Engineering Commons^™

Bending, Wrinkling, And Folding Of Thin Polymer Film/Elastomer Interfaces, Yuri Ebata

Open Access Dissertations

This work focuses on understanding the buckling deformation mechanisms of bending, wrinkling, and folding that occur on the surfaces and interfaces of polymer systems. We gained fundamental insight into the formation mechanism of these buckled structures for thin glassy films placed on an elastomeric substrate. By taking advantage of geometric confinement, we demonstrated new strategies in controlling wrinkling morphologies. We were able to achieve surfaces with controlled patterned structures which will have a broad impact in optical, adhesive, microelectronics, and microfluidics applications.

Wrinkles and strain localized features, such as delaminations and folds, are observed in many natural systems and are …

Discriminatory Bio-Adhesion Over Nano-Patterned Polymer Brushes, Saugata Gon

Open Access Dissertations

Surfaces functionalized with bio-molecular targeting agents are conventionally used for highly-specific protein and cell adhesion. This thesis explores an alternative approach: Small non-biological adhesive elements are placed on a surface randomly, with the rest of the surface rendered repulsive towards biomolecules and cells. While the adhesive elements themselves, for instance in solution, typically exhibit no selectivity for various compounds within an analyte suspension, selective adhesion of targeted objects or molecules results from their placement on the repulsive surface. The mechanism of selectivity relies on recognition of length scales of the surface distribution of adhesive elements relative to species in the …

Dynamic Modeling Of Synthetic Microbial Consortia To Optimize The Co-Fermentation Of Glucose And Xylose, Timothy Joseph Hanly

Open Access Dissertations

Second-generation biofuels have the potential to replace fossil fuels in the energy economy without negatively impacting the food supply. An effective biocatalyst must be able to convert all sugars found in lignocellulosic hydrolysates to biofuels. Few microbes exist in that have both a wide substrate range and high ethanol yields necessary for this process. Mixed culture biotechnology is a promising alternative to the use of single organisms in the production of fuels from lignocellulosic biomass. These systems mimic natural processes for the degradation of lignocellulose and exploit the native capabilities of each microbe. The segregation of metabolic pathways allows for …

Evaluation Of A Split-Root Nutrition System To Optimize Nutrition Of Basil, Ganisher Djurakulovich Abbasov

Open Access Dissertations

The plant-nutrient-water optimum interaction always has been a problematic program for plant growth and development. This work investigates this interaction using a split root nutrition system to determine possible changes in traditional hydroponics to enhance plant growth and development. While split root nutrition systems have been used experimentally to answer some specific questions, the technique has never been used in a production system for optimizing plant, nutrient, and water interaction. The introduction of hydroponics almost a hundred fifty years ago has not changed this situation fundamentally. Moreover, the norm of fertilizer application on agricultural crops has the advantage of increased …

Scaling Reversible Adhesion In Synthetic And Biological Systems, Michael David Bartlett

Open Access Dissertations

Geckos and other insects have fascinated scientists and casual observers with their ability to effortlessly climb up walls and across ceilings. This capability has inspired high capacity, easy release synthetic adhesives, which have focused on mimicking the fibrillar features found on the foot pads of these climbing organisms. However, without a fundamental framework that connects biological and synthetic adhesives from nanoscopic to macroscopic features, synthetic mimics have failed to perform favorably at large contact areas. In this thesis, we present a scaling approach which leads to an understanding of reversible adhesion in both synthetic and biological systems over multiple length …

Computer Simulation Of Viral-Assembly And Translocation, Jyoti Prakash Mahalik

Open Access Dissertations

We investigated four different problems using coarse grained computational models : self-assembly of single stranded (ss) DNA virus, ejection dynamics of double stranded(ds) DNA from phages, translocation of ssDNA through MspA protein pore, and segmental dynamics of a polymer translocating through a synthetic nanopore. In the first part of the project, we investigated the self-assembly of a virus with and without its genome. A coarse-grained model was proposed for the viral subunit proteins and its genome (ssDNA). Langevin dynamics simulation, and replica exchange method were used to determine the kinetics and energetics of the self-assembly process, respectively. The self-assembly follows …

