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Articles 61 - 90 of 184
Full-Text Articles in Engineering
Rheological Investigations Of Self-Assembled Block Copolymer Nanocomposites With Complex Architectures, Benjamin Yavitt
Rheological Investigations Of Self-Assembled Block Copolymer Nanocomposites With Complex Architectures, Benjamin Yavitt
Doctoral Dissertations
The self-assembly of block copolymers (BCP) into microphase separated structures is an attractive route to template and assemble functional nanoparticles (NP) into highly ordered nanocomposites and is central to the “bottom up” fabrication of future materials with tunable electronic, optical, magnetic, and mechanical properties. The optimization of the co-assembly requires an understanding of the fundamentals of phase behavior, intermolecular interactions and dynamics of the polymeric structure. Rheology is a novel characterization tool to investigate these processes in such systems that are not accessible by other means. With the combination of X-ray scattering techniques, structure-property relationships are determined as a function …
Quantitative Probing Of Vacancies And Ions Dynamics In Electroactive Oxide Materials, Jiaxin Zhu
Quantitative Probing Of Vacancies And Ions Dynamics In Electroactive Oxide Materials, Jiaxin Zhu
Doctoral Dissertations
Oxygen vacancy and ion dynamics in functional oxides are critical factors influencing electrical conductivity and electrochemical activity of oxides assemblies. The recent advancements in deposition and fabrication of oxide heterostructured films with atomic-level precision has led to discovery of intriguing physical properties and new artificial materials. While still under debate, researchers most often attribute these observed behaviors to unique oxygen vacancy distributions in the substrate near heterointerfaces. In electroactive oxides devices such as solid oxide cells (SOCs), oxygen vacancy and ion transport at the triple-phase boundary determines the performance of the device. This complex process motivates numerous remaining questions regarding …
Probing Quantized Excitations And Many-Body Correlations In Transition Metal Dichalcogenides With Optical Spectroscopy, Shao-Yu Chen
Probing Quantized Excitations And Many-Body Correlations In Transition Metal Dichalcogenides With Optical Spectroscopy, Shao-Yu Chen
Doctoral Dissertations
Layered transition metal dichalcogenides (TMDCs) have attracted great interests in recent years due to their physical properties manifested in different polytypes: Hexagonal(H)-TMDC,which is semiconducting, exhibits strong Coulomb interaction and intriguing valleytronic properties; distorted octahedral(T’)-TMDC,which is semi-metallic, is predicted to exhibit rich nontrivial topological physics. In this dissertation,we employ the polarization-resolved micron-Raman/PL spectroscopy to investigate the optical properties of the atomic layer of several polytypes of TMDC. In the first part for polarization-resolved Raman spectroscopy, we study the lattice vibration of both H and T’-TMDC, providing a thorough understanding of the polymorphism of TMDCs. We demonstrate that Raman spectroscopy is a …
Synthesis And Molecular Transport Studies In Zeolites And Nanoporous Membranes, Vivek Vattipalli
Synthesis And Molecular Transport Studies In Zeolites And Nanoporous Membranes, Vivek Vattipalli
Doctoral Dissertations
The advent of nanoporous materials such as zeolites and nanoporous membranes has provided cost-effective solutions to some of the most pressing problems of the 20th century such as the conversion of crude oil into fuels and valuable chemicals. Hierarchical zeolites and mesoporous inorganic membranes are showing great promise in addressing new problems such as the conversion of biomass into value-added chemicals and development of energy-efficient separation processes. The synthesis and fundamental aspects of molecular transport in these new materials with hierarchical porosities need to be better understood in order to rationally develop them for these desired applications. Pore narrowing …
Development Of Functional Biomaterials Using Protein Building Blocks, Li-Sheng Wang
Development Of Functional Biomaterials Using Protein Building Blocks, Li-Sheng Wang
Doctoral Dissertations
Proteins have intrinsic molecular properties that are highly useful for materials applications, especially for biomaterials. My research has focused on translating these molecular properties to materials surface behavior. In one approach, I developed a fluorous-based thermal treatment strategy to generate stable thin films from a variety of naturally abundant proteins. The different surface properties generated from the choice of protein were utilized to modulate cell-surface interactions, prevent bacterial adhesions, and control drug loading/release. I have used nanoimprint lithography to generate patterned protein films for cell alignment. Coupling with inkjet printing deposition, I have fabricated mixed protein films with spatial and …
