况下,储层中低渗透性夹层是允许的。     

High temperature dehydroxylation of muscovite-2M1: a kinetic study by in situ XRPD

Muscovite-2M₁ shows a major phase transition at about 800°C, which is generally attributed in the literature to the structural dehydroxylation process, although a number of structural models have been proposed for the dehydroxylated phase, and different transformation mechanisms have also been put forward. The observed first order transformation involves an increase in the cell volume, and it is not clear to date how the cell expansion is related to the loss of hydroxyl groups. The phase change has been re-investigated here by in situ high temperature powder diffraction, both in non-isothermal and isothermal modes, to combine for the first time the structural and the kinetic interpretation of the transformation. The results unequivocally confirm that the reaction taking place in the temperature range 700–1000°C is truly a dehydroxylation process, involving the nucleation and growth of the high temperature dehydroxylated phase, having Al in 5-fold coordination. Structural simulations of the basal peaks of the powder diffraction patterns indicate that the model originally proposed by Udagawa et al. (1974) for the dehydroxylated phase correctly describes the high temperature phase. The kinetic analysis of the isothermal data using an Avrami-type model yields values for the reaction order compatible with a reaction mechanism limited by a monodimensional diffusion step. Apparent activation energy of the process in vacuum is about 251 kJ/mol. Experiments carried out at temperatures much higher than the onset temperature of the reaction show that the dehydroxylation reaction overlaps with the reaction of formation of mullite, the final product in the reaction pathway. Received: 24 April 1998 / Revised, accepted: 12 October 1998     

Potential assessment of CO2 geological storage based on injection scenario simulation: A case study in eastern Junggar Basin

Carbon Capture and Storage (CCS) is one of the effective means to deal with global warming, and saline aquifer storage is considered to be the most promising storage method. Junggar Basin, located in the northern part of Xinjiang and with a large distribution area of saline aquifer, is an effective carbon storage site. Based on well logging data and 2D seismic data, a 3D heterogeneous geological model of the Cretaceous Donggou Formation reservoir near D7 well was constructed, and dynamic simulations under two scenarios of single-well injection and multi-well injection were carried out to explore the storage potential and CO₂ storage mechanism of deep saline aquifer with real geological conditions in this study. The results show that within 100 km² of the saline aquifer of Donggou Formation in the vicinity of D7 well, the theoretical static CO₂ storage is 71.967 × 10⁶ tons (P50)^①, and the maximum dynamic CO₂ storage is 145.295 × 10⁶ tons (Case2). The heterogeneity of saline aquifer has a great influence on the spatial distribution of CO₂ in the reservoir. The multi-well injection scenario is conducive to the efficient utilization of reservoir space and safer for storage. Based on the results from theoretical static calculation and the dynamic simulation, the effective coefficient of CO₂ storage in deep saline aquifer in the eastern part of Xinjiang is recommended to be 4.9%. This study can be applied to the engineering practice of CO₂ sequestration in the deep saline aquifer in Xinjiang.