The crystallization of a binary system is investigated in computer model which takes into account a temperature dependence of diffusion coefficient and a nonequilibrium partition of dissolved component of the alloy. The dependence of interface velocity on an undercooling at the dendrite tip is obtained during rapid solidification of Fe-B and Ni-B systems. The morphological transition which is conditioned by change from a diffusion growth regime to thermal growth at some critical undercooling is detected. This transition is characterized by discontinuous magnification of the dendrite growth velocity. Values of a critical undercooling and a growth velocity discontinuity depend both on a degree of an anisotropy of a kinetic coefficient, and on difference in energies of activation for atomic kinetics and for diffusion on an interface.
Soft magnetic materials have low coercive fields and high permeability. Recently, nanocrystalline alloys obtained using annealing amorphous alloys have attracted much interest since nanocrystalline alloys with small grain sizes of tens of nanometers exhibit low coercive fields comparable to that of amorphous alloys. Since nanocrystalline soft magnetic materials attain remarkable soft magnetic properties by controlling the grain size, the crystal grains' microstructure has a substantial influence on the soft magnetic properties. In this research, we examined the magnetic properties of Fe-Si-B-P…
Investigation of crystallization in an 5BDSR amorphous alloy by system Fe-Cu-Nb-Si-B under the influence of an incoherent optical radiation generated by gas discharge flash-lamp using X-ray diffraction scattering. It is shown that depending on the magnitude of the input power to the flash-lamp of structure of the alloy varies widely after radiation: a change in the short-range order during retaining the amorphous structure or the formation of several crystalline phases with different quantitative content in the alloy. Conditions are found for the formation of the nanocrystalline structure. Ana…
We have applied extended X-ray absorption fine structure (EXAFS) analyses and ab-initio molecular dynamics (AIMD) simulations to study the atomic structure of Ag-doped (up to 42%) Ge1Sb2Te4 alloys. Analysis of the models that are consistent with the EXAFS experiment reveals that the Ge environment is significantly modified by Ag doping whereas those of Sb and Te are barely affected (except for high Ag concentrations), and suggests that Ag prefers bonding with Te to Ge or Sb. Doping with Ag promotes the conversion of tetrahedral Ge sites to octahedral Ge sites and enhances the speed of crystall…
Kinetics of crystallization of two amorphous alloys, Fe70Cr10B20 and Fe80Zr10B10, have been followed up by neutron thermodiffractometry experiments performed in the two axis diffractometer D20 (ILL, Grenoble). The structural changes are directly correlated with the temperature dependence of the magnetization. Fe70Cr10B20 crystallizes following a two-step process: an eutectic crystallization of alfa-Fe (bcc) and the metastable tetragonal phase (Fe0.8Cr0.2)3B followed by another eutectic transformation to the stable phase (Fe0.75Cr0.25)2B and more segregation of alfa-Fe. These tetragonal phases …
We study the influence of the liquid-vapor surface on the crystallization kinetics of supercooled metal alloys. While a good glass former, $\rm{Cu}_{50}\rm{Zr}_{50}$, shows no evidence of surface enhancement of crystallization, $\rm{Ni}_{50}\rm{Al}_{50}$ exhibits an increased rate of crystallization due to heterogeneous nucleation at the free liquid surface. The difference in the compositional fluctuations at the interface is proposed as the explanation of the distinction between the two alloys. Specifically, we observe compositional ordering at the surface of $\rm{Ni}_{50}\rm{Al}_{50}$ while …
Using molecular simulations, we shed light on the mechanism underlying crystal nucleation in metal alloys and unravel the interplay between crystal nucleation and glass transition, as the conditions of crystallization lie close to this transition. While decreasing the temperature of crystallization usually results in a lower free energy barrier, we find an unexpected reversal of behavior for glass-forming alloys as the temperature of crystallization approaches the glass transition. For this purpose, we simulate the crystallization process in two glass-forming Copper alloys, $Ag_6Cu_4$, which h…
