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1.
Ultrasonic data for the velocities of the ilmenites MgTiO3 and CoTiO3 have been determined as a function of pressure to 7.5 kbar at room temperature for polycrystalline specimens hot-pressed in a piston-cylinder apparatus at pressures up to 30 kbar. Titanate and germanate ilmenites define divergent isostructural trends on a Birch diagram of bulk sound velocity (υφ) vs. density (ρ). On a υφ vs. mean atomic weight (M) diagram, however, all of the ilmenite consistent with a single υφM12 = constant trend. Elasticity systematics for isostructural sequences are used to e the bulk modulus (2.09 Mbar) and bulk sound velocity (7.4 km/sec) of MgSiO3-elmenite.  相似文献   

2.
Ultrasonic data for the velocities of the low- and high-pressure polymorphs of germanate compounds undergoing the pyroxene-garnet (CaGeO3, CdGeO3) and pyroxene-ilmenite (MgGeO3, MnGeO3) phase transformations have been determined as a function of pressure to 7.5 kbar at room temperature for polycrystalline specimens hot-pressed at pressures up to 60 kbar. These transitions are characterized by the following velocity (υ)-density (ρ) relationships: (1) the velocity jumps are comparable in percentage magnitude to the density jumps, with the exception of shear velocity for the pyroxene-ilmenite transition; (2) the ratio (υp/υs) of the compressional to shear velocity is constant or increases slightly across the transitions; and (3) low slopes (linear or logarithmic) on υ-ρ diagrams. The observed relationships (1) and (2) are similar to those for the coesite-stishovite transition, but are in marked contrast with those from the olivine-spinel and olivine-beta phase transformations. Coordination changes are thus important factors to be considered in establishing velocity-density systematics governing polymorphic transitions. The υ-ρ changes across the pyroxene-garnet and pyroxene-ilmenite transitions are also distinctly smaller than those produced by compression or thermal expansion of a homogeneous material or by varying composition at constant mean atomic weight. Systematic trends in the elastic properties for isostructural sequences support the concept of germanates as models for the elasticity of their silicate analogues; this scheme is applied to estimate the bulk moduli of the garnet (1.80 Mbar) and ilmenite (2.11 Mbar) polymorphs of MgSiO3.  相似文献   

3.
Ultrasonic data for the velocities of the ilmenite and perovskite polymorphs of CdTiO3 have been determined as a function of pressure to 7.5 kbar at room temperature for polycrystalline specimens hot-pressed at pressures up to 25 kbar. This transition is characterized by the following velocity (ν)-density (?) relationships: (1) the changes in compressional (νp) and bulk sound (ν?) velocities are comparable in percentage magnitude to the density jump, while the shear (νs) velocity jump is three times greater than that for ?; (2) (νp/νs) decreases across the transition from the low- to high-pressure phase; and (3) low slopes (linear or logarithmic) on ν-? diagrams. The (νp/νs) behaviour for the ilmenite-perovskite transformation is unusual for the transitions studied in our laboratory. The observed relationships (1) and (2) are typical of the elasticity behaviour across phase transformations which involve increases in cation-anion co-ordination and in nearest-neighbour interatomic distances, such as those exhibited by CdTiO3 in transforming from the ilmenite to the perovskite phase. Elasticity systematics for isostructural sequences are used to estimate the bulk moduli of the perovskite polymorphs of CaSiO3 (2.7 Mbar) and MgSiO3 (2.8 Mbar).  相似文献   

4.
The orthorhombic MgSiO3 perovskite has been synthesized with the aid of a double-stage split-sphere-type high-pressure apparatus at about 280 kbar and 1000°C. The unit cell dimensions are: a = 4.7754(3)Å, b = 4.9292(4)Å and c = 6.8969(5)Å with the probable space group Pbnm. Calculated density is 4.108 g cm?3. Crystal structure determination has been carried out by means of both the geometrical simulation (DLS) technique and the ordinary powder X-ray analysis. The results indicate that the MgSiO3 perovskite is closer to the ideal perovskite than ScAlO3 perovskite.  相似文献   

5.
The adiabatic single-crystal elastic moduli of SmAlO3, GdAlO3 and ScAlO3, all with the orthorhombic perovskite structure, have been measured by Brillouin spectroscopy under ambient conditions. These 3 compounds display various degrees of crystallographic distortion from the ideal cubic perovskite structure. We find that longitudinal moduli in directions parallel to the axes of a pseudocubic subcell are nearly equal and insensitive to distortions of the crystal structure from cubic symmetry, whereas, the moduli C11 and C22, parallel to the orthorhombic axes, display pronounced anisotropy with the exception of ScAlO3. The shear moduli also correlate with distortion from cubic symmetry, as measured by rotation, or tilt angles, of the AlO6 octahedra. Our data support the observations of Liebermann et al. that perovskite-structure compounds define consistent elasticity trends relating bulk modulus and molar volume, and sound speed and mean atomic weight. These relationships have been used to estimate bulk and shear moduli for the high-pressure polymorphs of CaSiO3 and MgSiO3 with the perovskite structure.  相似文献   

