Abstract: We investigate phase stability and vacancy formation in fcc Fe-Ni alloys over a broad composition-temperature range, via a density functional theory parametrized effective interaction model, which includes explicitly spin and chemical variables. On-lattice Monte Carlo simulations based on this model are used to predict the temperature evolution of the magnetochemical phase. The experimental composition-dependent Curie and chemical order-disorder transition temperatures are successfully predicted. We point out a significant effect of chemical and magnetic orders on the magnetic and chemical transitions, respectively. The resulting phase diagram shows a magnetically driven phase separation around 10-40% Ni and 570-700 K, between ferromagnetic and paramagnetic solid solutions, in agreement with experimental observations. We compute vacancy formation magnetic free energy as a function of temperature and alloy composition. We identify opposite magnetic and chemical disordering effects on vacancy formation in the alloys with 50% and 75% Ni. We find that thermal magnetic effects on vacancy formation are much larger in concentrated Fe-Ni alloys than in fcc Fe and Ni due to a stronger magnetic interaction. read less

Abstract: Alexis Front, ∗ Georg Daniel Förster, 2, † Van-Truong Tran, Chu-Chun Fu, Cyrille Barreteau, François Ducastelle, and Hakim Amara 5, ‡ Laboratoire d’Etude des Microstructures, ONERA-CNRS, UMR104, Université Paris-Saclay, BP 72, Châtillon Cedex, 92322, France Interfaces, Confinement, Matériaux et Nanostructures (ICMN), CNRS, Université d’Orléans, Orléans, France Université Paris-Saclay, CEA, Service de Recherches de Métallurgie Physique, 91191 Gif-sur-Yvette, France DRF-Service de Physique de l’Etat Condensé, CEA-CNRS, Université Paris-Saclay, F-91191 Gif-sur-Yvette, France Université de Paris, Laboratoire Matériaux et Phénomènes Quantiques (MPQ), CNRS-UMR7162, 75013 Paris, France read less

Abstract: We have studied the interfacial thermal conductance, G, of the flat Au(111)-water interface using non-equilibrium molecular dynamics simulations. We utilized two metal models, one based on the embedded atom method (EAM) and the other including metallic polarizability via a density readjusting EAM. These were combined with three popular water models, SPC/E, TIP4P, and TIP4P-FQ, to understand the role of polarizability in the thermal transport process. A thermal flux was introduced using velocity shearing and scaling reverse non-equilibrium molecular dynamics, and transport coefficients were measured by calculating the resulting thermal gradients and temperature differences at the interface. Our primary finding is that the computed interfacial thermal conductance between a bare metal interface and water increases when polarizability is taken into account in the metal model. Additional work to understand the origin of the conductance difference points to changes in the local ordering of the water molecules in the first two layers of water above the metal surface. Vibrational densities of states on both sides of the interface exhibit interesting frequency modulation close to the surface but no obvious differences due to metal polarizability. read less

Abstract: We present a model of pair interactions on rigid lattice to study the thermodynamic properties of iron-nickel alloys. The pair interactions are fitted at 0 K on ab initio calculations of formation enthalpies of ordered and disordered (special quasi-random) structures. They are also systematically fitted on the Gibbs free energy of the γ Fe-Ni solid solution as described in a CALPHAD (CALculation of PHAse Diagrams) study by Cacciamani et al. This allows the effects of finite temperature, especially those of magnetic transitions, to be accurately described. We show that the ab initio and CALPHAD data for the γ solid solution and for the FeNi 3 -L1 2 ordered phase can be well reproduced, in a large domain of composition and temperature, using first and second neighbor pair interactions which depend on temperature and local alloy composition. The procedure makes it possible to distinguish and separately compare magnetic, chemical and configuration enthalpies and entropies. We discuss the remaining differences between the pair interaction model and CAL-PHAD, which are mainly due to the treatment of the short-range order and configurational entropy of the solid solution. The FCC phase diagram of the Fe-Ni system is determined by Monte Carlo simulations in the semi-grand canonical ensemble and is compared with experimental studies and other models. We especially discuss the stability of the FeNi-L1 0 phase at low temperature. read less

Abstract: Interatomic potentials constitute the key component of large-scale atomistic simulations of materials. The recently proposed physically-informed neural network (PINN) method combines a high-dimensional regression implemented by an artificial neural network with a physics-based bond-order interatomic potential applicable to both metals and nonmetals. In this paper, we present a modified version of the PINN method that accelerates the potential training process and further improves the transferability of PINN potentials to unknown atomic environments. As an application, a modified PINN potential for Al has been developed by training on a large database of electronic structure calculations. The potential reproduces the reference first-principles energies within 2.6 meV per atom and accurately predicts a wide spectrum of physical properties of Al. Such properties include, but are not limited to, lattice dynamics, thermal expansion, energies of point and extended defects, the melting temperature, the structure and dynamic properties of liquid Al, the surface tensions of the liquid surface and the solid-liquid interface, and the nucleation and growth of a grain boundary crack. Computational efficiency of PINN potentials is also discussed. read less

Abstract: ABSTRACT A critic issue of the application of the conventional grand-canonical Monte Carlo (GCMC) method in high-density systems is the low acceptance ratio of insertion. Previous studies have revealed that this can be overcome by the cavity-biased (CB) insertion method in simulations of vapours, fluids and liquids. Here, we demonstrate that the method is also highly efficient in metals. Using the Fe–H system as an example, we find that the acceptance ratio of inserting H into Fe lattice is increased by several times using the CB GCMC method. The method is more valid than the conventional one at bulk H concentration over 5‰, implying that the CB GCMC method is highly efficient when there are deep traps for H in simulation systems, i.e. dislocations and interfaces. Application of the method in nanocrystalline Fe shows that the CPU time required for obtaining an equilibrium distribution of H is reduced by 60%. read less

Abstract: We present a methodology to predict magnetic systems using ab initio methods. By employing crystal structure method and spin-polarized calculations, we explore the relation between crystalline structures and their magnetic properties. In this work, testbed cases of transition metal alloys (FeCr, FeMn, FeCo and FeNi) are study in the ferromagnetic case. We find soft-magnetic properties for FeCr, FeMn while for FeCo and FeNi hard-magnetic are predicted. In particular, for the family of FeNi, a candidate structure with energy lower than the tetrataenite was found. The structure has a saturation magnetization (Ms) of 1.2 MA m−1, magnetic anisotropy energy (MAE) above 1200 kJ m−3 and hardness value close to 1. Theoretically, this system made of abundant elements could be the right candidate for permanent magnet applications. Comparing with the state-of-the-art (Nd2Fe14B) hard-magnet, (Ms of 1.28 MA m−1 and MAE of 4900 kJ m−3) is appealing to explore this low energy polymorph of FeNi further. Considering the relatively limited number of magnets, predicting a new system may open routes for free rare-earth magnets. Furthermore, the use of the computational algorithm as the one presented in this work, hold promises in this field for which in near future improvements will allow to study numerous complex systems, larger simulations cells and tackled long-range antiferromagnetic cases. read less

Abstract: Interstitial alloying in CrMnFeCoNi-based high-entropy alloys is known to modify their mechanical properties. Specifically, strength can be increased due to interstitial solid-solution hardening, while simultaneously affecting ductility. In this paper, first-principles calculations are carried out to analyze the impact of interstitial C atoms on CrMnFeCoNi in the fcc and the hcp phases. Our results show that C solution energies are widely spread and sensitively depend on the specific local environments. Using the computed solution-energy distributions together with statistical mechanics concepts, we determine the impact of C on the phase stability. C atoms are found to stabilize the fcc phase as compared to the hcp phase, indicating that the stacking-fault energy of CrMnFeCoNi increases due to C alloying. Using our extensive set of first-principles computed solution energies, correlations between them and local environments around the C atoms are investigated. This analysis reveals, e.g., that the local valence-electron concentration around a C atom is well correlated with its solution energy. read less

Abstract: The presence of the ordered γ ′ phase (Ni3Al) in Ni-base superalloys is fundamental to the performance of engineering components such as turbine disks and blades which operate at high temperatures and loads. Hence for these alloys it is important to optimize their microstructure and phase composition. This is typically done by varying their chemistry and heat treatment to achieve an appropriate balance between γ ′ content and other constituents such as carbides, borides, oxides and topologically close packed phases. In this work we have set out to investigate the onset of γ ′ ordering in Ni-Al single crystals and in Ni-Al bicrystals containing coincidence site lattice grain boundaries (GBs) and we do this at high temperatures, which are representative of typical heat treatment schedules including quenching and annealing. For this we use the atomistic simulation methods of molecular dynamics (MD) and density functional theory (DFT). In the first part of this work we develop robust Bayesian classifiers to identify the γ ′ phase in large scale simulation boxes at high temperatures around 1500 K. We observe significant γ ′ ordering in the simulations in the form of clusters of γ ′-like ordered atoms embedded in a γ host solid solution and this happens within 100 ns. Single crystals are found to exhibit the expected homogeneous ordering with slight indications of chemical composition change and a positive correlation between the Al concentration and the concentration of γ ′ phase. In general, the ordering is found to take place faster in systems with GBs and preferentially adjacent to the GBs. The sole exception to this is the Σ3 (111) tilt GB, which is a coherent twin. An analysis of the ensemble and time lag average displacements of the GBs reveals mostly ‘anomalous diffusion’ behaviour. Increasing the Al content from pure Ni to Ni 20 at.% Al was found to either consistently increase or decrease the mobility of the GB as seen from the changing slope of the time lag displacement average. The movement of the GB can then be characterized as either ‘super’ or ‘sub-diffusive’ and is interpreted in terms of diffusion induced grain boundary migration, which is posited as a possible precursor to the appearance of serrated edge grain boundaries. In the second part of this work we develop a method for the training of empirical interatomic read less

