Vacancy formation enthalpies of high-entropy FeCoCrNi alloy via first-principles calculations and possible implications to its superior radiation tolerance

Because atoms in high-entropy alloys （HEAs） coordinate in very different and distorted local environ- ments in the lattice sites, even for the same type of constituent, their point defects could highly vary. Therefore, theoretical determination of the thermodynamic quantities （i.e., defect formation enthalpies） of various point defects is rather challenging because each corresponding thermodynamic quantity of all involve constituents is not unique. The knowledge of these thermodynamic quantities is prerequisite for designing novel HEAs and understanding the mechanical and physical behaviors of HEAs. However, to date there has not been a good method to theoretically derive the defect formation enthalpies of HEAs. Here, using first-principles calculations within the density functional theory （DFT） in combina- tion of special quasi-random structure models （SQSs）, we have developed a general method to derive corresponding formation enthalpies of point defects in HEAs, using vacancy formation enthalpies of a four-component equiatomic fcc-type FeCoCrNi HEA as prototypical and benchmark examples. In difference from traditional ordered alloys, the vacancy formation enthalpies of FeCoCrNi HEA vary in a highly wide range from 0.72 to 2.89 eV for Fe, 0.88-2.90 eV for Co, 0.78-3.09 eV for Cr, and 0.91-2.95 eV for Ni due to high-level site-to-site lattice distortions and compositional complexities. On average, the vacancy formation enthalpies of 1.58 eV for Fe, 1.61 eV for Cr, 1.70 eV for Co and 1.89 eV for Ni are all larger than that （1.41 eV） of pure fcc nickel. This fact implies that the vacancies are much more difficult to be created than in nickel, indicating a reasonable agreement with the recent experimental observation that FeCoCrNi exhibits two orders of amplitudes enhancement of radiation tolerance with the suppression of void formation at elevated temperatures than in pure nickel.

A Concordant Shift Model for Flow in Bulk Metallic Glasses

The homogeneous plastic flow in bulk metallic glasses （BMGs） must be elucidated by an appropriate atomistic mechanism. It is proposed that a so-called concordant shifting model, based on rearrangements of five-atom subclusters, can describe the plastic strain behaviour of BMGs in a temperature range from room temperature to the supercooled liquid region. To confirm the effectiveness of the atomic concordant shifting model, a comparative investigation between the vacancy/atom model and the concordant shifting model is carried out based on the estimation of the strain rate deduced from two models. Our findings suggest that the atomic concordant shifting model rather than the vacancy/atom exchange model can well predict the large strain rate in the superplasticity of BMGs.

Effect of calcination temperature on B-site vacancy content of La0.75Sr0.25Mn0.92△0.08O3-δperovskite

Lanthanum manganite with cation vacancies from nominal La（0.75）Sr（0.25）Mn（0.92）△（0.08）O（3-δ） nanocrystalline powder was successfully prepared at different calcination temperatures using the sol-gel method. X-ray diffraction shows that as the calcination temperature（T（Cal）） increases, the crystal particle diameter increases, but the B-site vacancy content decreases. According to a powder diffraction profile fitting technique and transmission electron microscopy results, the vacancy content can be estimated as 0.08,0.01, and 0.005 for T（Cal） = 1073,1273, and 1473 K, respectively. Magnetization versus temperature curves show that the magnetic transition temperatures, including the Curie temperature, are influenced by both B-site vacancies and double-exchange interaction between Mn^（3＋） and Mn^（4＋） cations. A core-shell model is proposed for vacancies located on the surfaces of the crystal particles. As an application, the magnetic moment angle θ（ij） between Mn^（3＋） and Mn^（4＋） cations on the surface, which decreases with decreasing vacancy content, can be obtained.