Solution Assembly Of Conjugated Polymers, Felicia Bokel

Open Access Dissertations

This dissertation focuses on the solution-state polymer assembly of conjugated polymers with specific attention to nano- and molecular-scale morphology. Understanding how to control these structures holds potential for applications in polymer-based electronics. Optimization of conjugated polymer morphology was performed with three objectives: 1) segregation of donor and acceptor materials on the nanometer length-scale, 2) achieving molecular-scale ordering in terms of crystallinity within distinct domains, and 3) maximizing the number and quality of well-defined donor/acceptor interfaces.

Chapter 1 introduces the development of a mixed solvent method to create crystalline poly(3-hexyl thiophene) (P3HT) fibrils in solution. Chapter 2 describes fibril purification and …

Photo-Reaction Of Copolymers With Pendent Benzophenone, Scott Kenneth Christensen

Open Access Dissertations

This dissertation aims to both deepen and broaden our understanding of copolymers with pendent benzophenone (BP) in relation to both established applications and novel directions in materials science. Photo-reaction of these BP copolymers is explored in attempts to achieve three distinct goals: (1) robust and efficiently photo-crosslinkable solid polymer films, (2) photo-reacted polymer blends with disordered bicontinuous nanostructures, and (3) photo-patterned hydrogel materials with environmental UV stability. We begin by investigating the fundamental gelation behavior of solid polymer films, finding BP copolymers to be particularly effective crosslinkable materials. Gelation efficiency can be tuned according to comonomer chemistry, as BP hydrogen …

Particle Behavior On Anisotropically Curved Interfaces, Kathleen Mcennis

Open Access Dissertations

This dissertation presents experimental research investigating the behavior of particles on two different types of anisotropically curved liquid interfaces: cylinders and catenoids. The results are compared to the behavior predicted by theoretical models. Several types of liquids and many types of particles were examined. The size scale of the surfaces ranges from microns to millimeters, with nanometer and micron sized particles.

Semi-cylinders, a few hundred microns in diameter, were made by creating a line of liquid on a surface. Three different fluids were used to create the semi-cylinders: Gallium, ionic liquids, and molten polystyrene (PS). Particle behavior on semi-cylinder liquid …

Effect Of Colloidal Interactions On Formation Of Glasses, Gels, Stable Clusters And Structured Films, Anand Kumar Atmuri

Open Access Dissertations

Colloidal suspensions are ubiquitous because of their vast industrial and household usage. We demonstrate that interactions between colloidal particles play a crucial role in manipulating the phase behavior and thereby the macroscopic properties of a variety of colloidal materials, including structured films, gels, glasses and stable clusters. First, we examined films comprised of two different colloidal particles and investigated the impact of colloidal interactions in manipulating the extent of segregation in the dried films. A transport model was used to predict the volume fraction profiles of the particles as a function of film thickness, which showed that segregation could be …

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 …

Particle-Collector Interactions In Nanoscale Heterogeneous Systems, Marina Bendersky

Open Access Dissertations

Particle-surface interactions govern a myriad of interface phenomena, that span from technological applications to naturally occurring biological processes.

In the present work, particle-collector DLVO interactions are computed with the grid-surface integration (GSI) technique, previously applied to the computation of particle colloidal interactions with anionic surfaces patterned with O(10 nm) cationic patches. The applicability of the GSI technique is extended to account for interactions with collectors covered with topographical and chemical nanoscale heterogeneity. Surface roughness is shown to have a significant role in the decrease of the energy barriers, in accordance with experimental deposition rates that are higher than those predicted …

Molecular And Population Level Approaches To Understand Taxus Metabolism In Cell Suspension Cultures, Rohan Anil Patil