Abstract: Significance The cloudy zone is naturally occurring nanocomposite found in Fe–Ni metal-bearing meteorites. It not only is a potent carrier of paleomagnetic information from the early solar system but also shows promise as a sustainable alternative to rare earth-based permanent magnets. Here we explain how the remarkable magnetic properties of the cloudy zone are linked to its 3D chemical, crystallographic, and magnetic architecture, using a state-of-the-art combination of nanometer to subnanometer resolution tomography and micromagnetic simulations. We discover the mechanism by which paleomagnetic information becomes encoded into the cloudy zone and, inspired by our findings, point toward potential pathways to optimize synthetic analogues of the cloudy zone for industrial applications. Meteorites contain a record of their thermal and magnetic history, written in the intergrowths of iron-rich and nickel-rich phases that formed during slow cooling. Of intense interest from a magnetic perspective is the “cloudy zone,” a nanoscale intergrowth containing tetrataenite—a naturally occurring hard ferromagnetic mineral that has potential applications as a sustainable alternative to rare-earth permanent magnets. Here we use a combination of high-resolution electron diffraction, electron tomography, atom probe tomography (APT), and micromagnetic simulations to reveal the 3D architecture of the cloudy zone with subnanometer spatial resolution and model the mechanism of remanence acquisition during slow cooling on the meteorite parent body. Isolated islands of tetrataenite are embedded in a matrix of an ordered superstructure. The islands are arranged in clusters of three crystallographic variants, which control how magnetic information is encoded into the nanostructure. The cloudy zone acquires paleomagnetic remanence via a sequence of magnetic domain state transformations (vortex to two domain to single domain), driven by Fe–Ni ordering at 320 °C. Rather than remanence being recorded at different times at different positions throughout the cloudy zone, each subregion of the cloudy zone records a coherent snapshot of the magnetic field that was present at 320 °C. Only the coarse and intermediate regions of the cloudy zone are found to be suitable for paleomagnetic applications. The fine regions, on the other hand, have properties similar to those of rare-earth permanent magnets, providing potential routes to synthetic tetrataenite-based magnetic materials. read less

Abstract: A new interatomic potential has been developed for the Ni–Cr system in the angular-dependent potential (ADP) format by fitting the potential parameters to a set of experimental and first-principles data. The ADP potential reproduces a wide range of properties of both elements as well as binary alloys with reasonable accuracy, including thermal and mechanical properties, defects, melting points of Ni and Cr, and the Ni–Cr phase diagram. The potential can be used for atomistic simulations of solidification, mechanical behavior and microstructure of the Ni-based and Cr-based phases as well as two-phase alloys. read less

Abstract: ABSTRACT The displacements of atoms around Guinier–Preston 1 (GP1) zones in Al–Cu alloys at a temperature of 295 K have been investigated using molecular dynamics (MD) simulations. The magnitude of the displacements at the first Al layer adjacent to a GP1 zone reached 24% strain and this value decreased with distance from the zone to zero at about 40th Al layer. Strain fields near a GP1 zone were evaluated by calculating strain tensors around individual atoms. The obtained strain maps suggested that the equilibrium Cu content in a GP1 zone should be 100%. The atomic configurations determined by MD simulations were utilised for multislice image simulations of annular dark-field scanning transmission electron microscopy (ADF-STEM) to investigate the effect of foil thickness and the depth position of a GP1 zone in a foil on ADF-STEM images. The atomic displacements in ADF-STEM images were smaller than the MD result due to foil thickness and electron channelling. read less

Abstract: Effective interaction potentials suitable for Cu/δ-Ni2Si and Cu/β-Ni3Si are developed. We optimise the potential parameters of an embedded atom method potential to reproduce forces, energies, and stresses obtained from ab initio calculations. Details of the potential generation are given, and its validation is demonstrated. The potentials are used in molecular dynamics simulations of shear tests to study the interactions of edge dislocations with coherent δ-Ni2Si and β-Ni3Si precipitates embedded in a copper matrix. In spite of significantly different crystallographic structures of copper and δ-Ni2Si which usually result in circumvention of dislocations, we also observed cutting processes in our simulations. Dislocations cut for a specific orientation of the δ-Ni2Si precipitate and in some cases where dislocation loops originating from previous circumvention processes are present in the glide plane. It is found that β-Ni3Si precipitates have a similar effect on precipitation strengthening as δ-Ni2Si. Dislocations usually cut β-Ni3Si but increased coherency strain can lead to circumvention processes. read less

Abstract: We introduce atomicrex, an open-source code for constructing interatomic potentials as well as more general types of atomic-scale models. Such effective models are required to simulate extended materials structures comprising many thousands of atoms or more, because electronic structure methods become computationally too expensive at this scale. atomicrex covers a wide range of interatomic potential types and fulfills many needs in atomistic model development. As inputs, it supports experimental property values as well as ab initio energies and forces, to which models can be fitted using various optimization algorithms. The open architecture of atomicrex allows it to be used in custom model development scenarios beyond classical interatomic potentials while thanks to its Python interface it can be readily integrated e.g., with electronic structure calculations or machine learning algorithms. read less

Abstract: Ability to accelerate the morphological evolution of nanoscale precipitates is a fundamental challenge for atomistic simulations. Kinetic Monte Carlo (KMC) methodology is an effective approach for accelerating the evolution of nanoscale systems that are dominated by so-called rare events. The quality and accuracy of energy landscape used in KMC calculations can be significantly improved using DFT-informed interatomic potentials. Using newly developed computational framework that uses molecular simulator LAMMPS as a library function inside KMC solver SPPARKS, we investigated formation and growth of Guiner–Preston (GP) zones in dilute Al–Cu alloys at different temperature and copper concentrations. The KMC simulations with angular dependent potential (ADP) predict formation of coherent disc-shaped monolayers of copper atoms (GPI zones) in early stage. Such monolayers are then gradually transformed into energetically favored GPII phase that has two aluminum layers sandwiched between copper layers. We analyzed the growth kinetics of KMC trajectory using Johnson–Mehl–Avrami (JMA) theory and obtained a phase transformation index close to 1.0. In the presence of grain boundaries, the KMC calculations predict the segregation of copper atoms near the grain boundaries instead of formation of GP zones. The computational framework presented in this work is based on open source potentials and MD simulator and can predict morphological changes during the evolution of the alloys in the bulk and around grain boundaries. read less

Abstract: The effects of plateau width and step-edge kinking on carbon monoxide (CO)-induced restructuring of platinum surfaces were explored using molecular dynamics (MD) simulations. Platinum crystals displaying four different vicinal surfaces [(321), (765), (112), and (557)] were constructed and exposed to partial coverages of carbon monoxide. Platinum–CO interactions were fit to recent experimental data and density functional theory (DFT) calculations, providing a classical interaction model that captures the atop binding preference on Pt. The differences in Pt–Pt binding strength between edge atoms on the various facets were found to play a significant role in step-edge wandering and reconstruction events. Because the mechanism for step doubling relies on a stochastic meeting of two wandering edges, the widths of the plateaus on the original surfaces were also found to play a role in these reconstructions. On the Pt(321) surfaces, the CO adsorbate was found to assist in reordering the kinked step edges into st... read less

Abstract: Modelling the segregation of the various chemical species in the vicinity of crystallographic defects in FeNi alloys is essential because it affects the macroscopic properties of these materials, which are widely used in technological applications. We present here a theoretical study of surface segregation, within a mean-field approach based on the tight-binding Ising model grounded on density functional theory calculations. The most important result is that, although FeNi presents none of the driving forces (i.e. surface energy, size mismatch) which generally favour surface enrichment in the same element in the whole range of concentrations, there exists a wide temperature range in which Ni is found to segregate at the surface irrespective of the concentration. This is due to a complex interplay between magnetic and ordering/phase separation effects. read less

