Grain boundaries (GBs) can critically influence the microstructural evolution and various materials properties. However, a fundamental understanding of GBs in high-entropy alloys (HEAs) is lacking because of the complex couplings of the segregations of multiple elements and interfacial disordering, which can generate new phenomena and challenge the classical theories. Here, by combining large-scale atomistic simulations and machine learning, we demonstrate the feasibility of predicting the GB properties as functions of four independent compositional degrees of freedoms and temperature in a 5D space. Subsequently, GB counterparts to bulk phase diagrams are constructed for the first time for quinary HEAs. A data-driven discovery further reveals new coupled segregation and disordering effects in HEAs. Notably, an analysis of a large dataset discovers a critical compensation temperature at which the segregations of all elements virtually vanish simultaneously. While the machine learning model can predict GB properties via a black-box approach, a surrogate data-based analytical model (DBAM) is constructed to provide more physics insights and better transferability, with good accuracies. This study not only provides a new paradigm enabling prediction of GB properties in a 5D space, but also uncovers new GB segregation phenomena in HEAs beyond the classical GB segregation models.
Solute segregation plays an important role in formation of long-period stacking ordered (LPSO) structure in Mg-M-RE (M: Zn, Ni etc., RE: Y, Gd, etc.) alloy systems. In this work, the planar segregation in Mg-Al-Gd alloy is characterized by high angle annular dark field (HAADF) scanning transmission electron microscopy (STEM) and three-dimensional atom probe (3DAP). It is found there is no planar fault accompanying the segregation, and the spatial distribution of segregation may resemble the periodicity of LPSO structure. The segregation is further quantified by 3DAP, and it mainly enriches wit…
Bimetallic alloys have drawn extensive attentions in materials science due to their widespread applications in electronics, engineering and catalysis. A very fundamental question of alloy is its surface segregation phenomenon. Many recent observations have shown that reactive gases or supports may have strong effects on alloy segregation. However, segregation in water, the most common solvent and environment, has not received enough attention. In this paper we give the quantitative descriptions on the surface segregation energies of 23 transition-metal impurities in Cu hosts under the conditio…
Mg grain boundary (GB) segregation and GB diffusion can impact the processing and properties of Al-Mg alloys. Yet, Mg GB diffusion in Al has not been measured experimentally or predicted by simulations. We apply atomistic computer simulations to predict the amount and the free energy of Mg GB segregation, and the impact of segregation on GB diffusion of both alloy components. At low temperatures, Mg atoms segregated to a tilt GB form clusters with highly anisotropic shapes. Mg diffuses in Al GBs slower than Al itself, and both components diffuse slowly in comparison with Al GB self-diffusion. …
Microalloying elements tend to segregate to the matrix-precipitate phase boundaries to reduce the interfacial energy. The segregation mechanism is emerging as a novel design strategy for developing precipitation-hardened alloys with significantly improved coarsening resistance for high temperature applications. In this paper, we report a nanoscopic diffuse-interface thermodynamic model that describes multicomponent segregation behavior in two-phase substitutional alloys. Following classical approaches for grain boundaries, we employ the regular solution thermodynamics to establish segregation …
This paper studies how solute segregation and its relationship to grain boundary energy in binary alloys is captured in the phase field crystal (PFC) formalism, a continuum method that incorporates atomic scale elasto-plastic effects on diffusional time scales. Grain boundaries are simulated using two binary alloy PFC models --- the original binary model by Elder et al (2007) and the XPFC model by Greenwood et al (2011). In both cases, grain boundary energy versus misorientation data is shown to be well described by Read-Shockley theory. The Gibbs Adsorption Theorem is then used to derive a se…
We present a first-principles atomistic thermodynamics framework to describe the structure, composition and segregation profile of an alloy surface in contact with a (reactive) environment. The method is illustrated with the application to a Ag3Pd(111) surface in an oxygen atmosphere, and we analyze trends in segregation, adsorption and surface free energies. We observe a wide range of oxygen adsorption energies on the various alloy surface configurations, including binding that is stronger than on a Pd(111) surface and weaker than that on a Ag(111) surface. This and the consideration of even …
Grain boundary segregations were investigated by Atom Probe Tomography in an Al-Mg alloy, a carbon steel and Armco\trademark Fe processed by severe plastic deformation (SPD). In the non-deformed state, the GBs of the aluminium alloy are Mg depleted, but after SPD some local enrichment up to 20 at.% was detected. In the Fe-based alloys, large carbon concentrations were also exhibited along GBs after SPD. These experimental observations are attributed to the specific structure of GBs often described as "non-equilibrum" in ultra fine grained materials processed by SPD. The grain boundary segregat…
Grain boundary engineering via dopant segregation can dramatically change the properties of a material. For metallic systems, most current studies concerning interfacial segregation and subsequent transitions of grain boundary structure are limited to binary alloys, yet many important alloy systems contain more than one type of dopant. In this work, hybrid Monte Carlo/molecular dynamics simulations are performed to investigate the behavior of dopants at interfaces in two model ternary alloy systems: Cu-Zr-Ag and Al-Zr-Cu. Trends in boundary segregation are studied, as well as the propensity fo…
