Calorimetric study of high pressure polymorphism in FeTiO3: Stability of the perovskite phase

A calorimetric study of the ilmenite and lithium niobate polymorphs of FeTiO₃ was undertaken to assess the high-pressure stabilities of these phases. Ilmenite is known to be the stable phase at ambient pressure, but the lithium niobate form may be a quench phase from a perovskite form which has been previously observed in situ at high pressure.In this study, the lithium niobate phase of FeTiO₃ was synthesized from an ilmenite starting material at 15– 16 GPa and 1473 K, using a uniaxial split-sphere high-pressure apparatus (USSA 2000). The energetics of the ilmenite to lithium niobate transformation were investigated through transposed-temperature drop calorimetry. The heat of back-transformation of lithium niobate to ilmenite was measured by dropping the sample in argon from ambient conditions to a temperature where the transformation occurs spontaneously. In drops made at 977 K, an intermediate x-ray amorphous phase was encountered. At 1273 K, the transformation went to completion. A value of -13.5±1.2 kJ/mol was obtained for the heat of transformation.     

Low-temperature heat capacities,entropies and high-pressure phase relations of MgSiO<Subscript>3</Subscript> ilmenite and perovskite

Low-temperature isobaric heat capacities (C _p ) of MgSiO₃ ilmenite and perovskite were measured in the temperature range of 1.9–302.4 K with a thermal relaxation method using the Physical Properties Measurement System. The measured C _p of perovskite was higher than that of ilmenite in the whole temperature range studied. From the measured C _p , standard entropies at 298.15 K of MgSiO₃ ilmenite and perovskite were determined to be 53.7 ± 0.4 and 57.9 ± 0.3 J/mol K, respectively. The positive entropy change (4.2 ± 0.5 J/mol K) of the ilmenite–perovskite transition in MgSiO₃ is compatible with structural change across the transition in which coordination of Mg atoms is changed from sixfold to eightfold. Calculation of the ilmenite–perovskite transition boundary using the measured entropies and published enthalpy data gives an equilibrium transition boundary at about 20–23 GPa at 1,000–2,000 K with a Clapeyron slope of −2.4 ± 0.4 MPa/K at 1,600 K. The calculated boundary is almost consistent within the errors with those determined by high-pressure high-temperature in situ X-ray diffraction experiments.     

Clinopyroxene-perovskite phase transition of FeGeO3 under high pressure and room temperature

In order to confirm the possible existence of FeGeO₃ perovskite, we have performed in situ X-ray diffraction measurements of FeGeO₃ clinopyroxene at pressures up to 40 GPa at room temperature. The transition of FeGeO₃ clinopyroxene into orthorhombic perovskite is observed at about 33GPa. The cell parameters of FeGeO₃ perovskite are a=4.93(2) Å, b=5.06(6) Å, c=6.66(3) Å and V=166(3) ų at 40 GPa. On release of pressure, the perovskite phase transformed into lithium niobate structure. The previously reported decomposition process of clino-pyroxene into Fe₂GeO₄ (spinel)+GeO₂ (rutile) or FeO (wüstite) +GeO₂ (rutile) was not observed. This shows that the transition of pyroxene to perovskite is kinetically accessible compared to the decomposition processes under low-temperature pressurization.     

Phase equilibrium and calorimetric study of the transition of MnTiO3 from the ilmenite to the lithium niobate structure and implications for the stability field of perovskite