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 …
Direct Patterning Of Nature-Inspired Surfaces For Biointerfacial Applications, Feyza Dundar
Direct Patterning Of Nature-Inspired Surfaces For Biointerfacial Applications, Feyza Dundar
Doctoral Dissertations
There are three major challenges for the design of patterned surfaces for biointerfacial applications: (i) durability of antibacterial/antifouling mechanisms, (ii) mechanical durability, and (iii) lifetime of the master mold for mass production of patterned surfaces. In this dissertation, we describe our contribution for the development of each of these challenges. The bioinspired surface, Sharklet AFTM, has been shown to reduce bacterial attachment via a biocide-free structure-property relationship effectively. Unfortunately, the effectiveness of polymer-based sharkskin surfaces is challenged over the long term by both eventual bacteria accumulation and a lack of mechanical durability. To address these common modes of …
Direct Printing Of Conductive Inks For Organic Electronics And Wearable Microfluidics, Aditi Naik
Direct Printing Of Conductive Inks For Organic Electronics And Wearable Microfluidics, Aditi Naik
Doctoral Dissertations
This dissertation examines the direct printing of conductive inks on polymeric substrates for applications in organic electronics, microfluidic valving systems, and wearable sweat sensors. The inexpensive production of solution-based electrodes with high electrical conductivity is necessary to enable the next-generation of printed, flexible, and organic electronics. Specifically, the optimization and printing of liquid-phase graphene ink and nanoparticle-based silver ink by soft nanoimprint lithography and inkjet-printing is discussed to achieve printed functional devices. Using scalable low-cost patterning systems, these flexible applications are compatible with roll-to-roll processing, enabling large-scale manufacturing. This research expands the knowledge of high-resolution printing optimization for the direct …
The Investigation Of Surface Barrier During Molecular Transport In Hierarchical Zeolites, Xiaoduo Qi
The Investigation Of Surface Barrier During Molecular Transport In Hierarchical Zeolites, Xiaoduo Qi
Doctoral Dissertations
Hierarchical zeolites with micropore lengths on the order of nanometers have been synthesized with the aim of reducing mass transfer limitation. However, due to large external surface to volume ratios, the mass transport in these materials can be hindered by a secondary rate limitation step imposed on the external surface of the zeolites. This has led to the general phenomenon referred to as “surface barriers”, which cause the enhancement in mass transport being far lower than expected. In order to fully unlock the potential of hierarchical zeolites, it is imperative to fundamentally understand the molecular transport in these new types …
Engineering High Performance Epoxy Thermosets Using Next-Generation Impact Modification, Madhura Pawar
Engineering High Performance Epoxy Thermosets Using Next-Generation Impact Modification, Madhura Pawar
Doctoral Dissertations
Optimization of fracture toughness of high Tg thermosets was done through systematic investigation of different formulations of reactive functional modifiers using soft particle impact modification. Important parameters like particle size, interparticle distance (IPD) were varied by altering cure kinetics and modifying the molecular architecture of the additives. The best performing systems showed an increase in fracture toughness of 70-80% with an optimum Rp of 1.3 μm and IPD of 0.4 μm at 15 vol% impact modifier. In addition, a new platform of using block copolymer blends was studied for its feasibility to achieve non-spherical morphology for effective impact …
Fabrication Of High Refractive Index, Periodic, Composite Nanostructures For Photonic And Sensing Applications, Irene Howell
Fabrication Of High Refractive Index, Periodic, Composite Nanostructures For Photonic And Sensing Applications, Irene Howell
Doctoral Dissertations
