A quantitative microscopic view on the gas‐phase‐dependent phase transformation from tetragonal to monoclinic ZrO2

ZrO2 is a versatile material with diverse applications, including structural ceramics, sensors, and catalysts. The properties of ZrO2 are largely determined by its crystal structure, which is temperature‐ and atmosphere dependent. Thus, this work focuses on a quantitative analysis of the temperature‐ and gas atmosphere‐dependent phase transformation of tetragonal t‐ZrO2 into monoclinic m‐ZrO2 during heating–cooling cycles from room temperature to 1273 K. Synchrotron‐based in situ X‐ray diffraction (XRD) studies in gas atmospheres of different reduction strengths, namely, 5 vol% H2/Ar, He, CO2, and air, revealed a stabilizing effect of inert and reductive environments, directly yielding different temperature onsets in the phase transformation during cooling (i.e., 435, 510, 710, and 793 K for 5 vol% H2/Ar, He, CO2, and air, respectively). Rietveld refinement shows a direct influence of the atmosphere on grain size, unit cell, and weight fraction of both polymorphs in the product composite matrix. The tetragonal‐to‐monoclinic (t–m) phase transformation is suppressed in the sample heated only up to ∼850 K, independent of the gas atmosphere. The results of ex situ XRD, transmission electron microscopic, electron paramagnetic resonance, and oxygen titration experiments confirmed that the phase transformation is accompanied by a change in the crystallite/particle size and the amount of lattice defects (i.e., oxygen vacancy). Due to the different onset temperatures, a complex interplay between kinetic limitations of phase transformation and grain sintering yields different pathways of the phase transformation and, eventually, very different final crystallite sizes of both t‐ZrO2 and m‐ZrO2.