Materials Science and Engineering Commons^™

First-Principles Studies Of Structure-Property Relationships: Enabling Design Of Functional Materials, Qunfei Zhou

Theses and Dissertations--Chemical and Materials Engineering

First-principles calculations based on quantum mechanics have been proved to be powerful for accurately regenerating experimental results, uncovering underlying myths of experimental phenomena, and accelerating the design of innovative materials. This work has been motivated by the demand to design next-generation thermionic emitting cathodes and techniques to allow for synthesis of photo-responsive polymers on complex surfaces with controlled thickness and patterns. For Os-coated tungsten thermionic dispenser cathodes, we used first-principles methods to explore the bulk and surface properties of W-Os alloys in order to explain the previously observed experimental phenomena that thermionic emission varies significantly with W-Os alloy composition. Meanwhile, …

Optimizing Solvent Blends For A Quinary System, Thomas L. Hoy

Williams Honors College, Honors Research Projects

The Department of Polymer Engineering had received a grant from the Keck foundation to produce a process in which hundreds of copolymers can be formulated, synthesized, analyzed and then extrapolated to produce the optimal polymer for the desired material property. This process involves synthesizing approximately fifty polymers in a custom apparatus, none of which necessarily have the same monomer components. This leads to issue of which solvent or blend of solvents to use that would sufficiently dissolve both monomers and the resulting copolymer. If the monomers are not completely dissolved, a homogenous reaction will be impossible and if the copolymer …

Equi-Biaxial Fatigue Testing Of Epm Utilising Bubble Inflation, Mark Johnson, Niall Murphy, Ray Ekins, John Hanley, Stephen Jerrams

Articles

This paper describes an equi-biaxial tension fatigue test system which utilises the bubble inflation method to subject elastomers to equi-biaxial fatigue loading between user-defined limits of pressure, volume, stretch ratio or stress. The test system integrates a hydraulic inflation system, a high speed vision system and a control system. The high-speed vision system allows the stretch ratio and stress acting on the test specimen to be evaluated in real-time during testing. This in turn allows either stretch ratio or stress to be used as a direct control limit. In this research, constant maximum engineering stress control tests have been carried …

Eliminating Electromechanical Instability In Dielectric Elastomers By Employing Pre-Stretch, Liang Jiang, Tony Betts, David Kennedy, Stephen Jerrams

Articles

Electromechanical instability (EMI) is one of most common failure modes for dielectric elastomers (DEs). It has been reported that pre-stretching a DE sample can suppress EMI due to strain stiffening taking place for larger strains and a higher elastic modulus are achieved at high stretch ratios when a voltage is applied to the material. In this work, the influence of equi-biaxial stretch on DE secant modulus was studied using VHB 4910 and silicone rubber (SR) composites containing barium titanate (BaTiO3, BT) particles and also dopamine coated BT (DP-BT) particles. The investigation of equi-biaxial deformation and EMI failure for VHB 4910 …

Inhibition Of Bacterial Growth And Prevention Of Bacterial Adhesion With Localized Nitric Oxide Delivery, Julia Osborne

Dissertations, Master's Theses and Master's Reports

Bacterial infections continue to be a problem at the site of an indwelling medical device, and over the years, various bacterial strains have become more resistant to current antibiotic treatments. Bacterial infection at an indwelling medical device can be dangerous and affect the performance of the medical device which can ultimately lead to the failure of the device due to bacterial resistance to treatment.

Nitric Oxide (NO) has been shown to possess antibacterial properties to prevent and inhibit bacterial growth. NO releasing coatings on indwelling medical devices could provide a reduction in bacterial infections that occur at the device site …

Process Development For Compression Molding Of Hybrid Continuous And Chopped Carbon Fiber Prepreg For Production Of Functionally Graded Composite Structures, Corinne Marie Warnock

Master's Theses

Composite materials offer a high strength-to-weight ratio and directional load bearing capabilities. Compression molding of composite materials yields a superior surface finish and good dimensional stability between component lots with faster processing compared to traditional manufacturing methods. This experimental compression molding capability was developed for the ME composites lab using unidirectional carbon fiber prepreg composites. A direct comparison was drawn between autoclave and compression molding methods to validate compression molding as an alternative manufacturing method in that lab. A method of manufacturing chopped fiber from existing unidirectional prepreg materials was developed and evaluated using destructive testing methods. The results from …

Effects Of Expected Service Life Exposures On The Functional Properties And Impact Performance Of An American Football Helmet Outer Shell Material, David E. Krzeminski

