Date of Award

Summer 7-31-2025

Level of Access Assigned by Author

Open-Access Thesis

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry

First Committee Advisor

WIlliam Gramlich

Second Committee Member

Tomas Marangoni

Third Committee Member

Matthew Brichacek

Additional Committee Members

Brian Frederick

Barbara Cole

Abstract

Plastic pollution is a significant environmental issue that affects all forms of life on Earth, from marine animals to terrestrial ecosystems. To effectively reduce plastic pollution, advancements in scientific research are essential. This includes developing better waste management technologies and promoting biodegradable alternatives. Chemical recycling is an innovative process that transforms plastic waste into valuable feedstock chemicals, offering a broader application scope than traditional mechanical recycling. To combat plastic pollution effectively, incorporating biodegradable materials can further enhance sustainability, allowing products to be industrially composted or naturally degrade in marine or terrestrial environments. Herein, two investigations were conducted to explore the kinetics of a functionalized poly(methyl methacrylate) (PMMA) for chemical recycling, as well as a layer-by-layer filtration approach to developing a cellulose nanofibrils (CNF) and poly(vinyl alcohol) (PVOH) composite. For the former, controlled depolymerizations of PMMA via reversible addition-fragmentation chain transfer (RAFT) yield higher results in some solvents than in others, and the exact reasons are not fully understood. PMMA was synthesized with RAFT end groups to study depolymerization in toluene, a solvent that is poor for depolymerization. The depolymerization kinetics were found to have two regions: one assisted by solvent-derived impurities and another that is primarily self-initiated. Using a rate order analysis, we found evidence that initiation can lead to simultaneous homolysis of the RAFT end group and the depropagation of one monomer. Additionally, RAFT end groups were found to have different elimination rates and reactivity towards radical initiators. For the second investigation, CNF-PVOH composite coatings were prepared through a two-step filtration process, where a CNF coating was formed during the first step, acting as a matrix that absorbed PVOH in the second step. The CNFs used in this study were fibrillated through refining, which maintained some fiber presence, making the material more economical while creating pores for PVOH to fill. By adjusting the dewatering methods and the basis weight of the CNFs, we controlled the solids content of the CNF coatings prior to PVOH filtering. When filtering PVOH through CNF coatings prepared by various methods, PVOH accumulated on the surface more readily in CNF samples that underwent heated compression prior to filtration. Grease resistance and air/oxygen permeability of the CNF-PVOH coatings improved with the addition of PVOH.

Download

Available for download on Saturday, September 19, 2026

Share