Abstract: Empirical interatomic potentials are widely used in atomistic simulations due to their ability to compute the total energy and interatomic forces quickly relative to more accurate quantum calculations. The functional forms in these potentials are sometimes stored in a tabulated format, as a collection of data points (argument–value pairs), and a suitable interpolation (often spline-based) is used to obtain the function value at an arbitrary point. We explore the effect of these interpolations on the potential predictions by calculating the quasi-harmonic thermal expansion and finite-temperature elastic constant of a one-dimensional chain compared with molecular dynamics simulations. Our results show that some predictions are affected by the choice of interpolation regardless of the number of tabulated data points. Our results clearly indicate that the interpolation must be considered part of the potential definition, especially for lattice dynamics properties that depend on higher-order derivatives of the potential. This is facilitated by the Knowledgebase of Interatomic Models (KIM) project, in which both the tabulated data (‘parameterized model’) and the code that interpolates them to compute energy and forces (‘model driver’) are stored and given unique citeable identifiers. We have developed cubic and quintic spline model drivers for pair functional type models (EAM, FS, EMT) and uploaded them to the OpenKIM repository (https://openkim.org). read less

Abstract: In this study, we evaluate the functionals of different embedded-atom methods (EAM) by fitting their free parameters to ab-initio results for copper. Our emphasis lies on testing the transferability of the potentials between systems which vary in their spatial dimension and geometry. The model structures encompass zero-dimensional clusters, one-dimensional chains, two-dimensional tilings, and three-dimensional bulk systems. To avoid having to mimic charge transfer, which is outside the scope of conventional EAM potentials, we focus on structures, in which all atoms are symmetrically equivalent. We find that the simple, four-parameter Gupta EAM potential is overall satisfactory. Adding complexity to it decreases the errors on our set of structures only by marginal amounts, unless EAM is modified to depend also on density gradients, higher-order derivatives, or related terms. All tested conventional EAM functions reveal similar problems: the binding energy of closed-packed systems is overestimated in comparison to open or planar geometries, and structures with small coordination tend to be too rigid. These deficiencies can be fixed in terms of a systematically modified embedded-atom method (SMEAM), which reproduces DFT results on bond lengths, binding energies, and stiffnesses or bulk moduli by typically O(1%), O(5%), and O(15%) accuracy, respectively. SMEAM also predicts the radial distribution function of liquid copper quite accurately. Yet, it does not overcome the difficulty to reproduce the elastic tensor elements of a hypothetical diamond lattice. read less

Abstract: Using the first-principles calculations, the structural features, mechanical properties, formation enthalpies, electronic properties and hardness of osmium carbides with various stoichometries have been investigated systematically. The structural stability, thermodynamic stability together with mechanical stability show that Re2N–Os2C, OsB2–OsC2, trigonal P3m1 OsC2, trigonal P3m1 OsC3, orthorhombic Cmmm OsC4 and Ru2Ge3–Os2C3 are the most stable structure for each kind of compounds. But, OsB2–OsC2 and Ru2Ge3–Os2C3 are dynamically unstable based on the calculation of phonon dispersion. The formation enthalpies under high pressure indicate that the Re2N–Os2C, P3m1 OsC3, Cmmm OsC4 and Os2Si3–Os2C3 (P4c2) have structural stabilities in the entire range of pressure. While for OsC2, there is a high pressure phase transition exists above 40 GPa. In addition, all the studied osmium carbides exhibit metallic behavior and strong covalent bonding. According to the calculated Vicker hardness based on a semiempirica... read less

Abstract: Both quantum mechanical and molecular-dynamics (MD) simulations of α-boron are done at this work. Angular dependent interatomic potential (ADP) for boron is obtained using force-matching technique. Fitting data are based on ab initio results within  −20..100 GPa pressure range and temperatures up to 2000 K. Characteristics of α-boron, obtained using ADP potential such as bond lengths at equilibrium condition, bulk modulus, pressure-volume relations, Gruneisen coefficient, thermal expansion coefficient are in good agreement with both ab initio data, obtained in this work and known experimental data. As an example of application, the propagation of shock waves through a single crystal of α-boron is also explored by large-scale MD simulations. read less

Abstract: The thermodynamics of iron clusters of various sizes, from 76 to 2452 atoms, typical of the catalyst particles used for carbon nanotubes growth, has been explored by a flat histogram Monte Carlo (MC) algorithm (called the σ-mapping), developed by Soudan et al. [J. Chem. Phys. 135, 144109 (2011), Paper I]. This method provides the classical density of states, gp(Ep) in the configurational space, in terms of the potential energy of the system, with good and well controlled convergence properties, particularly in the melting phase transition zone which is of interest in this work. To describe the system, an iron potential has been implemented, called "corrected EAM" (cEAM), which approximates the MEAM potential of Lee et al. [Phys. Rev. B 64, 184102 (2001)] with an accuracy better than 3 meV/at, and a five times larger computational speed. The main simplification concerns the angular dependence of the potential, with a small impact on accuracy, while the screening coefficients S(ij) are exactly computed with a fast algorithm. With this potential, ergodic explorations of the clusters can be performed efficiently in a reasonable computing time, at least in the upper half of the solid zone and above. Problems of ergodicity exist in the lower half of the solid zone but routes to overcome them are discussed. The solid-liquid (melting) phase transition temperature T(m) is plotted in terms of the cluster atom number N(at). The standard N(at)(-1/3) linear dependence (Pawlow law) is observed for N(at) >300, allowing an extrapolation up to the bulk metal at 1940 ±50 K. For N(at) <150, a strong divergence is observed compared to the Pawlow law. The melting transition, which begins at the surface, is stated by a Lindemann-Berry index and an atomic density analysis. Several new features are obtained for the thermodynamics of cEAM clusters, compared to the Rydberg pair potential clusters studied in Paper I. read less

Abstract: An interatomic potential based on the angular-dependent potential model was developed for the neodymium magnet (Nd2Fe14B) and Nd crystal system. The developed potential very accurately reproduces the complex crystal structure of Nd2Fe14B together with other important crystal properties, including lattice parameters and elastic coefficients. Molecular dynamics simulations using the potential were performed for the Nd/Nd2Fe14B interfaces and a Nd2Fe14B grain boundary to determine their structures at the atomic level. The magnetoelastic anisotropy in the vicinity of the interfaces and the grain boundary was also evaluated. We find that the disorderliness of atomic structures and the magnetoelastic anisotropy strongly depend on the interface and grain boundary orientations. read less

Abstract: A model lattice ab initio parameterized Heisenberg-Landau magnetic cluster expansion Hamiltonian spanning a broad range of alloy compositions and a large variety of chemical and magnetic configurations has been developed for face-centered cubic Fe-Ni alloys. The thermodynamic and magnetic properties of the alloys are explored using configuration and magnetic Monte Carlo simulations over a temperature range extending well over 1000 K. The predicted face-centered cubic-body-centered cubic coexistence curve, the phase stability of ordered Fe3Ni, FeNi, and FeNi3 intermetallic compounds, and the predicted temperatures of magnetic transitions simulated as functions of alloy composition agree well with experimental observations. Simulations show that magnetic interactions stabilize the face-centered cubic phase of Fe-Ni alloys. Both the model Hamiltonian simulations and ab initio data exhibit a particularly large number of magnetic configurations in a relatively narrow range of alloy compositions corresponding to the occurrence of the Invar effect. read less

Abstract: Phase stability is important to the application of materials. By first-principles calculations, we establish the phase stability of chromium borides with various stoichiometries. Moreover, the phases of CrB3 and CrB4 have been predicted by using a newly developed particle swarm optimization (PSO) algorithm. Formation enthalpy-pressure diagrams reveal that the MoB-type structure is more energetically favorable than the TiI-type structure for CrB. For CrB2, the WB2-type structure is preferred at zero pressure. The predicted new phase of CrB3 belongs to the hexagonal P-6m2 space group and it transforms into an orthorhombic phase as the pressure exceeds 93 GPa. The predicted CrB4 (space group: Pnnm) phase is more energetically favorable than the previously proposed Immm structure. The mechanical and thermodynamic stabilities of predicted CrB3 and CrB4 are verified by the calculated elastic constants and formation enthalpies. The full phonon dispersion calculations confirm the dynamic stability of WB2 -type CrB2 and predicted CrB3. The large shear moduli, large Young's moduli, low Poisson ratios, and low bulk and shear modulus ratios of CrB4-PSC and CrB4-PSD indicate that they are potential hard materials. Analyses of Debye temperature, electronic localization function, and electronic structure provide further understanding of the chemical and physical properties of these borides. read less

Abstract: A novel n-body potential for an Zr–Nb system was developed in the framework of the embedded-atom method. All the parameters of the constructed potential have been systematically evaluated by fitting to the ground state properties obtained from experimental measurements and first-principles calculations for pure elements and some alloys. It is shown that most of the static thermodynamics properties for Zr and Nb can be well reproduced by using the present potential. Some calculation results based on the present model are even closer to the experimental data than those based on previous potential models. The ground state properties of hypothetical Zr–Nb alloys were also calculated and found to be in agreement with first-principles calculations. Furthermore, the formation energies of random solid solutions of Zr–Nb with lattices of body centered cubic (bcc) and hexagonal close packed (hcp) type were calculated by fitting the energy–volume relations to Rose’s equation of state. These values were compared with those obtained by first-principles calculations based on special quasirandom structure models and the Miedema-ZSL-07 model (the improved Miedema model proposed by Zhang, Sheng and Liu in 2007). It is indicated that our n-body constructed potential for a Zr–Nb alloy provides an effective description for the interaction between the dissimilar ion interactions for hcp–bcc systems. read less

