Chemistry Commons^™

Frontiers In The Self-Assembly Of Charged Macromolecules, Khatcher O. Margossian

Doctoral Dissertations

The self-assembly of charged macromolecules forms the basis of all life on earth. From the synthesis and replication of nucleic acids, to the association of DNA to chromatin, to the targeting of RNA to various cellular compartments, to the astonishingly consistent folding of proteins, all life depends on the physics of the organization and dynamics of charged polymers. In this dissertation, I address several of the newest challenges in the assembly of these types of materials. First, I describe the exciting new physics of the complexation between polyzwitterions and polyelectrolytes. These materials open new questions and possibilities within the context …

Enabling Nanoimprint Lithography Techniques Across Multiple Manufacturing Processes, Vincent Einck

Doctoral Dissertations

Advanced nanooptics in the areas of flat lenses, diffractive elements, and tunable emissivity require a route to high throughput manufacturing. Nanooptics are often demanding of high refractive index materials, nanometer precision and ease of fabrication. Nanoimprint lithography (NIL) is a low-cost, high throughput manufacturing technique beginning to be realized in commercial industry.^1,2 The NIL process is an ideal manufacturing candidate due to its ability to have a fast process time, efficient use of materials, repeatability and high precision while also having wide diversity of potential structures and material choices. Appling NIL techniques to other facets of manufacturing enable the …

Functional Bottlebrush Polymer Additives For Thin Films And Coatings, Travis S. Laws

Doctoral Dissertations

Bottlebrush polymers are a class of highly branched polymers consisting of polymeric side chains that are densely grafted to a linear backbone. Their highly branched architecture results in surface enrichment across a broad range of materials. The goal of my research has been centered around the design of functional bottlebrush polymers and their use as surface active additives in blend films and coatings.

In the first chapter, we examine the segregation behavior of polystyrene bottlebrushes that are blended with linear polystyrene. We systematically vary the lengths of the bottlebrush backbone (Nb), side-chain (Nsc), and the linear matrix (Nm) in order …

How Dynamic Bond Results In The Unique Viscoelastic Behavior Of The Associating Polymers, Sirui Ge

Doctoral Dissertations

Associating polymer is a special kind of polymer possessing transient reversible bonds in addition to the conventional covalent bonds. The reversible bonds provide unique dynamics and fascinating viscoelastic properties, resulting in attractive applications for these polymers, such as self-healing and shape memory materials. Despite many years of studies, the understanding of dynamics of polymers with reversible bonds, especially on molecular level, is still in the rudimentary stage, preventing the rational design of the potential novel functional materials based on associating polymers. In this dissertation, we provide a detailed and quantitative understanding of the dynamics and viscoelastic properties of associating polymers. …

Polynorbornenes For Advanced Applications And Processes, Xinyi Wang

Doctoral Dissertations

Polynorbornenes have dramatically different properties and various applications depending on their chemical structures. The modular nature of norbornene-based systems provides a facile route toward synthesizing diverse polymeric materials, thus making them ideal materials for systematic structure-property investigations. Herein, their application as gas separation membranes and the correlation between their gas-transport properties and polymer structures will be investigated. Though many valuable correlations between gas-permeability and polynorbornene structure have been studied previously, many of these efforts have focused heavily on designing materials with various chemical structures to achieve high permeabilities. In contrast, the influence of molecular structure on: a) polynorbornene chain packing …

Chiral Mesogen-Free Liquid Crystalline Polyethers With Sulfonylated Side Chains And Patchy Brush Nanoparticles, Caleb A. Bohannon

Doctoral Dissertations

Ferroelectric liquid crystalline polymers (LCPs) hold promise for various applications driven by low electric fields, e.g., electrocaloric materials, because of the higher molecular motion in the liquid crystalline (LC) state. However, traditional chiral smectic C (SmC*) LCPs exhibit small spontaneous polarizations due to the bulky aromatic mesogens and weak polar groups. This dissertation research is focused on the design of mesogen-free sulfonylated LCPs with a goal of seeking the ferroelectric SmC* phase. Such LCPs are expected to exhibit high polarizations owing to the sulfonyl’s large dipole moment. A series of poly(oxypropylene)s (POPs), with chirality being introduced into either the backbone …

Synthesis, Fabrication, And Assembly Of Mesoscale Polymer Filaments, Dylan M. Barber

Doctoral Dissertations

Mesoscale materials, with feature sizes in the range of one hundred nanometers to tens of micrometers, are ubiquitous in Nature. In organisms, mesoscale building blocks connect the properties of underlying molecular and nanoscructures to those of macroscale, organism-scale materials through hierarchical assemblies of recurring structural motifs. The collective action of large numbers of mesoscale features can afford stunning features like the structural color of the morpho butterfly wing, calcium ion-mediated movement in muscle, and wood structures like xylem that can support enormous external compressive loads and negative internal pressure to transport nutrients throughout an organism. In synthetic systems, the design, …

Designing Nonflammable Polymers And Blends Containing Deoxybenzoin Derivatives, Elizabeth Stubbs

Doctoral Dissertations

The importance of synthetic polymers in everyday life continues to grow, owing to their societal importance for improving our standard-of-living and enabling advances spanning medicine, electronics, construction materials, transportation. While niche applications occupy a small fraction of the overall volume of polymers produced, large scale applications tend to employ lower cost materials, such as polyethylene, polypropylene, and polystyrene. In addition to environmental considerations connected to these polymerized hydrocarbons, produced in excess of 380 million tons per year worldwide, their inherent flammability creates additional requirements associated with their manufacturing and use. Societal benefits of such polymers are extensive, and thus, there …

Tailoring Interfaces And Composition For Stable And Efficient Perovskite Solar Cells, Hamza Javaid

Doctoral Dissertations

Metal halide perovskite solar cells (PSCs) have revolutionized the field of thin film photovoltaics. Within a decade, the power conversion efficiencies (PCEs) have increased at a phenomenal rate, rising from 3.8% to more than 25% in single-junction devices, moving them ahead of the current silicon-based technology. The high efficiencies of perovskite solar cells (PSCs) and their other unique properties arise from a combination of organic and inorganic components and electronic-ionic conduction, making them excellent candidates for a plethora of applications. However, PSCs face a significant—and ironic—roadblock to commercialization: these light-harvesting materials degrade under sunlight—the very condition they would need …