Phase structure and thermal evolution in coating films and powders obtained by sol-gel process

Abstract

Powders and coatings of zirconia doped with 2.5 mole % yttria have been produced via the sol-gel route. The phase structure and subsequent thermal evolution in heating and cooling cycles have been investigated using mainly perturbed angular correlations spectroscopy. Thermal analyses and XRD as a function of temperature have also been performed to obtain complementary information. Upon heating, the amorphous gels crystallized into the tetragonal structure and showed the same hyperfine pattern and thermal behavior as observed in tetragonal zirconia obtained by the ceramic route: the two configurations of vacancies around zirconium ions denoted as t1 and t2 forms and their mutual t1 → t2 transformation. While the powder sample exhibited an incipient thermal instability above 1000 °C and underwent completely the t2 form to m–ZrO2 transition during subsequent, gradual cooling below 500 °C, the coating retained the tetragonal phase within the whole temperature range investigated. Hyperfine results suggest that the tetragonal phase stabilization is favored by the highly defective nature of the t1 form and consequently hardened by the availability of oxygen. The PAC derived activation energy for the fast diffusion of the oxygen vacancies inherent to the t2 form was determined as 0.54 ± 0.14 eV.