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1.
 In order to elucidate high-pressure transformations of high-P clinopyroxene (C2/c) at kinetically low temperature where atoms are not thermally activated, the transformation processes of FeGeO3 clinopyroxene (C2/c) have been investigated at pressures up to 20 GPa and 365 °C by powder X-ray diffraction using a synchrotron radiation source and TEM observation. With increasing pressure up to 20 GPa at room temperature, FeGeO3 high-P clinopyroxene (C2/c) reversibly transforms into a new high-pressure phase, FeGeO3(II). On increasing the temperature up to 365 °C, this phase rapidly transforms into FeGeO3 ilmenite within about 2 h. Intensity analysis of the X-ray diffraction pattern reveals that the high-pressure phase of FeGeO3(II) has an intermediate structure between clinopyroxene and ilmenite: the cation arrangement is similar to that of clinopyroxene and the oxygen arrangement is similar to that of ilmenite. The comparison of the crystal structures of these polymorphs suggests that clinopyroxene to FeGeO3(II) and FeGeO3(II) to ilmenite transformations are performed by the slight deformation of the oxygen packing and the short-range movement of cations, respectively. It is shown that this high-P clinopyroxene transforms into ilmenite through a low-activation energy path under the low-temperature condition. Received: 30 August 2000 / Accepted: 10 February 2001  相似文献   

2.
High-pressure phase transitions of CaRhO3 perovskite were examined at pressures of 6–27 GPa and temperatures of 1,000–1,930°C, using a multi-anvil apparatus. The results indicate that CaRhO3 perovskite successively transforms to two new high-pressure phases with increasing pressure. Rietveld analysis of powder X-ray diffraction data indicated that, in the two new phases, the phase stable at higher pressure possesses the CaIrO3-type post-perovskite structure (space group Cmcm) with lattice parameters: a = 3.1013(1) Å, b = 9.8555(2) Å, c = 7.2643(1) Å, V m  = 33.43(1) cm3/mol. The Rietveld analysis also indicated that CaRhO3 perovskite has the GdFeO3-type structure (space group Pnma) with lattice parameters: a = 5.5631(1) Å, b = 7.6308(1) Å, c = 5.3267(1) Å, V m  = 34.04(1) cm3/mol. The third phase stable in the intermediate P, T conditions between perovskite and post-perovskite has monoclinic symmetry with the cell parameters: a = 12.490(3) Å, b = 3.1233(3) Å, c = 8.8630(7) Å, β = 103.96(1)°, V m  = 33.66(1) cm3/mol (Z = 6). Molar volume changes from perovskite to the intermediate phase and from the intermediate phase to post-perovskite are –1.1 and –0.7%, respectively. The equilibrium phase relations determined indicate that the boundary slopes are large positive values: 29 ± 2 MPa/K for the perovskite—intermediate phase transition and 62 ± 6 MPa/K for the intermediate phase—post-perovskite transition. The structural features of the CaRhO3 intermediate phase suggest that the phase has edge-sharing RhO6 octahedra and may have an intermediate structure between perovskite and post-perovskite.  相似文献   

3.
Synthetic clinoenstatite (MgSiO3) has been converted to a single phase with the perovskite structure in complete reactions at approx. 300 kbar in experiments that utilize the laser-heated diamond-anvil pressure apparatus. The structure of this phase after quenching was determined by powder X-ray diffraction intensity measurement to be similar to that of the distorted rare-earth, orthoferrite-type, orthorhombic perovskites, but it is suggested that such distortion from ideal cubic perovskite would diminish at high pressure. The unit cell dimensions and density of perovskite-type MgSiO3 at ambient conditions (1 bar, 25°C) are a=4.780(1) Å, b=4.933(1) Å, c=6.902(1) Å, V=162.75 Å3, and ρ=4.098(1) g/cm3. This phase is 3.1% denser than the isochemical oxide mixture [periclase (MgO)+stishovite (SiO2)]. The small crystal-field stabilization energy of the cation site in the perovskite structure may play an important role in limiting the high-pressure stability field of perovskites that contain transition metal cations. Approximate calculations of the crystal-field effects indicate that perovskite of pure FeSiO3 composition may become stable at 400–600 kbar; pressures greater than 800 kbar would be required to stabilize CoSiO3 or NiSiO3 perovskite.  相似文献   

