Physical Sciences and Mathematics Commons^™

Elucidating Fundamental Mechanisms In Focused Electron- And Ion-Beam Induced Synthesis, Carlos M. Gonzalez

Doctoral Dissertations

A focused electron beam deposition process (FEBID) coupled with in-situ infrared pulsed laser assist (LA-EBID) has been implemented for higher purity tungsten nanowires using W(CO)₆ [tungsten hexacarbonyl] as parent precursor gas. Nanowires made of Co from Co₂(CO)₈ [dicobalt octacarbonyl] and Pt from MeCpPtIVMe₃ [trimethyl methylcyclopentadienyl platinum] have also been realized by using inert focused ion beams of helium and helium and neon, respectively. In all cases, higher electrical conductivities, higher purities and larger grain sizes have been obtained when compared with preceding traditional additive edit techniques. These new approaches will make possible successful nanoscale direct-write …

Synthesis And Thermodynamic Analysis Of Volatile Beta-Diketone Complexes Of Select Lanthanides Via Gas-Phase Separations, Daniel Hanson

Doctoral Dissertations

Rapid separation techniques for fission and activation products have long been desired to supplant the slow solution-based methodologies currently used. In this work, rare earth elements were derivatized with β [beta]-diketones to synthesize rare earth complexes with high volatility suitable for gas-phase separations. Rare earth elements samarium and dysprosium were combined with hfac (1,1,1,5,5,5-hexafluoro-2,4-pentadione) and fod (6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione) and analyzed using a gas-phase separation technique. Rare earth elements praseodymium and europium were combined with dpm (2,2,6,6-tetra-methyl-3,5-heptanedione) and similarly analyzed. Employing the data from the separations, the entropy (Δ [delta] S) and enthalpy (Δ [delta] H) of adsorption were evaluated mathematically based …

Functional Nanocomposites From Self-Assembly Of Block Copolymers With Nanoparticles, Xinyu Wang

Doctoral Dissertations

This dissertation studied the proper distribution and location control of nanoparticles (NPs) within block copolymer (BCP) templates. A facile ligand exchange reaction was introduced for the hydrophilic magnetic NPs (MNPs) that are readily dispersed in polar solvents with outstanding stability. Small molecule ligands were selected to associate strongly with particle surfaces, provide hydrophilic termini for polarity matching with polar solvents, and offer the potential for hydrogen-bonding interactions to facilitate NP incorporation into polymers. Areal ligand densities of NPs indicated a significant increase in the ligand coverage after the exchange reaction. Hydrophilic MNPs were shown to drive the self-assembly of BCPs …

Introducing The Newton-Poisson-Brillouin Model In The Quest For Plasmons In Metallic Carbon Nanotubes, Richard P. Zannoni

Doctoral Dissertations

A new method is presented to model carbon nanotubes (CNT) of micron length. The Newton-Poisson-Brillouin (NPB) model uses Newtonian physics to model the interaction of a population of thermally excited quasi-particles. The NPB model is self-consistent with Poisson’s equation, and the quasi-particles are confined to the CNT’s band structure. In this work, we explore the parameter space of the model.

Engineering Surface Functionality Of Nanoparticles For Biological Applications, Yi-Cheun Yeh

Doctoral Dissertations

Engineering the surface functionality of nanomaterials is the key to investigate the interactions between nanomaterials and biomolecules for potent biological applications such as therapy, imaging and diagnostics. My research has been orientted to engineer both of the surface monolayers and core materials to fabricate surface-functionalized nanomaterials through the synergistic multidisciplinary approach that combine organic chemistry, materials science and biology. This thesis illustrates the design and synthesis of the surface-funcitonalized quantum dots (QDs) and gold nanoparticles (AuNPs) for the fundamental studies and practical applications. For QDs, A new class of cationic QDs with quaternary ammonium derivatives was synthesized to provide permanent …

Patterning And Mechanical Analysis Of Fiber-Based Materials, Samuel A. Pendergraph

