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1.
In this study, we report the elastic properties of three ultrahigh-pressure phases of SiO2: pyrite, cotunnite and Fe2P types between 300 and 1,500 GPa calculated by means of the density functional ab initio method. It is generally thought
that materials tend to be more compact and isotropic with increasing pressure. These three ultrahigh-pressure phases of silica
are mechanically stable in the investigated pressure range according to the Born criteria, while the cotunnite and Fe2P types are unstable at lower pressure. The elastic azimuthal anisotropy of these ultrahigh-pressure phases of silica shows
that all the structures counterintuitively have considerable anisotropies even at multimegabar pressures. Among the three
investigated structures, the cotunnite type of SiO2 is the most elastically anisotropic phase due to a soft compression along the b axis combined with a large distortion of the polyhedrons that make the structure. This might also be related to its thermodynamic
unfavorability compared to the Fe2P type under extreme pressure condition. The bond property analyses clearly show that the Si–O bond remains an ionic-covalent
mixed bond even at multimegabar pressures with an invariable ionicity with pressure. This argument can explain the monotonously
pressure dependence of the elastic anisotropy in the case of pyrite, while the changes in the velocity distribution patterns
out of the thermodynamic instability range largely contribute to those of the cotunnite and Fe2P types. 相似文献
2.
The charge density and bond character of the rutile-type structure of SiO2 (stishovite) under compression to 30 GPa were investigated by X-ray diffraction study using synchrotron radiation and AgKα rotating anode X-ray generator through a newly devised diamond-anvil cell. The valence electron density was determined by
least-squares refinement including the κ parameter and the electron population in the X-ray atomic scattering parameters.
The oxygen κ-parameter of SiO2 is 0.94 under ambient conditions and 1.11 at 29.1 GPa and the silicon valence changes from +2.12(8) at ambient pressure to
+2.26(15) at 29.1 GPa. These values indicate that the electron distributions are more localized with increasing pressure.
The difference Fourier map shows the deformation of the valence electron distribution and the bonding electron population
in residual electron densities. The bonding electron observed from the X-ray diffraction study is interpreted by molecular
orbital calculations. The deformation of SiO6octahedra and the bonding electron density of stishovite structures are elucidated from the overlapping electron orbits. The
O–O distances of shared and unshared edge of SiO6 octahedra change with the cation ionicity. The repulsive force between the two cations in the adjacent octahedron makes its
shared edge shorter. The pressure changes of the apical and equatorial Si–O interatomic distances are explained by the electron
density of state (DOS) of Si and electron configuration.
Received: 7 January 2002 / Accepted: 6 May 2002 相似文献
3.
Vibrational density of states of the NaAlSi2O6 jadeite and NaAlSiO4 calcium ferrite (CF)-type, and SiO2 stishovite is calculated as a function of pressure up to 50 GPa using density functional perturbation theory. The calculated
frequencies are used to determine the thermal contribution to the Helmholtz free energy within the quasi-harmonic approximation
and to derive the equation of state and several thermodynamic properties of interest. A dissociation of jadeite into a mixture
of a CF-type phase and stishovite is predicted to occur at 23.4 GPa and 1,800 K with a positive Clapeyron slope of 2.8 MPa/K.
Elastic anisotropy for jadeite, the CF-type phase, and stishovite also computed clearly shows that stishovite and the CF-type
phase are the most anisotropic and isotropic in these three phases, respectively. 相似文献
4.
C. C. Lin 《Physics and Chemistry of Minerals》2001,28(4):249-257
The Raman spectra of synthetic α-Co2SiO4 and α-Ni2SiO4 olivines have been studied at room temperature and various pressures. All the Raman frequencies of the two olivines increase
with increasing pressure, and most of the frequency–pressure plots obtained under both quasi- and nonhydrostatic conditions
are nonlinear. It has been found that the average pressure derivative of Raman frequencies of the lattice modes in both Co-
and Ni-olivines is smaller than that of the internal modes of SiO4, indicating that the distortion of SiO4 tetrahedra under static compression may be more severe than that of MO6 octahedra. In addition, four new Raman bands were observed in Ni-olivine under nonhydrostatic compression and above 30 GPa.
