Configurational disorder can be compositionally engineered into mixed oxide by populating a single sublattice with many distinct cations. The formulations promote novel and entropy-stabilized forms of crystalline matter where metal cations are incorporated in new ways. Here, through rigorous experiments, a simple thermodynamic model, and a five-component oxide formulation, we demonstrate beyond reasonable doubt that entropy predominates the thermodynamic landscape, and drives a reversible solid-state transformation between a multiphase and single-phase state. In the latter, cation distributions are proven to be random and homogeneous. The findings validate the hypothesis that deliberate configurational disorder provides an orthogonal strategy to imagine and discover new phases of crystalline matter and untapped opportunities for property engineering.

Twelve different equiatomic five-metal carbides of group IVB, VB, and VIB refractory transition metals are synthesized via high-energy ball milling and spark plasma sintering. Implementation of a newly developed ab initio entropy descriptor aids in selection of candidate compositions for synthesis of high entropy and entropy stabilized carbides. Phase formation and composition uniformity are analyzed via XRD, EDS, S/TEM-EDS, and EXAFS. Nine of the twelve candidates form true single-phase materials with the rocksalt (B1) structure when sintered at 2473 K and can therefore be investigated as high entropy carbides (HECs). The composition (V 0.2 Nb 0.2 Ta 0.2 Mo 0.2 W 0.2)C is presented as a likely candidate for further investigation as an entropy stabilized carbide. Seven of the carbides are examined for mechanical properties via nanoindentation. The HECs show significantly enhanced hardness when compared to a rule of mixtures average of the constituent binary carbides and to the highest hardness of the binary constituents. The mechanical properties are correlated to the electronic structure of the solid solutions, offering a future route to tunability of the mechanical properties of carbide ceramics via exploration of a new complex composition space.

Manipulating a crystalline material's configurational entropy through the introduction of unique atomic species can produce novel materials with desirable mechanical and electrical properties. From a thermal transport perspective, large differences between elemental properties such as mass and interatomic force can reduce the rate at which phonons carry heat and thus reduce the thermal conductivity. Recent advances in materials synthesis are enabling the fabrication of entropy-stabilized ceramics, opening the door for understanding the implications of extreme disorder on thermal transport. Measuring the structural, mechanical, and thermal properties of single-crystal entropy-stabilized oxides, it is shown that local ionic charge disorder can effectively reduce thermal conductivity without compromising mechanical stiffness. These materials demonstrate similar thermal conductivities to their amorphous counterparts, in agreement with the theoretical minimum limit, resulting in this class of material possessing the highest ratio of elastic modulus to thermal conductivity of any isotropic crystal. CeramicsHigh-entropy alloys (HEAs), consisting of five or more approximately equimolar compositions of elements, [1,2] have proven to exhibit unique physical properties such as high hardness, [3] thermal stability, [4] structural stability, [5] as well as corrosion, oxidation, and wear resistance. [6][7][8] While microstructure and mechanical properties have been extensively studied, thermal

Entropy‐stabilized oxides (ESOs) provide an alternative route to novel materials discovery and synthesis. It is, however, a challenge to demonstrate that the constituent elements in an entropy‐stabilized crystal are homogeneously and randomly dispersed among a particular sublattice, resulting in a true solid solution with no evidence of local order or clustering. In this work, we present the application and analysis of extended X‐ray absorption fine structure (EXAFS) on the prototype ESO composition MgxNixCoxCuxZnxO (x=0.2). In so doing, we can quantify the local atomic structure on an element‐by‐element basis. We conclude that local bond lengths between metal and oxygen vary around each absorbing cation, with notable distortion around the Cu–O polyhedra. By the second near neighbor (i.e., the cation‐cation pair), interatomic distances are uniform to the extent that the collected data can resolve. Crystal models that best fit the experimental scattering data include cations that are distributed randomly on an FCC sublattice with minimal positional disorder, with an interleaved FCC anion sublattice with oxygen ions displaced from the ideal locations to accommodate the distortions in the cation polyhedra. Density functional theory calculations of the ESO system yield a significant broadening in the positional distribution for the oxygen sublattice compared to that for the cation sublattice for all peaks, showing consistency with the conclusion from the experimental data that the distortion from an ideal rock salt structure occurs primarily through disorder in the oxygen sublattice.

Density functional theory calculations were carried out for three entropic rocksalt oxides, (Mg0.1Co0.1Ni0.1Cu0.1Zn0.1)O0.5, termed J14, and J14 + Li and J14 + Sc, to understand the role of charge neutrality and electronic states on their properties, and to probe whether simple expressions may exist that predict stability. The calculations predict that the average lattice constants of the ternary structures provide good approximations to that of the random structures. For J14, Bader charges are transferable between the binary, ternary, and random structures. For J14 + Sc and J14 + Li, average Bader charges in the entropic structures can be estimated from the ternary compositions. Addition of Sc to J14 reduces the majority of Cu, which show large displacements from ideal lattice sites, along with reduction of a few Co and Ni cations. Addition of Li to J14 reduces the lattice constant, consistent with experiment, and oxidizes some of Co as well as some of Ni and Cu. The Bader charges and spin-resolved density of states (DOS) for Co+3 in J14 + Li are very different from Co+2, while for Cu and Ni the Bader charges form continuous distributions and the two DOS are similar for the two oxidation states. Experimental detection of different oxidation states may therefore be challenging for Cu and Ni compared to Co. Based on these results, empirical stability parameters for these entropic oxides may be more complicated than those for non-oxide entropic solids.