Asymmetric polymeric materials can be formed by either top-down or bottom-up methods. Bottom-up methods involve assembling the atoms and molecules to form small nanostructures by carefully controlled synthesis, which results in a reduction of some of the top-down limitations. In this dissertation, thermal, tribological and antireflective properties of polymeric materials have been enhanced by introducing structural asymmetry. The overall performance of commercial polymeric coatings, e.g. epoxy and polyvinyl chloride, has been improved by conducting the blending methods, specifically, chemical modification (α,ω-dihydroxydimethyl(methyl-vinyl)oligoorganosiloxane), cross-linking (triallyl isocyanurate), and antioxidant (tris(nonylphenyl) phosphite) incorporation. The nonequilibrium polymeric structures (moth-eye and square array) have been developed for the ultrahigh molecular weight block copolymers via the short-term solvent vapor annealing self-assembly. The large domain size of the moth eye structure allows for improvement of the light transmittance particularly in the visible and near infrared ranges, while the square arrangement of the block copolymer opens the possibility of magnetic data storage application by the large magnetic nanoparticles' embedment or masking of the superconductors.

Shape memory alloys (SMAs) represent a revolutionary class of active materials that can spontaneously generate strain based on an environmental input, such as temperature or stress. SMAs can provide potential solutions to many of today's engineering problems due to their compact form, high energy densities, and multifunctional capabilities. While many applications in the biomedical, aerospace, automotive, and defense industries have already been investigated and realized for nickel-titanium (NiTi) based SMAs, the effects of controlling and designing the microstructure through processing (i.e. extreme cold working) have not been well understood. Current Ni-Ti based SMAs could be improved upon by increasing their work output, improving dimensional stability, preventing accidental actuation, and reducing strain localization. Additionally, there is a strong need to increase the transformation temperature above 115 °C, the current limit for NiTi and is especially important for aerospace applications. Previous research has shown that the addition on ternary elements such as Au, Hf, Pd, Pt, and Zr to NiTi can greatly increase these transformation temperatures. However, there are several limiting factors with these ternary additions such as increased cost, especially with Au, Pd, and Pt, as well as, difficulty in conventionally processing these alloys. Therefore, the main objectives of this research …