Physical Sciences and Mathematics Commons^™

Characterization Of Interlayer Laser Shock Peening During Fused Filament Fabrication Of Polylactic Acid (Pla), Fabien Denise

Department of Mechanical and Materials Engineering: Dissertations, Theses, and Student Research

The field of additive manufacturing (AM) has gained a significant amount of popularity due to the increasing need for more sustainable manufacturing techniques and the adaptive development of complex product geometries. The problem is that AM parts routinely exhibit flaws or weaknesses that affect functionality or performance. Over the years, surface treatments have been developed to compensate certain flaws or weaknesses in manufactured products. Combining surface treatments with the modularity of additive manufacturing could lead to more adaptable and creative improvements of product functions in the future. The current work evaluates the feasibility of pursuing a new research axis in …

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 …

Stretching The Applications Of Biomass: Development Of Lignin Based Thermoplastic Elastomers And Composite Materials, Anthony Stephen Bova

Doctoral Dissertations

Bio-based plastics and composites have seen increased industry adoption in recent years due to growing demand for materials with a low carbon footprint. The use of lignin as a feedstock for polymers has seen growing interest as the concept of an integrated cellulosic biorefinery gains traction and advances the need to use all components of separated biomass for value-added applications. Historically, use of lignin in thermoplastic and elastomeric copolymers and blends has been bottlenecked by the inability to introduce lignin content above 30 weight percent due to difficulties with interfacial adhesion of lignin with other soft segments. Efforts to overcome …

Development Of Biomaterials For Drug Delivery, Raquel De Castro

Graduate Theses and Dissertations

Drug delivery systems (DDS) have highly evolved in the last decades with the development of hydrogels and nanoparticles. However, high systemic uptake, side effects, low bioavailability, and encapsulation efficiency continue to be a major hurdle faced by such DDSs.

Nanoparticles and hydrogels can be specifically designed for targeted DDSs to mitigate some of the problems. This dissertation aimed to design two DDSs for ocular drug delivery and one for cancer treatment. The first project sought to develop chitosan nanoparticles (Cs-NP) using PEGDA as a copolymer to encapsulate gentamicin (GtS) for ocular drug delivery. Cs-NPs contain positive charges that can interact …

Multi-Level Analysis Of Atomic Layer Deposition Barrier Coatings On Additively Manufactured Plastics For High Vacuum Applications, Nupur Bihari

Dissertations, Master's Theses and Master's Reports

While hardware innovations in micro/nano electronics and photonics are heavily patented, the rise of the open-source movement has significantly shifted focus to the importance of obtaining low-cost, functional and easily modifiable research equipment. This thesis provides a foundation of open source development of equipment to aid in the micro/nano electronics and photonics fields.

First, the massive acceptance of the open source Arduino microcontroller has aided in the development of control systems with a wide variety of uses. Here it is used for the development of an open-source dual axis gimbal system. This system is used to characterize optoelectronic properties of …

Towards Completely Automated Glycan Synthesis, Matteo Panza

Dissertations

Carbohydrates are ubiquitous both in nature as biologically active compounds and in medicine as pharmaceuticals. Although there has been continued interest in the synthesis of carbohydrates, chemical methods require specialized knowledge and hence remain cumbersome. The need for development of rapid, efficient and operationally simple procedures has come to the fore. This dissertation focuses on the development of a fully automated platform that will enable both experts and non-specialists to perform the synthesis of glycans. Existing automated methods for the synthesis of oligosaccharides are highly sophisticated, operationally complex, and require significant user know-how. By contrast, high performance liquid chromatography (HPLC) …

Polymeric Impulsive Actuation Mechanisms: Development, Characterization, And Modeling, Yongjin Kim

Doctoral Dissertations

Recent advances in the field of biomedical and life-sciences are increasingly demanding more life-like actuation with higher degrees of freedom in motion at small scales. Many researchers have developed various solutions to satisfy these emerging requirements. In many cases, new solutions are made possible with the development of novel polymeric actuators. Advances in polymeric actuation not only addressed problems concerning low degree of freedom in motion, large system size, and bio-incompatibility associated with conventional actuators, but also led to the discovery of novel applications, which were previously unattainable with conventional engineered systems. This dissertation focuses on developing novel actuation mechanisms …

Magnetic Ordering In A Vanadium-Organic Coordination Polymer Using A Pyrrolo[2,3-D:5,4-D']Bis(Thiazole)-Based Ligand, Yulia A. Getmanenko, Christopher S. Mullins, Vladimir N. Nesterov, Stephanie Lake, Chad Risko, Ezekiel Johnston-Halperin

