Study of molecular deformation mechanisms in the glassy state. I. Temperature effect on stress-birefringence and strain-birefringence responses of poly(methyl methacrylate)

In order to gain better understanding of the molecular deformation processes occurring in poly-(methyl methacrylate), a series of studies was carried out in uniaxial tension on the simultaneous stress and birefringence response in both constant-strain-rate and stress relaxation experiments. The former covered the temperature range ?120 to 75°C and the latter 0 to 90°C. Three deformation mechanisms, i.e., (i) change in intermolecular distance, (ii) distortion of the conformation of the COOCH₃ group from its thermal equilibrium state, and (iii) orientation of main-chain segments, are invoked to interpret the experimental results. It is concluded that, in the temperature range from ?120 to 75°C and possibly at higher temperatures as well, the polymer chains deform in the small-strain region by an orientation of those chain segments having lower potential-energy barriers to conformational changes and straining those chain segments having higher potential-energy barriers. Subsequent chain orientation of the already strained segments occur in the higher strain regions. Changes in intermolecular distances occur over the entire temperature range from ?120 to 90°C, but their magnitude decreases gradually as the temperature increases from ?40 to 40°C and then decreases sharply for temperatures above 40°C. Strain-induced distortion of the conformation of the COOCH₃ group may involve only rotation of the OCH₃ group around the C? O bond rather than rotation of the entire ester group itself.