The phase boundary between MnTiO₃ I (ilmenite structure) and MnTiO₃ II (lithium niobate structure) has been determined by analysis of quench products from reversal experiments in a cubic anvil apparatus at 1073–1673 K and 43–75 kbar using mixtures of MnTiO₃ I and II as starting materials. Tight brackets of the boundary give P(kbar)=121.2−0.045 T(K). Thermodynamic analysis of this boundary gives ΔH^o=5300±1000 J·mol⁻¹, ΔS^o = 1.98 ±1J·K⁻¹· mol⁻¹. The enthalpy of transformation obtained directly by transposed-temperature-drop calorimetry is 8359 ±2575 J·mol⁻¹. Possible topologies of the phase relations among the ilmenite, lithium niobate, and perovskite polymorphs are constrained using the above data and the observed (reversible with hysteresis) transformation of II to III at 298 K and 20–30 kbar (Ross et al. 1989). The observed II–III transition is likely to lie on a metastable extension of the II–III boundary into the ilmenite field. However the reversed I–II boundary, with its negative dP/ dT does represent stable equilibrium between ilmenite and lithium niobate, as opposed to the lithium niobate being a quench product of perovskite. We suggest a topology in which the perovskite occurs stably at low T and high P with a triple point (I, II, III) at or below 1073 K near 70 kbar. The I–II boundary would have a negative P-T slope while the II–III and I–III boundaries would be positive, implying that entropy decreases in the order lithium niobate, ilmenite, perovskite. The inferred positive slope of the ilmenite-perovskite transition in MnTiO₃ is different from the negative slopes in silicates and germanates. These thermochemical parameters are discussed in terms of crystal structure and lattice vibrations.     

Determination of the phase boundary between ilmenite and perovskite in MgSiO3 by in situ X-ray diffraction and quench experiments

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     

Phase boundary between ilmenite and perovskite structures in MnGeO3 determined by in situ X-ray diffraction measurements

In situ X-ray observations of the phase transition from ilmenite to perovskite structure in MnGeO₃ were carried out in a Kawai-type high-pressure apparatus interfaced with synchrotron radiation. The phase boundary between the ilmenite and perovskite structures in the temperature range of 700–1,400°C was determined to be P (GPa) = 16.5(±0.6) − 0.0034(±0.0006)T (°C) based on Anderson’s gold pressure scale. The Clapeyron slope, dP/dT, determined in this study is consistent with that for the transition boundary between the ilmenite and the perovskite structure in MgSiO₃.     

The transition of pyrope to perovskite

The stability field of Mg₃Al₂Si₃O₁₂-pyrope was examined for the first time under hydrostatic pressure conditions in a CO₂-laser heated diamond cell in the pressure range 21–30 GPa between 2300 and 3200 K. The phases were characterized using Raman and fluorescence spectroscopy. With increasing pressure pyrope transforms to an ilmenite phase above ∼21.5 GPa, to perovskite plus ilmenite above ∼24 GPa, and to perovskite above 29 GPa. The pressures of the first occurrence of perovskite in this study are about 2 GPa above the corresponding phase boundary between end-member MgSiO₃-ilmenite and perovskite. A small amount of Al₂O₃ coexists with perovskite up to 43 GPa, as evident from fluorescence spectra resembling those of ruby, but above 43 GPa the entire Al₂O₃ content of the pyrope starting material is accommodated in the perovskite structure. Received: 6 March 1997 / Revised, accepted: 23 July 1997     

High-pressure transitions and thermochemistry of MGeO3 (M=Mg, Zn and Sr) and Sr-silicates: systematics in enthalpies of formation of A2+B4+O3 perovskites

