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A series of nanocomposites prepared by melt-blending of Cloisite organoclays with ethylene-co-vinyl acetate (EVA) and ethylene-co-methyl acrylate (EMA) copolymers were investigated by using small-angle X-ray scattering (SAXS), wide-angle X-ray diffraction (WAXD), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and rheological techniques. SAXS and TEM results confirmed mixed clay intercalation and exfoliation in all tested nanocomposites. The melting temperature, Tm, and crystalline structure (orthorhombic) in EMA and EVA were not significantly affected by the presence of organoclays, indicating that the clay particles were predominantly confined to the amorphous phase. Rheological properties above Tm were very similar in EVA and EMA nanocomposites. Both systems exhibited pseudo-solid rheological behavior in small-strain oscillatory shear experiments, yet they could yield and flow under a steady shear, which is characteristic of physical gelation. The pseudo-solid rheological behavior in EVA and EMA nanocomposites becomes more pronounced at higher contents of organoclay and at higher temperatures. SAXS results indicated that the silicate gallery spacings (d), intercalated by EVA and EMA chains, decreased with increasing temperature. This can be attributed to the reduced compatibility between organoclay and polymer (i.e., a LCST-type phase behavior). The unusual rheological properties of the nanocomposites at high temperatures were probably due to the formation of a 3D network of clay tactoids. Novel analytic models were proposed to describe rheological data from meltlike to gellike behaviors in EVA− and EMA−organoclay nanocomposites.

The limited thermal stability of alkylammonium cations intercalated into smectite minerals (e.g., montmorillonite, MMT) and the processing instability of some polymers [polyamide-6 (PA-6) and polystyrene (PS)] in the presence of nanodispersed MMT have motivated the development of improved organophillic treatments for layered silicates. Success in this regard should enable the preparation of polymer/layered silicate nanocomposites from thermoplastic polymers that require high melt-processing temperatures or long residence times under high shear and from thermoset resins with high cure temperatures. Our efforts to address some of these issues focus on the use of new thermally stable imidazolium-treated layered silicates for the preparation of nanocomposites. Several trialkylimidazolium salt derivatives were prepared with propyl, butyl, decyl, and hexadecyl alkyl chains attached to the imidazolium through one of the nitrogens. These imidazolium salts were used to prepare the corresponding treated layered silicates. We report here that the use of 1-alkyl-2,3-dimethylimidazolium salts to replace the sodium in natural MMT gives organophillic MMT with a 100 °C improvement in thermal stability (in N2) as compared to the alkylammonium-treated MMT. The use of 1-alkyl-2,3-dimethylimidazolium salt in fluorinated synthetic mica (FSM) also gives a 100 °C improvement in thermal stability. The use of 1,2-dimethyl-3-hexadecylimidazolium-treated MMT gives an exfoliated PA-6 nanocomposite and, depending on processing conditions, either a partially exfoliated or an intercalated polystyrene nanocomposite.

Our continuing study of the mechanism of flammability reduction of polymer−layered-silicate nanocomposites has yielded results for polypropylene-graft-maleic anhydride and polystyrene−layered-silicate nanocomposites using montmorillonite and fluorohectorite. Cone calorimetry was used to measure the heat release rate and other flammability properties of the nanocomposites, under well-controlled combustion conditions. Both the polymer−layered-silicate nanocomposites and the combustion residues were studied by transmission electron microscopy and X-ray diffraction. We have found evidence for a common mechanism of flammability reduction. We also found that the type of layered silicate, nanodispersion, and processing degradation have an influence on the flammability reduction.