Probing the dynamics of instability in zeolitic materials

Zeolites collapse under modest pressure or temperature, their microporous structures transforming into glasses of conventional density. Using in situ synchrotron radiation diffraction methods we show how pressure and temperature-induced amorphization are equivalent processes and that these are mirrored by changes in the local structure of charge compensating cations. Evidence for a low density amorphous phase and a high density amorphous phase present during zeolite collapse emerges from small angle scattering experiments. Combining powder diffraction with increasing temperature or pressure, we find that the thermobaric characteristics for zeolite collapse have negative d T/d P slopes, consistent with increasing density during amorphization. However, this is not confined to a single melting curve but, instead, the regime extends over a significant region of T–P space. Moreover, zeolite amorphization involves depressurization and cavitation effects which can be used to set empirical boundaries for the stability of the low density amorphous phase. Within the region of zeolite instability the pressure or temperature of amorphization is found to be governed by the rate at which the stress is introduced—the more rapid this is, the higher the pressure or temperature the zeolite structure survives to. The temperature dependence of the rate of collapse is Arrhenian, suggesting that the initial low density amorphous phase has the characteristics of a superstrong liquid in contrast to the fragility of a conventionally melt quenched glass. Possibilities for creating 'perfect glasses' from the collapse of microporous crystals are discussed.