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Articles 1 - 30 of 113
Full-Text Articles in Engineering
Harnessing Nanocellulose For Sustainable Carbon Capture: Synthesis, Processing, And Performance Evaluation, Jerred C. Wassgren
Harnessing Nanocellulose For Sustainable Carbon Capture: Synthesis, Processing, And Performance Evaluation, Jerred C. Wassgren
Doctoral Dissertations
Scientists and governments have recognized the need for environmental remediation, most notably with the adoption of the Paris Agreement in 2016. One of the major concerns is the production of greenhouse gases (GHGs). The major GHG is carbon dioxide (CO2) in which humans emit over 36 gigatons yearly. Atmospheric CO2 is responsible for 60% of the heat retained by the earth – resulting in rising temperatures, melting ice caps, and increasing ocean acidification. Therefore, a major goal of the Paris Agreement was to reduce GHG emissions as well as the capture of CO2 from the atmosphere. …
Experimental Investigation Of The Vortex-Induced Vibration Response Of A Flexibly-Mounted Rigid Cylinder In The Shear-Thinning And Inertial-Viscoelastic Flow Regimes, Pieter Boersma
Doctoral Dissertations
Flexible or flexibly-mounted structures with bluff cross-sections in flow can shed vortices at frequencies that increase with increasing flow velocity. When this shedding frequency is equal to the structure's natural frequency, the structure can oscillate. This is called vortex-induced vibrations (VIV). VIV is present in multiple fluid-structure interaction (FSI) systems which can be found in industrial, medical, and engineering applications. These oscillations can be desirable or undesirable, so understanding the physics behind this phenomenon is important. This work seeks to investigate experimentally the VIV response in the inertial-viscoelastic regime where fluid inertia and elasticity influence the system. The subcritical Newtonian …
Electrostatic Effects On Lipid Bilayer Physicochemal Properties And Vesicle Adhesion, Oscar Zabala-Ferrera
Electrostatic Effects On Lipid Bilayer Physicochemal Properties And Vesicle Adhesion, Oscar Zabala-Ferrera
Doctoral Dissertations
Lipids are an integral part of cells, being the principal component of the cell membrane, and contributing to the function and regulation of biological processes. Lipid nanoparticles mimicking a cell’s endosomes or exosomes are of particular interest within the pharmaceutical industry for their ability to deliver cargo such as RNA into target cells. The delivery process faces a multitude of challenges, so a rational design approach for vesicles that considers a lipid’s physicochemical contribution to the membrane is desired. To that end, this thesis explores the creation of large area biomembranes along with the development of electromechanical and optical characterization …
Polyesters Derived From Biobased 1,5-Pentanediol For Coatings, Adhesives, And Biodegradable Plastics, Lei Zheng
Polyesters Derived From Biobased 1,5-Pentanediol For Coatings, Adhesives, And Biodegradable Plastics, Lei Zheng
Doctoral Dissertations
Biomass-derived polymers are drawing increased attention from researchers due to unique performance attributes, potential for biodegradability, new low-cost feedstocks, and improved sustainability. Biobased feedstocks are employed in both major applications of polymers thermosets and thermoplastics. For thermoset coatings and adhesives, biobased resins such as biobased alkyds, epoxy resins, benzoxazine resins, starch derivatives, and proteins from plants and animals, are promising candidates to replace petroleum-derived counterparts. Thermoplastics such as polyethylene are mainly produced from fossil resources, generally have poor degradability and are difficult to effectively recycle. Currently, in the United States, less than 10% plastics are recycled, and more than 70% …
Polymer Based Energy Storage And Thermal Management On Textile Devices, Wesley A. Viola
Polymer Based Energy Storage And Thermal Management On Textile Devices, Wesley A. Viola
Doctoral Dissertations
Humans developed textiles to manage thermal energy transfer with the environment and support homeostasis in a wide range of climates. With the anticipation of wearable technologies to transform healthcare via early, pre-symptomatic detection of illness, there is now a demand for electrical energy storage to support such on-body devices. Finding energy materials to merge seamlessly with textiles is basic requirement to ensure widespread adoption of wearable health monitors. Here we use a vapor deposition process to conformally coat ordinary fabrics with the doped conjugated polymer poly(3,4 ethylenedioxythiophene) (PEDOT-Cl), a soft material which possesses electronic and redox capabilities. We demonstrate PEDOT-Cl …
