Variation of Avrami parameter during non-isothermal surface crystallization of glass powders with different sizes

The influence of grain size on the surface crystallization kinetics is investigated by non-isothermal Differential Thermal Analysis and Scanning Electron Microscopy. For this purpose, different powder fractions of a model glass forming diopside via surface crystallization and crystallization induced porosity, are used. The activation energy of crystallization, EC, is determined from Kissinger plot, and the Avrami parameter, m, is estimated by both Ozawa and of Augis–Bennett methods. The values of EC decrease from 530 to 300 kJ/mol when grain size increases. Simultaneously, the m value drops from 2.5 to 1.3. This result contradicts to the widespread fallacy that the reaction order should be equal to one in the case of surface crystallization. During the initial stage of surface crystallization three dimensional growth takes place, a fact confirmed by the SEM investigations. Later on, one dimensional growth inwards the grain is observed, leading to the reaction order changes from 3 to 1.

► The Avrami parameter at surface crystallization increases with the decreasing of the grain size.
► In the beginning of crystallization and in fine particles the crystal growth is three-dimensional.
► Contrary, in the larger particles dendrite-like crystals with a significant anisotropy are formed.
► The formation of crystallization porosity additionally increases the value of Avrami parameter.