4.
The equation of state of MgGeO3 perovskite was determined between 25 and 66 GPa using synchrotron X-ray diffraction with the laser-heated diamond anvil cell. The data were fit to a third-order Birch–Murnaghan equation of state and yielded a zero-pressure volume (V 0) of 182.2 ± 0.3 Å3 and bulk modulus (K 0) of 229 ± 3 GPa, with the pressure derivative (K′0 = (?K 0/?P) T ) fixed at 3.7. Differential stresses were evaluated using lattice strain theory and found to be typically less than about 1.5 GPa. Theoretical calculations were also carried out using density functional theory from 0 to 205 GPa. The equation of state parameters from theory (V 0 = 180.2 Å3, K 0 = 221.3 GPa, and K′0 = 3.90) are in agreement with experiment, although theoretically calculated volumes are systematically lower than experiment. The properties of the perovskite phase were compared to MgGeO3 post-perovskite phase near the observed phase transition pressure (～65 GPa). Across the transition, the density increased by 2.0(0.7)%. This is in excellent agreement with the theoretically determined density change of 1.9%; however both values are larger than those for the (Mg,Fe)SiO3 phase transition. The bulk sound velocity change across the transition is small and is likely to be negative [?0.5(1.6)% from experiment and ?1.2% from theory]. These results are similar to previous findings for the (Mg,Fe)SiO3 system. A linearized Birch–Murnaghan equation of state fit to each axis yielded zero-pressure compressibilities of 0.0022, 0.0009, and 0.0016 GPa?1 for the a, b, and c axis, respectively. Magnesium germanate appears to be a good analog system for studying the properties of the perovskite and post-perovskite phases in silicates.  相似文献   

5.
The crystal structure of Pb6Bi2S9 is investigated at pressures between 0 and 5.6 GPa with X-ray diffraction on single-crystals. The pressure is applied using diamond anvil cells. Heyrovskyite (Bbmm, a = 13.719(4) Å, b = 31.393(9) Å, c = 4.1319(10) Å, Z = 4) is the stable phase of Pb6Bi2S9 at ambient conditions and is built from distorted moduli of PbS-archetype structure with a low stereochemical activity of the Pb2+ and Bi3+ lone electron pairs. Heyrovskyite is stable until at least 3.9 GPa and a first-order phase transition occurs between 3.9 and 4.8 GPa. A single-crystal is retained after the reversible phase transition despite an anisotropic contraction of the unit cell and a volume decrease of 4.2%. The crystal structure of the high pressure phase, β-Pb6Bi2S9, is solved in Pna2 1 (a = 25.302(7) Å, b = 30.819(9) Å, c = 4.0640(13) Å, Z = 8) from synchrotron data at 5.06 GPa. This structure consists of two types of moduli with SnS/TlI-archetype structure in which the Pb and Bi lone pairs are strongly expressed. The mechanism of the phase transition is described in detail and the results are compared to the closely related phase transition in Pb3Bi2S6 (lillianite).  相似文献   