Doctoral Dissertations

The ability to define and control the topography of a surface has been studied extensively due to its importance in a wide variety of applications. The control of a non-planar topography would be very valuable since a number of structures that are pervasive in artificial applications (e.g. fibers, lenses) are curved interfaces. This potential of enabling applications that incorporate non-planar geometries was the motivation for this thesis. The first study of this thesis comprises the study of patterning the circumference of micrometer sized fibers. Specifically, a unique technique was described to pattern the fiber with a periodic array of colloids. …

The Discovery And Study Of Fluvirucin B1 Polyketide Synthase, Tsung-Yi Lin

Doctoral Dissertations

Rapidly decreasing numbers of viable therapeutic leads in the pharmaceutical pipeline demand new, sustainable methods for improved drug discovery and development. Despite vast improvements in de novo drug design and target recognition, Nature remains the richest source of small molecule therapeutics. Among many natural products, polyketides are not only the most promising ones for developing new antibiotic leads, but also exhibit unusually high therapeutic value ranging from clinical use as anticancer, antiviral, and immunosuppressant drugs. Modular polyketide synthases (PKSs) are dedicated nano-machinery that can be manipulated to produce a structurally diverse library for drug discovery programs. The ability to manipulate …

Defining, Evaluating, And Improving The Process Of Verifying Patient Identifiers, Junghee Jo

Doctoral Dissertations

Patient identification errors are a major cause of medication errors. During medication administration, failure to identify patients correctly can lead to patients receiving incorrect medications, perhaps resulting in adverse drug events and even death. Most medication error studies to date have focused on reporting patient misidentification statistics from case studies, on classifying types of patient identification errors, or on evaluating the impact of technology on the patient identification process, but few have proposed specific strategies or guidelines to decrease patient identification errors. This thesis aims to improve the verification of patient identifiers (VPI) process by making three key contributions to …

Studies On The Wrinkling Of Thin Polymer Films Floating On Liquid, Kamil B. Toga

Doctoral Dissertations

This dissertation aims to broaden our understanding on wrinkling instabilities occurring on floating polymeric sheets, and tries to establish innovative methods that exploit these patterns in studies on material behavior and interfacial phenomena. We will address three major topics in this thesis including, i) characterization of the conditions required to buckle an annular disc, ii) characterization of wrinkles occurring around a droplet/bubble placed on a membrane that is kept taut at the liquid-air interface, and iii) using wrinkling patterns as a probe to understand the interfacial behavior and dynamics of ultrathin films. The first project in this thesis is about …

Reliable And Efficient Multithreading, Tongping Liu

Doctoral Dissertations

The advent of multicore architecture has increased the demand for multithreaded programs. It is notoriously far more challenging to write parallel programs correctly and efficiently than sequential ones because of the wide range of concurrency errors and performance problems. In this thesis, I developed a series of runtime systems and tools to combat concurrency errors and performance problems of multithreaded programs. The first system, Dthreads, automatically ensures determinism for unmodified C/C++ applications using the pthreads library without requiring programmer intervention and hardware support. Dthreads greatly simplifies the understanding and debugging of multithreaded programs. Dthreads often matches or even exceeds the …

Molecular Engineering Strategies For The Design And Synthesis Of New Organic Photovoltaic Materials, Paul J. Homnick

Doctoral Dissertations

Dramatic improvements in organic photovoltaic device efficiency can be obtained by optimizing spectral absorbance and frontier molecular orbital (FMO) energies, increasing solid state exciton/charge mobility, and utilizing p-/n-type nanoarchitecture. Combining all of these properties into a new material presents a considerable synthetic challenge because potential commercial applications require materials that are high-performance and inexpensive. Thus, it is advantageous to design new materials using a versatile, modular synthetic approach that allows each design criterion to be engineered individually, in a synthetically efficient manner. Several strategies were successfully pursued using simple interchangeable electron donor and acceptor components as functional modules, which …

Creasing Instability Of Hydrogels And Elastomers, Dayong Chen

Doctoral Dissertations

CREASING INSTABILITY OF HYDROGELS AND ELASTOMERS MAY 2014 DAYONG CHEN, B.S., TIANJIN UNIVERISTY M.S., TIANJIN UNIVERSITY M.S., UNIVERSITY OF MASSACHUSETTS AMHERST Ph.D., UNIVERSITY OF MASSACHUSETTS AMHERST Directed by: Professor Ryan C. Hayward Soft polymers placed under compressive stress can undergo an elastic creasing instability in which sharp folds spontaneously form on the free surfaces. This process may play an important role in contexts as diverse as brain morphogenesis, failure of tires, and electrical breakdown of soft polymer actuators. While the creasing instability has been used for collotype printing since as early as the 1850s, the scientific appreciation of this instability …