Dissertations

The purpose of this dissertation is to gain a greater scientific understanding of the changes in functional material properties and impact performance of an American football helmet outer shell material under expected service life exposures. The research goals are to (i) quantify chemical, physical, thermal, and mechanical degradation of an American football outer shell material under expected environmental conditions and (ii) develop a linear drop test impact protocol to employ expected on-field impact conditions to American football helmet components and a plaque-foam (i.e., shell-liner) surrogate. Overall, a step-wise progression of analysis was demonstrated to concurrently quantify and understand changes in …

A Platform For Fast Detection Of Let-7 Micro Rna Using Polyaniline Fluorescence And Image Analysis Techniques, Partha P. Sengupta

Master's Theses

The project describes a new strategy for transducing hybridization events through modulating intrinsic properties of the electroconductive polymer polyaniline (PANI). When DNA based probes electrostatically interact with PANI, its fluorescence properties are increased, a phenomenon that can be enhanced by UV irradiation. Hybridization of target nucleic acids results in dissociation of probes causing PANI fluorescence to return to basal levels. By monitoring restoration of base PANI fluorescence as little as 10^-11 M (10 pM) of target oligonucleotides could be detected within 15 minutes of hybridization. Detection of complementary oligos was specific, with introduction of a single mismatch failing to …

Hybrid Aryl-Ether-Ketone And Hyperbranched Epoxy Networks, John Misasi

Dissertations

In this dissertation, relationships between chemical structures, cure kinetics and network architectures are correlated to bulk mechanical properties for novel, hybrid epoxy-amine networks. The work is split into two primary sections: the first is the synthesis and characterization of multifunctional glassy networks based on aryl-ether-ketone diamine curatives, while the second is based on the synthesis and characterization of hyperbranched epoxy polymers and their resulting networks.

Three aryl-ether-ketone (AEK) diamines of increasing molecular weights were synthesized and used to cure 4,4’-tetraglycidylether of diaminodiphenylmethane (TGDDM); the resulting networks were compared to 4,4’-diaminodiphenyl sulfone cured TGDDM. Architectural differences were created by varying cure …

Polyacrylonitrile Copolymers: Effects Of Molecular Weight, Polydispersity, Composition, And Sequencing On Thermal Ring-Closing Stabilization, Jeremy D. Moskowitz

Dissertations

Controlled polyacrylonitrile (PAN)-based carbon fiber precursors with defined molecular weights, polydispersities, compositions, and architectures have been prepared for their study on thermal ring-closing stabilization behavior. PAN and its copolymers of number average molecular weights exceeding 170,000 g/mol were successfully synthesized via low temperature reversible addition-fragmentation chain transfer (RAFT) polymerization. RAFT polymerizations of PAN-based precursors were compared to conventional free radical solution polymerizations with a focus on the effects of molecular weight and polydispersity on structural evolution and cyclization efficiency. When RAFT polymerization was extended to copolymers, it was found that RAFT copolymers achieved greater cyclization intensities and improved thermal stability …

Development Of Dual-Cure Hybrid Polybenzoxazine Thermosets, Jananee Narayanan Sivakami

Dissertations

Polybenzoxazines are potential high performance thermoset replacements for traditional phenolic resins that can undergo an autocatalytic, thermally initiated ring - opening polymerization, and possess superior processing advantages including excellent shelf-life stability, zero volatile loss and limited volumetric shrinkage. The simplistic monomer synthesis and availability of a wide variety of inexpensive starting materials allows enormous molecular design flexibility for accessing a wide range of tailorable material properties for targeted applications. Despite the fact, once fully cured, benzoxazines are difficult to handle due to their inherent brittleness, leaving a very little scope for any modifications. The motivation of this dissertation is directed …

Volatile Condensible Material Deposition In Leo Simulated Environment, Jinya Pu

Department of Electrical and Computer Engineering: Dissertations, Theses, and Student Research

Room Temperature Vulcanized (RTV) silicone and compounds are widely used in outer-space for bonding or potting spacecraft components. In geosynchronous equatorial orbit (GEO), the silicone may outgas species which can condense on optically sensitive surfaces and degrade their performance, therefore shortening the lifetime of spacecraft. In low-earth-orbit (LEO), the silicone rubber is subject to an energetic and corrosive environment. Atomic oxygen (AO) and ultraviolet radiation can cause abrasion and degradation of the silicone rubber, cause changes in existing condensed VCM films and affect the properties of VCM films condensing in this atmosphere. Experiments were performed to simulate GEO conditions. In …

