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1.
Pseudopotential periodic Hartree-Fock calculations have been performed on the three polymorphs of Mg2SiO4 with a polarized split valence basis set. The energy differences between polymorphs at their experimental geometries are correctly predicted. The olivine to modified spinel and olivine to spinel phase transition pressures have been estimated and agree within a few GPa with their experimental values. The bonding in Mg2SiO4 is discussed from the point of view of the, band structures, projected density of states, electron density and electron localization function (ELF) curves. It is concluded that both Mg-O and Si-O bonds are highly ionic.  相似文献   

2.
Germanate olivines Mg2GeO4, Ca2GeO4 and CaMgGeO4 have been studied by high-pressure X-ray Diffraction and high-pressure X-ray Absorption Spectroscopy. The three compounds were compressed, in the 0–30 GPa pressure range, at room temperature in a diamond-anvil cell, silicon oil being used as the pressure transmitting medium. Values of K0 are 166 ± 15, 117 ± 15 and 152 ± 14 GPa for Mg2GeO4, Ca2GeO4 and CaMgGeO4 respectively. These olivines all exhibit compression anisotropy, the a axis being the least compressible. Crystal to crystal phase transitions have been observed in Mg2GeO4 and Ca2GeO4 above 12 GPa and 6 Gpa respectively. The nature of these structural changes remains unclear yet. The onset of amorphization has been observed in Mg2GeO4 and Ca2GeO4 at pressures above about 22 and 11 GPa respectively. These phase transitions and amorphization processes do not involve any detectable increase in the coordination number of germanium atoms. At higher pressure (P >23 GPa), we report the onset of a transition from a phase with fourfold coordinated germanium to a phase with higher germanium coordination number in CaMgGeO4.  相似文献   

3.
Pressure–temperature conditions of tourmaline breakdown in a metapelite were determined by high-pressure experiments at 700–900°C and 4–6 GPa. These experiments produced an eclogite–facies assemblage of garnet, clinopyroxene, phengite, coesite, kyanite and rare rutile. The modal proportions of tourmaline clearly decreased between 4.5 and 5 GPa at 700°C, between 4 and 4.5 GPa at 800°C, and between 800 and 850°C at 4 GPa, with tourmaline that survived the higher temperature conditions appearing corroded and thus metastable. Decreases in the modal abundance of tourmaline are accompanied by decreasing modal abundance of coesite, and increasing that of clinopyroxene, garnet and kyanite; the boron content of phengite increases significantly. These changes suggest that, with increasing pressure and temperature, tourmaline reacts with coesite to produce clinopyroxene, garnet, kyanite, and boron-bearing phengite and fluid. Our results suggest that: (1) tourmaline breakdown occurs at lower pressures and temperatures in SiO2-saturated systems than in SiO2-undersaturated systems. (2) In even cold subduction zones, subducting sediments should release boron-rich fluids by tourmaline breakdown before reaching depths of 150 km, and (3) even after tourmaline breakdown, a significant amount of boron partitioned into phengite could be stored in deeply subducted sediments.  相似文献   

4.
The thermodynamical stability of a newly observed wadsleyite II phase in the Mg2SiO4 system is studied by the density functional theory. The wadsleyite II equation of state has been derived. The phase boundaries of Mg2SiO4 polymorphs: wadsleyite, wadsleyite II and ringwoodite are studied using the quasi-harmonic approximation at high external pressures. Clapeyron slopes determined for wadsleyite II–ringwoodite and wadsleyite–wadsleyite II boundaries are 0.0047 and 0.0058 GPa/K, respectively. It is shown that the wadsleyite II phase is not thermodynamically preferred in the pure Mg2SiO4 system and will probably not occur between wadsleyite and ringwoodite phases.  相似文献   

5.
We used an in situ measurement method to investigate the phase transition of Fe2SiO4 polymorphs under high pressures and temperatures. A multi-anvil high-pressure apparatus combined with synchrotron X-ray radiation was used. The stability of each polymorph was identified by observing the X-ray diffraction data from the sample. In most experiments, the diffraction patterns were collected 10–30 min after reaching the desired pressure and temperature conditions. The transition boundary between the olivine and spinel phase at T = 1,000–1,500 K and P = 2–8 GPa was determined to occur at P (GPa) = 0.5 + 0.0034 × T (K). The transition pressure determined in this study was in general agreement with that observed in previous high-pressure experiments. However, the slope of the transition, dP/dT, determined in our study was significantly higher than that estimated by the previous study combined with the in situ X-ray method.  相似文献   

