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Articles 1 - 12 of 12
Full-Text Articles in Physical Sciences and Mathematics
Understanding The Influence Of Non-Covalent Interactions And Nanoparticle Geometries In Carbon Based Polymer Nanocomposites, Bradley Carroll Miller
Understanding The Influence Of Non-Covalent Interactions And Nanoparticle Geometries In Carbon Based Polymer Nanocomposites, Bradley Carroll Miller
Doctoral Dissertations
Low-loading polymer nanocomposites (PNC) are an area of great interest in polymer science. As nanoparticles (NP) are typically expensive in comparison to matrix materials; the low loading regime makes the most efficient use of materials, and represents the optimum for realizing cost effective, high-performance PNCs. However, formulating effective low-loading composites is not without challenges. In addition to the typical requirement of good dispersion for efficient translation of NP properties to the bulk, low-loading composites can sometimes exhibit anomalous (non-classical) dynamics, and unpredictable properties. It is within this context that this thesis aims to examine the effects of NP geometry and …
Contact Angles And Contact Lines Around Particles At Isotropic And Anisotropic Liquid Interfaces, Nesrin Senbil
Contact Angles And Contact Lines Around Particles At Isotropic And Anisotropic Liquid Interfaces, Nesrin Senbil
Doctoral Dissertations
Liquid interfaces, capillarity and self-assembly of particles at interfaces are important in nature and technology. When a particle is adsorbed to a liquid interface, the contact line of the particle with the liquid interface and the associated contact angle are the crucial parameters that drive assembly of the particles. We looked at how the shape of the liquid interface and the shape of the particle affect the contact angle and the shape of the contact line. We used millimeter-sized PDMS-coated glass spheres and measured the contact angles at isotropic (planar) and anisotropic interfaces (saddle and cylindrical in shape). Anisotropy of …
Impact Of Fabrication Parameters On The Internal Structure Of Poly(3-Hexylthiophene) Nanoparticles, Dana Desiree Algaier
Impact Of Fabrication Parameters On The Internal Structure Of Poly(3-Hexylthiophene) Nanoparticles, Dana Desiree Algaier
Doctoral Dissertations
Morphological control of organic functional materials is central to understanding and improving upon current technologies. The ability to create hierarchical assemblies with purposeful design from nano to meso scale has remained largely unattainable. This body of work aims to provide a foundation for creating nanoscale domains of poly (3-hexylthiophene) (P3HT) that can be used as building blocks to larger scale assemblies. We present a method for the fabrication of P3HT nanoparticles on the ability to vary the particle size and more importantly, the internal structure. We have identified the oil phase and surfactant as parameters able to influence the nature …
Quantum Calculations Of Aldol Condensation In Acidic Zeolites, Angela N. Migues
Quantum Calculations Of Aldol Condensation In Acidic Zeolites, Angela N. Migues
Doctoral Dissertations
We have used Density Functional Theory to model the mixed aldol condensation reaction catalyzed by acidic zeolites. We have studied the convergence of barriers for the keto-enol tautomerization of acetone in cluster models of HZSM-5 and HY ranging in size from 3-37T. A key finding was that activation barriers for keto-enol tautomerization of acetone in both zeolites (~20 kcal/mol) are significantly higher than those for the condensation reaction between the acetone enol and formaldehyde in 11T cluster models of HZSM-5 and HY. Moreover we found that three zeolite clusters of HZSM-5, similarly sized but including different structural features of the …
Protein Charge Anisotropy Mediated Self-Association And Phase Separation, Daniel P. Seeman
Protein Charge Anisotropy Mediated Self-Association And Phase Separation, Daniel P. Seeman
Doctoral Dissertations
Protein charge anisotropy results from the asymmetric distribution of charged residues on the exterior of a particular protein. Interactions between proteins and other macromolecules can be described in terms of attractive electrostatics; since electrostatic free energies, at optimal I, are on the order of kT, it is unlikely that such associations would result in desolvation, thus it is reasonable to consider such intermolecular attractions as being mediated by hydrated protein surfaces. Such interactions can be broken down in terms of a single protein interacting with a range of “binding partners”, including (1) protein-protein interactions, (2) protein-polymer interactions, and …
Design And Application Of Organic Electronic Materials: Pendant Tuning In Polymeric And Molecular Systems, Jonathan S. Tinkham
Design And Application Of Organic Electronic Materials: Pendant Tuning In Polymeric And Molecular Systems, Jonathan S. Tinkham
Doctoral Dissertations
Designing and synthesizing materials for use in organic electronic materials requires fine control over their optical and electronic properties. Variations through substitution can be used to tune solubility and electronic properties, but this can result in degradation of other properties. Substitution with orthogonal pendant groups in both molecular and polymeric systems has the potential for allowing tunability while decreasing the perturbation of other desirable properties of the parent system. This idea was explored through experimental and computational work. Computational modelling was used to understand and predict the properties of molecular and polymeric systems to narrow the wide number of choices …