Chemistry Faculty Publications

Here we present the synthesis and characterization of a hybrid vanadium-organic coordination polymer with robust magnetic order, a Curie temperature T_C of ∼110 K, a coercive field of ∼5 Oe at 5 K, and a maximum mass magnetization of about half that of the benchmark ferrimagnetic vanadium(tetracyanoethylene)_~2 (V·(TCNE)_~2). This material was prepared using a new tetracyano-substituted quinoidal organic small molecule 7 based on a tricyclic heterocycle 4-hexyl-4H-pyrrolo[2,3-d:5,4-d′]bis(thiazole) (C₆-PBTz). Single crystal X-ray diffraction of the 2,6-diiodo derivative of the parent C₆-PBTz, showed a disordered hexyl chain and …

Effect Of Crosslinking On Carbon Nanotube Materials Through Chemical Treatment And Irradiation, Xinyi Lu

Doctoral Dissertations

Carbon nanotubes (CNTs) exhibit a variety of exceptional properties, especially their ultrahigh tensile strength on the order of 100GPa show promise for constituting the next-generation carbon fiber. However, challenges remain to translate these properties into useful technology, primarily due to the sliding of the tubes past one another under tensile loading. The work presented in this dissertation is focused on enhancing the interaction between the CNTs and their bundles in a macro-assembly, in order to improve the tensile properties of the material.

Applying inter-tube crosslinks has been predicted to significantly enhance the stress transfer between the CNT components. We developed …

Synthesis Of Acceptors For Use In Donor-Acceptor Copolymers And Characterization Of These Polymers, William D. Walker

Honors Theses

In this thesis, a selenium-derivatized acceptor was synthesized to examine the heavy atom effects of selenium on the position of the frontier molecular orbitals (HOMO/LUMO band gap) as opposed to sulfur in a donor-acceptor copolymer for use in light harvesting and detection applications. Over the course of this research, standard operating protocols for ultraviolet-visible (UV-Vis-NIR) and Fourier transform infrared (FT-IR) spectroscopies, as well as cyclic voltammetry (CV) characterization techniques were established. Once synthesized, the polymers were characterized through use of the established characterization protocols. The selenium-derivatized polymer exhibited a bathochromic shift compared to the sulfur analogue, with a solid-state absorption …

Tunable Photonic Multilayers From Stimulus-Responsive, Photo-Crosslinkable Polymers, Maria C. Chiappelli

Doctoral Dissertations

This dissertation describes the synthesis of photo-crosslinkable copolymers and their utilization for the fabrication and testing of tunable and responsive one-dimensional (1D) photonic multilayers. Photonic multilayers exhibit structural color due to the interference of incident light at layer interfaces, providing a convenient route towards optically responsive materials that do not rely on potentially light- or oxygen-sensitive chromophore-containing pigments and dyes. A fabrication technique based on sequential spin-coating and crosslinking of photo-crosslinkable polymers is used to assemble tunable and responsive photonic multilayers. Chapter One introduces the fundamental underlying principles of 1D photonic structures and explores their importance in a variety of …

A Soft Condensed Matter Approach Towards Mathematical Modelling Of Mass Transport And Swelling In Food Grains, Michael Chapwanya, N. Misra

Articles

Soft condensed matter (SCM) physics has recently gained importance for a large class of engineering materials. The treatment of food materials from a soft matter perspective, however, is only at the surface and is gaining importance for understanding the complex phenomena and structure of foods. In this work, we present a theoretical treatment of navy beans from a SCM perspective to describe the hydration kinetics. We solve the transport equations within a porous matrix and employ the Flory–Huggin’s equation for polymer–solvent mixture to balance the osmotic pressure. The swelling of the legume seed is modelled as a moving boundary with …

Multipolymer Interactions In Bulk Heterojunction Photovoltaic Devices, Grant Olson

Physics

Multipolymer photovoltaics, single layer devices made up of multiple photoactive polymers, can create organic photovoltaics (OPVs) with a wider spectral response than single polymer systems without the difficult fabrication of a tandem. Our group has successfully created multipolymer solar devices with 2% power conversion efficiency. We have analyzed the optical and electrical properties of these devices, and found that it may be possible for polymers to assist each other with charge extraction, though combining polymers disrupts single polymer crystallinity.

Electron Irradiation Effects On Ferroelectric Copolymer Langmuir-Blodgett Films, Christina M. Othon, Stephen Ducharme

Christina M Othon

The effect of irradiation on the ferroelectric properties of Langmuir-Blodgett films of the copolymer poly(vinylidene fluoride-trifluorethelene) is investigating using 1.26 MeV electrons with dosages from 16 to 110 Mrad. Irradiation causes a systematic decrease in the phase transition temperature, coercive field and polarization of these thin films.

