Effects of mechanical constraint on thermally induced reverse martensitic transformation in granular shape memory ceramic packings

Zirconia-based ceramics exhibit shape memory and superelastic effects based on the reversible martensitic transformation between tetragonal and monoclinic crystal structures. In the form of granular packings, these shape memory ceramics can be scaled up for bulk applications despite their intrinsic brittleness, while displaying drastically different transformation characteristics than the monolithic counterparts. Here, we present a comparative study to understand the thermally induced reverse martensitic transformation in granular packings and the influence of mechanical constraints. This study employs ZrO2-CeO2 shape memory ceramics of the same composition but with different degrees of mechanical constraints. The explored material forms include loose and jammed granular packings, themselves consisting of polycrystalline or single crystal particles, as well as sintered bulk polycrystals. Except for the latter, no endothermic peak is observed in the heat flow measurement of the reverse transformation process. This unusual behavior is shown to stem from the weak inter-particle mechanical constraint and the transformation heterogeneity among individual particles, rather than stress relaxation or particle rearrangement. To compare, conspicuous endothermic peaks only appear in bursting-type transformations under a strong mechanical constraint. For granular packings, the intra-particle mechanical constraint does not affect the presence of any endothermic peaks in thermal reversion but can influence the austenite start temperature.