Assembly Of Polymer Colloids At Fluid Interfaces Through External Fields And Nanoscale Surface Topography, Samuel Trevenen
Assembly Of Polymer Colloids At Fluid Interfaces Through External Fields And Nanoscale Surface Topography, Samuel Trevenen
Doctoral Dissertations
The superposition of dipolar repulsion and capillary attraction energies between colloidal particles pinned at fluid interfaces dictates their microstructural organization and therefore the macroscopic interfacial material properties of particle-stabilized emulsions and 2D monolayer materials. While isotropic, spherical, particles have been extensively utilized, expanding the possible applications and material property tunability via anisotropic particles has been a challenge due to the propensity of particles to form disordered aggregates at the interface. My thesis presents the synthesis of anisotropic polymer ellipsoids and the development and use of experimental tools to study their interfacial behavior to reveal how dipolar and capillary interactions can …
Phosphorus-Containing Zeolites For Biofuel Production, Jason Gulbinski
Phosphorus-Containing Zeolites For Biofuel Production, Jason Gulbinski
Doctoral Dissertations
Fossil fuel consumption increases 2% a year due to transportation fuels and specialty chemicals for plastics and synthetic fibers such as p-xylene, a monomer of polyethylene terephthalate. p-Xylene demand was over 50 million tons in 2021 and will increase by 5% a year through 2026. Therefore, sustainable p-xylene production is desired. p-Xylene is produced renewably through Diels-Alder cycloaddition of biomassderived 2,5-dimethylfuran (DMF) with ethylene from bio-ethanol and dehydration over an acid catalyst. Industrial aluminosilicate zeolite catalysts achieve a selectivity of 75%, with loss to side products and coking. A new class of catalysts, phosphoric acid-containing aluminum-free zeolites, P-zeosils, like dealuminated …
Effect Of Chemical Identity And Morphology On Amphiphilic-Zwitterionic Block Copolymer Membranes, Ria Ghosh
Effect Of Chemical Identity And Morphology On Amphiphilic-Zwitterionic Block Copolymer Membranes, Ria Ghosh
Doctoral Dissertations
Amphiphilic block copolymers have gained a broad research interest attributed to their self-assembly properties over a range of pH, temperature, and ionic strength. Polyzwitterions have attracted special attention due to their hydrophilicity, charge sensitivity and coulombic attraction of the opposite charges over a range of environments making them a popular material of study in the field of stimuli responsive systems, for example in self-healing hydrogels, and water transport membranes. Combining the stimuli responsiveness and higher hydrophilicity of zwitterionic polymers with self-assembly behavior of amphiphilic block copolymers created an interest to study the effect of composition and identity of the zwitterionic …
Synthesis And Assembly Of Polymer Materials At Interfaces, Xiaoshuang Wei
Synthesis And Assembly Of Polymer Materials At Interfaces, Xiaoshuang Wei
Doctoral Dissertations
The overarching goal of the thesis is to understand growth and assembly of polymer materials at interfaces. Chapter 2 and Chapter 3 study simultaneous polymer growth and assembly at fluid interfaces, where in-situ photopolymerization and vapor phase deposition were utilized to grow polymers, respectively. Chapter 4 leverages capillary condensation to pattern polymer growth at solid substrates. Chapter 1 provides background information on polymer materials at interfaces, and vapor phase deposition method (initiated chemical vapor deposition, iCVD) to grow polymers. This chapter also reviews polymer thin film wetting, and colloidal assemblies at interfaces. In Chapter 2, we demonstrate the preparation …
Frontiers In The Self-Assembly Of Charged Macromolecules, Khatcher O. Margossian
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 …
Modeling Chain Packing In Complex Phases Of Self-Assembled Block Copolymers, Anugu Abhiram Reddy
Modeling Chain Packing In Complex Phases Of Self-Assembled Block Copolymers, Anugu Abhiram Reddy
Doctoral Dissertations