6.
We have carried out a Raman Spectroscopic study of single crystalline quartz samples shocked to peak pressures up to 31.4GPa. Samples shocked to above 22 GPa show shifts in peak positions consistent with the quartz being under tensile stress, and new broad bands associated with the formation of high density SiO2 glass appear in the spectra. These changes are accompanied by an increase in the lattice parameters of the quartz. Formation of the diaplectic glass could be due to a metastable melting event, or spinodal lattice collapse on attainment of a mechanical stability limit of crystalline quartz, as suggested by previous studies of pressure-induced amorphization in static pressurization experiments on SiO2 and GeO2 polymorphs.  相似文献   

7.
The unit-cell dimensions and crystal structure of sillimanite at various pressures up to 5.29 GPa have been refined from single-crystal X-ray diffraction data. As pressure increases, a and b decrease linearly, whereas c decreases nonlinearly with a slightly positive curvature. The axial compression ratios at room pressure are βa:βb:βc=1.22:1.63:1.00. Sillimanite exhibits the least compressibility along c, but the least thermal expansivity along a (Skinner et al. 1961; Winter and Ghose 1979). The bulk modulus of sillimanite is 171(1) GPa with K′=4 (3), larger than that of andalusite (151 GPa), but smaller than that of kyanite (193 GPa). The bulk moduli of the [Al1O6], [Al2O4], and [SiO4] polyhedra are 162(8), 269(33), and 367(89) GPa, respectively. Comparison of high-pressure data for Al2SiO5 polymorphs reveals that the [SiO4] tetrahedra are the most rigid units in all these polymorphic structures, whereas the [AlO6] octahedra are most compressible. Furthermore, [AlO6] octahedral compressibilities decrease from kyanite to sillimanite, to andalusite, the same order as their bulk moduli, suggesting that [AlO6] octahedra control the compression of the Al2SiO5 polymorphs. The compression of the [Al1O6] octahedron in sillimanite is anisotropic with the longest Al1-OD bond shortening by ～1.9% between room pressure and 5.29 GPa and the shortest Al1-OB bond by only 0.3%. The compression anisotropy of sillimanite is primarily a consequence of its topological anisotropy, coupled with the compression anisotropy of the Al-O bonds within the [Al1O6] octahedron.  相似文献   

8.
α-PbO2–type TiO2 (space group Pbcn, a thermodynamically predicted high-pressure polymorph of rutile) was synthesized by a number of investigators using shock and static compression experiments. Recently, in situ high-pressure and high-temperature studies employing the multi-anvil device and white-beam (using a synchrotron radiation source) energy-dispersive method indicated that the transformation pressure is lower for nanophase material (～4 GPa and 900°C) than for the bulk (～6 GPa and 850°C). In addition, the phase boundary of rutile/α-PbO2-type TiO2 changes from a negative to a positive slope with increasing temperature. This timely knowledge provides indicative pressure-temperature (P-T) constraints on the natural occurrence of α-PbO2-type TiO2, recently identified by analytical electron microscopy as an epitaxial nanometer-thick slab between twinned rutile bicrystals in almandine-rich garnet of diamondiferous quartzofeldspathic rocks from the Saxonian Erzgebirge, Germany. The stability field of “bulk” α-PbO2-structured TiO2 shows that the minimum stabilization pressure of transition is ～6 GPa and could have been up to 2 GPa lower as a result of the nanophase effect. This suggests burial of continental crustal rocks to depths of at least 130-200 kilometers. Thus, α-PbO2-type TiO2 inclusions in garnet may be a useful P-T indicator in the diamond stability field. Furthermore, the possibility of finding α-PbO2-type TiO2 or even a higher-P polymorph (e.g., baddeleyite-structured TiO2) at impact sites of meteorite craters is increased, in view of the recent identification of post-stishovite (isostructure of rutile) SiO2 polymorphs in the meteorite Shergotty, and the alleged identification of α-PbO2-type TiO2 by Raman spectroscopy in shocked gneisses from the Ries Meteorite Crater, Germany.  相似文献   

9.
We have used density functional theory to investigate the stability of MgAl2O4 polymorphs under pressure. Our results can reasonably explain the transition sequence of MgAl2O4 polymorphs observed in previous experiments. The spinel phase (stable at ambient conditions) dissociates into periclase and corundum at 14 GPa. With increasing pressure, a phase change from the two oxides to a calcium-ferrite phase occurs, and finally transforms to a calcium-titanate phase at 68 GPa. The calcium-titanate phase is stable up to at least 150 GPa, and we did not observe a stability field for a hexagonal phase or periclase + Rh2O3(II)-type Al2O3. The bulk moduli of the phases calculated in this study are in good agreement with those measured in high-pressure experiments. Our results differ from those of a previous study using similar methods. We attribute this inconsistency to an incomplete optimization of a cell shape and ionic positions at high pressures in the previous calculations.  相似文献   

