Polymorphic phase transition in Superhydrous Phase B

We synthesized superhydrous phase B (shy-B) at 22 GPa and two different temperatures: 1200°C (LT) and 1400°C (HT) using a multi-anvil apparatus. The samples were investigated by transmission electron microscopy (TEM), single crystal X-ray diffraction, Raman and IR spectroscopy. The IR spectra were collected on polycrystalline thin-films and single crystals using synchrotron radiation, as well as a conventional IR source at ambient conditions and in situ at various pressures (up to 15 GPa) and temperatures (down to −180°C). Our studies show that shy-B exists in two polymorphic forms. As expected from crystal chemistry, the LT polymorph crystallizes in a lower symmetry space group (Pnn2), whereas the HT polymorph assumes a higher symmetry space group (Pnnm). TEM shows that both modifications consist of nearly perfect crystals with almost no lattice defects or inclusions of additional phases. IR spectra taken on polycrystalline thin films exhibit just one symmetric OH band and 29 lattice modes for the HT polymorph in contrast to two intense but asymmetric OH stretching bands and at least 48 lattice modes for the LT sample. The IR spectra differ not only in the number of bands, but also in the response of the bands to changes in pressure. The pressure derivatives for the IR bands are higher for the HT polymorph indicating that the high symmetry form is more compressible than the low symmetry form. Polarized, low-temperature single-crystal IR spectra indicate that in the LT-polymorph extensive ordering occurs not only at the Mg sites but also at the hydrogen sites.     

Phase transition in Ca-poor clinopyroxenes

High(C2/c)-low(P2₁/c) phase transition in clinoenstatite and pigeonite was successfully observed in situ at high temperatures for the first time under a transmission electron microscope. The phase transition was revealed to possess the characteristics of a first-order transition, due to the coexistence of both phases separated by the sharp interfaces and the nucleation-growth process. The diffusionless and time-independent reaction suggests that the transition occurs athermal-martensitically. Furthermore, the small or even negative thermal hysteresis and the interface motion suggest that the transition is not a typical type but a thermoelastic type of the martensitic transformation. This type of the transformation, studied extensively in metallurgy in relation to shape memory effect, is first recognized in rock-forming minerals.     

Phase transitions in leucite: Dielectric properties and transition mechanism

To investigate the mechanisms for the cubic-tetragonal phase transition in leucite (KAlSi₂O₆), the frequency dependence of the dielectric constant (), and of the electric conductivity (), have been measured as a function of temperature. The dielectric loss function, tan , contains two main features: (i) a classical Debye peak, with activation energy of 0.77 eV, ascribed to hopping of K-atoms between their channel (W) sites, via the vacant side-channel (S) sites; (ii) a heavily-overdamped relaxational mode which softens when the crystal is cooled towards the phase transition temperature. The latter relaxational mode shows a critical behaviour, and is thus directly correlated with the transition mechanism. As it is only the potassium ions that could relax at frequencies well below the optical phonon branches, it appears that their movement is relaxational (i.e. heavily overdamped) rather than phonon-like. At temperatures above the transition point, the relaxation of K⁺ in an electric field is analysed in terms of collective motions within tetragonal domains. Direct evidence for the existence of such domains follows from the presence of diffuse intensity in single-crystal X-ray diffraction experiments.     

High-pressure isosymmetrical phase transition in calaverite

Using density functional theory, we perform ab initio calculations of the behaviour of calaverite, AuTe₂, at high pressures. Calaverite has a distorted CdI₂ structure, that presents a pronounced two-dimensional character and a rather anisotropic response to pressure. Increasing the pressure, we predict an isosymmetrical phase transition between 55 and 60 GPa, that is accompanied by an important distortion of the structure, observed in all its geometrical parameters, especially the c lattice parameter. Relaxing the pressure, the reverse phase transition is observed between 30 and 25 GPa.     

Dynamic character of the primitive to body-centered phase transition in anorthite

We show from elastic neutron diffraction data that anorthite CaAl₂Si₂O₈ (An₁₀₀) undergoes a primitive to body-centered phase transition at T _c =237±1°C. The transition is reversible, and T _c is well defined. Our measurements demonstrate that the I-lattice at the high temperature phase applies to all structural elements; in other words, the time-averaged lattice is exactly body-centered and not just in the space average of An₁₀₀, as concluded earlier by other authors.     