This dissertation examines methods of fabricating high refractive index, periodic structures and their applications. Structures with a refractive index periodicity in one-dimensionally are fabricated by stacking layers of (high-refractive index) nanoparticle-filled and unfilled layers. More complex two- and three-dimensional structures are fabricated by direct printing of nanoparticles via solvent-assisted soft nanoimprint lithography. Polymer-nanoparticle composites are an active area of research and development especially for photonic applications. We show use of two composite formulations, first for fabrication of one-dimensional photonic crystals, and second for scalable UV-nanoimprinting. One dimensional photonic crystals, which possess a periodicity in refractive index, result in a constructive …
Probing Local Vacancy-Driven Resistive Switching In Metal Oxide Nanostructures, Jiaying Wang
Probing Local Vacancy-Driven Resistive Switching In Metal Oxide Nanostructures, Jiaying Wang
Doctoral Dissertations
Novel nonvolatile memory technologies garner intense research interest as conventional ash devices approach their physical limit. Memristors, often comprising an insulating thin film between two metal electrodes to constitute a class of two-terminal devices, enable a variety of important large data storage and data-driven computing applications. In addition to nonvolatile behavior, other features such as high scalability, low power consumption, and sub-nanosecond response times make memristors among the most attractive candidate systems. Their strength in electronic storage relies on the unique properties of the tunable variations in resistance induced from the accumulation of charged defects based on the applied bias …
Swelling Induced Deformation Of Thermally Responsive Hydrogels, Ying Zhou
Swelling Induced Deformation Of Thermally Responsive Hydrogels, Ying Zhou
Doctoral Dissertations
Hydrogels are crosslinked polymeric networks imbibed with aqueous solutions. They undertake dramatic volume changes through swelling and deswelling processes, which can be stimulated by factors like temperature, pH or different chemicals. These unique properties render hydrogels particularly interesting for shape morphing related applications. In this thesis, we focus on the swelling induced deformation of thermally responsive hydrogels with lower critical solution temperatures (LCSTs), including poly(N-isopropylacrylamide) (PNIPAm) and poly(N,N-diethylacrylamide) (PDEAm). Particularly, benzophenone containing monomers are copolymerized with NIPAm or DEAm to create photocrosslinkable temperature-responsive polymers, which allows fabrication of hydrogels with controlled shapes and crosslinking …
Extreme Indentation And Fracture Of Soft Polymer Gels, Shruti Rattan
Extreme Indentation And Fracture Of Soft Polymer Gels, Shruti Rattan
Doctoral Dissertations
The mechanical properties of conventional hard materials, such as metals and ceramics, have received widespread attention in the past several decades; however mechanical characterization, failure in particular, of soft materials, such as polymer gels, elastomers, and biological tissues and organs, has largely been ignored. While practical issues such as difficulty in handling, processing, and slippage offer complexities in characterization, the breakdown of the fundamental assumptions of linear elastic fracture mechanics due to large strains prior to failure, significant energy dissipation ahead of a crack tip and rate and time dependent effects makes understanding of failure in soft materials even more …
Parallel Algorithms For Time Dependent Density Functional Theory In Real-Space And Real-Time, James Kestyn
Parallel Algorithms For Time Dependent Density Functional Theory In Real-Space And Real-Time, James Kestyn
Doctoral Dissertations
Density functional theory (DFT) and time dependent density functional theory (TDDFT) have had great success solving for ground state and excited states properties of molecules, solids and nanostructures. However, these problems are particularly hard to scale. Both the size of the discrete system and the number of needed eigenstates increase with the number of electrons. A complete parallel framework for DFT and TDDFT calculations applied to molecules and nanostructures is presented in this dissertation. This includes the development of custom numerical algorithms for eigenvalue problems and linear systems. New functionality in the FEAST eigenvalue solver presents an additional level of …
Increasing Organic Semiconductor Performance Through Chemical And Processing Modifications, Edmund Burnett
Increasing Organic Semiconductor Performance Through Chemical And Processing Modifications, Edmund Burnett
Doctoral Dissertations
