No abstract

Polymers adsorbed on nanoparticles (NPs) are important elements that determine the dispersion of NPs in polymer nanocomposite (PNC) films. While previous studies have shown that increasing the number of adsorbed polymers on NPs can improve their dispersion during the drying process, the exact mechanism remained unclear. In this study, we investigated the role of adsorbed polymers in determining the microstructure and dispersion of NPs during the drying process. Investigation of the structural development of NPs using the synchrotron vertical-small-angle X-ray scattering technique revealed that increasing polymer adsorption suppresses bonding between the NPs at later stages of drying, when they approach each other and come in contact. On the particle length scale, NPs with large amounts of adsorbed polymers form loose clusters, whereas those with smaller amounts of adsorbed polymers form dense clusters. On the cluster length scale, loose clusters of NPs with large amounts of adsorbed polymers build densely packed aggregates, while dense clusters of NPs with small amounts of adsorbed polymers become organized into loose aggregates. The potential for the quantitative control of NP dispersion in PNC films via modification of polymer adsorption was established in this study.

Since the degree of particle dispersion can determine the physical properties of polymer nanocomposites (PNCs), a great deal of studies has focused on the intrinsic parameters of PNCs such as...

What are the most important and decisive parameters that determine the structure and the property of polymer nanocomposites (PNCs)? Previous studies answered that controlling the nanoparticle interface is critical, which can be achieved with a choice of a compatible nanoparticle, a proper surface modification, and a change in the polymer chain length. In addition to these parameters, the processing condition of PNCs has recently emerged as an influential parameter for controlling PNC properties, suggesting the existence of the nonequilibrium effect of PNCs. In this regard, we chose the solvent as a main change in the processing condition and investigated the initial solvent-driven nonequilibrium effect of PNCs with varied nanoparticle (NP) sizes. We found that the type of the initial solvent is indeed crucial in determining the ultimate properties of the PNCs, and this becomes more influential as the size of NPs decreases. The decreasing size of NPs causes a conformational change in the adsorbed polymers from tightly packed layers to loosely dangling chains. This results in much greater differences in NP microstructures and rheological properties of PNCs, indicating a stronger nonequilibrium effect with smaller NPs.