Edge-dislocation-induced ultrahigh elevated-temperature strength of HfMoNbTaW refractory high-entropy alloys.

Over 150 refractory high-entropy alloys (RHEAs) have been proposed in the last decade. Early alloys such as MoNbTaW and MoNbTaVW still show an unparalleled yield strength of approximately 400 MPa at 1600°C. However, RHEAs with even elevated high-temperature strength are necessary in aerospace vehicles and nuclear reactors to cope with advanced technology in the future. Here, solid-solution strengthening calculation and melting point prediction are combined to design single-phase RHEA for attaining ultrahigh strength at 1600°C. The results show that Hf0.5MoNbTaW and HfMoNbTaW alloys after fully homogeneous treatment at 2100°C for 2 h reveal a homogenous body-centered cubic phase. HfMoNbTaW alloy exhibits a yield strength of 571 MPa at 1600°C, much higher than that of MoNbTaVW (477 MPa). It is found that a plateau of strength occurs from 800°C to 1200°C, which is important for raising the strength level of RHEAs at high temperatures. This strengthening mechanism is explained with the change of deformation mode from screw to edge dislocations, which contributes an edge-dislocation-induced strength. A similar alloy design strategy could be applied to develop more RHEAs with an ultrahigh strength level.

Effects of Mo, Nb, Ta, Ti, and Zr on Mechanical Properties of Equiatomic Hf-Mo-Nb-Ta-Ti-Zr Alloys.

Nowadays refractory high-entropy alloys (RHEAs) are regarded as great candidates for the replacement of superalloys at high temperature. To design a RHEA, one must understand the pros and cons of every refractory element. However, the elemental effect on mechanical properties remains unclear. In this study, the subtraction method was applied on equiatomic HfMoNbTaTiZr alloys to discover the role of each element, and, thus, HfMoNbTaTiZr, HfNbTaTiZr, HfMoTaTiZr, HfMoNbTiZr, HfMoNbTaZr, and HfMoNbTaTi were fabricated and analyzed. The microstructure and mechanical properties of each alloy at the as-cast state were examined. The solid solution phase formation rule and the solution strengthening effect are also discussed. Finally, the mechanism of how Mo, Nb, Ta, Ti, and Zr affect the HfMoNbTaTiZr alloys was established after comparing the properties of these alloys.

Clarifying the four core effects of high-entropy materials.

High-entropy materials emerged as a field of research in 2004, when the first research on high-entropy alloys was published. The scope was soon expanded from high-entropy alloys to medium-entropy alloys, as well as to ceramics, polymers and composite materials. A fundamental understanding on high-entropy materials was proposed in 2006 by the 'four core effects' - high-entropy, severe-lattice-distortion, sluggish-diffusion and cocktail effects - which are often used to describe and explain the mechanisms of various peculiar phenomena associated with high-entropy materials. Throughout the years, the effects have been examined rigorously, and their validity has been affirmed. This Perspective discusses the fundamental understanding of the four core effects in high-entropy materials and gives further insights to strengthen the understanding for these effects. All these clarifications are believed to be helpful in understanding low-to-high-entropy materials as well as to aid the design of materials when studying new compositions or pursuing their use in applications.

Solubility of Hydrogen in a WMoTaNbV High-Entropy Alloy.

The WMoTaNbV alloy has shown promise for applications as a solid state hydrogen storage material. It absorbs significant quantities of H directly from the atmosphere, trapping it with high energy. In this work, the dynamics of the absorption of hydrogen isotopes are studied by determining the activation energy for the solubility and the solution enthalpy of H in the WMoTaNbV alloy. The activation energy was studied by heating samples in a H atmosphere at temperatures ranging from 20 °C to 400 °C and comparing the amounts of absorbed H. The solution activation energy EA of H was determined to be EA=0.22±0.02 eV (21.2 ± 1.9 kJ/mol). The performed density functional theory calculations revealed that the neighbouring host atoms strongly influenced the solution enthalpy, leading to a range of theoretical values from -0.40 eV to 0.29 eV (-38.6 kJ/mol to 28.0 kJ/mol).

The effect of critical coupling constants on superconductivity enhancement.

In this study, we propose a phenomenological model to extend McMillan's results on a coupling strength equal to 2. We investigate possible strategies to enhance superconductivity by tuning the phonon frequency, carrier number, or pressure. In particular, we show that the critical coupling constants corresponding to the phonon frequency, carrier number, or pressure determine whether the variation of the critical temperature is positive or negative. These observations explain the contrasting behavior between weak and strong coupling superconductors and are consistent with experimental observations. We also demonstrate the dome observed in the carrier number effect and pressure effect. Additionally, these critical coupling constants systematically separate superconductivity into three regions: weak, intermediate, and strong coupling. We find that the enhancement strategies for weak and strong coupling regions are opposite, but both inevitably bring superconductivity into the intermediate coupling region. Finally, we propose general zigzag methods for intermediate coupling superconductors to further enhance the critical temperature.

