High-entropy alloys, near-equiatomic solid solutions of five or more elements, represent a new strategy for the design of materials with properties superior to those of conventional alloys. However, their phase space remains constrained, with transition metal high-entropy alloys exhibiting only face- or body-centered cubic structures. Here, we report the high-pressure synthesis of a hexagonal close-packed phase of the prototypical high-entropy alloy CrMnFeCoNi. This martensitic transformation begins at 14 GPa and is attributed to suppression of the local magnetic moments, destabilizing the initial fcc structure. Similar to fcc-to-hcp transformations in Al and the noble gases, the transformation is sluggish, occurring over a range of >40 GPa. However, the behaviour of CrMnFeCoNi is unique in that the hcp phase is retained following decompression to ambient pressure, yielding metastable fcc-hcp mixtures. This demonstrates a means of tuning the structures and properties of high-entropy alloys in a manner not achievable by conventional processing techniques.

In situ high-pressure X-ray diffraction and Raman spectroscopy were used to determine the influence of composition on the high-pressure behavior of A 2 B 2 O 7 pyrochlore (A ¼ Eu, Dy; B ¼ Ti, Zr) up to $50 GPa. Based on X-ray diffraction results, all compositions transformed to the highpressure cotunnite structure. The B-site cation species had a larger effect on the transition pressure than the A-site cation species, with the onset of the phase transformation occurring at $41 GPa for B ¼ Ti and $16 GPa B ¼ Zr. However, the A-site cation affected the kinetics of the phase transformation, with the transformation for compositions with the smaller ionic radii, i.e., A ¼ Dy, proceeding faster than those with a larger ionic radii, i.e., A ¼ Eu. These results were consistent with previous work in which the radius-ratio of the A-and B-site cations determined the energetics of disordering, and compositions with more similarly sized A-and B-site cations had a lower defect formation energy. Raman spectra revealed differences in the degree of short-range order of the different compositions. Due to the large phase fraction of cotunnite at high pressure for B ¼ Zr compositions, Raman modes for cotunnite could be observed, with more modes recorded for A ¼ Eu than A ¼ Dy. These additional modes are attributed to increased short-to-medium range ordering in the initially pyrochlore structured Eu 2 Zr 2 O 7 as compared with the initially defect-fluorite structured Dy 2 Zr 2 O 7 .

A 2 Sn 2 O 7 (A = Nd, Sm, Gd, Er, Yb, and Y) materials with the pyrochlore structure were irradiated with 2.2 GeV Au ions to systematically investigate disordering of this system in response to dense electronic excitation. Structural modifications were characterized, over multiple length scales, by transmission electron microscopy, x-ray diffraction, and Raman spectroscopy.Transformations to amorphous and disordered phases were observed, with disordering dominating the structural response of materials with small A-site cation ionic radii. Both the disordered and amorphous phases were found to possess weberite-type local ordering, differing only in that the disordered phase exhibits a long-range, modulated arrangement of weberite-type structural units into an average defect-fluorite structure, while the amorphous phase remains fully aperiodic. Comparison with the behavior of titanate and zirconate pyrochlores showed minimal influence of the high covalency of the Sn-O bond on this phase behavior. An analytical model of damage accumulation was developed to account for simultaneous amorphization and recrystallization of the disordered phase during irradiation.

Strain engineering is a promising method for next-generation materials processing techniques. Here, we use mechanical milling and annealing followed by compression in diamond anvil cell to tailor the intrinsic and extrinsic strain in pyrochlore, Dy2Ti2O7 and Dy2Zr2O7. Raman spectroscopy, X-ray pair distribution function analysis, and X-ray diffraction were used to characterize atomic order over short-, medium-, and long-range spatial scales, respectively, under ambient conditions. Raman spectroscopy and X-ray diffraction were further employed to interrogate the material in situ at high pressure. High-pressure behavior is found to depend on the species and concentration of defects in the sample at ambient conditions. Overall, we show that defects can be engineered to lower the phase transformation onset pressure by ~50% in the ordered pyrochlore Dy2Ti2O7, and lower the phase transformation completion pressure by ~20% in the disordered pyrochlore Dy2Zr2O7. These improvements are achieved without significantly sacrificing mechanical integrity, as characterized by bulk modulus.

Swift heavy ion (2 GeV 181 Ta) irradiation-induced amorphization and temperature-induced recrystallization of cubic pyrochlore Gd 2 Ti 2 O 7 (Fd 3m) are compared with the response of a compositionally-similar material with a monoclinic-layered perovskite-type structure, La 2 Ti 2 O 7 (P2 1 ). The averaged electronic energy loss, dE/dx, was 37 keV/nm and 35 keV/nm in Gd 2 Ti 2 O 7 and La 2 Ti 2 O 7 , respectively. Systematic analysis of the structural modifications was completed using transmission electron microscopy, synchrotron X-ray diffraction, Raman spectroscopy, and small-angle X-ray scattering. Increasing ion-induced amorphization with increasing ion fluence was evident in the X-ray diffraction patterns of both compositions by a reduction in the intensity of the diffraction maxima concurrent with the growth in intensity of a broad diffuse scattering halo. Transmission electron microscopy analysis showed complete amorphization within ion tracks (diameter: $10 nm) for the perovskite-type material; whereas a concentric, core-shell morphology was evident in the ion tracks of the pyrochlore, with an outer shell of disordered yet still crystalline material with the fluorite structure surrounding an amorphous track core (diameter: $9 nm). The radiation response of both titanate oxides with the same stoichiometry can be understood in terms of differences in their structures and compositions. While the radiation damage susceptibility of pyrochlore A 2 B 2 O 7 materials decreases as a function of the cation radius ratio r A /r B , the current study correlates this behavior with the stability field of monoclinic structures, where r La /r Ti > r Gd /r Ti . Isochronal annealing experiments of the irradiated materials showed complete recrystallization of La 2 Ti 2 O 7 at 775°C and of Gd 2 Ti 2 O 7 at 850°C. The annealing behavior is discussed in terms of enhanced damage recovery in La 2 Ti 2 O 7 , compared to the pyrochlore compounds Gd 2 Ti 2 O 7 . The difference in the recrystallization behavior may be related to structural constraints, i.e., reconstructing a low symmetry versus a high symmetry phase.