Epoxy and Silicone Optical Nanocomposites Filled with Grafted Nanoparticles.

摘要

Polymer nanocomposites, as a technologically important class of materials, exhibit diverse functional properties, and are used for applications ranging from structural and biomedical to electronic and optical. The properties of polymer nanocomposites are determined, in part, by the chemical composition of the polymer matrix and the nanofillers. Their properties are also sensitive to the geometry and size of the nanofillers, and to spatial distribution of the fillers. Control of the nanoparticle size and dispersion within a given polymer provides opportunities to tailor and optimize the properties of nanocomposites for specific application.;For optical applications such as encapsulation of light emitting diodes (LEDs), polymer nanocomposites filled with homogeneously dispersed nanoparticles would endow the polymer encapsulant with new functionality without sacrificing optical transparency. To this end, this thesis focuses on developing a simple and versatile approach towards the fabrication of epoxy and silicone transparent nanocomposites using matrix compatible chain-grafted nanoparticles as fillers, and studying the optical properties of the nanocomposites. The surface chemistry and grafted polymer chain design have been shown to play an important role in determining the dispersion state of the grafted nanoparticles and hence the final optical properties of the nanocomposites.;To prepare transparent epoxy nanocomposites, poly (glycidyl methacrylate) (PGMA) chains were grafted onto the optical nanoparticle surfaces via a combined phosphate ligand exchange process and azide-alkyne "click" chemistry. The dispersion behavior of PGMA-grafted nanoparticles within the epoxy matrix was investigated by systematically varying the grafting density and grafted chain length. It was found that within the small molecular weight epoxy resins, the dispersion states are more sensitive to the grafting density than the molecular weight of grafted chains. With high grafting densities, the grafted PGMA brushes effectively screen the van der Waals attraction between the particles, and homogenous nanoparticle dispersions of grafted nanoparticles were obtained. Transparent high refractive index TiO2/epoxy thin film and bulk nancomposites were obtained by dispersing PGMA brushes-grafted TiO2 nanoparticles into a commercial epoxy matrix. The refractive index of the nanocomposites showed a linear dependence on the volume fraction of TiO2 nanoparticles and the optical transparency could be generally described by the Rayleigh scattering model. This powerful dispersing technique was further employed to make visibly transparent, UV/IR blocking ITO/epoxy nanocomposites which can be easily applied onto glass and plastic substrates as energy saving optical coating materials.;To produce transparent silicone nanocomposites, we directly coupled phosphate-terminated PDMS chains onto the optical nanoparticle surface. It was observed that the mono-modal PDMS-grafted particles usually formed agglomerates within silicone matrices, whereas the bimodal PDMS-grafted particles were able to be individually dispersed even within high molecular weight matrices. Transparent high refractive index bulk TiO2/silicone nanocomposites were successfully prepared by filling with bimodal PDMS-grafted TiO2 nanoparticles. Furthermore, we used the PDMS-grafted TiO2/silicone nanocomposite as a model system to create a methodology to predict and control the dispersion behavior of grafted nanoparticles. The good agreement between experimental observation of dispersion of mono-modal and bimodal grafted particles and theoretical prediction would better guide future experiments and lead to predictability in polymer composite design. Finally, the bimodal grafted chain design was implemented in the preparation of transparent and luminescent CdSe/silicone nanocomposites with potential application as non-scattering light conversion materials for LEDs. The homogeneous dispersion of bimodal PDMS-grafted CdSe quantum dots not only minimizes the transparency loss due to scattering, but also benefits the uniformity and long-term stability of photoluminescence of the nanocomposites.