Modelling the Defect Processes of Materials for Energy Applications

In order to clarify controversial reports on the Fe–Re phase diagram, a new experimental investigation has been carried out. Three intermetallic phases have been evidenced, including the new report of the P phase found for the first time in a binary system. The phase relations involving the σ phase were established. In parallel, a first-principles study has been performed which provided the heat of formation of every ordered configuration for four intermetallic phases (D8b, A12, A13 and P). The mixing energy of solid solutions (fcc, bcc, hcp) was calculated using the special quasi-random structure method. Calculations were performed with the help of the density functional theory, with and without spin polarization. From these results, in the frame of the Compound Energy Formalism using the Bragg–Williams approximation, the Fe–Re phase diagram has been computed without the use of adjustable parameters. Different thermodynamic parameters obtained experimentally and theoretically, as the site occupancies, are compared. The computed phase diagram presents several differences with the experimental one. To understand these differences, the influence of several parameters on the phase stability, such as the magnetic contribution has been evaluated.

Mechanochemical synthesis (MS) of Ni70Al25Mo5 (composition 1) and Ni75Al20Mo5 (composition 2) mixtures, in which 5 at % Mo substitutes for the equal amount of Ni or Al, leads to the formation of Ni-based nanocrystalline (coherent domains are ∼7–12 nm in size) solid solutions; in this case, some amount of molybdenum remains free. A comparison of the lattice parameters of solid solutions, which were determined experimentally, with the magnitudes determined theoretically using Vegard law and Bozollo-Ferrante simulation, which takes into account volume modules of elasticity of elements, showed an increase in interactions between atoms composed the solid solution and the formation of regions characterized by short-range order. The heating of mechanically synthesized three-component Ni(Al, Mo) solid solutions to 720°C in a calorimeter chamber forms the ordered γ′ phase (L12) at T ∼ 450°C. An analysis of the ratio of relative intensities of superlattice and fundamental reflections showed that, whatever the composition of initial mixture, Mo atoms always occupy positions in the Al sublattice. This arrangement of Mo atoms was confirmed by calculations of coefficients of concentrational variations of the lattice parameters. When molybdenum is added to Ni3 Al, Mo atoms, rather than Ni atoms, complete the Al sublattice. In this case, vacancies compensate for the lack of atoms in the Ni sublattice.

We investigate, in the present study, the structural properties, magnetic moments and charge distribution of the solid solution in an immiscible Co–Cu system at equilibrium by first-principles calculation using special quasirandom structures (SQS). In order to mimic the pair and multisite correlation functions of the randomly substitutional fcc solid solutions, the original SQS is developed to include five 16-atom SQS unit cells, i.e., 1/16, 2/16, 3/16, 4/16, and 8/16, enabling to mimic at nine specific alloys compositions. Correspondingly, a new error analysis method is proposed for comparing the situations of various alloy compositions within the SQS unit cells having a same number of atoms. The developed SQS are then applied in the first-principles calculation to study the Co x Cu 1- x solid solutions ( x refers to the Co concentration). It turns out that the calculated results of the lattice constants and magnetic moments versus the Co concentration are in good agreement with the experimental data, an...

First-principles study of the relative stability of various zirconium hydrides using the special quasirandom structures approach

Prediction of mechanical properties of AlTiCrVNb high entropy alloys with B2 ordered structure

