Abstract: | Low-angle electron diffraction (LAED) was used to study the microstructure of crazes produced at different temperatures T and strain rates in thin films of monodisperse polystyrene (PS). At a slow strain rate of 4.1 × 10?6 s?1 both the fibril diameter D and the fibril spacing D0 of crazes in 1800k molecular weight PS remained constant with temperature up to T ≈ 70°C and then sharply increased as T approaches Tg. At a higher strain rate of ~ 10?2 s?1, both D and D0 increase only slightly with T. The values of D and D0 over a range of temperature are in very good agreement with those values obtained in bulk samples using small-angle x-ray scattering. The crazing stress was measured as a function of temperature in the thin films of the 1800k molecular weight PS strained at the same slow strain rate used for the LAED measurements. These measurements were analyzed using a simple model of craze growth to reveal the temperature and strain rate dependence of the craze surface energy Γ. At room temperature Γ ≈ 0.076 J/m2 (versus Γ ≈ 0.087 J/m2 predicted) and was observed to remain constant up to T ≈ 70°C and then decrease by approximately a factor of two at T = 90°C. This decrease in Γ is believed to result from chain disentanglement to form fibril surfaces at sufficiently high temperatures and occurs in the same temperature range in which the craze fibril extension ratio λ was observed to increase. |