Open Access Dissertations

Plant cell culture is an attractive platform technology for production and supply of important plant derived medicinals. A unique characteristic of plant cells is the ability to grow as multicellular aggregates in suspension. The presence of these non-uniform aggregates results in creation of distinct microenvironments, which can induce variations in cellular metabolism (e.g., growth, oxygen consumption and secondary metabolite synthesis). This heterogeneity can lead to unpredictable and suboptimal performance in large scale bioprocesses. One example is the Taxus cell culture system, which produces a widely used chemotherapeutic drug - paclitaxel (Taxol ®). Despite extensive process engineering efforts which have led …

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 …

Determining Detailed Reaction Kinetics For Nitrogen-And Oxygen-Containing Fuels, Nicole Jeanne Labbe

Open Access Dissertations

With the emergence of new biorenewable transportation fuels, the role of heteroatoms in combustion has increased tremendously. While petroleum-based fuels are primarily hydrocarbons, many biorenewable fuels contain heteroatoms such as oxygen and nitrogen, introducing new challenges associated with toxic emissions. A fundamental understanding of the chemical kinetics of combustion of these heteroatomic fuels is necessary to elucidate the pathways by which these toxic emissions are formed and may be achieved through the development of combustion models. Reaction sets, the core of these combustion models, may be assembled for individual fuels through a balance of employing vetted rate constants from prior …

Macroscopic Patterning Via Dynamic Self-Assembly And Wrinkling Instability, Hyun Suk Kim

Open Access Dissertations

My PhD work focuses on developing new methods to create the macroscopic patterns in a simple, robust, and versatile way. For macroscopic pattern formation, we first use flow coating as an assembly technique, uniquely balancing two driving forces: (i) evaporative deposition of nonvolatile solutes at a three-phase contact line and (ii) precision movement of a confined meniscus layer. This balance leads to the formation of line-based patterns that range in height and width from nanometers to microns, with lengths greater than centimeters. Moreover, we couple this deposition methodology with functional ligand chemistry on the nanoparticle surface, which allows us to …

Porous Metal Oxide Materials Through Novel Fabrication Procedures, Nicholas Hendricks

Open Access Dissertations

Porous metal oxide materials, particularly those comprised of silica or titania, find use in many applications such as low-k dielectric materials for microelectronics as well as chemical sensors, micro/nanofluidic devices, and catalyst substrates. For this dissertation, the focus will be on the processing of porous metal oxide materials covering two subjects: hierarchical porosity exhibited over two discrete length scales and incorporation of functional nanomaterials. To generate the porous silica materials, the technique of supercritical carbon dioxide infusion (scCO2) processing was heavily relied upon. Briefly, the scCO2 infusion processing utilizes phase selective chemistries within a pre-organized amphiphilic block copolymer template using …

Modeling Material Transformations In Biorefinement, Vishal Agarwal

Open Access Dissertations

Lignocellulosic biomass is a significant pool of energy resource, which can be harnessed to supplement or replace the dwindling fossil fuel reserves. This requires development of economically viable means to efficiently convert biomass to biofuels. A major requirement in biofuel industry is to develop highly active, selective and stable catalysts. Zeolites are an important class of micro-porous crystalline solids, and have proven to be effective and stable acid catalysts for a variety of petrochemical and fine-chemical processes. Nitrided zeolites -- i.e., those with Si-O-Si and Si-OH-Al groups substituted by Si-NH-Si and Si-NH₂-Al -- have shown promise as shape-selective …

Interactions And Morphology Of Triblock Copolymer - Ionic Liquid Mixtures And Applications For Gel Polymer Electrolytes, Daniel F. Miranda

Open Access Dissertations

Room temperature ionic liquids (ILs) are a unique class of solvents which are characterized by non-volatility, non-flammability, electrochemical stability and high ionic conductivity. These properties are highly desirable for ion-conducting electrolytes, and much work has focused on realizing their application in practical devices. In addition, hydrophilic and ionophilic polymers are generally miscible with ILs. The miscibility of ILs with ion-coordinating polymers makes ILs effective plasticizers for gel polymer electrolytes. Due to their unique properties, ILs present a means to realize the next generation of energy storage technology. In this dissertation, the fundamental interactions between poly(ethylene oxide) (PEO) and a variety …

