6533b85ffe1ef96bd12c23ff

RESEARCH PRODUCT

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

Bernhard A. Wolf

subject

chemistry.chemical_classificationMaterials sciencePolymers and PlasticsIntrinsic viscosityOrganic ChemistryFlow (psychology)Thermodynamics02 engineering and technologyFunction (mathematics)Quantum entanglementPolymer010402 general chemistry021001 nanoscience & nanotechnology01 natural sciences0104 chemical sciencesInorganic ChemistryVolume (thermodynamics)chemistryMaterials ChemistryNewtonian fluid0210 nano-technologyGlass transition

description

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 ≫ Tg (glass transition temperature) as a function of c but passes a pronounced minimum as T approaches Tg. 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 Tg; 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.

https://doi.org/10.1021/acs.macromol.9b00282