Magnetic and transport properties of near-stoichiometric metastable FexMnyGaz alloys (46<x<52, 17<y25, 26<z<30) with face-centered cubic (FCC), body-centered cubic (BCC), and two-phase (FCC+BCC) structures are investigated. The experimental results are analyzed in terms of first-principles calculations of stoichiometric Fe2MnGa alloy with the L21, L12, and the tetragonally distorted L21 structural orderings. It is shown that the pure BCC and FCC phases have distinct magnetic and transport properties. Two-phase Fe2MnGa alloys have magnetic and transport properties typical of the mixed BCC and FCC phases. Among the investigated alloys, Fe46Mn24Ga30 has a martensitic transformation accompanied by significant changes in its magnetic and transport properties.
Effect of ballistic re-solution on the nucleation kinetics of precipitates in diluted binary alloys under irradiation. Part 1: Stoichiometric gamma' precipitates in Ni-Al alloys
Nuclear Safety Institute (IBRAE), Russian Academy of Sciences（俄罗斯科学院核安全研究所（IBRAE））
We report a giant magnetocaloric effect near room temperature in an off-stoichiometric Mn-Co-Ge alloy, across the magnetostructural transition. The isothermal entropy change accompanying this transition has a peak value of nearly 40 J/kg-K near 297 K and a refrigerant capacity of 270 J/kg with the hot end at 302.5 K and cold end at 293.5 K. We also present an experimental protocol to avoid spurious peaks in the magnetocaloric effect across a sharp first order magnetostructural transition, not confined to Mn-Co-Ge alone, where metastability during the transition could influence the measured mag…
Ni$_2$Mn$_{2-y}$In$_y$ alloys transform from the martensitic $L1_0$ antiferromagnetic ground state near $y = 0$ to austenitic ferromagnetic $L2_1$ Heusler phase near $y = 1$ due to doping of In impurity for Mn. The off stoichiometric alloys prepared by rapid quenching are structurally metastable and dissociate into a mixture of $L2_1$ (Ni$_2$MnIn) and $L1_0$ (NiMn) phases upon temper annealing. Despite this structural disintegration, the martensitic transformation temperature remains invariant in the temper annealed alloys. Investigations of the local structure of the constituent atoms reveal …
We observe that pressure-induced amorphization of Ga2SeTe2 (a III-VI semiconductor) is directly influenced by the periodicity of its intrinsic defect structures. Specimens with periodic and semi-periodic two-dimensional vacancy structures become amorphous around 10-11 GPa in contrast to those with aperiodic structures, which amorphize around 7-8 GPa. The result is a notable instance of altering material phase-change properties via rearrangement of stoichiometric vacancies as opposed to adjusting their concentrations. Based on our experimental findings, we posit that periodic two-dimensional va…
We have calculated surface energies and surface magnetic order of various low-indexed surfaces of monoatomic Fe, Co, and Pt, and binary, ordered FePt, CoPt, and MnPt using density functional theory. Our results for the binary systems indicate that elemental, Pt-covered surfaces are preferred over Fe- and Co-covered and mixed surfaces of the same orientation. The lowest energy orientation for mixed surfaces is the highly coordinated (111) surface. We find Pt-covered (111) surfaces, which can be realized in the L11 structure only, to be lower in energy by about 400 meV/atom compared to the mixed…
This article presents a brief overview of our recent work on the nature of long period modulation in the premartensite and martensite phases of Ni2MnGa ferromagnetic shape memory alloy using high resolution synchrotron x-ray powder diffraction patterns. The commensurate structure model using the Pnnm space group is unable to account for the peak positions of the satellite reflections that appear due to modulations correctly. LeBail and Rietveld refinements using the (3+1)-D super space group $Immm(00γ)s00$ show that the peak positions of all the reflections, including the satellites, can be ex…
Using a combined approach of spin-resolved photoemission spectroscopy, band structure and photoemission calculations we investigate the influence of bulk defects and surface states on the spin polarization of Co2Mn(alpha)Si thin films with bulk L21 order. We find that for Mn-poor alloys the spin polarization at EF is negative due to the presence of Co_Mn antisite and minority surface state contributions. In Mn-rich alloys, the suppression of Co(Mn) antisites leads to a positive spin polarization at the Fermi energy, and the influence of minority surface states on the photoelectron spin polariz…
While the role of the free energy barrier during nucleation is a text-book subject the importance of the kinetic factor is frequently underestimated. We obtained both quantities from molecular dynamics (MD) simulations for the pure Ni and B2 phases in the Ni50Al50 and Cu50Zr50 alloys. The free-energy barrier was found to be higher in Ni but the nucleation rate is much lower in the Ni50Al50 alloy which was attributed to the ordered nature of the B2 phase. Since the Cu50Zr50 B2 phase can has even smaller fraction of the anti-site defects its nucleation is never observed in the MD simulation.
