The ZnSiO3 clinopyroxene-ilmenite transition: Heat capacity,enthalpy of transition,and phase equilibria

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,

Heat capacity calculations for Al2O3 corundum and MgSiO3 ilmenite

We have used Kieffer's vibrational model to calculate heat capacities and entropies for Al₂O₃ corundum and MgSiO₃ ilmenite, using available vibrational and elastic data for these phases. The calculated heat capacity for corundum is within 1–2 percent of the experimental values between 100 K and 1,800 K, while that for MgSiO₃ ilmenite is within 1–2 percent of the experimental data between 350 K and 500 K. We have calculated the heat capacity for MgSiO₃ ilmenite from 50 K to 1,800 K, which extends the range of available heat capacity data for this phase. The results of this calculation suggest that there may be differences in the vibrational properties of corundum and MgSiO₃ ilmenite. Finally, we have used the results of our calculation to obtain a transition entropy of near -18.8 J/mol.K for the MgSiO₃ pyroxene-ilmenite reaction.     

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.     

Formation of a solid solution in the MgSiO3–MnSiO3 perovskite system

Experiments using laser-heated diamond anvil cells combined with synchrotron X-ray diffraction and SEM–EDS chemical analyses have confirmed the existence of a complete solid solution in the MgSiO₃–MnSiO₃ perovskite system at high pressure and high temperature. The (Mg, Mn)SiO₃ perovskite produced is orthorhombic, and a linear relationship between the unit cell parameters of this perovskite and the proportion of MnSiO₃ components incorporated seems to obey Vegard’s rule at about 50 GPa. The orthorhombic distortion, judged from the axial ratios of a/b and \( \sqrt{2}\,a/c, \) monotonically decreases from MgSiO₃ to MnSiO₃ perovskite at about 50 GPa. The orthorhombic distortion in (Mg_0.5, Mn_0.5)SiO₃ perovskite is almost unchanged with increasing pressure from 30 to 50 GPa. On the other hand, that distortion in (Mg_0.9, Mn_0.1)SiO₃ perovskite increases with pressure. (Mg, Mn)SiO₃ perovskite incorporating less than 10 mol% of MnSiO₃ component is quenchable. A value of the bulk modulus of 256(2) GPa with a fixed first pressure derivative of four is obtained for (Mg_0.9, Mn_0.1)SiO₃. MnSiO₃ is the first chemical component confirmed to form a complete solid solution with MgSiO₃ perovskite at the P–T conditions present in the lower mantle.     

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.     

The Eocene corundum-bearing rocks in the Gangdese arc,south Tibet:Implications for tectonic evolution of the Himalayan orogen

The genesis of Liangguo corundum deposit in the southern Gangdese magmatic arc, east-central Himalaya, remains unknown. The present study shows that the corundum-bearing rocks occur as lenses with variable sizes in the Eocene gabbro that intruded into marble. These corundum-bearing rocks have highly variable mineral assemblage and mode. The corundum-rich rocks are characterized by containing abundant corundum, and minor spinel, ilmenite and magnetite, whereas the corundum-poor and corundum-free rocks have variable contents of spinel, plagioclase, sillimanite, cordierite, ilmenite and magnetite. The host gabbro shows variable degrees of hydration and carbonization. The corundum grains are mostly black, and rarely blue, and have minor Fe O and TiO_2. The spinel is hercynite, with high Fe O and low Mg O contents. The corundum-bearing rocks have variable but high Al_2O_3, FeO and TiO_2, and low SiO_2 contents. Inherited magmatic and altered zircons of the corundum-bearing rocks have similar U e Pb ages(~47 Ma) to the magmatic zircons of the host gabbro, indicating corundum-bearing rock formation immediately after the gabbro intrusion. We considered that emplacement of gabbro induced the contact metamorphism of the country-rock marble and the formation of silica-poor fluid. The channeled infiltration of generated fluid in turn resulted in the hydrothermal metasomatism of the gabbro, which characterized by considerable loss of Si from the gabbro and strong residual enrichment of Al. The metasomatic alteration probably formed under Pe T conditions of ~2.2 -2.8 kbar and ~650 -700℃. We speculate that SiO_2, CaO and Na_2O were mobile, and Al_2O_3, FeO, TiO_2 and high field strength elements remained immobile during the metasomatic process of the gabbro. The Liangguo corundum deposit, together with metamorphic corundum deposits in Central and Southeast Asia, were related to the Cenozoic Himalayan orogeny, and therefore are plate tectonic indicators.     

