Mihai Manitiu1, Steven E. Horsch2, Rangaramanujam M. Kannan1, and Esin Gulari3. (1) Chemical Engineering, Wayne State University, 5050 Anthony Wayne Drive, Detroit, MI 48202, (2) nanoScience Engineering Corporation, Detroit, MI 48202, (3) Clemson University, Clemson, SC
Effective dispersion of the fillers in a polymer matrix and improvement of polymer-clay interactions are two key challenges in the field of nanocomposites. Supercritical carbon dioxide (scCO2) appears to be a promising processing method to achieve high degrees of clay dispersion in polymers. The rheological behavior offers insight into the ability to process nanocomposites and is sensitive to the nanoscale/mesoscale structure of the nano-clay in the host polymer matrix. We have investigated the viscoelastic response for a series of scCO2 processed PVME/clay nanocomposites with varying polymer-clay interactions and nano-clay dispersion. Our findings indicate that even in the absence of "specific" interactions the mesoscale dispersion strongly influences the viscoelastic response of the system. Specifically, the cross-over frequency shifts lower as nano-clay dispersion increases and non-terminal behavior is observed when good exfoliation is achieved. As such, it may be possible to use the cross-over frequency as an indication of the extent of dispersion. In addition, the strength of the polymer-clay interaction plays a vital role in the ability of the mesoscale structure to support deformation. In the case of "non-specific" interacting intercalated systems with clay loadings well above the percolation threshold, terminal behavior is approached over the frequency range measured even for strains smaller than 7% (i.e. no low frequency plateau is observed). Conversely, for intercalated systems with hydrogen bonding interactions or good interaction between the surface surfactant and the polymer low frequency plateaus are observed as well as large decreases in the cross-over frequency. This suggests that polymer-clay interactions and clay-clay interactions are important in the ability to sustain a “so-called” percolated network.The degree to which these clays influence the composite system is a function of their state in the polymer matrix (i.e. intercalated, partially exfoliated, or totally exfoliated).
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