This result suggests that a new phase of Ni-olivine should be formed at 30 GPa or amorphization may occur at still higher
pressure.
Received: 11 July 2000 / Accepted: 19 December 2000 相似文献
5.
Single crystalline San Carlos olivine (1 mm cube) was transformed to (Mg,Fe)2SiO4β-phase at 13.5–15 GPa, 1030–1330 °C for 0–600 min using a multi-anvil high pressure apparatus. The α-β transformation occurred
by incoherent surface nucleation and interface-controlled growth and recovered partially transformed samples showed sharply
defined reaction rim. The growth rate of the β-phase rim significantly decreased with time and the growth eventually ceased.
TEM observations revealed that many dislocations were created in both the relict olivine just near the α-β interface and the
β-phase in the rim, which show evidence for deformation caused by interfacial stresses associated with the misfit elastic
strain of the transformation. The observed tangled dislocation texture in β-phase suggested that the β-phase rim was hardened
and relaxation of the interfacial stress was retarded. This probably caused a localized pressure drop in the relict olivine
and decreased the growth rate. Time-dependent growth rates of β-phase is possibly controlled by the rheology of β-phase, which
must be considered for the prediction of the olivine metastability in the subducting slabs.
Received: 24 January 1997 / Revised, accepted: 24 July 1998 相似文献
6.
The equation of state and crystal structure of pyrope were determined by single crystal X-ray diffraction under hydrostatic
conditions to 33 GPa, a pressure that corresponds to a depth of about 900 km in the lower mantle. The bulk modulus K
T0
and its pressure derivative K
'
T0
were determined simultaneously from an unweighted fit of the volume data at different pressures to a third order Birch-Murnaghan
equation of state. They are 171(2) GPa and 4.4(2), respectively. Over the whole pressure range, MgO8 polyhedra showed the largest compression of 18.10(8)%, followed by AlO6 and SiO4 polyhedra, with compression of 11.7(1)% and 4.6(1)%, respectively. The polyhedral bulk moduli for MgO8, AlO6 and SiO4 are 107(1), 211(11) and 580(24) GPa, respectively, with K
'
T0
fixed to 4. Significant compression of up to 1.8(1)% in the very rigid Si−O bonding in pyrope could be detected to 33 GPa.
Changes in the degree of polyhedral distortion for all three types of polyhedra could also be observed. These changes could
be found for the first time for AlO6 and SiO4 in pyrope. It seems that the compression of pyrope crystal structure is governed by the kinking of the Al−O−Si angle between
the octahedra and tetrahedra. No phase transition could be detected to 33 GPa.
Received: 24 March 1997 / Revised, accepted: 29 July 1997 相似文献
7.
The second-order elastic constants of CaF2 (fluorite) have been determined by Brillouin scattering to 9.3 GPa at 300 K. Acoustic velocities have been measured in the
(111) plane and inverted to simultaneously obtain the elastic constants and the orientation of the crystal. A notable feature
of the present inversion is that only the density at ambient condition was used in the inversion. We obtain high-pressure
densities directly from Brillouin data by conversion to isothermal conditions and iterative integration of the compression
curve. The pressure derivative of the isentropic bulk modulus and of the shear modulus determined in this study are 4.78 ± 0.13
and 1.08 ± 0.07, which differ from previous low-pressure ultrasonic elasticity measurements. The pressure derivative of the
isothermal bulk modulus is 4.83 ± 0.13, 8% lower than the value from static compression, and its uncertainty is lower by a
factor of 3. The elastic constants of fluorite increase almost linearly with pressure over the whole investigated pressure
range. However, at P ≥ 9 GPa, C
11 and C
12 show a subtle structure in their pressure dependence while C
44 does not. The behavior of the elastic constants of fluorite in the 9–9.3 GPa pressure range is probably affected by the onset
of a high-pressure structural transition to a lower symmetry phase (α-PbCl2 type). A single-crystal Raman scattering experiment performed in parallel to the Brillouin measurements shows the appearance
of new features at 8.7 GPa. The new features are continuously observed to 49.2 GPa, confirming that the orthorhombic high-pressure
phase is stable along the whole investigated pressure range, in agreement with a previous X-ray diffraction study of CaF2 to 45 GPa. The high-pressure elasticity data in combination with room-pressure values from previous studies allowed us to
determine an independent room-temperature compression curve of fluorite. The new compression curve yields a maximum discrepancy
of 0.05 GPa at 9.5 GPa with respect to that derived from static compression by Angel (1993). This comparison suggests that
the accuracy of the fluorite pressure scale is better than 1% over the 0–9 GPa pressure range.