Block copolymer (BCP) melts undergo microphase seperation and form ordered soft matter crystals with varying domain shapes and symmetries. We study the con- nection between diblock copolymer molecular designs and thermodynamic selection of ordered crystals by modeling features of variable sub-domain geometry filled with individual blocks within non-canonical sphere-like and network phases that together with layered, cylindrical and canonical spherical phases forms “natural forms” of self- assembled amphiphilic soft matter at large. First, we present a model to revise our understanding of optimal Frank-Kasper sphere-like morphologies by advancing the- ory to account for varying domain volumes. We then develop generic …
New Isomeric Silicones: Synthesis, Compositions And Surface Properties, Yan Cong
New Isomeric Silicones: Synthesis, Compositions And Surface Properties, Yan Cong
Doctoral Dissertations
This dissertation presents research performed in the field of silicone polymer science, which refers to polymers with alternating silicon-oxygen backbones. Three research topics will be explored. The first topic involves the synthesis of trimethylsiloxysilsesquioxane (MT) copolymers with vinyl and hydride functionalities as reactive liquid silicone precursors. The second topic describes titration of dimethylsiloxy (D) composition into trimethylsiloxysilsesquioxane (MT) copolymers for the purpose of controlling the mechanical properties and thermal stabilities of the material. The last topic explores the modification of hydrophobic silicone surfaces with oxygen plasma to form silica-like, hydrophilic surfaces and the behaviors of hydrophobic recovery. The first chapter …
Computational Rational Design Of Electrocatalysts For Electrochemical Ammonia And Hydrogen Synthesis, Akash Jain
Computational Rational Design Of Electrocatalysts For Electrochemical Ammonia And Hydrogen Synthesis, Akash Jain
Doctoral Dissertations
The electrochemical hydrogen evolution reaction (HER) and nitrogen reduction reaction (NRR) offer fossil-fuel-free routes for hydrogen and ammonia synthesis, respectively. However, currently, both processes lack suitable electrocatalysts for practical applications. Thus, this dissertation focuses on the computational rational design of HER and NRR electrocatalysts. HER is most efficiently catalyzed by platinum (Pt), which is expensive. To reduce the catalyst cost, we investigate core-shell nanoparticles of inexpensive tungsten-carbide (WC) and Pt (WC@Pt). Using first-principles density functional theory (DFT) calculations, we compare the suitability of two WC phases, α-WC and β-WC as support materials for Pt overlayers. We dope WC with titanium …
Development Of Crosslinking Technologies For Waterborne & Powder Coatings, Mengfei Huang
Development Of Crosslinking Technologies For Waterborne & Powder Coatings, Mengfei Huang
Doctoral Dissertations
Waterborne coatings and powder coatings are fast-growing sectors of the world coating market due to their environmentally friendliness as they have low or zero volatile organic compounds (VOCs) emission. However, compared with solventborne coatings, significant limitations need to be overcome to enable their broad applications. My dissertation will discuss several novel crosslinking strategies for waterborne and powder coating that could enable curing on-demand at ambient conditions, with facile polymerization and easy processing, and ultimately, exhibit a high degree of crosslinking and excellent performance that is comparable to solventborne coatings. We introduced and demonstrated the anionic polymerization mechanism and the high …
Advanced Materials Design Using Application-Based Processing Techniques, Daniel S. Camarda
Advanced Materials Design Using Application-Based Processing Techniques, Daniel S. Camarda
Doctoral Dissertations
This dissertation pertains to generating advanced materials using application-based processing techniques. First, billets consisting of PTFE sintering powders are evaluated using Thermomechancal Analysis. It was found that both shape change and volume change are associated with enthalpic and entropic recoil, respectively. These phenomena, due to melting and stored energy during the powder compaction process, were found to be molecular weight dependent. Additionally, kinetics of the recovery and sintering process were found to be slower in blended specimens than pure samples. Next, the creation of graft copolymers by selectively grafting a second polymer to the amorphous fraction of a semi-crystalline polymer …
Spectroscopic Investigations Of Zeolite-Catalyzed Carbenium Ion Chemistry, Eric David Hernandez
Spectroscopic Investigations Of Zeolite-Catalyzed Carbenium Ion Chemistry, Eric David Hernandez
Doctoral Dissertations
