High‐density polyethylene/clay nanocomposites were elongated until breakage to investigate the effect of the mechanical stretching on the crystal‐to‐crystal transformations and their morphology. Crystalline transformations of the polymer matrix were studied via Fourier transform infrared spectroscopy, differential scanning calorimetry, and X‐ray diffraction measurements. It was concluded that the stress‐induced crystal‐to‐crystal transformations from orthorhombic structures to monoclinic and pseudohexagonal structures as well as the back‐transformation during relaxation were hindered by the presence of the clay. X‐ray diffraction studies on stretched samples showed that the mechanical stretching led from an intercalated structure to an almost exfoliated structure. These findings agreed with scanning electron micrographs, in which the beneficial effect of stretching on the exfoliation of the clay was evident. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 914–924, 2006

Syndiotactic polypropylene nanocomposites based on layered silicates in various proportions were subjected to prolonged (246 h) ultraviolet (UV)-c irradiation. Fourier transform infrared (FT-IR) spectroscopy was used in order to investigate the molecular alterations of the polymeric matrix during the UV exposure relative to the concentration of nanoclay. It was found that a significant increase of the helical conformation upon the irradiation took place as a result of scissions of the polymeric chains. In addition, a simultaneous increase in the crystallinity was verified by X-ray diffraction (XRD) measurements. Furthermore, a variety of photooxidation products were detected, among them carboxylic acids, ketones, gamma-lactones, and esters. We report in this paper the impact of the clay on the degradation mechanism of syndiotactic polypropylene mostly by the production of additional free radicals. Therefore, the relative intensities of the produced photooxidative species are affected drastically as a function of the concentration of the layered silicate present. Finally, an interaction of the carbonyl groups formed in the polymer upon irradiation with the polar groups of the layered silicates was confirmed both from infrared and UV-visible spectroscopic studies.

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