Hydrostatic compression of ilmenite phase of ZnSiO3 and MgGeO3

Accurate measurements of cell parameters were performed on the ilmenite phases of ZnSiO₃ and MgGeO₃ using an X-ray diffraction method under hydrostatic conditions. The linear changes in cell parameter are represented by 1?a/a ₀=(1.06±0.04)×10^?4 P(kbar) and 1?c/c ₀=(2.11±0.04)×10^?4 P for ZnSiO₃, and 1?a/a ₀=(1.37±0.03)×10^?4 P and 1?c/c ₀=(2.05±0.04)×10^?4 P for MgGeO₃. A least-squares calculation using the first-order Birch-Murnaghan equation gives K _T =2.16±0.02 Mbar and K _T =1.87±0.02 Mbar for ZnSiO₃ and MgGeO₃, respectively. Elastic systematics assuming K _T V _m =constant give a predicted value K _T =2.14 Mbar for the ilmenite phase of MgSiO₃.     

High-pressure decomposition of MCr2O4 spinels (M=Mg, Mn, Zn) by ab initio methods

The high-pressure equation of state of the normal spinels MgCr₂O₄ (picrochromite), MnCr₂O₄ and ZnCr₂O₄, and their reaction of decomposition into Cr₂O₃ (eskolaite) and MO (rocksalt-type) component oxides, were investigated by periodic unrestricted Hartree-Fock calculations. All-electron basis sets, and an a posteriori correction for the electron correlation energy, based on Density-Functional-Theory, were employed. Interpolation of results by the P-V Murnaghan equation of state yielded the equilibrium volume and energy, and the bulk modulus and its pressure derivative, for each of the seven phases (three spinels, three rocksalt oxides and eskolaite) considered. The simulated behaviour of interatomic distances vs pressure shows similar compressibilities of M-O bonds in both octahedral and tetrahedral coordinations. Binding energies and formation enthalpies of spinels from oxides are also computed and compared to available experimental data. The predicted decomposition pressures of Mg, Mn and Zn chromium spinels are 19, 23 and 34 GPa, respectively. The greater stability of ZnCr₂O₄ is related to Zn²⁺ being better suited to tetrahedral coordination than the other M²⁺ cations. Such results are strongly supported by the excellent agreement previously obtained between simulated (11 GPa) and experimental (13 GPa) pressures of the decomposition of MgAl₂O₄ spinel into corundum and periclase. Received: 9 February 1998 / Accepted: 12 October 1998     

Crystallization of titaniferous chromite,magnesian ilmenite and armalcolite in tholeiitic suites in the Karoo Igneous Province