The catalytic conversion of methanol to olefins on zeolites is an industrially important process, yet the mechanistic details remain unresolved. Enylic cations (unsaturated carbenium ions) are active intermediates in the production of olefins and aromatics. However, these long-lived species are also precursors to carbonaceous deposits, the accumulation of which is responsible for catalyst deactivation. The aim of this work is to develop a mechanistic understanding that will ultimately allow steering the surface chemistry toward active intermediates. An in situ spectroscopic approach is applied to determine the nature of the relevant surface species and to track their transformations. The UV–vis and …
Direct Printing/Coating/Plating Of Key Components For Electronic Devices, Xiyu Hu
Direct Printing/Coating/Plating Of Key Components For Electronic Devices, Xiyu Hu
Doctoral Dissertations
Miniaturization has been a technological trend for several decades for electronic devices. From the practical point of view, the successful miniaturization of fully integrated systems mainly depends on their components. This dissertation examines the inkjet printing of copper oxide inks on flexible substrates for applications in microfluidic valving systems. We expand the knowledge of low-cost and high-performance electrowetting valves and fabricate the microfluidic device for fluidic control, which is necessary to enable the next-generation microfluidic devices. In addition, we also study the electromagnetic interference (EMI) shielding material, which is a crucial part of electronic devices. The basic theory of EMI …
Novel Approaches Towards Improved Purity In High Yield Transcription Reactions, Elvan Cavac
Novel Approaches Towards Improved Purity In High Yield Transcription Reactions, Elvan Cavac
Doctoral Dissertations
High yields of RNA (e.g., mRNA, gRNA, lncRNA) are routinely prepared following a two-step approach: high yield in vitro transcription using T7 RNA polymerase, followed by extensive purification using gel or chromatic methods. In high yield transcription reactions, as RNA accumulates in solution, T7 RNA polymerase rebinds and extends the encoded RNA (using the RNA as a template), resulting in a product pool contaminated with longer than desired, (partially) double stranded impurities. Current purification methods often fail to fully eliminate these impurities which, if present in therapeutics, can stimulate the innate immune response with potentially fatal consequences. This study establishes …
Surface Modification Of Cellulose Nanocrystals: Imparting Non-Native Properties On Sustainable Substrates, Allen C. Chang
Surface Modification Of Cellulose Nanocrystals: Imparting Non-Native Properties On Sustainable Substrates, Allen C. Chang
Doctoral Dissertations
Governments and scientists all over the planet have recognized the importance of pursuing and achieving sustainability. As the human population grows and technologies advance, the planet’s limited resources become less and less able to support our taxing demands. In 2015, the United Nations set forth 17 Sustainable Development Global Goals. Goal 12 “Responsible Production and Consumption” can be addressed quite readily by the integration of sustainable materials into advanced technologies; however, such materials have yet to be developed. Cellulose nanocrystals (CNCs) – an abundant, well-known sustainable nanomaterial hydrolyzed from bulk cellulose with high surface functionality and high strength properties – …
Synthesis Of Inorganic Porous Materials With Tunable Morphology For Molecular Adsorption And Separation, Sanket Sabnis
Synthesis Of Inorganic Porous Materials With Tunable Morphology For Molecular Adsorption And Separation, Sanket Sabnis
Doctoral Dissertations
Global industrial and economic development over the past century has largely relied on combustion of non-renewable fossil fuels, such as petroleum, coal, and natural gas, which are also harmful to environment because of the release of CO2, responsible for global warming and climate change. Establishing eco-friendly, energy-efficient and cost-effective processes to reduce environmental impact is currently one of the most urgent issues for the sustainable development of our society. Inorganic porous materials have found applications in the fields of renewable energy and environmental protection such as biomass conversion, fuel cells, thermal energy storage, CO2 capture and conversion, …
Electrospinning Fibers Via Complex Coacervation, Xiangxi Meng
Electrospinning Fibers Via Complex Coacervation, Xiangxi Meng
Doctoral Dissertations
