Length scale of heterogeneities in glassy propylene carbonate probed by oxygen diffusion.
A new method using the quenching of guest molecule phosphorescence by molecular oxygen is proposed for determination of heterogeneity size in glassy matrixes. The method is based on the high sensitivity of the diffusion of oxygen molecules to spatial density fluctuations. Phenanthrene phosphorescence decay was monitored at different concentrations of molecular oxygen in propylene carbonate below T(g). An unusual dependence of the phosphorescence decay on oxygen concentration was observed: an increase in the concentration leads to anomalously large increase in the quenching rate at short times. This dependence is considered to be caused by matrix heterogeneity. To describe the phosphorescence decay, we use a model of glass as a heterogeneous medium where oxygen jump rates are spatially correlated. The length of spatial correlation for the jump rates is taken as heterogeneity size. Using the model, the value of 1.5+/-0.5 nm was obtained for the size of structural heterogeneities in glassy propylene carbonate. The dispersion of barriers for oxygen jumps is estimated to be 4+/-1 kJ/mole and the average barrier energy is found to be 50 kJ/mole.
Syutkin
V M
VM
Institute of Chemical Kinetics and Combustion, Novosibirsk 630090, Russian Federation. syutkin@kinetics.nsc.ru
Vyazovkin
V L
VL
Korolev
V V
VV
Grebenkin
S Yu
SY