共查询到20条相似文献，搜索用时 15 毫秒
1.
Orthorhombic MgSiO 3 perovskite is thought to be the most abundant mineral in the mantle of the Earth. Its bulk properties have been widely studied, but many geophysical and rheological processes are also likely to depend upon its surface and grain boundary properties. As a first step towards modelling these geophysical properties, we present here an investigation of the structures and energetics of the surfaces of MgSiO 3-perovskite, employing both shell-model atomistic effective-potential simulations, and density-functional-theory (DFT) calculations. Our shell-model calculations predict the {001} surfaces to be the energetically most stable surfaces: the calculated value of the surface energy being 2.2 J/m 2 for the MgO-terminated surface, which is favoured over the SiO 2-terminated surface (2.7 J/m 2). Also for the polar surfaces {111}, {101} and {011} the MgO-terminated surfaces are energetically more stable than the Si-terminated surfaces. In addition we report the predicted morphology of the MgSiO 3 perovskite structure, which is dominated by the energetically most stable {001} and {110} surfaces, and which appears to agree well with the shape of grown single crystals. 相似文献
2.
We describe the application of atomistic simulation techniques to investigate the effect of associative and dissociative
adsorption of water on the structures and stabilities of the low-index surfaces of forsterite. All surfaces are amenable to
associative adsorption of water, while dissociative adsorption is energetically favourable on all but the non-dipolar {1 0 0}
surface. Often, otherwise unstable (dipolar) surfaces are stabilised to a large extent by hydration, e.g. the dipolar {0 1 0}
surface. However, on thermodynamic grounds we do not expect associatively adsorbed water to dissociate on all surfaces, as
the energies released for dissociative adsorption of water on the non-dipolar {0 1 0} and {1 0 0} surfaces are less than those
released for associative adsorption. As such, there is no energetic incentive for the associatively adsorbed water molecules
to dissociate. The stabilities of the two terminations of the {0 1 0} surface, the main cleavage plane of forsterite, are
reversed when hydroxylated, indicating that some dissolution of the magnesium ions may occur upon hydration, which is shown
to be an exothermic process for both surface terminations. The equilibrium morphology was calculated as a way of assessing
the change in surface energies. The experimental morphology of forsterite is adequately reproduced, suggesting that the relative
stabilities of the surfaces, both unhydrated and hydroxylated, are calculated correctly.
Received: 4 August 1999 / Revised, accepted: 11 October 1999 相似文献
3.
We present the results of atomistic simulations to calculate the effect of impurities on vacancy migration at the {4 1 0}
tilt grain boundary of MgO. We show that impurities within the mantle could significantly modify vacancy migration within
the mantle due to segregation to grain boundaries. This segregation increases with increasing impurity size and with increasing
pressure. The impurities have little effect on vacancy migration at 0 GPa but at higher pressures the impurities alter the
activation energies such that the vacancies prefer to migrate towards them. This suggests that at mantle conditions the vacancies
will be pinned both by the compression of the boundary and also the impurities, slowing diffusion.
Received: 22 February 1999 / Revised, accepted: 1 June 1999 相似文献
4.
The growth of K-jarosite was evaluated using scanning electron microscopy (SEM), atomic force microscopy (AFM), and molecular
simulations. SEM micrographs show crystals with almost quadratic and, to a minor extent, triangular faces. These were identified
to be {0 1 2} and (0 0 1) faces, respectively, using an X-ray single-crystal diffractometer. These results are in agreement
with molecular simulations that show that the dipole-free {0 1 2} face is the most stable surface, followed by the (0 0 1)
surface, that can lower its dipole moment perpendicular to the surface during relaxation. On the {0 1 2} face, the most stable
step directions were identified. From these, an idealized equilibrium growth island can be constructed when the corner energies
are minimized by the successive removal of corner ions until a stoichiometric growth island is obtained. Such an equilibrium
growth island is the basis for developing a spiral growth model that explains the mechanism of spiral formation as observed
using AFM. Furthermore, reactive sites that are potential candidates for the incorporation of foreign ions can be located.
Received: 2 January 2001 / Accepted: 30 April 2001 相似文献
5.