Recently, several research groups have reported on the observation of super-large more than 5% magneto-strain effect in some non-stoichiometric Ni-Mn-Ga alloys close to 5.78% value expected from the tetragonality aspect ratio of the martensite crystal lattice. New Ni-Mn-Ga alloys showing giant magneto-strain effect display simultaneously few interesting physical effects and new behavior for some magnetic and mechanical properties which is very different from that earlier observed in Ni-Mn-Ga showing lower magneto-strain effect. This report represents some new experimental results and the quant…
Previous studies indicated that intrinsic point defects play a crucial role for the density of states of ferromagnetic half-metals in the band gap region: At large concentrations, defect-derived bands might close the gap at the Fermi energy in the minority spin channel. In this work, structural disorder in the Co- and Mn-sublattices of the full Heusler alloy Co_2-xMn_1+xSi (-1 < x < 2) is investigated with a cluster expansion approach, parametrized using all-electron density functional theory calculations. By establishing two separate cluster expansions, one for the formation energy and one fo…
A model lattice ab initio parameterised 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. Thermodynamic and magnetic properties of the alloys are explored using configuration and magnetic Monte Carlo simulations in a temperature range extending well over 1000 K.
We show by first-principles calculations that the skew-scattering anomalous Hall and spin-Hall angles of L$1_0$-ordered FePt drastically depend on different types of disorder. A different sign of the AHE is obtained when slightly deviating from the stoichiometric ratio towards the Fe-rich side as compared to the Pt-rich side. For stoichiometric samples, short-range ordering of defects has a profound effect on the Hall angles and can change them by a factor of $2$ as compared to the case of uncorrelated disorder. This might explain the vast range of anomalous Hall angles measured in experiments…
Off-stoichiometric variable doping for exceptional power factors in L2$_1$ Fe$_2$VAlM$_x$ (M=Ti, W) epitaxial thin films
Instituto de Micro y Nanotecnología, IMN-CNM, CSIC (CEI UAM+CSIC)（微纳技术研究所，IMN-CNM，西班牙国家科学研究委员会（CEI UAM+CSIC））；Departamento de Química Física, Facultad de Química, Universidad de Sevilla（塞维利亚大学化学学院物理化学系）；Institute of Solid-State Physics, Technische Universität Wien（维也纳工业大学固体物理研究所）
A Magnetic Cluster Expansion (MCE) model for ternary face-centered cubic Fe-Ni-Cr alloys has been developed using DFT data spanning binary and ternary alloy configurations. Using this MCE model Hamiltonian, we perform Monte Carlo simulations and explore magnetic structures of alloys over the entire range of alloy compositions, considering both random and ordered alloy structures. In random alloys, the removal of magnetic collinearity constraint reduces the total magnetic moment but does not affect the predicted range of compositions where the alloys adopt low temperature ferromagnetic configur…
Ab initio molecular dynamics simulations are used to investigate the structure and electronic properties of the liquid Ag-Se system at three compositions. The realism of the simulations is demonstrated by comparison with diffraction data for the stoichiometric case Ag$_2$Se. As the Se content is increased beyond the stoichiometric value, short-lived Se$_n$ complexes are formed. The concentration of complexes and the associated changes of electronic structure can be explained using a simple ionic model.