Abstract: The microstructure of Cu80Fe10Ni10 (at. %) granular ribbons was investigated by means of three-dimensional field ion microscopy (3D FIM). This ribbon is composed of magnetic precipitates embedded in a nonmagnetic matrix. The magnetic precipitates have a diameter smaller than 5 nm in the as-spun state and are coherent with the matrix. No accurate characterization of such a microstructure has been performed so far. A tomographic characterization of the microstructure of melt spun and annealed Cu80Fe10Ni10 ribbon was achieved with 3D FIM at the atomic scale. A precise determination of the size distribution, number density, and distance between the precipitates was carried out. The mean diameter for the precipitates is 4 nm in the as-spun state. After 2 h at 350°C, there is an increase of the size of the precipitates, while after 2 h at 400°C the mean diameter of the precipitates decreases. Those data were used as inputs in models that describe the magnetic and magnetoresistive properties of this alloy. read less

Abstract: We develop two new modified embedded-atom method (MEAM) potentials for elemental iron, intended to reproduce the experimental phase stability with respect to both temperature and pressure. These simple interatomic potentials are fitted to a wide variety of material properties of bcc iron in close agreement with experiments. Numerous defect properties of bcc iron and bulk properties of the two close-packed structures calculated with these models are in reasonable agreement with the available first-principles calculations and experiments. Performance at finite temperatures of these models has also been examined using Monte Carlo simulations. We attempt to reproduce the experimental iron polymorphism at finite temperature by means of free energy computations, similar to the procedure previously pursued by Müller et al (2007 J. Phys.: Condens. Matter 19 326220), and re-examine the adequacy of the conclusion drawn in the study by addressing two critical aspects missing in their analysis: (i) the stability of the hcp structure relative to the bcc and fcc structures and (ii) the compatibility between the temperature and pressure dependences of the phase stability. Using two MEAM potentials, we are able to represent all of the observed structural phase transitions in iron. We discuss that the correct reproductions of the phase stability among three crystal structures of iron with respect to both temperature and pressure are incompatible with each other due to the lack of magnetic effects in this class of empirical interatomic potential models. The MEAM potentials developed in this study correctly predict, in the bcc structure, the self-interstitial in the 〈110〉 orientation to be the most stable configuration, and the screw dislocation to have a non-degenerate core structure, in contrast to many embedded-atom method potentials for bcc iron in the literature. read less

Abstract: An angular-dependent analytic bond-order potential (ABOP) for copper and Fe–Cu system was developed, based on the ABOP of pure iron introduced by Müller et al (2007 J. Phys.: Condens. Matter 19 326220). The potential parameters for the present ABOP model of copper were determined by fitting to the experimental data of the basic properties of fcc Cu and ab initio calculated properties of bcc Cu. The model predicts the vacancy formation energy in good agreement with the experimental result, although no vacancy formation information was used in the fitting of the model parameters. The melting point of Cu is also properly reproduced. The Fe–Cu binary system was described by adding two independent cross parameters in the potential model. The cross parameters were fitted using the ab initio data of the formation energies and lattice parameters of fictitious Fe–Cu alloys. The potential was applied to investigate the point defects and small defect clusters in dilute Fe–Cu alloys. The results were compared with the ab initio data and the values obtained with other potentials. read less

Abstract: The effects of magnetism on the Bain transformation of α-phase FeNi systems are investigated by using the full potential linearized augmented plane wave method based on the generalized gradient approximation. We found that Ni impurity in bcc Fe increases the lattice constant in the ferromagnetic (FM) states, but not in the nonmagnetic (NM) states. The shear modulus, G, and Young’s modulus, E, of bcc Fe are also increased by raising the concentration of nickel. All the compositions considered show high shear anisotropy, and the ratio of the bulk to shear modulus is greater than 1.75, implying ductility. The mean sound velocities in the [100] directions are greater than in the [110] directions. The Bain transformation, which is a component of martensitic transformation, has also been studied to reveal that NixFe1−x alloys are elastically unstable in the NM states, but not so in the FM states. The electronic structures explain these results in terms of the density of states at the Fermi level. It is evident ... read less

Abstract: Highly optimized embedded-atom-method (EAM) potentials have been developed for 14 face-centered-cubic (fcc) elements across the periodic table. The potentials were developed by fitting the potential-energy surface (PES) of each element derived from high-precision first-principles calculations. The as-derived potential-energy surfaces were shifted and scaled to match experimental reference data. In constructing the PES, a variety of properties of the elements were considered, including lattice dynamics, mechanical properties, thermal behavior, energetics of competing crystal structures, defects, deformation paths, liquid structures, and so forth. For each element, the constructed EAM potentials were tested against the experiment data pertaining to thermal expansion, melting, and liquid dynamics via molecular dynamics computer simulation. The as-developed potentials demonstrate high fidelity and robustness. Owing to their improved accuracy and wide applicability, the potentials are suitable for high-quality atomistic computer simulation of practical applications. read less

Abstract: The authors express their appreciation to Dr. H. M. Zapolsky, Prof. D. Blavette and Prof. D. Ledue (GPM, UMR 6634 CNRS, Universite de Rouen, France) for very constructive discussion of the results obtained in the course of a given work. One of the authors (S. M. B.) acknowledges the partial financial assistance he has received from GPM (Rouen, France) as well as Nanoscience Foundation (Grenoble, France). We thank Prof. M. S. Blanter (Moscow State Academy of Instrumental Engineering and Information Science, Russia), Dr. R. V. Chepulskii (Duke University, U.S.A.), Prof. B. Schonfeld (ETH, Laboratory of Metal Physics and Technology, Switzerland), Dr. G. E. Ice (Oak Ridge National Laboratory, U.S.A.) and Mr. D. Pavlyuchkov (Forschungszentrum Jьlich GmbH, Germany) for kindly providing their publications and communicating important references. We apologize to other researchers, which have actively worked on the various problems related with our work, whose relevant publications are not referenced and discussed in a given paper because of volume limitations. This work has been inspired by discussions at the several congresses and conferences, primarily, European Congress on Advanced Materials and Processes ‘EUROMAT2007’ (10—13 Sept. 2007, Nurnberg, FRG), ‘Contemporary Problems of Metal Physics’ (7—9 Oct. 2008, Kyyiv, Ukraine), etc. read less

Abstract: The phase stability and elastic properties of ReB system were systematically investigated by use of the density functional theory. The formation enthalpies are negative for Re3B, Re7B3, Re2B, ReB, Re2B3, and ReB2, indicating that they are thermodynamically stable. Re7B3, Re2B, ReB, Re2B3, and ReB2 are mechanically stable. Combining the study of enthalpy and pressure relationship with the convex hull, it was found that the ground state phases are Re3B, Re7B3, and ReB2 at zero pressure, in agreement with the experimental observations. At the pressure of 90 GPa, Re3B, and ReB2 are the most stable phases. © 2010 Wiley Periodicals, Inc. J Comput Chem 2010 read less

Abstract: In computational materials science, many atomistic methods hinge on an interatomic potential to describe material properties. In alloys, besides a proper description of problem-specific properties, a reasonable reproduction of the experimental phase diagram by the potential is essential. In this framework, two complementary methods were developed to fit interatomic potentials to the thermodynamic properties of an alloy. The first method involves the zero Kelvin phase diagram and makes use of the concept of the configuration polyhedron. The second method involves phase boundaries at finite temperature and is based on the cluster variation method. As an example for both techniques, they are applied to the Fe–Cu, Fe–Ni and Cu–Ni systems. The resulting potentials are compared to those found in the literature and are found to reproduce the experimental phase diagram more consistently than the latter. read less

Abstract: We construct an interatomic potential for the Ni-Al system within the embedded-atom method formalism. The potential is based on previously developed accurate potentials for pure Ni and Al. The cross-interactions are fitted to experimental cohesive energy, lattice parameter and elastic constants of B2-NiAl, as well as to ab initio formation energies of several real or imaginary intermetallic compounds with different crystal structures and chemical compositions. The potential accurately reproduces a variety of physical properties of the NiAl and Ni3Al phases, and shows reasonable agreement with experimental and ab initio data for phase stability across the Ni-Al phase diagram. Most of the properties reproduced by the new potential were not involved in the fitting process, which demonstrates its excellent transferability. Advantages and certain weaknesses of the new potential in comparison with other existing potentials are discussed in detail. The potential is expected to be especially suitable for simulations of heterophase interfaces and mechanical behavior of Ni-Al alloys. read less

