Influence of molecular structure on rheological properties of polyethylenes I. Creep recovery measurements in shear

Elastic properties of melts of a long-chain branched low density polyethylene (LDPE) with a broad molecular mass distribution and a short-chain branched linear low-density polyethylene (LLDPE) with a more narrow molecular mass distribution were investigated by creep recovery measurements in shear. The results obtained by means of a magnetic bearing torsional creep apparatus in the linear-viscoelastic region, showed that the steady state recoverable compliance of the LLDPE is greater by a factor of two than that of the LDPE. In the short-time region up to 1000 s, however, the time-dependent recoverable compliance of the LDPE is higher than that of the LLDPE. The retardation times for the LLDPE are considerably longer than for the LDPE. For the LDPE the temperature dependence of the entanglement transition is consistent with that of the terminal zone of the creep compliance. The activation energy of 58 kJ/mole lies in the typical range for long-chain branched polyethylenes. in the case of the LLDPE the creep compliances can be shifted to give a mastercurve with an activation energy of 34 kJ/mole, whereas the recoverable compliances do not follow the time-temperature superposition principle. The molecular characterization using TREF showed that the LLDPE has a bimodal branching structure. In addition to a short-chain branched component, a low percentage of a linear constituent with high molecular mass was found. It is postulated that this linear component forms a dispersed phase in the matrix of the short-chain branched constituent. The resulting interfacial tension could be the reason for the long retardation times, the high steady state recoverable compliance and the fact that the time-temperature superposition principle is not fulfilled in the case of the LLDPE investigated.