Influence Of Carbon Nanofillers On The Curing Kinetics Of Epoxy-Amine Resin, Luigi Vertuccio, Salvatore Russo, Marialuigia Raimondo, Khalid Lafdi, Liberata Guadagno

Chemical and Materials Engineering Faculty Publications

The cure kinetics of an epoxy resin based on the tetrafunctional epoxy precursor N,N′-tetraglycidyl methylene dianiline-(TGMDA) hardened with 4,4-diaminodiphenyl sulfone is investigated. The influence of carbon nanofillers (carbon nanotubes, carbon nanofibers, and graphene based nanoparticles) on the cure kinetic is studied. Kinetic analysis is performed by dynamic and isothermal differential scanning calorimetry (DSC).

In dynamic experiments, the activation energy was computed using an advanced isoconversional method while under isothermal conditions, the Kamal’s model of diffusion control was applied to simulate the systems throughout the curing process. The isothermal analysis shows that the introduction of the diluent decreases, …

Characterization Of Hydrogel Curing Methods For Manufacturability, Hannah E. Brown, Rebecca K. Kramer, Edward L. White

The Summer Undergraduate Research Fellowship (SURF) Symposium

In the field of soft robotics, hydrogels possess material properties that allow them to function as both soft strain sensors and dielectric elastomer actuators. However, there is still much that needs to be understood about the curing process of hydrogels and the resulting material characteristics before manufacturing these devices can be accomplished. In this study, we investigated the effect of curing time and sample volume on the as-cured material properties of acrylamide-based hydrogels hydrated with lithium and magnesium chloride salt solutions. Samples were cured at room temperature, 60° C and 100° C, and the resulting changes in mechanical stiffness and …

Fracture Mechanics-Based Simulation Of Pv Module Delamination, Dominic I. Jarecki, Johanna B. Palsdottir, Peter Bermel, Marisol Koslowski

The Summer Undergraduate Research Fellowship (SURF) Symposium

Photovoltaic (PV) cells are rapidly growing as a renewable alternative to fossil fuels like coal, oil, and natural gas. However, greater adoption has also reduced government subsidies, placing the onus of making solar panels economically competitive on innovative research. While multiple methods have been considered for reducing costs, with each reduction in cost comes the associated peril of reduction in quality and useful lifetime. Several problems considered solved have now resurfaced as potential failure mechanisms with the introduction of cheaper PV cell technologies. However, to remain economically viable, PV modules will not only have to become cheaper, they will have …

Synthesis, Characterization, And Thermoelectric Properties Of Radical Siloxanes, Arnold J. Eng, Bryan Boudouris, Edward P. Tomlinson, Martha Emily Hay

The Summer Undergraduate Research Fellowship (SURF) Symposium

More than half of the annual energy consumption in the United States is lost as waste heat. Polymer-based thermoelectric devices have the potential to utilize this waste heat both sustainably and cost-effectively. Although conjugated polymers currently dominate research in organic thermoelectrics, the potential of using polymers with radical pendant groups have yet to be realized. These polymers have been found to be as conductive as pristine (i.e., not doped) poly(3-hexylthiophene) (P3HT), a commonly-used charge-transporting conjugated polymer. This could yield promising avenues for thermoelectric material design as radical polymers are more synthetically tunable and are hypothesized to have a high Seebeck …

Thermal And Mechanical Properties Of Polymers Using Molecular Dynamics, Daniel Glass, Alejandro Strachan, Lorena Alzate-Vargas, Chunyu Li, Benjamin Haley

The Summer Undergraduate Research Fellowship (SURF) Symposium

Polymer systems have gained attention during the past years because of their technological and industrial applications. Simulations, particularly molecular dynamics, are very useful for exploring properties of amorphous polymers, without using experiments. Our goal is to create a readily-available tool that will perform MD simulations in order to get thermal and mechanical properties (Glass transition temperature, Young Modulus) of the polymers. The work that has been done will be part of a tool to help people to learn about polymer properties including Glass Transition Temperature. We model some polymers at a scale of 10,000 atoms. The tool uses LAMMPS to …

Morphology-Property Relationship For Binary Organic Thin Films, Alyssa Lynn Griffin

Master's Theses

Organic thin films can be readily mass-produced through solution-based fabrication methods including ink-printing and solution-casting because their light weight, flexibility, and inexpensive sources. Their applications range from organic field-effect transistors (OFET), organic solar cells (OSC), to organic light emitting diodes (OLEDs). Compared with pure component films, binary organic thin films (BOTF) allows for novel characteristics and specialized features to handle more demanding tasks. Due to the complex intermolecular interactions in BOTF, various microscopic phases with different morphological and electronic properties may be formed and this information is difficult to extract through conventional bulk measurements.

