Dmytro M. Trots

Thermal Stability of LiCoPO4 Cathodes

The thermal stability of LiCoPO 4 cathodes charged to different lithium contents was studied by synchrotron diffraction and differential thermal analysis. Both olivine-like phases Li Z COPO 4 (z = 0.6) and CoPO 4 appearing during the delithiation of LiCoPO 4 are unstable upon heating, and decompose readily in the range 100-200°C. The decomposition of lithium-poor phases leads to gas evolution and the crystallization of CO 2 P 2 O 7 . The role of carbon present in the electrochemically delithiated samples is discussed. The significantly lower stability of charged LiCoPO 4 in comparison with LiFePO 4 is a serious challenge for the application of this material in rechargeable Li-ion batteries.

Peierls distortion, magnetism, and high hardness of manganese tetraboride

We report crystal structure, electronic structure, and magnetism of manganese tetraboride, MnB4, synthesized under high-pressure, high-temperature conditions. In contrast to superconducting FeB4 and metallic CrB4, which are both orthorhombic, MnB4 features a monoclinic crystal structure. Its lower symmetry originates from a Peierls distortion of the Mn chains. This distortion nearly opens the gap at the Fermi level, but despite the strong dimerization and the proximity of MnB4 to the insulating state, we find indications for a sizable paramagnetic effective moment of about 1.7 μB /f.u., ferromagnetic spin correlations, and, even more surprisingly, a prominent electronic contribution to the specific heat. However, no magnetic order has been observed in standard thermodynamic measurements down to 2 K. Altogether, this renders MnB4 a structurally simple but microscopically enigmatic material; we argue that its properties may be influenced by electronic correlations.

In situ observation of the breakdown of magnetite (Fe3O4) to Fe4O5 and hematite at high pressures and temperatures

Abstract In situ synchrotron X-ray powder diffraction measurements using a Paris-Edinburgh pressure cell were performed to investigate the nature of the high-pressure breakdown reaction of magnetite (Fe3O4). Refinement of diffraction patterns reveals that magnetite breaks down via a disproportionation reaction to Fe4O5 and hematite (Fe2O3) rather than undergoing an isochemical phase transition. This result, combined with literature data indicates (1) that this reaction occurs at ~9.5-11 GPa and 973-1673 K, and (2) these two phases should recombine at yet higher pressures to produce an h-Fe3O4 phase.

The Sm:YAG primary fluorescence pressure scale

Primary pressure determinations involve the measurement of pressure without recourse to secondary standard materials. These measurements are essential for ensuring the accuracy of pressures measured in gasketed high-pressure devices. In this study, the wavelength of optical fluorescence bands and the density of single crystal Sm-doped yttrium aluminum garnet Y3Al5O12 (Sm:YAG) have been calibrated as a primary pressure scale up to 58 GPa. Absolute pressures were obtained by integrating the bulk modulus determined via Brillouin spectroscopy with respect to volumes measured simultaneously by X-ray diffraction. A third-order Birch-Murnaghan equation of state of Sm:YAG yields V0 = 1735.15(26) A3, KT0 = 185(1.5) GPa, and K` = 4.18(5). The accompanied pressure-induced shifts of the fluorescence lines Y1 and Y2 of Sm:YAG were calibrated to the primary pressure, thus creating a highly accurate fluorescence pressure scale. These shifts are described as P = (A/B) * {[1 + (Δλ/λ0)]B − 1} with A = 2089.91(23.04), B = −4.43(1.07) for Y1, and A = 2578.22(48.70), B = −15.38(1.62) for Y2 bands, where ∆λ = λ − λ0, λ and λ0 are wavelengths in nanometer at pressure and ambient conditions. The sensitivity in the pressure determination of the Sm:YAG fluorescence shift is 0.32 nm/GPa, which is identical to that of the ruby scale. Sm:YAG can be considered elastically isotropic up to 58 GPa, implying insensitivity of the determined pressure to the crystallographic orientation under nonhydrostatic or quasi-hydrostatic conditions. The Sm:YAG fluorescence shift is apparently also independent of crystallographic orientation, in contrast to that of ruby. Since the Y fluorescence band of Sm:YAG is insensitive to temperature changes, this material is highly suitable for the measurement of pressure at elevated temperatures.

