Engineering Commons^™

Impact Resistant Glassy Polymers: Pre-Stress And Mode Ii Fracture, Jared Steven Archer

Open Access Dissertations

Model glassy polymers, polymethyl methacrylate (PMMA) and polycarbonate (PC) are used to experimentally probe several aspects of polymer fracture. In Chapter 1, the method of pre-stress is employed as a means of improving the fracture properites of brittle PMMA. Samples are tested under equi-biaxial compression, simple shear and a combination of biaxial compression and shear. Equi-biaxial compression is shown to increase the threshold stress level for projectile penetration whereas shear pre-stress has a large effect on the overall energy absorbed during an impact. There is also an apparent interaction observed between compression and shear to dramatically increase the threshold stress. …

Characterization Of Self-Assembled Functional Polymeric Nanostructures: I. Magnetic Nanostructures From Metallopolymers Ii. Zwitterionic Polymer Vesicles In Ionic Liquid, Raghavendra Raj Maddikeri

Open Access Dissertations

Two diverse projects illustrate the application of various materials characterization techniques to investigate the structure and properties of nanostructured functional materials formed in both bulk as well as in solutions. In the first project, ordered magnetic nanostructures were formed within polymer matrix by novel metallopolymers. The novel metal-functionalized block copolymers (BCPs) enabled the confinement of cobalt metal ions within nanostructured BCP domains, which upon simple heat treatment resulted in room temperature ferromagnetic (RTFM) materials. On the contrary, cobalt functionalized homopolymer having similar chemical structure and higher loading of metal-ion are unstructured and exhibited superparamagnetic (SPM) behavior at room temperature. Based …

Helical Ordering In Chiral Block Copolymers, Wei Zhao

Open Access Dissertations

The phase behavior of chiral block copolymers (BCPs*), namely, BCPs with at least one of the constituent block is formed by chiral monomers, is studied both experimentally and theoretically. Specifically, the formation of a unique morphology with helical sense, the H* phase, where the chiral block forms nanohelices hexagonally embedded in the matrix of achiral block, is investigated. Such unique morphology was first observed in the cast film of polystyrene-b-poly(L-lactide) (PS-b-PLLA) from a neutral solvent dichloromethane at room temperature with all the nanohelices being left-handed, which would switch to right-handed if the PLLA block changes to …

Dynamics And Kinetics Of Model Biological Systems, Stephen William Mirigian

Open Access Dissertations

In this work we study three systems of biological interest: the translocation of a heterogeneously charged polymer through an infinitely thin pore, the wrapped of a rigid particle by a soft vesicle and the modification of the dynamical properties of a gel due to the presence of rigid inclusions.

We study the kinetics of translocation for a heterogeneously charged polyelectrolyte through an infinitely narrow pore using the Fokker-Planck formalism to compute mean first passage times, the probability of successful translocation, and the mean successful translocation time for a diblock copolymer. We find, in contrast to the homopolymer result, that details …

Tuning The Properties Of Metal-Ligand Complexes To Modify The Properties Of Supramolecular Materials, Ian Henderson

Open Access Dissertations

Supramolecular chemistry is the study of discreet molecules assembled into more complex structures though non-covalent interactions such as host-guest effects, pi-pi stacking, electrostatic effects, hydrogen bonding, and metal-ligand interactions. Using these interactions, complex hierarchical assembles can be created from relatively simple precursors.

