<p dir="ltr">Increasing power density and power consumption in electronic devices require heat dissipating components with high thermal conductivity to prevent overheating and improve performance and reliability. Polymers offer the advantages of low cost and weight over conventional metallic components, but their intrinsic thermal conductivity is low. Previous studies have shown that the thermal conductivity of polymers can be enhanced by aligning the polymer chains or by adding high thermal conductivity fillers to create percolation paths within the polymeric matrix. To further enhance the in-plane thermal conductivity, the conductive fillers can be aligned preferentially, but this leads to a lower increase in performance in the cross-plane direction. Yet, the cross-plane thermal conductivity plays a vital role in dissipating heat from active devices and transmitting it to the surrounding environment. Alternatively, when the fillers are aligned to enhance cross-plane thermal transport, the enhancement in the in-plane direction is limited. There is a need to develop polymer composites with an approximately isotropic increase in thermal performance compared to their neat counterparts.</p><p dir="ltr">To achieve this goal, in this study, I combine conductive fibers and fillers to enhance thermal conductivity of polymers without significantly inducing thermal anisotropy while preserving the mechanical performance of the matrix. I employ three approaches to enhance the thermal conductivity () of thermoset polymeric matrices. In the first approach, I fabricate thermally conductive polymer composites by creating an emulsion consisting of eutectic gallium indium alloy (EGaIn) liquid metal in the uncured polydimethylsiloxane (PDMS) matrix. In the second approach, I infiltrate mats formed from chopped fibers of Ultra High Molecular Weight Polyethylene (UHMWPE) with an uncured epoxy resin. Finally, the third approach combines the two previous methods by infiltrating the UHMWPE fiber mat with an emulsion of the liquid metal and uncured epoxy matrix.</p><p dir="ltr">To evaluate the thermal performance of the composites, I use infrared thermal microscopy with two different experimental setups, enabling independent measurement of in-plane and cross-plane thermal conductivity. The results demonstrate that incorporating thermally conductive fillers enhances the overall conductivity of the polymer composite. Moreover, I demonstrate that the network structure achieved by the fiber mat, in combination with the presence of liquid metal, promotes a more uniform increase in the thermal conductivity of the composite in all directions. Additionally, I assess the impact of filler incorporation and filler concentration on matrix performance through tension, indentation, and bending tests for mechanical characterization of my materials.</p><p dir="ltr">This work demonstrates the potential of strategic composite design to achieve polymeric materials with isotropically high thermal conductivity. These new materials offer a solution to the challenges posed by higher power density and consumption in electronics and providing improved heat dissipation capabilities for more reliable devices.</p>

The scope of this research entailed the synthesis of novel polyorganosiloxanes with pendent phosphine, phosphine oxide, nitrile and carboxylic acid moieties. Such polysiloxanes were prepared with controlled concentrations of both the polar moieties and hydrido or vinyl pendent crosslinkable sites to afford precursor materials for well-defined networks. The intention was to generate stable microcomposite dispersions with very high concentrations of polar thermally conductive fillers. Lightly crosslinked elastomeric networks with controlled amounts of polar moieties were prepared via a hydrosilation curing mechanism. High concentrations of thermally conductive micro-fillers were dispersed throughout the resins and the microcomposites were investigated as thermally conductive adhesives. Random polysiloxane copolymers containing controlled number average molecular weights (Mns) and compositions with systematically varied concentrations of hydridomethylsiloxy- or vinylmethylsiloxy- units were prepared via ring-opening equilibrations of cyclosiloxane tetramers. These precursors were functionalized with precise concentrations of polar pendent moieties via hydrosilation (nitrile) or free radical addition reactions (phosphine and carboxylic acids). Valuable additions to the family of polysiloxanes were prepared by oxidizing the phosphine moieties to form phosphine oxide containing polysiloxanes. Defined concentrations of residual hydrido- or vinyl- reactive sites were crosslinked via hydrosilation to yield elastomeric adhesives. Specific interactions between the nitrile and phosphine oxide substituted polysiloxanes and the acidic proton of chloroform were shown using 1H NMR. The magnitude of the shift for the deshielded chloroform proton increased with the degree of hydrogen bonding, and was larger for the phosphine oxide species. The polar polysiloxane resins were filled with high concentrations of thermally conductive fillers including silica-coated AlN, Al spheres, BN and Ag flake, then hydrosilated to form microcomposite networks. Microcomposite adhesive strengths, thermal properties (glass transition temperature (Tg) and high temperature stability), and thermal conductivities were studied. An unfilled polysiloxane network containing only 15 mole percent phosphine oxide exhibited a dramatic improvement (46 N/m) in adhesive strength to Al adherends relative to a control polydimethylsiloxane network (2.5 N/m). Importantly, stable polysiloxane micro-dispersions were obtained with up to 67 volume percent (86 weight percent) silica-coated AlN. TEM data confirmed the dispersion homogeneity and XPS demonstrated that the particle surfaces were well-coated with the functionalized polysiloxanes. A microcomposite comprised of 67 volume percent silica-coated AlN and a polysiloxane containing only 9 molar percent nitrile groups had a thermal conductivity of 1.42 W/mK. The glass transition temperatures of the microcomposites were controlled by the amounts of polar functional moieties on the resins and the network crosslink densities. All of the microcomposites exhibited Tgs lower than -44°C and the materials remained stable in dynamic TGA measurements to approximately 400°C in both air and nitrogen. / Ph. D.

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