This thesis focuses on tuning molecular packing of organic semiconductors through processing or chemical modifications to increase performance and establish structure-property relationships. Chapter 2 utilizes differing processing techniques to alter the molecular packing of bistetracene in the thin film and thorough polymorph characterization to relate the modification of molecular packing to the increase in charge mobility and mechanism. Chapter 3 introduces the oligomer as a model system to resolve issues that would be difficult or impossible using polymeric systems, due to their monodispersity and increased crystallinity allows for more detailed structural characterization. In this chapter we determine a crystal packing …
Phonon Transport At Boundaries And Interfaces In Two-Dimensional Materials, Cameron Foss
Phonon Transport At Boundaries And Interfaces In Two-Dimensional Materials, Cameron Foss
Masters Theses
A typical electronic or photonic device may consist of several materials each one potentially meeting at an interface or terminating with a free-surface boundary. As modern device dimensions reach deeper into the nanoscale regime, interfaces and boundaries become increasingly influential to both electrical and thermal energy transport. While a large majority of the device community focuses on the former, we focus here on the latter issue of thermal transport which is of great importance in implementing nanoscale devices as well as developing solutions for on-chip heat removal and waste heat scavenging. In this document we will discuss how modern performance …
Dynamics And Structure Of Polyelectrolyte Complexes, Hamidreza Shojaei-Mahib
Dynamics And Structure Of Polyelectrolyte Complexes, Hamidreza Shojaei-Mahib
Doctoral Dissertations
Interaction of charged macromolecules among themselves and with charged interfaces in salty aqueous medium is a common phenomenon prevalent in biology and synthetic systems. We have addressed several inter-related issues in this general context. First we present a theory of adsorption of polyelectrolytes on the interior and exterior surfaces of a charged spherical vesicle. We derive the critical adsorption condition and the density profile of the polymer in terms of various characteristics of the polymer, vesicle, and the solution, such as the length and charge density of polymer, the radius and charge of the vesicle, the salt concentration of the …
Self-Assembling Networks In Soft Materials, Ishan Prasad
Self-Assembling Networks In Soft Materials, Ishan Prasad
Doctoral Dissertations
This dissertation presents a study on heterogeneous network structure in two distinct classes of soft material systems: disordered assemblies of jammed binary spheres and ordered morphologies of block copolymer melts. The aim is to investigate the combined role of geometry and entropy in structure formation of soft matter assemblies. First, we investigate the influence of particle size asymmetry on structural properties of jammed binary sphere mixtures. We give evidence of two distinct classes of materials separated by a critical size ratio that marks the onset of a sharp transition due to simultaneous jamming of a sub-component of the packing. We …
Engineering Next Generation Anisotropic Materials And Composites, Nihal Kanbargi
Engineering Next Generation Anisotropic Materials And Composites, Nihal Kanbargi
Doctoral Dissertations
Polymer-based composite systems have been developed for a wide variety of applications ranging from aerospace to electronics. My work has focused on the structure-process-property relationships of anisotropic polymeric materials and composites, aimed primarily for structural applications. Anisotropic materials such as fibers have superior mechanical properties along the axial direction and this property can be exploited to engineer exceptionally strong and light materials. In the first chapter, we discuss the physics of degradation of Poly(p-phenylene-2,6-benzobisoxazole) (PBO) fibers. PBO, a fiber of extraordinary tensile modulus and strength has been found to degrade rapidly under moderate conditions of humidity and heat. Solid-state NMR …
High Strain Rate Dynamic Response Of Aluminum 6061 Micro Particles At Elevated Temperatures And Varying Oxide Thicknesses Of Substrate Surface, Carmine Taglienti
High Strain Rate Dynamic Response Of Aluminum 6061 Micro Particles At Elevated Temperatures And Varying Oxide Thicknesses Of Substrate Surface, Carmine Taglienti
Masters Theses
