Pore-Confined Polymers Enhance the Thermal Conductivity of Polymer Nanocomposites.

Molecularly confined polymer fillers in nanopores were found to give superior mechanical properties of polymer nanocomposites. In this work, we study the thermal conductivity of such nanocomposites and unveil the effect of polymer confinement on thermal conductivity. Using the time-domain thermoreflectance method, we measure the cross-plane thermal conductivity of polymer nanocomposites that consist of polystyrene fillers confined within a nanoporous organosilicate matrix. Compared to unconfined bulk polystyrene fillers, we find that pore-confined polystyrene fillers enhance the thermal conductivity of the polymer nanocomposites. This enhancement is attributed to the better aligned and less entangled chains in the confined phase, where chain-chain phonon scatterings are reduced. Our work provides essential insights into the thermal conductivity of polymer nanocomposites for multifunctional thermal and mechanical applications.

Fundamental limits of material toughening in molecularly confined polymers.

The exceptional mechanical properties of polymer nanocomposites are achieved through intimate mixing of the polymer and inorganic phases, which leads to spatial confinement of the polymer phase. In this study we probe the mechanical and fracture properties of polymers in the extreme limits of molecular confinement, where a stiff inorganic phase confines the polymer chains to dimensions far smaller than their bulk radius of gyration. We show that polymers confined at molecular length scales dissipate energy through a confinement-induced molecular bridging mechanism that is distinct from existing entanglement-based theories of polymer deformation and fracture. We demonstrate that the toughening is controlled by the molecular size and the degree of confinement, but is ultimately limited by the strength of individual molecules.

Imaging thin films of nanoporous low-k dielectrics: comparison between ultramicrotomy and focused ion beam preparations for transmission electron microscopy.

Ultramicrotomy, the technique of cutting nanometers-thin slices of material using a diamond knife, was applied to prepare transmission electron microscope (TEM) specimens of nanoporous poly(methylsilsesquioxane) (PMSSQ) thin films. This technique was compared to focused ion beam (FIB) cross-section preparation to address possible artifacts resulting from deformation of nanoporous microstructure during the sample preparation. It was found that ultramicrotomy is a successful TEM specimen preparation method for nanoporous PMSSQ thin films when combined with low-energy ion milling as a final step. A thick, sacrificial carbon coating was identified as a method of reducing defects from the FIB process which included film shrinkage and pore deformation.