An earlier publication 1 considered the properties of circular conical failure surfaces whose axes coincide with the space diagonal in principal stress space. The present work uses a similar approach to analyse conical surfaces that are offset from the space diagonal. It is shown that cones fitted to the Mohr–Coulomb surface in triaxial compression contain a potential singularity. The occurrence and location of the singularity depends on the Mohr–Coulomb friction angle to which the surface is fitted in triaxial extension. It is shown that for a cone fitted to the same friction angle in both triaxial extension and compression, singular conditions occur when that angle reaches \documentclass{article}\pagestyle{empty}\begin{document}$ \sin ^{ - 1} \left({\sqrt 7 - 2} \right)\left({ = 40.22^\circ } \right) $\end{document}. Even cones fitted to smaller friction angles give significant overestimations of material strength for certain stress paths. 相似文献
6.
在1981—1986年野外工作的基础上,作者对胶东三县四个金矿床黄铁矿晶体形态进行了系统研究,对其中2495粒晶体进行了统计,对300粒晶体进行了测角,对60粒晶体进行了微形貌观察。根据以上实际工作及国内外有关资料提出了黄铁矿晶休常见单形出现频率的定量资料与晶体微形貌的特点,特别是{210}面上负条纹的特征与成因探讨。并讨论了黄铁矿晶体形态与分带性,与形成温度,与主、微量成分,与共生组合及与矿化等的关系。查明黄铁矿形态及其晶面微形貌的发育与硫逸度、温度、冷却速度等密切相关。在以上基础上提出了胶东四个金矿床中蚀变岩型金矿及石英脉型金矿两种成因类型黄铁矿形态特征上的五点差异。最后对黄铁矿研究方法要点进行了总结。 相似文献
7.
This paper is concerned with the atomistic simulation of the surfaces of MgO, CaO, SrO, Li 2O, c-ZrO 2, SrTiO 3, -Al 2O 3 and -Fe 2O 3. Details are reported of the structure and energy of pure, non-defective surfaces and the constant electrostatic potential in the bulk that results from surface relaxation and electronic polarisation. Cation impurity segregation is discussed in some detail with an emphasis on calculated heats of segregation, equilibrium surface coverages, the lattice structure of segregated surfaces and the energy of impure surfaces.Paper from Conference on Quantum Theory and Experiment, July 1986 相似文献
8.
We evaluate balanced metasomatic reactions and model coupled reactive and isotopic transport at a carbonatite-gneiss contact at Alnö, Sweden. We interpret structurally channelled fluid flow along the carbonatite-gneiss contact at ～640°C. This caused (1) metasomatism of the gneiss, by the reaction: ${\hbox{biotite} + \hbox{quartz} + \hbox{oligoclase} + \hbox{K}_{2} \hbox{O} +\,\hbox{Na}_{2}\hbox{O} \pm \hbox{CaO} \pm \hbox{MgO} \pm \hbox{FeO} = \hbox{albite} + \hbox{K-feldspar} + \hbox{arfvedsonite} + \hbox{aegirene-}\hbox{augite} + \hbox{H}_{2} \hbox{O} + \hbox{SiO}_{2}}We evaluate balanced metasomatic reactions and model coupled reactive and isotopic transport at a carbonatite-gneiss contact
at Aln?, Sweden. We interpret structurally channelled fluid flow along the carbonatite-gneiss contact at ∼640°C. This caused
(1) metasomatism of the gneiss, by the reaction: , (2) metasomatism of carbonatite by the reaction: calcite + SiO2 = wollastonite + CO2, and (3) isotopic homogenization of the metasomatised region. We suggest that reactive weakening caused the metasomatised
region to widen and that the metasomatic reactions are chemically (and possibly mechanically) coupled. Spatial separation
of reaction and isotope fronts in the carbonatite conforms to a chromatographic model which assumes local calcite–fluid equilibrium,
yields a timescale of 102–104 years for fluid–rock interaction and confirms that chemical transport towards the carbonatite interior was mainly by diffusion.
We conclude that most silicate phases present in the studied carbonatite were acquired by corrosion and assimilation of ijolite,
as a reactive by-product of this process and by metasomatism. The carbonatite was thus a relatively pure calcite–H2O−CO2–salt melt or fluid. 相似文献
9.
AP 3+-Si 4+ disordering in sillimanite cannot be considered as ideal mixing on tetrahedral sites. Ideal free energy of mixing in sillimanite corresponding to slight disordering results in changing the kyanite-sillimanite phase equilibrium boundary by impossible magnitude. A regular solution model for the sites yields the following expression for the free energy of mixing: 1 $$G_{sill}^M = W \{ (X_{Al - T1} )^2 + (X_{Al - T2} )^2 \} + RT ln X_{Al - T1} X_{Al - T2}$$ . Calculations using the phase equilibrium data show that even small disequilibrium in intra-crystalline distribution results in significant change in pressure of the kyanite-sillimanite “equilibrium”. If information on interaction energies such as W is not available for disordering silicates, it is not advisable to use the ideal configurational entropy in calculations of phase equilibria. 相似文献
10.
