Jean-Claude Crivello

First principles calculations of the σ and χ phases in the Mo-Re and W-Re systems

The total energies of all the ordered configurations of the σ and χ phases have been calculated by using first principles methodology in both Mo-Re and W-Re systems. These two complex structures possess 5 and 4 inequivalent sites generating 32 and 16 different ordered configurations, respectively, for a binary A-B system. The converged total energies of all the fully relaxed structures have been used to compute the occupancy of the inequivalent sites as a function of composition and temperature by using the Bragg-Williams approximation in the complete composition range. It is shown that the configurational entropy stabilizes the σ and χ phases in the Mo-Re and W-Re systems. The results evidence the preference of Re for lower coordination number site occupancy and are in very good agreement with the experimental measurements. Tentative ab initio phase diagrams have also been drawn.

χ and σ phases in binary rhenium-transition metal systems: a systematic first-principles investigation.

The Frank-Kasper phases, known as topologically close-packed (tcp) phases, are interesting examples of intermetallic compounds able to accommodate large homogeneity ranges by atom mixing on different sites. Among them, the χ and σ phases present two competing complex crystallographic structures, the stability of which is driven by both geometric and electronic factors. Rhenium (Re) is the element forming the largest number of binary χ and σ phases. Its central position among the transition metals in the periodic table plays an important role in the element ordering in tcp phases. Indeed, it has been shown that Re shows an opposite site preference depending on which elements it is alloyed with. In the present work, χ- and σ-phase stability in binary Re-X systems is systematically studied by a first-principles investigation. The heats of formation of the complete set of ordered configurations (16 for χ and 32 for σ) have been calculated in 16 well-chosen systems to identify stability criteria. They include not only the systems in which χ-Re-X (X = Ti, Mn, Zr, Nb, Mo, Hf, Ta, W) or σ-Re-X (X = V, Cr, Mn, Fe, Nb, Mo, Ta, W) exist but also the systems in which both phases are not stable, including systems in which X is a 3d element from Ti to Ni, a 4d element from Zr to Ru, and a 5d element from Hf to Os. Careful analysis is done of the energetic tendencies as a function of recomposition, size effect, and electron concentration. Moreover, the site preference and other crystallographic properties are discussed. Conclusions are drawn concerning the relative stability of the two phases in comparison with the available experimental knowledge on the systems.

Comparison of the site occupancies determined by combined Rietveld refinement and density functional theory calculations: example of the ternary Mo-Ni-Re σ phase.

The site occupancies of the Mo-Ni-Re σ phase have been studied as a function of the composition in the ternary homogeneity domain by both experimental measurements and calculations. Because of the possible simultaneous occupancy of three elements on the five sites of the crystal structure, the experimental determination of the site occupancies was achieved by using combined Rietveld refinement of X-ray and neutron diffraction data, whereas calculation of the site occupancies was carried out by using the density functional theory results of every ordered (i.e., 3(5) = 243) configuration appearing in the ternary system. A comparison of the experimental and calculation results showed good agreement, which suggests that the topologically close-packed phases, such as the σ phase, could be described by the Bragg-Williams approximation (i.e., ignoring the short-range-order contributions). On the other hand, the atomic distribution on different crystallographic sites of the Mo-Ni-Re σ phase was found to be governed by the atomic sizes. Ni, having the smallest atomic size, showed a preference for low-coordination-number (CN) sites, whereas Mo, being the largest in atomic size, preferred occupying high-CN sites. However, the preference of Re, having intermediate atomic size, varied depending on the composition, and a clear reversal in the preference of Re as a function of the composition was evidenced in both the calculated and experimental site-occupancy results.

CO2 hydrogenation on a metal hydride surface

The catalytic hydrogenation of CO(2) at the surface of a metal hydride and the corresponding surface segregation were investigated. The surface processes on Mg(2)NiH(4) were analyzed by in situ X-ray photoelectron spectroscopy (XPS) combined with thermal desorption spectroscopy (TDS) and mass spectrometry (MS), and time-of-flight secondary ion mass spectrometry (ToF-SIMS). CO(2) hydrogenation on the hydride surface during hydrogen desorption was analyzed by catalytic activity measurement with a flow reactor, a gas chromatograph (GC) and MS. We conclude that for the CO(2) methanation reaction, the dissociation of H(2) molecules at the surface is not the rate controlling step but the dissociative adsorption of CO(2) molecules on the hydride surface.

Study of the magnetic and electronic properties of nanocrystalline PrCo3 by neutron powder diffraction and density functional theory

Nanocrystalline PrCo(3) powder has been synthesized by high-energy milling and was subsequently annealed from 873 to 1273 K for 30 min to optimize the extrinsic properties. The structure and magnetic properties of the nanocrystalline PrCo(3) have been investigated by means of x-ray and neutron diffraction as well as magnetization measurements. All compounds crystallize in the same PuNi(3) type structure, with grain sizes between 28 and 47 nm. As the annealing temperature increases, a maximum coercive field of 12 kOe at 300 K (55 kOe at 10 K) was obtained by annealing at 1023 K for a grain size of 35 nm. The refinement of the neutron powder diffraction patterns (NPD) of PrCo(3) from 1.8 to 300 K shows an expansion of the parameter a and a contraction of the parameter c, leading to a decrease of the ratio c/a. The evolution of the Co and Pr magnetic sublattices measured by NPD indicates that this compound is a highly anisotropic uniaxial ferromagnet with the easy magnetization axis parallel to c(-->). This experimental study has been completed by a theoretical investigation of the electronic structure of the PrCo(x) (x = 2, 3 and 5) compounds. Band structure calculations with collinear spin polarization were performed by using the local approximation of the density functional theory scheme implemented in the projector-augmented wave method. The electronic structure of PrCo(3) compound in both directions of spin shows that the majority of occupied states are dominated by the 3d states of Co, with a strong electronic charge transfer from Pr to Co. The PrCo(3) electronic structure can be explained by a superimposition of those of PrCo(2) and PrCo(5), as expected from its crystal structure. The magnetic anisotropy has been confirmed for PrCo(3), as a non-collinear spin calculation with the polarization along the c axis is shown to be more stable than with the polarization in the (a(-->),b(-->)) plane.

Magnetic and structural properties of nanocrystalline PrCo3

The structure and magnetic properties of nanocrystalline PrCo

Experimental and computed phase diagrams of the Fe?Re system

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Systematic First-Principles Study of Binary Metal Hydrides

obtained from high energy milling technique are investigated by X-ray diffraction, Curie temperature determination and magnetic properties measurements are reported. The as-milled samples have been annealed in a temperature range of 1023 K to 1273 K for 30 mn to optimize the extrinsic properties. The Curie temperature is 349\,K and coercive fields of 55\,kOe at 10\,K and 12\,kOe at 293\,K are obtained on the samples annealed at 1023\,K. A simulation of the magnetic properties in the framework of micromagnetism has been performed in order to investigate the influence of the nanoscale structure. A composite model with hard crystallites embedded in an amorphous matrix, corresponding to the as-milled material, leads to satisfying agreement with the experimental magnetization curve. [ K. Younsi, V. Russier and L. Bessais, J. Appl. Phys. {\bf 107}, 083916 (2010)]. The microscopic scale will also be considered from DFT based calculations of the electronic structure of

Looking for new thermoelectric materials among TMX intermetallics using high-throughput calculations

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Structural stability of ternary C22–Zr{sub 6}X{sub 2}Co (X=Al, Ga, Sn, As, Sb, Bi, Te) and C22–Zr{sub 6}Sn{sub 2}T′ (T′=Fe, Co, Ni, Cu) compounds

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