Photoviscoelastic behavior of amorphous polymers during transition from the glassy to rubbery state

Abstract
Tensile stress‐relaxation experiments with simultaneous measurements of Young's relaxation modulus, E, and the strain‐optical coefficient, Cϵ, were performed on two amorphous polymers—polystyrene (PS) and polycarbonate (PC)—over a wide range of temperatures and times. Master curves of these material functions were obtained via the time‐temperature superposition principle. The value of Cϵ of PS is positive in the glassy state at low temperature and time; then it relaxes and becomes negative and passes through a minimum in the transition zone from the glassy to rubbery state at an intermediate temperature and time and then monotonically increases with time, approaching zero at a large time. The stress‐optical coefficient of PS is calculated from the value of Cϵ. It is positive at low temperature and time, decreases, passes through zero, becomes negative with increasing temperature and time in the transition zone from the glassy to rubbery state, and finally reaches a constant large negative value in the rubbery state. In contrast, the value of Cϵ of PC is always positive being a constant in the glassy state and continuously relaxes to zero at high temperature and time. The value of Cσ of PC is also positive being a constant in the glassy state and increases to a constant value in the rubbery state. The obtained information on the photoelastic behavior of PS and PC is useful for calculating the residual birefringence and stresses in plastic products. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2252–2262, 2001