The three binary garnet solid solutions (Fe3Al2Si3O12)-Al-II-(X3Al2Si3O12)-Al-II (X-II= Mg-II, Mn-II, Ca-II) have been investigated by Fe-57 Mossbauer spectroscopy at 298 and 77 K and by electronic structure calculations in the local spin density approximation. The spectra yield isomer shifts and quadrupole splittings that are typical for Fe-II in the dodecahedral X-site of 222 point symmetry and are similar for each of the three binaries recorded. Conversely, electronic structure calculations based on the experimental crystal structure of the different end-member garnets exhibit pronounced variations in some of the electronic properties of Fe-II that are not reflected in the spectroscopic data. These results are interpreted as indicating that the different X-O bonds in garnet solid solutions retain to a large degree the intrinsic lengths that they possess in their respective end members, and that the Fe-O bond does not change greatly as a function of composition. This is evidence for the state of alternating bonds and not for the virtual crystal approximation in describing the X-O bond types or lengths in aluminosilicate garnet solid solutions. The observed degree and behavior of the Fe-II doublet asymmetry in the Mossbauer spectra for the three solid solution series do not indicate major variations in the anisotropic recoil-free fraction of Fe-II. Variations in doublet asymmetry are more likely a result of complex next-nearest X-site neighbor interactions and/or some degree of short-range cation ordering, though doublets representing different local X-site cation configurations cannot be resolved or fitted to the experimental spectra.

Thermodynamic stability and disordering in La cSr 1− cMnO 3 solid solutions

Intermetallic compounds, due to their well-defined stoichiometry, arrangement of atoms and controlled crystal structure, are a promising alternative to expensive noble metal catalysts. In this paper, the catalytic properties of Al-13.5 at.% Cr and Al-13.5 at.% V alloys, corresponding to the quasicrystalline approximants Al45Cr7 and Al45V7, were investigated for the first time.The alloys in the form of fragmented brittle ribbons were produced by the melt-spinning. The microstructure of the ribbons, both in the as-spun state and after heat treatment (100 h at 600 °C), was characterized by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. In the as-spun state, the ribbons showed a multiphase microstructure. In addition to the Al45Cr7 phase in the Al-Cr alloy and the Al3V phase in the Al-V alloy, they also contained α(Al) solid solution and icosahedral quasicrystalline phases. After heat treatment, the alloys became almost single phase, consisting mainly of stable monoclinic phases: Al45Cr7 or Al45V7. The catalytic performance of the phenylacetylene hydrogenation reaction was tested on as-spun and heat-treated alloys that had previously been pulverized and sieved to select a powder fraction of less than 32 µm. All the tested materials show high substrate conversion, above 80% after 1 h reaction, along with high activity rate. The homogenized powders demonstrated a slightly better properties in relation to as-spun materials. These results confirm the potential of intermetallic catalysts, including the tested alloys, in hydrogenation reactions and verify the possibility of using the metallurgical method to obtain catalytically active materials.Graphical abstract

Dislocation motion in random and nonrandom (fcc) solid solutions

Synthesis, electrical transport, magnetic properties and electronic structure of Ti1-xScxCoSb semiconducting solid solution

The effects of applied strain on the arrangement of atoms in AuPd∕Pd(100) surface alloys are studied using Monte Carlo simulations and cluster expansion Hamiltonians. The strain effects are found to be significant, with heteronuclear (Au-Pd) interactions more strongly enhanced by biaxial compression than homonuclear (Pd-Pd) ones. In particular, compressive strain causes an increase in the population of Pd monomers and second nearest-neighbor pairs of Pd monomers, both of which have been identified previously as important ensembles for various catalytic reactions. We also discuss the origin of these effects using density functional theory calculations of the surface electronic structure of strained AuPd∕Pd(100). Our findings may suggest an additional means of employing strain to tune the catalytic properties of surface alloys.

Transparency enhancement for SrVO3 by SrTiO3 mixing: A first-principles study

Elastic properties of disordered binary hcp-Fe alloys under high pressure: Effects of light elements

The aim of this paper is to investigate the contribution of the mixing enthalpy to the stability of the faced-centered cubic (fcc) phase of the Co–Cr–Fe–Mn–Ni system. For this purpose, systematic first principles calculations on Special Quasirandom Structures (SQS) were performed in a comprehensive manner on the fcc solution in every \(\left( {\begin{array}{c}5\\ 2\end{array}}\right) =10\) binary, \(\left( {\begin{array}{c}5\\ 3\end{array}}\right) =10\) ternary, \(\left( {\begin{array}{c}5\\ 4\end{array}}\right) =5\) quaternary and the quinary systems. The magnetic contributions have been considered carefully i.e. including non-collinear spin polarization. An analysis of the different system order interactions to the enthalpy of mixing is detailed. This concludes that, at equiatomic composition, there is no special “cocktail” effect with an increase of components and that the thermodynamic properties can be well anticipated from the lower order systems, essentially binary and ternary systems.

