Photon correlation spectroscopy of bulk poly(n‐hexyl methacrylate) near the glass transition

Slowly relaxing longitudinal density fluctuations in an optically perfect sample of bulk poly(n-hexyl methacrylate) (PHMA) have been studied by photon correlation spectroscopy in the temperature range 10-36°C. The glass transition temperature for this sample was in the temperature range 10-36°C. The glass transition temperature for this sample was measured to be T g = -3°C by differential scanning calorimetry. The optical purity of the sample was verified by Rayleigh Brillouin spectroscopy and the Landau Placzek ratio was observed to be 2.3 at 25°C. Light-scattering relaxation functions were obtained over the time range 10 6 -l s. The shape of the relaxation functions broadened as the temperature was lowered towards the glass transition. Quantitative analysis of the results was carried out using the Kohlrausch-Williams-Watts (KWW) function to obtain average relaxation times , and width parameters, β. The width parameter decreased from 0.43 to 0.21 over the temperature interval, as suggested by visual inspection. Average relaxation times shifted with temperature in a manner consistent with previous mechanical studies of the primary glass-rubber relaxation in PHMA. The relaxation functions were also analyzed in terms of a distribution of relaxation rates, G(T). The calculated distributions were unimodal at all temperatures. The average relaxation times obtained from G(T) were in agreement with the KWW analysis, and the shape of the distribution broadened as the sample was cooled. The rate at which G(T) displayed a maximum correlated well with the corresponding frequency of maximum dielectric loss for PHMA. The temperature dependence of these two quantities could be reproduced with an Arrhenius activation energy of 21 Kcal/mol. A consistent picture of the molecular dynamics of PHMA near the glass transition requires a strong secondary relaxation process with a different temperature dependence from the primary glass-rubber relaxation. The present results suggest that the behavior of PHMA is similar to the other poly(alkyl methacrylates).