Composition and non-equilibrium crystallization in partially devitrified co-rich soft magnetic nanocomposite alloys

The body-centered cubic (bcc) phase tends to preferentially nucleate during solidification of highly undercooled liquid droplets of binary alloy systems, including Fe–Co, Fe–Ni and Fe–Cr–Ni. We investigate a similar tendency during the partial devitrification of Co-rich amorphous precursors of composition (Co_1?xFe_x)₈₈Zr₇B₄Cu₁ by identifying the structure and composition of the nanocrystalline grains. The Co:Fe ratio of the bcc nanocrystals varies linearly with the Co:Fe ratio of the amorphous precursor, and can lie well within the single-phase face-centered cubic (fcc) region of the Fe–Co phase diagram at the crystallization temperature. Classical nucleation theory therefore suggests several potential explanations for the preferential nucleation of bcc phase from an amorphous precursor, including: (i) a reduced amorphous/bcc interface energy as compared to the close-packed phases; (ii) a lower strain of precipitation for bcc nuclei as compared to close-packed fcc and hexagonal close-packed nuclei; and (iii) stabilization of the bcc phase by dissolved glass-formers such as Zr and B.     

Fe基合金连续冷却相变的分子动力学模拟

采用分子动力学模拟了Fe99Cu1合金在1×1014 K/s冷速下从fcc奥氏体结构转变为bcc铁素体结构的相变过程.结果表明,Fe99 Cu1合金在900～800℃之间开始发生相变,600 ℃时相变明显,100℃时55％的原子转变为bcc结构.Cu元素阻碍合金相变,并且促进bcc孪晶形成.     

Nucleation of Ni–Fe alloy near the spinodal

In molecular dynamics simulations, “non-classical” nucleation around the spinodal in Fe–Ni alloys is observed by controlling the composition. With increasing Fe concentration, metastable body-centered cubic (bcc) clusters are formed during pre-crystallization under the influence of the spinodal, and then grow into face-centered cubic (fcc)-ordered critical nuclei. When the composition reaches 75 at.% Fe, this transformation is suppressed and the bcc, rather than fcc, symmetry dominates the structure of critical nuclei, a typical nucleation behavior near the spinodal. Further increase in the Fe concentration depresses nucleation below the spinodal temperature. As a consequence, two transient bcc phases characterized by high and low densities appear upon reaching the critical size.     

A modified embedded-atom method interatomic potential for the Fe–H system

A modified embedded-atom method (MEAM) interatomic potential for the Fe–H binary system has been developed using previously developed MEAM potentials of Fe and H. The potential parameters were determined by fitting to experimental data on the dilute heat of solution of hydrogen in body-centered cubic (bcc) and face-centered cubic (fcc) Fe, the vacancy–hydrogen binding energy in bcc Fe, and to a first-principles calculation for the lattice parameter and bulk modulus of a hypothetical NaCl-type FeH. The potential accurately reproduces the known physical properties of hydrogen as an interstitial solute element in bcc and fcc Fe. The applicability of the potential to atomistic approaches for investigating interactions between hydrogen atoms and other defects such as vacancies, dislocations and grain boundaries, and also for investigating the effects of hydrogen on various deformation and mechanical behaviors of iron is demonstrated.     

EXAFS STUDY OF THE SHORT RANGE STRUCTURE OF NANOCRYSTALLINE BCC-Fe_(80)Cu_(20) SOLID SOLUTION

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Cr对CoFeNiAl0.6Ti0.4的合金化行为与组织的影响

采用"机械合金化+SPS烧结"制备了CoFeNiAl0.6Ti0.4和CrCoFeNiAl0.6Ti0.4块体高熵合金,研究元素Cr对CoFeNiAl0.6Ti0.4高熵合金的合金化行为和组织的影响。结果表明:Cr元素并不影响CoFeNiAl0.6Ti0.4高熵合金的合金化顺序,而影响完全合金化后的晶体结构,使CoFeNiAl0.6Ti0.4高熵合金原本单一的fcc结构转变为fcc+bcc结构。SPS烧结后,CoFeNiAl0.6Ti0.4高熵合金主要为fcc+bcc主相+微量bcc白相,而Cr元素的添加促使合金转变成fcc主相+微量bcc白相。同时,合金元素Cr的加入,使CoFeNiAl0.6Ti0.4高熵合金中的微量白相,由原本富Al和Fe元素转变为富Al和Ti元素;且Cr元素不影响CoFeNiAl0.6Ti0.4高熵合金中fcc结构的纳米孪晶组织的形成。     