6.
By using the diamond-anvil pressure cell coupled with laser heating, Ca2GeO4 in the K2NiF4-type structure has been found to decompose into the mixture Ca3Ge2O7 plus CaO at pressures greater than 200 kbar and at about 1000°C, and the same type of structure for Ca2MnO4 has been found to decompose into the mixture CaMnO3 (perovskite) plus CaO at pressures greater than 100 kbar and at about 1400°C. The decomposition product of Ca3Ge2O7 is a new compound which is isostructural with Sr3Ti2O7 and has the lattice parameters of a = 3.72 ± 0.01 and c = 19.32 ± 0.05 A? at room temperature and 1 bar pressure. The results of the study of Ca2GeO4 and Ca2MnO4 (both with the K2NiF4-type structure) strongly support the view that compounds possessing the K2NiF4-type structure are unstable relative to corresponding mixtures possessing the perovskite and rocksalt structures. It is concluded that, in the earth's mantle, the K2NiF4-type Ca2SiO4 would ultimately decompose into the mixture CaSiO3 (perovskite) + CaO or would otherwise transform to other as-yet-unknown phase(s), and that the mixture of MgSiO3 (perovskite) + MgO (the post-spinel phase of Mg2SiO4) would not adopt the K2NiF4-type structure.  相似文献   

7.
CO2 has been investigated up to 514 kbar at23 ± 2°C by both optical and in situ X-ray diffraction studies using a diamond-anvil pressure cell. CO2 solidifies in an unknown structure in the pressure range 5 to 23 kbar, and transforms to ordinary dry-ice structure above 23 kbar at room temperature. Isothermal compression data for dry ice have been obtained above about 24 kbar. These appear to be the first data at room temperature known in the literature. The data fitted to the Birch equation of state yieldK0 = 29.3 ± 1.0kbar andK0′ = 7.8 assuming the volume of the hypothetical dry ice at zero-pressure and room temperature is 31.4 ± 0.2 cm3/mole. The isothermal bulk modulus(K0) thus derived is consistent with the compression data and compressibilities for dry ice obtained at low temperatures using dilatometry and ultrasonic techniques, respectively, reported in the literature. By comparing shock-wave data for relevant materials, it is suggested that CO2 is not likely to transform to one of the crystalline forms of SiO2 which is otherwise expected from empirical grounds, but may instead decompose into C (diamond) + O2, at high pressures.  相似文献   

8.
The high-pressure and temperature phase transformations of MgSiO3 have been investigated in a diamond-anvil cell coupled with laser heating from 150 to 300 kbar at 1000–1400°C. X-ray diffraction study of the quenched samples reveals that the sequence of phase transformations for this compound is clinoenstatite → β-Mg2SiO4 plus stishovite → Mg2SiO4(spinel) plus stishovite → ilmenite phase → perovskite phase with increasing pressure. The hexagonal form of MgSiO3 observed by Kawai et al. is demonstrated to have the ilmenite structure and the “hexagonal form” of MgSiO3 observed by Ming and Bassett is shown to be predominantly the orthorhombic perovskite phase plus the ilmenite phase. The mixture of oxides, periclase plus stishovite, reported by Ming and Bassett was not observed in this study. The very wide stability field for the ilmenite phase of MgSiO3 found in this study suggests that this phase is of importance in connection with the observed rapid increase of velocity in the transition zone of the earth's mantle. On the basis of the extremely dense-packed structure of the perovskite phase of MgSiO3, this phase should be the most important component for the lower mantle.  相似文献   

9.
Pressure effects on the lattice parameters of β- and γ-Mg2SiO4 have been measured at room temperature and at pressures up to 100 kbar using a multi-anvil high-pressure X-ray diffraction apparatus. The volume changes (ΔV/V0) at 90 kbar are 5.4 · 10?2 and 4.2 · 10?2 for β- and γ-Mg2SiO4, respectively. Isothermal bulk moduli at zero pressure have been calculated from least-square fits of the data to straight lines. They turn out to be 1.66 ± 0.4 and 2.13 ± 0.1 Mbar for β- and γ-Mg2SiO4, respectively. The α → γ transition obeys Wang's linear Vφ?ρ relation but the α → β transition does not.  相似文献   

