Refractory medium/high-entropy alloys (M/HEAs) are emerging as promising alternative materials for hydrogen storage and hydrogen combustion engines due to their favorable thermodynamic and kinetic conditions for hydrogen accommodation (for the former) and promising high-temperature mechanical properties (for the latter). A better understanding of hydrogen-metal interactions is necessary to advance the development of this material class, thus helping leverage hydrogen-based applications. Here we reveal the microstructural evolution of a TiNbZr MEA by in-situ synchrotron high-energy X-ray diffraction (HEXRD) during hydrogenation in pure H₂ gas at atmospheric pressure. At 500 °C, dissolved hydrogen atoms gradually expand the crystal lattice isotropically, and the body-centered cubic crystal remains stable up to a hydrogen concentration of ∼46.4 at.%. The thermodynamics of hydrogen accommodation associated with experimental observations in the crystal lattice is elucidated using density functional theory (DFT). The calculations suggest that tetrahedral interstitial sites are the thermodynamically favorable positions for hydrogen accommodation in both cases (i) for a single hydrogen in the special quasirandom structure supercell and (ii) at a high hydrogen concentration (∼45.4 at.%). In the latter case, hydrogen interstitials are randomly distributed on the tetrahedral sites. Upon cooling, it is observed that the body-centered cubic lattice transforms to a body-centered tetragonal structure. The DFT calculations show that this change is related to the ordering distribution of hydrogen interstitials within the TiNbZr lattice. By combining in-situ HEXRD experiments and DFT calculations, the study provides fundamental insights into hydrogen accommodation in the interstitial positions and its impact on the lattice symmetry in TiNbZr MEA.

Higher strength and higher ductility are desirable for structural materials. However, ultrastrong alloys inevitably show decreased strain-hardening capacity, limiting their uniform elongation. We present a supranano (<10 nanometers) and short-range ordering design for grain interiors and grain boundary regions, respectively, in fine-grained alloys based on vanadium, cobalt, and nickel, with additions of tungsten, copper, aluminum, and boron. The pronounced grain boundary-related strengthening and ductilization mechanism is realized through segregation of the short-range ordering near the grain boundary. Furthermore, the supranano ordering with a larger size has an enhanced pinning effect for dislocations and stacking faults, multiplied and accumulated in grain interiors during plastic deformation. These mechanisms promote continuously increased flow stress until fracture of the alloy at 10% strain with 2.6-gigapascal tensile stress.