10.
A new high-pressure polymorph of merrillite with the structure of trigonal γ-Ca3(PO4)2 was found in the shock-produced veins of the Suizhou meteorite, where it coexists with ringwoodite, majorite, NaAlSi3O8-hollandite, and majorite-pyrope garnet. The crystallographic nature of this natural γ-Ca3(PO4)2 phase was characterized by Raman spectroscopy and X-ray diffraction, and all data compare favorably to the same data obtained from γ-Ca3(PO4)2 synthesized at 14 GPa and 1400°C. The cell parameters of this new high-pressure mineral are a = 5.258(1) angstroms and c = 18.727(3) angstroms, space group R-3m, and density = 3.447 (g/cm3), where the number in parentheses are standard deviations in the last significant digits. The natural occurrence of the γ-Ca3(PO4)2 phase together with other high-pressure minerals constrains the pressure of the shock veins at about 23 GPa. The Suizhou meteorite provides the first naturally occurring example of γ-Ca3(PO4)2 polymorph.  相似文献   

11.
Raman spectra of the two high-pressure polymorphs of SiO2 (coesite and stishovite) were investigated in the temperature range 105–875 K at atmospheric pressure. Coesite remained intact after the highest temperature run, but stishovite became amorphous at temperatures above about 842～872 K. Most Raman modes exhibit a negative frequency shift with temperature for these polymorphs, but positive trends were also observed for some modes. Except for some weak modes, nonlinear temperature variation were established for these polymorphs within the experimental uncertainty and temperature range spanned. The slopes of the variation (δvi/δT)P for these polymorphs were compared with the published values. When compared with quartz and stishovite, the four-membered rings of SiO4-tetrahedra in coesite exhibit very little change with both temperature and pressure. It is also suggested that temperature and pressure should have opposite effects on the Raman shift of each vibrational mode.  相似文献   

12.
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13.
 The relative stabilities of orthozoisite, Ca2Al3[O|OH|Si2O7|SiO4], space group Pnma, and the monoclinic polymorph, clinozoisite, space group P21/m, have been investigated using calculations based on density functional theory. It is found that orthozoisite is more stable than clinozoisite by about 1 kJ mol−1 at zero pressure in the athermal limit. The bulk moduli of the two polymorphs have been calculated to be Bortho=117.5(1.7) GPa and Bclino=136(4) GPa. Received: 20 March 2000 / Accepted: 26 February 2001  相似文献   

14.
We present a Raman spectroscopic study of the structural modifications of several olivines at high pressures and ambient temperature. At high pressures, the following modifications in the Raman spectra are observed: 1)?in Mn2GeO4, between 6.7 and 8.6?GPa the appearance of weak bands at 560 and 860?cm?1; between 10.6 and 23?GPa, the progressive replacement of the olivine spectrum by the spectrum of a crystalline high pressure phase; upon decompression, the inverse sequence of transformations is observed with some hysteresis in the transformation pressures; this sequence may be interpreted as the progressive transformation of the olivine to a spinelloid where Ge tetrahedra are polymerized, and then to a partially inverse spinel; 2)?in Ca2SiO4, the olivine transforms to larnite between 1.9 and 2.1?GPa; larnite is observed up to the maximum pressure of 24?GPa and it can partially back-transform to olivine during decompression; 3)?in Ca2GeO4, the olivine transforms to a new structure between 6.8 and 8?GPa; the vibrational frequencies of the new phase suggest that the phase transition involves an increase of the Ca coordination number and that Ge tetrahedra are isolated; this high pressure phase is observed up to the maximum pressure of 11?GPa; during decompression, it transforms to a disordered phase below 5?GPa; 4)?in CaMgGeO4, no significant modification of the olivine spectrum is observed up to 15?GPa; between 16 and 26?GPa, broadening of some peaks and the appearance of a weak broad feature at 700–900?cm?1 suggests a progressive amorphization of the structure; near 27?GPa, amorphization is complete and an amorphous phase is quenched down to ambient pressure; this unique behaviour is interpreted as the result of the incompatibilities in the high pressure behaviour of the Ca and Mg sublattices in the olivine structure.  相似文献   

15.
Single-crystal structure determinations at pressure have shown that the structural response of synthetic (Mg0.6Fe0.4)SiO3 orthopyroxene to compression is the same as that previously observed in MgSiO3 orthoenstatite. At pressure below ～4?GPa there is no significant compression of the SiO4 tetrahedra, while above ～4?GPa the tetrahedra decrease in volume as a result of Si?O bond shortening. A study of the compressional behaviour of synthetic FeSiO3 orthoferrosilite also shows the same behaviour below 4?GPa, but studies at higher pressures are precluded due to the transformation of the sample to the higher density C2/c high-clinoferrosilite polymorph. A further single-crystal study to 6?GPa of a Ca2+-containing natural orthopyroxene shows that chemical substitution of, primarily, Al3+ and Ca2+ into the structure of orthopyroxene inhibits the initial rapid compression of the M2?O3 bonds observed in the synthetic samples, and no significant tetrahedral compression is observed in this sample. Raman data collected from synthetic MgSiO3 orthoenstatite show that there is a change in the rate of change of frequency with pressure, δν/δP, between 3.5 and 6.0?GPa, but no changes in the number of observed bands. These observations indicate a non-symmetry-breaking change in the properties of the orthoenstatite, which is associated with the change in compression mechanism observed using X-ray diffraction techniques at this pressure.  相似文献   