We extend the Weak Crystallization theory to the case of metallic alloys. The additional ingredient -- itinerant electrons -- generates nontrivial dependence of free energy on the angles between ordering wave vectors of ionic density. That leads to stabilization of FCC, Rhombohedral, and icosahedral quasicrystalline (iQC) phases, which are absent in the generic theory with only local interactions. The condition for stability of iQC that we find, is consistent with the Hume-Rothery rules known empirically for majority of stable iQC; namely, the length of the primary Bragg peak wavevector is app…
X-ray measurements reveal a crystalline monolayer at the surface of the eutectic liquid Au_{82}Si_{18}, at temperatures above the alloy's melting point. Surface-induced atomic layering, the hallmark of liquid metals, is also found below the crystalline monolayer. The layering depth, however, is threefold greater than that of all liquid metals studied to date. The crystallinity of the surface monolayer is notable, considering that AuSi does not form stable bulk crystalline phases at any concentration and temperature and that no crystalline surface phase has been detected thus far in any pure li…
New determination of the magnetic anisotropy from single crystals of (Fe$_{1-x}$Co$_x$)$_2$B alloys are presented. The anomalous temperature dependence of the anisotropy constant is discussed using the standard Callen-Callen theory, which is shown to be insufficient to explain the experimental results. A more material specific study using first-principles calculations with disordered moments approach gives a much more consistent interpretation of the experimental data. Since the intrinsic properties of the alloys with $x=0.3-0.35$ are promising for permanent magnets applications, initial inves…
Solidification pattern during nonequilibrium crystallization is among the most important microstructures in the nature and technical realms. Phase field crystal (PFC) model could simulate the pattern formation during equilibrium crystallization at atom scale, but cannot grasp the nonequilibrium ones due to the absence of proper elastic-relaxation time scale. In this work, we propose a minimal classical-density-functional-theory-based model for crystal growth in supercooled liquid. Growth front nucleation (GFN) and various nonequilibrium patterns, including the faceting growth, spherulite, dend…
Crystallization from an amorphous atomic structure is usually seen as a spontaneous process in pursuit of a lower energy state, but for alloy systems it is often hard to elucidate because of the intrinsic structural and compositional complexity. Here, by means of electron beam irradiation, we found surface-limited, and thus size-dependent crystallization in a system of monoatomic Pd metallic glass, which is ascribed to the structural differences between the surface and the interior. The equilibrium thickness of the surface crystallization is controllable, presenting a promising approach to fab…
A correlation between the change in magnetic susceptibility (Δ\c{hi}exp) upon crystallization of Cu-Zr, Hf metallic glasses (MG) with their glass forming ability (GFA) observed recently is found to apply to Cu-Ti and Zr-Ni alloys, too. In particular, a small Δ\c{hi}exp , which reflects similar electronic structures, ES, of glassy and corresponding crystalline alloys, corresponds to high GFA. Here, we studied Δ\c{hi}exp in five Cu-Ti and four Cu-Zr and Ni-Zr MGs. The fully crystalline final state of all alloys was verified from X-ray diffraction patterns. The variation of GFA with composition i…
A bulk metallic glass forming alloy is subjected to shear flow in its supercooled state by compression of a short rod to produce a flat disc. The resulting material exhibits enhanced crystallization kinetics during isothermal annealing as reflected in the decrease of the crystallization time relative to the non-deformed case. The transition from quiescent to shear-accelerated crystallization is linked to strain accumulated during shear flow above a critical shear rate $\dotγ_c\approx 0.3$ s$^{-1}$ which corresponds to Péclet number, $Pe\sim\mathcal{O}(1)$. The observation of shear accelerated …
The effect of nonequilibrium solute trapping by a growing solid under rapid solidification conditions is studied using a phase-field model. Considering a continuous steady-state concentration profile across the diffuse solid-liquid interface, a new definition of the nonequilibrium partition coefficient in the phase-field context is introduced. This definition leads, in particular for high growth velocities, to a better description of the available experimental data in comparison with other diffuse interface and sharp-interface predictions.