Received: 10 July 2001 / Accepted: 7 March 2002 相似文献
8.
H. Yang R. M. Hazen L. W. Finger C. T. Prewitt R. T. Downs 《Physics and Chemistry of Minerals》1997,25(1):39-47
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
9.
High pressure phase relation of the system Fe2SiO4–Fe3O4 was investigated by synthesis experiments using multi-anvil high pressure apparatus. A complete solid solution with spinel
structure along Fe2SiO4–Fe3O4 join occurs above 9 GPa at 1200 °C. Lattice constants of the solid solution show almost linear variation with composition.
A spinelloid phase is stable for intermediate compositions in the pressure range from 3 to 9 GPa. the synthesized spinelloid
phase is successfully indexed assuming nickel aluminosilicate V type structure.
Received: October 16, 1995 / Revised, accepted: March 19, 1997 相似文献
10.
Tomoo Katsura Sho Yokoshi Kazuyuki Kawabe Anton Shatskiy Maki Okube Hiroshi Fukui Eiji Ito Akifumi Nozawa Ken-ichi Funakoshi 《Physics and Chemistry of Minerals》2007,34(4):249-255
The electrical conductivity of (Mg0.93Fe0.07)SiO3 ilmenite was measured at temperatures of 500–1,200 K and pressures of 25–35 GPa in a Kawai-type multi-anvil apparatus equipped
with sintered diamond anvils. In order to verify the reliability of this study, the electrical conductivity of (Mg0.93Fe0.07)SiO3 perovskite was also measured at temperatures of 500–1,400 K and pressures of 30–35 GPa. The pressure calibration was carried
out using in situ X-ray diffraction of MgO as pressure marker. The oxidation conditions of the samples were controlled by
the Fe disk. The activation energy at zero pressure and activation volume for ilmenite are 0.82(6) eV and −1.5(2) cm3/mol, respectively. Those for perovskite were 0.5(1) eV and −0.4(4) cm3/mol, respectively, which are in agreement with the experimental results reported previously. It is concluded that ilmenite
conductivity has a large pressure dependence in the investigated P–T range. 相似文献
11.
K. Kuroda T. Irifune T. Inoue N. Nishiyama M. Miyashita K. Funakoshi W. Utsumi 《Physics and Chemistry of Minerals》2000,27(8):523-532
Determination of the phase boundary between ilmenite and perovskite structures in MgSiO3 has been made at pressures between 18 and 24 GPa and temperatures up to 2000 °C by in situ X-ray diffraction measurements
using synchrotron radiation and quench experiments. It was difficult to precisely define the phase boundary by the present
in situ X-ray observations, because the grain growth of ilmenite hindered the estimation of relative abundances of these phases.