The bcc-based Fe_{1-x}Al_{x} exhibit interesting magnetic and anomalous structural properties as a function of composition and sample processing conditions arising from thermal or off-stoichiometric chemical disorder, and, although well studied, these properties are not understood. In stoichiometric B2 FeAl, including the effects of partial long-range order (i.e., thermal antisites), we find the observed paramagnetic response (with non-zero local moments), in contrast to past investigations which find ferromagnetism based on local density approximation (LDA) to density functional theory or whi…
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…
Energy efficiency is motivating the search for new high-temperature metals. Some new body-centered-cubic random multicomponent "high entropy alloys (HEAs)" based on refractory elements (Cr-Mo-Nb-Ta-V-W-Hf-Ti-Zr) possess exceptional strengths at high temperatures but the physical origins of this outstanding behavior are not known. Here we show, using integrated neutron-diffraction (ND), high-resolution transmission electron microscopy (HRTEM), and theory, that the high strength and strength retention of a NbTaVTi alloy and a new high-strength/low-density CrMoNbV alloy are attributable to edge d…
We have systemically studied the effects of annealing temperature and alloy composition on the structural and magnetic properties of bulk Ni$_{2}$MnGe and Ni$_{2.1}$Mn$_{0.9}$Ge Heusler alloys. We have observed that both annealing temperature and the alloy composition drastically alter the phases found in the samples due to the presence of competing ternary phases. Annealing at 900 and 950 $^{\circ}$C for both alloy compositions facilitate the formation of L2$_{1}$ Heusler phase. Nevertheless, formation of Ni$_{5}$Mn$_{4}$Ge$_{3}$ and Ni$_{16}$Mn$_{6}$Ge$_{7}$ phases cannot be prevented for Ni…
The temperature dependencies of the resistivity and magnetization of a series of Ni2+XMn1-XGa (X = 0 - 0.09) alloys were investigated. Along with the anomalies associated with ferromagnetic and martensitic transitions, well-defined anomalies were observed at the temperature of premartensitic transformation. The premartensitic phase existing in a temperature range 200 - 260 K in the stoichiometric Ni2MnGa is suppressed by the martensitic phase with increasing Ni content and vanishes in Ni2.09Mn0.91Ga composition.
Magnetic, transport, and x-ray diffraction measurements of ferromagnetic shape memory alloy Ni$_{2.16}$Mn$_{0.84}$Ga revealed that this alloy undergoes an intermartensitic transition upon cooling, whereas no such a transition is observed upon subsequent heating. The difference in the modulation of the martensite forming upon cooling from the high-temperature austenitic state [5-layered (5M) martensite], and the martensite forming upon the intermartensitic transition [7-layered (7M) martensite] strongly affects the magnetic and transport properties of the alloy and results in a large thermal hy…
In traditional body-centered cubic (bcc) metals, the core properties of screw dislocations play a critical role in plastic deformation at low temperatures. Recently, much attention has been focused on refractory high-entropy alloys (RHEAs), which also possess bcc crystal structures. However, unlike face-centered cubic high-entropy alloys (HEAs), there have been far fewer investigations on bcc HEAs, specifically on the possible effects of chemical short-range order (SRO) in these multiple principal element alloys on dislocation mobility. Here, using density functional theory, we investigate the…
A simple fitting approach is used for modeling the compressive yield strength of body centered cubic (bcc) solid solution high entropy alloys in Al-Hf-Nb-Mo-Ta-Ti-V-Zr system. It is proposed that the yield strength could be modeled by a polynomial where the experimental data can be used for finding the polynomial coefficients. The results show that the proposed polynomial could model the yield strength of solid solution alloys relatively well. The developed polynomial is used for predicting the strength of RHEAs in Hf-Mo-Nb-Ta-Ti-V-Zr system. It is observed that the yield strength of alloys wi…
With the aim of the discovery of face-centered-cubic (fcc) high-entropy alloy (HEA) superconductor, we have carried out materials research on Nb or Pb-containing multi-component alloys. Although the X-ray diffraction (XRD) patterns of some Nb-containing samples exhibited the dominant fcc phases, no superconducting signals were observed down to 3 K. Examination with an energy dispersive X-ray spectrometer revealed that all samples were multi-phase, but the existence of several new Nb-containing HEA phases was found in them. It was confirmed that the synthesis of Pb-containing an HEA or quaterna…