Of the supramolecular interactions listed above, metal-ligand interactions are of particular interest due to the wide possible properties which they present. Factors such as the denticity, polarizability, steric hindrance, ligand structure, and the metal used (among others) contribute to a dramatic range in the physical properties of the metal-ligand complexes. Particularly affected by these factors are the kinetic …

Surface Instabilities For Adhesion Control, Chelsea Simone Davis

Open Access Dissertations

Controlling the specific adhesive properties of surfaces is a technologically complex challenge that has piqued the interest of many research groups around the world. While many scientists have used complex topographic and chemically altered surfaces to tune adhesion, others have shown that naturally occurring phenomena, such as elastic instabilities, can impact adhesion. We provide a thorough investigation into the effects of periodic surface buckling instabilities, or wrinkles, on adhesion. Wrinkles are an attractive surface patterning alternative as they form spontaneously over large areas and their dimensions, namely wavelength and amplitude, can be controlled on length scales relevant for adhesion control. …

Controlling Morphology In Swelling-Induced Wrinkled Surfaces, Derek Breid

Open Access Dissertations

Wrinkles represent a pathway towards the spontaneous generation of ordered surface microstructure for applications in numerous fields. Examples of highly complex ordered wrinkle structures abound in Nature, but the ability to harness this potential for advanced material applications remains limited. This work focuses on understanding the relationship between the patterns on a wrinkled surface and the experimental conditions under which they form. Because wrinkles form in response to applied stresses, particular attention is given to the nature of the stresses in a wrinkling surface. The fundamental insight gained was then utilized to account for observed wrinkle formation phenomena within more …

Phase Behavior Of Block Copolymers In Compressed Co2 And As Single Domain-Layer, Nanolithographic Etch Resists For Sub-10 Nm Pattern Transfer, Curran Matthew Chandler

Open Access Dissertations

Diblock copolymers have many interesting properties, which first and foremost include their ability to self-assemble into various ordered, regularly spaced domains with nanometer-scale feature sizes. The work in this dissertation can be logically divided into two parts - the first and the majority of this work describes the phase behavior of certain block copolymer systems, and the second discusses real applications possible with block copolymer templates. Many compressible fluids have solvent-like properties dependent on fluid pressure and can be used as processing aids similar to liquid solvents. Here, compressed CO₂ was shown to swell several thin homopolymer films, including …

Electrostatic Effects In Aggregation Of Crystallin Proteins, Deniz Elizabeth Civay

Open Access Dissertations

The three projects utilized polymer physics theories to investigate polymer aggregation mechanics. Dynamic light scattering (DLS), static light scattering (SLS) and small angle light scattering (SALS) were the primary characterization tools. The goal of the first project was to study the aggregation of bovine βL-crystallin and apply that knowledge towards cataract formation, which is caused by aggregation of the crystallins. The first series of experiments characterized the kinetics of α-crystallin and βL-crystallin in water at room temperature. α-crystallin’s equilibrium hydrodynamic radius value was kinetically independent. βL-crystallin formed an aggregate with an Rh that was kinetically dependent. The packing structure of …

Aspects Of Network Formation And Property Evolution In Glassy Polymer Networks, Andrew Thomas Detwiler

Open Access Dissertations

Experimental and theoretical characterization techniques are developed to illuminate relationships between molecular architecture, processing strategies, and physical properties of several model epoxy-amine systems. Just beyond the gel point partially cured networks are internally antiplasticized by unreacted epoxy and amine which leads to enhanced local chain packing and strain localization during deformation processes. Additional curing causes the antiplasticization to be removed, resulting in lower modulus, density, yield stress, and less strain localization. Physical and mechanical probes of network formation are discussed with respect to several different partially cured model epoxy-amine chemistries. The non-linear fracture energy release rate and the molecular architecture …

Organic Photovoltaics Based On P3ht/Pcbm: Correlating Efficiency And Morphology, Dian Chen

Open Access Dissertations

Controlling the morphology of thin films is key in optimizing the efficiency of polymer-based photovoltaic (PV) devices. The morphology and interfacial behavior of the multicomponent active layers confined between electrodes are strongly influenced by the preparation conditions. Results obtained in this work quantitatively show the photovoltaic device performance is strongly affected by the nanoscopic morphology, crystal orientation, composition distribution and the interdiffusion behavior of the photoactive layer. To better understand the physics of the photoactive layer in the organic photovoltaic devices, it is necessary to gain a quantitative understanding of the morphology and the manner in which it develops. A …

