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Articles 1 - 30 of 109
Full-Text Articles in Engineering
Effects Of Polymer-Nanoparticle Interactions On The Dynamics Of Attractive Polyhedral Oligomeric Silsesquioxane Nanocomposites, Walter W. Young
Effects Of Polymer-Nanoparticle Interactions On The Dynamics Of Attractive Polyhedral Oligomeric Silsesquioxane Nanocomposites, Walter W. Young
Doctoral Dissertations
Polyhedral oligomeric silsesquioxane (POSS) had long been recognized as a critical building block for inorganic-organic hybrid materials with unique and desirable properties and performance. Through synthesis and characterization of polymer/POSS nanocomposites, direct insights into the significant effects of the polymer/POSS interactions on the resulting material properties are obtained. Random copolymers of a hydrogen-bond accepting monomer and a non-interacting monomer are synthesized and loaded with a model amine-functionalized hydrogen bond donating POSS molecule via solution casting, to create a material with well-controlled dynamical heterogeneity. The increase in the glass transition temperature (Tg) of these materials is found to strongly depend on …
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 …
Controlling Mechanical Properties Of Well-Defined Polymer Networks, Ipek Sacligil
Controlling Mechanical Properties Of Well-Defined Polymer Networks, Ipek Sacligil
Doctoral Dissertations
Polymer networks are one of the most versatile and highly studied material class that revolutionized many aspects of life. Connecting the final network properties to the molecular parameters of its building blocks remains a major research thrust. Recent advances in network synthesis techniques allowed for accurate predictions of elastic modulus in model networks. Tew Group has developed highly efficient, thiol-norbornene networks with controllable mechanical properties. Chapter 2 focuses on modifying the gel fracture energy predicted by Lake-Thomas theory by accounting for loop defects. This study allowed for a priori estimates of gel fracture energy by combining theory, experiments, and simulations. …
Bottom-Up Morphological Control Of Biphasic Polymer Particles Via Heterogeneous Polymerization, Heather S.C. Hamilton
Bottom-Up Morphological Control Of Biphasic Polymer Particles Via Heterogeneous Polymerization, Heather S.C. Hamilton
Doctoral Dissertations
Heterogeneous polymerization techniques are industrially relevant, scalable methods to synthesize polymer colloids and they have emerged in recent decades as viable methods to produce biphasic and morphologically complex polymer particles. The overarching goal of this thesis is to understand how heterogeneous polymerization techniques can be modified and optimized to control particle morphology through the systematic study of process parameters. Chapter 1 introduces relevant nomenclature and provides a brief historical perspective on the development of heterogeneous polymerization. This chapter also reviews the state-of-the-art techniques used to prepare morphologically complex polymer particles, with an emphasis on the heterogeneous polymerization processes studied in …
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 …
Vapor Deposition Of Self-Wrinkling Polymer Films, Robert N. Enright
Vapor Deposition Of Self-Wrinkling Polymer Films, Robert N. Enright
Doctoral Dissertations
Initiated chemical vapor deposition is used to grow polymer films on substrates of various three-dimensional shapes which exhibit wrinkling during film growth, termed self-wrinkling. Self-wrinkling avoids separate film growth and compression steps and more-closely mimics processes observed in nature. The self-wrinkling process is elucidated on flat elastic substrates, revealing control over the amount of compressive stress by changing deposition conditions. Next, a study of films grown on liquid substrates with interface profiles that either resemble cylinders or contain repeating concave cones, saddles, and bowls affirms the principle that the wrinkle roundness increases with interface curvature. The selection of high versus …
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 …
Quantifying Elasto-Adhesion And Fluid-Elastic Dynamics For Ultra-Soft Hydrogel Interfaces, Hongbo Fu
Quantifying Elasto-Adhesion And Fluid-Elastic Dynamics For Ultra-Soft Hydrogel Interfaces, Hongbo Fu
Doctoral Dissertations
Hydrogels are constructed with polymer networks swollen with water, which are soft and with much smaller shear moduli than bulk moduli. Due to the similar moduli to biological tissues, synthetic hydrogels have been used for biological applications. While interfacial properties are important for many of the applications of soft materials, quantifying these properties is challenging for ultra-soft materials. Ultra-softness causes difficulties in measuring interfacial properties with conventional force-based methods. For example, soft specimens deform largely under gravity and external forces, and thus the assumptions of the established methods are invalid. Additionally, many of the applications for hydrogels require them to …
Enabling Nanoimprint Lithography Techniques Across Multiple Manufacturing Processes, Vincent Einck
Enabling Nanoimprint Lithography Techniques Across Multiple Manufacturing Processes, Vincent Einck
Doctoral Dissertations