6.
Sr2Fe2O5 is a typical oxygen-deficient perovskite and adopts brownmillerite phase (Ibm2, Z = 4) at ambient conditions. Its high-pressure structural behavior has been investigated by both synchrotron radiation X-ray diffraction with diamond anvil cell technique and first principles calculations. Experimental results clearly show that the brownmillerite Sr2Fe2O5 transforms into a tetragonal perovskite-type phase at 12.0 GPa and room temperature, and then into a Sr2Mn2O5-type phase (Pbam, Z = 2) at 23.3 GPa after high-temperature annealing. The Sr2Mn2O5-type phase is stable up to at least 60 GPa and it further undergoes a reversible transition to a lower symmetry phase at 79.1 GPa and ~2,000 K. The results from theoretical calculation not only confirm that the tetragonal phase of Sr2Fe2O5 is isostructural with the high-temperature structure of Ba2In2O5 (I4/mcm, Z = 4), but also predict a series of phase transitions from brownmillerite phase to Ba2In2O5-type phase at 6.9 GPa, and then to Sr2Mn2O5-type phase at 19.7 GPa, which coincides with present experiment results. Isothermal pressure–volume relationship of the Sr2Mn2O5-type phase can be well described by the Birch–Murnaghan Equation of State with V 0 = 111.6(10) Å3, B 0 = 122(9) GPa, B 0 ′  = 4(fixed) experimentally and V 0 = 115.8(3) Å3, B 0 = 92(4) GPa, B 0 ′  = 4(fixed) theoretically. The transition mechanism from brownmillerite to Ba2In2O5-type phase is the displacement of four-coordinated Fe3+ ions to higher coordinated positions upon compression. In addition, a semiconductor-to-metal crossover is predicted from brownmillerite to Ba2In2O5-type or Sr2Mn2O5-type phase.  相似文献   

7.
Three isotypic crystals, SiO2 (α-cristobalite), ε-Zn(OH)2 (wülfingite), and Be(OH)2 (β-behoite), with topologically identical frameworks of corner-connected tetrahedra, undergo displacive compression-driven phase transitions at similar pressures (1.5–2.0 GPa), but each transition is characterized by a different mechanism resulting in different structural modifications. In this study, we report the crystal structure of the high-pressure γ-phase of beryllium hydroxide and compare it with the high-pressure structures of the other two minerals. In Be(OH)2, the transition from the ambient β-behoite phase with the orthorhombic space group P212121 and ambient unit cell parameters a = 4.5403(4) Å, b = 4.6253(5) Å, c = 7.0599(7) Å, to the high-pressure orthorhombic γ-polymorph with space group Fdd2 and unit cell parameters (at 5.3(1) GPa) a = 5.738(2) Å, b = 6.260(3) Å, c = 7.200(4) Å takes place between 1.7 and 3.6 GPa. This transition is essentially second order, is accompanied by a negligible volume discontinuity, and exhibits both displacive and reversible character. The mechanism of the phase transition results in a change to the hydrogen bond connectivities and rotation of the BeO4 tetrahedra.  相似文献   

8.
The elastic properties of CaSnO3 perovskite have been measured by both ultrasonic interferometry and single-crystal X-ray diffraction at high pressures. The single-crystal diffraction data collected using a diamond-anvil cell show that CaSnO3 perovskite does not undergo any phase transitions at pressures below 8.5?GPa at room temperature. Ultrasonic measurements in the multianvil press to a maximum pressure of ～8?GPa at room temperature yielded S- and P-wave velocity data as a function of pressure. For a third-order Birch-Murnaghan EoS the adiabatic elastic moduli and their pressure derivatives determined from these velocity data are K S0=167.2±3.1?GPa, K ′ S0=4.89±0.17, G 0=89.3±1.0?GPa, G ′ 0=0.90±0.02. The quoted uncertainties include contributions from uncertainties in both the room pressure length and density of the specimen, as well as uncertainties in the pressure calibration of the multianvil press. Because the sample is a polycrystalline specimen, this value of K S0 represents an upper limit to the Reuss bound (conditions of uniform stress) on the elastic modulus of CaSnO3 perovskite. If the value of αγT is assumed to be 0.01, the value of K S0 corresponds to K T0=165.5±3.1?GPa. The 10 P-V data obtained by single-crystal diffraction were fit with a third-order Birch–Murnaghan equation-of-state to obtain the parameters V 0=246.059±0.013 Å3, K T0=162.6±1.0?GPa, K ′ T0=5.6±0.3. Because single-crystal measurements under hydrostatic conditions are made under conditions of uniform stress, they yield bulk moduli equivalent to the Reuss bound on a polycrystalline specimen. The results from the X-ray and ultrasonic experiments are therefore consistent. The bulk modulus of CaSnO3 perovskite lies above the linear trend of K 0 with inverse molar volume, previously determined for Ca perovskites. This prevents an estimation of the bulk modulus of CaSiO3 perovskite by extrapolation. However, our value of G 0 for CaSnO3 perovskite combined with values for CaTiO3 and CaGeO3 forms a linear trend of G 0 with octahedral tilt angle. This allows a lower bound of 150?GPa to be placed on the shear modulus of CaSiO3 by extrapolation.  相似文献   