Organic thin films can be readily …

Efficiency Enhancement In Solution Processed Organic And Organic–Inorganic Hybrid Perovskite Solar Cells, Zhengguo Xiao

Department of Mechanical and Materials Engineering: Dissertations, Theses, and Student Research

Solution processed thin film photovoltaic devices are one of the most promising renewable energy sources. Organic solar cells have been intensively studied due to their advantages of light-weight, flexibility and low-cost materials and manufacturing. The organic-inorganic hybrid perovskite materials have recently shown great potential application in solar cells. The PCE increased dramatically from 3.8% in 2009 to a certified efficiency of 20.1% in 2014. In this dissertation, we focus on the efficiency enhancement for solution processed organic and organic-inorganic solar cells.

In Chapter 2, I demonstrated that the crystallinity of the ferroelectric polymer P(VDF-TrFE) at the organic active layer/ electrode …

Spotlight On Graphene Research From The Middle East, Kathleen A. Lehman

University Libraries Faculty Publications and Presentations

In an extension to the 2011 article “Reviews of Science for Science Librarians: Graphene” (Lehman 2011), this paper seeks to continue exploring the trend of graphene research but limits its focus to the research production of countries in the Middle East. In addition to reporting on the research output of this group of countries, this article will also examine the most prolific Middle Eastern graphene authors,their supporting institutions and funding agencies, the most cited publications from this group, the journals most used for publication of their work, and the general trend in graphene research growth in the Middle East. As …

Temperature Dependent Surface Reconstruction Of Freely Suspended Films Of 4-N-Heptyloxybenzylidene-4-N-Heptylaniline, Daniel E. Martinez Zambrano

Lawrence University Honors Projects

Surfaces of freely suspended thick films of 4-n-heptyloxybenzylidene-4-n-heptylaniline (7O.7) in the crystalline-B phase have been imaged using non-contact mode atomic force microscopy. Steps are observed on the surface of the film with a height of 3.0 +/- 0.1 nm corresponding to the upright molecular length of 7O.7. In addition, we find that the step width varies with temperature between 56 and 59 degrees C. The steps are many times wider than the molecular length, suggesting that the steps are not on the surface but instead originate from edge dislocations in the interior. Using a strain model for liquid crystalline layers …

Effect Of Heat Treatment On The Mechanical Properties In Natural Bamboo, Austin Levy, Mackenzie Kirkpatrick

Materials Engineering

Previous studies have shown that heat treatments have the ability to improve mechanical strength and stiffness in hardwood species. Compared to structural hardwoods, bamboo is a more sustainable and globally viable renewable resource. Therefore, Bambusoides vivax (timber bamboo) culms were fabricated into flat, rectangular cross-section samples with varying cellulose content to be heat treated and tested for mechanical properties. All samples were heat treated (HT) twice. The first HT was a normalization of all samples at 103 +/- 3 °C. The second HT was performed at various times and temperatures ranging from 130°C to 170°C for 0.5 to 3 hours. …

Minimizing Sheet Resistance Of Organic Photovoltaic Cell Top Contact Electrode Layer: Silver Nanowire Concentration Vs. Conductive Polymer Doping Concentration, Caitlyn Cook

Materials Engineering

The top contact electrode layers of nine organic photovoltaic cells were prepared with two varying factors: three Silver nanowire (AgNW) densities deposited on a conductive polymer doped with three concentrations. Silver’s low sheet resistance of 20-Ω/sq is hypothesized to lower the sheet resistance of the anode layer and thus enhance the overall efficiency of the cell. Four-point probe measurements indicated that increasing AgNW density in the top contact electrode layer of an organic photovoltaic cell significantly reduces sheet resistance from 52.2k-Ω/sq to 18.0 Ω/sq. Although an increase in doping concentration of the conductive polymer reduced sheet resistance in low AgNW …

Effect Of Time Delay Between Etching And Adhesive Bonding (“Outlife” Time) On Lap-Shear Strength Of Aluminum Alloys Using Environmentally-Friendly P2 Etch, Josh Barkhimer, Matthew Erich, Gokul Nair