Application of classical nucleation theory to phase selection and composition of nucleated nanocrystals during crystallization of Co-rich (Co,Fe)-based amorphous precursors

Classical steady-state nucleation theory is applied to Co-rich Fe,Co-based alloys to provide a rationale for experimental observations during the nanocrystallization of Co-rich (Co,Fe)₈₉Zr₇B₄ and (Co,Fe)₈₈Zr₇B₄Cu₁ amorphous precursors. The amorphous precursor free energy is estimated using density functional theory. This simple theory suggests: (i) strain or interface energy effects could explain a tendency for a body-centered cubic (bcc) phase to form during crystallization. Dissolved glass formers (Zr,B) in crystalline phases may also contribute; (ii) similar face-centered cubic (fcc) and hexagonal close-packed (hcp) free energies could explain the presence of some hcp phase after crystallization even though fcc is stable at the crystallization temperature; (iii) nanocrystal compositions vary monotonically with the Co:Fe ratio of the amorphous precursor even when multiple phases are nucleating because nucleation is not dictated by the common tangency condition governing bulk phase equilibria; and (iv) Fe-enrichment of the bcc phase can be attributed to a relatively small free energy difference between the amorphous and bcc phases for high Co-containing alloys.     

连续升温、降温过程中纯Fe的微观结构分析

通过分子动力学模拟,采用较先进的键型指数法HA及原子团类型指数法CTIM-2,对Fe连续升温、降温过程中微观结构进行模拟研究.结果表明:连续升温过程,Fe的微观结构变化是bcc→fcc\hcp→bcc→液体；连续降温过程,Fe的微观结构变化是液体→fcc\hcp.Fe凝固结束没有形成大量的高温bcc晶体,原因是在高温液态中bcc结构原子稳定性较差,fcc和hcp结构原子更易稳定存在.此外,温度变化速率过快,可诱导晶体生长过程中发生层错,促使Fe在升温、降温过程出现fcc和hcp晶体的交替分层分布,这与fcc和hcp晶体的原子能量相近、晶体的致密度相同、原子空间堆垛方式局部相同有关.     

Solid-state reactions upon mechanical alloying of an Fe32Al68 binary mixture

The sequence of solid-state reactions that occur upon mechanical alloying of powder mixtures of Al and Fe taken in an atomic ratio of 68: 32 has been studied by the methods of X-ray diffraction analysis, M?ssbauer spectrometry, and Auger spectrometry. Upon the formation of a nanocrystalline state (<10 nm), there takes place a mutual penetration of Al atoms into Fe and Fe atoms into Al particles. The rate of consumption of the fcc Al is substantially higher than that of the bcc Fe. The process of the mechanical alloying (MA) was found to be two-stage. At the first stage, up to 2 at % Fe is dissolved in the fcc Al, and an amorphous Fe₂₅Al₇₅ phase is formed in the interfaces, whose amount reaches 70 at % at the finish of the initial stage. In the interfaces of the ??-Fe phase, a disordered bcc phase of composition Fe₆₆Al₃₄ is formed, which contains up to 12 at % Al segregates. At the second stage, the amorphous phase crystallizes into an orthorhombic intermetallic compound Fe₂Al₅. The residual ??-Fe, bcc Fe₆₆Al₃₄, and segregated Al form a bcc phase of composition Fe₃₅Al₆₅.     