Effects Of Molecular Architecture On Crystallization Behavior Of Pol(Lactic Acid) And Ethylene-Vinyl Acetate, Jeffrey Paul Kalish

Open Access Dissertations

The relationship between polymer chain architecture, crystallization behavior, and morphology formation was investigated. The structures formed are highly dependent on chain configuration and crystallization kinetics. Poly(lactic acid) (PLA) and Poly(ethylene-co-vinyl acetate) (EVA) random copolymers were studied. Sample characterization was performed using a variety of techniques, including spectroscopy, scattering, and calorimetry. In PLA, structural differences between α’ and α crystalline phases were analyzed using cryogenic infrared and Raman spectroscopy. Compared to the  crystal, the ’ crystal has slightly looser packing and weaker intermolecular interactions involving carbonyl and methyl functional groups. Simulations in conjunction with Raman scattering analyzed the …

Ion Mobility Studies Of Functional Polymeric Materials For Fuel Cells And Lithium Ion Batteries, Shilpi Sanghi

Open Access Dissertations

The research presented in this thesis focuses on developing new functional polymeric materials that can conduct ions, H⁺, or OH^- or Li⁺. The motivation behind this work was to understand the similarities and/or differences in the structure property relationships between polymer membranes and the conductivity of H⁺ and OH^- ions, and between polymer membranes and the anhydrous conductivity of H⁺ and Li⁺ ions. This understanding is critical to developing durable polymer membranes with high H⁺, OH^- and Li⁺ ion conductivity for proton exchange membrane fuel cells (PEMFCs), …

In Situ Reinforced Polymers Using Low Molecular Weight Compounds, Onur Sinan Yordem

Open Access Dissertations

The primary objective of this research is to generate reinforcing domains in situ during the processing of polymers by using phase separation techniques. Low molecular weight compounds were mixed with polymers where the process viscosity is reduced at process temperatures and mechanical properties are improved once the material system is cooled or reacted. Thermally induced phase separation and thermotropic phase transformation of low molar mass compounds were used in isotactic polypropylene (iPP) and poly(ether ether ketone) (PEEK) resins. Reaction induced phase separation was utilized in thermosets to generate anisotropic reinforcements. A new strategy to increase fracture toughness of materials was …

Fiber Formation From The Melting Of Free-Standing Polystyrene, Ultra-Thin Films: A Technique For The Investication Of Thin Film Dynamics, Confinement Effects And Fiber-Based Sensing, Jeremy M. Rathfon

Open Access Dissertations

Free-standing ultra-thin films and micro to nanoscale fibers offer a unique geometry in which to study the dynamics of thin film stability and polymer chain dynamics. By melting these films and investigating the subsequent processes of hole formation and growth, and fiber thinning and breakup, many interesting phenomena can be explored, including the nucleation of holes, shear-thinning during hole formation, finite-extensibility of capillary thinning viscoelastic fibers, and confinement effects on entanglement of polymer chains. Free-standing films in the melt are unstable and rupture due to instabilities. The mechanism of membrane failure and hole nucleation is modeled using an energy barrier …

Mechanics Of Hydrogels And Biological Tissues, Jessica A. Zimberlin

Open Access Dissertations

The relationship between cells and their environment is one of dynamic reciprocity, whereby cells can influence their surrounding and the surroundings can influence the cells. One example of this relationship arises from the effect of the mechanical properties of an environment on a cell and of a cell on its environment. Inspired by this relationship, we investigate 1) the local environment of biological materials, both native and synthetic, and 2) the forces that cell sheets exert on surfaces. We do this by developing techniques that focus on local mechanical properties and experimental strategies that provide insight into intercellular mechanics. We …

Atomic-Scale Analysis Of Plastic Deformation In Thin-Film Forms Of Electronic Materials, Kedarnath Kolluri