Phase transitions in MgGeO₃ and ZnGeO₃ were examined up to 26 GPa and 2,073 K to determine ilmenite–perovskite transition boundaries. In both systems, the perovskite phases were converted to lithium niobate structure on release of pressure. The ilmenite–perovskite boundaries have negative slopes and are expressed as P(GPa)=38.4–0.0082T(K) and P(GPa)=27.4−0.0032T(K), respectively, for MgGeO₃ and ZnGeO₃. Enthalpies of SrGeO₃ polymorphs were measured by high-temperature calorimetry. The enthalpies of SrGeO₃ pseudowollasonite–walstromite and walstromite–perovskite transitions at 298 K were determined to be 6.0±8.6 and 48.9±5.8 kJ/mol, respectively. The calculated transition boundaries of SrGeO₃, using the measured enthalpy data, were consistent with the boundaries determined by previous high-pressure experiments. Enthalpy of formation (ΔH _f°) of SrGeO₃ perovskite from the constituent oxides at 298 K was determined to be −73.6±5.6 kJ/mol by calorimetric measurements. Thermodynamic analysis of the ilmenite–perovskite transition boundaries in MgGeO₃ and ZnGeO₃ and the boundary of formation of SrSiO₃ perovskite provided transition enthalpies that were used to estimate enthalpies of formation of the perovskites. The ΔH _f° of MgGeO₃, ZnGeO₃ and SrSiO₃ perovskites from constituent oxides were 10.2±4.5, 33.8±7.2 and −3.0±2.2 kJ/mol, respectively. The present data on enthalpies of formation of the above high-pressure perovskites were combined with published data for A²⁺B⁴⁺O₃ perovskites stable at both atmospheric and high pressures to explore the relationship between ΔH _f° and ionic radii of eightfold coordinated A²⁺ (R _A) and sixfold coordinated B⁴⁺ (R _B) cations. The results show that enthalpy of formation of A²⁺B⁴⁺O₃ perovskite increases with decreasing R _A and R _B. The relationship between the enthalpy of formation and tolerance factor ( R _o: O²⁻ radius) is not straightforward; however, a linear relationship was found between the enthalpy of formation and the sum of squares of deviations of A²⁺ and B⁴⁺ radii from ideal sizes in the perovskite structure. A diagram showing enthalpy of formation of perovskite as a function of A²⁺ and B⁴⁺ radii indicates a systematic change with equienthalpy curves. These relationships of ΔH _f° with R _A and R _B can be used to estimate enthalpies of formation of perovskites, which have not yet been synthesized.     

Unquenchable high-pressure perovskite polymorphs of MnSnO3 and FeTiO3

New high-pressure orthorhombic (GdFeO₃-type) perovskite polymorphs of MnSnO₃ and FeTiO₃ have been observed using in situ powder X-ray diffraction in a diamond-anvil cell with synchrotron radiation. The materials are produced by the compression of the lithium niobate polymorphs of MnSnO₃ and FeTiO₃ at room temperature. The lithium niobate to perovskite transition occurs reversibly at 7 GPa in MnSnO₃, with a volume change of -1.5%, and at 16 GPa in FeTiO₃, with a volume change of -2.8%. Both transitions show hysteresis at room temperature. For MnSnO₃ perovskite at 7.35 (8) GPa, the orthorhombic cell parameters are a=5.301 (2) A, b=5.445 (2) Å, c=7.690 (8) Å and V= 221.99 (15) ų. Volume compression data were collected between 7 and 20 GPa. The bulk modulus calculated from the compression data is 257 (18) GPa in this pressure region. For FeTiO₃ perovskite at 18.0 (5) GPa, cell parameters are a=5.022 (6) Å, b=5.169 (5) Å, c=7.239 (9) Å and V= 187.94 (36) ų. Based on published data on the quench phases, the FeTiO₃ perovskite breaks down to a rocksalt + baddelyite mixture of FeO and TiO₂ at 23 GPa. This is the first experimental verification of the pressure-induced breakdown of a perovskite to simple oxides.     

Calorimetric study of high-pressure phase transitions among the CdGeO3 polymorphs (pyroxenoid,garnet, ilmenite,and perovskite structures)

At high pressures, CdGeO₃ pyroxenoid transforms to garnet, then to ilmenite, and finally to perovskite. Enthalpies of transition among the four phases were measured by high temperature calorimetry. The entropies of transition and slopes of the boundaries were calculated using the measured enthalpies and free energies calculated from the phase equilibrium data. Pyroxenoid and garnet are very similar energetically. However garnet is a high pressure phase because of its lower entropy and smaller volume. The pyroxenoid-garnet transition has a small positiveP-T slope. Ilmenite is intermediate in enthalpy between garnet and perovskite, but is lower in entropy than both phases. Therefore the garnet-ilmenite transition has a positivedP/dT, while a negativedP/dT is calculated for the ilmenite-perovskite transition. The thermochemical data for the CdGeO₃ phases are generally consistent with the observed high pressure phase relations. The high entropy of perovskite relative to ilmenite, observed in several ABO₃ comounds including CdGeO₃, is related to the structural features of perovskite, in which relatively small divalent cations occupy the large sites of 8–12 fold coordination. The thermochemistry of the CdGeO₃ polymorphs shows several similarities to that of the CaGeO₃ system.     