Computational thermodynamics and the kinetics of martensitic transformation

To assist the science-based design of alloys with martensitic microstructure, a multicomponent database kMART (kinetics of MARtensitic Transformation) encompassing the components Al, C, Co, Cr, Cu, Fe, Mn, Mo, N, Nb, Ni, Pd, Re, Si, Ti, V, and W has been developed to calculate the driving force for martensitic transformation. Built upon the SSOL database of the Thermo-Calc software system, a large number of interaction parameters of the SSOL database have been modified, and many new interaction parameters, both binary and ternary, have been introduced to account for the heat of transformation, T ₀ temperatures, and the composition dependence of magnetic properties. The critical driving force for face-centered cubic (fcc) → body-centered cubic (bcc) heterogeneous martensitic nucleation in multicomponent alloys is modeled as the sum of a strain energy term, a defect-size-dependent interfacial energy term, and a composition-dependent interfacial work term. Using our multicomponent thermodynamic database, a model for barrierless heterogeneous martensitic nucleation, a model for the composition and temperature dependence of the shear modulus, and a set of unique interfacial kinetic parameters, we have demonstrated the efficacy of predicting the fcc → bcc martensitic start temperature (M _s ) in multicomponent alloys with an accuracy of ± 40 K over a very wide composition range.     

Nanoindentation study on the creep characteristics of high-entropy alloy films: fcc versus bcc structures

Using the magnetron sputtering technique, two typical high-entropy alloy (HEA) films namely CoCrFeNiCu (Al-0) with a face-centered cubic (fcc) structure and CoCrFeNiCuAl_2.5 (Al-2.5) with a body-centered cubic (bcc) structure were prepared by alloy targets. The as-deposited HEA films have a columnar-growth mode and nanocrystalline grains. The creep behaviors of both HEA films were systematically investigated by nanoindentation with a Berkovich indenter. The bcc Al-2.5 exhibited a stronger creep resistance than the fcc Al-0. In addition, with the increase of holding load and/or loading rate, the creep deformation was significantly enhanced in the fcc Al-0. Interestingly, it was almost history-independent in the bcc Al-2.5. The creep characteristics of HEA films could be related to the distinct lattice structures, which apparently affect the kinetics of plastic deformation. The strain rate sensitivity (SRS) and activation volume of the dislocation nucleation were carefully estimated for both HEA films. In view of the large differences of activation volumes between Al-0 and Al-2.5, we present discussions to explain the observed creep characteristics in HEA films.     

Changes in the vibrational energies and interatomic spacings upon the formation of vacancies in the volumes and in the cores of crystallite-conjugation regions of polycrystalline transition metals with cubic lattices

The changes in the vibrational energies and the signs of changes in the interatomic spacings upon the formation of vacancies in the bulk of metal and in the cores of the crystallite-conjugation regions (CCR) in polycrystalline transition metals with bcc and fcc lattices have been determined. The vibrational energy increases upon the formation of a vacancy in the bulk of metal because of a positive “relaxation” contribution to the change in the force constant of the atoms surrounding a vacancy. Positive “relaxation” contributions to the changes in the force constants and, correspondingly, an increase in the vibrational energy of the atoms surrounding a vacancy arise also upon the formation of “split” vacancies (S vacancies) in the cores of CCRs of polycrystalline transition metals with a face-centered cubic lattice. The positive “relaxation” contributions to the changes of the force constant of atoms in the region of localization of S vacancies are caused by a decrease in the interatomic spacings upon their formation, just as upon the formation of conventional vacancies in the bulk of metals. The vibrational energy of the nearest environment of the vacancies that are formed in the CCR cores in the polycrystalline d transition metals with a bcc lattice decreases because of a negative “relaxation” contribution to the change in the force constants. The cores of the high-angle CCRs in polycrystalline d transition metals with a bcc lattice are characterized by a negative internal pressure. Therefore, vacancies with positive relaxation volumes ν_BCC > 0 are formed in them, causing an increase in the interatomic distances in the nearest environment of such vacancies.     

