We investigate the strain-rate-dependent mechanical behavior and deformation mechanisms of a refractory high entropy alloy, Ti29Zr24Nb23Hf24 (at.%), with a single-phase body-centered cubic (BCC) structure. High-temperature compression tests were conducted at temperatures from 700 to 1100°C at strain rates ranging from 10-3 to 10 s-1. A sudden stress drop after yield point was observed at higher temperatures and lower strain rates with the Zener-Holloman parameter, lnZ, in the range of 17.2-20.7. Such a softening behavior can be related to the interaction of dislocations with short-range clustering. However, at higher strain rates or lower temperatures (lnZ>25.0), kink bands were activated being responsible for the continuous strengthening of the alloy in competition with the softening mechanism. Systematic TEM investigations reveal that dislocation walls formed along {110} planes and dislocation loops were observed at a low strain of 6% at a high strain rate of 1 s-1 and 800°C. Kink band induced dynamic recrystallization is evident upon further straining. On the other hand, at low strain rate of 10-3 s-1 and 800°C, discontinuous recrystallization mechanisms become dominant with arrays of dislocations forming in front of the bulged boundaries of parent grains. These sub-grain boundaries eventually turn into high-angle grain boundaries. We also investigate the deformation mechanism of the alloy under extremely high strain rate (103 s-1) at room temperature. The specimen exhibits extensive kink bands with arrays of dislocation walls. As further strained, multiple slip systems can be activated and the interaction of dislocation walls plays a vital role in the strain hardening of the alloy.
New approaches for the design of alloy systems with multiprincipal elements is recently researched in refractory materials field. However, most research aimed at arc melting process with weakness of coarsening of grains and inhomogeneous microstructure of segregation of elements during the cooling. This study aims to design and fabricate high-entropy alloy with powder metallurgy. In this study, a refractory high entropy alloys with composition near AlMo0.5NbTa0.5TiZr were produced by powder metallurgy. The alloy consists of two body-centered cubic (BCC) phases. One phase was disordered BCC enr…
This paper experimentally investigated the effects of silicone oil on the tribological behaviour of AZ31B/86CrMoV7 contact pair under a pin-on-disk configuration. A commercial silicone oil was used as an oxidation inhibiter for the AZ31B at elevated temperatures to 300 oC. The wear mechanism of the contact pair was explored by SEM morphologies of worn surfaces. The analysis revealed that silicone oil can effectively minimize surface oxidation. Compared with dry sliding, silicone oil can considerably lower down the friction coefficient and specific wear rate. Under lubrication, the abrasive wea…
Enhanced Elevated-Temperature Strength in Refractory Complex Concentrated Alloys via Temperature-Induced Transition from Screw-to-Edge Dislocation Control
Mn-based room-temperature ferromagnets attract considerable attention due to their high ordered Mn moment. We have found that a Pd0.75Mn0.25 alloy with added B (Pd0.75Mn0.25Bx) shows room-temperature soft ferromagnetism, whereas the parent Pd0.75Mn0.25 alloy is a spin-glass system. The saturated Mn moment at room temperature systematically increases to 2.68\muB/Mn as x increases to 0.125. The maximum Curie temperature of 390 K is also realized at an x of 0.125. The experimental results suggest a tunable soft ferromagnetism, which is governed only by the boron concentration. Our results will pa…
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…
The effect of alloy disorder on the optical density of states and the average room temperature carrier statistics in GaInNAs quantum wells is discussed. A red shift between the peak of the room temperature photoluminescence and the surface photovoltage spectra, that systematically increases with the nitrogen content within the quantum wells is observed. The relationship between this Stokes' shift and the absorption linewidth in different samples suggests that the photoexcited carriers undergo a continuous transition, from being in quasi-thermal equilibrium with the lattice to being completely …
In this article we investigate the surface spin polarization in a 100 nm Co2Cr0.6Fe0.4Al (CCFA) film grown ex situ epitaxially on MgO(100) with a 10 nm Fe buffer layer by means of spin resolved photoemission. We show that a careful in situ preparation of the sample surface leads to values for the room temperature spin polarization up to 45% at the Fermi level. To our knowledge, this is the highest value measured so far at the surface region of a full Heusler alloy at room temperature.
