Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
We use first first-principle methods and the Peierls-Nabarro model to evaluate the resistance to glide, characterized by the Peierls stress, of glide systems for end-member MgSiO3 Perovskite at mantle pressures. [010](100) is the easiest glide system in Mg-Perovskite at all pressures. Peierls stresses increase systematically with pressure for all systems except [001](010), indicating the importance of lattice friction at lower mantle pressures. The ratio of the maximum Peierls stress for each system relative to the [010](100) value defines their critical resolved shear stress (CRSS). These CRSS are used in a visco-plastic self-consistent homogenization model to predict the evolution of crystal preferred orientations (CPO) during deformation of polycrystalline Mg-Perovskite. In axial compression, [100] tends to align with the compression direction, in agreement with in situ observations in axial compression experiments. In simple shear, [010] concentrates near the shear direction and (100), although more dispersed, tends to align near the shear plane, consistent with the dominant activity of the easier [010](100) system. The calculated seismic anisotropy for a 100% Mg-Perovskite aggregate using the CPO in simple shear and the elastic constants Of MgSiO3 perovskite at lower mantle pressures and temperatures is weak (>3% for P-waves with and >2% for S-waves) and decreases with increasing temperature and pressure. P-waves show the fastest propagation parallel to the lineation and S-waves fast polarization is in the foliation at 38 GPa and normal to the lineation at 88 GPa. This weak anisotropy is consistent with global seismological observations of a nearly isotropic lower mantle. There are however two regions where strain-induced Mg-Perovskite CPO could contribute to anisotropy; a) low temperature regions in the uppermost lower mantle, where the predicted S-wave polarization anisotropy may attain 1.6% with a fast polarization parallel to the foliation, b) in high high-temperature domains in the D '' layer, where Mg-Perovskite may be the major stable phase, leading to polarization of fast S-waves normal to the lineation for propagation directions at high angle to the lineation and an apparent isotropy for all other propagation directions.
ISSN: 0012-821X

hal-00411460
https://hal.archives-ouvertes.fr/hal-00411460
DOI : 10.1016/j.epsl.2008.03.058

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Here we show that copper substitution in perovskite-type barium strontium cobalt copper oxide (BSCC) membranes confers extremely high oxygen fluxes well beyond the state of art, reaching 27.5 ml cm−2 min−1at 950 °C. A key feature of BSCC is the formation of a mixed matrix catalyst-perovskite membrane caused by the segregation of copper, leading to the formation of an intergranular network of copper-rich oxide between perovskite grains. BSCC membranes delivered pressure normalised oxygen flux (i.e. permeance) of up to 86 times higher, above pressure difference of 18 kPa, as compared to best perovskite membrane, BBSC, due to the catalytic effect of segregated copper oxide. Unlike conventional dual-phase membranes which contain ion and electron conducting phases, this work shows for the first time perovskite-type membranes consisting of a mixed matrix of oxygen ion/electron conducting (perovskite) and catalytic (copper oxide) phases, thus paving the way to the development of high performance membranes for oxygen separation from air for clean energy applications. © 2016 Elsevier B.V.
ISSN: 0376-7388

hal-01683219
https://hal.univ-antilles.fr/hal-01683219
DOI : 10.1016/j.memsci.2016.12.035