Computational thermodynamics and the kinetics of martensitic transformation

To assist the science-based design of alloys with martensitic microstructure, a multicomponent database kMART (kinetics of MARtensitic Transformation) encompassing the components Al, C, Co, Cr, Cu, Fe, Mn, Mo, N, Nb, Ni, Pd, Re, Si, Ti, V, and W has been developed to calculate the driving force for martensitic transformation. Built upon the SSOL database of the Thermo-Calc software system, a large number of interaction parameters of the SSOL database have been modified, and many new interaction parameters, both binary and ternary, have been introduced to account for the heat of transformation, T ₀ temperatures, and the composition dependence of magnetic properties. The critical driving force for face-centered cubic (fcc) → body-centered cubic (bcc) heterogeneous martensitic nucleation in multicomponent alloys is modeled as the sum of a strain energy term, a defect-size-dependent interfacial energy term, and a composition-dependent interfacial work term. Using our multicomponent thermodynamic database, a model for barrierless heterogeneous martensitic nucleation, a model for the composition and temperature dependence of the shear modulus, and a set of unique interfacial kinetic parameters, we have demonstrated the efficacy of predicting the fcc → bcc martensitic start temperature (M _s ) in multicomponent alloys with an accuracy of ± 40 K over a very wide composition range.     

On the mechanism of nucleation of copper precipitates upon aging of Fe-Cu alloys

Structure of the Fe-5.5% Cu alloy has been studied after aging at 500°C to show that the lattice of copper precipitates changes with increasing time of holding at a temperature from bcc to 9R to fcc. The free energy of the solid solutions and the phase-separation diagrams of the bcc and fcc phases of copper have been calculated. Barriers for the nucleation of copper particles with the bcc and fcc lattices have been evaluated. Factors that favor the appearance of intermediate structural forms of copper, which precede the formation of the stable fcc phase, are discussed.     

Formation and chemical leaching effects of nonequilibrium Al0.6(Fe25Cu75) alloy powder produced by rod milling

The formation and chemical leaching effects of a nonequilibrium Al_0.6(Fe₂₅Cu₇₅)_0.4 powder produced by rod milling is described. X-ray diffraction, transmission electron microscopy, differential scanning calorimetry and vibrating sample magnetometry were used to characterize both the as-milled and leached specimens. After 400 h of milling, only the bcc AlFe phase with an amorphous phase was detected in the XRD patterns. The crystallite size for the bcc AlFe phase (110) after 400 h of milling was about 5.3 nm. The peak temperature and the crystallization temperature of the as-milled powders were 448.7 and 428.0 °C, respectively. Al atoms leaching from the as-milled bcc AlFe powders in the L1 condition did not alter the diffraction pattern significantly, even though Al atoms had been removed. After the L1 specimen was annealed at 500 °C for 1 h, the bcc AlFe phase transformed to the fcc Cu, Fe, and CuFe₂O₄ phases. The peak widths of L1 and L2 specimens were similar, but became broader than that of the as-milled powder. The saturation magnetization decreased with increasing milling time, and a value of 10.4 emu/g was reached after 400 h of milling. After cooling the specimen from 750 °C, the magnetization slowly increased at approximately 491.4 °C, indicating that the bcc AlFe phase had transformed to the fcc Cu and Fe phases.     

Atomic-scale compositional characterization of a nanocrystalline AlCrCuFeNiZn high-entropy alloy using atom probe tomography

We have studied a nanocrystalline AlCrCuFeNiZn high-entropy alloy synthesized by ball milling followed by hot compaction at 600 °C for 15 min at 650 MPa. X-ray diffraction reveals that the mechanically alloyed powder consists of a solid-solution body-centered cubic (bcc) matrix containing 12 vol.% face-centered cubic (fcc) phase. After hot compaction, it consists of 60 vol.% bcc and 40 vol.% fcc. Composition analysis by atom probe tomography shows that the material is not a homogeneous fcc–bcc solid solution but instead a composite of bcc structured Ni–Al-, Cr–Fe- and Fe–Cr-based regions and of fcc Cu–Zn-based regions. The Cu–Zn-rich phase has 30 at.% Zn α-brass composition. It segregates predominantly along grain boundaries thereby stabilizing the nanocrystalline microstructure and preventing grain growth. The Cr- and Fe-rich bcc regions were presumably formed by spinodal decomposition of a Cr–Fe phase that was inherited from the hot compacted state. The Ni–Al phase remains stable even after hot compaction and forms the dominant bcc matrix phase. The crystallite sizes are in the range of 20–30 nm as determined by transmission electron microscopy. The hot compacted alloy exhibited very high hardness of 870 ± 10 HV. The results reveal that phase decomposition rather than homogeneous mixing is prevalent in this alloy. Hence, our current observations fail to justify the present high-entropy alloy design concept. Therefore, a strategy guided more by structure and thermodynamics for designing high-entropy alloys is encouraged as a pathway towards exploiting the solid-solution and stability idea inherent in this concept.     

