On morphology and polymer blends: polystyrene and polyethylene

Abstract

This paper compares the morphologies observed in two blend systems, namely blends of isotactic and atactic polystyrene, and blends of linear and branched polyethylene. Crystallization of isotactic polystyrene at high temperatures ( ≳ 200°C) produces immature sheaf-like aggregates of lamellae. Addition of atactic polymer results in modified morphologies that are based upon bundles of lamellae, separated from one another by non-crystalline regions. At high atactic contents sheaf-like objects are no longer observed, crystallization occurring to give structures that are better described as multilayered crystals. At temperatures below ∼ 200°C, mature spherulites develop. Addition of atactic polystyrene again results in morphologies in which lamellae are grouped into stacks separated from one another by non-crystalline regions. Again, at high atactic contents a less complex (sheaf-like) overall morphology is observed. In all the above microstructures, lamellae exhibit an inherently hexagonal habit. However, at lower crystallization temperatures observations suggest that lateral lamellar growth may be restricted. Isothermal crystallization of linear polyethylene at temperatures above ∼ 125°C results in morphologies in which a complex lamellar hierarchy exists, as a consequence of molecular fractionation during crystallization. Addition of branched polyethylene, which is unable to crystallize at these temperatures, suppresses fractionation such that the resulting morphologies may be described in terms of only one dominant and one subsidiary lamellar population. When viewed along the crystallographic b axis, dominant lamellae appear planar or mildly S-shaped in profile, whilst subsidiary lamellae are planar and inclined at an angle of ∼25° to the local dominant population. In blends with a high branched content, apparently non-crystalline regions can be seen between individual lamellae. Thus, in polyethylene blends, the non-crystallizing component is located between individual lamellae rather than between bundles of lamellae, as is the case in polystyrene. This difference arises from the parallel growth of dominant and subsidiary lamellae in polystyrene as opposed to the inclined development of subsidiaries with respect to the dominant lamellae in the polyethylene blends. In all the samples studied, spherulite growth occurs via a dominant/ subsidiary mechanism.