Risk Quantification Of Maple Trees Subjected To Wind Loading, Cihan Ciftci

Open Access Dissertations

Because of property damage and people injuries in, almost, every year in different locations of the earth, unfortunately the topic of understanding trees and their risk assessments under wind forces has not lost its importance since approximately a half of the last century. In contrast to loss its importance, the number of researchers or studies increases with time thanks to inter-disciplinary studies on that topic. In this Thesis, tree dynamics and their risk assessments subjected to wind forces were addressed by two different disciplines (civil engineering and environmental conservation).

To mention includes of this inter-disciplinary study, first, a finite element …

Modeling The Relaxation Dynamics Of Fluids In Nanoporous Materials, John R. Edison

Open Access Dissertations

Mesoporous materials are being widely used in the chemical industry in various environmentally friendly separation processes and as catalysts. Our research can be broadly described as an effort to understand the behavior of fluids confined in such materials. More specifically we try to understand the influence of state variables like temperature and pore variables like size, shape, connectivity and structural heterogeneity on both the dynamic and equilibrium behavior of confined fluids. The dynamic processes associated with the approach to equilibrium are largely unexplored. It is important to look into the dynamic behavior for two reasons. First, confined fluids experience enhanced …

Modeling The Self-Assembly Of Ordered Nanoporous Materials, Lin Jin

Open Access Dissertations

Porous materials have long been a research interest due to their practical importance in traditional chemical industries such as catalysis and separation processes. The successful synthesis of porous materials requires further understanding of the fundamental physics that govern the formation of these materials. In this thesis, we apply molecular modeling methods and develop novel models to study the formation mechanism of ordered porous materials. The improved understanding provides an opportunity to rational control pore size, pore shape, surface reactivity and may lead to new design of tailor-made materials. To attain detailed structural evolution of silicate materials, an atomistic model with …

Chemistry At Silicone - Inorganic Oxide Interfaces, Joseph W. Krumpfer

Open Access Dissertations

This dissertation describes research performed using siloxane polymers. This includes the reactions of siloxane polymers with inorganic oxide surfaces to form covalently attached monolayers, and the electrical properties of crosslinked silicone composite films fabricated by compounding with nickel particles. In addition to these topics, the use of contact line pinning as a practical and controllable method for the deposition of materials on superhydrophobic and chemically patterned surfaces is also described The first chapter provides a general review of siloxane polymer chemistry, focusing in particular on the relationship between molecular structure and physical properties. The use and fabrication of silicone composite …

Catalytic Fast Pyrolysis Of Furan Over Zsm-5 Catalysts: A Model Biomass Conversion Reaction, Yu-Ting Cheng

Open Access Dissertations

Due to its low cost and availability, lignocellulosic biomass is receiving significant attention worldwide as a feedstock for renewable liquid bio-fuels. We have recently shown that zeolites can be added to a pyrolysis reactor to directly make aromatics from solid biomass in one single step in a process called catalytic fast pyrolysis (CFP). The advantage of this approach is that valuable petrochemicals can be made directly from solid biomass in a single catalytic step using zeolite catalysts. However, little is known about the conversion chemistry that occurs within the zeolites during CFP. The objective of this thesis is to identify …

On The Effect Of Elasticity On Drag Reduction Due To Polymer Additives Using A Hybrid D.N.S. And Langevin Dynamics Approach, Arnout Boelens

Open Access Dissertations

In this work the effect of elasticity on turbulent drag reduction due to polymers is investigated using a hybrid Direct Numerical Simulation (D.N.S) and Langevin dynamics approach. Simulations are run at a friction Reynolds number of Re_&tau = 560 for 960.000 dumbbells with Deborah numbers of De = 0, De = 1, and De = 10. The conclusions are that it is possible to simulate a drag reduced flow using hybrid D.N.S. with Langevin dynamics, that polymers, like other occurrences of drag reduction, reduce drag through streak stabilization, and that the essential property of polymers and fibers in having a …