Open Access Dissertations

Nanometer-scale-thick films of metals and semiconductor heterostructures are used increasingly in modern technologies, from microelectronics to various areas of nanofabrication. Processing of such ultrathin-film materials generates structural defects, including voids and cracks, and may induce structural transformations. Furthermore, the mechanical behavior of these small-volume structures is very different from that of bulk materials. Improvement of the reliability, functionality, and performance of nano-scale devices requires a fundamental understanding of the atomistic mechanisms that govern the thin-film response to mechanical loading in order to establish links between the films' structural evolution and their mechanical behavior. Toward this end, a significant part of …

Oligopeptide-Functionalized Graft Copolymers: Synthesis And Applications In Nucleic Acid Delivery, Rebecca Boudreaux Breitenkamp

Open Access Dissertations

Utilizing the diverse functionality of amino acids, a new class of amphiphilic graft copolymers has been synthesized, characterized, and explored for applications in biomaterials and nucleic acid delivery. This thesis research focused on the syntheses of oligopeptide-functionalized polyesters and polyolefins. Polyester functionalization was geared towards applications in biomaterials, tissue engineering, and drug delivery by incorporating sequences that promote cell-adhesion. These polyester- graft -oligopeptide materials were prepared by a 1,3-Huisgen cycloaddition reaction, "click" chemistry, of an azide-terminated oligopeptide (prepared by Fmoc-based solid phase peptide synthesis (SPPS)) and alkyne-containing polyester (synthesized by ring-opening polymerization). Following the syntheses of these materials, they were …

Polymer Confinement And Translocation, Chiu Tai Andrew Wong

Open Access Dissertations

Single polymer passage through geometrically confined regions is ubiquitous in biology. Recent technological advances have made the direct study of its dynamics possible. We studied the capture of DNA molecules by the electroosmotic flow of a nanopore induced by its surface charge under an applied electric field. We showed theoretically that the DNA molecules underwent coil-stretch transitions at a critical radius around the nanopore and the transition assisted the polymer passage through the pore. To understand how a polymer worms through a narrow channel, we investigated the translocation dynamics of a Gaussian chain between two compartments connected with a cylindrical …

Synthesis And Interfacial Behavior Of Functional Amphiphilic Graft Copolymers Prepared By Ring-Opening Metathesis Polymerization, Kurt E. Breitenkamp

Open Access Dissertations

This thesis describes the synthesis and application of a new series of amphiphilic graft copolymers with a hydrophobic polyolefin backbone and pendent hydrophilic poly(ethylene glycol) (PEG) grafts. These copolymers are synthesized by ruthenium benzylidene-catalyzed ring-opening metathesis polymerization (ROMP) of PEG-functionalized cyclic olefin macromonomers to afford polycyclooctene- graft -PEG (PCOE- g -PEG) copolymers with a number of tunable features, such as PEG graft density and length, crystallinity, and amphiphilicity. Macromonomers of this type were prepared first by coupling chemistry using commercially available PEG monomethyl ether derivatives and a carboxylic acid-functionalized cycloctene. In a second approach, macromonomers possessing a variety of PEG …

Effect Of Loading And Process Conditions On The Mechanical Behavior In Sebs Thermoplastic Elastomers (Tpes), Mohit Mamodia

Open Access Dissertations

Styrenic block copolymer thermoplastic elastomers are one of the most widely used thermoplastic elastomers (TPEs) today. The focus of this research is to fundamentally understand the structure-processs-property relationships in these materials. Deformation behavior of the block copolymers with cylindrical and lamellar morphologies has been investigated in detail using unique techniques like deformation calorimetry, transmission electron microscopy (TEM), combined in-situ small angle x-ray and wide angle x-ray scattering (SAXS/WAXS). The research involves the study of structural changes that occur at different length scales along with the energetics involved upon deformation. The structural changes in the morphology of these systems on deformation …