The mechanism of thermal transformation hysteresis in ZrO2-CeO2 shape-memory ceramics

ABSTRACT Hysteresis is an important phase transformation property to understand and control in shape-memory materials. While a detailed understanding of hysteresis has been developed in shape-memory alloys (SMAs), it is far less understood in emerging shape-memory ceramics (SMCs). Here, we systematically study thermal hysteresis of the tetragonal-monoclinic martensitic transformation in ZrO2-CeO2 SMCs. We present calorimetry measurements of thermal hysteresis, which reveal a non-monotonic trend with CeO2 content as well as significant rate dependence, and correlate these findings with the transformation crystallography measured by in situ X-ray diffraction. We quantitatively analyze these results in the framework of martensite nucleation theory and conclude that the initial decrease in hysteresis with CeO2 content can be attributed to improving interface compatibility (λ2) for coherent nucleation whereas the sharp increase in hysteresis at higher CeO2 contents (below temperatures of ~773 K) is a result of interface friction consistent with thermally-activated interactions with the Peierls barrier of the crystal. Our analysis gives an activation energy of ~136 kJ/mol, which is consistent with previously reported activation energies of isothermal transformation in these materials. These findings clarify contradicting reports in the ZrO2 literature and confirm that the same controlling factors of hysteresis in SMAs, namely λ2 and thermal friction, are also operative in SMCs.