Production Of Green Aromatics And Olefins From Lignocellulosic Biomass By Catalytic Fast Pyrolysis: Chemistry, Catalysis, And Process Development, Jungho Jae

Open Access Dissertations

Diminishing petroleum resources combined with concerns about global warming and dependence on fossil fuels are leading our society to search for renewable sources of energy. In this respect, lignocellulosic biomass has a tremendous potential as a renewable energy source, once we develop the economical processes converting biomass into useful fuels and chemicals.

Catalytic fast pyrolysis (CFP) is a promising technology for production of gasoline range aromatics, including benzene, toluene, and xylenes (BTX), directly from raw solid biomass. In this single step process, solid biomass is fed into a catalytic reactor in which the biomass first thermally decomposes to form pyrolysis …

Systematic Synthesis Of Organic Semiconductors With Variable Band Gaps, Christopher Thomas Scilla

Open Access Dissertations

Polymeric materials are attractive candidates for the fabrication of low cost, large area photovoltaic devices. Controlling the band gap of the electroactive polymer is an essential factor in optimizing the resulting devices. In this dissertation, a methodology for the synthesis of well-defined semiconducting materials with tunable band gaps is described. First, the synthesis, characterization, and computational analysis of a variety of trimers consisting of two 3-hexylthiophene units flanking a central moiety consisting of thiophene, or one of the electron donating monomers isothianaphthene or thieno[3,4,b]thiophene will be described. From this analysis the influences of the electronic and steric structure of the …

Enhanced Mechanical Performance Of Low Dielectric Constant Thin Films Synthesized In Supercritical Co2, And Sans Studies Of Microemulsions Induced Or Destabilized By Compressed Co2, Alvin Horatio Romang

Open Access Dissertations

Block copolymer (BCP) phase segregation and self-assembly into two or more distinct domains are primarily dictated by two parameters: the block volume fraction, f, and the product of the segment-segment interaction parameter and the length of polymer chain, XN. The volume fraction determines a block copolymer's phase segregated morphology, whereas XN dictates its overall segregation strength, or phase stability. In order to achieve smaller domain sizes, the interaction parameter must be increased to compensate for the decrease in chain length. In the melt, PEO-b-PPO-b-PEO (Pluronic) triblock copolymer surfactants do not phase segregate primarily due to their low molecular weights …

Kinetically Trapping Co-Continuous Morphologies In Polymer Blends And Composites, Le Li

Open Access Dissertations

Co-continuous structures generated from the phase separation of polymer blends present many opportunities for practical application. Due to the large interfacial area in such structures and the incompatibility between the components, such non-equilibrium structures tend to coarsen spontaneously into larger sizes and eventually form dispersed morphologies. Here, we utilize various strategies to kinetically stabilize the co-continuous structures in polymer blend systems at nano- to micro- size scales.

In the partially miscible blend of polystyrene and poly(vinyl methyl ether), we took advantage of the spinodal decomposition (SD) process upon thermal quenching, and arrested the co-continuous micro-structures by the addition of nanoparticles. …

Microtechnologies For Mimicking Tumor-Imposed Transport Limitations And Developing Targeted Cancer Therapies, Bhushan Jayant Toley

Open Access Dissertations

Intravenously delivered cancer drugs face transport limitations at the tumor site and cannot reach all parts of tumors at therapeutically effective concentrations. Transport limitations also prevent oxygen from distributing evenly in tumors resulting in hypoxia, which plays a critical role in cancer progression. In this dissertation, I present the development of micro-devices that mimic transport limitations of drugs and nutrients on three dimensional tumor tissues, enable visualization and quantification of the ensuing gradients, and enable simple analysis and mathematical modeling of obtained data. To measure the independent effects of oxygen gradients on tumor tissues, an oxygen delivery device that used …