Structural evolution of rutile-type and CaCl2-type germanium dioxide at high pressure

 Germanium dioxide was found to undergo a transition from the tetragonal rutile-type to the orthorhombic CaCl₂-type phase above 25 GPa. The detailed structural evolution of both phases at high pressure in a diamond anvil cell has been investigated by Rietveld refinement using angle-dispersive, X-ray powder-diffraction data. The square of the spontaneous strain (a−b)/(a+b) in the orthorhombic phase was found to be a linear function of pressure and no discontinuities in the cell constants and volume were observed, indicating that the transition is second-order and proper ferroelastic. Compression of the GeO₆ octahedra was found to be anisotropic, with the apical Ge-O distances decreasing to a greater extent than the equatorial distances and becoming shorter than the latter above 7 GPa. Above this pressure, the GeO₆ octahedron exhibits the common type of tetragonal distortion predicted by a simple ionic model and observed for most rutile-type structures such as those of the heavier group-14 dioxides and the metal difluorides. Above the phase transition, the columns of edge-sharing octahedra tilt about their two fold axes parallel to c and the rotation angle reaches 10.2(5)° by 36(1) GPa so as to yield a hexagonal close-packed oxygen sublattice. The compressibility increases at the phase change as is expected for a second-order transition at which an additional compression mechanism becomes available.     

A new phase transition in MnTiO3: LiNbO3-perovskite structure

The stable polymorph of MnTiO₃ at room temperature and pressure has the ilmenite structure. At high temperatures and pressures, MnTiO₃ ilmenite transforms to a LiNbO₃ structure through a cation reordering process (Ko and Prewitt 1988). Single crystals of both phases have been studied with X-ray diffraction to 5.0 GPa. We have obtained the first experimental verification of the close relationship between the LiNbO₃ and perovskite structures, first postulated by Megaw (1968). MnTiO₃ with the LiNbO₃ structure (MnTiO₃ II) transforms directly to an orthorhombic perovskite structure (MnTiO₃ III) between 2.0 and 3.0 GPa. The transition involves a change of volume of -5%, is reversible and has pronounced hysteresis. Only pressure is required to drive the transition because it involves no breaking of bonds; it simply involves rotation of the [TiO₆] octahedra about their triad axes accompanied by displacement of the Mn cations to the distorted twelve-coordinated sites formed by the rotations. An unusual aspect of this transition is that twinned MnTiO₃ II crystals transform to untwinned MnTiO₃ III crystals with increasing pressure. The twin plane of MnTiO₃ II, , corresponds to the (001) mirror plane of the orthorhombic perovskite structure. MnTiO₃ III examined at 4.5 GPa is very distorted from the ideal cubic perovskite structure. The O(2)-O(2)-O(2) angle describing the tilting in the ab plane is 133.3(7)°, in contrast to 180° for a cubic perovskite and the O(2)-O(2)-O(2) angle describing the tilting in the ac plane is 109.3(4)°, as opposed to 90° in a cubic perovskite.     

CdGeO3-phase transformations at high pressure and temperature and structural refinement of the perovskite polymorph

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.     

High-pressure phase behavior of MnTiO<Subscript>3</Subscript>: decomposition of perovskite into MnO and MnTi<Subscript>2</Subscript>O<Subscript>5</Subscript>

The phase relations and compression behavior of MnTiO₃ perovskite were examined using a laser-heated diamond-anvil cell, X-ray diffraction, and analytical transmission electron microscopy. The results show that MnTiO₃ perovskite becomes unstable and decomposes into MnO and orthorhombic MnTi₂O₅ phases at above 38 GPa and high temperature. This is the first example of ABO₃ perovskite decomposing into AO + AB₂O₅ phases at high pressure. The compression behavior of volume, axes, and the tilting angle of TiO₆ octahedron of MnTiO₃ perovskite are consistent with those of other A²⁺B⁴⁺O₃ perovskites, although no such decomposition was observed in other perovskites. FeTiO₃ is also known to decompose into two phases, instead of transforming into the CaIrO₃-type post-perovskite phase and we argue that one of the reasons for the peculiar behavior of titanate is the weak covalency of the Ti–O chemical bonds.     

