Extension of the Concept of Intrinsic Viscosities to Arbitrary Polymer Concentration: From [η] via {η} to Intrinsic Bulkiness

The capabilities of an alternative definition of intrinsic viscosities [η] published some years ago is being studied by means of comprehensive viscometric data reported in the early days of polymer science. It introduces the generalized intrinsic viscosity {η} as the specific hydrodynamic volume at arbitrary polymer concentration c. {η} quantifies the size of the flow unit and decreases monotonously for T ≫ T g (glass transition temperature) as a function of c but passes a pronounced minimum as T approaches T g. In the limit of the pure polymer melt, {η} becomes ; this newly introduced property is termed intrinsic bulkiness, by analogy to the intrinsic viscosity, and provides noncalorimetric experimental access to T g; it also allows estimates of entanglement molecular weights based on the Newtonian flow behavior. Moreover, the molecular weight dependence of provides information on the contributions of endgroups to the flow behavior.