Structure and thermal stability of polyethylene nanolayers

Confinement of the crystallizable polymer chain to the lamellar size scale is expected to affect nucleation and growth habit to the extent that new crystalline structures might be created. In this study, films with hundreds of extremely thin layers of high density polyethylene (HDPE) sandwiched between thicker polystyrene (PS) layers were fabricated by ‘forced assembly’ using layer multiplying coextrusion. Thermal analysis showed that as the HDPE layers became thinner, the crystallinity decreased from about 60% to almost 30%. Decreased crystallinity was accompanied by a change in morphology from banded discoids in HDPE microlayers (>100 nm) to long bundles of edge-on lamellae in HDPE nanolayers (<100 nm) as shown by atomic force microscopy and wide angle X-ray diffraction. Changes in crystallinity and crystalline morphology were responsible for an increase in oxygen permeability of the HDPE layer by a factor of 3 as the layer thickness decreased from 1.1 μm to 20 nm. It is inherent to the concept of forced assembly that nanolayers may not be stable when they are heated into the melt state. Heating films above the melting temperature of HDPE resulted in fractionated crystallization as indicated by two crystallization exotherms in thermograms. The lower temperature exotherm at 80 °C was identified with homogeneous nucleation. The droplets responsible for fractionated crystallization resulted from instability and breakup of the layers when they were taken into the melt. The number of nanodroplets formed by breakup of nanolayers was large enough that the majority did not contain an active heterogeneity and crystallization occurred primarily by homogeneous nucleation.