Improvement of the creep resistance of FeCo–2V alloy arising from a small addition of Cr

This work presents our recent findings that a small addition (0.5 at. %) of Cr to FeCo–2V alloy leads to a great improvement in creep resistance. High resolution electron microscopy was applied to study microstructural evolution of the Cr added alloy during the creep process performed at 600 °C under 200 MPa. At an initial step of the creep, there appear plate-like precipitates with bcc/fcc structure as well as some rod-like ones with hcp structure. A coherent relationship is identified between the precipitates and bcc FeCo matrix. With prolonging the creep, the rod-like hcp precipitates are revealed to remain in the bcc matrix, showing a good stability under the creep condition and in turn resulting in piling-up of dislocations to a great extent around the precipitates. In addition, the Cr added alloy is shown to have a large stress exponent of 8.4, indicating a strong interaction between dislocations and the hcp precipitates.     

Changes in vibrational entropy during the early stages of chemical unmixing in fcc Cu–6% Fe

A nanocrystalline face-centered cubic (fcc) solid solution of 6% Fe in Cu was prepared by high-energy ball milling, and annealed at temperatures from 200 to 360 °C to induce chemical unmixing. The chemical state of the material was characterized by three-dimensional atom probe microscopy, Mössbauer spectrometry and X-ray powder diffractometry. The unmixing was heterogeneous, with iron atoms forming iron-rich zones that thicken with further annealing. The phonon partial density of states (pDOS) of ⁵⁷Fe was measured by nuclear resonant inelastic X-ray scattering, showing the pDOS of the as-prepared material to be that of an fcc crystal. The features of this pDOS became broader in the early stages of unmixing, but only small changes in average phonon frequencies occurred until the body-centered cubic (bcc) phase began to form. The vibrational entropy calculated from the pDOS underwent little change during the early stage of annealing, but decreased rapidly when the bcc phase formed in the material.     

Depletion and Voids Formation in the Substrate During High Temperature Oxidation of Ni–Cr Alloys

A numerical model to treat the kinetics of vacancy annihilation at the metal/oxide interface but also in the bulk metal has been implemented. This was done using EKINOX, which is a mesoscopic scale 1D-code that simulates oxide growth kinetics with explicit calculation of vacancy fluxes. Calculations were performed for high temperature Ni–Cr alloys oxidation forming a single chromia scale. The kinetic parameters used to describe the diffusion in the alloy were directly derived from an atomistic model. Our results showed that the Cr depletion profile can be strongly affected by the cold work state of the alloy. In fact, the oversaturation of vacancies is directly linked to the efficiency of the sinks which is proportional to the density of dislocations. The resulting vacancy profile highlights a supersaturation of vacancy within the metal. Based on the classical nucleation theory, the possibility and the rate of void formation are discussed.     

Aluminization of high purity iron and stainless steel by powder liquid coating

Powder liquid coating is investigated metallographically as an aluminization technique for high-purity iron [Acta Mater., in press] and stainless steel. In this process, Fe₂Al₅ forms initially during heat treatment, with c axis preferentially aligned with the sample normal. In Fe–18mass%Cr alloy, Cr exhibits almost the same concentration profile as Fe except for the temporary formation of a Cr₅Al₈ network in the early stage of heat treatment. Fe–25Cr–18Ni alloy forms a thinner aluminized layer compared to the other substrates, and contains an Al–Ni-rich layer and spherical precipitates (ordered B2). The diffusion of Al and Ni in the system (B2/bcc/fcc) is simulated using a new formulation of the diffusion equation for the ternary Fe–Al–Ni system taking the concentration-dependent interdiffusion coefficient into account. The bcc layer is found to be predominantly in a steady state due to the large interdiffusion coefficients, and characteristic uphill diffusion of Al in the B2 layer is attributed to the existence of Ni.