Various features of melt strain hardening of polymeric materials in uniaxial extension and their relation to molecular structure: review of experimental results and their interpretation

Strain hardening of polymer melts is able to improve the uniformity of items in processing operations with elongational deformation. Of particular interest in this aspect is the dependence of strain hardening on elongational rate. In its first part, the paper presents a review on melt strain hardening obtained in uniaxial extensional experiments. Its dependence on elongational rate is of particular interest insofar as besides non-strain-hardening polymers, strain hardening increasing or decreasing with rate can be found. Results on linear polymers like polystyrene (PS), polypropylene (PP), high-density polyethylene (HDPE), and linear low-density polylethylene (LLDPE) in dependence on molecular parameters are discussed, as well as those of various blends. Particularly interesting are the strain-hardening features of certain HDPEs and LLDPEs, which could be understood by the assumption of a non-homogeneous chemical structure of the samples. Blends of various compositions of a linear and a long-chain branched PP throw light on the complex relation between branching structure and rate dependence of strain hardening. In the second part of the paper, the different strain-hardening behavior of linear polymers is interpreted by assessing the Rouse times as decisive physical quantity. For blends of certain linear species like HDPE and PP and those of linear with long-chain branched polymers, the existence of separate phases in the molten state is postulated. The assumptions are discussed in the light of the various studies on miscibility of linear and branched polyolefins from the literature. Graphical Abstract