Role of Casting Solvent on Nanoparticle Dispersion in Polymer Nanocomposites

We investigate the influence of casting solvent on the final spatial dispersion of nanoparticles (NPs) in polymer nanocomposites (PNCs). We prepared nanocomposites of bare silica NPs and poly­(2-vinylpyridine) (P2VP) by casting from two different solventsmethyl ethyl ketone (MEK) and pyridinewhich are theta/good solvents, respectively, for both the polymer and the NPs. In MEK, we show that P2VP strongly adsorbs onto the silica surface to create a temporally stable bound polymer layer. The resulting “hairy” particles are sterically stabilized against agglomeration, and thus good NP dispersion in PNCs is always achieved, independent of P2VP molecular weight, concentration, or NP loading. On the contrary, in pyridine, P2VP does not adsorb on the silica NPs. The phase behavior in this case is thus governed by a subtle balance among electrostatic repulsion, polymer-induced depletion attraction, and the kinetic slowdown of diffusion-limited NP aggregation. While there is little remnant solvent in the dry PNC, and since these dispersion states are hardly altered on annealing, these results serve to emphasize the crucial role played by the casting solvent in the spatial dispersion state of NPs in a polymer matrix

Bound Polymer Layer in Nanocomposites

There has been considerable interest in characterizing the polymer layer that is effectively irreversibly bound to nanoparticles (NPs) because it is thought to underpin the unusual thermomechanical properties of polymer nanocomposites (PNC). We study PNCs formed by mixing silica nanoparticles (NPs) with poly-2-vinylpyridine (P2VP) and compare the bound layer thickness δ determined by three different methods. We show that the thickness obtained by thermogravimetric analysis (TGA) and assuming that the bound layer has a density corresponding to a dense melt clearly underestimates the real bound layer thickness. A more realistic extent of the bound layer is obtained by in situ measurements of the interaction pair potential between NPs in PNCs via analysis of TEM micrographs; we verify these estimates using Dynamic Light Scattering (DLS) in θ solvent. Our results confirm the existence of long-ranged interactions between NPs corresponding roughly in size to the radius of gyration of the bound chains

Enhanced Glassy State Mechanical Properties of Polymer Nanocomposites via Supramolecular Interactions

It is now well accepted that the addition of nanoparticles (NPs) can strongly affect the thermomechanical properties of the polymers into which they are incorporated. In the solid (glassy) state, previous work has implied that optimal mechanical properties are achieved when the NPs are well dispersed in the matrix and when there is strong interfacial binding between the grafted NPs and the polymer matrix. Here we provide strong evidence supporting the importance of intermolecular interactions through the use of NPs grafted with polymers that can hydrogen bond with the matrix, yielding to significant improvements in the measured mechanical properties. Our finding thus supports the previously implied central role of strong interfacial binding in optimizing the mechanical properties of polymer nanocomposites

Polymer Chain Behavior in Polymer Nanocomposites with Attractive Interactions

Chain behavior has been determined in polymer nanocomposites (PNCs) comprised of well-dispersed 12 nm diameter silica nanoparticles (NPs) in poly­(methyl methacrylate) (PMMA) matrices by Small-Angle Neutron Scattering (SANS) measurements under the Zero Average Contrast (ZAC) condition. In particular, we directly characterize the bound polymer layer surrounding the NPs, revealing the bound layer profile. The SANS spectra in the high-<i>q</i> region also show no significant change in the bulk polymer radius of gyration on the addition of the NPs. We thus suggest that the bulk polymer conformation in PNCs should generally be determined using the high <i>q</i> region of SANS data