Electrospun fibers are high-surface-area materials widely used in applications ranging from batteries to wound dressings. Typically, an electrospinning precursor solution is prepared by dissolving a high-molecular-weight polymer in an organic solvent to form a sufficiently entangled solution. Our approach bypasses the requirement for entanglements and completely avoids toxic chemicals by focusing on using an aqueous complex coacervates solution. Coacervates are a dense, polymer-rich liquid phase resulting from the associative electrostatic complexation of oppositely charged macroions. We were the first to demonstrate that liquid complex coacervates could be successfully electrospun into polyelectrolyte complex (PEC) fibers. A canonical coacervate system was formed …
Metabolic Modeling Of Gas Fermentation For Renewable Fuel And Chemical Production, Xiangan Li
Metabolic Modeling Of Gas Fermentation For Renewable Fuel And Chemical Production, Xiangan Li
Doctoral Dissertations
Gas fermentation has emerged as a technologically and economically attractive option for producing renewable fuels and chemicals from carbon monoxide (CO) rich waste streams. As compared to traditional catalyst technologies, microbial systems have several advantages including operation near ambient temperature and pressure, high conversion efficiencies, robustness to gas impurities and high product yields that have motivated both fundamental research and commercial development. While microbial production of high-value products from waste gases is challenging because wild-type strains capable of gas consumption tend to synthesize these products at low yields, strategy like metabolically engineering the gas fermenting acetogens have been studied to …
Experimental Study Of Viscoelastic Fluid-Structure Interactions, Anita Anup Dey
Experimental Study Of Viscoelastic Fluid-Structure Interactions, Anita Anup Dey
Doctoral Dissertations
It is well known that when a flexible or flexibly-mounted structure is placed perpendicular to a Newtonian fluid flow, it can oscillate due to the shedding of vortices at high Reynolds numbers. Unlike Newtonian fluids, viscoelastic fluid flow can become unstable even at infinitesimal Reynolds numbers due to a purely elastic flow instability occurring at large Weissenberg numbers. This thesis focuses on exploring the mechanisms of viscoelastic fluid-structure interactions (VFSI) through experimental investigations on several different combinations of flexible and flexibly-mounted circular cylinders, micro and macro-scale cantilevered beams and viscoelastic fluids such as wormlike micelle solutions and polymer solutions. VFSI …
Encapsulation And Stabilization Of Biomacromolecules, Whitney Blocher Blocher Mctigue
Encapsulation And Stabilization Of Biomacromolecules, Whitney Blocher Blocher Mctigue
Doctoral Dissertations
Recent work in the area of protein encapsulation has turned away from traditional methods of sequestration toward gentler, purely aqueous techniques. Among them, complex coacervation has become a topic of discussion. Complex coacervation is an all-aqueous liquid-liquid phase separation phenomenon dominated by electrostatic interactions and entropic gains. The use of coacervates as protein encapsulants has garnered much attention, but there has been little headway in determining a set of design rules. We considered coacervation between two oppositely-charged polypeptides and a biomacromolecule cargo to investigate the effects of changing aspects of the coacervating polymers and/or various solution parameters. We characterized the …
Micro-Physiological Models To Mimic Mucosal Barrier Complexity Of The Human Intestine In Vitro, Abhinav Sharma
Micro-Physiological Models To Mimic Mucosal Barrier Complexity Of The Human Intestine In Vitro, Abhinav Sharma
Doctoral Dissertations
The mucosal barrier in the intestine is vital to maintain selective absorption of nutrients while protecting internal tissues and maintaining symbiotic relationship with luminal microbiota. This bio-barrier consists of a cellular epithelial barrier and an acellular mucus barrier. Secreted mucus regulates barrier function via in situ biochemical and biophysical interaction with luminal content that continually evolves during digestion and absorption. Increasing evidence suggests that a mucus barrier is indispensable to maintain homeostasis in the gastrointestinal tract. However, the importance of mucus barrier is largely underrated for in vitro mucosal tissue modeling. The major gap is the lack of experimental material …
Nano- And Micro-Structured Temperature-Sensitive Hydrogels For Rapidly Responsive Devices, Qi Lu