Advanced nanooptics in the areas of flat lenses, diffractive elements, and tunable emissivity require a route to high throughput manufacturing. Nanooptics are often demanding of high refractive index materials, nanometer precision and ease of fabrication. Nanoimprint lithography (NIL) is a low-cost, high throughput manufacturing technique beginning to be realized in commercial industry.1,2 The NIL process is an ideal manufacturing candidate due to its ability to have a fast process time, efficient use of materials, repeatability and high precision while also having wide diversity of potential structures and material choices. Appling NIL techniques to other facets of manufacturing enable the …
Additive Manufacturing Of Sub-Micron Features And Mechanical Linkages, David K. Limberg
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 …
Phase Behavior Of Oppositely Charged Polymerized Ionic Liquids In Solution, Bulk, And Crosslinked Network States, Minjung Lee
Phase Behavior Of Oppositely Charged Polymerized Ionic Liquids In Solution, Bulk, And Crosslinked Network States, Minjung Lee
Doctoral Dissertations
Polymerized ionic liquids (PILs), a class of polyelectrolytes, are fascinating materials for various applications utilizing ion transport, especially due to their advantageous properties including negligible vapor pressure, low flammability, thermal stability, high conductivity, and wide electrochemical stability windows. Furthermore, PILs are tunable in their properties such as ionic conductivity, glass transition temperature (Tg), solubility, and (electro-)chemical stability. In this thesis, we focus on fundamental studies of phase behaviors of PILs in the solution and bulk states in chapters 2 and 3, respectively. Specifically, non-aqueous systems are used to study the effect of solvent quality in the regime …
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 …
Synthesis, Fabrication, And Assembly Of Mesoscale Polymer Filaments, Dylan M. Barber
Synthesis, Fabrication, And Assembly Of Mesoscale Polymer Filaments, Dylan M. Barber
Doctoral Dissertations
Mesoscale materials, with feature sizes in the range of one hundred nanometers to tens of micrometers, are ubiquitous in Nature. In organisms, mesoscale building blocks connect the properties of underlying molecular and nanoscructures to those of macroscale, organism-scale materials through hierarchical assemblies of recurring structural motifs. The collective action of large numbers of mesoscale features can afford stunning features like the structural color of the morpho butterfly wing, calcium ion-mediated movement in muscle, and wood structures like xylem that can support enormous external compressive loads and negative internal pressure to transport nutrients throughout an organism. In synthetic systems, the design, …
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 …
Designing Nonflammable Polymers And Blends Containing Deoxybenzoin Derivatives, Elizabeth Stubbs
Designing Nonflammable Polymers And Blends Containing Deoxybenzoin Derivatives, Elizabeth Stubbs
Doctoral Dissertations
The importance of synthetic polymers in everyday life continues to grow, owing to their societal importance for improving our standard-of-living and enabling advances spanning medicine, electronics, construction materials, transportation. While niche applications occupy a small fraction of the overall volume of polymers produced, large scale applications tend to employ lower cost materials, such as polyethylene, polypropylene, and polystyrene. In addition to environmental considerations connected to these polymerized hydrocarbons, produced in excess of 380 million tons per year worldwide, their inherent flammability creates additional requirements associated with their manufacturing and use. Societal benefits of such polymers are extensive, and thus, there …
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 …
Designing Stimuli-Responsive Nanocomposites To Investigate Interface Dynamics, Huyen Vu
Designing Stimuli-Responsive Nanocomposites To Investigate Interface Dynamics, Huyen Vu
Doctoral Dissertations
Inspired by nature, this research focuses on designing multifunctional renewable nanocomposites with high toughness and stimuli-responsiveness. In recent years, cellulose nanocrystals (CNCs) have been explored due to their abundance, renewable resource, and unique mechanical strength and structural coloration. CNCs naturally self-assemble into the helicoidal (Bouligand) structure that effectively endure high impacts but is brittle without an attendant soft phase. A thermoresponsive polymer, poly(diethylene glycol methyl ether methacrylate) (PMEO2MA), was incorporated into CNCs via evaporation-induced self-assembly to improve toughness of the resulting nanocomposites and to study responses in polymer dynamics under varying temperature and humidity conditions. To study microscopic …
Thermoelectric Transport In Disordered Organic And Inorganic Semiconductors, Meenakshi Upadhyaya
Thermoelectric Transport In Disordered Organic And Inorganic Semiconductors, Meenakshi Upadhyaya
Doctoral Dissertations
The need for alternative energy sources has led to extensive research on optimizing the conversion efficiency of thermoelectric (TE) materials. TE efficiency is governed by figure-of-merit (ZT) and it has been an enormously challenging task to increase ZT > 1 despite decades of research due to the interdependence of material properties. Most doped inorganic semiconductors have a high electrical conductivity and moderate Seebeck coefficient, but ZT is still limited by their high lattice thermal conductivity. One approach to address this problem is to decrease thermal conductivity by means of alloying and nanostructuring, another is to consider materials with an inherently low …
Engineering Advanced Material Properties For Polymeric Materials Through Miscible And Immiscible Additives, Chinmay M. Saraf
Engineering Advanced Material Properties For Polymeric Materials Through Miscible And Immiscible Additives, Chinmay M. Saraf