Moreover, the slow reaction kinetics between these two phases made it difficult to determine the phase boundary by changing
pressure and temperature conditions during in situ X-ray diffraction measurements. Nevertheless, the phase boundary was well
constrained by quench method with a pressure calibration based on the spinel-postspinel boundary of Mg2SiO4 determined by in situ X-ray experiments. This yielded the ilmenite-perovskite phase boundary of P (GPa) = 25.0 (±0.2) – 0.003
T (°C) for a temperature range of 1200–1800 °C, which is generally consistent with the results of the present in situ X-ray
diffraction measurements within the uncertainty of ∼±0.5 GPa. The phase boundary thus determined between ilmenite and perovskite
phases in MgSiO3 is slightly (∼0.5 GPa) lower than that of the spinel-postspinel transformation in Mg2SiO4.
Received: 19 May 1999 / Accepted: 21 March 2000 相似文献
12.
The second-order elastic constants up to 30 GPa, which encompass the stability field of the spinel forms, their pressure derivatives and the third-order elastic constants of both hydrous and anhydrous -Mg2SiO4 have been obtained theoretically. A combination of deformation theory and finite strain elasticity theory has been employed to arrive at the expressions for second-order and third-order elastic constants from the strain energy of the lattice. The strain energy is calculated by taking into account the interactions up to second nearest neighbours in the -Mg2SiO4 lattice. This is then compared with the strain-dependent lattice energy from continuum model approximation to obtain the expression of elastic constants. The second-order elastic constants Cij compare favourably with the measurements in the case of anhydrous as well as hydrous -Mg2SiO4 and with other calculations on the anhydrous phase. All the third-order elastic constants of both the compounds are negative. The third-order elastic constant C144(–52.41 and –45.07 GPa for anhydrous and hydrous -Mg2SiO4, respectively) representing the anisotropy of shear mode has a smaller value than C111 (–2443.94 and –2101.25 GPa for anhydrous and hydrous phases, respectively), which corresponds to the longitudinal mode. The pressure-induced variations in the longitudinal elastic constants (i.e.,dC11/dp) are relatively large (4.08 and 4.09 for dry and hydrous ringwoodite, respectively) compared with those for the shear (0.22 and 0.32 for dry and hydrous ringwoodite, respectively) and off-diagonal constants (1.40 and 1.41 for dry and hydrous ringwoodite, respectively). The variation of the shear moduli Cs
and anisotropy factor A with pressure have also been studied. The average value of elastic anisotropy is 0.835 in the case of anhydrous -Mg2SiO4 and 0.830 in the hydrous phase. The reversal of sign of the Cauchy pressure C12
– C44, which describes the angular character of atomic bonding in metals and other compounds, at around 21 GPa for both the compounds may be a precursor to the phase transition from ringwoodite to periclase and perovskite at an elevated temperature. The aggregate elastic properties like the adiabatic bulk modulus K (175.4 and 150.2 GPa for anhydrous and hydrous phases, respectively), and the isotropic compressional (P) and shear (S) wave velocities were calculated and the mode Grüneisen Parameters (GPs) of the acoustic waves were determined based on the quasi-harmonic approximation. The low temperature limit
of both hydrous and anhydrous phases of -Mg2SiO4 are positive (1.69 and 1.78, respectively, for hydrous and anhydrous phases) and hence we expect the thermal expansion to be positive down to absolute zero. The Anderson–Grüneisen parameter obtained for hydrous as well as anhydrous phases of -Mg2SiO4 from the second-order and third-order elastic constants are 2.30 and 2.29, respectively. 相似文献
13.
Wenjun Yong E. Dachs A. C. Withers E. J. Essene 《Physics and Chemistry of Minerals》2007,34(2):121-127
A multi-anvil device was used to synthesize 24 mg of pure γ-Fe2SiO4 crystals at 8.5 GPa and 1,273 K. The low-temperature heat capacity (C
p) of γ-Fe2SiO4 was measured between 5 and 303 K using the heat capacity option of a physical properties measurement system. The measured
heat capacity data show a broad λ-transition at 11.8 K. The difference in the C
p between fayalite and γ-Fe2SiO4 is reduced as the temperature increases in the range of 50–300 K. The gap in C
p data between 300 and 350 K of γ-Fe2SiO4 is an impediment to calculation of a precise C
p equation above 298 K that can be used for phase equilibrium calculations at high temperatures and high pressures. The C
p and entropy of γ-Fe2SiO4 at standard temperature and pressure (S°298) are 131.1 ± 0.6 and 140.2 ± 0.4 J mol−1 K−1, respectively. The Gibbs free energy at standard pressure and temperature (ΔG°
f,298) is calculated to be −1,369.3 ± 2.7 J mol−1 based on the new entropy data. The phase boundary for the fayalite–γ-Fe2SiO4 transition at 298 K based on current thermodynamic data is located at 2.4 ± 0.6 GPa with a slope of 25.4 bars/K, consistent
with extrapolated results of previous experimental studies. 相似文献
14.
