Coarsening kinetics in demixed lead borate melts

J Chem Phys. 2013 Jun 14;138(22):224502. doi: 10.1063/1.4808162.

Abstract

Lead borate melts have been demixed at temperatures in range from 723 to 773 K for times up to 20 h. It is found that increasing time and temperature lead to characteristic changes in the size distribution of boron trioxide drops in the lead-rich glassy matrix (<80.7 mol. % B2O3). The increase of the mean drop size with annealing time followed the cube root time dependence of diffusion controlled coarsening. The diffusivity of the coarsening process was determined using liquid-liquid interfacial energy associated with drop deformation in glass specimens subjected to uniaxial compression. Diffusion coefficients of coarsening were found to match with those of (207)Pb and (18)O tracer ions in the lead borate system but differ up to four orders of magnitude from the Eyring diffusivity and by a factor of ≈7 from the activation energy of viscous flow. The results indicate that coarsening in demixed lead borate melts is most likely controlled by the short range dynamics of the interaction between lead cations and BO4 units, which are decoupled from the time scales of cooperative rearrangements of the glassy network at T < 1.1 Tg.