Classification of thermorheological complexity for linear and branched polyolefins

Thermorheological complexity in polyolefins has been reported many times but so far it has not been systematically investigated. Here, a classification of the different types of thermorheologically complex behavior is proposed, which categorize the available data in five different types and describe key characteristics. These definitions are based on polyethylene, but other polymers show similar patterns for materials with comparable branching structure. Linear materials are thermorheologically simple as long as many very long short-chain branches do not introduce phase separation. Sparsely branched materials show the most significant thermorheological complexity, with significant shape changes of rheological functions with temperature, while higher amounts of branching (such as trees or combs) reduce thermorheological complexity and increase E_a at the same time. Low-density polyethylene shows a significant modulus shift at different temperatures probably due to excessive low molecular components.