Single-crystal X-ray diffraction at extreme conditions: a review

The latest developments in single-crystal X-ray diffraction at high pressure and high temperature are described. Advances in diamond anvil cell designs and X-ray sources allow collecting single-crystal diffraction data at pressures up and above 100 GPa and at temperatures above 1000°C. The technical details of single-crystal X-ray diffraction at high pressure such as the choice of pressure-transmitting media or the different methods for measuring pressures and temperatures have been reviewed. Examples of structural solution of complex structures and new materials, structural refinements of high pressure polymorphs as well as accurate compressibility data are described in order to outline the several advantages of using single crystals instead of powdered samples in high pressure diffraction experiments.

High-temperature structural behaviors of anhydrous wadsleyite and forsterite

Abstract The thermal expansion of anhydrous Mg2SiO4 wadsleyite and forsterite was comprehensively studied over the temperature ranges 297-1163 and 297-1313 K, respectively, employing X-ray powder diffraction. Experiments were carried out with two separately synthesized samples of wadsleyite (numbered z626 and z627), for which room temperature unit-cell volumes differed by 0.05%, although the determined thermal expansions were identical within error. The high-temperature thermal expansions of wadsleyite and forsterite were parameterized on the basis of the first-order Grüneisen approximation using a Debye function for the internal energy. Values for hypothetical volume at T = 0 K, Debye temperature and Grüneisen parameter are 536.86(14) Å3, 980(55) K, 1.28(2) and 537.00(13) Å3, 887(50) K, 1.26(1) for z626 and z627, respectively, with the bulk modulus fixed to a literature determination of 161 GPa. For forsterite, the respective values are 288.80(2) Å3, 771(9) K, and 1.269(2) with a constrained bulk modulus of 125 GPa. These quantities are in good agreement with literature values obtained independently from sound velocity and heat capacity measurements, giving strong support to the applicability of Grüneisen theory in describing the thermal expansion of wadsleyite and forsterite. In addition, high-temperature structural variations were determined for wadsleyite from Rietveld analysis of the X-ray diffraction data. The pronounced anisotropy in thermal expansion of wadsleyite with a more expandable c-axis, similar to the compressional anisotropy, arises from specific features of the crystal structure consisting of the pseudolayers of MgO6 octahedra parallel to the a-b plane with cross-linking Si2O7 dimers along the c-axis. Although anisotropic compression and expansion originate from the same structural features, the details of structural changes with pressure differ from those caused by temperature. The longest Mg-O bonds, which are roughly parallel to the c-axis in all three octahedral sites of wadsleyite, dominate the compression, but these bonds do not exhibit the largest expansivities.

Hexagonal Na0.41[Na0.125Mg0.79Al0.085]2[Al0.79Si0.21]6O12 (NAL phase): Crystal structure refinement and elasticity

Abstract At lower mantle conditions, subducted mid oceanic ridge basalts (MORB) will crystallize more than 20 vol% of an aluminum-rich phase, which is referred to generally as the new aluminum (NAL) phase. Given that a significant proportion of the lower mantle may be comprised of subducted crust, the NAL phase may contribute to the bulk elastic properties of the lower mantle. In this study we report for the first time the structure, Raman spectrum and elasticity of single crystals of Na0.41 [Na0.125Mg0.79Al0.085]2[Al0.79 Si0.21]6O12 NAL phase, synthesized at 2260 °C and 20 GPa. The single-crystal structure refinement of NAL, which is consistent with the space group P63/m, reveals dynamic disorder of Na atoms along channels within the structure. The elastic tensor was experimentally determined at ambient conditions by Brillouin scattering spectroscopy. The elastic modulii obtained from the Voigt- Reuss-Hill approximation using the elastic constants determined in this study are KS = 206 GPa and μ = 129 GPa, whereas the isotropic compressional and shear sound velocities are vP = 9.9 km/s and vS = 5.8 km/s. The NAL phase is elastically anisotropic, displaying 13.9% compressional and shear wave anisotropy. Elastic constants as well as Raman active modes of NAL have also been calculated using density-functional theory and density-functional perturbation theory.