Modeling Of Metal-Ferroelectric-Insulator-Semiconductor Structures Based On Langmuir–Blodgett Copolymer Films, Timothy J. Reece, Stephen Ducharme

Stephen Ducharme Publications

Among the ferroelectric thin films used in field-effect transistor devices; the ferroelectric copolymer of polyvinylidene fluoride PVDF –CH2–CF2–, with trifluoroethylene TrFE –CHF–CF2–, has distinct advantages, including low dielectric constant, low processing temperature, low cost, and compatibility with organic semiconductors. The operation of a metal-ferroelectric insulatorsemiconductor structure with PVDF-TrFE as the ferroelectric layer was analyzed and optimized by numerical solution of the Miller and McWhorter model. A model device consisting of 20 nm PVDF/TrFE on a 10-nm-thick high-k dielectric buffer exhibits a memory window of 5 V with an operating voltage of 15 V. The operating voltage can be reduced to …

Dielectric Nanocomposites: An Inside-Out Approach To Storing Electrostatic Energy, Stephen Ducharme

Stephen Ducharme Publications

The ability to achieve high-energy densities is the central challenge in energy storage and recovery. A promising strategy for increasing energy storage is to use highperformance dielectric materials, such as highly polarizable nanoparticles or polymers, or nanocomposites of the two. In this issue, Kim et al. use a molecular coating and clever chemistry to combine oxide nanoparticles with a polymer matrix, thereby producing an improved nanocomposite dielectric. Some advantages and challenges of using nanocomposites as improved dielectric materials are presented in this Perspective.

Polarization Switching Kinetics Of Ferroelectric Nanomesas Of Vinylidene Fluoride-Trifluoroethylene Copolymer, R. V. Gaynutdinov, O. A. Lysova, S. G. Yudin, A. L. Tolstikhina, A. L. Kholkin, V. M. Fridkin, Stephen Ducharme

Stephen Ducharme Publications

The polarization switching kinetics of ferroelectric polymer nanomesas was investigated using piezoresponse force microscopy. The nanomesas were made by self-organization from Langmuir–Blodgett films of a 70% vinylidene fluoride and 30% trifluoroethylene copolymer. The polarization switching time exhibits an exponential dependence on reciprocal voltage that is consistent with nucleation-type switching dynamics.

Investigation Of Ferroelectricity In Newly Synthesized Nitrile Polymer Systems, Matt Poulsen, Stephen Ducharme, Alexander V. Sorokin, Sahadeva Reddy, James M. Takacs, Y. Wen, Jihee Kim, Shireen Adenwalla

Stephen Ducharme Publications

The ferroelectric and piezoelectric properties of newly synthesized polymer systems have been studied. To date PVDF and its copolymers P(VDF-TrFE) have provided the bulk of the knowledge pertaining to ferroelectricity in polymers. Recently, ultrathin ferroelectric films of P(VDF-TrFE) 70:30 have been fabricated using the Langmuir-Blodgett technique [4]. In this study, various new polymers have been synthesized by chemically altering the PVDF structure. This alteration was performed in order to enhance the amphiphilic nature of the polymer and thus improve the LB film quality and control. Various chemical groups have been used to replace the electropositive hydrogen and electronegative fluorine found …

Mapping Surface Polarization In Thin Films Of The Ferroelectric Polymer P(Vdf-Trfe)., Bradley W. Peterson, Stephen Ducharme, Vladimir M. Fridkin, Timothy J. Reece

Stephen Ducharme Publications

Pyroelectric Scanning Microscopy (PSM) has been developed to enable mapping of surface polarization in ferroelectric thin films, in particular the copolymer polyvinylidene fluoride trifluororethylene, or P(VDF-TrFE). The Chynoweth method for dynamically measuring pyroelectric current is employed in conjunction with a micropositioning system to construct two-dimensional images of the film polarization. These images have revealed enhancement of the polarization near the edges of the film below the average coercive field, with the center's polarization increasing thereafter to meet the edge value at saturation.

Electron Irradiation Effects On Ferroelectric Copolymer Langmuir-Blodgett Films, Christina M. Othon, Stephen Ducharme

Stephen Ducharme Publications

The effect of irradiation on the ferroelectric properties of Langmuir-Blodgett films of the copolymer poly(vinylidene fluoride-trifluorethelene) is investigating using 1.26 MeV electrons with dosages from 16 to 110 Mrad. Irradiation causes a systematic decrease in the phase transition temperature, coercive field and polarization of these thin films.