16.
Cathodoluminescence (CL) techniques are used to investigate the defect structures of pure synthetic silicon dioxide (SiO2) polymorphs. Pure, synthetic Types I, II, III and IV amorphous SiO2 polymorphs, pure, synthetic crystal α-SiO2 and pure, synthetic amorphized crystal α-SiO2 have been investigated and their characteristic defects have been determined and compared. The CL emission from pure SiO2 polymorphs is generally related to local point defects in the tetrahedrally coordinated SiO2 host lattice. A range of CL emissions associated with non bridging oxygen defects, oxygen deficient defects and the radiative recombination of self trapped excitons are observed from both the pure synthetic crystal and amorphous SiO2 polymorphs. In addition CL emissions associated with residual concentrations of Aluminium impurities are also observed from α-SiO2 (quartz) and Type I and II a-SiO2 (fused quartz). Localised amorphous micro-volumes may exist within natural α-SiO2 due to the presence of a high concentration of pre-existing or induced defects. Amorphization of α-SiO2 diminishes the difference between the defect structures and associated CL from α-SiO2 and a-SiO2. Thus CL investigation of the defect structure of a-SiO2 polymorphs provides useful insight into the microstructure of amorphized α-SiO2.  相似文献   

17.
High pressure phase transformations for all the mineral phases along the joins Mg2SiO4-Ca2-SiO4 and MgO-CaSiO3 in the system MgO-CaO-SiO2 were investigated in the pressure range between 100 and 300 kbar at about 1,000 °C, by means of the technique involving a diamond-anvil press coupled with laser heating. In addition to the four end-members, there are three stable intermediate mineral components in these two joins. Phase behaviour of all the end-member components at high pressure have been reported earlier and are reviewed here. Results of this study reveal that the three intermediate components are all unstable relative to the end-members at pressures greater than 200 kbar. Ultimately, monticellite (CaMgSiO4) decomposes into CaSiO3 (perovskite-type)+MgO; merwinite (Ca3MgSi2O8) decomposes into Ca2SiO4(K2NiF4-type)+CaSiO3 (perovskite-type)+MgO; and akermanite (Ca2MgSi2O7) decomposes into CaSiO3 (perovskite-type)+MgO. Note that the decomposition reactions of all phases studied here result in the formation of MgO. Intermediate Ca-Mg silicates transform to pure Ca-silicates plus MgO, while pure Mg2SiO4 transforms to MgSiO3+MgO.  相似文献   

18.
The crystal structures and energies of SiO2 stishovite, MgO periclase, Mg2SiO4 spinel, and MgSiO3 perovskite were calculated as a function of pressure with the polarization-included electron gas (PEG) model. The calculated pressures of the spinel to perovskite phase transitions in the Mg2SiO4 and MgSiO3 systems are 26.0 GPa and 27.0 GPa, respectively, compared to the experimental zero temperature extrapolations of 27.4 GPa and 27.7 GPa. The two oxide phases are found to be the most stable form in the pressure range 24.5 GPa to 31.5 GPa, compared to the experimental zero temperature extrapolation of 26.7 GPa to 28.0 GPa. The volume changes associated with the phase transitions are in good agreement with experiment. The transition pressures calculated with the PEG model, which allows the ions to distort from spherical symmetry, are in much better agreement with experiment than those calculated with the modified electron gas (MEG) model, which constrains the ions to be spherical.  相似文献   

19.
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  相似文献   

20.
Pressure-induced amorphization of α-quartz type GeO2 was studied with a newly developed X-ray diffraction system which consists of a 4-circle goniometer and a curved position sensitive detector. Single-crystal diffraction was measured under pressurs up to 7.3 GPa at room temperature in order to investigate pretransitional phenomena. Diffraction intensity and line width of the diffraction profiles showed no remarkable change up to 5.9 GPa. However, no sharp diffraction line was observed at pressures over 6.5 GPa. The bulk modulus at 0.1 MPa and its pressure derivative of α-quartz type GeO2 were determined to be K T =32.8(3.3) GPa and K′ T =6.0(2.0), respectively. In situ microscopic observations of the amorphization transformation was also performed. The large volume change due to amorphization was observed and estimated to be about 10%.  相似文献   

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