Impact of nonstoichiometry on the mechanical properties and thermal conductivity of gadolinium zirconate ceramics

Low elastic properties, high hardness, and low thermal conductivity are desirable for a rare-earth zirconate thermal barrier coating material. Realizing nonstoichiometry is a significant way to improve the elastic properties, hardness and thermal conductivity of rare-earth zirconate to further meet the requirements of thermal barrier coating materials, nonstoichiometric Gd2-xZr2+xO7+0.5x (x = 0, ±0.125, and ±0.25) was studied by first-principles calculations first and then verified by the solid-state reaction methods. Calculations revealed that excess Gd3+ and Zr4+ decrease the elastic modulus, sound velocity, and Debye temperature of Gd2Zr2O7, and increase its ductility. The elastic properties of the material exhibit significant anisotropy, which further increases with increasing Gd3+ and Zr4+ contents, resulting from lattice distortion caused by excess Gd3+ and Zr4+ entering the lattice. The hardness of Gd2Zr2O7 increases with a moderate excess of Zr4+, while it decreases with an excess of Zr4+ and Gd3+. In addition, with the disordered occupation of lattice atoms, the anharmonicity of lattice waves is increased, and phonon scattering is enhanced as the concentrations of Gd3+ and Zr4+ increase, resulting in the reduction of the phonon thermal conductivity. Moreover, Zr4+ is more conducive to the decrease in the thermal conductivity. The experimental consequences match well with the calculation consequences. This work is expected to provide support for improving mechanical properties and thermal conductivity of rare-earth zirconate materials.