Properties of amorphous and crystallizable hydrocarbon polymers. I. Melt rheology of fractions of linear polyethylene

The dynamic moduli G′(ω) and G″(ω) for two groups of linear polyethylene fractions (reported M _w/M _n < 1.2) were measured in the melt state using the eccentric rotating disk method. Values of zero shear viscosity η₀ were obtained and compared with published results on similar fractions. Molecular weight data were converted to a common basis through intrinsic viscosities in trichlorobenzene (TCB) at 135°C. With recent data on M _w (light scattering) vs. η]_TCB, for linear polyethylene, the relationship at 190°C, η₀ = 3.40 × 10^?14(M _w)^3.60, was obtained. The flow activation energy E_a was 6.4 kcal (T = 140–195°C). The plateau modulus G at 190°C was determined from the area under the loss modulus peak in one high-molecular-weight sample. The value obtained, G = 1.5₈ × 10⁷ dyn/cm², corresponds to an apparent molecular weight between entanglements of 1850. The storage compliance J′(ω) becomes anomalously large at low frequencies. The recoverable compliance J could not be determined for any of the fractions.