The devitrification of the 45S5 variety of bioactive glasses (BGs) in relation to phase separation is studied with scanning electron microscopy, X-ray powder diffraction, Fourier transform infrared spectroscopy, differential scanning calorimetry and positron annihilation lifetime spectroscopy techniques. It is shown that the type of phase separation (such as spinodal vs. droplet-like) has a pronounced effect on the activation energy of viscous flow and crystallization, the onset temperature of crystallization and the void size distribution at the nanoscale. Generally, the Johnson-Mehl-Avrami (JMA) relation does not describe crystallization kinetics in bulk 45S5 BG. However, for powder samples (<300 μm) the difference in crystallization kinetics, which is surface-driven for the two kinds of glasses, becomes much smaller, and can be described with the JMA relation under some circumstances.
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