Linear complexions are defect states that have been recently discovered along dislocations in body centered cubic Fe-based alloys. In this work, we use atomistic simulations to extend this concept and explore segregation-driven structural transitions at dislocations in face centered cubic alloys. We identify a variety of stable, nanoscale-size structural and chemical states, which are confined near dislocations and can be classified as linear complexions. Depending on the alloy system and thermodynamic conditions, such new states can preserve, partially modify, or completely replace the origin…
Edge Dislocation Mediated Anomalous Charge Transfer in Face Centered Cubic High Entropy Alloys
School of Materials Science and Technology, IIT-BHU（印度理工联合学院瓦拉纳西分校材料科学与技术学院）；National Centre for Computational Sciences, Oak Ridge National Laboratory（橡树岭国家实验室国家计算科学中心）；Department of Metallurgy and Materials Engineering, IIEST Shibpur（IIEST Shibpur冶金与材料工程系）
We have synthesized a new crystallographically ordered quaternary Heusler alloy, MnNiCuSb. The crystal structure of the alloy has been determined by Rietveld refinement of the powder x-ray diffraction data. This alloy crystallizes in the LiMgPdSb type structure with F-43m space group. MnNiCuSb is a ferromagnet with a high TC ~ 690K and magnetic moment of 3.85MuB/f.u. Besides this we have also studied two other off-stoichiometric compositions; one Cu rich and the other Ni rich (MnNi0.9Cu1.1Sb and MnNi1.1Cu0.9Sb) which are also ferromagnets. It must be stressed that MnNiCuSb is one of the very f…
The first-principles calculations of the electronic structures and the interband optical conductivity (OC) spectra have been performed for the stoichiometric Fe$_{2}$MnGa alloy with L2$_{1}$ and L1$_{2}$ types of atomic ordering. The calculated optical properties of Fe$_{2}$MnGa alloy for the L2$_{1}$ and L1$_{2}$ phases are complemented by the experimental OC spectra for bulk and thin film Fe-Mn-Ga alloy samples near the stoichiometry 2:1:1 with L2$_{1}$ and L1$_{2}$ (for bulks) as well as the body-centered-cubic and face-centered-cubic (for films) structures, respectively. A reasonable agree…
We report on measurements of the adiabatic second order elastic constants of the off-stoichiometric Ni$_{54}$Mn$_{23}$Al$_{23}$ single crystalline Heusler alloy. The variation in the temperature dependence of the elastic constants has been investigated across the magnetic transition and over a broad temperature range. Anomalies in the temperature behaviour of the elastic constants have been found in the vicinity of the magnetic phase transition. Measurements under applied magnetic field, both isothermal and variable temperature, show that the value of the elastic constants depends on magnetic …
A polycrystalline and single-crystal samples of near-stoichiometric Ni2MnGa alloys have been investigated. It was confirmed that martensite short crystallographic axis (c-axis) is the easy axis of magnetization. The reversible reorientation of the easy magnetization direction of martensite samples after 5% compression is found. The same reversible reorientation of the easy magnetization direction under applied magnetic field occurs in the single-crystal samples. The field-induced reorientation of the easy magnetization direction is accompanied with more than 4% of sample's dimension change. Ab…
We resolve issues that have plagued reliable prediction of relative phase stability for solid-solutions and compounds. Due to its commercially important phase diagram, we showcase Al-Li system because historically density-functional theory (DFT) results show large scatter and limited success in predicting the structural properties and stability of solid-solutions relative to ordered compounds. Using recent advances in an optimal basis-set representation of the topology of electronic charge density (and, hence, atomic size), we present DFT results that agree reasonably well with all known exper…