Titaniferous chromite (up to 8 wt% TiO₂) and magnesian ilmenite (up to 10 wt% MgO) coexist at the base of the differentiated tholeiitic Mount Ayliff Intrusion in the Karoo Province of southern Africa, suggesting that the original magma was TiO₂-rich. Picritic lavas with 3% TiO₂ from the Lebombo monocline of the Karoo Province also contain microphenocrysts of magnesian ilmenite (up to 6 wt% mgO) and armalcolite (up to 7 wt% MgO). These oxide mineral associations and compositions are atypical of tholeiitic magmas, in which chromite usually has less than 1 wt% TiO₂, ilmenite less than 3 wt% MgO and armalcolite is rarely a primary mineral. Experiments have been conducted at one atmosphere pressure on a range of compositions to determine the effect of TiO₂ on the crystallization and composition of chromite, ilmenite and armalcolite. The results indicate that increasing the TiO₂ content of picritic magmas increases the TiO₂ content of the spinel, mainly at the expense of Al₂O₃, whereas Cr₂O₃ is not affected. Spinel compositions in the Mount Ayliff Intrusion (with over 45 wt% Cr₂O₃, less than 10 wt% Al₂O₃ and 8 wt% TiO₂) were duplicated in experiments on a picrite at temperatures of about 1,200°C at the Ni/NiO buffer. Increasing fO₂ from fayalite-magnetite-quartz to Ni/NiO buffer is shown to increase the crystallization temperature of armalcolite and to decrease that of ilmenite. The total FeO content of the liquid has little influence on the crystallization temperature of these phases. The TiO₂ content of the liquid, when either ilmenite or armalcolite crystallizes, varies inversely with SiO₂ content. The MgO content of the liquid at which ilmenite or armalcolite crystallizes depends upon the TiO₂ content of the starting composition, with naturally occurring and experimetally determined saturation being demonstrated for liquids with 5 wt% MgO and 5.5 wt% TiO₂. The partition coefficent for MgO between armalcolite or ilmenite and liquid is about 1.5. Observed magnesian armalcolite and ilmenite compositions in picrite lavas (both minerals) and in the Mount Ayliff Intrusion (ilmenite only) are consistent with crystallization from a TiO₂-rich magma with approximately 5 wt% MgO. The Fe ₂ ³⁺ TiO₅ component of armalcolite in the picrite lavas matches those formed experimentally at temperatures of 1,150–1,110°C and fO₂ of the Ni/NiO to Ni/NiO+1 log unit. Similarities also exist between the compositions of chromite, ilmenite and armalcolite and liquid fraction-ation trends of some Hawaiian high-TiO₂ lavas and the experimental studies presented here.     

Interaction of Titanium Minerals and Their Melts with Diamond-Forming Media (Experiments at 7–8 GPa)

Melting relations in the multicomponent diamond-forming systems of the upper mantle with a boundary of K–Na–Mg–Fe–Ca carbonate, phases of the model peridotite and eclogite, carbon, and titanium minerals from kimberlite (ilmenite FeTiO₃, perovskite CaTiO₃, and rutile TiO₂) were studied experimentally at 7–8 GPa and 1600–1650°C. Perovskite reacts with the formation of rutile in the diamond-forming silicate–carbonate melts. We discovered liquid immiscibility between melts of titanium minerals, on the one hand, and carbonate–carbon, peridotite–carbonate–carbon, and eclogite–carbonate–carbon diamond-forming melts, on the other. The solubility of titanium mineral in diamond-forming melts is negligible independent of their concentration in the experimental systems. Growth melts retain high diamond-forming efficiency. In general, the experimental results are evident for the xenogenic nature of titanium minerals in inclusions in diamond and, therefore, in diamond-forming melts. It is shown that the physicochemical factors that may correlate the diamond content with the concentration of Ti in kimberlite do not occur during the diamond genesis in silicate–carbonate–carbon parental melts containing titanium minerals and their melts.     

Structure, thermodynamic and transport properties of liquid MgSiO3: Comparison of molecular models and laboratory results