Effect of Homogenization on the Transformation Temperatures and Mechanical Properties of Cu15Ni35Hf12.5Ti25Zr12.5 and Cu15Ni35Hf15Ti20Zr15 High-Entropy Shape Memory Alloys.

The major challenge of high-temperature shape memory alloys (SMAs) is the collocation of phase transition temperatures (TTs: Ms, Mf, As, Af) with the mechanical properties required for application. Previous research has shown that the addition of Hf and Zr into NiTi shape memory alloys (SMAs) increases TTs. Modulating the ratio of Hf and Zr can control the phase transformation temperature, and applying thermal treatments can also achieve the same goal. However, the influence of thermal treatments and precipitates on mechanical properties has not been widely discussed in previous studies. In this study, we prepared two different kinds of shape memory alloys and analyzed their phase transformation temperatures after homogenization. Homogenization successfully eliminated dendrites and inter-dendrites in the as-cast states, resulting in a reduction in the phase transformation temperatures. XRD patterns indicated the presence of B2 peaks in the as-homogenized states, demonstrating a decrease in phase transformation temperatures. Mechanical properties, such as elongation and hardness, were improved due to the uniform microstructures achieved after homogenization. Moreover, we discovered that different additions of Hf and Zr resulted in distinct properties. Alloys with lower Hf and Zr had lower phase transformation temperatures, followed by higher fracture stress and elongation.

Investigation of Microstructure and Wear Properties of Precipitates-Strengthened Cu-Ni-Si-Fe Alloy.

Based on multi-component alloys using precipitation hardening, a Cu-Ni-Si-Fe copper alloy was prepared and studied for hardness, electrical conductivity, and wear resistance. Copper Nickel Silicon (Cu-Ni-Si) intermetallic compounds were observed as precipitates, leading to an increase in mechanical and physical properties. Further, the addition of Fe was discussed in intermetallic compound formation. Moreover, microstructures, age hardening, and dry sliding wear resistances of the present alloy were analyzed and compared with C17200 beryllium copper. The results showed that the present alloy performed extraordinarily, with 314 HV in hardness and 22.2 %IACS in conductivity, which is almost similar to C17200 alloy. Furthermore, the dry sliding wear resistance of the present alloy was 2199.3 (m/MPa·mm3) at an ambient temperature, leading to an improvement of 208% compared with the C17200 alloy.

High Entropy Nonlinear Dielectrics with Superior Thermally Stable Performance.

A high configurational entropy, achieved through a proper design of compositions, can minimize the Gibbs free energy and stabilize the quasi-equilibrium phases in a solid-solution form. This leads to the development of high-entropy materials with unique structural characteristics and excellent performance, which otherwise could not be achieved through conventional pathways. This work develops a high-entropy nonlinear dielectric system, based on the expansion of lead magnesium niobate-lead titanate. A dense and uniform distribution of nano-polar regions is observed in the samples owing to the addition of Ba, Hf, and Zr ions, which lead to enhanced performance of nonlinear dielectrics. The fact that no structural phase transformation is detected up to 250 °C, and no noticeable change or a steep drop in structural and electrical characteristics is observed at high temperatures suggests a robust thermal stability of the dielectric systems developed. With these advantages, these materials hold vast potential for applications such as dielectric energy storage, dielectric tunability, and electrocaloric effect. Thus, this work offers a new high-entropy configuration with elemental modulation, with enhanced dielectric material features.

Effect of Mo on the Mechanical and Corrosion Behaviors in Non-Equal Molar AlCrFeMnNi BCC High-Entropy Alloys.

Co-free body-centered cubic (bcc) high-entropy alloys (HEAs) are prepared, and the elevated mechanical property and corrosion property of the Al0.4CrFe1.5MnNi0.5Mox (x = 0 and 0.1) alloys are studied. The Vickers hardness (HV) of the as-homogenized state is between HV 350 and HV 400. Both alloys are provided with nano-scale NiAl-rich B2 precipitates which contribute to the strength at high-temperature. In addition, adding Mo in the present alloy strengthens by σ phase. Al0.4CrFe1.5MnNi0.5Mo0.1 exhibited outstanding tensile properties, with a yield strength of 413 MPa and ultimate tensile strength of 430 MPa in the elevated tensile test at 600 °C, which is better than that of Al0.4CrFe1.5MnNi0.5 alloy. Through potentiodynamic polarization testing in 0.5 M H2SO4 solution and electrochemical impedance spectroscopy (EIS), it is shown that adding Mo can effectively reduce the corrosion current density and improve the impedance of passive film, since the passivation layer is formed and stable.