Composition Dependence Of The Flory-Huggins Interaction Parameter In Polymer Blends: Structural And Thermodynamic Calculations, Travis H. Russell

Doctoral Dissertations

Flory-Huggins Theory has been the basis for understanding polymer solvent and blended polymer thermodynamics for much of the last 60 years. Within this theory, a parameter (χ) [chi] was included to quantify the enthalpic energy of dispersion between distinct components. Thin film self-assembly of polymer melts and block copolymers depends critically on this parameter, and in application, χ has generally been assumed to be independent of the concentrations of the individual components of the system. However, Small-Angle Neutron Scattering data on isotopic polymer blends, such as polyethylene and deuterated polyethylene, have shown a roughly parabolic concentration dependency for …

Impacts Of Climate Change On The Evolution Of The Electrical Grid, Melissa Ree Allen

Doctoral Dissertations

Maintaining interdependent infrastructures exposed to a changing climate requires understanding 1) the local impact on power assets; 2) how the infrastructure will evolve as the demand for infrastructure changes location and volume and; 3) what vulnerabilities are introduced by these changing infrastructure topologies. This dissertation attempts to develop a methodology that will a) downscale the climate direct effect on the infrastructure; b) allow population to redistribute in response to increasing extreme events that will increase under climate impacts; and c) project new distributions of electricity demand in the mid-21^st century.

The research was structured in three parts. The first …

3d Robotic Sensing Of People: Human Perception, Representation And Activity Recognition, Hao Zhang

Doctoral Dissertations

The robots are coming. Their presence will eventually bridge the digital-physical divide and dramatically impact human life by taking over tasks where our current society has shortcomings (e.g., search and rescue, elderly care, and child education). Human-centered robotics (HCR) is a vision to address how robots can coexist with humans and help people live safer, simpler and more independent lives.

As humans, we have a remarkable ability to perceive the world around us, perceive people, and interpret their behaviors. Endowing robots with these critical capabilities in highly dynamic human social environments is a significant but very challenging problem in practical …

Theoretical Studies Of The Growth And Functionality Of Layered Materials, Wei Chen

Doctoral Dissertations

In this thesis, we present several projects on the growth and functionality of layered materials, using density functional theory (DFT) method and phenomenological modeling approach. Beyond the understanding of growth mechanisms and exploration of properties, we propose novel avenues to realize controllable growth processes and layered materials with desirable properties. The contents have three major parts:

(1) Graphene growth on Cu(111) and Ni(111) substrates. We first demonstrate that the inherent multi-orientational degeneracy of the graphene islands on Cu(111) in the early stages of nucleation could result in the prevalence of grain boundaries (GBs). Next, we propose a possible solution to …

Quantum Tuning Of Plasmons In Ultrathin Metal Films, Ao Teng

Doctoral Dissertations

The surface plasmon is a coherent charge density oscillation localized at a metal surface. It can couple with light and the resulting plasmon-polariton hybrid mode is confined to volumes that are much smaller than the classical diffraction limit of light. Nano-plasmonics is a rapidly evolving field where light manipulation at the nanoscale may lead to novel applications. However, as the size of plasmonic devices approaches the quantum-size regime, the macroscopic picture of plasmon may no longer be valid. To elucidate the influence of the discretization of the single particle spectrum on the collective plasmon response, we performed a systematic study …

Structural Dynamics And Charge Transport In Room Temperature Ionic Liquids, Philip James Griffin

Doctoral Dissertations

Room temperature ionic liquids are an important class of materials due to their chemical tunability and numerous advantageous physicochemical properties. As a result, ionic liquids are currently being investigated for use in a wide array of chemical and electrochemical applications. Despite their great potential, however, the relationship between the chemical structure and physicochemical properties of ionic liquids is not well understood.