In situ straining experiments were performed in a TEM on an equimolar CoCrFeMnNi (Cantor) high entropy alloy at room and cryogenic temperature. Perfect and partial dislocation activity were recorded in both cases. Twinning directly follows the development of partial dislocation shearing that has various origins (perfect dislocation splitting, anchoring). It is shown that, although twinning is more frequently observed at liquid nitrogen temperature, its prevalence depends mainly on crystal orientation. As a result, twinning and perfect dislocation plasticity are likely to occur jointly in rando…
Glasses are nonequilibrium solids with properties highly dependent on their method of preparation. In vapor-deposited molecular glasses, structural organization could be readily tuned with deposition rate and substrate temperature. Herein, we show the atomic arrangement of strong network forming GeO2 glass is modified at medium range (< 2 nm) through vapor deposition at elevated temperatures. Raman spectral signatures distinctively show the population of 6-membered GeO4 rings increases at elevated substrate temperatures. Deposition near the glass transition temperature is more efficient than p…
Digital alloys of GaSb/Mn have been fabricated by molecular beam epitaxy. Transmission electron micrographs showed good crystal quality with individual Mn-containing layers well resolved; no evidence of 3D MnSb precipitates was seen in as-grown samples. All samples studied exhibited ferromagnetism with temperature dependent hysteresis loops in the magnetization accompanied by metallic p-type conductivity with a strong anomalous Hall effect (AHE) up to 400 K (limited by the experimental setup). The anomalous Hall effect shows hysteresis loops at low temperatures and above room temperature very …
Here we analyze a three-dimensional distribution of crystallographic slip measured in-situ during the uniaxial deformation of hexagonal Ti-7Al. The slip field is reconstructed using a novel methodology that combines spatially resolved lattice orientation fields and grain-averaged stresses measured using high-energy X-ray diffraction microscopy (HEDM) with crystal plasticity. Analysis is performed to explore lattice orientation dependence, stress dependence, and connectivity (network relationships) of grains experiencing elevated amounts of slip. Elevated slip is found to be primarily associate…
The direct control of carriers spin by electric field under room temperature is one of the most important challenges in the field of spintronics. For this purpose, we here propose a quaternary Heusler alloy FeVTiSi. Based on first principles calculations, FeVTiSi alloy is found to be an intrinsic bipolar magnetic semiconductor in which the valence band and conduction band approach the Fermi level through opposite spin channels. Thus FeVTiSi alloy can conduct completely spin-polarized currents with tunable spin-polarization direction simply by applying a gate voltage. Furthermore, by Monte Carl…
Magnetic skyrmions are topological spin structures having immense potential for energy efficient spintronic devices. However, observations of skyrmions at room temperature are limited to patterned nanostructures. Here, we report the observation of stable skyrmions in unpatterned Ta/Co2FeAl(CFA)/MgO thin film heterostructures at room temperature and in zero external magnetic field employing magnetic force microscopy. The skyrmions are observed in a trilayer structure comprised of heavy metal (HM)/ferromagnet (FM)/Oxide interfaces which result in strong interfacial Dzyaloshinskii-Moriya interact…
Nanocrystalline materials are well known for their beneficial mechanical and physical properties. However, it is of utmost importance to stabilize the microstructure at elevated temperatures to broaden the window of application e.g. by pinning grain boundaries through impurities or oxides. CuCo alloys, severe plastically deformed using high-pressure torsion, were used to investigate the evolution of oxides upon annealing. These investigations were performed using electron microscopy, synchrotron high-energy X-ray scattering and atom probe tomography. Monitoring the evolution of oxides by in-si…
It has been widely accepted that the introduction of titanium carbides into titanium-based alloys can significantly enhance the oxidation resistance due to their superior physicochemical stability at elevated temperatures. The present study reported for the first time that the ordered C vacancies within titanium carbides could lead to an uncommon phenomenon particularly at the very initial stage of oxidation. The intrinsic micro-to-macro oxidation mechanisms were systematically clarified with the aids of transmission electron microscope and ab-initio molecular dynamics simulation.