While it is known that alloy components can segregate to grain boundaries (GBs), and that the atomic mobility in GBs greatly exceeds the atomic mobility in the lattice, little is known about the effect of GB segregation on GB diffusion. Atomistic computer simulations offer a means of gaining insights into the segregation-diffusion relationship by computing the GB diffusion coefficients of the alloy components as a function of their segregated amounts. In such simulations, thermodynamically equilibrium GB segregation is prepared by a semi-grand canonical Monte Carlo method, followed by calculat…
The segregation behavior of Cr in dilute Fe-Cr alloys is known to be anomalous since the main barrier for surface segregation of Cr in these alloys arises not from the topmost surface layer but from the subsurface layer where the solution energy of Cr is much more endothermic as compared to the topmost surface layer. The Fe-Cr alloys are candidate structural materials for the new generation of nuclear reactors. The surfaces of these alloys will be exposed to hydrogen or its isotopes in these reactors, and although hydrogen is soluble neither in Fe nor in Fe-Cr alloys, it is known that the adso…
X-ray reflectivity studies reveal atomic-level surface-segregation at the free surface of the eutectic Au71Sn29 liquid alloy. The surface-segregation extends up to three layers, in which the top layer is almost a pure monolayer of Sn, the second layer is almost a pure monolayer of Au and the third layer appears to be slightly enhanced in Au. Although the surface-segregation concentration profiles can be qualitatively accounted for by the theories of Defay-Prigogine and Strohl-King, they cannot satisfactorily account for the measured surface tension. PACS numbers: 61.20.-p, 61.10.-i, 68.03.-g
The dynamic behaviour of thermally driven segregation of Cr to the surface of WCrY smart alloy is studied with low energy ion scattering (LEIS). Sputtering the WCrY sample with 500 eV D$_2^+$ ions at room temperature results in preferential removal of the lighter alloy constituents and causes an almost pure W surface layer. At elevated temperatures above 700 K the segregation of Cr atoms towards the surface sets in and prevents the formation of a pure W layer. The simultaneous heating and sputtering of the sample leads to a surface state which reflects the balance between sputter removal and s…
An age-hardenable Al-Cu-Mg alloy (A2024) was processed by high-pressure torsion (HPT) for producing an ultrafine-grained structure. The alloy was further aged for extra strengthening. The tensile strength then reached a value as high as ~1 GPa. The microstructures were analyzed by transmission electron microscopy and atom probe tomography. The mechanism for the high strength was clarified in terms of solid-solution hardening, cluster hardening, work hardening, dispersion hardening and grain boundary hardening. It is shown that the segregation of solute atoms at grain boundaries including subgr…
Based on ab-initio simulations, we report on the nature of principally different mechanisms for interaction of Mg and Zn atoms with grain boundaries in Al alloys leading to different morphology of segregation. The Mg atoms segregate in relatively wide GB region with heterogeneous agglomerations due to the deformation mechanism of solute-GB interaction. In contrast, in the case of Zn atoms an electronic mechanism associated with the formation of directional bonding is dominating in the solute-GB interaction. As a result, for Zn atoms it is energetically beneficial to occupy interstitial positio…
The segregation behavior of the bimetallic alloys PtPd and CoCr in the case of bare surfaces and in the presence of an oxygen ad-layer has been studied by means of first-principles modeling based on density-functional theory (DFT). For both systems, change of the d-band filling due to charge transfer between the alloy components, resulting in a shift of the d-band center of surface atoms compared to the pure components, drives the surface segregation and governs the chemical reactivity of the bimetals. In contrast to previous findings but consistent with analogous PtNi alloy systems, enrichmen…
Bimetallic catalysts can undergo segregation or redistribution of the metals driven by oxidizing and reducing environments. Bragg coherent diffraction imaging (BCDI) was used to relate displacement fields to compositional distributions in crystalline Pt-Rh alloy nanoparticles. 3D images of internal composition showed that the radial distribution of compositions reverses partially between the surface shell and the core when gas flow changes between O2 and H2. Our observation suggests that the elemental segregation of nanoparticle catalysts should be highly active during heterogeneous catalysis …
Ferromagnetism in certain B2 ordered alloys such as Fe$_{60}$Al$_{40}$ can be switched on, and tuned, via antisite disordering of the atomic arrangement. The disordering is accompanied by a $\sim$1 % increase in the lattice parameter. Here we performed a systematic disordering of B2 Fe$_{60}$Al$_{40}$ thin films, and obtained correlations between the order parameter ($S$), lattice parameter ($a_0$), and the induced saturation magnetization ($M_{s}$). As the lattice is gradually disordered, a critical point occurs at 1-$S$=0.6 and $a_0$=291 pm, where a sharp increase of the $M_{s}$ is observed.…
The occurrence of segregation in highly dilute alloys under irradiation is an unusual phenomenon that has so far eluded theoretical explanation. Using ab initio calculations, we are able to explain the origin of radiation-induced rhenium segregation in dilute tungsten-rhenium alloys.