Abstract: A many-body interatomic potential for the Fe–Ni system is fitted, capable of describing both the ferritic and austenitic phase. The Fe–Ni system exhibits two stable ordered intermetallic phases, namely, L10 FeNi and L12 FeNi3, that are key issues to be tackled when creating a Fe–Ni potential consistent with thermodynamics. A procedure, based on a rigid lattice Ising model and the theory of correlation functions space, is developed to address all the intermetallics that are possible ground states of the system. While controlling the ground states of the system, the mixing enthalpy and defect properties were fitted. Both bcc and fcc defect properties are compared with density functional theory calculations and other potentials found in the literature. Finally, the potential is thermodynamically validated by constructing the alloy phase diagram. It is shown that the experimental phase diagram is reproduced reasonably well and that our potential gives a globally improved description of the Fe–Ni system in the whole concentration range with respect to the potentials found in the literature. read less

Abstract: The bonding of C to Fe and Ni in Fe50Ni50(L10) alloy with a stacking fault (SF) is analyzed using density functional calculations (DFT). The changes in the electronic structure of the bulk alloy upon SF introduction and after C absorption is addressed. C locates in an octahedral site with Ni atoms in its base and capped with Fe atoms. The Fe–Ni and Ni–Ni bonding decrease while the Fe–Fe bonding increases when the SF is introduced. The effect of C is to reduce the Fe–Ni and Ni–Ni overlap population (OP) up to 75% of its original value, while the Fe–Fe OP only changes by 3.6%. Both Fe and Ni bond to C atom at a distance of 1.80 Å, which is close to that in Fe and Ni carbides metallic, clusters or C as a impurity at grain boundaries or dislocations. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) read less

Abstract: The structural stability and theoretical strength of BCC crystal Fe under uniaxial loading have been investigated with the modified analytic embedded‐atom method (MAEAM). Even if an orthorhombic path is applied, the deformation is spontaneous along the tetragonal path till Milstein modified Born criterion B22‐B23>0 is violated at λ1=0.9064 in the compressive region. The branched orthogonal path with lower compressive stress σ1 and energy E is preferred over the conventional tetragonal Bain path. A stress‐free FCC phase with the local maximum energy of ‐4.2186eV appearing either in compressive region (orthorhombic path) at λ1=0.8923 or in tensile region (tetragonal path) at λ1=1.2619 is unstable and would slip spontaneously into its near neighbor stress‐free mBCT phase with the local minimum energy of ‐4.2270eV. The initial BCC phase with the lowest energy of ‐4.280eV is the most stable in correspondence with the actual behavior of Fe. Furthermore, the stable region ranges from ‐79.7eV/nm3 to 30.6eV/nm3 in the theoretical strength or from 0.9064 to 1.1788 in the stretch λ1 correspondingly. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) read less

Abstract: The evolution of the microstructure of a granular Cu80Fe10Ni10 (at%) melt-spun ribbon is studied by transmission electron microscopy (TEM), energy-filtered transmission electron microscopy (EFTEM) and X-ray diffraction. This system is interesting as large giant magnetoresistance (GMR) values have been measured for this composition. We have shown the presence of two face-centred cubic phases, an (Fe,Ni)-rich phase and a Cu-rich phase. The lattice parameters of these two phases are close and no diffraction or elastic contrast is involved in displaying the two phases in TEM bright-field mode. With EFTEM imaging, we have shown the presence of a fine-scale (Fe,Ni)-rich precipitation inside the Cu-rich fcc matrix. The precipitates are 2–4 nm in the as-spun state and 4–6 nm after annealing for 2 h at 400°C. The lattice parameter of the Cu-rich phase in the as-spun sample is 0.3608 nm and 0.3610 nm for the (Fe,Ni)-rich phase. After a 24-h annealing treatment at 600°C, the mean diameter of the particle is 20 nm and the lattice parameter of the (Fe,Ni)-rich phase has decreased to 0.3600 nm, while that of the Cu-rich phase has increased to 0.3613 nm, which is consistent with a segregation of Fe and Ni in the precipitates. The composition and volume fraction of the two phases measured for this annealed sample are in good agreement with the Thermocalc® predictions. read less

Abstract: A new analytic bond-order potential for iron is presented that has been fitted to experimental data and results from first-principles calculations. The angular-dependent functional form allows a proper description of a large variety of bulk, surface and defect properties, including the Bain path, phonon dispersions, defect diffusivities and defect formation energies. By calculating Gibbs free energies of body-centred cubic (bcc) and face-centred cubic (fcc) iron as a function of temperature, we show that this potential is able to reproduce the transitions from α-iron to γ-iron and δ-iron before the melting point. The results are compared to four widely used embedded-atom-method potentials for iron. read less

