How different is mechanical activation from thermal activation?: A case study with PZN and PZN-based relaxors

Using Pb(Zn1/3Nb2/3)O3 (PZN) and PZN-based relaxor ferroelectrics, we demonstrate that the solid state reactions triggered by mechanical activation of mixed oxides can proceed via a completely different route from that in the conventional solid state reactions, where the process is controlled by one or more interfacial reactions and diffusions. Nanocrystallites of perovskite Pb(Zn1/3Nb2/3)O3 are formed in a highly activated state of mixed oxides where a degree of amorphization has taken place, followed by a steady growth with increasing degree of mechanical activation. The absence of transitional pyrochlores, such as the Pb3Nb4O13-type phases which have always been observed in the conventional solid state reactions, and the considerably low local temperature at the collision points suggest that the perovskite phase occurs via a process involving nucleation and subsequent diffusionless growth.