Machine learning via artificial neural networks coupled with density functional theory and experiments for thermodynamic optimization of high-entropy alloys for hydrogen storage at room temperature
WPI, International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu University（九州大学）；Department of Automotive Science, Graduate School of Integrated Frontier Sciences, Kyushu University（九州大学）；Institute for Materials Science, University of Stuttgart（斯图加特大学）
Strain heterogeneity at the microstructural level plays a vital role in the deformation and fracture behaviour of dual or multi-phase materials. In the present work, the strain heterogeneity, localization and partitioning arising at the sub-micron scale during elevated temperature (170 °C) tensile deformation of an Mg-5Al-3Ca alloy was investigated using quasi in-situ μ-DIC experiments. The results reveal that the strain is mainly carried by the α-Mg phase, while the intermetallic Laves phase plays a critical role in that strain concentrations build up at the α-Mg matrix and Laves phase interf…
Machine learning to explore high-entropy alloys with desired enthalpy for room-temperature hydrogen storage: Prediction of density functional theory and experimental data
Heusler alloys are widely studied due to their interesting structural and magnetic properties, like magnetic memory shape ability, coupled magneto-structural phase transitions and half-metallicity; ruled, for many cases, by the valence electrons number ($N_v$). The present work focuses on the magnetocaloric potentials of half-metals, exploring the effect of $N_v$ on the magnetic entropy change, preserving half-metallicity. The test bench is the Si-rich side of the half-metallic series Fe$_2$MnSi$_{1-x}$Ga$_x$. From the obtained experimental results it was possible to obtain $|ΔS|_{max}=ΔH^{0.8…
First-principles alloy theory is used to establish the $γ$-surface of Fe-Cr-Ni alloys as function of chemical composition and temperature. The theoretical stacking fault energy (SFE) versus chemistry and temperature trends agree well with experiments. Combining our results with the recent plasticity theory based on the $γ$-surface, the stacking fault formation is predicted to be the leading deformation mechanism for alloys with effective stacking fault energy below about 18 mJ m$^{-2}$. Alloys with SFE above this critical value show both twinning and full slip at room temperature and twinning …
This work demonstrates the development of a strong and ductile medium entropy alloy by employing conventional alloying and thermomechanical processing to induce partial recrystallization (PR) and precipitation strengthening in the microstructure. The combined usage of electron microscopy and atom probe tomography reveals the sequence of microstructural evolution during the process. First, the cold working of homogenized alloy resulted in a highly deformed microstructure. On annealing at 700°C, B2 ordered precipitates heterogeneously nucleate on the highly misoriented sites. These B2 promotes p…
Tracer diffusion of the substitutional components in (CoCrFeNiMn)$_{1-x}$C$_x$ high-entropy alloys with x = 0.002, 0.005 and 0.008 (in at. fractions) is measured at elevated temperatures from 1173 to 1373 K. Two different characteristic effects of interstitial carbon addition on substitutional diffusion in these FCC alloys are distinguished. At the highest temperature of 1373 K, alloying by C with relatively low concentrations (x = 0.002) retards diffusion of the substitutional elements with respect to those in the C-free alloy. At lower temperatures and/or higher C concentrations (x > 0.005),…
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. …
We have studied the effect of magnetic field on a non-stoichiometric Heusler alloy Ni$_{50}$Mn$_{35}$In$_{15}$ that undergoes a martensitic as well as a magnetic transition near room temperature. Temperature dependent magnetization measurements demonstrate the influence of magnetic field on the structural phase transition temperature. From the study of magnetization as a function of applied field, we show the occurrence of inverse-magnetocaloric effect associated with this magneto-structural transition. The magnetic entropy change attains a value as high as 25 J/kg-K (at 5 T field) at room tem…