9.
Compressibility of perovskite-structured Ca3Al2Si3O12 grossular (GrPv) was investigated at high pressure and high temperature by means of angle-dispersive powder X-ray diffraction using a laser-heated diamond anvil cell. We observed the Pbnm orthorhombic distortion for the pure phase above 50 GPa, whereas below this pressure, Al-bearing CaSiO3 perovskite coexists with an excess of corundum. GrPv has a bulk modulus (K 0 = 229 ± 5 GPa; \(K_{0}^{{\prime }}\) fixed to 4) almost similar to that reported for pure CaSiO3 perovskite. Its unit-cell volume extrapolated to ambient conditions (V 0 = 187.1 ± 0.4 Å3) is found to be ~2.5 % larger than for the Al-free phase. We observe an increasing unit-cell anisotropy with increasing pressure, which could have implications for the shear properties of Ca-bearing perovskite in cold slabs subducted into the Earth’s mantle.  相似文献   

10.
Single crystals of the garnet Mn2+ 3Mn3+ 2[SiO4]3 and coesite were synthesised from MnO2-SiO2 oxide mixtures at 1000°C and 9 GPa in a multianvil press. The crystal structure of the garnet [space group Ia3¯d, a=11.801(2) Å] was refined at room temperature and 100 K from single-crystal X-ray data to R1=2.36% and R1=2.71%, respectively. In contrast to tetragonal Ca3Mn3+ 2[GeO4]3 (space group I41/a), the high-pressure garnet is cubic and does not display an ordered Jahn-Teller distortion of octahedral Mn3+. A disordered Jahn-Teller distortion either dynamic or static is evidenced by unusual high anisotropic displacement parameters. The room temperature structure is characterised by following bond lengths: Si-O=1.636(4) Å (tetrahedron), Mn3+-O=1.995 (4) Å (octahedron), Mn2+-O=2.280(5) and 2.409(4) Å (dodecahedron). The cubic structure was preserved upon cooling to 100 K [a=11.788(2) Å] and upon compressing up to 11.8 GPa in a diamond-anvil cell. Pressure variation of the unit cell parameter expressed by a third-order Birch-Murnaghan equation of state led to a bulk modulus K 0=151.6(8) GPa and its pressure derivatives K′=6.38(19). The peak positions of the Raman spectrum recorded for Mn2+ 3Mn3+ 2[SiO4]3 were assigned based on a calderite Mn2+ 3Fe3+ 2[SiO4]3 model extrapolated from andradite and grossular literature data.  相似文献   

11.
In-situ X-ray powder diffraction measurements conducted under high pressure confirmed the existence of an unquenchable orthorhombic perovskite in ZnGeO3. ZnGeO3 ilmenite transformed into perovskite at 30.0 GPa and 1300±150 K in a laser-heated diamond anvil cell. After releasing the pressure, the lithium niobate phase was recovered as a quenched product. The perovskite was also obtained by recompression of the lithium niobate phase at room temperature under a lower pressure than the equilibrium phase boundary of the ilmenite–perovskite transition. Bulk moduli of ilmenite, lithium niobate, and perovskite phases were calculated on the basis of the refined X-ray diffraction data. The structural relations among these phases are considered in terms of the rotation of GeO6 octahedra. A slight rotation of the octahedra plays an important role for the transition from lithium niobate to perovskite at ambient temperature. On the other hand, high temperature is needed to rearrange GeO6 octahedra in the ilmenite–perovskite transition. The correlation of quenchability with rotation angle of GeO6 octahedra for other germanate perovskites is also discussed.  相似文献   