The effect of crystal structure relaxation in oxygen-based Cr3+-containing minerals on the crystal field stabilization energy (CFSE) is considered. It is shown that the dependence of
\textCFSE\textCr 3+ {\text{CFSE}}_{{{\text{Cr}}^{ 3+ } }} , which is found from optical absorption spectra, on the average interatomic distances is described by the power function
with a negative exponent
c \mathord | / |
\vphantom c [`(R)]n [`(R)]n {c \mathord{\left/ {\vphantom {c {\bar{R}^{n} }}} \right. \kern-\nulldelimiterspace} {\bar{R}^{n} }} , where n approaches 5, as predicted theoretically, for pure Cr3+ compounds, but decreases to 1.0–1.5 for Cr3+-containing oxide and silicate solid solutions. The deviation of the experimental dependence for solid solutions from the
theoretical curve is due to structure relaxation, which tends to bring the local structure of Cr3+ ions closer to the structure in the pure Cr compound, thus producing changes in interatomic distances between the nearest
neighbors with respect to those in the average structure determined by X-ray diffraction. As a consequence, the mixing enthalpy
of Cr3+-bearing solid solutions can be represented by the sum of contributions from lattice strain and CFSE. The latter contribution
is most often negative in sign and, therefore, brings the Al–Cr solid solutions close to an ideal solid solution. It is supposed
that the increased Cr content in minerals from deep-seated mantle xenoliths and mineral inclusions in diamonds results from
the effect of
\textCFSE\textCr 3+ {\text{CFSE}}_{{{\text{Cr}}^{ 3+ } }} enhanced by high pressure. 相似文献
11.
Based on microprobe work, we present arguments that the size relations of the two common prisms {100} and {110} of accessory granite zircons are strongly influenced by chemical factors. Magmatic growth zoning patterns, which we have studied by means of backscattered electron imaging in special zircon sections orientated perpendicular to the c-axis, do not support previous models which assumed temperature or the degree of ZrSiO 4 supersaturation to be the primary prism-form-directing factors. The element U, which usually occupies the Zr-sites of granite zircoms to some degree, is strongly suspected of producing an (adsorptive) growth-blocking effect for {110}-type faces thus creating crystals with {110}-dominated prism morphology. A second independent mechanism that is likely to form zircons with large {110} prisms is the common substitution Zr 4++Si 4+ versus Y(REE) and P contents (relative to Zr) are, according to our model, predestinated to produce zircons with large {100} prisms and vice versa.Dedicated to Prof. Günther Frasl on the occasion of his seventieth birthday 相似文献
12.
Calcium carbonate (CaCO 3) is an important component of the near-surface environment. Understanding the nature of its precipitation is important for a variety of environmental processes, as well as for the geologic sequestration of anthropogenic carbon dioxide. Calcite is the most thermodynamically stable bulk polymorph, but energy crossovers may exist that could favor the precipitation of vaterite or aragonite with decreasing particle size. The purpose of this study is to determine the surface energy of calcite, which is the first step towards understanding the effect of particle size on thermodynamic stability in the calcium carbonate system. The enthalpies of five well-characterized calcite samples (four nanophase and one bulk) were measured by acid solution isothermal and water adsorption calorimetric techniques. From the calorimetric data, the surface energies of calcite were determined to be 1.48 ± 0.21 and 1.87 ± 0.16 J/m 2 for hydrous and anhydrous surfaces. These values are similar to those measured for many oxides but larger than predicted from computational models for idealized calcite surfaces. The surfaces of synthetic CaCO 3 particles contain a range of planes and defect structures, which may give rise to the difference between the experimental and modeled values. 相似文献
13.