Éditeur(s) : HAL CCSD Oxford University Press (OUP)
Résumé : International audience
Phase equilibrium data pertaining to melting of simplified carbonated peridotite in the systems CaO-MgO-SiO2-CO2 and CaO-MgO-Al2O3-SiO2-CO2 at pressures of 10-26 GPa, corresponding to similar to 300-750 km depths in the Earth, are presented. In both the studied systems, liquid compositions, with changing crystalline phase assemblage, are carbonatitic throughout the studied pressure range. In the system CMS-CO2, melting phase relations are isobarically invariant; liquid is in equilibrium with forsterite + clinoenstatite + clinopyroxene + magnesite, forsterite + majorite + clinopyroxene + magnesite, wadsleyite + majorite + clinopyroxene + magnesite, ringwoodite + majorite + calcium-silicate perovskite + magnesite, magnesium-silicate perovskite + periclase + calcium-silicate perovskite + magnesite at 12, 14, 16, 20, and 26 GPa, respectively. In the system CMAS-CO2, a phase assemblage consisting of forsterite + orthopyroxene + clinopyroxene + magnesite + garnet + melt from 10 to 14 GPa is isobarically invariant. However, owing to the disappearance of orthopyroxene at pressures greater than 14 GPa, from 16 and up to at least 26 GPa, the solidus of simplified carbonated peridotite spans a divariant surface in pressure-temperature space. The liquid coexists with wadsleyite + clinopyroxene + garnet + magnesite, ringwoodite + calcium-silicate perovskite + garnet + magnesite, and magnesium-silicate perovskite + periclase + calcium-silicate perovskite + magnesite at 16, 20, and 26 GPa, respectively. A curious, and as yet unexplained, feature of our study is an abrupt drop in the solidus temperature between 14 and 16 GPa that causes a small amount of melting of carbonated mantle in the Transition Zone of the Earth. In the systems CMS-CO2 and CMAS-CO2 liquid compositions at 16 and 20 GPa are highly calcic bona fide carbonatites; however, these liquids revert to being magnesiocarbonatites at 10-14 and 26 GPa. In the system CMS-CO2, at 16 GPa we locate an isobaric invariant point consisting of wadsleyite + clinopyroxene + anhydrous B + magnesite + melt. The presence of anhydrous B at 16 GPa and 1475 degrees C is interesting, as it lies outside the composition space of the mantle peridotite analog we have studied. However, despite the presence of two highly magnesian silicate crystalline phases, wadsleyite and anhydrous B, at 16 GPa and 1475 degrees C, the liquid composition remains calcic with molar Ca-number [Ca/(Ca + Mg) x 100] of about 63. The melting reactions at 16 and 20 GPa (with or without anhydrous B) show that lime-bearing crystalline silicates play a fairly large part in generating and controlling the composition of the liquids. At 16 GPa, in the system CMS-CO2, we also report an experimental run at 1575 degrees C, in which liquid coexists with only wadsleyite and majorite. The liquid composition is less calcic (Ca-number 54) than that for other runs at lower temperatures, but is still more calcic than liquids at 10-14 and 26 GPa in both the studied systems. At present, the likely cause for these changes in the reported phase relations is not known. For normally assumed mantle temperatures, melting in the Transition Zone of the Earth, owing to the presence of carbonate, is probably unavoidable. The depth range of the drop in the carbonated peridotite solidus closely matches that of commonly observed low seismic velocities at similar to 400-600 km depth in the Earth.
ISSN: 0022-3530

hal-00669945
https://hal.archives-ouvertes.fr/hal-00669945
DOI : 10.1093/petrology/egr048

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
In this study, we propose a theoretical approach to test the validity of the isomechanical analogues for post-perovskite structures. Intrinsic plastic properties are evaluated for three materials exhibiting a post-perovskite phase: MgSiO3, MgGeO3 and CaIrO3. Dislocation properties of each structure are determined using the Peierls-Nabarro model based on first-principles calculations of generalised stacking fault and the plastic properties are extended to crystal-preferred orientations using a visco-plastic self-consistent method. This study provides intrinsic parameters of plastic deformation such as dislocation structures and Peierls stresses that can be directly compared between the three materials. It appears that it is very difficult to draw any simple conclusions on polycrystalline deformation simply by comparing single crystal properties. In particular, contrasting single crystal properties of MgSiO3 and CaIrO3 lead to similar crystal-preferred orientation of the polycrystal aggregates.
ISSN: 0031-9201

hal-00420104
https://hal.archives-ouvertes.fr/hal-00420104
DOI : 10.1016/j.pepi.2008.04.003

Éditeur(s) : HAL CCSD American Geophysical Union
Résumé : International audience
We determine the elasticity of FeSiO3 perovskite for various spin configurations using density-functional theory calculations. The elastic moduli and the bulk seismic wave velocities are weakly affected by the spin transition. However we show that the intrinsic differences in seismic anisotropy between the high-spin and low-spin phases of Fe-bearing perovskite coupled with lattice preferred orientation that can develop due and during the convection may lead to distinct seismic signatures between the top and the bottom of the lower mantle. These signatures should be detectable in observations and they need to be taken into account in tomographic studies of the Earth's lower mantle.
ISSN: 0094-8276

hal-00512662
https://hal.archives-ouvertes.fr/hal-00512662
DOI : 10.1029/2010GL043320

