Non-linear stress-orientation behavior of flexible chain polymers under fast elongational flow

Abstract

Closed-form analytical formulas are proposed for non-linear stress-orientation relation valid in the entire range of tensile stresses, intermediate and high, basing on the inverse Langevin chain statistics. Tensile force and orientation characteristics for single, flexible chain macromolecule are reconsidered in a closed-form Padè approximation of the inverse Langevin function in the entire range of chain extensions, as well as the dynamics of molecular deformation and orientation for systems of chains subjected to uniaxial elongational flow. Average stress and orientation tensors, not collinear in the non-linear range, as well as the tensile stress and axial orientation factor of the chain segments in the system are calculated. For the intermediate tensile stresses, the closed-form formula is derived in the first non-Gaussian term approximation of the inverse Langevin function with the assumption of dominating longitudinal elongation of the chains. The high-stress non-linearity formula is derived with the Padè and Peterlin modulus approximations and aligned chain end-to-end vectors by the flow. Both formulas are validated by exact numerical calculations without the assumptions and influence of the approximations is estimated. Ranges of applicability of the formulas are illustrated and examples of their application are presented.