Development of reliable interatomic potentials is crucial for theoretical studies of relationship between chemical composition, structure and observable properties in glass-forming metallic alloys. Due to ambiguity of potential parametrization procedure, some crucial properties of the system, such as crystallization stability or symmetry of the ground state crystal phase, may not be correctly reproduced in computer simulations. Here we address this issue for ${\rm Cu_{64.5}Zr_{35.5}}$ alloy described by two modifications of embedded atom model potential as well as by \textit{ab initio} molecul…
Achieving the compositionally ordered state in a substitutional alloy of two or more species can often be even critical for improving its functional properties. To produce a highly ordered alloy, a longtime high-temperature (up to T=1000 K) treatment of the alloy is typically necessary because of insufficient vacancy concentration (c_v) and their mobility. However, such processing affects the morphology and complicates the technology of functional alloys. We show theoretically that the ordering in the practically important FePt system (Fe_xPt_1-x with x being close to 0.5) is already achievabl…
The search for effective methods to fabricate bulk single-phase quasicrystalline Al-Cu-Fe alloys is currently an important task. Crucial to solving this problem is to understand mechanisms of phase formation in this system. Here we study crystallization sequence during solidification as well as the conditions of solid phase formation in slowly solidified Al-Cu-Fe alloys in a wide range of compositions. Concentration dependencies of undercoolability were also constructed by differential thermal analysis method. These experimental results are compared with data on chemical short-range order in t…
Element-Specific Solute Trapping and Grain Structure Evolution during Laser Powder Bed Fusion of Multicomponent Alloys
University of Michigan, Dearborn（密歇根大学迪尔伯恩分校）；Texas A&M University（德克萨斯农工大学）；AlphaSTAR Technology Solutions（AlphaSTAR技术解决方案）；University of Michigan, Ann Arbor（密歇根大学安娜堡分校）
We determine the non-equilibrium grain size distribution during the crystallization of a solid in $d$ dimensions at fixed thermodynamic conditions, for the random nucleation and growth model, and in absence of grain coalescence. Two distinct generalizations of the theory established earlier are considered. A closed analytic expression of the grain size distribution useful for experimental studies is derived for anisotropic growth rates. The main difference from the isotropic growth case is the appearance of a constant prefactor in the distribution. The second generalization considers a Gaussia…
Crystallization represents a fundamental process engendering solidification of a material and determines its microstructure. Driven by complex phenomena at the atomic scale, its understanding for alloys still remains elusive. The present work proposes a large scale molecular dynamics simulation study of the homogeneous crystal nucleation pathways of prototypical undercooled Al-Ni binary alloys. An unsupervised topological learning analysis shows that the nucleation sets in first from a chemical ordering, followed by a bond-orientational ordering of the underlying crystal phase. Our results ind…
From a simple bulk model for the one-dimensional steady-state solidification of a dilute binary alloy we derive an interface description, allowing arbitrary values of the growth velocity. Our derivation leads to exact expressions for the fluxes and forces at the interface and for the set of Onsager coefficients. We, moreover, discover a continuous symmetry, which appears in the low-velocity regime, and there deletes the Onsager sign and symmetry properties. An example is the generation of the sometimes negative friction coefficient in the crystallization flux-force relation.
Tailoring the degree of structural disorder in Ge-Sb-Te alloys is important for the development of non-volatile phase-change memory and neuro-inspired computing. Upon crystallization from the amorphous phase, these alloys form a cubic rocksalt-like structure with a high content of intrinsic vacancies. Further thermal annealing results in a gradual structural transition towards a layered structure and an insulator-to-metal transition. In this work, we elucidate the atomic-level details of the structural transition in crystalline GeSb2Te4 by in situ high-resolution transmission electron microsco…
We have proposed a qualitative model for the structure of binary systems similar to Pd-Er alloys, which explains their nonmonotonic relaxation after the hydrogen saturation. It is based on the assumption that such a solid solution involves two kind heterogeneities. The former are caused by spinodal decomposition of the initially homogeneous state of the solid solution into the phases enriched and depleted of Er atoms. The latter are crystalline defects that trap an additional amount of Er atoms, which leads also to their local accumulation, changing the defect properties. Hydrogen atoms penetr…