Pressure-induced phase transition in synthetic trioctahedral Rb-mica

 The crystal structure of a synthetic Rb analog of tetra-ferri-annite (Rb–TFA) 1M with the composition Rb_0.99Fe²⁺ _3.03(Fe³⁺ _1.04 Si_2.96)O_10.0(OH)_2.0 was determined by the single-crystal X-ray diffraction method. The structure is homooctahedral (space group C2/m) with M1 and M2 occupied by divalent iron. Its unit cell is larger than that of the common potassium trioctahedral mica, and similar lateral dimensions of the tetrahedral and octahedral sheets allow a small tetrahedral rotation angle α=2.23(6)°. Structure refinements at 0.0001, 1.76, 2.81, 4.75, and 7.2 GPa indicate that in some respects the Rb–TFA behaves like all other micas when pressure increases: the octahedra are more compressible than the tetrahedra and the interlayer is four times more compressible than the 2:1 layer. However, there is a peculiar behavior of the tetrahedral rotation angle α: at lower pressures (0.0001, 1.76, 2.81 GPa), it has positive values that increase with pressure [from 2.23(6)° to 6.3(4)°] as in other micas, but negative values −7.5(5)° and −8.5(9)° appear at higher pressures, 4.75 and 7.2 GPa, respectively. This structural evidence, together with electrostatic energy calculations, shows that Rb–TFA has a Franzini A-type 2:1 layer up to at least 2.81 GPa that at higher pressure yields to a Franzini B-type layer, as shown by the refinements at 4.75 and 7.2 GPa. The inversion of the α angle is interpreted as a consequence of an isosymmetric displacive phase transition from A-type to B-type structure between 2.81 and 4.75 GPa. The compressibility of the Rb–TFA was also investigated by single-crystal X-ray diffraction up to a maximum pressure of 10 GPa. The lattice parameters reveal a sharp discontinuity between 3.36 and 3.84 GPa, which was associated with the phase transition from Franzini-A to Franzini-B structure. Received: 21 October 2002 / Accepted: 25 February 2003     

A room-temperature phase transition in maximum microcline

A type of hysteresis, similar to that observed in the heat capacity measurements (Openshaw et al., 1979), has been found in the room temperature unit cell parameters of a microcline sample 71104 and likewise indicates the existence of two forms of this microcline. The A-form (obtained on cooling the sample to approximately 80 K) has significantly different values of b, β and V to the B-form which is the more stable form above 300±10 K. The transition from the A- to the B-form occurs over a period of months and has an associated ΔV of ?0.0011 nm³. The cell parameters of the B-form have been measured up to 1278 K and show significant changes: a and V increase, b constracts, and c is unchanged on increasing temperature. The calculated thermal expansion ellipsoid is nearly uniaxial and similar in shape to that for sanidine. Below room temperature the isobaric thermal expansion coefficent α_p, for a natural microcline is nearly four times as large as that for sanidine. Above room temperature α_p for 71104 microcline decreases markedly with increasing temperature. This implies a rapid change in the thermal expansion behavior of microcline which has been correlated with the proposed phase transition.     

Structural phase transition in titanite,CaTiSiO5: A ramanspectroscopic study

The structural phase transition in titanite is correlated with a strong temperature dependence of Raman scattering cross sections and, to a somewhat lesser extent, with shifts of the phonon frequencies. Their quantitative temperature evolution in the low-symmetry phase (P2₁/a) is compatible with a nearly 2D Ising behaviour with β≈0.12 and T _c = 497 K. At temperatures above 860 K, the phonon signals agree with A 2/a symmetry but not in the temperature interval between 497 K and 860 K. In this temperature range new structural states give rise to additional phonon signals. A model based on mobile APBs between slabs of P2₁/a material, first proposed by van Heurck et al. (1991), is in qualitative agreement with our experimental observations.     