12.
Four polymorphs of CdGeO3 were synthesized at high temperatures (600 ～ 1200° C) and high pressures up to 12 GPa. The pyroxenoid phase synthesized under ambient pressure transforms to garnet, ilmenite and perovskite phases with increasing pressure. The phase boundary of ilmenite-perovskite had a slightly negative P-T slope in contrast to the positive P-T slopes of the pyroxenoid-garnet and garnet-ilmenite transition boundaries. CdGeO3III has the ilmenite structure with hexagonal lattice parameters, a=5.098 Å and c =14.883 Å. The c/a ratio of 2.919 is greater than that of any other ilmenite. CdGeO3IV has a distorted perovskite structure with orthorhombic lattice parameters a = 5.209 Å, b = 5.253 Å and c = 7.434 Å. Synthesis of a CdGeO3IV single crystal was successful and structural refinement revealed that the structure is isomorphic to GdFeO3 with the space group Pbnm. The increase of density with the CdGeO3III→CdGeO3IV transformation is the largest (9.8%) for any ilmenite-perovskite transition studied so far.  相似文献   

13.
The nickel arsenide (B81) and related crystal structures are among the most important crystallographic arrangements assumed by Fe and Ni compounds with light elements such as Si, O, S, and P, expected to be present in planetary cores. Despite the simple structure, some of these materials like troilite (FeS) exhibit complex phase diagrams and rich polymorphism, involving significant changes in interatomic bonding and physical properties. NiP (oP16) represents one of the two principal structure distortions found in the nickel arsenide family and is characterized by P–P bonding interactions that lead to the formation of P2 dimers. In the current study, the single-crystal synchrotron X-ray diffraction technique, aided by first principles density functional theory (DFT) calculations, has been applied to examine the compression behavior of NiP up to 30 GPa. Two new reversible displacive phase transitions leading to orthorhombic high-pressure phases with Pearson symbols oP40 and oC24 were found to occur at approximately 8.5 and 25.0 GPa, respectively. The oP40 phase has the primitive Pnma space group with unit cell a = 4.7729(5) Å, b = 16.6619(12) Å, and c = 5.8071(8) Å at 16.3(1) GPa and is a superstructure of the ambient oP16 phase with multiplicity of 2.5. The oC24 phase has the acentric Cmc21 space group with unit cell a = 9.695(6) Å, b = 5.7101(9) Å, and c = 4.7438(6) Å at 28.5(1) GPa and is a superstructure of the oP16 phase with multiplicity of 1.5. DFT calculations fully support the observed sequence of phase transitions. The two new phases constitute logical next stages of P sublattice polymerization, in which the dilution of the P3 units, introduced in the first high-pressure phase, decreases, leading to compositions of Ni20(P3)4(P2)4 and Ni12(P3)4, and provide important clues to understanding of phase relations and transformation pathways in the NiAs family.  相似文献   

14.
High-pressure single-crystal X-ray diffraction measurements of synthetic LiCrSi2O6 clinopyroxene (with space group P21/c) were performed in a diamond-anvil cell up to 7.970 GPa. No phase transition has been observed within the pressure range investigated, but the elastic behavior at lower pressures (up to ~2.5 GPa) is affected by an anomalous softening due to the proximity of the phase transition to the HT-C2/c phase at 330 K and at ambient pressure. A third-order Birch–Murnaghan equation of state fitted to the compression data above 2.5 GPa yields a bulk modulus K T0 = 93(2) GPa and its first derivative K′ = 8.8(6). The structural data measured up to 7.970 GPa confirm that the space group P21/c is maintained throughout the whole pressure range investigated. The atomic parameters, obtained from the integrated diffraction intensities, suggest that the Li coordination polyhedron changes its coordination number from 5 to 6 at 6–7 GPa by means of the approach of the bridging O atom, related to the increased kinking of the B tetrahedral chain. Furthermore, at higher pressures, the structural evolution of LiCrSi2O6 provides evidence in the variation of kinking angles and bond lengths of a potential phase transition above 8 GPa to the HP-C2/c space group. A comparison of the Li-clinopyroxenes (M1 = Cr, Al, Sc, Ga, Mg + Fe) previously investigated and our sample shows that their elastic behavior and structural mechanisms of compression are analogous.  相似文献   