15.
Using experimental results at 1·0 GPa for the systemsCaO–SiO2, MgO–SiO2, CaMgSi2O6–SiO2 and CaMgSi2O6–Mg2SiO4,and all the currently available phase equilibria and thermodynamicdata at 1 bar, we have optimized the thermodynamic propertiesof the liquid phase at 1·0 GPa. The new optimized thermodynamicparameters indicate that pressure has little effect on the topologyof the CaO–SiO2, CaMgSi2O6–SiO2, and CaMgSi2O6–Mg2SiO4systems but a pronounced one on the MgO–SiO2 binary. Themost striking change concerns passage of the MgSiO3 phase fromperitectic melting at 1 bar to eutectic melting at 1·0GPa. This transition is estimated to occur at 0·41 GPa.For the CaMgSi2O6–SiO2 and CaMgSi2O6–Mg2SiO4 pseudo-binaries,the size of the field clinopyroxene + liquid increases withincreasing pressure. This change is related to the shift ofthe piercing points clinopyroxene + silica + liquid (from 0·375mol fraction SiO2 at 1 bar to 0·414 at 1·0 GPa)and clinopyroxene + olivine + liquid (from 0·191 molfraction SiO2 at 1 bar to 0·331 at 1·0 GPa) thatbound the clinopyroxene + liquid field in the CaMgSi2O6·SiO2and CaMgSi2O6·Mg2SiO4 pseudo-binaries, respectively. KEY WORDS: CaO–SiO2; CaMgSi2O6–Mg2SiO4; CaMgSi2O6–SiO2; experiments; MgO–SiO2 相似文献
16.
Synchrotron X-ray powder diffraction experiments at high pressure conditions (0.0001–13 GPa) were performed at ESRF (Grenoble-F),
on the beamline ID9, to investigate the bulk elastic properties of natural P2/n-omphacites, with quasi-ideal composition. The monoclinic cell parameters a, b, c and β were determined as a function of pressure, and their compressibility coefficients are 0.00277(7), 0.00313(8), 0.00292(5)
and 0.00116(4) GPa−1, respectively. The third-order Birch-Murnaghan equation of state was used to interpolate the experimental P−V data, obtaining K
0=116.6(±2.5) GPa and K′0=6.03(±0.60). K
0 was also determined by means of the axial and angular compressibilities [122.5(±1.7) GPa], and of the finite Lagrangian strain
theory [121.5(±1.0) GPa]. The discrepancies on K
0 are discussed in the light of a comparison between techniques to determine the bulk modulus of crystalline materials from
static compression diffraction data.
Received: 22 February 2000 / Accepted: 10 July 2000 相似文献
17.
An in situ high pressure powder diffraction study, using high-brilliance synchrotron radiation, on lead feldspar (PbAl2Si2O8) was performed. Two samples, with Q
od=0.68 and 0.76, were loaded in a diamond anvil cell and were compressed up to 11 GPa. Up to P=7.1 GPa the only phase present
is lead feldspar. In the range 7.1–9.4 GPa sudden changes in the position of the reflections suggest the transformation of
lead feldspar to a new phase (probably feldspar-like). The absence of split that would be compatible with triclinic symmetry
rules out the monoclinic-triclinic transition, that was reported for the structurally similar strontium feldspar. At P>9.4 GPa some new extra reflections not indexable in the feldspar cell are present as well. During decompression the lead
feldspar was the only phase present at P<6 GPa. Peak enlargement was observed with pressure, probably preliminary to amorphization. However almost complete amorphization
was observed only after fortuitous shock compression at ∼18 GPa; the crystallinity was recovered at room pressure after decompression.
