No abstract

A series of nanocomposites prepared by melt‐blending of cloisite‐based organoclays with poly(ethylene‐vinylacetate) (EVA) and neutralized poly (ethylene‐methacrylic acid) (EMA) copolymers were investigated via DSC, small‐angle X‐ray scattering (SAXS), and rheological techniques. SAXS results indicated partial clay exfoliation in all samples. In both EMA and EVA systems, the nominal melting temperature Tm and bulk crystallinity are not significantly affected by the presence of organoclays, suggesting that clay particles are predominantly confined in the amorphous phase. In rheological measurements (above Tm), the EVA‐clay system demonstrated a solid‐like rheological behavior under the small‐strain oscillatory shear, yet it was able to yield and flow under a steady shear, which is the characteristic of physical crosslinking. In contrast, the EMA‐clay system exhibited a melt‐like rheological behavior, where the influence of organoclay on the thermorheological behavior of the EMA composite was quite minimal. We propose that the carbonyl groups of vinylacetate in EVA interact with the clay surface, resulting in a strong physically crosslinking like interaction in the melt. On the other hand, the interaction between EMA and clay is weak because of repulsion between carboxyl anions and negatively charged clay surface.

Dynamic secondary ion mass spectrometry (DSIMS) measurements were performed to measure the effects of functionlized organosilicate clay (Cloisite 6A) on the tracer diffusion coefficient, D, in polystyrene (PS) and poly(methyl methacrylate) (PMMA) matrices. The results indicate that D is unaffected by the addition of 5% (by volume) of PS and is reduced by a factor of 3 with the addition of the same volume fraction in a PMMA matrix. The same ratio was also obtained for the extrapolated zero shear rate viscosity of PS and PMMA melt-mixed composites with the same volume fraction of clay. DSIMS was also used to measure the mobility of the clay platelets, which was found to be much lower than the polymer chains in both matrices. Examination of the sample morphology with scanning force and transmission electron microscopy indicated that in contrast to melt mixing, spin casting produced a large degree of exfoliation in both PS and PMMA matrices. Hence the difference in the dynamics in the presence of clay was ascribed to preferential interactions between the PMMA polymer and the platelet surface, rather than the extent of exfoliation.

No abstract