Paraelectric-antiferroelectric phase transition in titanite,CaTiSiO5

The paraelectric to antiferroelectric phase transition in titanite at ～500 K involves a displacement of the titanium atom from the center of the [TiO₆] octahedron in the paraelectric phase (A2/a) to an off-center position in the antiferroelectric (P2 ₁/a) phase. We have carried out a detailed single crystal high temperature x-ray diffraction study of the phase transition including structure refinements at 294, 350, 400, 430, 440, 450, 500, 600, and 700 K. The unit cell dimensions show a pronounced hysteresis effect in the 450–500 K range on heating and cooling during the first cycle along with a reduction of the transition temperature, T _c from 495 ± 5 K on heating to 445 ± 5 K on cooling. The hysteresis effect disappears on further heating and the superstructure reflections show residual intensities above T _c (445 K). An order parameter treatment of the phase transition is presented in terms of Landau theory and induced representation theory. The Ti-displacements parallel and antiparallel to a are taken as the primary order parameter η, which transforms as the Y ₂ ⁺ representation. A coupling of Y ₂ ⁺ with T ₁ ⁺ results in the linear-quadratic coupling of the spontaneous strain components, ? _ij with η. The Ti-displacements are coupled linearly to the Cadisplacements. Both sets of displacements predicted from induced representation theory are observed experimentally. The phase transition is initially driven by the soft mode at the zone boundary point Y ₂ ⁺ ; near T _c critical fluctuations set in and an order-disorder mechanism finally drives the phase transition, whereby parallel and antiparallel Ti-displacements related by [0, 1/2, 1/2] in adjacent domains are dynamically interchanged. Immediately above T _c , the high temperature (A2/a) phase is a statistical average of small dynamic antiphase domains of the low temperature (P2 ₁/a) phase. Vacancies and defects pinning the domain boundaries may drastically alter the transition behavior and affect the domain mobility.     

A commensurate-incommensurate phase transition in iron-bearing åkermanites

Synthetic melilites on the join Ca₂MgSi₂O₇ (åkermanite) — Ca₂FeSi₂O₇ (iron åkermanite) with Fe/(Fe+Mg) from 0.0 to 0.7 exhibit, at room temperature, an incommensurate phase with a rectangular modulation of a wavelength of about 19 Å in the [110] direction. Upon increase of temperature, they transform to a commensurate melilite structure at about 80° C for Fe/(Fe+Mg)=0.0 and about 250° C for Fe/(Fe+Mg)=0.6. In addition to the T(2) positions of the melilite structure filled by Si, the incommensurate phase exhibits two distinguishable T(1) sites containing the Mg and Fe²⁺. These two sites merge into one site during the phase transition from the incommensurate to the commensurate phase. A structural model for the incommensurate phase is based on the misfit between the tetrahedral (Mg, Fe²⁺)Si₂O ₇ ^4? sheets and the Ca²⁺ ions.     

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.     

Chromium solubility in anhydrous Phase B

The crystal structure and chemical composition of a crystal of (Mg_14?x Cr _x )(Si_5?x Cr _x )O₂₄ (x ≈ 0.30) anhydrous Phase B (Anh-B) synthesized in the model system MgCr₂O₄–Mg₂SiO₄ at 12 GPa and 1600 °C have been investigated. The compound was found to be orthorhombic, space group Pmcb, with lattice parameters a = 5.900(1), b = 14.218(2), c = 10.029(2) Å, V = 841.3(2) Å³ and Z = 2. The structure was refined to R ₁ = 0.065 using 1492 independent reflections. Chromium was found to substitute for both Mg at the M3 site (with a mean bond distance of 2.145 Å) and Si at the octahedral Si1 site (mean bond distance: 1.856 Å), according to the reaction Mg²⁺ + Si⁴⁺ = 2Cr³⁺. Such substitutions cause a reduction in the volume of the M3 site and an increase in the volume of the Si-dominant octahedron with respect to the values typically observed for pure Anh-B and Fe²⁺-bearing Anh-B. Taking into account that Cr³⁺ is not expected to be Jahn–Teller active, it appears that both the Cr³⁺–for–Mg and Cr³⁺–for–Si substitutions in the Anh-B structure decrease the distortion of the octahedra. Electron microprobe analysis gave the Mg_13.66(8)Si_4.70(6)Cr_0.62(4)O₂₄ stoichiometry for the studied phase. The successful synthesis of this phase provides new information for the possible mineral assemblages occurring in the Earth’s deep upper mantle and shed new light on the so-called X discontinuity that has been observed at 275–345 km depth in several subcontinental and subduction zone environments.     