Time-And Polarization-Resolved Photoluminescence Studies Of Directional Coupling In Isolated Semiconductor Nanostructures, Joelle A. Labastide
Time-And Polarization-Resolved Photoluminescence Studies Of Directional Coupling In Isolated Semiconductor Nanostructures, Joelle A. Labastide
Doctoral Dissertations
TIME-AND POLARIZATION-RESOLVED STUDIES OF DIRECTIONAL COUPLING IN ISOLATED SEMICONDUTOR NANOSTRUCTURES MAY 2015 JOELLE A. LABASTIDE, B.S. UNIVERSITY OF MASSACHUSESSTS AMHERST Ph.D., UNIVERSITY OF MASSACHUSETTS AMERST Directed by Professor Michael D. Barnes Development of new materials and assembly strategies for organic semiconductor-based optoelectronic materials is a problem of great interest worldwide, as researchers seek to resolve the questions pertinent to the creation of inexpensive, reliable, efficient, and stable active layer components. Organic semiconductors as the basis for photovoltaic active layers show significant promise for these applications. However, there is still much that needs to be understood about the molecular scale structural …
An Investigation Of Inorganic Compound Scattering., Karl Jay Bernstein
An Investigation Of Inorganic Compound Scattering., Karl Jay Bernstein
Doctoral Dissertations
Raman and its associated forms of spectroscopy are powerful tools that have been under-utilized. Presented within are three inorganic compounds studied with some form of Raman spectroscopy: normal Raman, hyper-Raman (HR), surface-enhanced Raman spectroscopy (SERS), surface-enhanced hyper-Raman spectroscopy (SEHRS), or resonance Raman spectroscopy (RR).
The first study involves the investigation of phosphine binding with silver metal. Phosphines find wide use in synthetic circles yet have had little study into their method of binding, unlike similar compounds comprised of sulfur. In order to understand the binding of phosphines, several tertiary phosphines, secondary phosphines and secondary phosphine oxides are examined with SERS. …
Computational Electrodynamics And Second Hyper-Raman Scattering, Philip Dwaine Simmons Jr.
Computational Electrodynamics And Second Hyper-Raman Scattering, Philip Dwaine Simmons Jr.
Doctoral Dissertations
Surface-enhanced second hyper-Raman spectroscopy is a type of nonlinear light scattering in which three photons are simultaneously annihilated to produce one photon whose color is slightly shifted from its third harmonic. This process, while incredibly weak, can be magnified by many orders of magnitude with the aid of plasmonic substrates. In this dissertation, three different studies are presented probing both the nature of plasmonics and nonlinear Raman scattering. In the first, nanoparticle aggregates were dosed with two isotopologues of Rhodamine 6G to determine single-molecule activity. Plasmon maps of the aggregates were then generated from electron energy-loss spectroscopy (EELS) and 3D …
Development And Demonstration Of Critical Components Of Aluminum Based Energy Storage Devices Using The Chloroaluminate Ionic Liquids, Mengqi Zhang
Doctoral Dissertations
This dissertation considers the development of porous carbon materials as the substrates for Al deposition/dissolution in an Al based ionic liquid flow battery (ILFB) and demonstration of an Al based hybrid supercapacitor. The Aluminum chloride/ 1-ethyl-3-methylimidazolium chloride chloroaluminate ionic liquid is utilized as the electrolyte for these Al based energy storage devices. The ILFB has less capital cost than the all-vanadium redox flow battery because of the inexpensive AlCl3. The feasibility to equip a tank of solid aluminum chloride in an ILFB system aiming to improve energy density is investigated. A critical range of temperature data (50-130 celsius …
Design, Syntheses And Study Of Bodipy-Based Materials For Use As Electron Transporters In Organic Electronics, Ambata Poe
Doctoral Dissertations
Organic photovoltaics (OPVs) are desirable for the harvesting of solar energy. They provide distinct advantages over their inorganic counterparts, especially the high absorption coefficients of organic materials and their ability to be processed using inexpensive solution methods. This allows for potential development of lightweight and flexible devices for portable electronics. One of the drawbacks of organic photovoltaics is the low power conversion efficiency of the devices. Efforts to improve the efficiency often take place through molecular design of the electron rich donor material to improve light absorption of the active layer. However, significantly less effort has been put into modifying …
Aggregation And Interfacial Behavior Of Charged Surfactants In Ionic Liquids, Lang Chen
Aggregation And Interfacial Behavior Of Charged Surfactants In Ionic Liquids, Lang Chen
Doctoral Dissertations
Room-temperature ionic liquids (ILs) exhibit a unique set of properties, leading to opportunities for numerous applications such as green solvents, batteries and lubricants. Their properties can be greatly tuned and controlled by addition of surfactants. It is therefore critical to obtain a better understanding of the aggregation and interfacial behavior of surfactants within ILs. Firstly, the phase diagram and aggregation isotherms of surfactants in several distinct ILs were investigated by solubility and tensiometry. A connection between solubility of the surfactant and the physical properties of the underlying ionic liquid was established. We found that the interfacial energy was crucial in …