Irradiation Damage Independent Deuterium Retention in WMoTaNbV.

High entropy alloys are a promising new class of metal alloys with outstanding radiation resistance and thermal stability. The interaction with hydrogen might, however, have desired (H storage) or undesired effects, such as hydrogen-induced embrittlement or tritium retention in the fusion reactor wall. High entropy alloy WMoTaNbV and bulk W samples were used to study the quantity of irradiation-induced trapping sites and properties of D retention by employing thermal desorption spectrometry, secondary ion mass spectrometry, and elastic recoil detection analysis. The D implantation was not found to create additional hydrogen traps in WMoTaNbV as it does in W, while 90 at% of implanted D is retained in WMoTaNbV, in contrast to 35 at% in W. Implantation created damage predicted by SRIM is 0.24 dpa in WMoTaNbV, calculated with a density of 6.044×1022 atoms/cm3. The depth of the maximum damage was 90 nm. An effective trapping energy for D in WMoTaNbV was found to be about 1.7 eV, and the D emission temperature was close to 700 °C.

Strength through high slip-plane density.

Subjecting a multicomponent alloy to cyclic torsion can create a strong, ductile material.

Rapid Fabrication of High-Entropy Ceramic Nanomaterials for Catalytic Reactions.

Although high-entropy alloys have been intensively studied in the past decade, there are still many requirements for manufacturing processes and application directions to be proposed and developed, but most techniques are focused on high-entropy bulk materials and surface coatings. We fabricated high-entropy ceramic (HEC) nanomaterials using simple pulsed laser irradiation scanning on mixed salt solutions (PLMS method) under low-vacuum conditions. This method, allowing simple operation, rapid manufacturing, and low cost, is capable of using various metal salts as precursors and is also suitable for both flat and complicated 3D substrates. In this work, we engineered this PLMS method to fabricate high-entropy ceramic oxides containing four to seven elements. To address the catalytic performance of these HEC nanomaterials, we focused on CoCrFeNiAl high-entropy oxides applied to the oxygen-evolution reaction (OER), which is considered a sluggish process in water. We performed systematic material characterization to solve the complicated structure of the CoCrFeNiAl HEC as a spinel structure, AB2O4 (A, B = Co, Cr, Fe, Ni, or Al). Atoms in A and B sites in the spinel structure can be replaced with other elements; either divalent or trivalent metals can occupy the spinel lattice using this PLMS process. We applied this PLMS method to manufacture electrocatalytic CoCrFeNiAl HEC electrodes for the OER reaction, which displayed state-of-the-art activity and stability.

Thermodynamic Routes to Ultralow Thermal Conductivity and High Thermoelectric Performance.

Thermoelectric (TE) research is not only a course of materials by discovery but also a seedbed of novel concepts and methodologies. Herein, the focus is on recent advances in three emerging paradigms: entropy engineering, phase-boundary mapping, and liquid-like TE materials in the context of thermodynamic routes. Specifically, entropy engineering is underpinned by the core effects of high-entropy alloys; the extended solubility limit, the tendency to form a high-symmetry crystal structure, severe lattice distortions, and sluggish diffusion processes afford large phase space for performance optimization, high electronic-band degeneracy, rich multiscale microstructures, and low lattice thermal conductivity toward higher-performance TE materials. Entropy engineering is successfully implemented in half-Huesler and IV-VI compounds. In Zintl phases and skutterudites, the efficacy of phase-boundary mapping is demonstrated through unraveling the profound relations among chemical compositions, mutual solubilities of constituent elements, phase instability, microstructures, and resulting TE properties at the operation temperatures. Attention is also given to liquid-like TE materials that exhibit lattice thermal conductivity at lower than the amorphous limit due to intensive mobile ion disorder and reduced vibrational entropy. To conclude, an outlook on the development of next-generation TE materials in line with these thermodynamic routes is given.

Hierarchical microstructure strengthening in a single crystal high entropy superalloy.

A hierarchical microstructure strengthened high entropy superalloy (HESA) with superior cost specific yield strength from room temperature up to 1,023 K is presented. By phase transformation pathway through metastability, HESA possesses a hierarchical microstructure containing a dispersion of nano size disordered FCC particles inside ordered L12 precipitates that are within the FCC matrix. The average tensile yield strength of HESA from room temperature to 1,023 K could be 120 MPa higher than that of advanced single crystal superalloy, while HESA could still exhibit an elongation greater than 20%. Furthermore, the cost specific yield strength of HESA can be 8 times that of some superalloys. A template for lighter, stronger, cheaper, and more ductile high temperature alloy is proposed.

