This Is AuburnElectronic Theses and Dissertations

Smart Materials for Advanced Applications: Self-Decontaminating Polymers, Photofunctional Composites, and Electroconductive Fibers




Little, Brian

Type of Degree



Chemistry and Biochemistry


Materials capable of providing multifunctional properties controllable by some external stimulus (pH, light, temperature, etc) are highly desirable and obtainable given recent advancements in material science. Development of these so called “Smart” materials spanned across many disciplines of science with applications in industrial areas such as medical, military, security, and environmental. Furthermore, next-generation materials require the ability to not only sense/respond to changes in their external/internal environment, but process information in regards to these changes and adapt accordingly in a dynamic fashion, autonomously, so called “Intelligent” materials. Findings reported in this manuscript detail the synthesis, characterization, and application of smart materials in the following three areas: 1) self-cleaning polymers 2) photoresponsive composites and 3) electroconductive fibers. Self-Cleaning Polymers: Self-decontaminating polymers are unique materials capable of degrading toxic organic chemicals (TOCs). Barriers composed of or coated with our photochemical reactive polymer matrix could be applied to multiple surfaces for defense against TOCs; for example, military garments for protection against chemical warfare agents. This study investigates conditions necessary for formation of peroxides via O2 reduction induced by long-lived, strongly reducing benzophenyl ketyl (BPK) polymer radicals. Photolysis of aqueous solutions composed of sulphonated poly(ether etherketone), SPEEK, and poly(vinyl alcohol), PVA lead to the formation of the BPK radicals. Experiments investigate the formation and decomposition of peroxides in aqueous solutions of SPEEK/PVA under photolysis. Photofunctional Composites: Photoresponsive nanoporous (PN) films and powders were studied and evaluated as possible additives to sensitize the initiation of CH3NO2 via a mechanism involving coalescence of reaction sites. Such materials consist of a 3-D mesoporous silica framework possessing open interconnected pores. Attached to the pore walls are azobenzene ligands that undergo trans to cis isomerization upon exposure to 350-360 nm photons; the reverse reaction occurs with heat or under illumination with λ > 420 nm. PN films were studied to ascertain the mass transport properties for the filling/releasing of CH3NO2 from within the pores of the films in the absence/presence of UV-Vis light. PN powders were evaluated for pore morphology, ligand mobility, and particle size and shape in order to determine their ability to be utilized as an effective sensitizing agent. Electroconductive Fibers: This study investigates electroless and electrochemical techniques for purposes of producing highly conductive metal coatings on the surface of high strength fibers. Metallized fibers were envisioned to be utilized as high strength low weight tethers for space applications. Findings suggest that these materials could be valuable as components within “Intelligent” textiles, but, at present, not suitable for conditions witnessed in space (high energy UV irradiation, Atomic Oxygen, etc). Kevlar fibers were coated utilizing an electroless and then electrochemical deposition processes. Metallized fibers were evaluated for their resistivity, power output, tensile strength, uniform coverage, and mass gain. Presented in this section are the results of such measurements.