Abstract: Ab initio electronic structure theory has achieved considerable reliability concerning predictions of physical and chemical properties and phenomena. It provides understanding of matter at the atomic and electronic scale with an unprecedented level of details and accuracy. In the present contribution, the electronic structure theory and state-of-the-art ab initio calculation methods in solids are briefly reviewed and the application of the calculated total energy differences between various phases (lattice stabilities) is illustrated on construction of phase diagrams by the CALPHAD (CALculation of PHAse Diagrams) method in systems containing phases with complex structures, as e.g. Laves phases or sigma phase. Particular examples include description of the Laves phases in the Cr-Nb, Cr-Ta and Cr-Zr systems, sigma-phase in the Fe-Cr system and prediction of the phase composition of ternary Fe-Cr-Mo system and super-austenitic steels. It is shown that the utilization of ab initio results introduces a solid basis of the energetics of systems with complex phases, allows to avoid unreliable estimates and extrapolations of Gibbs energies and brings more physics into the CALPHAD method.
Abstract: Cahn-Hilliard type of phase field model coupled with elasticity is used to derive governing equations for the stress-mediated diffusion and phase transformation in thin films. To solve the resulting equations, a finite element (FE) model is presented. The partial differential equations governing diffusion and mechanical equilibrium are of different orders; Mixed-order finite elements, with C0 interpolation functions for displacement, and C1 interpolation functions for concentration are implemented. To validate this new numerical solver for such coupled problems, we test our implementation on thin film diffusion couples.
Abstract: The statistical-thermodynamics and kinetics models of atomic ordering in a metal-doped graphene (binary two-dimensional planar graphene-type crystal lattice) at 1/8, 1/4, and 1/2 stoichiometries are proposed. Impossibility of (completely) atomic-ordered distribution at 1/6 and 1/3 stoichiometries is ascertained in a graphene-type crystal lattice (in case of a short-range interatomic interactions at least). If a graphene is doped by the short-range interacting metal atoms, the superstructures described only by a one LRO parameter are possible; and if it is doped by the long-range interacting metal atoms, the new superstructures with the two or three LRO parameters may appear as well. If stoichiometry is 1/4, the structure has a one long-range order (LRO) parameter is more thermodynamically favorable than those have one or two LRO parameters. It is established that kinetics curves of LRO parameters can be non-monotonic for structures where there are two or three LRO parameters (because graphene-type lattice contains two sublattices, and mixing energy is different for each of them). It is shown that the most ordered is structure with equal atomic fractions of carbon and metal atoms, while the least one is structure with a maximal difference of carbon and metal atoms. Kinetics results confirm statistical-thermodynamic ones: firstly, equilibrium values of LRO parameter coincide within the framework of both models, secondly, equilibrium (and instantaneous) value of LRO parameter in a nonstoichiometric binary graphene-type structure (where atomic fraction of a doping component deviates from the stoichiometry to the side of the higher concentrations) may be higher than it is in a stoichiometric one. The dominance of the same physical mechanisms of atomic ordering in both mixed nanosystems and macrosystems is assumed.
Abstract: Monte Carlo simulations and finite-size scaling analysis have been carried out to study the critical behavior in a submonolayer lattice-gas, which mimics a nanoporous environment. In this model, one-dimensional chains of atoms were arranged in a triangular cross-sectional structure. Two kinds of lateral interaction energies have been considered: (1) wL, interaction energy between nearest-neighbor particles adsorbed along a single channel and (2) wT, interaction energy between particles adsorbed across nearest-neighbor channels. We focus on the case of repulsive transverse interactions (wT > 0), where a rich variety of structural orderings are observed in the adlayer, depending on the value of the parameters kBT/wT (kB being the Boltzmann constant) and wL /wT. For wL /wT = 0, successive planes are uncorrelated, the system is equivalent to the triangular lattice, and the well-known [ ] ordered phase is found at low temperatures and a coverage, , of 1/3 [2/3]. In the more general case (wL /wT 0), the competition between interactions along a single channel and the transverse coupling between sites in neighboring channels leads to a three-dimensional adsorbed layer. Consequently, the and structures “propagate” along the channels and new ordered phases appear in the adlayer. The influence of each ordered phase on adsorption isotherms, differential heat of adsorption and configurational entropy of the adlayer has been analyzed and discussed in the context of the lattice-gas theory. Finally, the Monte Carlo technique was combined with the recently reported free energy minimization criterion approach (FEMCA) [F. Romá et al.: Phys. Rev. B Vol. 68 (2003), art. no. 205407] to predict the critical temperatures of the surface-phase transformations occurring in the adsorbate. The excellent qualitative agreement between simulated data and FEMCA results allows us to interpret the physical meaning of the mechanisms underlying the observed transitions.
