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The study of defect phases is important for designing nanostructured metals and alloys. Grain boundaries (GBs) form one class of defects that directly influence materials properties, such as deformability and strength. At the same time, alloying can introduce GB phase transformations and can therewith alter mechanical performance. In this work, the defect phases of a $\Sigma$7 $(12\bar{3}0)$ [0001] 21.78$^\circ$ symmetric tilt GB in hcp Mg are investigated. Ab-initio simulations as a function of stress and temperature (using quasi-harmonic approximation) are performed, and different types of phase transformations are revealed. To this end, the influence of the chemical degree of freedom on the defect phases is studied for the example of Ga addition, using an efficient screening approach that combines empirical potentials and accurate ab-initio calculations. By exploiting the concept of defect phase diagrams, a phase transformation from the T to the A structural type and as well as a systematic transition of the segregation site preference is revealed. The results qualitatively agree well with experimental observations from scanning transition electron microscopy. The underlying physical mechanisms have an impact on grain-boundary engineering in metallic alloys.

Laves phases often form as secondary phases in metallic alloys and have a significant effect on their structural properties. Thus, phase stability studies for these chemically and structurally complex phases in addition to mechanical behavior studies are of great interest. In this work, we use the concept of metastable bulk phase and defect phase diagrams to augment the understanding of the bulk phase and defect phase stability in Laves phases in Mg-based alloys. In this way, we resolve the discrepancy between bulk phase diagrams and experimental observations regarding the formation of Mg-rich C14 and Al-rich C15 Laves phases in MgAlCa alloys at moderate temperatures. Moreover, the effect of the thermodynamic state of alloys on the competition between solute-rich hcp-like planar defects and stoichiometric basal stacking faults is clarified, which determines the brittleness of these alloys. \end{abstract}

Thermodynamic bulk phase diagrams have become the roadmap used by researchers to identify alloy compositions and process conditions that result in novel materials with tailored microstructures. Recent experimental studies show that changes in the alloy composition can drive not only transitions in the bulk phases present in a material, but also in the concentration and type of defects they contain. Defect phase diagrams in combination with density functional theory provide a natural route to study these chemically driven defects. Our results show, however, that direct application of thermodynamic approaches can fail to reproduce the experimentally observed defect formation. Therefore, we extend the concept to metastable defect phase diagrams to account for kinetic limitations that prevent the system from reaching equilibrium. We successfully applied this concept to explain the formation of large concentrations of planar defects in supersaturated Fe-Nb solid solutions and to identify in a joint study with experiments conditions in Mg-Al-Ca alloys for defect phase occurrence. The concept offers new avenues for designing materials with tailored defect structures.

Climate change motivates the search for non-carbon-emitting energy generation and storage solutions. Metal hydrides show promising characteristics for this purpose. They can be further stabilized by tailoring the negative pressure of microstructural and structural defects. Using systematic ab initio and atomistic simulations, we demonstrate that an enhancement in the formation of hydrides at the negatively pressurized crack tip region is feasible by increasing the mechanical tensile load on the specimen. The theoretical predictions have been used to reassess and interpret atom probe tomography experiments for a high-strength 7XXX-aluminium alloy that show a substantial enhancement of hydrogen concentration at structural defects near a stress-corrosion crack tip. These results contain important implications for enhancing the capability of metals as H-storage materials., Comment: 22 pages, 9 figures

Hydrogen embrittlement in Zr alloy fuel cladding is a primary safety concern for water based nuclear reactors. Here we investigated the stabilisation of planar defects within the forming hydrides by Sn, the primary alloying element of Zircaloy-4 used in the cladding. In order to explain formation of hydrides and planar defects observed in our experiments, we performed atomic-scale ab initio calculations focusing on the solute interactions with generalized stacking faults in hcp $\alpha$-Zr and fcc zirconium hydrides. Our calculations showed that an increase in Sn concentration leads to a stabilisation of stacking faults in both $\alpha$-Zr and hydride phases. However, the solution enthalpy of Sn is lower in the $\alpha$-Zr as compared to the other hydride phases indicative of two competing processes of Sn depletion/enrichment at the Zr hydride/matrix interface. This is corroborated by experimental findings, where Sn is repelled by hydrides and is mostly found trapped at interfaces and planar defects indicative of stacking faults inside the hydride phases. Our systematic investigation enables us to understand the presence and distribution of solutes in the hydride phases, which provides a deeper insight into the microstructural evolution of such alloy's properties during its service lifetime., Comment: 17 pages, 8 figures

