Physical Sciences and Mathematics Commons^™

Understanding Corrosion Protection And Failure Through Model Polymers In Thin Films, Joshua Smith Hanna

Dissertations

When developing a model polymeric system to facilitate in the detection of molecular and microscopic events that preface macroscopic corrosive failure; a better understanding of how polymers can indicate corrosion was accomplished. Initially, the thought that molecular chain scission as a necessity for corrosion to occur had to be tested. Through the utilization of high molecular weight thermoplastic (HMWTP) model polymers, it was found that corrosion protection did not correlate to the quantity of weak bonds within an epoxy-amine polymer matrix. Therefore more sensitive methods of detecting corrosion had to be developed since changes within the polymer matrix did not …

Polymer Surface Engineering Via Thiol-Mediated Reactions, Ryan Matthew Hensarling

Dissertations

Synthesis of polymer brushes to decorate a surface with desired functionality typically involves surface-initiated polymerization (SIP) of functional, but non-reactive monomers. This approach suffers major drawbacks associated with synthesizing sufficiently thick polymer brushes containing surface-attached polymer chains of high molecular weight at high grafting density (i.e. cost, synthetic effort and functional group intolerance during polymerization). The research herein seeks to circumvent these limitations by the decoration of surfaces with polymer chains bearing specific pendent functional groups amenable to post-polymerization modification (PPM). In particular, this dissertation leverages PPM via a specific class of click reactions – thiol-click – that 1) enables …

New Dual Initiators For Polyisobutylene-Based Block And Star Polymers, Yaling Zhu

Dissertations

Polyisobutylene (PIB), available solely by living carbocationic polymerization (LCP), is a commercially important polymer with excellent thermal stability, good flexibility and extraordinary impermeability to gases. Due to these attractive properties, coupling PIB to other polymer blocks is expected to result in new and useful products. Two types of new dual initiators possessing initiating sites for both LCP and atom transfer radical polymerization (ATRP), have been designed for the preparation of AB linear and A2B miktoarm star copolymers, where A is PIB-based block copolymer that grows cationically and B is polyacrylate or other radically-derived polymer block, without intermediate modification.

Mono-cationic mono-radical …

Modern Approaches For Multifunctional Hydrolyzying Thiol-Ene Networks, Nicole Marie Mackey

Dissertations

Marine fouling has been an expensive and time-consuming process for navies and fishermen by the accumulation of marine algae and animals on artificial surfaces. Many coatings have been proposed to combat marine fouling in efforts to extend the lifetime of objects immersed in sea water. However, all coatings tested have either failed to resist fouling for a significant length of time or have released toxins into the environment. We have investigated an environmentally friendly approach to address the problem of marine fouling through the synthesis and preparation of a biocidal and a self-polishing coating. Both novel monomers were prepared containing …

Surface, Bulk, And Rheological Properties Of Polyhedral Oligomeric Silsesquioxane/High Density Polyethylene Nanocomposites, Robert Douglas Cook Jr.

Dissertations

In the formulation of high performance nanocomposites, control of miscibility and dispersion of filler material through a polymer matrix is of utmost importance. Due to their inorganic nature most nanofillers are insoluble in polymers, leading to costly/complicated surface modification as a primary means of increasing miscibility and interaction with organic matrices. Polyhedral oligomeric silsesquioxane (POSS) nanostructured chemicals offer an attractive alternative to conventional nanofillers. Due to their hybrid organic-inorganic nature, POSS has the potential to be tailored for miscibility in a wide range of organic matrices not by chemical surface modification but through modification of the molecular structure of the …

A Bisphenol-A-Based Resin System That Cures Via Triazole Ring Formation For Marine Composite Applications, Irene Elizabeth Gorman

Dissertations

Large composite panels, such as those utilized in marine applications, cannot be economically cured in an autoclave. For these structures the elevated temperatures necessary to achieve high crosslink density must come from the curing reaction itself. We are developing a resin system that cures via triazole ring formation (cycloaddition reaction of azides with terminal alkynes) instead of the traditional oxirane/amine reaction. The high exothermicity of the azido/alkyne reaction is expected to yield higher extents of reaction under ambient-cure conditions, making the resin system potentially suitable for "out-of-autoclave" curing processes. This work was conducted through a multi-tiered approach involving synthesis, kinetic …

Molecular Network Development Of A Thermosetting Epoxy-Amine Polymer, Christopher Michael Sahagun

Dissertations

i ABSTRACT MOLECULAR NETWORK DEVELOPMENT OF A THERMOSETTING EPOXY-AMINE POLYMER by Christopher Michael Sahagun May 2012 Epoxy-amine resins find wide application as the matrix material of high performance polymer composites due to their favorable mechanical properties, thermal properties and solvent stability. These properties are derived from the complicated, highly crosslinked molecular network that is characteristic of these thermoset polymers. The connectivity of the molecular network has a strong influence on the physical performance of the finished part. Non-homogeneity in the network structure can degrade these favorable properties through the introduction of low-energy pathways for solvent penetration or fracture propagation. This …