Abstract: Der Fokus dieser Arbeit lag zunachst auf einer simulationsgestutzen Untersuchung uber die Entsteh- ungsmechanismen von Oxidteilchen in ODS-Stahlen. Hierbei bilden empirische Wechselwirkungs- potenziale von Eisen-Yttrium-Sauerstoff (Fe-Y-O) die Grundlage fur eine Beschreibung dieser Oxid- teilchen-Bildungs-Prozesse in Molekulardynamik (MD) Simulationen, die auch Eigenschaften von Versetzungen und anderen Bestrahlungs-Panomenen detailiert zur weiteren Aufklarung behandeln konnen. Zu diesem Zweck ist das speziell auf die Simulation zugeschnittene Anfitten der o.g. MD Potenziale (hier fur Fe-Y-O) notwendig. Hierzu dienen die zuvor durchgefuhrten ab-initio (DFT) Rechnungen als Daten- referenzgrundlage (z.B. von Phasen oder Defekten) zur Optimierung der Potenzialparameter wahrend des Anfittens, um ein moglichst exaktes MD Potenzial zu erzeugen, dass die ab-initio Daten auf groseren MD Skalen detailgetreu abbildet. Im ersten Drittel dieses Projektes wurden mehrere Potenziale fur die einzelnen Metall-Komponenten, Fe-Fe und Y-Y, erzeugt. Dabei stellte sich heraus, dass etablierte Standardmethoden nicht in der Lage sind genaue Fe-Y Potenziale als Teillosung fur das Fe-Y-O Problem zu erzeugen. Dabei wurde eine Kombination aus dem (M)EAM Modell und zur Optimierung eine LSM gestutzte Software (POTFIT) genutzt. Die Komplexitat des Problems liegt in den richtungsabhangigen Atombindungen, die die hier entwickelten fortgeschrittenen Simulations- und Fitmethoden benotigen. Im ersten Schritt von drei Schritten (chapter 3) wurden zunachst einmal die Defizite der Standard-Fittechniken evaluiert, indem die wahrend des Fitting-Prozesses gefundenen Parametersets im EAM Formalismus mit der flexiblen Software POTFIT auf ihre Eignung hin grundlich untersucht worden sind. Die hierfur genutzten Fitfunktionen wurden ursprunglich Anfang 2000 von Zhou und Wadley entwickelt. Hierbei liegt die Ursache fur die dann entdeckte Parameterset-Problematik darin, dass zur Beschreibung des Fe-Y Systems das Model aus drei Potentialkomponenten besteht: Fe-Fe, Y-Y und Fe-Y. Fur diese einzelnen Komponenten sind die Potentialparameter erfolgreich angefittet worden mit Bezug zur Gitterkonstante und Bindungs- bzw. Kohasionsenergie (beides mit 1% Genauigkeit bezgl. DFT Rechnungen) sowie zu allen elastischen Konstanten (5% Genauigkeit bezgl. Experimente). All dies unter Zuhilfenahme von Parametersuchraum-beschrankenden Techniken, die zur Einhaltung der oben genannten Eigenschaften dienen und urspurnglich von Johnson & Oh sind. Selbst kompliziertere Defekteigenschaften, wie Zwischengitter- und Leerstellenbildungsenergien wurden erfolgreich angefittet. Das hier entwickelte EAM Potenzial fur Y-Y ist z.B. in der Lage bei Eigenzwischengitteratomen die basal oktaedrische Position von Zwischengitteratomen (ZA) im Yttrium hcp-Gitter als Grundzustand und die Transition eines jeden ZAs aus einer anderen Position, wie zuvor in DFT berechnet, zu reproduzieren. Zur Bildung des angestrebten Fe-Y Potenzials wurden diese beiden Komponenten, Fe-Fe und Y-Y, zum weiteren Fitten in dem weitgefacherten und komplexen Fe-Y Potzenzialsuchraum genutzt. Die Parametersets wurden mit sogenannten hier entwickelten Hauptparameter (Key Driver) systematisch untersucht. Ein flexibleres Konzept statt der starreren Universal Binding Relations in Abhangigkeit von der Rose Gleichung. Dieser Hauptparameter zeigte eindeutig, dass die Nutzung der Rose Gleichung zur Parametersuchraum-Minimierung den Suchraum dahingehend einschrankt, sodass ein akkurates Anfitten der hier genutzten 900 DFT Datensets nicht mehr moglich ist. Allerdings ist die Orientierung im Parametersuchraum mit dieser Rose Gleichung bei standardmasigen Optimierungsmethoden (wie LSM) unabdingbar, da ohne diese die benotigten globalen Optima fur die Parameter nicht auffindbar sind. Als aufklarendes Testverfahren zur weiteren Ergrundung dieser Problematik und Prufung zur Eignung fur Fe-Y Potenziale und den anschliesenden Simulationen diente der Versuch, 9 verschiedene Bindungs-energien von Yttrium-Leerstellenclustern mit ansteigender Leerstellenzahl zu reproduzieren. Dieser Test konnte von diesen Potenzialen nur teilweise erfullt werden und wurde auf die fehlende Beschreibung der Bindungswinkelabhangigkeit im Modell zuruckgefuhrt. Die Erweiterung von EAM durch MEAM mit Winkelabhangigkeit ist jedoch keineswegs eine zufriedenstellende Losung, da MEAM alternativlos auf der irrefuhrenden Rose Gleichung beruht. Daher war die Benutzung des ubersichtlicheren EAM Typs aus zwei Grunden nutzlich: 1. MEAM braucht die Rose Gleichung um diesen komplexen Formalismus zu beherrschen mit denselben Problemen wie in EAM, aber dieses grundlegende Problem ist in MEAM deutlich schwerer zu identifizieren als in EAM. 2. Die mit EAM gefundenen, angefitteten Parameter sind eine hervorragende Startparameter-Grundlage fur den verbesserten darauffolgenden RF-MEAM Typ. Im zweiten Schritt wurde das Problem aus dem ersten Schritt gelost, indem ein modifizierter MEAM Spezialtyp im referenzlosen Format (RF-MEAM) angewandt worden ist. Im Gegensatz zum herkommlichen MEAM wird hier die Rose Gleichung durch mehr DFT Daten und insbesondere einer intelligenteren Machine Learning ahnlichen Genetic Algorithmus (GA) Optimiertechnik ersetzt, die allerdings eine bedachte Startparameterwahl vorraussetzt, womit Schritt 1 wieder ins Spiel kommt. Die genutzte fortgeschrittene MEAMfit Software, die per GA funktioniert, wurde zwischen 2016 und 2017 funktionierend eigens dafur implementiert. Mit den in Schritt 1 gefitteten Parametern und Set-Auswahltechniken konnten die weiterfuhrenden Fits mit optimalen Startparametern durchgefuhrt werden. Auf dieser Stufe waren diese Fits mit der speziell verbesserten Technik in der Lage ein detailgetreues Fe-Y Potenzial zu generieren, das sowohl alle Phasen (Fe2Y, Fe3Y, Fe5Y, Fe23Y6 und Fe17Y2 sowohl als auch reines Fe und Y) als auch die gesamte Defektdatenbasis mit einer durchschnittlichen Abweichung von ≈11% erfolgreich abbildet. Zusatzlich bestatigend zu dieser allgemeinen Ubereinstimmung wurde konsequenterweise der in Schritt 1 entwickelte Test hervorragend mit einmaliger Genauigkeit bestanden, mit max. 5% Abweichung von den komlexen o.g. Y-Leerstellen Bildungsenergien. Allerdings konnte ein systematischer Fehlertrend aufgespurt werden, der Schwachen in der Fe-Fe Komponente offenbarte. Als Folge dessen wurde umgehend diese Komponente durch ein anderes etabliertes Fe-Fe Potenzial von G. Ackland mit einer extrem genauen Schmelztemperatur (nur 3% Abweichung vom Exp.) ausgetauscht. Mit diesem genauen Potenzial konnte zum ersten Mal die Clusterbildung von gelosten Yttrium Atomen in einer Eisenschmelze erfolgreich per MD Simulation auf atomarer Ebene nachgestellt werden oberhalb von 1750 K. Temperaturen darunter hatten eine Ausscheidungsbildung von Y mit sehr geringer Y-Loslichkeit (<0.1%) in Ubereinstimmung mit den Experimenten zur Folge. Dies wurde durch den Pot. Typ A ermoglicht, der aber die energetische Reihenfolge bei den Fe-Y Phasen nicht ganz genau einhalt. Typ B hingegen halt diese ein, dort fehlt aber die Y-Clusterbildungsneigung. Durch den gebotenen Praxisbezug zur Metallurgie mussen die Loslichkeit und Clusterbildung gleichzeitig in der Simulation genau reproduzierbar sein, was aber weder Typ A noch B kann, was zum Typ A/B Dilemma fuhrt. Dieses Typ A/B Dilemma (Phasen oder Defekt Genauigkeit) fuhrt zum letzten dritten Schritt (chapter 5). Darin ist zusatzlich die Strukturaufklarung von der Fe17Y2 Phase mit Vergleichen zu exp. EXAFS Spektren unserer Kollaborationspartner vom ISSP (Riga) enthalten. Diese Aufklarung dient auch dazu die fehlenden magnetischen Abhangigkeiten im Potenzial zu kompensieren, da die Phasenreihenfolge mit sehr feinen Energieunterschieden wohl stark von magnetischen Wechselwirkungen gepragt ist. Obwohl Potenzial Typ B diesen (Magnetismus) nicht direkt beachtet, ist es in der Lage das tatsachlich gemessene EXAFS Spektrum grostenteils genau wiederzugeben. Allerdings offenbart eine einzige ausgepragte Phasenverschiebung, dass die angenommene hcp Struktur durch eine unterschwellige rhombohedrale Komponente, die sporadisch in der c-Gitterrichtung auftritt, korrigiert werden muss. AIMD (DFT) Berechnungen in Kooperation mit der University of Edinburgh bestatigen dies und zeigen sogar, dass magnetische Wechselwirkungen diese Strukturmischung stabilisieren. Endgultig bestatigt werden konnte dies mit der genauen EXAFS Spektren Reproduktion mit dem durch AIMD verbesserten nochmals gefitteten Potenzialtyp B, der als neuer Typ C durch AIMD indirekt den Einfluss der magnetischen Wechselwirkungen mit einschliest. Diese erstmalige nahezu deckungsgleiche MD Simulation eines EXAFS Spektrums von einem komplexen metallischen Alloy, hier Fe-Y, stellt eine bisher unerreichte Verbesserung dar. Schlieslich lost Typ C das Typ A/B Dilemma und ernoglicht eine genaue gleichzeitige MD Modellierung von Phasen- und Defekten in Fe-Y – ein Durchbruch in der MD-Potenzialentwicklung. read less

Abstract: Tetrataenite is an equiatomic and highly ordered, non-cubic Fe-Ni alloy mineral that forms in meteorites from the distortion of fcc taenite due to extremely slow cooling. The mineral has drawn much attention of the scientific community because of its superb magnetic properties, which may make the phase an alternative to the REE-based permanent magnets. Barring only a few passing mentions, the mineral has never been described from any terrestrial rock. Here we report the characteristics of terrestrial tetrataenite from an ophiolite-hosted Ni-bearing magnetite body from the Indo-Myanmar ranges, northeast India. Although the mineral assemblage surrounding it is very similar to that found in the meteorites, the postulated cooling regimes cannot be similar. The mineral is formed as a consequence of hydrothermal alteration of ferromagnesian minerals of the olivine and pyroxene groups. Iron and nickel were released from the silicates and precipitated in the form of Fe-Ni alloy at low temperature in extremely reducing conditions with a lack of sulfur. Our findings suggest a low-temperature hydrothermal origin of tetrataenite warrants a re-examination of the Fe-Ni phase diagram at low temperatures and puts a question mark on the age-old concept of tetrataenite formation as due solely to extremely slow cooling of fcc taenite in meteorites. It also opens up a new vista for adoption of a hydrothermal route to synthesize this rare material. read less