Liquid MgSiO₃ is a model for the Earth’s magma ocean and of remnant melt present near the core-mantle boundary. Here, models for molten MgSiO₃ are computed employing empirical potential molecular dynamics (EPMD) and results are compared to published results including two EPMD studies and three first-principles molecular dynamics (FPMD) models and to laboratory data. The EPMD results derived from the Oganov (OG) potential come closest to the density of MgSiO₃ liquid at the 1-bar melting point inferred from the melting curve. At higher P, EPMD densities calculated from the OG potential and FPMD broadly match shock wave studies, with the OG potential yielding the better comparison. Matsui (M) potential results deviate from other studies above ∼50 GPa. Overall, results based on the OG potential compare best to experimental densities over the P-T range of the mantle. Isothermally, upon increasing P the mean coordination numbers () of oxygen around Si and Mg monotonically increase with pressure. Tetrahedral Si and octahedral Si monotonically increase and decrease, respectively, whereas pentahedral Si maximizes at 10-20 GPa. Tetrahedral Mg decreases monotonically as P increases whereas pentahedral, octahedral and higher coordination polyhedra each show similar behavior first increasing and then decreasing after attaining a maximum; the P of the maximum for each polyhedra type migrates to higher P as the CN increases. Free oxygen and oxygen with one nearest neighbor of either Si or Mg decreases whereas Si or Mg with two or three nearest oxygens (i.e., tricluster oxygen) increases with increasing P isothermally. The increase of tricluster oxygen is consistent with spectroscopy on MgSiO₃ glass quenched from 2000 K and 0-40 GPa and high-energy X-ray studies constraining the coordination of O around Mg and around Si at 2300 K and 1 bar. Coordination statistics from FPMD studies for O around Si and Si around O are in agreement with the EPMD results based on the M and OG potentials. Mg self-diffusivity is greater than O and Si self-diffusivities for both the M and OG potentials. All D values monotonically decrease with increasing pressure isothermally and all atoms are more diffusive in the M liquid compared to the OG liquid except at T > ∼5000 K and P > 100 GPa. Previously published EPMD diffusivities fall between values given by the M and OG potentials, at least up to 45 GPa. The M liquid is generally less viscous than the OG liquid except at P > ∼80 GPa. Activation energy and volume are around 96 kJ/mol and 1.5 cm³/mol, respectively. The FPMD viscosity results at 120 GPa and 4000 and 4500 K are essentially identical to the values from the M and OG potentials. FPMD viscosity results are similar to the OG results for P < 60 GPa; at higher P, the FPMD viscosities are higher. At 4000 K and 100 GPa the shear viscosity of liquid MgSiO₃ is ∼0.1 Pa s. More extensive laboratory results are required to better define the thermodynamic, transport and structural properties of MgSiO₃ liquids and for comparison with computational studies.     

Effects of mineralogical and textural characteristics of ilmenite concentrate on synthetic rutile production

The effect of mineralogy and texture of Qara-aghaj ilmenite concentrate on titanium dioxide prepared via reduction-slagging acid leaching process as a raw material in chloride route was investigated. The concentrate contains 44.5 % TiO₂ and its content in ilmenite lattice varies from 41.6–48 %. Hematite exsolved lamellae inside ilmenite which affect the reduction process positively are host of the most of the Cr and V as pigment colorizer metals. Apatite fine inclusions inside ilmenite as the source of Ca and P could have negative effects on synthetic rutile. Spinel ultrafine particles inside ilmenite containing Al and Si could also affect the synthetic rutile negatively. The other important elements which have been substituted in ilmenite lattice are Mg and Mn. The prepared titanium dioxide concentrate containing 91 % TiO₂ and 0.6 % Fe₂O₃ is mainly formed by rutile and small amount of anatase and Ti₂O₃ phases. The solid solution of rutile inside Ti₂O₃ was also observed. The content of Cr, V, Mn, and Al are decreased to permissible amount during slagging and leaching process while the quantity of other impurities such as Mg, Si, and Ca are relatively high in the product, and they cause some difficulties in pigment production via chloride route. The Mg and Ca sourced from ilmenite lattice and apatite inclusions, respectively, can affect the precipitation process. So, it is predicted that Qara-aghaj ilmenite concentrate will be suitable for sulfate route, but it is necessary to investigate comprehensively.     