To this end, this dissertation presents experimental studies of the reorientational structural dynamics and charge transport properties of a variety of room temperature ionic liquids using quasielastic light scattering spectroscopy and broadband dielectric spectroscopy.

Studies of a series of …

Quantum Levitation Using Metamaterials, Venkatesh K. Pappakrishnan

Doctoral Dissertations

The emergence of an attractive vacuum force (Casimir force) between two purely dielectric materials can lead to an increase in the friction and the stiction effects in nanoscale devices, resulting in degradation or decreased performance. Thus, it is of high practical importance that the conditions for the reversal of the Casimir force from attractive to repulsive are identified. Although the repulsive Casimir force has been considered for high dielectric materials as an intermediate (between the plates) medium, so far no realistic system has been proposed that can demonstrate quantum levitation with air/vacuum as a host medium. Since air is the …

A Knowledge Discovery Approach For The Detection Of Power Grid State Variable Attacks, Nathan Wallace

Doctoral Dissertations

As the level of sophistication in power system technologies increases, the amount of system state parameters being recorded also increases. This data not only provides an opportunity for monitoring and diagnostics of a power system, but it also creates an environment wherein security can be maintained. Being able to extract relevant information from this pool of data is one of the key challenges still yet to be obtained in the smart grid. The potential exists for the creation of innovative power grid cybersecurity applications, which harness the information gained from advanced analytics. Such analytics can be based on the extraction …

On Electromagnetic And Quantum Invisibility, Pattabhiraju Chowdary Mundru

Doctoral Dissertations

The principle objective of this dissertation is to investigate the fundamental properties of electromagnetic wave interactions with artificially fabricated materials i.e., metamaterials for application in advanced stealth technology called electromagnetic cloaking. The main goal is to theoretically design a metamaterial shell around an object that completely eliminates the dipolar and higher order multipolar scattering, thus making the object invisible.

In this context, we developed a quasi-effective medium theory that determines the optical properties of multi-layered-composites beyond the quasi-static limit. The proposed theory exactly reproduces the far-field scattering/extinction cross sections through an iterative process in which mode-dependent quasi-effective impedances of the …

Ab Initio Studies Of Proton Transport In Proton Exchange Membranes, Jeffrey Keith Clark

Doctoral Dissertations

A molecular-level understanding of the factors that contribute to transport properties of proton exchange membranes (PEMs) for fuel cell applications is needed to aid in the development of superior membrane materials. Ab initio electronic structure calculations were undertaken on various PEM ionomer fragments to explore the effects of local hydration, side chain connectivity, protogenic group separation, and specific side chain chemistry on proton dissociation and transfer at low hydration. Cooperative interactions between both intra- and inter-molecular acidic groups and hydrogen bond connectivity were found to enhance proton dissociation at very low degrees of hydration. The energetics associated with proton transfer …

Synthesis And Characterization Of Magnetic Nanowires Prepared By Chemical Vapor Deposition, Siwei Tang

Doctoral Dissertations

Various metal silicide and germanide magnetic nanowires were synthesized using a home-built CVD [chemical vapor deposition] system. The morphology, composition, and magnetic properties of the nanowires were studied and correlated with growth parameters such as temperature, pressure, time, and source-substrate distance.

One of the compositions targeted for synthesis was MnSi [manganese silicide]. In bulk, this material orders helimagnetically at T_c [curie temperature] = 30K, with a helical pitch of about 20 nm. After extensive study, we learned that the thickness of the silicon dioxide layer on the substrate is a critical parameter for the growth of MnSi nanowires. An …

Stability, Erosion, And Morphology Considerations For Sustainable Slope Design, Isaac Andres Jeldes Halty

Doctoral Dissertations

The construction of more natural and sustainable earth slopes requires the consideration of erosion and runoff characteristics as an integral part of the design. These effects not only result in high costs for removal of sediment, but also a profound damage to the ecosystem. In this dissertation, innovative techniques are developed such that more natural appearing slopes can be designed to minimize sediment delivery, while meeting mechanical equilibrium requirements. This was accomplished by: a) examining the fundamental failure modes of slopes built with minimum compaction (FRA) to enhance quick establishment of forest, b) investigating the geomechanical and erosion stability of …

