The Relaxation Distribution Function of Polyisobutylene in the Transition from Rubber-Like to Glass-Like Behavior

Abstract

The steady flow viscosity of a sample of polyisobutylene of viscosity‐average molecular weight 1.35 million, distributed by the National Bureau of Standards, has been measured from 15° to 100°C. Its logarithm is a linear function of 1/T². Application of the method of reduced variables to dynamic mechanical data from −45° to 100°, previously reported for this polyisobutylene, yields composite curves reduced to 25°C for the real and imaginary parts of the complex compliance and complex shear modulus; the real part of the complex dynamic viscosity; and the mechanical loss tangent. The latter exhibits a broad and peculiarly asymmetric maximum. The reduced time scale extends from 1 to 10⁻⁹ sec. The reduction factors a_T obtained in this way are slightly higher than those derived either from the viscosity or from stress relaxation measurements of Tobolsky and associates. The distribution functions of relaxation and retardation times have been calculated by second approximation methods and their detailed shapes are defined in the transition region between rubber‐like and glass‐like behavior. The relaxation distribution function is compared with the idealized distribution of Tobolsky.