An oxidation resistant refractory high entropy alloy protected by CrTaO4-based oxide.

Although refractory high entropy alloys (RHEAs) have shown potentials to be developed as structural materials for elevated temperature applications, most of the reported oxidation behaviours of RHEA were associated with short term exposures for only up to 48 hours, and there is a lack of understanding on the oxidation mechanism of any RHEA to-date. In this work, by using thermogravimetric analysis, isothermal oxidation was conducted on a novel RHEA at 1000 °C and 1100 °C for up to 200 hours, which is an unprecedented testing duration. The external oxide layer strongly influenced the weight gain behaviours, and it consisted of CrTaO4-based oxide with some dispersion of Al2O3 and Cr2O3. At 1000 °C, the inability to form dense CrTaO4-based oxide layer resulted an exponential dependence of weight gain throughout 200 hours. At 1100 °C, mass gain curve showed two parabolic dependences associated with the formation of protective CrTaO4-based oxide layer and the weight gain after 200 hours was 4.03 mg/cm2, which indicates that it is one of the most oxidation resistant RHEAs comparing to literature data to-date. This work can also provide insights on how to further develop RHEA to withstand long term oxidation at elevated temperatures.

Influence of Ti Content on the Partial Oxidation of TixFeCoNi Thin Films in Vacuum Annealing.

This study investigated the effects of Ti content and vacuum annealing on the microstructure evolution of TixFeCoNi (x = 0, 0.5, and 1) thin films and the underlying mechanisms. The as-deposited thin film transformed from an FCC (face center cubic) structure at x = 0 into an amorphous structure at x = 1, which can be explained by determining topological instability and a hard ball model. After annealing was performed at 1000 °C for 30 min, the films presented a layered structure comprising metal solid solutions and oxygen-deficient oxides, which can be major attributed to oxygen traces in the vacuum furnace. Different Ti contents provided various phase separation and layered structures. The underlying mechanism is mainly related to the competition among possible oxides in terms of free energy production at 1000 °C.

The High Temperature Tensile and Creep Behaviors of High Entropy Superalloy.

This article presents the high temperature tensile and creep behaviors of a novel high entropy alloy (HEA). The microstructure of this HEA resembles that of advanced superalloys with a high entropy FCC matrix and L12 ordered precipitates, so it is also named as "high entropy superalloy (HESA)". The tensile yield strengths of HESA surpass those of the reported HEAs from room temperature to elevated temperatures; furthermore, its creep resistance at 982 °C can be compared to those of some Ni-based superalloys. Analysis on experimental results indicate that HESA could be strengthened by the low stacking-fault energy of the matrix, high anti-phase boundary energy of the strengthening precipitate, and thermally stable microstructure. Positive misfit between FCC matrix and precipitate has yielded parallel raft microstructure during creep at 982 °C, and the creep curves of HESA were dominated by tertiary creep behavior. To the best of authors' knowledge, this article is the first to present the elevated temperature tensile creep study on full scale specimens of a high entropy alloy, and the potential of HESA for high temperature structural application is discussed.

Effect of one-step recrystallization on the grain boundary evolution of CoCrFeMnNi high entropy alloy and its subsystems.

In this study, the grain boundary evolution of equiatomic CoCrFeMnNi, CoCrFeNi, and FeCoNi alloys after one-step recrystallization were investigated. The special boundary fraction and twin density of these alloys were evaluated by electron backscatter diffraction analysis. Among the three alloys tested, FeCoNi exhibited the highest special boundary fraction and twin density after one-step recrystallization. The special boundary increment after one-step recrystallization was mainly affected by grain boundary velocity, while twin density was mainly affected by average grain boundary energy and twin boundary energy.

Experiments and Model for Serration Statistics in Low-Entropy, Medium-Entropy, and High-Entropy Alloys.

High-entropy alloys (HEAs) are new alloys that contain five or more elements in roughly-equal proportion. We present new experiments and theory on the deformation behavior of HEAs under slow stretching (straining), and observe differences, compared to conventional alloys with fewer elements. For a specific range of temperatures and strain-rates, HEAs deform in a jerky way, with sudden slips that make it difficult to precisely control the deformation. An analytic model explains these slips as avalanches of slipping weak spots and predicts the observed slip statistics, stress-strain curves, and their dependence on temperature, strain-rate, and material composition. The ratio of the weak spots' healing rate to the strain-rate is the main tuning parameter, reminiscent of the Portevin-LeChatellier effect and time-temperature superposition in polymers. Our model predictions agree with the experimental results. The proposed widely-applicable deformation mechanism is useful for deformation control and alloy design.