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POLARIZATION COUPLING IN SEMICONDUCTOR NANO-DIMERS IN THE TERAHERTZ RANGE
Title
POLARIZATION COUPLING IN SEMICONDUCTOR NANO-DIMERS IN THE TERAHERTZ RANGE
Creator
Hu, Zhijing
Date
2017, 2017-05
Description
Surface plasmon resonance (SPR) occurs at the interface of a semiconductor and a dielectric when certain conditions are satisfied. SPR is...
Show moreSurface plasmon resonance (SPR) occurs at the interface of a semiconductor and a dielectric when certain conditions are satisfied. SPR is impetus to new sensor and device development in the optical range, with nanoparticles of noble metals taking up major roles. Typical conduction band electron concentrations in semiconductors lead to resonance frequencies in the terahertz and infrared bands. While the response strength is weaker than those exhibited by metals, it can be made up for by the formation of aggregates. The added degree of freedom by doping or carrier injection further enhances the versatility of semiconductor nanoclusters. To obtain a first principle solution to the coupled set of equations for charge carrier transport and electrodynamics in a conductive cluster is a formidable task with a high computational cost. Employing a finite-element based tool, the COMSOL Multiphysics Simulation Software, the interaction inside and outside some elementary semiconductor structures such as slab and sphere have been solved, which revealed the screening of the internal field while displaying dispersion and absorptions effects. The study of semiconductor dimer also showed a significant field enhancement and frequency shift. Under strong applied field, asymmetric polarization within the particles is revealed. The accompanying nonlinear polarization response can be employed to develop new devices. These model structures can serve to provide insight to the analysis and synthesis more complex structures.
Ph.D. in Electrical Engineering, May 2017
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RISE OF A SINGLE BUBBLE IN A VERTICAL TUBE FILLED WITH NANOFLUIDS
Title
RISE OF A SINGLE BUBBLE IN A VERTICAL TUBE FILLED WITH NANOFLUIDS
Creator
Cho, Heon Ki
Date
2018, 2018-05
Description
The motion of air bubbles in tubes filled with nanofluids is of practical interests. Thus, this study focuses on the dynamics of air bubbles...
Show moreThe motion of air bubbles in tubes filled with nanofluids is of practical interests. Thus, this study focuses on the dynamics of air bubbles rising in tubes in nanofluids. Many authors experimentally and analytically proposed the rising air bubble velocity in vertical tubes in common liquids when Capillary number is large. We report here a systematic study of an air bubble rising in vertical tube filled with nanofluids when the Capillary number is small. The presence of the nanoparticles creates a significant change in the bubble velocity compared with the bubble rising in the common liquids. We observed a novel phenomenon of a step-wise decreases in the bubble rising velocity vs. bubble length for small Capillary number. The step-wise velocity increases is attributed to the nanoparticles self-layering phenomenon in the film adjacent to the tube wall. The effect of volume fraction of the nanoparticles and the tube diameters are investigated. Also, we measured the film thickness and calculated the film structural energy isotherm vs. the film thickness from the film meniscus contact angle measurement using the reflected light interferometric method. Based on the experimental measurement of the film thickness and the calculated values of the film structural energy barrier, we estimated the structural film viscosity vs. the number of nanoparticles/micelles. Due to thenanoparticle film self-layering phenomenon, we observed a gradual increasing the film viscosity with the decrease in the film thickness. But, we found a significant increase in the film viscosity accompanied by a step-wise decrease in the bubble velocity when the number of nanoparticles/micelles decreased from three to two particle layers due to the structural transition in the film. