Engineering Commons^™

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 …

Additive Manufacturing Of Sub-Micron Features And Mechanical Linkages, David K. Limberg

Doctoral Dissertations

In recent years material constraints have become the limiting factor in several fields, including batteries, robotics, and medicine, and these needs have prompted the development of materials with programmable properties. To this end, much effort has been dedicated to designing metamaterials that have unprecedented optical, mechanical, and thermal properties, along with systems for additive manufacturing to build their complex structures with high precision and throughput. The field of additive manufacturing has proved to be a platform for innovation across many industries yet is still limited with regards to feature sizes, print rates, and diversity of materials. Mechanical devices like linkages …

Cmos Compatible Carbonization Of Polymer For Elctrochemical Sensors, Mohammad Aminul Haque

Doctoral Dissertations

Carbon-based electrodes that are integrable with CMOS readout electrodes possess great potential in a wide range of cutting-edge applications. The primary scientific contribution is the development of a processing sequence which can be implemented on CMOS chips to fabricate pyrolyzed carbon microelectrodes from 3D printed polymer microstructures to develop lab-on-CMOS monolithic electrochemical sensor systems. Specifically, optimized processing conditions to convert 3D printed polymer micro- and nano-structures to carbonized electrodes have been explored in order to obtain sensing electrodes for lab-on- CMOS electrochemical systems. Processing conditions have been identified, including a sequel of oxidative and inert atmosphere anneals to form pyrolyzed …

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 …

Surface Driven Flows : Liquid Bridges, Drops And Marangoni Propulsion, Samrat Sur

Doctoral Dissertations

Molecules sitting at a free liquid surface against vacuum or gas have weaker binding than molecules in the bulk. The missing (negative) binding energy can therefore be viewed as a positive energy added to the surface itself. Since a larger area of the surface contains larger surface energy, external forces must perform positive work against internal surface forces to increase the total area of the surface. Mathematically, the internal surface forces are represented by surface tension, defined as the normal force per unit of length. One common manifestation of surface tension is the difference in pressure it causes across a …

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 …

Chemical Stability And Performance Influence Of Choice Substituents And Core Conjugation Of Organic Semiconductors, Jack Ly

Doctoral Dissertations

Realizing organic based active materials for electronic devices, such as thin film transistors and photovoltaics, has been long sought after. Advancement in the field driven by chemists, engineers, and physicists alike have bolstered organic based semiconductor performance levels to rival those of traditional inorganic amorphous silicon-based devices. Within the field of organic semiconductors (OSC), two categories of active materials may be generalized: (1) polymer and (2) small molecule semiconductors. Each class of OSC inherently have their own advantages and disadvantages. Polymer semiconductors (PSC) allow a wide range in tunability via choice monomers and side chain engineering to illicit desirable energy …

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 …

Strategies For Controlling Bulk Heterojunction Morphology, Zach Daniel Seibers

Doctoral Dissertations

Organic photovoltaic devices have been extensively studied as a means to produce sustainable energy. However, the performance of organic-photovoltaic (OPV) devices is dependent upon a number of factors including the morphology of the active layer, device architecture, and processing conditions. Recent research has indicated that fullerenes in the bulk heterojunction are entropically driven to the silicon and air interfaces upon crystallization of P3HT, which occurs during thermal annealing. The first chapter of this research focuses on investigating the structure and function of end-tethered poly(3-hexylthiophene) chains to a transparent electrode as an anode buffer layer. Neutron reactivity reveals that these P3HT …

Magnetic, Optical And Electrical Properties Of Electron-Hole Pairs In Polymer And Organo-Metal Halide Perovskite Photovoltaic Cells, Yu-Che Hsiao

Doctoral Dissertations

Organic polymer and organo-metal halide perovskite (OMHP) materials have attracted extensive attention during the past decade due to their various applications, like solar cells, light emitting diode, even lasing action (OMHP). Especially, the organo-metal halide perovskite solar cell shows a remarkable power conversion efficiency of about 20%, which is comparable to the amorphous silicon solar cell. Therefore, OMHP solar cell had been considered as a promising substitution for the next generation of renewable energy source. The OMHP materials contain both advantages of organic and inorganic semiconductors, like solution processable thin film fabrication, long-range ambipolar transport characteristics, high dielectric constants, low …

Synthesis And Characterizations Of Stimuli-Responsive Polymeric Materials For Biomedical Applications, Shuangcheng Tang

Doctoral Dissertations

Stimuli-responsive polymeric materials have been now widely researched toward the biomedical applications including therapeutic delivery, bio-sensor surface modification, and tissue-engineering, etc., considering their desirable biocompatibility, tunable properties, and sensitivity toward physiological stimuli. Beyond the monoresponsive materials, polymers with responsiveness simultaneously toward multiple stimuli are paid great attention to because the control of responsive behaviors could be achieved at a more accurately and delicately level in a complex local environment. However, many challenges still exist such as maintaining integrity of the structure, shaping the morphology at micro- and macro-scale, and regulating a controllable and predictable transition behavior.

The objectives of this …

Effect Of Processing History And Material Properties On The Growth Of Wrinkle Amplitude, Yu-Cheng Chen

Doctoral Dissertations

Wrinkling has been employed by many organisms to form unique topography, such as fingerprints, gut villi, and surface of flower petal cells. The wavy wrinkle structure provides friction enhancement, surface area increase, optical, and wetting properties improvement. Inspired by Nature, scientists have created wrinkles synthetically and proposed numerous uses for them. However, wrinkling surfaces encounters limitations on achieving massive area and high amplitude-to-wavelength ratio (aspect ratio). The three phase contact line wrinkling technique creates well-defined wrinkles in a continuous fashion, and has great potential to scale-up for massive production. In addition to the velocity dependent adhesion force, we find the …

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 …

The Effect Of Processing Parameters On Barrier Properties Of Polymers, Russell Louis Hallman Jr.

Doctoral Dissertations

The intent of this work was to learn if polyethylene could be made with predictable water transfer rates by control of the microstructure. A series of films were formed from three different polyethylenes with a range crystallinities using melt pressing, a controlled cooling rate, and subsequent heat treatments. The samples were tested on a novel device called the polymer characterization device that measures the water transfer flux as a function of temperature. The samples’ morphology was examined using differential gradient column, differential scanning calorimetry, Fourier transform infrared microscopy, wide-angle X-ray diffractions, small-angle X-ray scattering, and small angle light scattering, and …

Tuning Cell Fate On Self-Assembled Structures, Xiaohui Wu

Doctoral Dissertations

This dissertation presents novel biodegradable copolymers with dendritic architecture, classic polymers, and inorganic materials with controlled surface topography, stiffness, and surface energy for investigating cell-material interactions and targeting tissue engineering applications. Chapter I reviews the recent progress in bone and nerve regeneration, the key factors of materials influencing cell-material interaction, and self-assembled polymer structures. Chapter II presents a divergent method to synthesize biodegrable com-dendritic tri-block copolymers consisting of poly(ethylene glycol) and poly(L-lactide) or poly(ε-caprolactone) and the MC3T3-E1 cell response to their spherulites. Chapter III presents the fabrication of deformable poly(ε-caprolactone) honeycomb films prepared via a surfactant-free breath figure method in …

Roles Of Polymer Crosslinking Density And Crystallinity In Regulating Surface Characteristics And Pre-Osteoblastic Mc3t3 Cell Behavior, Kan Wang

Doctoral Dissertations

This dissertation presents material design strategies to investigate cell-biomaterial interactions on specific biocompatible polymers and polymer blends by using mouse pre-osteoblastic MC3T3 cells aiming for potential applications in bone tissue engineering. Chapter 1 reviews some related background knowledge including polymeric biomaterials for tissue engineering, cell-biomaterial interaction, synthetic photo-crosslinkable and degradable polymers, and the effect of surface features on osteoblast cell responses. Chapter 2 presents photo-crosslinkable composites of poly(propylene fumarate) (PPF), an injectable and biodegradable polyester, and methacryl-polyhedral oligomeric silsesquioxane (mPOSS), which has eight methacryl groups tethered with a cage-like hybrid inorganic-organic nanostructure, for bone tissue engineering applications. Blending mPOSS with …