Toughness mechanism in semi-crystalline polymer blends: I. High-density polyethylene toughened with rubbers

Abstract

The mechanical response of rubber-modified high density polyethylene (HDPE) was investigated. The rubbers were either ethylene–propylene copolymers (EPDM) or ethylene–octene copolymers (EOR), blended into HDPE at volume fractions of up to 0.22. These rubbers were in the form of finely dispersed spherical inclusions with sizes well below 1 μm. The incorporation of rubber into HDPE does not substantially change its crystallinity, but produces special forms of preferential crystallization around the rubber particles. The notch toughness of the rubber-modified HDPE increases by more than 16-fold as a result. The single parameter, controlling the notch toughness of these blends was found to be the matrix ligament thickness between rubber inclusions. When this thickness is above a certain critical value, the notch toughness of the material remains as low as that of the unmodified HDPE. When the average ligament thickness is less than the critical value a dramatic toughness jump results. The critical ligament thickness for the HDPE–rubber systems was found to be around 0.6 μm, independent of the type of the rubber used. The sharp toughness threshold in the rubber-modified HDPEs results from a specific micro-morphology of the crystalline component of HDPE surrounding the rubber particles. The PE crystallites of approximately 0.3 μm length perpendicular to the interface are primarily oriented with their (100) planes parallel to the particle interfaces. Material of this constitution has an anisotropic plastic resistance of only about half that of randomly oriented crystallites. Thus, when the interparticle ligaments of PE are less than 0.6 μm in thickness the specially oriented crystalline layers overlap, and percolate through the blend, resulting in overall plastic resistance levels well under that which results in notch brittle behaviour, once rubbery particles cavitate in response to the deformation-induced internal negative pressure. This renders ineffective the usual strength-limiting microstructural flaws and results in superior toughness at impact strain rates.