15.
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   

16.
High-pressure phase transformations were investigated for two silicates, MgSiO3 and ZnSiO3; six germanates, MGeO3 and six titanates, MTiO3 (M=Ni, Mg, Co, Zn, Fe, and Mn) at about 1,000°C and pressures up to ca. 30 GPa. CoGeO3 was found to assume the ilmenite form. The ilmenite phases were confirmed to transform in the following schemes: to perovskite in MgSiO3 and MnGeO3, to corundum in MgGeO3 and ZnGeO3, to rocksalt plus rutile in ZnSiO3 and CoGeO3 and to rocksalt plus TiO2 (possibly of some denser structure) in NiTiO3, MgTiO3, CoTiO3, ZnTiO3 and FeTiO3. In the case of FeTiO3, the corundum form appeared as an intermediate phase. The possibility that the corundum type MnTiO3 might transform to some denser modification could not be excluded. The compound NiGeO3 was nonexistent throughout the pressure range studied. High-pressure phases of ABO3 (A=Ni, Mg, Co, Zn, Fe, and Mn; B=Si, Ge and Ti) are summarized, and those stabilized at pressures higher than 20 GPa are discussed.  相似文献   

17.
The existence of an incomplete solid solution series between loparite (NaLREETi2O6), a member of the perovskite mineral group, and thorutite (ThTi2O6) is established on the basis of experimental and mineralogical data. The products of low- and high-pressure synthesis in the system NaLaTi2O6– ThTi2O6 were studied by energy-dispersive spectrometry, X-ray diffractometry and Rietveld analysis. At atmospheric pressure, Th is incorporated in loparite as both ThTi2O6 and Na2ThTi3O9. In synthetic systems, the maximum determined ThTi2O6 content of loparite is 18 mol%, with a corresponding A-site cation deficiency of 9%. The structure of such loparite is tetragonal and presumably derived from the cubic aristotype by octahedral rotation [I4/mcm, a=5.4652(1) Å, c=7.7476(2) Å]. At a pressure of 6 GPa, no solubility between loparite and ThTi2O6 is observed, and Th is accommodated in the loparite structure entirely as Na2ThTi3O9 (up to 30 mol%). Naturally occurring loparite contains up to 29 mol% ThTi2O6, based on the conventional method of analysis recalculation, or 23.5 mol% ThTi2O6, assuming the presence of protons at the vacant A-sites. ThTi2O6 synthesized by the solid-state reaction, crystallizes with monoclinic symmetry [C2/m, a=9.8140(2) Å, b=3.8228(1) Å, c=7.0313(2) Å,β=118.82(1)°]. Atomic coordinates for ThTi2O6 obtained in this study from X-ray powder data, as well as structural parameters derived from the new data, are in a good agreement with those known from single-crystal refinement. ThTi2O6 does not crystallize at high pressure, and Th is accommodated in perovskite-type compounds and cubic ThO2 that provide a twelve- and eight-fold coordination site for Th, respectively.  相似文献   