10.
The most abundant mineral on Earth has a perovskite crystal structure and a chemistry that is dominated by MgSiO3 with the next most abundant cations probably being aluminum and ferric iron. The dearth of experimental elasticity data for this chemically complex mineral limits our ability to calculate model seismic velocities for the lower mantle. We have calculated the single crystal elastic moduli (cij) for (Mg, Fe3 +)(Si, Al)O3 perovskite using density functional theory in order to investigate the effect of chemical variations and spin state transitions of the Fe3+ ions. Considering the favored coupled substitution of Mg2+-Si4 + by Fe3+-Al3+, we find that the effect of ferric iron on seismic properties is comparable with the same amount of ferrous iron. Ferric iron lowers the elastic moduli relative to the Al charge-coupled substitution. Substitution of Fe3+ for Al3+, giving rise to an Fe/Mg ratio of 6%, causes 1.8% lower longitudinal velocity and 2.5% lower shear velocity at ambient pressure and 1.1% lower longitudinal velocity and 1.8% lower shear velocity at 142 GPa. The spin state of the iron for this composition has a relatively small effect (< 0.5% variation) on both bulk modulus and shear modulus.  相似文献   

11.
High-pressure phase transformations for three intermediate compositions (including diopside) in the system enstatite (MgSiO3)-wollastonite (CaSiO3) were investigated in the pressure range 100–300 kbar at about 1000°C in a diamond-anvil press coupled with laser heating. The phase behaviour of the two end components (enstatite and wollastonite) at high pressure has been reported earlier. The results of this study reveal that there is very limited solid solution of diopside (CaMgSi2O6) in the various high-pressure phase assemblages of enstatite. At pressures greater than about 200 kbar, diopside and a composition between diopside and wollastonite were found to transform into non-quenchable phases, as does wollastonite. It is thought probable that diopside and wollastonite form solid solutions with the perovskite structure at high pressure, but that on release of pressure it is not possible to preserve the high-pressure modification.  相似文献   

12.
A polycrystalline specimen of clinopyroxene diopside has been hot-pressed at P = 15 kbar and T = 850°C in a piston-cylinder apparatus. Compressional (νP) and shear (νS) velocities are determined as a function of pressure to 7.5 kbar at room temperature by an ultrasonic pulse transmission technique. The velocities at 7.5 kbar are νP = 8.06 km/sec and νS = 4.77 km/sec. These data are consistent with velocity-density trends for orthopyroxenes due to the compensating effects of the monoclinic structure (positive) and Ca content (negative). With the addition of the new data for diopside, it is possible to calculate directly the velocities of various upper-mantle mineral assemblages.  相似文献   

13.
The elastic moduli of polycrystalline ringwoodite, (Mg0.91Fe0.09)2SiO4, were measured up to 470 K by means of the resonant sphere technique. The adiabatic bulk (KS) and shear (μ) moduli were found to be 185.1(2) and 118.22(6) GPa at room temperature, and the average slopes of dKS/dT and dμ/dT in the temperature range of the study were determined to be −0.0193(9) and −0.0148(3) GPa/K, respectively. Using these results, we estimate seismic wave velocity jumps for a pure olivine mantle model at 520 km depth. We find that the jump for the S-wave velocity is about 1.5 times larger than that for the P-wave velocity at this depth. This suggests that velocity jumps at the 520 km discontinuity are easier to detect using S-waves than P-waves.  相似文献   

14.
The elasticity of ferropericlase with a potential mantle composition of (Mg0.83,Fe0.17)O is determined using ultrasonic interferometry in conjunction with in situ X-radiation techniques (X-ray diffraction and X-radiography) in a DIA-type cubic anvil high-pressure apparatus to pressures of 9 GPa (NaCl pressure scale) at room temperature. In this study, we demonstrate that it is possible to directly monitor the specimen length using an X-ray image technique and show that these lengths are consistent with those derived from X-ray diffraction data when no plastic deformation of the specimen occurs during the experiment. By combining the ultrasonic and X-ray diffraction data, the adiabatic elastic bulk (KS) and shear (G) moduli and specimen volume can be measured simultaneously. This enables pressure scale-free measurements of the equation of state of the specimen using a parameterization such as the Birch-Murnaghan equation of state. The elastic moduli determined for (Mg0.83,Fe0.17)O are KS0=165.5(12) GPa, G0=112.4(4) GPa, and their pressure derivatives are KS0′=4.17(20) and G0′=1.89(6). If these results are compared with those for MgO, they demonstrate that KS0 and KS0′ are insensitive to the addition of 17 mol% FeO, but G0 and G0′ are reduced by 14% and 24%, respectively. We calculate that the P and S wave velocities of a perovskite plus ferropericlase phase assemblage with a pyrolite composition at the top of the lower mantle (660 km depth) are lowered by 0.8 and 2.3%, respectively, when compared with those calculated using the elastic properties of end-member MgO. Consequently, the magnitudes of the calculated wave velocity jumps across the 660 km discontinuity are reduced by about 11% for P wave and 20% for S wave, if this discontinuity is considered as a phase transformation boundary only (ringwoodite→perovskite+ferropericlase).  相似文献   