High Entropy Alloys (HEAs) are designed by mixing multiple metallic species in nearly the same amount to obtain crystalline or amorphous materials with exceptional mechanical properties. Here we use molecular dynamics simulations to investigate the role of positional and compositional disorder in determining the low-frequency vibrational properties of CrMnFeCoNi HEAs. Our results show that the expected dependence of the density of states on the frequency as $D(ω)\simω^4$ is recovered for amorphous HEAs and is also observed for partially crystallized alloys with deviations that depend on the de…
On the basis of local nonequilibrium approach, the one-dimensional model of the solute diffusion during rapid solidification of the binary alloy in the semi-infinite volume is considered. Within the scope of the model it is supposed that mass transport is described by the telegrapher equation. The basic assumption concerns the behavior of the diffusion flux and the solute concentration at the interface. Under the condition that these quantities are given by the superposition of the exponential functions the solutions of the telegrapher equation determining the flux and the solute distributions…
In this work, using the methods of viscosimetry and thermal analysis, the concentration changes in the values of the supercooling viscosity of Al-Mg melts with Mg content from 2.5 to 95 at.% are studied. It is shown that the temperature dependences of viscosity are well described by an exponential dependence. The concentration dependence of viscosity is not monotonous and reflects a change in the chemical short-range order in the liquid phase. The concentration dependence of supercooling of Al-Mg melts is determined by the type of solid phase formed during solidification, and also reflects the…
Thin film metallic glasses undergoing devitrification can form partially crystallized or fully crystallized materials with novel structural and magnetic properties. The development of desired and tunable properties of such systems drives the need to understand the mechanism of their thermal evolution at the atomic level. Co-sputtered amorphous Ni-Zr alloy thin films which were thermally annealed in steps of 200 deg C from room temperature up to 800 deg C, were observed to undergo an amorphous-to-crystalline transformation. Evolutions in local atomic structure, including oxide formation and dep…
Crystal nucleation and growth processes induced by an externally applied shear strain in a model metallic glass are studied by means of nonequilibrium molecular dynamics simulations, in a range of temperatures. We observe that the nucleation-growth process takes place after a transient, induction regime. The critical cluster size and the lag-time associated with this induction period are determined from a mean first-passage time analysis. The laws that describe the cluster growth process are studied as a function of temperature and strain rate. A theoretical model for crystallization kinetics …
We have developed a methodology to study the thermodynamics of order-disorder transformations in n-component substitutional alloys that combines nonequilibrium methods, which can efficiently compute free energies, with Monte Carlo simulations, in which configurational and vibrational degrees of freedom are simultaneously considered on an equal footing basis. Furthermore, by appropriately constraining the system, we were able to compute the contributions to the vibrational entropy due to bond proportion, atomic size mismatch, and bulk volume effects. We have applied this methodology to calculat…
NPs are ultrafine-grain crystal or amorphous substances which are as small as 100nm. They have unique physical, chemical and mechanical properties, which are very different from those of large scale materials. This uniqueness is attributed to the fact that the number of atoms in the surface layer and in the bulk is commensurable. As the atoms in the surface layer of nanoparticles have their counterparts from one side only, their balance is impaired, and the resulting structure relaxation leads to the displacement of atomic spacing in a 2-3nm layer. Therefore the surface layers expand while int…
We introduce a new phase-field formulation of rapid alloy solidification that quantitatively incorporates nonequilibrium effects at the solid-liquid interface over a very wide range of interface velocities. Simulations identify a new dynamical instability of dendrite tip growth driven by solute trapping at velocities approaching the absolute stability limit. They also reproduce the formation of the widely observed banded microstructures, revealing how this instability triggers transitions between dendritic and microsegregation-free solidification. Predicted band spacings agree quantitatively w…
High-temperature, high-dose, neutron irradiation of W results in the formation of Re-rich clusters at concentrations one order of magnitude lower than the thermodynamic solubility limit. These clusters may eventually transform into brittle W-Re intermetallic phases, which can lead to high levels of hardening and thermal conductivity losses. Standard theories of radiation enhanced diffusion and precipitation cannot explain the formation of these precipitates and so understanding the mechanism by which nonequilibrium clusters form under irradiation is crucial to predict materials degradation and…