Cold spray is a unique additive manufacturing process, where a large number of ductile metal micro particles are deposited to create new surface coatings or free-standing structures. Metallic particles are accelerated through a gas stream, reaching velocities of over 1 km/s. Accelerated particles experience a high-strain-rate microscopic ballistic collisions against a target substrate. Large amounts of kinetic energy results in extreme plastic deformation of the particles and substrate. Though the cold spray process has been in use for decades, the extreme material science behind the deformation of particles has not been well understood due to experimental difficulties arising from the …
Role Of Rigidity And Flexibility Of Functional Groups Within The Interior Of Supramolecular Assemblies And Their Implications, Oyuntuya Munkhbat
Role Of Rigidity And Flexibility Of Functional Groups Within The Interior Of Supramolecular Assemblies And Their Implications, Oyuntuya Munkhbat
Doctoral Dissertations
Engineering of supramolecular assemblies at molecular level renders functional nanomaterials that present explicit response to certain environmental changes. Systematic structure-property correlation studies will unravel the fundamental design constraints of these functional nanomaterials that fulfill the emergent need. This dissertation will primarily focus on understanding the role of rigidity and flexibility of functional groups within amphiphilic assemblies and employing this basic concept in drug delivery and diagnostics applications. Supramolecular assemblies formed by amphiphilic dendrimers and polymers are preferred for this study as they exhibit high thermodynamic stability and structural flexibility. The role of aromatic interaction on the unimer-aggregate dynamic equilibrium was …
Modeling Deformation Behavior And Strength Characteristics Of Sand-Silt Mixtures: A Micromechanical Approach, Mehrashk Meidani
Modeling Deformation Behavior And Strength Characteristics Of Sand-Silt Mixtures: A Micromechanical Approach, Mehrashk Meidani
Doctoral Dissertations
This dissertation is comprised of six chapters. In the first chapter the motivation of this research, which was modeling the deformation behavior and strength characteristics of soils under internal erosion, is briefly explained. In the second chapter a micromechanis-based stress-strain model developed for prediction of sand-silt mixtures behavior is presented. The components of the micromechanics-based model are described and undrained behavior of six different types of sand-silt mixtures is predicted for several samples with different fines contents. The need for a more comprehensive compression model for sand-silt mixtures is identified at the end of this chapter. This desired compression model …
The Rheology And Roll-To-Roll Processing Of Shear-Thickening Particle Dispersions, Sunilkumar Khandavalli
The Rheology And Roll-To-Roll Processing Of Shear-Thickening Particle Dispersions, Sunilkumar Khandavalli
Doctoral Dissertations
Particle dispersions are ubiquitous in our daily lives ranging from food and pharmaceutical products to inks. There has been great interest in the recent years in formulation of functional inks to fabricate myriad flexible electronic devices through high-throughput roll-to-roll technologies. The formulations often contain several functional additives or rheological modifiers that can affect the microstructure, rheology and processing. Understanding the rheology of formulations is important for tuning the formulation for optimal processing. This thesis presents investigations on the rheology of particle dispersions and their impact on roll-to-roll technologies. Shear-thickening behavior is common in particle dispersions, particularly, concentrated particulate inks. We …
The Role Of Chain Configuration In Governing The Rational Design Of Polymers For Adhesion, Onyenkachi Wamuo
The Role Of Chain Configuration In Governing The Rational Design Of Polymers For Adhesion, Onyenkachi Wamuo
Doctoral Dissertations
ABSTRACT THE ROLE OF CHAIN CONFIGURATION IN GOVERNING THE RATIONAL DESIGN OF POLYMERS FOR ADHESION SEPTEMBER 2017 ONYENKACHI C. WAMUO, B.Eng., FEDERAL UNIVERSITY OF TECHNOLOGY, OWERRI (FUTO), NIGERIA M.S., UNIVERSITY OF MASSACHUSETTS AMHERST Ph.D., UNIVERSITY OF MASSACHUSETTS AMHERST Directed by: Professor Shaw Ling Hsu The chain configurational control of polymers used in adhesion can be utilized as a means of tuning the cohesive properties of hot melt adhesives (HMAs). The cohesive properties control the solidification, strength, setting speed. Propylene-Ethylene copolymers (PP-co-PE) and thermoplastic polyurethanes (TPUs) were studied. In the first project, the effects of sequence distribution of the two types …
Computational Studies Of Structure–Function Relationships Of Supported And Unsupported Metal Nanoclusters, Hongbo Shi
Computational Studies Of Structure–Function Relationships Of Supported And Unsupported Metal Nanoclusters, Hongbo Shi
Doctoral Dissertations