The yield strengths of High Entropy Alloys have recently been correlated with measured picometer-scale atomic distortions. Here, the root mean square microdistortion in a multicomponent alloy is shown to be nearly proportional to the misfit-volume parameter that enters into a predictive model of solute strengthening. Analysis of two model ternary alloy families, face-centered cubic Cr-Fe-Ni and body-centered cubic Nb-Mo-V, demonstrates the correlation over a wide composition space. The reported correlation of yield strength with microdistortion is thus a consequence of the correlation between …
We here show by first principles theory that it is possible to achieve a structural and magnetic phase transition in common steel alloys like Fe$_{85}$Cr$_{15}$, by alloying with Ni or Mn. The predicted phase transition is from the ferromagnetic body centered cubic (bcc) phase to the paramagnetic face centered cubic (fcc) phase. The relatively high average magnetic moment of $\sim1.4μ_{B}$/atom predicted at the transition suggests that stainless steel potentially can present a magnetocaloric effect strong enough to make these alloys good candidates for refrigeration applications operating at a…
Linear complexions are defect phases that form in the presence of dislocations and thus are promising for the direct control of plasticity. In this study, atomistic simulations are used to model the effect of linear complexions on dislocation-based mechanisms for plasticity, demonstrating unique behaviors that differ from classical dislocation glide mechanisms. Linear complexions impart higher resistance to the initiation and continuation of dislocation motion when compared to solid solution strengthening in all of the face-centered cubic alloys investigated here, with the exact strengthening …
First-principles-based materials screening is systematically performed to discover new combinations of chemical elements possibly making shape-memory alloys (SMAs). The B2, D03, and L21 crystal structures are considered as the parent phases, and the 2H and 6M structures are considered as the martensitic phases. 3,384 binary and 3,243 ternary alloys (6,627 in total) with stoichiometric composition ratios are investigated by the materials screening in terms of energetic and dynamical stabilities of the martensitic phases as well as structural compatibility between the parent and the martensitic …
Laves phases often form as secondary phases in metallic alloys and have a significant effect on their structural properties. Thus, phase stability studies for these chemically and structurally complex phases in addition to mechanical behavior studies are of great interest. In this work, we use the concept of metastable bulk phase and defect phase diagrams to augment the understanding of the bulk phase and defect phase stability in Laves phases in Mg-based alloys. In this way, we resolve the discrepancy between bulk phase diagrams and experimental observations regarding the formation of Mg-rich…
Electrical- and magneto-transport across the thermo-elastic martensitic transformation in anti-site-disordered off-stoichiometric Co-Fe-Ti-Si Heusler alloy thin films
The influence of the physical mechanisms activated during deformation and annealing on the microstructure and texture evolution as well as on the mechanical properties in the equiatomic CoCrFeMnNi high-entropy alloy (HEA) were investigated. A combination of cold rolling and annealing was used to investigate the HEA in the deformed, recovered, partially recrystallized, and fully recrystallized states. Detailed microstructure and texture analysis was performed by electron backscatter diffraction, transmission electron microscopy, and X-ray diffraction. The mechanical properties were evaluated us…
The large magnetocaloric effect (MCE) observed in Ni-Mn based shape-memory Heusler alloys put them forward to use in magnetic refrigeration technology. It is associated with a first-order magnetostructural (martensitic) phase transition. We conducted a comprehensive study of the MCE for the off-stoichiometric Heusler alloy Ni$_{2.2}$Mn$_{0.8}$Ga in the vicinity of its first-order magnetostructural phase transition. We found a reversible MCE under repeated magnetic field cycles. The reversible behavior can be attributed to the small thermal hysteresis of the martensitic phase transition. Based …
Off-stoichiometric Ni$_2$MnIn Heusler alloys have drawn recent attention due to their large magnetocaloric entropy change associated with the first-order magneto-structural transition. Here we present crystal structural, calorimetric and magnetic studies of three compositions. Temperature-dependent X-ray diffraction shows clear structural transition from a 6M modulated monoclinic to a L2$_1$ cubic. A significant enhancement of relative cooling power (RCP) was achieved by tuning the magnetic and structural stability through minor compositional changes, with the measured results quantitatively c…
