Optical and X-Ray Single Crystal Studies of the Monoclinic ⇌ Tetragonal Transition in ZrO2

The monoclinic ? tetragonal phase transition in ZrO₂ single crystals was studied at temperature by transmission optical microscopy and X-ray diffraction techniques. A series of timelapse photographs illustrated the relations between the events that occur during the transition. The events themselves were recognized by direct observation using a high-temperature microscope stage and by scrutiny of several high-temperature Laue photographs. During heating the monoclinic phase transforms to the tetragonal by the motion of an interface parallel to the (100) _m plane; simultaneous twinning also occurs behind the advancing interface. The tetragonal phase is usually twinned on the (1 2) _bct or ( 12) _bct plane, and the extent of twinning is influenced by the heating rate. Cooling transforms the untwinned tetragonal form into a twinned monoclinic form with the orientation of the monoclinic twins parallel to the trace of the (001) _m plane when observations are made in the (100) _m plane. Transformation of a twinned tetragonal crystal results in twins on the {110} _m and {001} _m planes. Orientation relations in the ZrO₂ transformation are: (100) _m ‖(110) _bct , 010] _m ‖001] _bct , and by the virtue of twinning, (100) _m ‖(110) _bct , 001] _m ‖001] _bct . During cooling the same topotaxial relations are maintained.