The energy of segregation of Cr from the bulk to the topmost surface layer in dilute Fe-Cr alloys is endothermic but small. On the other hand, the segregation energy from the bulk to the subsurface layer is not only endothermic but relatively large. Thus, the subsurface layer presents a huge barrier, not only for the segregation of Cr from the bulk to the surface, but also for its diffusion from the surface into the bulk. This means that the topmost layer alone cannot be used to determine the barrier for Cr segregation (the segregation energy), which is determined in these alloys by the subsur…
We study order transitions and defect formation in a model high-entropy alloy (CuNiCoFe) under ion irradiation by means of molecular dynamics simulations. Using a hybrid Monte-Carlo/molecular dynamics scheme a model alloy is generated which is thermodynamically stabilized by configurational entropy at elevated temperatures, but partly decomposes at lower temperatures by copper precipation. Both the high-entropy and the multiphase sample are then subjected to simulated particle irradiation. The damage accumulation is analyzed and compared to an elemental Ni reference system. The results reveal …
The control of solute segregation at grain boundaries (GBs) is essential in engineering alloy properties, however the structure-activity relationship of the key parameter-the segregation energies-still remains elusive. Here we propose the electronic and geometric descriptors of GB segregation based on the valence, electronegativity and size of solutes and the non-local coordination number of free surfaces, with which we build a predictive framework to determine the segregation energies across different solutes, matrices, GB structures and segregation sites. This framework uncovers not only the…
Grain size engineering, particularly reducing grain size into the nanocrystalline regime, offers a promising pathway to further improve the strength-to-weight ratio of Al alloys. Unfortunately, the fabrication of nanocrystalline metals often requires non-equilibrium processing routes, which typically limit the specimen size and require large energy budgets. In this study, multiple dopant atoms in ternary Al alloys are deliberately selected to enable segregation to the grain boundary region and promote the formation of amorphous complexions. Three different fully dense bulk nanocrystalline Al a…
Compositionally complex alloys or concentrated solid solutions are the latest frontier in catalyst design, but mixing different elements in one catalyst may result in surface segregation. Atomistic simulations can predict segregation patterns, but standard approaches based on mean-field models, cluster expansion, or classical interatomic potentials are often limited for the description of multicomponent alloys. We present machine learning potentials that can describe surface segregation with near DFT accuracy. The method is used to study a complex Co-Cu-Fe-Mo-Ni quinary alloy. For this alloy, …
In this paper we report phonon dynamics in chemically synthesized Zn1- xMgxO (0\leqx\leq0.07) and Zn1-yCdyO (0\leqy\leq0.03) alloy nanostructures of sizes ~10 nm using non-resonant Raman and Fourier Transformed Infrared Spectroscopy (FTIR). Substitution by Mg makes the unit cell compact while Cd substitution leads to unit cell expansion. On alloying, both A1(LO) and E1(LO) mode of wurtzite ZnO show blue shift for Zn1-xMgxO and red shift for Zn1-yCdyO alloy nanostructures due to mass defect and volume change induced by the impurity atoms. Significant shift has been observed in E1(LO) mode for Z…
Grain boundaries have been shown to dramatically influence the behavior of relatively simple materials such as monatomic metals and binary alloys. The increased chemical complexity associated with multi-principal element alloys is hypothesized to lead to new grain boundary phenomena. To explore the relationship between grain boundary structure and chemistry in these materials, hybrid molecular dynamics/Monte Carlo simulations of a faceted Σ11 <110> tilt boundary, chosen to sample both high- and low-energy boundary configurations, are performed in face-centered cubic CrFeCoNiCu and CrFeCoNi equ…
This paper compares two approaches for investigating the near-surface composition profile that results from surface segregation in the so-called Cantor alloy, an equi-molar alloy of CoCrFeMnNi. One approach consists of atomistic computer simulations by a combination of Monte Carlo, molecular dynamics and molecular statics techniques, and the other is a nearest neighbor analytical calculation performed in the regular solution approximation with a multilayer model, developed here for the first time for a N-component system and tested for the 5-component Cantor alloy. This type of comparison is u…