Intending to optimize the giant magnetocaloric properties of HoB$_{2}$, we synthesized and magnetocalorically characterized Ho$_{1-x}$Gd$_{x}$B$_{2}$(0.1 $\leq$ x $\leq$ 0.4) alloys. We found out that Gd enters stoichiometrically and randomly into the Ho site, leading to a Vegard-type structural change. The addition of spherical S$^{7/2}$ Gd$^{3+}$ moments prompts an enhancement in Curie temperature, a reduction in peak value of the magnetic entropy change while still being relatively high, and a broadening of the magnetic entropy change curves. The overall influence is a relatively high refri…
We have studied the effect of ageing within the miscibility gap on the electric, magnetic and thermodynamic properties of a non-stoichiometric Heusler Cu-Al-Mn shape-memory alloy, which undergoes a martensitic transition from a $bcc$-based ($β$-phase) towards a close-packed structure ($M$-phase). Negative magnetoresistance which shows an almost linear dependence on the square of magnetization with different slopes in the $M$- and $β$-phases, was observed. This magnetoresistive effect has been associated with the existence of Mn-rich clusters with the Cu$_2$AlMn-structure. The effect of an appl…
We investigated the homogenous nucleation of the stoichiometric B2 and B33 phases in the Ni50Zr50 alloy using the persistent embryo method and the classical nucleation theory. The two phases become very close competitors at large supercoolings, which is consistent with the experimental observations. In the case of the B2 phase, the linear temperature dependence of the solid-liquid interface (SLI) free energy extrapolated to the melting temperature leads to the same value as the one obtained from the capillarity fluctuation method (CFM). In the case of the B33 phases, the SLI free energy is als…
We report the synthesis of polycrystalline (poly)-SiGe alloy thin films through solid state reaction of Si/Ge multilayer thin films on Si and glass substrates at low temperature of 500 °C. The pristine thin film was deposited using electron beam evaporation with optimized in-situ substrate heating. Our results show the co-existence of amorphous Si (a-Si) phase along with the poly-SiGe phase in the pristine thin film. The a-Si phase was found to subsume into the SiGe phase upon post deposition annealing in the temperature range from 600 to 800 °C. Additionally, dual energy band gaps could be ob…
Intermetallic compounds Zr7Ni10 and Hf7Ni10 have been studied by perturbed angular correlation (PAC) spectroscopy considering the fact that Zr7Ni10 has application as hydrogen storage material in fuel cell. In stoichiometric Zr7Ni10, the phase Zr2Ni7 is found to be dominant (~38%) while a fraction of ~25% is found for the Zr7Ni10 phase at room temperature. In this compound, a phase due to Zr8Ni21 (~10%) is found from room temperature up to 773 K but, this is not found at 873 K and above. In the stoichiometric Hf7Ni10 sample, the phase due to Hf7Ni10 is found as a minor phase (~22%) at room tem…
The stoichiometric Ni$_{50}$Mn$_{25}$In$_{25}$ Heusler alloy transforms from a stable ferromagnetic austenitic ground state to an incommensurate modulated martensitic ground state with a progressive replacement of In with Mn without any pre-transition phases. The absence of pre-transition phases like strain glass in Ni$_{50}$Mn$_{25+x}$In$_{25-x}$ alloys is explained to be the ability of the ferromagnetic cubic structure to accommodate the lattice strain caused by atomic size differences of In and Mn atoms. Beyond the critical value of $x$ = 8.75, the alloys undergo martensitic transformation …
We present a systematic study of the magnetic properties of L1$_0$ binary alloys FeNi, CoNi, MnAl and MnGa via two different density functional theory approaches. Our calculations show large magnetocrystalline anisotropies in the order $1~\text{MJ/m}^3$ or higher for CoNi, MnAl and MnGa while FeNi shows a somewhat lower value in the range $0.48 - 0.77 ~\text{MJ/m}^3$. Saturation magnetization values of $1.3~\text{MA/m}$, $1.0~\text{MA/m}$, $0.8~\text{MA/m}$ and $0.9~\text{MA/m}$ are obtained for FeNi, CoNi, MnAl and MnGa respectively. Curie temperatures are evaluated via Monte Carlo simulation…
