Date of Award

12-2017

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

School of Materials Science and Engineering

Committee Member

Dr. Igor Luzinov, Committee Chair

Committee Member

Dr. Marek Urban

Committee Member

Dr. Olin Thompson Mefford

Committee Member

Dr. Mark Roberts

Abstract

Modification of materials properties such as surface energy, wettability, ability to absorb, contain or release specific type of chemicals enables practical application of these materials in various scientific and engineering set-ups. However, designing protocol that could be easily adapted for different situations and simultaneously unlock multiple variations of the resulting properties is a non-trivial task. This dissertation is devoted to application of glycidyl methacrylate-based graft copolymers for the purposes of surface modification, establishing fundamental trends and dependencies of this process and exploring the possible range of applications. These materials have extremely valuable property to undergo controllable post-synthetic modifications including surface attachment and cross-linking. Deep understanding of the relationship between structure, properties and composition of these polymeric materials was made possible with the current study and can play pivotal role in introducing GMA-based functional interfaces into industrial practice.

First part of this dissertation is focused on GMA-copolymer films prepared by “grafting to” method. As I have demonstrated, such nanoscale layers are promising elements of photonic sensors leading to creation of new generation of highly selective devices. Photonic technologies represent state-of-the-art answer to chemical weapon proliferation and ensure safety and security of global population, which necessitates research in highly responsive but stable and reliable polymer films for chemical detection. Here, I show that GMA-copolymer films are not only able to fulfill this task, but also can be actuated in a special way that allows them to operate as post-exposure sensing elements recording information of the chemical exposure. This groundbreaking finding has clear and evident applicability, but also great fundamental value as the investigation that I have performed gives new insights on the metastable polymer networks.

Second part of the dissertation is devoted to GMA-copolymers prepared by “grafting through” method which results in water-soluble polymers that enable use of GMA-based reactions in aqueous environment. This not only reduces the use of organic solvents in polymer processing, but also opens new venues of modification of objects such as enzymes that would not be able to be processed otherwise. Through the rigorous study of the synthesis and relevant properties, I have identified the possible range of resulting properties and highlighted composition-dependent trends which serve as a practical guide for preparation of copolymers with desired properties. I demonstrated the applicability of GMA-copolymers for preparation of thermally-stable polymer-enzyme conjugates, mechanically resistant drug-loaded coatings, chemical sensors and preparation of transparent conductive coatings using graphene oxide as a precursor.

Overall, this dissertation provides novel insights on surface modification of various materials and actualizes the role that GMA-based copolymers can play. Unique combination of fine control over surface properties and preparation practicality makes these materials a novel technological solution for advanced functional interface design.

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