Competing tetragonal and monoclinic phases in Ni2.2Mn0.80Ga

Temperature dependent synchrotron x-ray powder diffraction, differential scanning calorimetry, and magnetic measurements were performed on Ni2+xMn1-xGa (x=0.20 and 0.35) magnetic shape memory alloys. For x=0.20, though the monoclinic phase is thermodynamically stable, a trace of residual stress can stabilize a tetragonal phase. The residual-stress-induced tetragonal phase transforms to the cubic austenite phase over an unusually large temperature range (348 K < T < 693 K), suggesting extremely slow kinetics of transformation. In contrast to x=0.20, the thermodynamically stable phase of x=0.35 is tetragonal and this composition exhibits the usual features of a reversible martensitic transformation. The results suggest that for x=0.20 the monoclinic and tetragonal phases are nearly degenerate.

The determination of hydrogen positions in superhydrous phase B

Abstract Nominally hydrous high-pressure silicate phases such as the superhydrous phase B are of considerable importance for the understanding of the water-cycle between the surface and the interior of the Earth. This study tackles the controversial issue of hydrogen positions in superhydrous phase B, a phase believed to be potentially stable in cold subducting ultramafic slabs. To investigate the nature of hydrogen incorporation into the structure of superhydrous phase B, neutron powder diffraction experiments have been performed. A structural model based on Pnn2 symmetry has been used for the analysis of the data, which is consistent with earlier spectroscopic studies. Application of Fourier synthesis with subsequent analyses of difference nuclear density maps and Rietveld fits reveal two distinct positions for deuterium, at 4c (0.194, 0.052, 0.596) and at 4c (0.186, 0.119, 0.388). This unambiguously shows that deuterium lies within large channels, which are formed between the edgeshared octahedra and vertex-linked tetrahedra along the b-axis of the structure. These results contrast with recent polarized single-crystal infrared spectroscopy studies where the position of one of two H atoms was estimated to lie close to the octahedral edge of an MgO6 octahedron, thereby leaving the large structural channel empty.

Extending the single-crystal quartz pressure gauge up to hydro­static pressure of 19 GPa

In situ high-pressure diffraction experiments on single-crystal α-quartz under quasi-hydrostatic conditions up to 19 GPa were performed with diamond-anvil cells. Isotropic pressures were calibrated through the ruby-luminescence technique. A 4:1 methanol–ethanol mixture and the densified noble gases helium and neon were used as pressure media. The compression data revealed no significant influence of the pressure medium at room temperature on the high-pressure behavior of α-quartz. In order to describe its compressibility for use as a pressure standard, a fourth-order Birch–Murnaghan equation of state (EoS) with parameters KT0 = 37.0 (3) GPa, KT0′ = 6.7 (2) and KT0′′ = −0.73 (8) GPa−1 was applied to fit the data set of 99 individual data points. The fit of the axial compressibilities yields MT0 = 104.5 (8) GPa, MT0′ = 13.7 (4), MT0′′ = −1.04 (11) GPa−1 (a axis) and MT0 = 141 (3) GPa, MT0′ = 21 (2), MT0′′ = 8.4 (6) GPa−1 (c axis), confirming the previously reported anisotropy. Assuming an estimated standard deviation of 0.0001% in the quartz volume, an uncertainty of 0.013 GPa can be expected using the new set of EoS parameters to determine the pressure.