Stochastic growth of binary alloys on a weakly interacting substrate is studied by kinetic Monte Carlo simulation. The underlying lattice model relates to fcc alloys, and the kinetics are based on deposition, atomic migration with bond-breaking processes and exchange processes mediated by nearest neighbor hopping steps. We investigate the interrelation between surface processes and the emerging nonequilibrium structure at and below the growing surface under conditions where atoms in the bulk can be regarded as immobile. The parameters of the model are adapted to CoPt_3 alloys. Growing nanoclus…
Microcompression testing is used to probe the uniaxial stress-strain response of a nanocrystalline alloy, with an emphasis on exploring how grain size and grain boundary relaxation state impact the complete flow curve and failure behavior. The yield strength, strain hardening, strain-to-failure, and failure mode of nanocrystalline Ni-W films with mean grain sizes of 5, 15, and 90 nm are studied using taper-free micropillars that are large enough to avoid extrinsic size effects. Strengthening is observed with grain refinement, but catastrophic failure through strain localization is found as wel…
The mechanisms of stability or instability in the strained alloy film growth are of intense current interest to both theorists and experimentalists. We consider dislocation-free, coherent, growing alloy films which could exhibit a morphological instability without nucleation. We investigate such strained films by developing a nonequilibrium, continuum model and by performing a linear stability analysis. The couplings of film-substrate misfit strain, compositional stress, deposition rate, and growth temperature determine the stability of film morphology as well as the surface spinodal decomposi…
Differential thermal analysis has been conducted for the Al-Cu-Co alloys with the composition range of 15 at.% Co and 10 to 30 at.% Cu, and 25 at.% Co and 2.5 to 20 at.% Co. The features of the formation of solid phases have been studied during the crystallization in a crucible in the conditions of slow cooling (rate of cooling to 1 K s-1) at normal pressure. On the state diagram of the Al-Cu-Co system with 15 at.% Co and 25 at.% Cu the concentration sections have been built, which allows to determine the concentration ranges from which different phases are formed during the first stage of cry…
The interface stability against small perturbations of the planar solid-liquid interface is considered analytically in linear approximation. Following the analytical procedure of Trivedi and Kurz (Trivedi R, Kurz W. Acta Metall 1986;34:1663), which is advancing the original treatment of morphological stability by Mullins and Sekerka (Mullins WW, Sekerka RF. J Appl Phys 1964;35:444) to the case of rapid solidification, we extend the model by introducing the local nonequilibrium in the solute diffusion field around the interface. A solution to the heat- and mass-transport problem around the pert…
During the formation of Si nanocrystals (Si NC) in Si$_x$C$_{1-x}$ layers via solid-phase crystallization, the unintended formation of nanocrystalline SiC reduces the minority carrier lifetime and therefore the performance of Si$_x$C$_{1-x}$ as an absorber layer in solar cells. A significant reduction in the annealing time may suppress the crystallization of the SiC matrix while maintaining the formation of Si NC. In this study, we investigated the crystallization of stoichiometric SiC and Si-rich SiC using conventional rapid thermal annealing (RTA) and nonequilibrium millisecond range flash l…
Molecular dynamics (MD) simulation has been employed to study the nonequilibrium structure formation of two types of particles in a colloidal suspension, driven by type-dependent forces. We examined the time evolution of structure formation as well as the structural properties of the resulting aggregation by studying the radial distribution function (RDF). The resulting aggregation is well described by a binary colloidal gelation. We compared the structural properties to those for one type of particles. From the MD results, it is evident that there are significant differences between the RDF's…
Fe-B-Si system is a matrix for synthesis of new functional materials with exceptional magnetic and mechanical properties. Progress in this area is associated with the search for optimal doping conditions. This theoretical and experimental study is aimed to address the influence of Ta alloying on the structure of undercooled (Fe0.75B0.15Si0.1)100-xTax (x=0-2) melts, their undercoolability and the processes of structure formation during solidification. Small concentration of Ta complicates standard ab initio and machine learning investigations. We developed a technique for fast and stable traini…
Almost three quarters of a century ago, Charles Frank proposed that the deep supercooling observed in metallic liquids is due to icosahedral short-range order (ISRO), which is incompatible with the long-range order of crystal phases. Some evidence in support of this hypothesis has been published previously. However, those studies were based on a small population of maximum supercooling measurements before the onset of crystallization. Here, the results of a systematic statistical study of several hundred maximum supercooling measurements on Ti39.5Zr39.5Ni21 and Zr80Pt20 liquids are presented. …