Investigations were undertaken into the quality of surface water and groundwater bodies within the Upper Tigris Basin in Turkey to determine their suitability for potable and agricultural use. In the study area, the majority of the groundwater and surface water samples belong to the calcium–magnesium–bicarbonate type (Ca–Mg–HCO 3) or magnesium–calcium–bicarbonate type (Mg–Ca–HCO 3). Chemical analysis of all water samples shows that the mean cation concentrations (in mg/L) were in the order Ca 2+ > Mg 2+ > Na + > K + and that of anions are in the order \( \text{HCO}_{3}^{ - } \) > \( \text{SO}_{4}^{2 - } \) > Cl ? > \( \text{CO}_{3}^{ - } \) for all groundwater and surface water samples. The Mg 2+/Ca 2+ ratio ranges from 0.21 to 1.30 with most of the values greater than 0.5, indicating that weathering of dolomites is dominant in groundwater. The analysis reveals that all of the samples are neutral to slightly alkaline (pH 7.0–8.7). Groundwater and surface water suitability for drinking usage was evaluated according to the World Health Organization and Turkish Standards (TSE-266) and suggests that most of the samples are suitable for drinking. Various determinants such as sodium absorption ratio, percent sodium (Na %), residual sodium carbonate and soluble sodium percentage revealed that most of the samples are suitable for irrigation. According to MH values, all of the well water samples were suitable for irrigation purposes, but 80 and 81.82% of Zillek springs and surface water samples were unsuitable. As per the PI values, the water samples from the study area are classified as Class I and Class II and are considered to be suitable for irrigation. 相似文献
14.
The results of chromatographic study of the formation of rhombododecahedral diamonds synthesized in the Fe-Ni-(Ti)-C system at 5.5–6.0 GPa and 1350–1450°C are presented, including crystals with rounded surfaces of the rhombododecahedron with parallel striation, which are morphological analogues of natural diamonds abundant at various kimberlite, lamproite, and placer deposits. Chromatography was performed at 150°C with mechanical breakup of diamonds. The stable release of methane when diamonds of habit {110} are crushed is established. It is concluded that the appearance of the habit rhombododecahedron may be related not only to the effect of temperature and pressure on crystal growth but also to reductive conditions of crystallization. At the same time, the appearance of significant amounts of hydrocarbons in the system probably results in stopping of the growth of faces {110} and {100} and, instead, formation of specific surfaces that are composed of microscopic accessories faced by planes {111}. 相似文献
15.
This paper deals with the growth behaviour of the Mn-Ca-CO 3-H 2O solid solution-aqueous solution system on calcite {104} surfaces. This system represents a model example, which allows us to study the effect of a number of controlling factors on the crystallisation: (1) the supersaturation function, β(x), and nucleation rate function, J(x), for the Mn-Ca-CO 3-H 2O system, (2) the relationship of such functions to the molecular scale growth mechanisms operating on growing surfaces, and (3) the surface structure of the calcite {104} faces. In situ atomic force microscopy (AFM) growth experiments revealed a wide variety of surface phenomena, such as the transition between growth mechanisms, anisotropic changes in the step rates, and the influence of the Mn-bearing newly formed surface on subsequent growth (step stoppage followed by the formation of two-dimensional nuclei and the reproduction of the original calcite {104} surface microtopography). These phenomena result from the interplay between the controlling parameters and are explained in those terms. 相似文献
16.
Several mechanisms have been proposed to explain the interactions between proteins and mineral surfaces, among them a combination of electrostatic, stereochemical interactions and molecular recognition between the protein and the crystal surface. To identify the mechanisms of interaction in the lysozyme-calcium carbonate model system, the effect of this protein on the precipitation kinetics and morphology of calcite crystals was examined. The solution chemistry and morphology of the solid were monitored over time in a set of time-series free-drift experiments in which CaCO 3 was precipitated from solution in a closed system at 25°C and 1 atm total pressure, in the presence and absence of lysozyme. The precipitation of calcite was preceded by the precipitation of a metastable phase that later dissolved and gave rise to calcite as the sole phase. With increasing lysozyme concentration, the nucleation of both the metastable phase and calcite occurred at lower Ω calcite, indicating that lysozyme favored the nucleation of both phases. Calcite growth rate was not affected by the presence of lysozyme, at least at protein concentrations ranging from 0 mg/mL to 10 mg/mL.Lysozyme modified the habit of calcite crystals. The degree of habit modification changed with protein concentration. At lower concentrations of lysozyme, the typical rhombohedral habit of calcite crystals was modified by the expression of {110} faces, which resulted from the preferential adsorption of protein on these faces. With increasing lysozyme concentration, the growth of {110}, {100}, and finally {001} faces was sequentially inhibited. This adsorption sequence may be explained by an electrostatic interaction between lysozyme and calcite, in which the inhibition of the growth of {110}, {100}, and {001} faces could be explained by a combined effect of the density of carbonate groups in the calcite face and the specific orientation (perpendicular) of these carbonate groups with respect to the calcite surface. Overgrowth of calcite in the presence of lysozyme demonstrated that the protein favored and controlled the nucleation on the calcite substrate. Overgrowth crystals nucleated epitaxially in lines which run diagonal to rhombohedral {104} faces. 相似文献
17.
