An assessment of the lattice strain in the CrMnFeCoNi high-entropy alloy

The formation of single phase solid solutions from combinations of multiple principal elements, with differing atomic radii, has led to the suggestion that the lattices of high-entropy alloys (HEAs) must be severely distorted. To assess this hypothesis, total scattering measurements using neutron radiation have been performed on the CrMnFeCoNi alloy and compared with similar data from five compositionally simpler materials within the same system. The Bragg diffraction patterns from all of the studied materials were similar, consistent with a face-centered cubic structure, and none showed the pronounced dampening that would be expected from a highly distorted lattice. A more detailed evaluation of the local lattice strain was made by considering the first six coordination shells in the pair distribution functions (PDF), obtained from the total scattering data. Across this range, the HEA exhibited the broadest PDF peaks but these widths were not disproportionately larger than those of the simpler alloys. In addition, of all the materials considered, the HEA was at the highest homologous temperature, and hence the thermal vibrations of the atoms would be greatest. Consequently, the level of local lattice strain required to rationalise a given PDF peak width would be reduced. As a result, the data presented in this study do not indicate that the local lattice strain in the equiatomic CrMnFeCoNi HEA is anomalously large.The authors would like to thank the EPSRC/Rolls-Royce Strategic Partnership for funding (EP/M005607/1 and EP/H022309).This is the final version of the article. It first appeared from Elsevier via https://doi.org/10.1016/j.actamat.2016.09.03

Nanoscale polar heterogeneities and branching Bi-displacement directions in K0.5Bi0.5TiO3

K0.5Bi0.5TiO3 (KBT)—one of the few perovskite-like ferroelectric compounds with room-temperature tetragonal symmetry—differs from other members of its family (BaTiO3 and PbTiO3) by the presence of a disordered mixture of K and Bi on cuboctahedral sites. This disorder is expected to affect local atomic displacements and their response to an applied electric field. We have derived nanoscale atomistic models of KBT by refining atomic coordinates to simultaneously fit neutron/X-ray total scattering and extended X-ray absorption fine-structure data. Both Bi and Ti ions were found to be offset relative to their respective oxygen cages in the high-temperature cubic phase; in contrast, the coordination environment of K remained relatively undistorted. In the cubic structure, Bi displacements prefer the ⟨100⟩ directions and the probability density distribution of Bi features six well-separated sites; a similar preference exists for the much smaller Ti displacements, although the split sites for Ti could not be resolved. The cation displacements are correlated, yielding polar nanoregions, whereas on average, the structure appears as cubic. The cubic ↔ tetragonal phase transition involves both order/disorder and displacive mechanisms. A qualitative change in the form of the Bi probability density distribution occurs in the tetragonal phase on cooling to room temperature because Bi displacements “branch off” to ⟨111⟩ directions. This change, which preserves the average symmetry, is accompanied by the development of nanoscale polar heterogeneities that exhibit significant deviations of their polarization vectors from the average polar axis

Neutron and muon characterisation techniques for battery materials

Neutron and muon characterisation techniques offer unique capabilities for investigating the complex structure and dynamics of rechargeable battery systems. Whilst the non-monotonic interaction of the neutron with the nuclei of atoms makes it sensitive to light and neighbouring elements in the periodic table, its weakly interacting nature allows it to penetrate deep into the sample without damaging it, enabling the flexible use of complex sample environments such as in situ/in operando cells. Meanwhile, the also non-invasive nature of an implanted positive muon allows it to be used as a probe to study bulk ionic diffusion phenomena within materials at different depths by tuning the energy of the incident muons. This review discusses the application of relevant neutron and muon characterisation techniques to the study of specific phenomena in ion batteries, highlighting key literature cases that serve as the archetypal example for the utility of each technique. Furthermore, this review includes an accessible overview of the working principles of each technique that has been condensed and optimised to provide a basic understanding of their relevance to the particular challenges they can address

Structure, spin correlations, and magnetism of the S = 1/2 square-lattice antiferromagnet Sr2CuTe1–xWxO6 (0 ≤ x ≤ 1)

Quantum spin liquids are highly entangled magnetic states with exotic properties. The S = 1/2 square-lattice Heisenberg model is one of the foundational models in frustrated magnetism with a predicted, but never observed, quantum spin liquid state. Isostructural double perovskites Sr2CuTeO6 and Sr2CuWO6 are physical realizations of this model but have distinctly different types of magnetic order and interactions due to a d10/d0 effect. Long-range magnetic order is suppressed in the solid solution Sr2CuTe1–xWxO6 in a wide region of x = 0.05–0.6, where the ground state has been proposed to be a disorder-induced spin liquid. Here, we present a comprehensive neutron scattering study of this system. We show using polarized neutron scattering that the spin liquid-like x = 0.2 and x = 0.5 samples have distinctly different local spin correlations, which suggests that they have different ground states. Low-temperature neutron diffraction measurements of the magnetically ordered W-rich samples reveal magnetic phase separation, which suggests that the previously ignored interlayer coupling between the square planes plays a role in the suppression of magnetic order at x ≈ 0.6. These results highlight the complex magnetism of Sr2CuTe1–xWxO6 and hint at a new quantum critical point between 0.2 < x < 0.4

Separation of static and dynamic displacements in the CrMnFeCoNi high entropy alloy

Assessing the local lattice strains in high-entropy alloys (HEAs) is essential if their mechanical properties are to be rationalised and the validity of the highly distorted lattice hypothesis is to be determined. To accomplish this, direct measurements of local distortions need to be made, and the thermal component separated. In this study, variable temperature neutron total scattering measurements were made on the exemplar HEA CrMnFeCoNi, along with pure nickel and an alloy of Ni-37.5Co25Cr25at.%. A number of methods of determining local atomic displacements from such measurements were used and their efficacy for determining local lattice strains discussed. Using these methods, the local lattice strains have been effectively quantified. The data suggest the HEA does have a comparatively higher strain than the NiCoCr alloy, however, the alloying strains are small in comparison to the thermal component in all cases. As such, whether the local lattice strains are significant and can class the alloy as highly strained remains inconclusive

The mediation of bond strain by vacancies and displacive disorder in A-site-deficient perovskites

Local distortions in perovskite-like A-site-deficient (Sr,La)TiO3 solid solutions have been determined by refining large-scale atomic configurations against neutron/X-ray total-scattering and extended-X-ray-absorption-fine-structure data. Structural relaxations in this system are driven by the competing bonding requirements of Sr, La, and the undercoordinated oxygen atoms that surround vacant A-sites, which form upon substitution of La for Sr. La cations exhibit significant, disordered off-center displacements within their oversized oxygen cages required by the larger Sr cations. The resulting split-site probability density distributions of La vary with the Sr/La ratio and the state of the A-site ordering, which together modify the structure's ability to relieve the tensile bond strain around La through octahedral rotation and displacements of oxygens surrounding the vacancies. The displacive disorder of La can provide a hitherto overlooked mechanism for reducing the thermal conductivity, which is relevant to thermoelectric properties of this system. A comparison of the local structural behaviors in (Sr,La)TiO3 and the previously studied (Na,Bi)NbO3 solid solutions permits generalizations about A-site deficient perovskites. We find that A-site vacancies provide the nearest-neighbor oxygens with a degree of freedom to mediate the strain in the system, and their effects on local structural relaxations are determined by cation chemistry and stoichiometry