In recent years, various environmental problems such as rising temperature, droughts, and extreme weather events have become more serious in many parts of the world because of global warming. One of the causes of the global warming is an increase in emissions of greenhouse gases such as CO2, CH4, and N2O, those are emitted during a combustion of fossil fuels such as coal, oil, and natural gas in thermal power generation. As energy consumption accelerates year by year, the depletion of fossil fuels is also becoming an issue. Therefore, hydrogen energy is attracting attention. Hydrogen is known as a clean energy because it reacts with oxygen to produce only water and chemical energy.Fuel cells are attracting attention as a new power generation device that produces electricity from hydrogen energy. Fuel cells generate electricity directly through chemical reactions, resulting in minimal power generation loss from energy conversion. Solid oxide fuel cells (SOFC), in which solid oxide electrolyte membrane (SOEM) is used as the electrolyte membrane, have particularly high-power generation efficiency. On the other hand, the operating temperature of SOFCs is extremely high (over 1000 K), which accelerates degradation of SOEM. Therefore, it is necessary to lower the operating temperature from high to medium (about 700 K) while maintaining high power generation efficiency.To solve this problem, we focus on dual-phasing and nano-structuring of SOEMs. Previous studies of SOEM have shown that dual-phase membranes have better ion transport performance than a single-phase membrane. For example, a dual-phase SOEM is composed of SSC (SrSc0.1Co0.9O3-d) with perovskite structure and SDC (Sm0.2Ce0.8O2-d) with fluorite structure. One the other hand, nano-structuring are nano-thin film and nano-crystalline. Nano-thin film is a method of forming an electrolyte film of several μm by layering nano-films of several nm in size. Nano-crystalline is a method to reduce a crystal size to several tens of nanometers. By these nano structures, the resistance of ion conduction is reduced, and ion conductivity is improved.However, the number of interfaces in dual-phase SOEM and nano structured membrane is expected to increase. Previous studies have reported a decrease in ion conductivity near the interface between different structures of membrane. This decrease in ion conductivity at the interface is caused by an increase in the energy barrier as the conduction path passes through the interface. The correlation between the reduction of ion conductivity and nano structures in membrane has not been clarified clearly.In this study, we analyze the mechanism of oxygen ion conductivity reduction near the interface by numerical simulations. Molecular simulations are performed to build up information by multi-scale analysis. Specifically, density functional theory (DFT), molecular dynamics (MD), and kinetic Monte Carlo (kMC) are performed in a bottom-up manner. First, MD simulations were performed using a potential model constructed from the energy states in the atomic arrangement at the interface obtained by DFT. We analyzed the ion conductivity at the interface and its crystal size dependence. We also create a hopping model of oxygen ions moving from site to site for kMC simulations. Next, kMC simulations are performed to analyze the oxygen ion conductivity in the dual-phase SOEM including interface, on a time and spatial scale similar to that of a real SOEMs.In this presentation, we report on the results of MD simulation. A dual-phase SOEM model consisting of SSC and SDC was used as the simulation model (Fig.1(a)). The diffusion coefficient of oxygen ions was obtained as an indicator of ionic conductivity. Because the ionic conductivity is determined by the balance between the energy barrier of the conduction path and the kinetic energy of the ions involved in ionic conduction. In this study, the activation energy for the diffusion was calculated as the energy barrier. The activation energy was estimated from Arrhenius relation of diffusion coefficient. The number of unit cells in the dual-phase SOEM model was varied to change the crystal size. As a result, both the diffusion coefficient and activation energy increase as the crystal size of SSC increases. On the other hand, as the crystal size of SDC increases, although the diffusion coefficient decreases, the activation energy increases (Fig.1(b)). These results show the dependence of the diffusion coefficient and activation energy on the crystal size in a dual-phase SOEM. Figure 1