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Ionic Nano-Aggregates in Polyethylene-Based Ionomers: Comparison of Stem and Saxs Results

Semicrystalline ionomers are industrially important materials in adhesives, packaging, engineering thermoplastics, coatings, and more. The most common of these are based on poly(ethylene-ran-methacrylic acid), E/MAA random copolymers partially neutralized with various cations and produced by DuPont under the tradename Surlyn®. In 1990, Register and Cooper described the morphology of semicrystalline ionomers as crystalline lamellae separated by an amorphous polymeric matrix that contains isolated cation-rich domains. Their anomalous small angle X-ray scattering experiments are consistent with the relative electron densities associated with this “three-phase” morphological model. Despite this agreement and the commercial importance of semicrystalline ionomers, a number of fundamental issues have remained unresolved regarding both the morphology of the ionic nanoaggregates and the efficiency of aggregation. Recently, we have imaged the ionic aggregates using a scanning transmission electron microscope equipped with a field emission electron gun. This microscopy method offers the advantages of reduced phase contrast, high spatial resolution, and enhanced atomic number contrast relative to transmission electron microscopy.