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,

High-pressure phase transition in MnTiO3 from the ilmenite to the LiNbO3 structure

Crystals of a high-pressure phase of MnTiO₃ have been synthesized at pressures of 60 kbar using the SAM-85 cubic-anvil high pressure apparatus. Although all crystals examined were twinned on (10 \(\bar 1\) \(\bar 2\) ), a set of diffraction intensities that are essentially unaffected by the twinning were obtained. Three possible structure models were considered: (1) the corundum (completely disordered Mn and Ti), (2) the partially-disordered ilmenite, and (3) the LiNbO₃ structures. The R factors of the corundum and the disordered ilmenite models were much larger than that of LiNbO₃. Using structure factors unaffected by twinning, the final LiNbO₃-type refinement gave R _w=0.037 and R=0.034. The averaged bond lengths for Mn-O and Ti-O were consistent with ones calculated using Shannon and Prewitt's (1969) radii. The study concludes that MnTiO₃ II actually has an ordered LiNbO₃-type structure rather than the disordered one as reported previously. From the analysis of the two MnTiO₃ structures, the transition can be related to a cation reordering process, in which half of the cations participate, accompanied by the rotation of oxygens to accommodate the cations.     

Solid carbon at high pressure: Electrical resistivity and phase transition

The electrical resistivity of polycrystalline graphite and amorphous carbon are measured at high pressures and room temperature. The results show that the resistivity of these carbon phases decreases with increasing pressure below 19 GPa. The pressure dependence of the resistivity (dln?/dP) is determined to be-0.037 GPa^?1 for the polycrystalline graphite and-0.039 GPa^?1 for the amorphous carbon. A phase transition, interpreted as the transformation to hexagonal diamond phase, is observed in the polycrystalline graphite at about 20 GPa but not in the amorphous carbon. The present experimental results support the assumption that this phase transition is martensitic in nature.     

Non-convergent ordering and displacive phase transition in pigeonite: in situ HT XRD study

A natural Ca-rich pigeonite (En₄₇Fs₄₃Wo₁₀), free of augite exsolution products, was studied by in situ high-temperature single-crystal X-ray diffraction. The sample, monoclinic P2 ₁ /c (a=9.719(7) Å, b=8.947(9) Å, c=5.251(3) Å, β=108.49(5), V=433.0(6) ų), was annealed up to 1000 °C to induce a phase transition from P2 ₁ /c to C2/c symmetry. Complete single-crystal X-ray diffraction data collections were carried out in situ at 650, 750, 850 and 950 °C after the crystal had reached equilibrium for the Fe–Mg intracrystalline exchange reaction at each temperature. The variation, with increasing temperature, of lattice parameters, of intensity of hkl reflections with h + k=2n + 1 (which vanish at high temperature) and of some geometrical parameters from structure refinement, showed that the displacive phase transition P2 ₁ /c?C2/c was continuous in character. This contrasts with the first-order character for the HT phase transition in pigeonite containing significantly less calcium.     

Phase transition of zircon at high P-T conditions

Abstract In situ observations of the zircon-reidite transition in ZrSiO₄ were carried out using a multianvil high-pressure apparatus and synchrotron radiation. The phase boundary between zircon and reidite was determined to be P (GPa) = 8.5+0.0017×(T-1200) (K) for temperatures between 1100–1900 K. When subducted slabs, including igneous rocks and sediments, descend into the upper mantle, the zircon in the subducted slab transforms into reidite at pressures of about 9 GPa, corresponding to a depth of 270 km. Reidite found in an upper Eocene impact ejecta layer in marine sediments is thought to have been transformed from zircon by a shock event. The peak pressure generated by the shock event in this occurrence is estimated to be higher than 8 GPa.Editorial responsibility: J. Hoefs