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Full-Text Articles in Engineering

The Rheology And Roll-To-Roll Processing Of Shear-Thickening Particle Dispersions, Sunilkumar Khandavalli Nov 2017

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 Nov 2017

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 Nov 2017

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 Nov 2017

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 Nov 2017

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 Nov 2017

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 Nov 2017

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 …


Solution-Based Assembly Of Conjugated Polymers Into Nanofibers For Organic Electronics, Daniel E. Acevedo Cartagena Nov 2017

Solution-Based Assembly Of Conjugated Polymers Into Nanofibers For Organic Electronics, Daniel E. Acevedo Cartagena

Doctoral Dissertations

Solution-based crystallization of conjugated polymers offers a scalable and attractive route to develop hierarchical structures for electronic devices. The introduction of well-defined nucleation sites into metastable solutions provides a way to regulate the crystallization behavior, and therefore the morphology of the material. A crystallization method for generating metastable solutions of poly(3-hexylthiophene) (P3HT) was established. These metastable solutions allow P3HT to selectively crystallize into nanofibers (NFs) on graphene-coated surfaces. It was found that the crystallization kinetics is faster with increasing P3HT molecular weight and concentration. Through in situ atomic force microscopy, it was confirmed that NFs grow vertically in a face-on …


Guiding The Self-Assembly Of Block Copolymers In 2d And 3d With Minimal Patterning, Jaewon Choi Nov 2017

Guiding The Self-Assembly Of Block Copolymers In 2d And 3d With Minimal Patterning, Jaewon Choi

Doctoral Dissertations

Directed self-assembly (DSA) of block copolymers (BCPs) based on topographic patterns is one of the most promising strategies for overcoming resolution limitations in the current lithographic process and fabricating the next generation data storage devices. While the DSA of BCPs with deep topographic patterning has been extensively studied both experimentally and theoretically over the past two decades, less attention has been paid to the development of the DSA process using minimal topographic patterning. This dissertation focuses on understanding the effect of minimal topographic patterning on guiding the self-assembly of BCPs in 2D and 3D. We demonstrate that minimal trench patterns …


Numerical Simulation Of Multi-Phase Core-Shell Molten Metal Drop Oscillations, Kaushal Sumaria Oct 2017

Numerical Simulation Of Multi-Phase Core-Shell Molten Metal Drop Oscillations, Kaushal Sumaria

Masters Theses

The surface tension of liquid metals is an important and scientifically interesting parameter which affects many metallurgical processes such as casting, welding and melt spinning. Conventional methods for measuring surface tension are difficult to use for molten metals above temperatures of 1000 K. Containerless methods are can be used to measure the surface tension of molten metals above 1000 K. Oscillating drop method is one such method where a levitated droplet is allowed to undergo damped oscillations. Using the Rayleigh’s theory for the oscillation of force-free inviscid spherical droplets, surface tension and viscosity of the sample can be calculated from …


Development Of High Early-Strength Concrete For Accelerated Bridge Construction Closure Pour Connections, Stephanie Castine Jul 2017

Development Of High Early-Strength Concrete For Accelerated Bridge Construction Closure Pour Connections, Stephanie Castine

Masters Theses

Accelerated bridge construction (ABC) has become a popular alternative to using traditional construction techniques in new bridge construction and existing bridge deck replacement because of the reduction of time spent in field activities. A key feature of bridges built using ABC techniques is the extensive use of prefabricated components. Prefabricated components are joined in the field using small volume closure pours involving high performance materials (steel and concrete) to ensure adequate transfer of forces between components. To date, the materials developed for closure pours have been based on proprietary components, so a need has arisen for development of mixes that …


Synthesis, Characterization And Application Of Block Copolymer And Nanoparticle Composites, Yue Gai Jul 2017

Synthesis, Characterization And Application Of Block Copolymer And Nanoparticle Composites, Yue Gai

Doctoral Dissertations

The “bottom-up” fabrication of functional hybrid material can be achieved by using directed self-assembly of functional nanoparticles (NP) and block copolymers (BCP) as templates. The versatile nanostructures of BCP provide possibilities to precisely control NPs spatial distribution and the resulting hybrid materials exhibit enhanced electrical, mechanical and optical functionalities. Three main topics related to BCP/NP composites are discussed in this dissertation: I) the spatial distribution of large NP in linear BCP; II) the morphology control of BCP templates with new architectures; and III) the magneto-optical properties of hybrid material using magnetic NPs. For well-ordered BCP/NP composite, the ratio of NP …


Characterization Of Electronic And Ionic Transport In Soft And Hard Functional Materials, Lawrence A. Renna Jul 2017

Characterization Of Electronic And Ionic Transport In Soft And Hard Functional Materials, Lawrence A. Renna

Doctoral Dissertations

Control over concurrent transport of multiple carrier types is desired in both soft and hard materials. For both types of materials, I demonstrate ways to characterize and execute governance over both electronic and ionic transport, and apply these concepts in the fabrication of devices with applications in conducting composites, photovoltaics, electrochemical energy storage, and memristors. In soft materials, such as polymers, the topology of the binary polymer mesoscale morphology has major implications on the charge/ion transport. Traditional approaches to co-continuous structures involve either using blends of polymers or diblock copolymers. In polymer blends, the structures are kinetically trapped and …