MgSiO3 ilmenite: Heat capacity,thermal expansivity,and enthalpy of transformation

A new determination, using high temperature drop-solution calorimetry, of the enthalpy of transformation of MgSiO₃ pyroxene to ilmenite gives H ₂₉₈ = 59.03 ±4.26 kJ/mol. The heat capacity of the ilmenite and orthopyroxene phases has been measured by differential scanning calorimetry at 170–700 K; C_p of MgSiO₃ ilmenite is 4–10 percent less than that of MgSiO₃ pyroxene throughout the range studied. The heat capacity differences are consistent with lattice vibrational models proposed by McMillan and Ross (1987) and suggest an entropy change of -18 ± 3 J-K^-1 ·mol^-1, approximately independent of temperature, for the pyroxene-ilmenite transition. The unit cell parameters of MgSiO₃ ilmenite were measured at 298–876 K and yield an average volume thermal expansion coefficient of 2.44 × 10^-5 K^-1. The thermochemical data are used to calculate phase relations involving pyroxene, -Mg₂SiO₄ plus stishovite, Mg₂SiO₄ spinel plus stishovite, and ilmenite in good agreement with the results of high pressure studies.     

Electron density distribution of FeTiO<Subscript>3</Subscript> ilmenite under high pressure analyzed by MEM using single crystal diffraction intensities

Many of ilmenites ABO₃ compounds bearing transition elements have semiconductive, ferroelectric and antiferromagnetic properties. The high-pressure diffraction studies of FeTiO₃ have been conducted up to 8.2 GPa using synchrotron radiation in KEK at Tsukuba with diamond anvil cell. The compression mechanism of FeTiO₃ ilmenite has been investigated by the structure refinements converged to the reliable factors R = 0.05. The deformations of the FeO₆ and TiO₆ octahedra were reduced with increasing pressure. In order to elucidate the electric conductivity change with pressure, electron density distribution of ilmenite have been executed by maximum entropy method (MEM) using single-crystal diffraction intensity data. MEM based on F _obs(hkl) of FeTiO₃ clearly shows electron density in comparison with the difference Fourier synthesis based on F _obs(hkl) − F _calc(hkl). The radial distribution of the electron density indicates electron localization around the cation positions. The bonding electron density found in bond Fe–O and Ti–O is lowered with pressure. The isotropic temperature factors B _iso become smaller with increasing pressure. Nevertheless the thermal vibration is considerably restrained by the compression, the electric conductivity is enhanced with pressure. Neither charge transfer nor electron hopping between Fe and Ti along the c axis in FeTiO₃ is plausible under high pressure. But the electric conductivity due to electron super-exchange in Fe–Fe and Ti–Ti has been clarified by the MEM electron density distribution. The anisotropy in the electric conductivity has been clarified.     

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.     

Displacive phase transitions in C-centred clinopyroxenes: spodumene, LiScSi2O6 and ZnSiO3

The clinopyroxenes spodumene (LiAlSi₂O₆), LiScSi₂O₆ and ZnSiO₃, all with space group C2/c at ambient conditions, were studied under high pressures by single-crystal X-ray diffraction in a diamond-anvil cell. Changes in the evolution of the unit-cell parameters, optical properties and the appearance of h + k odd reflections characteristic of a primitive lattice, indicate that all three pyroxenes undergo phase transitions. The transitions are mostly displacive in character, and are non-quenchable. Transition pressures are 3.19 GPa in spodumene, ∼0.6 GPa in LiScSi₂O₆ and 1.92 GPa in ZnSiO₃. The space group of all three high-pressure phases was determined to be P2₁/c by structure refinement to single-crystal X-ray intensity data collected in the DAC. In the ZnSiO₃ clinopyroxene the intermediate P2₁/c phase further transforms to a second C2/c phase (HP-C2/c) at 4.9 GPa (confirmed by structure refinement). The volume change at this transition is about 2.6%, three times larger than in the first phase transition, and typical of the P2₁/c→ HP-C2/c phase transitions found previously in MgSiO₃, FeSiO₃, etc. These results therefore provide the first direct evidence that the HP-C2/c and the HT-C2/c structures of pyroxenes are distinct polymorphs with the same space group. The phase transition from C2/c to P2₁/c symmetry in spodumene and LiScSi₂O₆ therefore occurs because the polymorphs stable at ambient conditions are isotypic to the high-temperature C2/c phases of clinopyroxenes such as pigeonite and clinoenstatite. Received: 22 December 1999 / Accepted: 7 June 2000     