Increasing The Throughput Of Liquid Chromatography, Joseph John Stankovich

Doctoral Dissertations

In this manuscript the ramifications of operating very high pressure chromatographic (VHPLC) instruments at high linear velocities is discussed. Operating at higher inlet pressures causes thermal conditions inside the column to change to an extent that can alter the reproducibility and accuracy of the chromatograms produced. The experiments discussed in this dissertation were focused on the manner in which the mobile phase is eluted through the column; by either constant flow, constant pressure, operator controlled or programmed constant pressure, and conditions which keep the heat loss at the columns wall constant. Additional experiments included other practical considerations in system performance …

Ionic Copolymers For Alkaline Anion Exchange Membrane Fuel Cells (Aaemfcs), Tsung-Han Tsai

Doctoral Dissertations

The advantages of alkaline anion exchange membrane fuel cells (AAEMFCs) over proton exchange membrane fuel cells is the motivation for this dissertation. The objectives of this dissertation were to develop durable membranes with high anion conductivity and an understanding of the ion conductivity relationship with morphology. The research results presented in this dissertation focuses on developing different architectures of ionic copolymers including diblock copolymers and random copolymers for AAEMFCs. A novel, and stable cobaltocenium cation, was incorporated into polymer for stable AAEM. Because of its 18 electron closed valence-shell configuration, the cobaltocenium cation is promising for use in AAEMFC. Two …

Methods Of Engine Degradation Assessment In The Time-Scale Domain, Jeffrey Charles Simmons

Doctoral Dissertations

This dissertation addresses health monitoring of aircraft engines. Two methods are offered for engine degradation assessment: (1) a direct method to isolate degradation of engine components in-flight, and (2) an inverse method to quantify the level of degradations post-flight. The noted feature of the degradation isolation method is its independence from training, which makes it suitable for on-board implementation. The degradation quantification method, on the other hand, is a multi-output method of parameter estimation with the advantage of leveraging the shape attributes of model outputs. The representation of the shape attributes of the various time series, by continuous wavelet transforms …

Exploiting Energy Harvesting For Passive Embedded Computing Systems, Jeremy Joel Gummeson

Doctoral Dissertations

The key limitation in mobile computing systems is energy - without a stable power supply, these systems cannot process, store, or communicate data. This problem is of particular interest since the storage density of battery technologies do not follow scaling trends similar to Moore's law. This means that depending on application performance requirements and lifetime objectives, a battery may dominate the overall system weight and form factor; this could result in an overall size that is either inconvenient or unacceptable for a particular application. As device features have scaled down in size, entire embedded systems have been implemented on a …

Degradable Nanocomposite Preformed Particle Gel For Chemical Enhanced Oil Recovery Applications, Paul Tongwa

Doctoral Dissertations

”This work presents two new materials that can be potentially used in conformance control to increase ultimate oil recovery from mature oilfields.

The first product is a degradable nanocomposite preformed particle gel for enhanced in-depth mobility control. Three different types of degradable nanocomposite preformed particle gels were synthesized. These three nanocomposite hydrogels were made using Laponite XLG, Calcium Montmorillonite, and Sodium Montmorillonite nanomaterials. It was observed that after degradation, Laponite XLG nanocomposite hydrogels had the highest post-degradation viscosity (4437 cp), followed by sodium nanocomposite hydrogels (129 cp), and lastly calcium nanocomposite hydrogels (75.5 cp). Thus, degradable Laponite XLG nanocomposite hydrogels …

Automated Classification Of Malignant Melanoma Based On Detection Of Atypical Pigment Network In Dermoscopy Images Of Skin Lesions, Nabin K. Mishra

Doctoral Dissertations

“Melanoma causes more deaths than any other form of skin cancer. Early melanoma detection is important to prevent progression to a more deadly stage. Automated computer-based identification of melanoma from dermoscopic images of skin lesions is the most efficient method in early diagnosis. An automated melanoma identification system must include multiple steps, involving lesion segmentation, feature extraction, feature combination and classification. In this research, a classifier-based approach for automatically selecting a lesion border mask for segmentation of dermoscopic skin lesion images is presented. A logistic regression based model selects a single lesion border mask from multiple border masks generated by …