Solid-Liquid Phase Diagrams for Binary Metallic Alloys: Adjustable Interatomic Potentials

We develop a new approach to determining LJ-EAM potentials for alloys and use these to determine the solid-liquid phase diagrams for binary metallic alloys using Kofke's Gibbs-Duhem integration technique combined with semigrand canonical Monte Carlo simulations. We demonstrate that it is possible to produce a wide-range of experimentally observed binary phase diagrams (with no intermetallic phases) by reference to the atomic sizes and cohesive energies of the two elemental materials. In some cases, it is useful to employ a single adjustable parameter to adjust the phase diagram (we provided a good choice for this free parameter). Next, we perform a systematic investigation of the effect of relative atomic sizes and cohesive energies of the elements on the binary phase diagrams. We then show that this approach leads to good agreement with several experimental binary phase diagrams. The main benefit of this approach is not the accurately reproduction of experimental phase diagrams, but rather to provide a method by which material properties can be continuously changed in simulations studies. This is one of the keys to the use of atomistic simulations to understand mechanisms and properties in a manner not available to experiment

Development of an interatomic potential for the simulation of defects, plasticity, and phase transformations in titanium

New interatomic potentials describing defects, plasticity, and high temperature phase transitions for Ti are presented. Fitting the martensitic hcp-bcc phase transformation temperature requires an efficient and accurate method to determine it. We apply a molecular dynamics method based on determination of the melting temperature of competing solid phases, and Gibbs-Helmholtz integration, and a lattice-switch Monte Carlo method: these agree on the hcp-bcc transformation temperatures to within 2 K. We were able to develop embedded atom potentials which give a good fit to either low or high temperature data, but not both. The first developed potential (Ti1) reproduces the hcp-bcc transformation and melting temperatures and is suitable for the simulation of phase transitions and bcc Ti. Two other potentials (Ti2 and Ti3) correctly describe defect properties and can be used to simulate plasticity or radiation damage in hcp Ti. The fact that a single embedded atom method potential cannot describe both low and high temperature phases may be attributed to neglect of electronic degrees of freedom, notably bcc has a much higher electronic entropy. A temperature-dependent potential obtained from the combination of potentials Ti1 and Ti2 may be used to simulate Ti properties at any temperature.</p

Ab initio melting temperatures of bcc and hcp iron under the Earth's inner core condition

There has been a long debate on the stable phase of iron under the Earth's inner core conditions. Because of the solid-liquid coexistence at the inner core boundary, the thermodynamic stability of solid phases directly relates to their melting temperatures, which remains considerable uncertainty. In the present study, we utilized a semi-empirical potential fitted to high-temperature ab initio data to perform a thermodynamic integration from classical systems described by this potential to ab initio systems. This method provides a smooth path for thermodynamic integration and significantly reduces the uncertainty caused by the finite-size effect. Our results suggest the hcp phase is the stable phase of pure iron under the inner core conditions, while the free energy difference between the hcp and bcc phases is tiny, on the order of 10s meV/atom near the melting temperature.Comment: 4 figure

Grain shape, grain boundary mobility and the Herring relation

Abstract Motivated by recent experiments on grain boundary migration in Al, we examine the question: does interface mobility depend on the nature of the driving force? We investigate this question in the Ising model and conclude that the answer is &apos;&apos;no.&apos;&apos; This conclusion highlights the importance of including the second derivative of the interface energy with respect to inclination c 00 in the Herring relation in order to correctly describe the motion of grain boundaries driven by capillarity. The importance of this term can be traced to the entropic part of c 00 , which can be highly anisotropic, such that the reduced mobility (i.e., the product of interface stiffness c þ c 00 and mobility) can be nearly isotropic even though the mobility itself is highly anisotropic. The cancellation of these two anisotropies (associated with stiffness and mobility) originates in the Ising model from the fact that the number of geometrically necessary kinks, and hence the kink configurational entropy, varies rapidly with inclination near low-energy/low mobility, but slowly near high-energy/high-mobility interfaces, where the kink density is high. This implies that the stiffness is high where the mobility is low and vice versa. Consequently, the grain shape can appear isotropic or highly anisotropic depending on whether its motion is driven by curvature or an external field, respectively, but the mobility itself is independent of driving force. We discuss the implications of these results for interpreting experimental observations and computer simulations of microstructural evolution, where c 00 is routinely neglected

Unveiling the effect of Ni on the formation and structure of Earth's inner core

Ni is the second most abundant element in the Earth's core. Yet, its effects on the inner core's structure and formation process are usually disregarded because of its similar atomic numbers with Fe. Using ab initio molecular dynamics simulations, we find that the bcc phase can spontaneously crystallize in liquid Ni at temperatures above Fe's melting point at inner core pressures. The melting temperature of Ni is shown to be 700-800 K higher than that of Fe at 323-360 GPa. Phase relations among hcp, bcc, and liquid differ between Fe and Ni. Ni can be a bcc stabilizer for Fe at high temperatures and inner core pressures. A small amount of Ni can accelerate Fe's crystallization under core pressure. These results suggest Ni may substantially impact the structure and formation process of the solid inner core

Structural hierarchy as a key to complex phase selection in Al-Sm

Investigating the unknown structure of the complex cubic phase, previously observed to crystallize from melt-spun amorphous Al–10 at.% Sm alloy, we determine the structure in full site-occupancy detail, highlighting several critical structural features that govern the far-from-equilibrium phase selection pathway. Using an efficient genetic algorithm combining molecular dynamics, density functional theory, and x-ray diffraction, the structure is clearly identified as body-centered cubic Im¯3m (No. 229) with ∼140 atoms per cubic unit cell and a lattice parameter of 1.4 nm. The complex structure is further refined to elucidate the detailed site occupancy, revealing full Sm occupancy on 6b sites and split Sm/Al occupancy on 16f sites. Based on the refined site occupancy associated with the experimentally observed phase, we term this phase ɛ−Al60Sm11(bcc), corresponding to the limiting situation when all 16f sites are occupied by Sm. However, it should be recognized that the range of solubility enabled by split occupancy at Sm sites is an important feature in phase selection under experimental conditions, permitting an avenue for transition with little or no chemical partitioning. Our analysis shows that the ɛ−Al60Sm11(bcc) exhibits a “3-6-6-1” first-shell packing around Sm centers on 16f sites, the same dominant motif exhibited by the undercooled liquid. The coincident motif supports the notion that liquid/glass ordering at high undercooling may give rise to topological invariants between the noncrystalline and crystalline states that provide kinetic pathways to metastable phases that are not accessible during near-equilibrium processing