Doctoral Dissertations
This dissertation focuses on engineering polymeric formulations using strategically selected additives or novel processes to achieve advanced material properties. The first chapter reviews the state-of-the-art impact modification and discusses micro-mechanics associated with soft particle toughening of polymeric materials. We present an analytical solution to elucidate the effect of concentration of rubbery domains on matrix yielding and energy absorption. Soft particle toughening relies on particle size, interparticle spacing, and concentration of rubbery phase. The second chapter demonstrates developing impact modified stereolithography (SLA) resins for the superior energy absorption of the SLA printed thermosets. SLA resins are engineered using additives that remain …
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 …
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 – …
Theory And Improved Methods For Probing The Cavitation To Fracture Transition, Christopher Barney
Theory And Improved Methods For Probing The Cavitation To Fracture Transition, Christopher Barney
Doctoral Dissertations
A material is considered soft when its bulk modulus is significantly greater than its shear modulus. Rubbery polymers are a class of soft materials where resistance to extension is mainly entropic in nature. Polymeric soft solids differ from liquids due to the presence of a percolated network of strong bonds that resist deformation and flow on a given time scale. The incompressible nature, entropically driven elasticity, and molecular scale network structure of soft polymeric solids combine to impart unique mechanical behavior that often results in complex material responses to simple loading situations. An important example of this is cavitation in …
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. …
Resistive Switching Characteristics Of Nanostructured And Solution-Processed Complex Oxide Assemblies, Zimu Zhou
Doctoral Dissertations
Miniaturization of conventional nonvolatile (NVM) memory devices is rapidly approaching the physical limitations of the constituent materials. An emerging random access memory (RAM), nanoscale resistive RAM (RRAM), has the potential to replace conventional nonvolatile memory and could foster novel type of computing due to its fast switching speed, high scalability, and low power consumption. RRAM, or memristors, represent a class of two terminal devices comprising an insulating layer, such as a metal oxide, sandwiched between two terminal electrodes that exhibits two or more distinct resistance states that depend on the history of the applied bias. While the sudden resistance reduction …
Surface Driven Flows : Liquid Bridges, Drops And Marangoni Propulsion, Samrat Sur
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 …
Top-Down And Bottom-Up Fabrication Of Key Components In Miniature Energy Storage Devices, Wenhao Li
Top-Down And Bottom-Up Fabrication Of Key Components In Miniature Energy Storage Devices, Wenhao Li
Doctoral Dissertations
The advent of miniature electronic devices demands power sources of commensurate form factors. This spurs the research of micro energy storage devices, e.g., 3D microbatteries. A 3D microbattery contains nonplanar microelectrodes with high aspect ratio and high surface area, separated by a nanoscale electrolyte. The device takes up a total volume as small as 10 mm3, allowing it to serve on a chip and to provide power in-situ. The marriage of nanotechnology and electrochemical energy storage makes microbattery research a fascinating field with both scientific excitement and application prospect. However, successful fabrication of well-functioned key components …
Bioinspired Complex Nanoarchitectures By Dna Supramolecular Polymerization, Laura A. Lanier
Bioinspired Complex Nanoarchitectures By Dna Supramolecular Polymerization, Laura A. Lanier
Doctoral Dissertations
Bioinspired nanoarchitectures are of great interest for applications in fields such as nanomedicine, tissue engineering, and biosensing. With this interest, understanding how the physical properties of these complex nanostructures relate to their function is increasingly important. This dissertation describes the creation of complex nanoarchitectures with controlled structure and the investigation of the effect of nanocarrier physical properties on cell uptake for applications in nanomedicine. DNA self-assembly by supramolecular polymerization was chosen to create complex nanostructures of controlled architectures. We demonstrated that the supramolecular polymerization of DNA known as hybridization chain reaction (HCR) is in fact a living polymerization. The living …
Engineering Nanomaterials For Imaging And Therapy Of Bacteria And Biofilm-Associated Infections, Akash Gupta
Engineering Nanomaterials For Imaging And Therapy Of Bacteria And Biofilm-Associated Infections, Akash Gupta
Doctoral Dissertations
Infections caused by multidrug-resistant (MDR) bacteria pose a serious global burden of mortality, causing thousands of deaths each year. The “superbug” risk is further exacerbated by chronic infections generated from antibiotic-resistant biofilms that are highly resistant to available treatments. Synthetic macromolecules such as polymers and nanoparticles have emerged as promising antimicrobials. Moreover, ability to modulate nanomaterial interaction with bacterial cellular systems plays a pivotal role in improving the efficacy of the strategy. In the initial studies on engineering nanoparticle surface chemistry, I investigated the role played by surface ligands in determining the antimicrobial activity of the nanoparticles. In further study, …