We study magnon properties in terms of spin stiffness, Curie temperatures and magnon spectrum of Fe-Ni, Co-Ni and Fe-Co random alloys using a combination of electronic structure calculations and atomistic spin dynamics simulations. Influence of the disorder are studied in detail by use of large supercells with random atomic arrangement. It is found that disorder affects the magnon spectrum in vastly different ways depending on the system. Specifically, it is more pronounced in Fe-Ni alloys compared to Fe-Co alloys. In particular, the magnon spectrum at room temperature in Permalloy (Fe$_{20}$N…
Conventional crystalline alloys usually possess a low atomic size difference in order to stabilize its crystalline structure. However, in this article, we report a single phase chemically complex alloy which possesses a large atomic size misfit usually unaffordable to conventional alloys. Consequently, this alloy develops a rather complex atomic-scale chemical order and a highly distorted crystalline structure. As a result, this crystalline alloy displays an unusually high elastic strain limit (~2%), about ten times of that of conventional alloys, and an extremely low internal friction (< 2E-4…
Realizing record-high transverse thermoelectric figure of merit at room temperature in artificially tilted multilayers based on high power factor NiFe alloy
National Institute for Materials Science（物质材料研究机构）；University of Tsukuba（筑波大学）；The University of Tokyo（东京大学）；Resonac Corporation（瑞萨科株式会社）
The structural and magnetic behavior of Mn-site doped intermetallic manganese silicide alloys of nominal compositions Mn$_{5-x}$A$_x$Si$_3$ ($x$ = 0.05, 0.1, 0.2 and A = Ni, Cr) have been investigated with a focus to the inverted hysteresis behavior and thermomagnetic irreversibility. Room temperature x-ray powder diffraction data confirm that all the doped alloys crystallize in hexagonal $D8_8$ type structure with space group $P6_3/mcm$. The doped alloys are found to show paramagnetic (PM) - collinear antiferromagnetic (AFM2) - noncollinear antiferromagnetic (AFM1) transitions during cooling …
Cracking the case: fluctuations enhance ductility in refractory alloys
École Polytechnique Fédérale de Lausanne (EPFL)（洛桑联邦理工学院）；Laboratory of materials design and simulation (MADES), Institute of Materials, École Polytechnique Fédérale de Lausanne (EPFL)（洛桑联邦理工学院材料研究所材料设计与模拟实验室）；National Centre for Computational Design and Discovery of Novel Materials (MARVEL), École Polytechnique Fédérale de Lausanne (EPFL)（洛桑联邦理工学院新型材料计算设计与发现国家中心）；EMPA - Swiss Federal Laboratories for Materials Science and Technology（瑞士联邦材料科学与技术研究院）；Laboratory for Multiscale Modeling in Mechanics (LAMMM), Institute of Mechanical Engineering, École Polytechnique Fédérale de Lausanne (EPFL)（洛桑联邦理工学院机械工程学院多尺度力学建模实验室）；School of Engineering, Brown University, Providence, RI 02906 USA（布朗大学工程学院）
The electronic band structure of the (Ga,Mn)As system has been one of the most intriguing problems in solid state physics over the past two decades. Determination of the band structure evolution with increasing Mn concentration is a key issue to understand the origin of ferromagnetism. Here we present room temperature photoluminescence and ellipsometry measurements of Ga_{100%-x}Mn_{x}As alloy. The up-shift of the valence-band is proven by the red shift of the room temperature near band gap emission from the Ga_{100%-x}Mn_{x}As alloy with increasing Mn content. It is shown that even a doping b…
Despite high interest in compact and safe storage of hydrogen in the solid-state hydride form, the design of alloys that can reversibly and quickly store hydrogen at room temperature under pressures close to atmospheric pressure is a long-lasting challenge. In this study, first-principles calculations are combined with experiments to develop high-entropy alloys (HEAs) for room-temperature hydrogen storage. TixZr2-xCrMnFeNi (x = 0.4-1.6) alloys with the Laves phase structure and low hydrogen binding energies of -0.1 to -0.15 eV are designed and synthesized. The HEAs reversibly store hydrogen in…