Éditeur(s) : HAL CCSD Elsevier
Résumé : The dense hydrous magnesium silicate called the D phase is the most likely candidate to recycle hydrogen into the lower mantle in subduction zones. As seismology represents the preferred method to detect this mineral in subduction zones, the single crystal elastic tensor has been calculated using first principle methods. A triple cell (View the MathML source) was used to account for an ordered ideal composition of the D phase to lower mantle pressures. The elastic tensor of the mineral at ambient conditions is predicted to be C11 = 387.7, C33 = 287.7, C44 = 100.4, C12 = 108.0, C13 = 51.1, C14 = − 14.6 in GPa with bulk modulus at zero pressure Ko = 163 GPa and a statistical error of about 4.0 GPa for all constants. The pressure derivatives of the elastic constants have been determined to pressure of 80 GPa. Our tensor correctly predicts the published experimental measurements of linear compressibility along the a- and c-axes, the logarithmic pressure derivative of the c/a axial ratio and bulk modulus at zero pressure. It contradicts the experimentally measured elastic tensor reported by (Liu, L.-G., Okamoto, K., Yang, Y.-J., Chen, C.-C., Lin, C.-C., 2004. Elasticity of single-crystal phase D (a dense hydrous magnesium silicate) by Brillouin spectroscopy. Solid State Commun. 132, 517–520), which fails to reproduce the experimental compressibility data. Using the elastic constants and density predicted to 85 GPa, the seismic anisotropy of P- and S-waves has been calculated as a function of pressure. The single crystal has high P-wave velocities and shear wave splitting in the basal plane below 20 GPa. At high pressures, the maximum P-wave velocities have threefold symmetry normal to a-axes in the basal plane, whereas the maximum shear wave splitting is parallel to a-axes with twofold symmetry. The D phase has high Vp and Vs anisotropy at ambient pressure, 17.6% for Vp and 19.9% for Vs. The Vp anisotropy decreases with increasing pressure to about 30 GPa, while it remains constant at 8% from 30 to 85 GPa. The Vs anisotropy decreases to 17% at 20 GPa and then increases to 22% at 85 GPa. The isotropic velocity ratios of S to P (Rs/p), bulk sound to S (Rphi/s) and density to S (Rρ/s) are calculated as a function of pressure. The Rs/p shows very little variation with pressure with low value of 0.6, whereas both Rphi/s and Rρ/s increase with pressure to peak values of 2.8 and 2.0 respectively at about 60 GPa. The presence of the D phase in subducted horizontal ‘stagnant' plates in the circum Pacific could contribute to a number of seismic observations, such as the observed velocity heterogeneity at depths between 500 and 1000 km and the fast S-waves travelling horizontally with horizontal polarization in this depth range. Further the lower density of the D phase compared with anhydrous minerals could influence buoyancy of the hydrated ‘stagnant' slabs. The transformation of the D phase to perovskite plus ferripericlase during thermal annealing may be responsible for horizontal slab seismogenesis.
ISSN: 0012-821X

hal-00406379
https://hal.archives-ouvertes.fr/hal-00406379
DOI : 10.1016/j.epsl.2007.04.053

Éditeur(s) : HAL CCSD American Geophysical Union
Résumé : International audience
Solidus melting phase relations are reported for carbonated eclogite in the system CaO-MgO-Al2O3-SiO2-CO2 at 12 to 25 GPa. From 12 to 16 GPa, melts are in equilibrium with clinopyroxene, stishovite, garnet, aragonite, and magnesite. At 20 and 25 GPa, melts are in equilibrium with garnet, stishovite, calcium-alumino silicate, calcium perovskite, and magnesite. Melting reactions demonstrate that from 12 to 16 GPa, stishovite is in reaction with the melt. At 20 and 25 GPa, garnet and stishovite together are produced upon melting of model, carbonated eclogite. At 20 and 25 GPa, calcium perovskite is also the phase that contributes the most toward liquid production. Melt compositions at all pressures are carbonatitic, with roughly 37-40 wt% dissolved CO2. From 12 to 16 GPa, the liquids are calciocarbonatites with Ca#(molar) of similar to 69-71; liquid compositions become less calcic with Ca# of similar to 52-55 at 20 and 25 GPa. Given these melting phase relations, suitable subduction zone adiabats do not intersect the solidus of model carbonated eclogite at depths investigated in the present study. Hence, on this basis, it is fair to say that carbonated eclogite possibly avoids melting in subduction zone settings, thereby delivering carbonate to at least moderate depths in the Earth. However, owing to local heating events, small-degree melting of carbonated eclogite is not completely precluded, and the liquids liberated from this melting can be viewed as agents of chemical mass transfer in the deep Earth. At present, however, geochemical consequences of subduction-related melting of carbonated eclogite are difficult to evaluate.
ISSN: 0148-0227

hal-00566560
https://hal.archives-ouvertes.fr/hal-00566560
DOI : 10.1029/2009JB006457