Chromium solubility in MgSiO3 ilmenite at high pressure

The crystal structure and chemical composition of crystals of (Mg_1?x Cr _x )(Si_1?x Cr _x )O₃ ilmenite (with x = 0.015, 0.023 and 0.038) synthesized in the model system Mg₃Cr₂Si₃O₁₂–Mg₄Si₄O₁₂ at 18–19 GPa and 1,600 °C have been investigated. Chromium was found as substitute for both Mg at the octahedral X site and Si at the octahedral Y site, according to the reaction Mg²⁺ + Si⁴⁺ = 2Cr³⁺. Such substitutions cause a shortening of the <X–O> and a lengthening of the <Y–O> distances with respect to the values typically observed for pure MgSiO₃ ilmenite and eskolaite Cr₂O₃. Although no high Cr contents are considered in the pyrolite model, Cr-bearing ilmenite may be the host for chromium in the Earth’s transition zone. The successful synthesis of ilmenite with high Cr contents and its structural characterization are of key importance because the study of its thermodynamic constants combined with the data on phase relations in the lower-mantle systems can help in the understanding of the seismic velocity and density profiles of the transition zone and the constraining composition and mineralogy of pyrolite in this area of the Earth.     

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.     

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     

Rhombohedral ilmenite group nickel titanates with Zn, Mg, and Mn: synthesis and crystal structures

Binary, ternary, and quaternary rhombohedral ordered titanates, Ni_1/2Mn_1/2TiO₃, Ni_1/2Mg_1/2TiO₃, Ni_1/3Zn_1/3Mg_1/3TiO₃, and Ni_1/4Zn_1/4Mg_1/4Mn_1/4TiO₃, were obtained by solid-state synthesis at 1095°C at ambient pressure in a nitrogen atmosphere. All of the compounds adopt ATiO₃ (A = Ni, Mn, Zn, and Mg) stoichiometry. Crystal structures were refined by the Rietveld method from powder X-ray diffraction data. Unit cell parameters and unit cell volumes decrease with decreasing average radius of the ^vi A ²⁺ cation. All the synthetic titanates adopt the space group and the ilmenite structure consisting of distorted AO₆ and TiO₆ octahedra. The divalent cations and Ti⁴⁺ are distributed in layers of octahedra alternating along c with no evidence for disorder. In common with pyrophanite, NiTiO₃, and ilmenite sensu stricto, the distortion of the AO₆ octahedra is less than that of the TiO₆ octahedra. The Ti⁴⁺ and A-site cations in the titanates are off-centred within the coordination polyhedra. Deviation of the z positional parameters from their theoretical values for the A and Ti atoms indicate that in the titanates with the larger A ²⁺ cations and Goldschmidt tolerance factors, t ≥ 0.745, the AO₆ octahedral layer is more “puckered” above and below planes parallel to (001) than that of the TiO₆ octahedra, and vice versa in the titanates with smaller R _A ²⁺ for which t≤0.745. Data are given for the volumes and distortion indices of all the coordination polyhedra. This study confirms the existence and stability of complex solid solutions between ordered rhombohedral titanates of Ni and first-row transition metals at ambient conditions over a range of t from 0.786 to 0.737. These experimental data suggest that the formation of ilmenite-type titanates enriched in Ni is possible in exotic mineral-forming systems at low pressure and/or in extraterrestrial rocks.