The bulk modulus for lead feldspar was K=71.0(9) and 67.6(1.2) GPa for the two samples, in the range reported for feldspars.
The cell parameters show a compression pattern which is similar to that observed in anorthite, with Δa/a
0>Δc/c
0>Δb/b
0; comparison with the high temperature behaviour shows that for lead feldspar the strain tensor with pressure is more isotropic
and the deformation along a is less prominent. A turnover in the behaviour of the β angle with pressure suggests a change in the compression behaviour
at P∼2 GPa. Rietveld refinement of the Pb coordinates was performed in a series of spectra with pressure ranging from 0.6 to 6.5
GPa. The combined analysis of cell parameters and Pb coordinates with pressure showed that the compression of the structure
is mainly achieved by an approach of Pb atoms along a
*.
Received: 21 July 1998 / Revised, accepted: 13 October 1998 相似文献
18.
In situ time-resolved measurements of shock wave profiles for anisotropic fluorite crystals with two different crystal orientations
were carried out up to a pressure of 34 GPa that is above the transition pressure for the fluorite to cotunnite phase. They
indicate that the Hugoniot elastic limit varies with the crystal orientation and final pressure and that high-pressure phase
transition from fluorite to a cotunnite-type structure occurs at 13 GPa in 10–20 ns for CaF2 [100]-oriented crystals and at 17 GPa in more than 50 ns for CaF2 [111]-oriented crystals, respectively. These results are in disagreement with those from static compression. The phase transition
at static pressures has been known to be very sluggish, but the present results indicate a large sensitivity of kinetics to
the relationship between crystallographic orientation and shock direction, supporting a martensitic mechanism for the fluorite
to cotunnite phase transition that is enhanced by the effect of shock-induced shear. It is also helpful to explain the observation
that the in situ emission spectra for shocked Eu-doped fluorite became weak and had no shift above ~15 GPa. 相似文献
19.
20.
Prograde evolution of Sulu UHP metamorphic rock in Yangzhuang,Junan region,deduced by combined Raman and petrological studies 
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下载免费PDF全文 The prograde metamorphic history of the Sulu ultrahigh‐pressure metamorphic terrane has been revealed using Raman‐based barometry of the SiO2 phases and other mineral inclusions in garnet porphyroblasts of a coesite eclogite from Yangzhuang, Junan region, eastern China. Garnet porphyroblasts have inner and outer segments with the boundary being marked by discontinuous changes in the grossular content. In the inner segment, the SiO2 phase inclusions are α‐quartz with no coesite or relict features such as radial cracks. The residual pressures retained by the quartz inclusions systematically increase from the crystal centre to the margin of the inner segment. The metamorphic conditions estimated by calculation from the residual pressure and conventional thermodynamic calculation range from 500 to 630 °C and 1.3 to 2.3 GPa for the stage of the inner segment. Coesite and its pseudomorph occur as inclusions in the outer segment of the garnet and matrix omphacite. This occurrence of coesite is consistent with the pressure and temperature conditions of 660–725 °C and 3.1 GPa estimated by conventional geothermobarometry. Our results suggest that the quartz inclusions in the inner segment were trapped by garnet under α‐quartz‐stable conditions and survived phase transition to coesite at the peak metamorphic stage. The SiO2 phases and other inclusions in the garnet have retained evidence of the pre‐eclogite prograde stage even during exhumation stage. The combined Raman spectroscopic and petrological approaches used here offers a powerful means for obtaining more robust constraints prograde stages involving garnet growth where different SiO2 phases are present as inclusions. 相似文献