15.
Ultrasonic data for the velocities of SiO2-stishovite have been determined as a function of pressure to 10 kbar at room temperature for polycrystalline specimens hot-pressed at pressures P = 120kbar and temperatures T = 900°C. These cylindrical specimens are 2 mm in diameter and 0.9–1.4 mm long and have a grain size less than 10 μm. Compressional and shear wave velocities were measured both parallel and perpendicular to the axis of pressing and were found to be isotropic at 10 kbar with νp = 11.0 ± 0.2km/sec andνs = 6.9 ± 0.3km/sec; this shear velocit is substantially higher than that of Mizutani et al. (1972) perhaps due to the presence of crack orientations in their specimen which affected νs but not νp. The Murnaghan P-V trajectories calculated from the ultrasonic data [bulk modulus Ks = 2.5 ± 0.3Mbar and assuming (?Ks/?P)T = 6 ± 2] are consistent with recent hydrostatic compression data and with the shock wave compression data above 600 kbar. The combined evidence from the data of the ultrasonic and hydrostatic compression techniques suggests that the most probable value of the bulk modulus of stishovite at zero pressure is close to the upper limit of the uncertainty of our ultrasonically determined value, K0 = 2.7?2.8Mbar. Elasticity data for rutile-type oxides are not compatible with normal Ks-V0 systematics perhaps due to the neglect of non-central forces in the lattice model. These new stishovite data would make it impossible to satisfy the elasticity-density data of the lower mantle using an oxide mixture with either olivine or pyroxene stoichiometry.  相似文献   

16.
Tin dioxide (SnO2) in the rutile structure as starting material has been found to transform to the orthorhombic α-PbO2 structure (S.G. Pbcn) at about 155 kbar and 1000–1400°C when compressed in a diamond-anvil cell and heated by irradiation with a YAG laser. The lattice parameters at room temperature and 1 bar are ao = 4.719 ± 0.002, bo = 5.714 ± 0.002, and co = 5.228 ± 0.002 A?with Z = 4 for the orthorhombic form of SnO2, which is 1.5% more dense than the rutile form. Crystal-chemical arguments suggest that stishovite (SiO2) may also transform to the α-PbO2 structure at elevated pressure and temperature with an increase in zero-pressure density of about 2–3%. Mineral assemblages containing the orthorhombic SiO2 are unstable relative to those containing the perovskite MgSiO3 under lower-mantle conditions.  相似文献   

17.
K-Ar ages have been determined for sulfide minerals for the first time. The occurrence of adequate amounts of potassium-bearing sulfides with ideal compositions K3Fe10S14 (～10 wt.% K) and KFe2S3 (～16 wt.% K) in samples from a mafic alkalic diatreme at Coyote Peak, California, prompted an attempt to date these materials. K3Fe10S14, a massive mineral with conchoidal fracture, gives an age of 29.4 ± 0.5m.y.(40Ar/39Ar), indistinguishable from the 28.3 ± 0.4m.y.(40Ar/39Ar) and 30.2 ± 1.0m.y.8 (conventional K-Ar) ages obtained for associated phlogopite (8.7 wt.% K). KFe2S3, a bladed, fibrous sulfide, gives a younger age, 26.5 ± 0.5m.y.(40Ar/39Ar), presumably owing to Ar loss.  相似文献   