18.
The structural changes associated with the incommensurate (IC)-normal (N) phase transition in akermanite have been studied with high-pressure single-crystal X-ray diffraction up to 3.79?GPa. The IC phase, stable at room pressure, transforms to the N phase at ～1.33?GPa. The structural transformation is marked by a small but discernable change in the slopes of all unit-cell parameters as a function of pressure. It is reversible with an apparent hysteresis and is classified as a tricritical phase transition. The linear compressibility of the a and c axes are 0.00280(10) and 0.00418(6)?GPa?1 for the IC phase, and 0.00299(11) and 0.00367(8)?GPa?1 for the N phase, respectively. Weighted volume and pressure data, fitted to a second-order Birch-Murnaghan equation of state (K′≡4.0), yield V0=307.4(1)?Å3 and K0=100(3)?GPa for the IC phase and V0=307.6(2)?Å3 and K0=90(2)?GPa for the N phase. No significant discontinuities in Si–O, Mg–O and Ca–O distances were observed across the transition, except for the Ca–O1 distance, which is more compressible in the IC phase than in the N phase. From room pressure to 3.79?GP the volume of the [SiO4] tetrahedron is unchanged (2.16?Å3), whereas the volumes of the [MgO4] and [CaO8] polyhedra decrease from 3.61 to 3.55(1)?Å3 and 32.8 to 30.9(2)?Å3, respectively. Intensities of satellite reflections are found to vary linearly with the isotropic displacement parametr of Ca and the librational amplitude of the [SiO4] tetrahedron. At room pressure, there is a mismatch between the size of the Ca cations and the configuration of tetrahedral sheets, which appears to be responsible for the formation of the modulated structure; as pressure increases, the misfit is diminished through the relative rotation and distortion of [MgO4] and [SiO4] tetrahedra and the differential compression of individual Ca–O distances, concurrent with a displacement of Ca along the (110) mirror plane toward the O1 atom. We regard the high-pressure normal structure as a result of the elimination of microdomains in the modulated structure.  相似文献   

19.
Magnesium silicate perovskite is the predominant phase in the Earth’s lower mantle, and it is well known that incorporation of iron has a strong effect on its crystal structure and physical properties. To constrain the crystal chemistry of (Mg, Fe)SiO3 perovskite more accurately, we synthesized single crystals of Mg0.946(17)Fe0.056(12)Si0.997(16)O3 perovskite at 26 GPa and 2,073 K using a multianvil press and investigated its crystal structure, oxidation state and iron-site occupancy using single-crystal X-ray diffraction and energy-domain Synchrotron Mössbauer Source spectroscopy. Single-crystal refinements indicate that all iron (Fe2+ and Fe3+) substitutes on the A-site only, where \( {\text{Fe}}^{ 3+ } /\Upsigma {\text{Fe}}\sim 20\,\% \) based on Mössbauer spectroscopy. Charge balance likely occurs through a small number of cation vacancies on either the A- or the B-site. The octahedral tilt angle (Φ) calculated for our sample from the refined atomic coordinates is 20.3°, which is 2° higher than the value calculated from the unit-cell parameters (a = 4.7877 Å, b = 4.9480 Å, c = 6.915 Å) which assumes undistorted octahedra. A compilation of all available single-crystal data (atomic coordinates) for (Mg, Fe)(Si, Al)O3 perovskite from the literature shows a smooth increase of Φ with composition that is independent of the nature of cation substitution (e.g., \( {\text{Mg}}^{ 2+ } - {\text{Fe}}^{ 2+ } \) or \( {\text{Mg}}^{ 2+ } {\text{Si}}^{ 4+ } - {\text{Fe}}^{ 3+ } {\text{Al}}^{ 3+ } \) substitution mechanism), contrary to previous observations based on unit-cell parameter calculations.  相似文献   

20.
ZnSiO3 clinopyroxene stable above 3 GPa transforms to ilmenite at 10–12 GPa, which further decomposes into ZnO (rock salt) plus stishovite at 20–30 GPa. The enthalpy of the clinopyroxene-ilmenite transition was measured by high-temperature solution calorimetry, giving ΔH0=51.71 ±3.18 kJ/mol at 298 K. The heat capacities of clinopyroxene and ilmenite were measured by differential scanning calorimetry at 343–733 and 343–633 K, respectively. The C p of ilmenite is 3–5% smaller than that of clinopyroxene. The entropy of transition was calculated using the measured enthalpy and the free energy calculated from the phase equilibrium data. The enthalpy, entropy and volume changes of the pyroxene-ilmenite transition in ZnSiO3 are similar in magnitude to those in MgSiO3. The present thermochemical data are used to calculate the phase boundary of the ZnSiO3 clinopyroxene-ilmenite transition. The calculated boundary,
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