We present an experimental investigation on the creep behavior of molten polypropylene organically modified clay nanocomposites. The nanocomposite hybrids were prepared by melt intercalation in an extruder in the presence or absence of a compatibilizer. They were subsequently annealed and simultaneously characterized using high-temperature wide-angle X-ray diffraction and controlled stress rheometry. The creep resistance of compatibilized hybrids was significantly higher than that of uncompatibilized hybrids and also increased with annealing time. The microstructure of the nanocomposites as investigated by TEM and high-temperature WAXD showed the presence of clay crystallites dispersed within the polymer matrix. The creep data together with the microstructural investigation are probably indicative of a small amount of exfoliation from the edges of the clay crystallites during extrusion and annealing. The zero shear viscosity of the compatibilized nanocomposites containing greater than 3 wt % clay was at least 3 orders of magnitude higher than that of matrix resin and the uncompatibilized hybrids. Importantly, the large increase in zero shear viscosity was not accompanied by any increase in the flow activation energy compared to the matrix polymer. The compatibilized hybrids also showed an apparent “yield” behavior. We conclude that the solidlike rheological response of the molten nanocomposite originates from large frictional interactions of the clay crystallites. Compatibilizer has a significant influence in modifying the rheological behavior.

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Polyethylene–clay nanocomposites were synthesized by in situ polymerization with 2,6‐bis[1‐(2,6‐diisopropylphenylimino)ethyl] pyridine iron(II) dichloride supported on a modified montmorillonite clay pretreated with methylaluminoxane (MAO). The catalysts and the obtained nanocomposites were examined with wide‐angle X‐ray scattering. The exfoliation of the clay was further established by transmission electron microscopy. Upon the treatment of the clay with MAO, there was an increase in the d‐spacing of the clay galleries. No further increase in the d‐spacing of the galleries was observed with the iron catalyst supported on the MAO‐treated clay. The catalyst activity for ethylene polymerization was independent of the Al/Fe ratio. The exfoliation of the clay inside the polymer matrix depended on various parameters, such as the clay content, catalyst content, and Al/Fe ratio. The crystallinity percentage and crystallite size of the nanocomposites were affected by the degree of exfoliation of the clay. Moreover, when ethylene was polymerized with a mixture of the homogeneous iron(II) catalyst and clay, the degree of exfoliation was significantly lower than when the polymerization was performed with a preformed clay‐supported catalyst. This observation suggested that in the supported catalyst, at least some of the active centers resided within the galleries of the clay. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 304–318, 2005

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