Tilting and distortion of CaSnO<Subscript>3</Subscript> perovskite to 7 GPa determined from single-crystal X-ray diffraction

The structural changes of CaSnO₃, a GdFeO₃-type perovskite, have been investigated to 7 GPa in a diamond-anvil cell at room temperature using single-crystal X-ray diffraction. Significant changes are observed in both the octahedral Sn–O bond lengths and tilt angles between the SnO6 octahedra. The octahedral (SnO6) site shows anisotropic compression and consequently the distortion of SnO6 increases with pressure. Increased pressure also results in a decrease of both of the inter-octahedral angles, Sn–O1–Sn and Sn–O2–Sn, indicating that octahedral tilting increases with increasing pressure, chiefly equivalent to rotation of the SnO6 octahedra about the pseudocubic <001>_p axis. The distortion in the CaO12 and SnO6 sites, along with the octahedral SnO6 tilting, is attributed to the SnO6 site being less compressible than the CaO12 site.Acknowledgments The authors acknowledge with gratitude the financial support for this work from NSF grant EAR-0105864. Ruby pressure measurements were conducted with the Raman system in the Vibrational Spectroscopy Laboratory in the Department of Geosciences at Virginia Tech with the help of Mr. Charles Farley.     

Pressure dependence of electrical conductivity of (Mg,Fe)SiO<Subscript>3</Subscript> ilmenite

The electrical conductivity of (Mg_0.93Fe_0.07)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 (Mg_0.93Fe_0.07)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.     

Computational model of the structural and elastic properties of the ilmenite and perovskite phases of MgSiO3

The structural and elastic properties of the ilmenite and perovskite phases of MgSiO₃ are investigated with a computational model based on energy minimization. The potential energies of these two crystals are approximated by the sum of Coulomb, van der Waals, and repulsion terms between atoms. Required energy parameters are derived by fitting the parameters to the observed crystal structures of these two phases as well as to the measured elastic constants of the ilmenite phase. The resulting potential model is applied to predicting the elastic constants of the perovskite phase. The calculated bulk modulus of the perovskite phase compares favorably with the data obtained from volume-compression experiments as well as the values estimated from empirical elasticity systematics of perovskite type compounds. The predicted shear modulus of the perovskite phase is also in reasonable agreement with the values proposed from similar empirical elasticity systematics. Subsequently, the model is used to simulate the high pressure behaviors of the crystal structures and elastic constants of these two phases.     

High-pressure phase transitions of CaRhO<Subscript>3</Subscript> perovskite

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.     

High-pressure behavior of MnGeO3 and CdGeO3 perovskites and the post-perovskite phase transition

The stability and high-pressure behavior of perovskite structure in MnGeO₃ and CdGeO₃ were examined on the basis of in situ synchrotron X-ray diffraction measurements at high pressure and temperature in a laser-heated diamond-anvil cell. Results demonstrate that the structural distortion of orthorhombic MnGeO₃ perovskite is enhanced with increasing pressure and it undergoes phase transition to a CaIrO₃-type post-perovskite structure above 60 GPa at 1,800 K. A molar volume of the post-perovskite phase is smaller by 1.6% than that of perovskite at equivalent pressure. In contrast, the structure of CdGeO₃ perovskite becomes less distorted from the ideal cubic perovskite structure with increasing pressure, and it is stable even at 110 GPa and 2,000 K. These results suggest that the phase transition to post-perovskite is induced by a large distortion of perovskite structure with increasing pressure.     

High-pressure transformations in silicates,germanates, and titanates with ABO3 stoichiometry

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.