Abstract: The class of Complex Metallic Alloys (CMAs) is interesting for its wide range of physical properties. There are materials that exhibit high hardness at low density or good corrosion resistance, which is important for technological applications. Other compounds are superconductors, have strong anisotropic transport coefficients or exhibit a novel magnetic memory effect. The theoretical investigation of CMAs is often very challenging because of their inherent complexity and large unit cells with up to several thousand atoms. Molecular dynamics simulations with classical interaction potentials are well suited for this task – they can handle hundreds of thousands of atoms in reasonable time. Such simulations can provide insight into static and dynamic processes at finite temperatures on an atomistic level. The accuracy of these simulations depends strongly on the quality of the employed interaction potentials. To generate physically relevant potentials the force-matching method can be applied. A computer code called potfit has been developed at the Institute for Theoretical and Applied Physics (ITAP) especially for this task. It uses a large database of quantum-mechanically calculated reference data, forces on individual atoms and cohesive energies, to generate effective potentials. The parameters of the potential are optimized in such a way that the reference data are reproduced as accurately as possible. The potfit program has been greatly enhanced as part of this thesis. The optimization of analytic potentials, new interaction models as well as a new optimization algorithm were implemented. Potentials for two different complex metallic alloy systems have been generated and used to study their properties with molecular dynamics simulations. The first system is an approximant to the decagonal Al-Pd-Mn quasicrystal. A potential which can reproduce the cohesive energy with high accuracy was generated. With the help of this potential a refinement of the experimentally poorly determined structure model could be performed. The second class of potentials was fitted for intermetallic clathrate systems. They have interesting thermoelectric properties which originate from their special structure. Silicon- and germanium-based clathrate potentials were derived and the influence of the complex structure on the thermal conductivity has been studied. Komplexe Intermetallische Verbindungen (CMAs) sind aufgrund ihrer vielfaltigen physikalischen Eigenschaften sehr interessant fur technologische Anwendungen. Dabei ist z.B. hohe Harte bei geringer Dichte und Korrosionsbestandigkeit wichtig. Neben Supraleitern gibt es Materialien mit anisotropen Transporteigenschaften oder einem neuartigen magnetischen Memory Effekt. Theoretische Untersuchungen von CMAs stellen durch ihre inharente Komplexitat und die riesigen Einheitszellen mit mehreren tausend Atomen oft eine grose Herausforderung dar. Molekulardynamiksimulationen mit effektiven Potenzialen konnen dazu eingesetzt werden; sie ermoglichen die Berechnung von hunderttausenden von Atome in annehmbarer Zeit. Damit kann ein Einblick in sowohl statische als auch dynamische Prozesse auf atomarer Ebene gewonnen werden. Die Ergebenisse solcher Simulationen hangen jedoch sehr stark von der Qualitat der eingesetzten Wechselwirkung ab. Um physikalisch gerechtfertigte Potenziale zu erzeugen, kann die Force-Matching-Methode angewandt werden. Dazu wurde am Institut fur Theoretische und Angewandte Physik (ITAP) ein Programm mit dem Namen potfit entwickelt. Es verwendet eine grose Datenbank von quantenmechanisch berechneten Referenzgrosen wie z.B. Krafte auf die einzelnen Atome und die Kohasionsenergie, um effektive Potenziale zu generieren. Die freien Parameter des Potenzials werden optimiert, um die Referenzdaten so gut wie moglich zu reproduzieren. Fur diese Arbeit wurde potfit deutlich erweitert. Es konnen nun analytisch definierte Potenziale optimiert werden, neue Wechselwirkungen wurden implementiert und ein neuer Optimierungsalgorithmus wurde hinzugefugt. Damit wurden effektive Potenziale fur zwei verschiedene CMA Systeme gefittet und deren Eigenschaften mit Molekulardynamik untersucht. Fur die Approximanten eines decagonalen Al-Pd-Mn Quasikristalls, den Xi-Phasen, wurde ein Potenzial fur die Strukturbestimmung erzeugt. Es kann die Kohasionsenergien verschiedener Strukturen mit groser Genauigkeit wiedergeben. Ein aus experimentellen Daten ungenau bestimmtes Strukturmodell konnte damit erheblich verbessert werden. Auserdem wurden Potenziale fur Intermetallische Klathrate erzeugt. Diese Systeme besitzen interessante thermoelektrische Eigenschaften aufgrund ihrer speziellen Kafigstruktur. Effektive Wechselwirkungen fur silizium- und germaniumbasierte Klathrate wurden erzeugt. Damit wurde der Einfluss der komplexen Struktur auf die thermische Leitfahigkeit des Gitters untersucht. read less

Abstract: In this work, a method for computer simulations of laser ablation in metals is presented. The ambitious task to model the physical processes, that occur on different time and length scales, is overcome to some extent by the combination of two techniques: Molecular dynamics and finite differences. The former is needed to achieve atomistic resolution of the processes involved. Material failure like melting, vaporization or spallation occur on the atomic scale. Light absorption and electronic heat conduction, which plays the major role in metals, is described by a generalized heat conduction equation solved by the finite differences method. From the so-called Two-Temperature Model temperature, density and pressure evolution - both in time and space - can be derived. With this, various studies on laser heated metals were done. For reasons discussed in more detail later, aluminum was chosen as a model system for most simulations on isotropic materials. As a more complex structure, the metallic alloy Al13Co4 was used because of its special material properties. As an approximant to the decagonal phase of Al-Ni-Co, the alloy shows an anisotropy in its transport properties, e.g. an anisotropic heat conduction. It will be shown, that the model is able to describe the physics in laser heated solids on time scales from 100 fs up to the ns-scale properly. Great insight was gained about the processes occuring during and shortly after the laser pulse. Many of the quantities interesting for experimentalists can be predicted by the theory. From the simulations relevant parameters like the electron-cooling time or the important ablation threshold were calculated. All values match their experimental counterpart very well. Die vorliegende Arbeit beschaftigt sich mit der Laserablation in Metallen. Ziel ist es, mit Hilfe von numerischen Simulationen das Verhalten von Metallen nach der Bestrahlung mit intensiven Laserpulsen vorherzusagen. Die Arbeit ist inhaltlich in zwei Teile gegliedert. In der ersten Halfte werden theoretische Grundlagen, eine qualitative Beschreibung der Ablation und die Implementierung des Modells gegeben. Im zweiten Teil folgen Ergebnisse sowie, falls vorhanden, Vergleiche mit Experimenten. Die Arbeit schliest mit einer Zusammenfassung und einem Ausblick. read less

Abstract: Throughout this thesis the lattice dynamics in CMA phases with different structural and dynamical peculiarities have been studied in experiment and simulation. While inelastic neutron and X-ray scattering enabled an experimental approach to dynamical quantities as dispersion curves, vibrational density of states or dynamical structure factors, the theoretical approach was based on ab-initio and molecular dynamics simulations. Experimental results could be analyzed and interpreted by means of computer simulations, thus yielding insight into dynamical processes on an atomistic level. Indeed, this combination of experiment and simulation proved to be a powerful tool for the investigation of different dynamical phenomena. In the Mg-Zn system the impact of structural complexity on vibrational properties was studied. Pure hcp Zn and the MgZn2 Laves phase were used as rather simple reference structures and compared to the structurally more complex Mg2Zn11 Pauling triacontahedral phase. While MgZn2 showed the behavior of an almost perfectly harmonic solid, Mg2Zn11 turned out to exhibit quite unusual dynamical features. In the case of MgZn2 experimental results from INS could be reproduced with high accuracy. For Mg2Zn11 experimental results and DFT calculations first evidenced non-negligible discrepancies. After reinvestigating the structure of Mg2Zn11 with both, experimental and computational methods, a partially occupied Zn site could be spotted as possible source of the occurring discrepancies. Surprisingly, the partially vacant Zn1 position, at the center of the mini-Bergman cluster proved to exert a strong influence on stability and dynamics of this system. After taking vacancy disorder into account, the experimental results could be decently reproduced and differences could be understood. With this knowledge the experimental GVDOS was finally interpreted in terms of distinct atomic motions, thus connecting macroscopic properties with processes on atomistic scale. The second Zn-based CMA phase that was explored, is the ScZn6 1/1-approximant. The structure of this phase is closely related to the Cd-based binary icosahedral quasicrystals in the Cd-Yb and Cd-Ca system, thus making it an interesting phase with respect to structure and dynamics of quasicrystals like Mg-Zn-Sc. Secondly, the ScZn6 1/1-approximant evidences an order-disorder phase transition at about 150 K. The dynamical aspects of this phase transition were investigated throughout this work, using quasielastic neutron scattering and molecular dynamics methods. Interestingly, the phase transition could be shown to be closely related to a freezing in of the tetrahedral shell in the center of the Tsai-type cluster building blocks. In fact, experiment and calculation clearly evidenced a dynamic disorder of the tetrahedral shell above the transition temperature. The tetrahedral shell is constantly reorienting between different, energetically equivalent configurations. From neutron scattering experiments the residence time between two tetrahedron jumps could be estimated to be of the order of a few ps, while it was overestimated by the conducted MD simulations. These results thus answer the controversially debated question about the nature of the disorder in ScZn6 in favor of a dynamic process. Finally the dynamic reorientations of the tetrahedron are highly interesting with respect to entropical stabilization, a possible candidate for quasicrystal stabilization. In the last part of the thesis the clathrate system Ba-Ge-Ni, was studied with respect to its cage-like structure and the resulting effects on its dynamical properties. Inelastic neutron scattering experiments nicely evidenced a flat dispersionless optic-like phonon branch, which by means of DFT could be shown to stem from localized motions of the encaged Ba atoms - so-called rattling modes. The cage structure of the Ba-Ge-Ni clathrates furthermore made a decomposition into different subsystems possible, such that their contributions to the vibrational spectrum could be analyzed. A comparison to a hypothetical Ge46 structure could be used to elaborate the influence of the encaged Ba-atoms and the host-lattice, respectively. Interestingly, the introduction of Ba-atoms creates a localized, dispersionless phonon branch at rather low energy, which interacts with the acoustic modes of the host structure, resulting in a reduction of the velocity of sound. Thus the low lattice thermal conductivity in this phase seems to be related to both, rattling modes of Ba guest atoms and reduced velocity of sound of the host framework. Im Rahmen dieser Arbeit wurde die Gitterdynamik verschiedener CMA-Phasen mit Neutronen- bzw. Rontgenstreuung experimentell untersucht und dann anhand von Simulationen bezuglich verschiedener dynamischer Aspekte analysiert und interpretiert. Im Mg-Zn System konnte der konkrete Einfluss von struktureller Komplexitat auf die Vibrationseigenschaften studiert und am Beispiel der bei den Phasen MgZn2 und Mg2Zn11 dargestellt werden. Ein besonderes Augenmerk wurde hierbei auf die Analyse der auftretenden niedrigenergetischen Moden in Mg2Zn11 gelegt. Fur den ScZn6 1/1-Approximanten gelang es, den engen Zusammenhang der inneren Tetraederschalen mit dem Ordnungs-Unordnungs-Phasenubergang herauszuarbeiten und zu zeigen, dass die Unordnung oberhalb des Phasenuberganges von dynamischer Natur ist. Somit war es moglich, die viel diskutierte Frage uber die Tetraederunordnung oberhalb des Phasenuberganges eindeutig zu beantworten. Im Clathrat-System Ba-Ge-Ni wurde das Phononenspektrum mit Bezug auf die niedrige thermische Leitfahigkeit des Gitters im Detail untersucht. Die bei tiefen Energien auftretenden rattling modes sowie deren Einfluss auf die die akustischen Phononmoden konnten hier als Ursachen fur die niedrige thermische Leitfahigkeit ausgemacht werden. read less

