Graduation Year
2013
Document Type
Dissertation
Degree
Ph.D.
Degree Granting Department
Chemistry
Major Professor
Julie P. Harmon
Keywords
carbon nanotubes, functionalization, hydrogels, reductive alkylation, rheometer, time-temperature superposition
Abstract
From medicine to aerospace, innovation in multiple fields will not occur without addressing current questions that still exist in polymer behavior and manipulation. This dissertation represents the research carried out over the course of three separate experiments using rheometry as the key technique to explore the behavior of polymer composites. In all three studies, polymer composites were investigated for changes to their known physical properties caused through the addition of a filler or functionalization.
Chapter Two examines the possibility of enhancing poly(4-methyl-1-pentene) through the use of soluble carbon nanotubes. In this series of experiments, carbon nanotubes were covalently functionalized using reductive alkylation with a dodecyl group to render them easily soluble in the same organic solvents as low molecular weight poly(4-methyl-1-pentene). The polymer and the functionalized nanotubes were dissolved together in carbon tetrachloride then the solvent is removed leaving the functionalized nanotubes uniformly dispersed in the polymer matrix. The composites were then compression molded and the changes to the physical properties were explored. The functionalized nanotube filler generally acted to plasticize the samples producing transparent but colored polymers. The samples had a lower modulus and glass transition which was the opposite found by Clayton et al. using sonicated pristine carbon nanotubes.
Polyurethanes have a growing significance in the biomedical field, and we explore the possibility fine tuning the properties of a polyurethane for such uses in Chapter Three. Here, self healing Polycarbonate polyurethanes (PCU) were synthesized with two different soft segments, Nippollan 964 and T-5652, and characterized with dielectric analysis (DEA), differential scanning calorimetry (DSC) and rheometry. The extra methyl group acted to produce a crystalline-like ordered hard segment that caused the 964 PCU to become Arrhenius in the glass transition region where the 5652 PCU had followed WLF behavior. Results showed the pendent methyl group acted to impart a crystalline-like character to the 964 PCU making it a candidate for applications that would be suited to a stiffer polymer.
In Chapter Four we explore the possibility of increasing the wearability and comfort of contact lenses through increased hydration. The hydrogels 2-hydroxyethylmethacrylate (HEMA) and glycidyl methacrylate (GMA) solutions were created in three concentrations; neat, 50/50 and 60/40. Into these samples [Cu2({μ2-CO2}R)4(axial)2] (Cu(II) 4-hydroxybenzoic acid (MHBC) were dissolved 0.05% by weight. The samples were then polymerized via UV polymerization and compression molded. The experiments performed included penetration resistance , water absorption, micro hardness and glass transition. Addition of the MHBC acted to increase the water uptake of the samples but also reduced their ability to withstand mechanical penetration. With further study into crosslinking of the polymers, the MHBC could show promise in increasing hydration for commercial use.
Scholar Commons Citation
Knudsen, Bernard, "A Rheological Examination of Polymer Composites: Including Functionalized Carbon Nanotubes, Viable Polyurethane Alternates, and Contact Lens Hydrogels" (2013). USF Tampa Graduate Theses and Dissertations.
https://digitalcommons.usf.edu/etd/4522