Nano- And Micro-Structured Temperature-Sensitive Hydrogels For Rapidly Responsive Devices, Qi Lu
Doctoral Dissertations
This thesis aims to extend the understanding and explore the application of temperature-responsive hydrogel systems by integrating microelectromechanical systems (MEMS). Stimuli-responsive hydrogel systems are immensely investigated and applied in numerous fields, and interfacing with micro- and nano-fabrication techniques will open up more possibilities. In Chapter 2, the first biologically relevant, in vitro cell stretching device based on hydrogel surface instability was developed. This dynamic platform is constructed by embedding micro-heater devices under temperature-responsive surface-attached hydrogels. The fast and regional temperature change actuates the stretching and relaxation of the seeded human artery smooth muscle cell (HASMC) via controllable surface creasing instability. …
Sequence Control Of Complex Coacervation, Li-Wei Chang
Sequence Control Of Complex Coacervation, Li-Wei Chang
Doctoral Dissertations
Complex coacervation is a liquid-liquid phase separation driven by the complexation of oppositely charged polyelectrolytes. The resulting coacervate phase has been used for many applications, such as underwater adhesives, drug delivery, food and personal care products. There also has been increasing interest in coacervate-like droplets occurring in biological systems. The majority of these “membraneless organelles” involve a combination of intrinsically-disordered proteins and RNA, and phase separate due to long-range charge effects and short-range hydrophobic effects. While evolution has optimized the self-assembly of these types of biological polymers, our ability to design such materials remains limited, in part because the relevant …
Development And Characterization Of Robust And Cost-Effective Catalysts For Selective Biomass Upgrading To Fuels And Chemicals By Deoxydehydration, Bryan E. Sharkey
Development And Characterization Of Robust And Cost-Effective Catalysts For Selective Biomass Upgrading To Fuels And Chemicals By Deoxydehydration, Bryan E. Sharkey
Doctoral Dissertations
The use of biomass-derived ligno-cellulose as a possible alternative source of fuels and chemicals to fossil-based hydrocarbons, however, biomass offers many challenges based on processing and its high oxygen content. One promising upgrading route is deoxydehydration, a reaction which combines a deoxygenation by a sacrificial reductant and dehydration in a single step to selectively convert vicinal diols into an olefin. This reaction is highly selective when using homogeneous oxo-rhenium catalysts, which can easily undergo the necessary changes in coordination and oxidation state, however the high cost of rhenium and difficulty of homogeneous catalyst recovery make these catalysts untenable for large …
Elucidating Mechanisms Of Metastasis With Implantable Biomaterial Niches, Ryan Adam Carpenter
Elucidating Mechanisms Of Metastasis With Implantable Biomaterial Niches, Ryan Adam Carpenter
Doctoral Dissertations
Metastasis is the leading cause of cancer related deaths, yet it remains the most poorly understood aspect of tumor biology. This can be attributed to the lack of relevant experimental models that can recapitulate the complex and lengthy progression of metastatic relapse observed in patients. Mouse models have been widely used to study cancer, however they are critically limited to study metastasis. Most models generate aggressive metastases in the lung without the use of unique cell lines or specialized injection techniques. This limits the ability to study disseminated tumor cells (DTCs) in other relevant metastasis prone tissues. Prolonged observation of …
Kinetics Of The Crystal-Melt Phase Transformation In Semicrystalline Polymers, Kiran Subramaniam Iyer
Kinetics Of The Crystal-Melt Phase Transformation In Semicrystalline Polymers, Kiran Subramaniam Iyer
Doctoral Dissertations
The assembly of long-chain polymers into an ordered state is a process that has puzzled polymer scientists for several decades. A process that is largely controlled by the strength of intermolecular attractions in small molecular systems, this crystallization in the case of polymers is controlled by a competition between the aforementioned force of attraction between monomers and the formidable conformational entropy of polymer chains. Any factor that affects this conformational entropy, whether that is an equilibrium thermodynamic factor or a kinetic factor, has the ability to control polymer crystallization. In this thesis, we focus on understanding the underlying kinetic processes …