Doctor of Philosophy, Case Western Reserve University, 2024, Macromolecular Science and Engineering
Extensional flows control a variety of industrial processes that involve spraying, printing, and droplet deposition. Within these applications, polymers are used as rheology modifiers to control the flow and droplet breakup, properties which are largely dictated by the polymer's architecture. For example, high molecular weight polymers are often used because of the backbone's ability to deform under stress adds elasticity to solutions. But, by modifying the architecture of a polymer, these elastic contributions can be significantly altered. We have studied the extensional flows of graft polymers as a function of side chain density and length, and liquid crystalline rigid rods using drop-on-substrate rheology (DOSR), a technique that offers strong insights into the fluid dynamics of non-Newtonian droplet breakup.
To understand the effects of polymer backbone extension and graft density on extensional flows, polyacrylamide-graft-poly(ethylene glycol) amine (PAM-g-PEGa) was synthesized at grafting densities of 2.5%, 5.5%, 8%, and 30% and characterized via NMR and light scattering. DOSR was then used to determine the extensional relaxation times as a function of concentration for each polymer. We find that as a function of grafting density, the trend in relaxation times is nonmonotonic. At low grafting densities, the viscous friction of the added side chains counteracts the effects of backbone extension, whereas at higher grafting densities, the effects of the extended backbone dominate extensional flow properties. In the continuation of our study of graft polymers in extensional flows, PAM-g-PEGa with varying side chain lengths at a fixed grafting density were also investigated. The trend in relaxation times were also found to be non-monotonic.
In contrast to flexible PAM-g-PEGa, poly(γ-benzyl-L-glutamate) (PBLG) forms rigid rods. This conformation allows for PBLG to develop cholesteric liquid crystalline phases at high volume fractions, which can also be used (open full item for complete abstract)
Committee: Svetlana Morozova (Advisor); Metin Karayilan (Committee Member); Michael Hore (Committee Member); Ica Manas-Zloczower (Committee Member)
Subjects: Fluid Dynamics; Materials Science; Organic Chemistry