Materials Engineering

Raytheon Company currently uses a Forest Products Laboratory (FPL) paste etchant for preparing aluminum surfaces for adhesive bonding, and FPL is a source of hazardous hexavalent chromium. The goal of this study was to evaluate a less-toxic P2 paste etchant as a possible replacement. Coupons of 2024-T3, 6061-T6, and 7075-T6 grades of aluminum alloy were solvent-degreased, abrasively cleaned, and etched at room temperature using P2 paste following a strict protocol adopted from Raytheon. Coupons were then left exposed to air for assigned time intervals (or “outlife” times) of 0, 1, 4, 8, 16, and 63 or 72 hours. The aluminum …

Molecular Dynamics Investigation Of The Arabinan-Cellulose Interface For Cellulose Nanocomposite Applications, Luke Thornley

Materials Engineering

Atom level computer simulations of the arabinan and cellulose interface were performed to better understand the mechanisms that give arabinan-cellulose composites (ArCCs) their strength with the goal to improve man-made ArCCs. The molecular dynamics (MD) software LAMMPS was used in conjunction with the ReaxFF/c force field to model the bond between cellulose and arabinan. A cellulose nanocrystal with dimensions 51 x 32 x 8 Å was minimized with various weight percent of water, 0%, 3%, 5%, 8%, 10%, and 12%. After the system was equilibrated for at least 100,000 femtoseconds, an arabinan molecule composed of 8 arabinose rings was added …

Effect Of Surfactant Architecture On Conformational Transitions Of Conjugated Polyelectrolytes, Greg A. Braggin

Master's Theses

Water soluble conjugated polyelectrolytes (CPEs), which fall under the category of conductive polymers, possess numerous advantages over other conductive materials for the fabrication of electronic devices. Namely, the processing of water soluble conjugated polyelectrolytes into thin film electronic devices is much less costly as compared to the processing of inorganic materials. Moreover, the handling of conjugated polyelectrolytes can be performed in a much more environmentally friendly manner than in the processing of other conjugated polymers because conjugated polyelectrolytes are water soluble, whereas other polymers will only dissolve in toxic organic solvents. The processing of electronic devices containing inorganic constituents such …

Self-Contained Breathing Apparatus For Firefighter With A Permanent Stoma, Jason Delgadillo, Aaron Wheeler, Zachary Wishbow

Biomedical Engineering

The purpose of this project was to create a unique SCBA (self-contained breathing apparatus) for a firefighter named Chris Gauer. This prototype consists of a SCBA headgear connected to a polycarbonate-formed stoma mask with a medical-grade sanitary silicone hose.

Predictive Modeling Of Oxygen Transmission Through Micro-Perforations For Packaging Applications, Ayman Abdellatief, Bruce A. Welt, Jason Butler, Eric Mclamore, Arthur Teixeira, Sanjay Shukla

Journal of Applied Packaging Research

Methods for creating precise perforations in respiring produce packaging are being increasingly adopted. Knowledge of oxygen transfer through perforated packaging and oxygen distribution in packages is necessary for successful packaging design of fresh produce. An approach to modeling perforated packaging performance was developed using a cylindrical chamber with precision perforations using Fick’s second law. The model was simulated using two techniques including Finite Element Method (FEM) using commercially available software and Finite Volume Method (FVM) through programming. Perforations were approximated as a source term in the second method. Both simulation techniques showed trends similar to experimental data.

Feasibility Study: The Evaluation Of Polymer Coatings To Prevent Weathering Of Weak Rocks, Lauren Distler

Senior Honors Projects, 2010-2019

The weathering and erosion of weak rocks along roadways can cause dangerous and potentially fatal rockfalls.   Various slope stabilization methods exist, but each presents a set of challenges and trade-offs.   The focus of the project is to understand the feasibility of utilizing of a polymerbased slope stabilization technique. Rock samples were collected along US Route 33 in Virginia and West Virginia, and preliminary tests were conducted to evaluate the absorption of water (% mass) and durability. The study evaluates three polymer options in regard to the following criteria: adhesion to rock, layer thickness, semi-permeability, insolubility, and non-toxicity. The polymer selection …

Material Coefficient Of Thermal Expansion Investigation For Use In Additive Manufacturing Fused Deposition Modeling For Composite Tooling, Daniel Joseph Miller

Master's Theses

Polymer matrix composites are being used to manufacture light weight, high stiffness aircraft structures. These structures are often manufactured from carbon fiber reinforced epoxy. When these structures are damaged, they must be repaired to restore strength to the component to avoid the cost and logistics of having replacements parts. Occasionally, these repairs require tooling in order to make a quality repair, however, tooling generally has a long lead time. Additive manufacturing could be used to manufacture rapid tooling to create tooling for composite repairs. The issue is that polymer printed tooling has a much higher coefficient of thermal expansion (CTE) …