A major challenge of developing faster and smaller microelectronic devices is that high flux of heat needs to be removed efficiently to prevent overheating of devices. The conventional way of heat removal using liquid reaches a limit due to low thermal conductivity and limited heat capacity of fluids. Adding solid nanoparticles into fluids has been proposed as a way to enhance thermal conductivity of fluids, but recent results show inconclusive anomalous enhancements in thermal conductivity. A possible way to improve heat transfer is to increase the heat capacity of liquid by adding phase change nanoparticles with large latent heat of fusion into the liquid. Such nanoparticles absorb heat during solid to liquid phase change. However, the colloidal suspension of bare phase change nanoparticles has limited use due to aggregation of molten nanoparticles, irreversible sticking on fluid channels, and dielectric property loss. This dissertation describes a new method to enhance the heat transfer property of a liquid by adding encapsulated phase change nanoparticles (nano-PCMs), which will absorb thermal energy during solid-liquid phase change and release heat during freeze. Specifically, silica encapsulated indium nanoparticles, and polymer encapsulated paraffin (wax) nanoparticles have been prepared using colloidal method, and dispersed into poly-α-olefin (PAO) and water for high temperature and low temperature applications, respectively. The shell, with a higher melting point than the core, can prevent leakage or agglomeration of molten cores, and preserve the dielectric properties of the base fluids. Compared to single phase fluids, heat transfer of nanoparticle-containing fluids have been significantly enhanced due to enhanced heat capacities. The structural integrity of encapsulation allows repeated uses of nanoparticles for many cycles. iv By forming porous semi crystalline silica shells obtained from water glass, supercooling has been greatly reduced due to low energy barrier of heterogeneous nucleation. Encapsulated phase change nanoparticles have also been added into exothermic reaction systems such as catalytic and polymerization reactions to effectively quench local hot spots, prevent thermal runaway, and change product distribution. Specifically, silica-encapsulated indium nanoparticles, and silica encapsulated paraffin (wax) nanoparticles have been used to absorb heat released in catalytic reaction, and to mitigate the gel effect during polymerization, respectively. The reaction rates do not raise significantly owing to thermal buffering using phase change nanoparticles at initial stage of thermal runaway. The effect of thermal buffering depends on latent heats of fusion of nanoparticles, and heat releasing kinetics of catalytic reactions and polymerizations. Micro/nanoparticles of phase change materials will open a new dimension for thermal management of exothermic reactions.

This work describes the synthesis pathways to the development of optically and thermally responsive nanovalves with fast response times in nanoporous membranes. As an approach, we developed synthesis pathways to couple a thermally responsive polymer with metallic nanoparticles and build a nanocomposite that synergizes the capability of metallic nanoparticles to convert light into heat, and the fast thermal response exhibited by the polymeric material. In addition, we developed a technique to immobilize the synthesized nanocomposite to the surface of nanoporous membranes, which allowed building valves with light and heat triggering responses. This dissertation describes two syntheses pathways developed to produce optically and thermally responsive nanocomposites by coupling metallic nanoparticles, gold and silver, with a thermally responsive polymer, p-N-isopropyl acrylamide (PNIPAM). The coupling is achieved by using PNIPAM as a capping and nucleating agent in the in situ redox reaction of a silver salt with sodium borohydride, and using PNIPAM as a capping and stabilizing agent in the redox reaction of a gold salt with ascorbic acid. The size and shape of the nanoparticles were controlled and the synthesized nanocomposites exhibit “cocoon-like” structures due to the PNIPAM surrounding the metal nanoparticles, giving the capability to aggregate and resolubilize, through many thermal (shown for gold and silver nanocomposites) and optical (shown by exposing to 532 nm wavelength low-power lasers) cycles. The steady state and dynamic heat conduction of the heat generated from the particles was modeled and the results agreed with the observed optical switching at our experimental conditions. Finally, a method to incorporate nanocomposites into nanoporous membranes (NPM) was developed. It involved prior immobilization of PNIPAM through plasma-induced grafting, followed by a reduction in situ of a metallic salt. The composite NPMs showed thermal responses and through simulation of heat conduction within the pores using the model developed in this work we were able to conclude that the synthesized composite membranes will exhibit optical switching when exposed to focused low power lasers. The nanovalves developed in this work have potential applications as optothermally responsive valves for the spatio-temporal delivery of bioactive agents, cell array, and advanced cell culture systems. / text