The sphalerite oxidative kinetics under hypergene condition was simulated and studied by means of a mixed flow reactor over a pH range of 1.0 7.8,and at dissolution temperatures from 20 to 55℃,ferric ion concentrations from 1.0×10-5 to 1.0×10-2 mol/L,O 2 flux of 0.5 L/min,and oxidants of ferric ion and O 2.It is indicated that with ferric ion as oxidant,the oxidation rate of sphalerite increases with increasing ferric ion concentration,temperature and decreasing pH value,and under the studied conditions,the dissolution rates of Zn and Cd are approximately identical,with the values of activation energy being 41.75 and 42.51 kJ·mol-1,respectively,suggesting that the oxidation rate of sphalerite is controlled by chemical reactions on mineral surface.However,with O 2 as oxidant,the oxidation mechanism of sphalerite varies with pH value.Oxidation rate decreases with increasing pH value when pH is lower than 5.95,whereas the increase of pH value results in an increase in oxidation rate when pH value is higher than 7.The oxidation rate of sphalerite can be expressed as:R Zn =10 1.1663 [Fe3+] 0 0.154 ·[H+] 0.2659 ·e-41.75/RT or R Cd =10 1.7292 [Fe3+] 0 0.170 ·[H+] 0.2637 ·e-42.51/RT 相似文献
18.
In situ atomic force microscopy (AFM) experiments, scanning electron microscopy (SEM) imaging and composition analysis, and X-ray diffraction have provided information about the growth, dissolution and transformation processes promoted by Sr 2+–Ca 2+–CO 32− aqueous solutions in contact with calcite {101̄4} surfaces. Experiments have shown a wide variety of surface phenomena, such as the influence of the Sr-bearing newly-formed surface on the subsequent growth (template effect), the growth and subsequent dissolution of surfaces and the nucleation of secondary three-dimensional nuclei on calcite surfaces. These phenomena reveal the metastability of the crystallisation system and are a consequence of the interplay between thermodynamics (the relative stability of the two calcite and aragonite structure solid solutions that can be formed), supersaturation of the aqueous solution with respect to the two possible solid solutions, and the crystallographic control of the surfaces on cation incorporation. 相似文献
19.
The morphological theory of Hartman and Perdok (1955, 1956) allows to deduce the character of a growth form {hkl} on the basis of structural data alone. Its application to the structure of whewellite leads to the identification of forms {100}, {010}, {021}, {011}, {12 \(\bar 1\) } and {121} which show during the growth a flat surface profile (flat forms F). These forms occur very frequently in the crystals we grew from pure aqueous solutions at supersaturation β≦1,90. Other forms, {001} and {10 \(\bar 1\) }, possibly show a double character ( F or S, where S stays for related faces showing a stepped profile during the growth) according to the bonds assumed within some periodic bond chains (PBCs). Alternative ways of bonding water molecules lead to different structures of the same PBC. The different energy corresponding to these structures may explain the complex morphology of both natural and synthetic crystals grown at high β values. 相似文献
20.
Cleaved and mechanically polished surfaces of olivine from peridotite xenoliths from San Carlos, Arizona, were chemically etched using the techniques of Wegner and Christie (1974). Dislocation etch pits are produced on all surface orientations and they tend to be preferentially aligned along the traces of subgrain boundaries, which are approximately parallel to (100), (010), and (001). Shallow channels were also produced on (010) surfaces and represent dislocations near the surface that are etched out along their lengths. The dislocation etch channel loops are often concentric, and emanate from (100) subgrain boundaries, which suggests that dislocation sources are in the boundaries. Data on subgrain misorientation and dislocation line orientation and arguments based on subgrain boundary energy minimization are used to characterize the dislocation structures of the subgrain boundaries. (010) subgrain boundaries are of the twist type, composed of networks of [100] and [001] screw dislocations. Both (100) and (001) subgrain boundaries are tilt walls composed of arrays of edge dislocation with Burgers vectors b=[100] and [001], respectively. The inferred slip systems are {001} 〈100〉, {100} 〈001〉, and {010} 〈100〉 in order of diminishing importance. Exploratory transmission electron microscopy is in accord with these identifications. The flow stresses associated with the development of the subgrain structure are estimated from the densities of free dislocations and from the subgrain dimensions. Inferred stresses range from 35 to 75 bars using the free dislocation densities and 20 to 100 bars using the subgrain sizes. 相似文献
|