The concept of quasi-particles forms the theoretical basis of our microscopic understanding of emergent phenomena associated with quantum mechanical many-body interactions. However, quasi-particle theory in disordered materials has proven difficult, resulting in the predominance of mean-field solutions. Here we report first-principles phonon calculations and inelastic x-ray and neutron scattering measurements on equiatomic alloys (NiCo, NiFe, AgPd, and NiFeCo) with force constant dominant disorder - confronting a key 50-year-old assumption in the Hamiltonian of all mean-field quasi-particle solutions for off-diagonal disorder. Our results have revealed the presence of a large, and heretofore unrecognized, impact of local chemical environments on the distribution of the species-pair-resolved force constant disorder that can dominate phonon scattering. This discovery not only identifies a critical analysis issue that has broad implications for other elementary excitations such as magnons and skyrmions in magnetic alloys, but also provides an important tool for the design of materials with ultra-low thermal conductivity., Comment: 25 pages, 6 figures

Carbides play a central role for the strength and ductility in many materials. Simulating the impact of these precipitates on the mechanical performance requires the knowledge about their atomic configuration. In particular, the C content is often observed to substantially deviate from the ideal stoichiometric composition. In the present work, we focus on Fe-Mn-Al-C steels, for which we determined the composition of the nano-sized kappa carbides (Fe,Mn)3AlC by atom probe tomography (APT) in comparison to larger precipitates located in grain boundaries. Combining density functional theory with thermodynamic concepts, we first determine the critical temperatures for the presence of chemical and magentic disorder in these carbides. Secondly, the experimentally observed reduction of the C content is explained as a compromise between the gain in chemical energy during partitioning and the elastic strains emerging in coherent microstructures.

The premartensite phase of shape memory and magnetic shape memory alloys (MSMAs) is believed to be a precursor state of the martensite phase with preserved austenite phase symmetry. The thermodynamic stability of the premartensite phase and its relation to the martensitic phase is still an unresolved issue, even though it is critical to the understanding of the functional properties of MSMAs. We present here unambiguous evidence for macroscopic symmetry breaking leading to robust Bain distortion in the premartensite phase of 10% Pt substituted Ni2MnGa. We show that the robust Bain distorted premartensite (T2) phase results from another premartensite (T1) phase with preserved cubic-like symmetry through an isostructural phase transition. The T2 phase finally transforms to the martensite phase with additional Bain distortion on further cooling. Our results demonstrate that the premartensite phase should not be considered as a precursor state with the preserved symmetry of the cubic austenite phase.

For modeling the magnetic properties of concentrated and diluted magnetic semiconductors, we use the Kondo-lattice model. The magnetic phase diagram is derived by inspecting the static susceptibility of itinerant band electrons, which are exchange coupled to localized magnetic moments. It turns out that rather low band occupations favour a ferromagnetic ordering of the local moment systems due to an indirect coupling mediated by a spin polarization of the itinerant charge carriers. The disorder in diluted systems is treated by adding a CPA-type concept to the theory. For almost all moment concentrations x, ferromagnetism is possible, however, only for carrier concentrations n distinctly smaller than x. The charge carrier compensation in real magnetic semiconductors (in Ga_{1-x}Mn_{x}As by e.g. antisites) seems to be a necessary condition for getting carrier induced ferromagnetism., Comment: 9 pages (REVTeX), 6 figures, to be published in Phys. Rev. B

The periodic s-d(f) exchange model is characterized by a wide variety of interesting applications, a simple mathematical structure and a limited number of reliable approximations which take care of the quantum nature of the participating spins. We suggest the use of a projection-operator method for getting information perturbationally, which are not accessible via diagrammatic approaches. In this paper we present in particular results beyond perturbation theory, which are obtained such that almost all exactly known limiting cases are incorporated correctly. We discuss a variety of possible methods and evaluate their consequences for one-particle properties. These considerations serve as a guideline for a more effective approach to the model., Comment: 11 pages, 6 figures; accepted by Phys. Rev. B

The correlated Kondo-lattice model is used to describe the interaction of electrons in a single conduction band with localized magnetic moments as well as their mutual repulsion. It is our intension to provide an analytical exact result for this model by considering a two-site cluster. An equation-of-motion approach as well as the spectral theorem is chosen to obtain the complete expression for the one-particle Green's function. In a forgoing article the problem has been solved for an insulator, the present paper is devoted to the technical more demanding task of a metal., Comment: 13 pages, 7 figures

The Kondo-lattice model is well established as a method to describe an exchange coupling between single conduction electrons and localized magnetic moments. As a nontrivial exact result the zero-bandwidth limit (atomic limit) can be used to test approximations for this model. As soon as the translational symmetry is broken (for instance by sublattice structures) it is necessary to consider more than one lattice site. Therefore, we study as a starting point for generalizations the situation of a two-site cluster. An equation-of-motion approach is chosen to obtain the one-particle Green's function. In order to determine the spectral weights of its energy poles, we derive different possibilities for the calculation of the involved correlation functions. In this paper the analytical exact result for the situation of an insulator is presented. In a forthcoming article we generalize the calculations to arbitrary electron densities, keeping as the only constraint S=1/2., Comment: 11 pages, 6 figures