Fuel cells have been demonstrated to be promising power generation devices to address the current global energy and environmental challenges. One of the many barriers to commercialization is the cost of precious catalysts needed to achieve sufficient power output. Platinum-based materials play an important role as electrocatalysts in energy conversion technologies. In order to improve catalytic efficiency and facilitate rational design and development of new catalysts, structure–function relationships that underpin catalytic activity must be understood at a fundamental level. First, we present a systematic analysis of CO adsorption on Pt nanoclusters in the 0.2-1.5 nm size range with the aim …
Analyses Of Densely Crosslinked Phenolic Systems Using Low Field Nmr, Jigneshkumar Patel
Analyses Of Densely Crosslinked Phenolic Systems Using Low Field Nmr, Jigneshkumar Patel
Doctoral Dissertations
A uniform dispersion of reactants is necessary to achieve a complete reaction involving multi-components, especially for the crosslinking of rigid high-performance materials. In these reactions, miscibility is crucial for curing efficiency. This miscibility is typically enhanced by adding a third component, a plasticizer. For the reaction of the highly crystalline crosslinking agent hexamethylenetetramine (HMTA) with a strongly hydrogen-bonded phenol formaldehyde resin, furfural has been traditionally used as the plasticizer. However, the reason for its effectiveness is not clear. In this doctoral thesis work, miscibility and crosslinking efficiency of plasticizers in phenolic curing reactions are studied by thermal analysis and spectroscopic …
Fabrication Of Functional Nano-Structured Materials And Devices Using Supercritical Fluids, Shengkai Li
Fabrication Of Functional Nano-Structured Materials And Devices Using Supercritical Fluids, Shengkai Li
Doctoral Dissertations
Nano-structured materials possess unconventional properties and enable miniaturization of devices. However, fabrications of such materials and devices are challenging and in many cases cumbersome, and development of nanofabrication techniques are essential to realizing novel designs and commercializing scientific ideas. Supercritical fluids possess a unique combination of gas-like diffusion properties and liquid-like dissolution power, and are suitable reaction media for fabricating materials at the nanometer scale. This dissertation focuses on developing supercritical fluids-related techniques for fast and large-scale fabrication of novel composite materials and devices. Using supercritical fluid deposition (SFD) technique, cobalt thin films were deposited on a variety of substrates, …
Polyorganosiloxanes: Molecular Nanoparticles, Nanocomposites And Interfaces, Daniel H. Flagg
Polyorganosiloxanes: Molecular Nanoparticles, Nanocomposites And Interfaces, Daniel H. Flagg
Doctoral Dissertations
Five research projects described. First, a reproducible, lab-scale synthesis of MQ silicone copolymers is presented. MQ copolymers are commercially important materials that have been ignored by the academic community. One possible reason for this is the difficulty of controlling and reproducing the preparative copolymerizations that have been reported. A reproducible method for lab-scale preparation was developed that controls molecular weight by splitting the copolymerization into the discrete steps of sol growth from silicate precursor and end-capping by trimethylsiloxy groups. Characterization of MQ products implicates that they are composed of highly condensed, polycyclic structures. The MQ copolymers prepared in the first …
Synthesis And Structure-Property Relationships Of Polymeric Membranes For Small Molecule Transport, Haomiao Yuan
Synthesis And Structure-Property Relationships Of Polymeric Membranes For Small Molecule Transport, Haomiao Yuan
Doctoral Dissertations
One key challenge for alkaline anion exchange membrane fuel cells is the lack of alkaline stable polycations. The synthesis of random, crosslinked and block copolymers based on the cobaltocenium phenylene norbornene (NPC) monomer is described. The polymers were synthesized from ring-opening metathesis polymerization (ROMP) of the NPC monomer showed excellent thermo-alkaline and thermo-oxidative stability. Random copolymers, crosslinked networks and amphiphilic diblock copolymers were prepared by copolymerizing NPC with different hydrophobic monomers: norbornene for random copolymers, dicyclopentadiene for crosslinked networks and a norbornene dibenzyl ether monomer for amphiphilic diblock copolymers. Mechanical robust membranes were prepared from all these copolymers. Polymers with …