The influence of branch length on the deformation and microstructure of polyethylene

The length and number of side chain branches have a profound influence on the microstructure and physical properties of polyethylene (PE). For a series of linear PE copolymers: environmental stress cracking resistance (ESCR), melting points, creep resistance and modulus, and equilibrium spherulite size were all found to increase with increasing branch length (methyl to hexyl) at a given density and molecular weight. It is proposed that (at a fixed molecular weight) branch length and branch concentration determine spherulite size and, consequently, spherulitic boundary areas, in which the dry crazing/voiding occurs during the incubation period of environmental stress cracking (ESC). At a fixed density, decreased spherulite size contributes to greater spherulite boundary slip and increased creep at low (less than 2 MPa) stresses.