18.
We have investigated the effect of Al3+ on the room-temperature compressibility of perovskite for stoichiometric compositions along the MgSiO3-AlO1.5 join with up to 25 mol% AlO1.5. Aluminous Mg-perovskite was synthesized from glass starting materials, and was observed to remain a stable phase in the range of ∼30-100 GPa at temperatures of ∼2000 to 2600 K. Lattice parameters for orthorhombic (Pbnm) perovskite were determined using in situ X-ray diffraction at SPring8, Japan. Addition of Al3+ into the perovskite structure increases orthorhombic distortion and unit cell volume at ambient conditions (V0). Compression causes anisotropic decreases in axial length, with the a axis more compressive than the b and c axes by about 25% and 3%, respectively. The magnitude of orthorhombic distortion increases with pressure, but aluminous perovskite remains stable to pressures of at least 100 GPa. Our results show that substitution of Al3+ causes a mild increase in compressibility, with the bulk modulus (K0) decreasing at a rate of −67±35 GPa/XAl. This decrease in K0 is consistent with recent theoretical calculations if essentially all Al3+ substitutes equally into the six- and eight-fold sites by charge-coupled substitution with Mg2+ and Si4+. In contrast, the large increase in compressibility reported in some studies with addition of even minor amounts of Al is consistent with substitution of Al3+ into six-fold sites via an oxygen-vacancy forming substitution reaction. Schematic phase relations within the ternary MgSiO3-AlO1.5-SiO2 indicate that a stability field of ternary defect Mg-perovskite should be stable at uppermost lower mantle conditions. Extension of phase relations into the quaternary MgSiO3-AlO1.5-FeO1.5-SiO2 based on recent experimental results indicates the existence of a complex polyhedral volume of Mg-perovskite solid solutions comprised of a mixture of charge-coupled and oxygen-vacancy Al3+ and Fe3+ substitutions. Primitive mantle with about 5 mol% AlO1.5 and an Fe3+/(Fe3++Fe2+) ratio of ∼0.5 is expected to be comprised of ferropericlase coexisiting with Mg-perovskite that has a considerable component of Al3+ and Fe3+ defect substitutions at conditions of the uppermost lower mantle. Increased pressure may favor charge-coupled substitution reactions over vacancy forming reactions, such that a region could exist in the lower mantle with a gradient in substitution mechanisms. In this case, we expect the physical and transport properties of Mg-perovskite to change with depth, with a softer, probably more hydrated, defect dominated Mg-perovskite at the top of the lower mantle, grading into a stiffer, dehydrated, charge-coupled substitution dominated Mg-perovskite at greater depth.  相似文献   

19.
In a diamond-anvil press coupled with YAG laser heating, the spinels of Co2GeO4 and Ni2GeO4 have been found to disproportionate into their isochemical oxide mixtures at about 250 kbar and 1400–1800°C in the same manner as their silicate analogues. At about the same P-T conditions MnGeO3 transforms to the orthorhombic perovskite structure (space group Pbnm); the lattice parameters at room temperature and 1 bar are a0 = 5.084 ± 0.002, b0 = 5.214 ± 0.002, and c0 = 7.323 ± 0.003Å with Z = 4 for the perovskite phase. The zero-pressure volume change associated with the ilmenite-perovskite phase transition in MnGeO3 is ?6.6%. Mn2GeO4 disproportionates into a mixture of the perovskite phase of MnGeO3 plus the rocksalt phase of MnO at P = 250kbar and T = 1400–1800°C. The concept of utilizing germanates as high-pressure models for silicates is valid in general. The results of this study support the previous conclusion that the lower mantle comprises predominantly the orthorhombic perovskite phase of ferromagnesian silicate.  相似文献   

20.
Rock physics analysis plays a vital role in time‐lapse seismic interpretation because it provides the link between changes in rock and fluid properties and the resulting seismic data response. In this case study of the Schiehallion Field, we discuss a number of issues that commonly arise in rock physics analyses for time‐lapse studies. We show that:
  • 1 Logarithmic fits of dry bulk (Kdry) and shear (Gdry) moduli vs. effective pressure (Peff) are superior to polynomial fits.
  • 2 2D surface fits of Kdry and Gdry over porosity (φ) and effective pressure using all the core data simultaneously are more useful and accurate than separate 1D fits over φ and Peff for each individual core.
  • 3 One average set (facies) of Kdry(φ, Peff) and Gdry(φ, Peff) can be chosen to represent adequately the entire Schiehallion reservoir.
  • 4 Saturated velocities and densities modelled by fluid substitution of Kdry(φ, Peff), Gdry(φ, Peff) and the dry bulk density ρdry(φ) compare favourably with well‐log velocities and densities.
  • 5 P‐ and S‐wave impedance values resulting from fluid substitution of Kdry(φ, Peff), Gdry(φ, Peff) and ρdry(φ) show that the largest impedance changes occur for high porosities and low effective pressures.
  • 6 Uncertainties in Kdry(φ, Peff) and Gdry(φ, Peff) derived for individual cores can be used to generate error surfaces for these moduli that represent bounds for quantifying uncertainties in seismic modelling or pressure–saturation inversion.
  相似文献   

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