Energy elastic effects and the concept of temperature in flowing polymeric liquids

The incorporation of energy elastic effects in the modeling of flowing polymeric liquids is discussed. Since conformational energetic effects are determined by structural features much smaller than the end-to-end vector of the polymer chains, commonly employed single conformation tensor models are insufficient to describe energy elastic effects. The need for a local structural variable is substantiated by studying a microscopic toy model with energetic effects in the setting of a generalized canonical ensemble. In order to examine the dynamics of flowing polymeric liquids with energy elastic effects, a thermodynamically admissible set of evolution equations is presented that accounts for the evolution of the microstructure in terms of a slow tensor, as well as a fast, local scalar variable. It is demonstrated that the temperature used in the definition of the heat flux is directly related to the Lagrange multiplier of the microscopic energy in the generalized canonical partition function. The temperature equation is discussed with respect to, first, the dependence of the heat capacity on the polymer conformation and, second, the possibility to measure experimentally the effects of the conformational energ

Simultaneous stress and birefringence measurements during uniaxial elongation of polystyrene melts with narrow molecular weight distribution

Tensile stress and flow-induced birefringence have been measured during uniaxial elongation at a constant strain rate of two polystyrene melts with narrow molecular weight distribution. For both melts, the stress- optical rule (SOR) is found to be fulfilled upto a critical stress of 2.7MPa, independent of strain rate and temperature. Estimation of the Rouse times of the melts, from both the zero-shear viscosity and the dynamic-shear moduli at high frequency, shows that the violation of the SOR occurs when the strain rate multiplied by the Rouse time of the melt exceeds by approximately 3. The presented results indicate that in contrast to current predictions of molecular theories, the regime of extensional thinning observed by Bach et al. (2003) extends well beyond the onset of failure of the SOR, and therefore the onset of chain stretch in the non-Gaussian regim

Energy elastic effects and the concept of temperature in flowing polymeric liquids

ISSN:0035-4511ISSN:1435-152

Simultaneous stress and birefringence measurements during uniaxial elongation of polystyrene melts with narrow molecular weight distribution

ISSN:0035-4511ISSN:1435-152