Chlorination of Ball-milled Zirconia

The effects of mechanochemical treatment of monoclinic zirconia in high energy planetary ball mill on its phase transformation were investigated. The mechanical treatment in ball mill reduces the grain size, increases microstrain, and causes phase transition to metastable nanostructured tetragonal and cubic phases. XRD and TEM results show considerable amounts of amorphous phase during ball milling. Surface area measurements by BET method over long milling times reveal that ZrO2 particles are agglomerated with an amorphous phase as a binder. The mechanical treatment increases the reactivity of zirconia in chlorine gas. Annealing of ball milled zirconia in the chlorine atmosphere produces oxygen vacancy in zirconia (ZrO2-x) and causes the amorphous phase to be crystallized and to change into cubic and tetragonal phases. The chlorine atmosphere increases the stability temperatures of cubic and tetragonal phases to 800°C and 1000°C, respectively. In this situation, the energy of grain boundary and oxygen vacancy play important roles in the stability of tetragonal and cubic phases.