Origin of age softening in the refractory high-entropy alloys.

Refractory high-entropy alloys (RHEAs) are emerging materials with potential for use under extreme conditions. As a newly developed material system, a comprehensive understanding of their long-term stability under potential service temperatures remains to be established. This study examined a titanium-vanadium-niobium-tantalum alloy, a promising RHEA known for its superior high-temperature strength and room-temperature ductility. Using a combination of advanced analytical microscopies, Calculation of Phase Diagrams (CALPHAD) software, and nanoindentation, we investigated the evolution of its microstructure and mechanical properties upon aging at 700°C. Trace interstitials such as oxygen and nitrogen, initially contributing to solid solution strengthening, promote phase segregation during thermal aging. As a result of the depletion of solute interstitials within the metal matrix, a progressive softening is observed in the alloy as a function of aging time. This study, therefore, underscores the need for a better control of impurities in future development and application of RHEAs.

Liquid-Phase Approach to Glass-Microfiber-Reinforced Sulfide Solid Electrolytes for All-Solid-State Batteries.

Deformable, fast-ion conducting sulfides enable the construction of bulk-type solid-state batteries that can compete with current Li-ion batteries in terms of energy density and scalability. One approach to optimizing the energy density of these cells is to minimize the size of the electrolyte layer by integrating the solid electrolyte in thin membranes. However, additive-free thin membranes, as well as many membranes based on preprepared scaffolds, are difficult to prepare or integrate in solid cells on a large scale. Here, we propose a scalable solution-based approach to produce bulk-type glass-microfiber-reinforced composites that restore the deformability of sulfide electrolytes and can easily be shaped into thin membranes by cold pressing. This approach supports both the ease of preparation and enhancement of the energy density of sulfide-based solid-state batteries.

Dendrite initiation and propagation in lithium metal solid-state batteries.

All-solid-state batteries with a Li anode and ceramic electrolyte have the potential to deliver a step change in performance compared with today's Li-ion batteries1,2. However, Li dendrites (filaments) form on charging at practical rates and penetrate the ceramic electrolyte, leading to short circuit and cell failure3,4. Previous models of dendrite penetration have generally focused on a single process for dendrite initiation and propagation, with Li driving the crack at its tip5-9. Here we show that initiation and propagation are separate processes. Initiation arises from Li deposition into subsurface pores, by means of microcracks that connect the pores to the surface. Once filled, further charging builds pressure in the pores owing to the slow extrusion of Li (viscoplastic flow) back to the surface, leading to cracking. By contrast, dendrite propagation occurs by wedge opening, with Li driving the dry crack from the rear, not the tip. Whereas initiation is determined by the local (microscopic) fracture strength at the grain boundaries, the pore size, pore population density and current density, propagation depends on the (macroscopic) fracture toughness of the ceramic, the length of the Li dendrite (filament) that partially occupies the dry crack, current density, stack pressure and the charge capacity accessed during each cycle. Lower stack pressures suppress propagation, markedly extending the number of cycles before short circuit in cells in which dendrites have initiated.

Effect of Ion Irradiation on Nanoindentation Fracture and Deformation in Silicon Carbide.

Silicon carbide is desirable for many nuclear applications, making it necessary to understand how it deforms after irradiation. Ion implantation combined with nanoindentation is commonly used to measure radiation-induced changes to mechanical properties; hardness and modulus can be calculated from load-displacement curves, and fracture toughness can be estimated from surface crack lengths. Further insight into indentation deformation and fracture is required to understand the observed changes to mechanical properties caused by irradiation. This paper investigates indentation deformation using high-resolution electron backscatter diffraction (HR-EBSD) and Raman spectroscopy. Significant differences exist after irradiation: fracture is suppressed by swelling-induced compressive residual stresses, and the plastically deformed region extends further from the indentation. During focused ion beam cross-sectioning, indentation cracks grow, and residual stresses are modified. The results clarify the mechanisms responsible for the modification of apparent hardness and apparent indentation toughness values caused by the compressive residual stresses in ion-implanted specimens. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s11837-021-04636-8.