Dynamic Range Limitations Of Low-Noise Microwave Transistors At Cryogenic Temperatures, Ahmet Hakan Coskun Jul 2017

Dynamic Range Limitations Of Low-Noise Microwave Transistors At Cryogenic Temperatures, Ahmet Hakan Coskun

Doctoral Dissertations

Dynamic range is an important metric that specifies the limits of input signal amplitude for the ideal operation of a given receiver. The low end of dynamic range is defined by the noise floor whereas the upper limit is determined by large-signal distortion. While dynamic range can be predicted in the temperature range where compact transistor models are valid, the lack of large-signal models at temperatures below -55 C prevents the prediction and optimization of dynamic range for applications that require cryogenic cooling. For decades, the main goal concerning the performance of these applications was lowering the noise floor of …


High Performance Silver Diffusive Memristors For Future Computing, Rivu Midya Mar 2017

High Performance Silver Diffusive Memristors For Future Computing, Rivu Midya

Masters Theses

Sneak path current is a significant remaining obstacle to the utilization of large crossbar arrays for non-volatile memories and other applications of memristors. A two-terminal selector device with an extremely large current-voltage nonlinearity and low leakage current could solve this problem. We present here a Ag/oxide-based threshold switching (TS) device with attractive features such as high current-voltage nonlinearity (~1010), steep turn-on slope (less than 1 mV/dec), low OFF-state leakage current (~10-14 A), fast turn ON/OFF speeds (<75/250 ns), and good endurance (>108 cycles). The feasibility of using this selector with a typical memristor has been demonstrated by physically integrating them …


The Impact Of Quantum Size Effects On Thermoelectric Performance In Semiconductor Nanostructures, Adithya Kommini Mar 2017

The Impact Of Quantum Size Effects On Thermoelectric Performance In Semiconductor Nanostructures, Adithya Kommini

Masters Theses

An increasing need for effective thermal sensors, together with dwindling energy resources, have created renewed interests in thermoelectric (TE), or solid-state, energy conversion and refrigeration using semiconductor-based nanostructures. Effective control of electron and phonon transport due to confinement, interface, and quantum effects has made nanostructures a good way to achieve more efficient thermoelectric energy conversion. This thesis studies the two well-known approaches: confinement and energy filtering, and implements improvements to achieve higher thermoelectric performance. The effect of confinement is evaluated using a 2D material with a gate and utilizing the features in the density of states. In addition to that, …


Thiol-Ene Chemistry As An Enabler Of New Polymer Structures And Architectures, Joel M. Sarapas Mar 2017

Thiol-Ene Chemistry As An Enabler Of New Polymer Structures And Architectures, Joel M. Sarapas

Doctoral Dissertations

This dissertation focuses on two distinct projects: the synthesis and design of novel cell penetrating peptides mimics (CPPMs), and the implementation of the thiol-ene click reaction to generate new polymer architectures and chemistries. Guanidinium-rich CPPMs were generated through both ROMP and RAFT polymerizations, allowing for a comparison to be made across polymer backbone chemistries with respect to both siRNA and protein cellular internalization. A particularly effective methacrylate derived block copolymer was able to deliver siRNA to nearly an entire Jurkat T cell population. The thiol-ene reaction was implemented initially within the context of improving material design for solid polymer electrolytes …


Deformation And Adhesion Of Soft Composite Systems For Bio-Inspired Adhesives And Wrinkled Surface Fabrication, Michael Imburgia Mar 2017

Deformation And Adhesion Of Soft Composite Systems For Bio-Inspired Adhesives And Wrinkled Surface Fabrication, Michael Imburgia

Doctoral Dissertations

The study of soft material deformation and adhesion has broad applicability to industries ranging from automobile tires to medical prosthetics and implants. When a mechanical load is imposed on a soft material system, a variety of issues can arise, including non-linear deformations at interfaces between soft and rigid components. The work presented in this dissertation embraces the occurrence of these non-linear deformations, leading to the design of functional systems that incorporate a soft elastomer layer with application to bio-inspired adhesives and wrinkled surface fabrication. Understanding the deformation of a soft elastomer layer and how the system loading and geometry influence …


New Synthetic Platforms For Functional Polymer Zwitterions And Degradable Materials, Chiachih Chang Mar 2017

New Synthetic Platforms For Functional Polymer Zwitterions And Degradable Materials, Chiachih Chang

Doctoral Dissertations

This thesis describes new synthetic platforms for a series of functional polymeric materials containing hydrophilic and/or zwitterionic moieties as pendent groups. The hydrophilicity, biocompatibility, and degradability of these polymers hinged on innovative monomer designs and adaption of appropriate polymerization strategies including controlled radical polymerization, metathesis polymerization, and ring-opening polymerization. Novel, functional sulfobetaine polymers having functional groups (i.e, alkenes and alkynes) directly attached to the zwitterionic moieties were prepared and shown to stabilize oil-water interfaces, allowing for interfacial crosslinking to afford robust polymer capsules. This represents the first example of inserting functionality directly into the zwitterionic moieties of polymer zwitterions, allowing …