Abstract: An introduction is presented to numerical methods, by which the behavior of complex metallic alloys can be simulated. We primarily consider the molecular dynamics (MD) technique as implemented in our software package IMD, where Newton’s equations of motion are solved for all atoms in a solid. After a short discourse on integration algorithms, some possible types of interactions are addressed. Already simple model potentials, as for example the Lennard-Jones-Gauss potential, can give rise to complex structures, where the characteristic length scales of the order by far exceed the range of the pair interaction. Realistic interactions are modelled by highly parametrized effective potentials, like the EAM (Embedded Atom Method) potential. Our program potfit allows to fit the parameters such that data from experiment or from ab-initio calculations are well reproduced. Several applications of the methods are outlined, notably the simulation of aluminium diffusion in quasicrystalline d-Al-Ni-Co, the computation of the phonon dispersion via the dynamical structure factor of MgZn2, the propagation of cracks in NbCr2, and an order-disorder phase transition in CaCd6. read less

Abstract: Complex metallic alloys and quasicrystals show extraordinary physical properties relevant for technological applications, for example hardness at low density. In the study of these systems, atomistic simulation with classical interaction potentials is a very promising tool. Such simulations require classical effective potentials describing the cohesive energy as a function of the atomic coordinates. The quality of the simulation depends crucially on the accuracy with which this potential describes the real interactions. One way to generate physically relevant potentials is the force matching method, where the parameters of a potential are adjusted to optimally reproduce the forces on individual atoms determined from quantum-mechanical calculation. The programme package potfit developed as part of this thesis implements the force matching method efficiently. Potentials are generated for a number of complex metallic alloy systems. A potential for the decagonal basic Ni-rich Al-Co-Ni quasicrystal is used to simulate diffusion processes and melting. In the CaCd6 system built from multishelled clusters, the shape and orientation of the innermost cluster shell is studied. Finally, phonon dispersion in the Mg-Zn system is determined and compared to experiment. The programme potfit is shown to be an effective tool for generating physically justified effective potentials. Potentials created with potfit can greatly improve the understanding of complex metallic alloys through atomistic simulations. Komplexe intermetallische Verbindungen und Quasikristalle zeigen ausergewohnliche physikalische Eigenschaften, wie z.B. Harte bei geringer Dichte. Bei der Untersuchung dieser Systeme sind atomistische Simulationen mit klassischen Wechselwirkungspotenzialen ein wichtiges Werkzeug. Fur solche Simulationen benotigt man klassische effektive Potenziale, die die Bindungsenergie als eine Funktion der Atomkoordinaten beschreiben. Die Qualitat der Simulation hangt entscheidend von der Genauigkeit ab, mit der diese Potenziale die echten Wechselwirkungen wiedergeben. Eine Moglichkeit, physikalisch relevante Potenziale zu erzeugen, ist die Force-Matching-Methode. Dabei werden die Parameter eines Potenzials so angepasst, dass die mit quantenmechanischen Methoden bestimmten Krafte auf die einzelnen Atome bestmoglich reproduziert werden. Das als Teil dieser Arbeit entwickelte Programmpaket potfit implementiert die Force-Matching-Methode effizient. Fur einige komplexe intermetallische Verbindungen werden Potenziale bestimmt. In dekagonalen Al-Co-Ni-Quasikristallen werden mit Hilfe eines Potenzials Diffusionsprozesse und Schmelzvorgange simuliert. In der aus mehrschaligen Clustern bestehenden CaCd6-Verbindung wird die Struktur der innersten Clusterschale untersucht. Schlieslich wird die Phononendispersion im Mg-Zn-System bestimmt und mit experimentellen Ergebnissen verglichen. Es wird gezeigt, dass das Programm potfit ein effektives Werkzeug zur Erzeugung physikalisch gerechtfertigter Wechselwirkungen ist. Potenziale, die mit potfit erzeugt werden, konnen zum Verstandnis komplexer metallischer Verbindungen durch atomistische Simulationen viel beitragen. read less

Abstract: This study addresses the fabrication of nanocrystalline Fe–Co–Ni alloy using two operations: mechanical alloying (MA) of elemental powders and hot pressing (HP). The evolution of the phase composition and structure of the powder particles after MA was investigated. Ball milling with rotation speed 700 rpm for 15–20 min allows the production of a bcc Fe-based supersaturated solid solution. During the HP of this powder, this solution decomposes into a bcc (Fe) solid solution and fcc Fe3Ni precipitates, which act as a recrystallization barrier at elevated temperatures. This factor, along with the solid solution strengthening of the (α–Fe) matrix and high concentration of lattice defects (dislocations and twins), provides high mechanical properties (ultimate bending strength of 2000 MPa and hardness of 108 HRB) and wear resistance of the alloy. The developed Fe–Co–Ni alloy is promising for use as a binder in diamond tools designed for machining abrasive materials. read less

Abstract: Fitted interatomic potentials are widely used in atomistic simulations thanks to their ability to compute the energy and forces on atoms quickly. However, the simulation results crucially depend on the quality of the potential being used. Force matching is a method aimed at constructing reliable and transferable interatomic potentials by matching the forces computed by the potential as closely as possible, with those obtained from first principles calculations. The potfit program is an implementation of the force-matching method that optimizes the potential parameters using a global minimization algorithm followed by a local minimization polish. We extended potfit in two ways. First, we adapted the code to be compliant with the KIM Application Programming Interface (API) standard (part of the Knowledgebase of Interatomic Models project). This makes it possible to use potfit to fit many KIM potential models, not just those prebuilt into the potfit code. Second, we incorporated the geodesic Levenberg–Marquardt (LM) minimization algorithm into potfit as a new local minimization algorithm. The extended potfit was tested by generating a training set using the KIM environment-dependent interatomic potential (EDIP) model for silicon and using potfit to recover the potential parameters from different initial guesses. The results show that EDIP is a ‘sloppy model’ in the sense that its predictions are insensitive to some of its parameters, which makes fitting more difficult. We find that the geodesic LM algorithm is particularly efficient for this case. The extended potfit code is the first step in developing a KIM-based fitting framework for interatomic potentials for bulk and two-dimensional materials. The code is available for download via https://www.potfit.net. read less

Abstract: Magnetic properties are sensitive proxies to characterize FeNi metal phases in meteorites. We present a data set of magnetic hysteresis properties of 91 ordinary chondrite falls. We show that hysteresis properties are distinctive of individual meteorites while homogeneous among meteorite subsamples. Except for the most primitive chondrites, these properties can be explained by a mixture of multidomain kamacite that dominates the induced magnetism and tetrataenite (both in the cloudy zone as single‐domain grains, and as larger multidomain grains in plessite and in the rim of zoned taenite) dominates the remanent magnetism, in agreement with previous microscopic magnetic observations. The bulk metal contents derived from magnetic measurements are in agreement with those estimated previously from chemical analyses. We evidence a decreasing metal content with increasing petrologic type in ordinary chondrites, compatible with oxidation of metal during thermal metamorphism. Types 5 and 6 ordinary chondrites have higher tetrataenite content than type 4 chondrites. This is compatible with lower cooling rates in the 650–450 °C interval for higher petrographic types (consistent with an onion‐shell model), but is more likely the result of the oxidation of ordinary chondrites with increasing metamorphism. In equilibrated chondrites, shock‐related transient heating events above approximately 500 °C result in the disordering of tetrataenite and associated drastic change in magnetic properties. As a good indicator of the amount of tetrataenite, hysteresis properties are a very sensitive proxy of the thermal history of ordinary chondrites, revealing low cooling rates during thermal metamorphism and high cooling rates (e.g., following shock reheating or excavation after thermal metamorphism). Our data strengthen the view that the poor magnetic recording properties of multidomain kamacite and the secondary origin of tetrataenite make equilibrated ordinary chondrites challenging targets for paleomagnetic study. read less