High-Entropy Alloys for Advanced Nuclear Applications.

The expanded compositional freedom afforded by high-entropy alloys (HEAs) represents a unique opportunity for the design of alloys for advanced nuclear applications, in particular for applications where current engineering alloys fall short. This review assesses the work done to date in the field of HEAs for nuclear applications, provides critical insight into the conclusions drawn, and highlights possibilities and challenges for future study. It is found that our understanding of the irradiation responses of HEAs remains in its infancy, and much work is needed in order for our knowledge of any single HEA system to match our understanding of conventional alloys such as austenitic steels. A number of studies have suggested that HEAs possess `special' irradiation damage resistance, although some of the proposed mechanisms, such as those based on sluggish diffusion and lattice distortion, remain somewhat unconvincing (certainly in terms of being universally applicable to all HEAs). Nevertheless, there may be some mechanisms and effects that are uniquely different in HEAs when compared to more conventional alloys, such as the effect that their poor thermal conductivities have on the displacement cascade. Furthermore, the opportunity to tune the compositions of HEAs over a large range to optimise particular irradiation responses could be very powerful, even if the design process remains challenging.

Amorphization in extreme deformation of the CrMnFeCoNi high-entropy alloy.

Ever-harsher service conditions in the future will call for materials with increasing ability to undergo deformation without sustaining damage while retaining high strength. Prime candidates for these conditions are certain high-entropy alloys (HEAs), which have extraordinary work-hardening ability and toughness. By subjecting the equiatomic CrMnFeCoNi HEA to severe plastic deformation through swaging followed by either quasi-static compression or dynamic deformation in shear, we observe a dense structure comprising stacking faults, twins, transformation from the face-centered cubic to the hexagonal close-packed structure, and, of particular note, amorphization. The coordinated propagation of stacking faults and twins along {111} planes generates high-deformation regions, which can reorganize into hexagonal packets; when the defect density in these regions reaches a critical level, they generate islands of amorphous material. These regions can have outstanding mechanical properties, which provide additional strengthening and/or toughening mechanisms to enhance the capability of these alloys to withstand extreme loading conditions.

Sodium/Na ß″ Alumina Interface: Effect of Pressure on Voids.

Three-electrode studies coupled with tomographic imaging of the Na/Na-ß″-alumina interface reveal that voids form in the Na metal at the interface on stripping and they accumulate on cycling, leading to increasing interfacial current density, dendrite formation on plating, short circuit, and cell failure. The process occurs above a critical current for stripping (CCS) for a given stack pressure, which sets the upper limit on current density that avoids cell failure, in line with results for the Li/solid-electrolyte interface. The pressure required to avoid cell failure varies linearly with current density, indicating that Na creep rather than diffusion per se dominates Na transport to the interface and that significant pressures are required to prevent cell death, >9 MPa at 2.5 mA·cm-2.

Size effects resolve discrepancies in 40 years of work on low-temperature plasticity in olivine.

The strength of olivine at low temperatures and high stresses in Earth's lithospheric mantle exerts a critical control on many geodynamic processes, including lithospheric flexure and the formation of plate boundaries. Unfortunately, laboratory-derived values of the strength of olivine at lithospheric conditions are highly variable and significantly disagree with those inferred from geophysical observations. We demonstrate via nanoindentation that the strength of olivine depends on the length scale of deformation, with experiments on smaller volumes of material exhibiting larger yield stresses. This "size effect" resolves discrepancies among previous measurements of olivine strength using other techniques. It also corroborates the most recent flow law for olivine, which proposes a much weaker lithospheric mantle than previously estimated, thus bringing experimental measurements into closer alignment with geophysical constraints. Further implications include an increased difficulty of activating plasticity in cold, fine-grained shear zones and an impact on the evolution of fault surface roughness due to the size-dependent deformation of nanometer- to micrometer-sized asperities.