Abstract: Owing to the technological importance of M-type hexaferrites of general formula MFe12O19 (M = Ba, Sr and Pb) and their substituted analogues, a staggering number of research activities on their synthesis, magnetic properties and thermal properties are being pursued in recent years. However, many critical issues on the effect of aliovalent ion substitution either on the M-site or Fe-sites are still unexplored. This paper deals with a survey of crystallochemical and thermodynamic properties of this important class of ferrimagnetic oxides.
Abstract: The study of high pressure structural stability and equation of state of f-electron based binary intermetallics of type AXBY, where A belongs to either rare earth of actinide atom and B any other d or p block metal, is interesting from both basic as well as applied research point of view. These studies have lead to some general systematic patterns emerging. Firstly, the AB type of compounds in general stabilizes in NaCl type cubic structure and transform to CsCl type under the action of pressure. The AB2 type of compounds is very interesting and under pressure undergoes a series of structural transitions. However, the AB3 type systems are highly stable and do not show structural transitions under pressure up to as high as 30 GPa. We found that it is interesting and enlightening to explore: (i) the reason for their stability by examining the electronic structure and (ii) look for general trends in the structural transformations. In this paper, we have presented some of our studies on f-electron based intermetallics (f-IMCs), elaborate on the trends seen in the structural transitions and correlate the results obtained with the electronic structure calculations.
Abstract: The most extensively studied Heusler alloys are those based on the Ni-Mn-Ga system. However, to overcome the high cost of Gallium and the usually low martensitic transformation temperature, the search for Ga-free alloys has been recently attempted, particularly, by introducing In, Sn or Sb. In this work, Mn50Ni40In10, Mn50Ni34In16, Ni50Mn36-xIn14+x (x = 0, 0.5, 1, 1.5) and Ni50Mn37Sn13 ribbons has been obtained by melt spinning. We outline their structural and thermomagnetic behavior. Columnar grains and preferential orientation has been obtained. The martensitic, Tm, and the Curie, TC, temperatures of the ribbons are lower than those of the bulk samples with similar compositions. This effect is probably due to the ribbons small and constrained grains. For it, a large under-cooling is necessary for the martensitic transformation. The decrease of TC in the ribbons could be associated with the increased degree of quenched-in short-range disorder around defects.
Abstract: Shear deformation and shuffling of atomic planes are elementary mechanisms of collective atomic motion that take place during displacive phase transformations. General displacements of atomic planes are examined, i.e. -surface type calculations extensively used for the stacking faults and crystal dislocations are applied to single plane shuffling and alternate shuffling of every other atomic plane producing in combination with homogeneous deformation the hcp structure (martensitic type) from the initial bcc structure (austenitic type). Similar approach considering shear type planar displacements leads to the Zener path between the bcc and fcc lattices. The effect of additional deformation required to obtain the close-packed atomic arrangements is examined as well. Finally, the influence of volume modification on phase transitions is investigated. The energies of various structural configurations are calculated using many-body potentials for the description of interatomic forces. Such atomic models are tested to check their suitability for investigation of the role of interfaces in the displacive structural transitions.
Abstract: Interest in hydrogen as a future energy carrier in mobile applications has led to a strong increase in research on the structural properties of complex alkali metal and alkaline earth hydrides, with the aim to find structural phases with higher hydrogen densities. This contribution reviews recent work on the structural properties and phase diagrams of these complex hydrides under elevated pressures, an area where rapid progress has been made over the last few years. The materials discussed in greatest detail are LiAlH4, NaAlH4, Li3AlH6, Na3AlH6, LiBH4, NaBH4, and KBH4. All of these have been studied under high pressure by various methods such as X-ray or neutron scattering, Raman spectroscopy, differential thermal analysis or thermal conductivity measurements in order to find information on their structural phase diagrams. Based mainly on experimental studies, preliminary or partial phase diagrams are also given for six of these materials. In addition to this information, data are provided also on experimental results for a number of other complex hydrides, and theoretical predictions of new phases and structures under high pressures are reviewed for several materials not yet studied experimentally under high pressure.