The search for new hard materials is often challenging from both theoretical and experimental points of view. Furthermore, using materials for biomedical applications calls for alloys with high biocompatibility which are even more sparse. The Ti$_{1-x}$Au$_x$ ($0.22 \leq x \leq 0.8$) exhibit extreme hardness and strength values, elevated melting temperatures (compared to those of constituent elements), reduced density compared to Au, high malleability, bulk metallicity, high biocompatibility, low wear, reduced friction, potentially high radio opacity, as well as osseointegration. All these pro…
The high entropy alloy containing refractory metals Mo-Nb-Ta-W has a body centered cubic structure, which is not surprising given the complete mutual solubility in BCC solid solutions of all pairs of the constituent elements. However, first principles total energy calculations for the binaries reveal a set of distinct energy minimizing structures implying the likelihood of chemically ordered low temperature phases. We apply a hybrid Monte Carlo and molecular dynamics method to evaluate the temperature-dependent chemical order. At 300K a cesium-chloride ordering emerges between mixed (Nb,Ta) si…
We investigate the magnetocaloric effect (MCE), relative cooling power (RCP) and crystalline structure in Sb substituted CrTe_{1-x}Sb_{x} (0 \leq x \leq 0.2) alloy. The Rietveld refinement of the XRD pattern of CrTe1-xSbx showed the emerging of pure hexagonal NiAs structure with P63/mmc (194) space group with increasing Sb substitution. We detect a slight increase in the basal plane a-lattice parameter, with a much larger reduction in the c-axis. Magnetic isotherms were measured in the temperature range of 50-400K. The results revealed an increase in the maximum entropy change |S_{M}(T,H)| wit…
The compositional dependence of the lowest direct and indirect band gaps in $\text{Ge}_{1-y}\text{Sn}_{y}$ has been determined from room-temperature photoluminescence measurements. This technique is particularly attractive for a comparison of the two transitions because distinct features in the spectra can be associated with the direct and indirect gaps. However, detailed modeling of these room temperature spectra is required to extract the band gap values with the high accuracy required to determine the Sn concentration $y_{c}$ at which the alloy becomes a direct gap semiconductor. For the di…
First principles calculations are performed to investigate the thermodynamical stability, dynamical, mechanical, electronic and magnetic properties of CrTiCoZ (Z= Al/Si) novel quaternary Heusler alloys. Y-type III atomic configuration is found to be the most stable structure for both compounds. The melting temperatures of both compounds are as high as 2142 K and 2420 K for CrTiCoAl and CrTiCoSi, respectively. The electronic structure calculations using GGA-PBE approach show a half metallic behavior of CrTiCoAl. The spin-down channel exhibits a direct band gap of 0.15 eV, whereas the spin-up ch…
Stabilization of Martensite and Austenite Phases and Realization of Two-way Martensitic Transition in Co-Ni-Ga Ferromagnetic Shape Memory Alloy Nanoparticles
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 …
Future spintronics requires the realization of thin film of half-metallic ferromagnets having high Curie temperature and 100\% spin polarization at the Fermi level for potential spintronics applications. In this paper, we report the epitaxial thin films growth of half-metallic CoFeMnGe Heusler alloy on MgO (001) substrate using pulsed laser deposition system, along with the study of structural, magnetic and transport properties. The magnetic property measurements of the thin film suggest a soft ferromagnetic state at room temperature with an in-plane magnetic anisotropy and a Curie temperature…
We report on both experimental and theoretical study of conduction-electron spin polarization dynamics achieved by pulsed optical pumping at room temperature in GaAs(1-x)N(x) alloys with a small nitrogen content (x = 2.1, 2.7, 3.4%). It is found that the photoluminescence circular polarization determined by the mean spin of free electrons reaches 40-45% and this giant value persists within 2 ns. Simultaneously, the total free-electron spin decays rapidly with the characteristic time ~150 ps. The results are explained by spin-dependent capture of free conduction electrons on deep paramagnetic c…
The two-dimensional dislocation dynamics approach has been recently used for analyzing plastic deformation in metals and alloys at elevated temperatures. The two-dimensional approach, however, only accounts for the dislocation climbing process, and it assumes that dislocation bypassing and shearing of precipitates are negligible. To examine the validity of this assumption, this study quantifies dislocation bypassing and shearing of precipitates in terms of critical resolved shear stress, interaction time, and thermal activation energy for various precipitate strength levels, temperatures, and …
The temperature dependence of thermodynamic and mechanical properties of six fcc transition metals (Ni, Cu, Ag, Au, Pt, Rh) and the alloying behavior of Ag-Au and Cu-Ni are studied using molecular dynamics (MD). The structures are described at elevated temperatures by the force fields developed by Sutton and co-workers within the context of tight binding approach. MD algorithms are based on the extended Hamiltonian formalism from the works of Andersen, Parinello and Rahman, Nose, Hoover and Cagin.The SIMULATOR program that we use generates information about various physical properties during t…
Electronic structure calculations are used to examine the magnetic properties of Fe$_2$P-based alloys and the mechanisms through which the Curie temperature and magnetocrystalline anisotropy can be optimized for specific applications. It is found that at elevated temperatures the magnetic interaction in pure Fe$_2$P develops a pronounced two-dimensional character due to the suppression of the magnetization in one of the sublattices, but the interlayer coupling is very sensitive to band filling and structural distortions. This feature suggests a natural explanation of the observed sharp enhance…
Room temperature solute clustering in aluminium alloys, or natural ageing, despite its industrial relevance, is still subject to debate, mostly due to its experimentally challenging nature. To better understand the complex multi-constituents' interactions at play, we have studied ternary and quaternary subsystems based on the Al-Cu alloys, namely Al-Cu-Mg, Al-Cu-Li and Al-Cu-Li-Mg. We used a recently introduced correlative technique using small-angle neutrons and X-ray scattering (SANS and SAXS) to extract the chemically resolved kinetics of room temperature clustering in these alloys, which w…
Spinning of a common aluminum automotive casting alloy A356 (Al-7Si-0.3 Mg) at elevated temperatures has been investigated experimentally with a novel industrial-scale apparatus. This has permitted the implementation of a fully coupled thermomechanical finite element model aimed at quantifying the processing history (stress, strain, strain-rate and temperature) and predicting the final geometry. The geometric predictions of this model have been compared directly to the geometry of the workpieces obtained experimentally. This study is novel in regards to both the size and shape of the component…
We investigate the structure and magneto-transport properties of thin films of the Co_2Cr_xFe_(1-x)Al full-Heusler compound, which is predicted to be a half-metal by first-principles theoretical calculations. Thin films are deposited by magnetron sputtering at room temperature on various substrates in order to tune the growth from polycrystalline on thermally oxidized Si substrates to highly textured and even epitaxial on MgO(001) substrates, respectively. Our Heusler films are magnetically very soft and ferromagnetic with Curie temperatures up to 630 K. The total magnetic moment is reduced co…
Employing $ab$ $intito$ electronic structure calculations, we have investigated electronic and magnetic properties of the Zr-based quanternary Heusler alloys: ZrCoVIn, ZrFeVGe, ZrCoFeP, ZrCoCrBe and ZrFeCrZ (Z=In and Ga). Our $ab$ $intito$ calculation results show that all the alloys are (or nearly) spin-gapless semiconductors. All the alloys have large band gaps, indicating the stability of them at room temperature. The Slater-Pauling behaviours of these alloys are discussed as well. The values of Curie temperature of all the alloys are estimated. And it is found that the values of the Curie …