θ' (Al2Cu) precipitates in Al-Cu-Ag alloys were examined using high angle annular dark field scanning transmission electron microscopy (HAADF-STEM). The precipitates nucleated on dislocation loops on which assemblies of γ' (AlAg2) precipitates were present. These dislocation loops were enriched in silver prior to θ' precipitation. Coherent, planar interfaces between the aluminium matrix and θ' precipitates were decorated by a layer of silver of two atomic layers in thickness. It is proposed that this layer lowers the chemical component of the Al-θ' interfacial energy. The lateral growth of the…
Due to their high strength and advantageous high-temperature properties, tungsten-based alloys are being considered as plasma-facing candidate materials in fusion devices. Under neutron irradiation, rhenium, which is produced by nuclear transmutation, has been found to precipitate in elongated precipitates forming thermodynamic intermetallic phases at concentrations well below the solubility limit. Recent measurements have shown that Re precipitation can lead to substantial hardening, which may have a detrimental effect on the fracture toughness of W alloys. This puzzle of sub-solubility preci…
Grain boundary embrittlement occurs when a solute enriches at a grain boundary and lowers its cohesive energy. While grain boundary enrichment is often attributed to equilibrium segregation effects, most models of embrittlement consider either the energetics of decohesion or the equilibrium adsorption at the boundary, but not both phenomena together. We develop a model for the change in cohesive energy of a grain boundary of a pure metal upon introduction of solute under conditions of equilibrium segregation prior to fracture. A heuristic grain boundary cohesion map is presented to delineate w…
The temperature driven segregation of Cr to the surface of the tungsten-based WCrY alloy is analysed with low energy ion scattering of He+ ions with an energy of 1 keV in the temperature range from room temperature to 1000 K. Due to the high surface sensitivity, these measurements probe only the composition of the outermost monolayer. The surface concentration of Cr increases slightly when the temperature of the sample is increased up to 700 K and exhibits a much stronger increase when the sample temperature is further raised. The segregation enthalpy for Cr is obtained from the Langmuir-McLea…
Interfacial segregation and chemical short-range ordering influence the behavior of grain boundaries in complex concentrated alloys. In this study, we use atomistic modeling of a NbMoTaW refractory complex concentrated alloy to provide insight into the interplay between these two phenomena. Hybrid Monte Carlo and molecular dynamics simulations are performed on columnar grain models to identify equilibrium grain boundary structures. Our results reveal extended near-boundary segregation zones that are much larger than traditional segregation regions, which also exhibit chemical patterning that b…
In the drive towards higher strength alloys, a diverse range of alloying elements is employed to enhance their strength and ductility. Limited solid solubility of these elements in steel leads to segregation during casting which affects the entire down-stream processing and eventually the mechanical properties of the finished product. Although it is thought that the presence of continuous bands lead to premature failure, it has not been possible to verify this link. This poses as increasingly greater risk for higher alloyed, higher strength steels which are prone to centre-line segregation: it…
We investigate segregation behavior of additive elements M (= Ni, Cr) at the C11b/D8m interface for MoSi2- Mo5Si3 alloys, based on first-principles calculation. We first find energetically stable interface structure with interface energy of 0.08 eV/A^2. Based on the stable interface, segregation energy for additive elements is calcu- lated for individual atomic layer, which is applied to Monte Carlo statistical simulation under grand-canonical ensemble to quantitatively predict interface segregation profile. We find that our simulation successfully capture the characteristics in measured segre…
We developed a generalized model that considers light as energy contributed through the thermalization of excited carriers to generate excitation-intensity- and temperature-dependent phase diagrams. We find that the model replicates the light-induced phase segregation behavior of the MAPb(I,Br)3 system. From there, we sought to study how best to design new, stable, mixed-halide alloys. The resultant first-principles predictions show that the pseudo halide anion BF4- suppresses phase segregation in FA0.83Cs0.17Pb(I0.6Br0.4)3, resulting in enhanced operating stability. The findings reveal that p…
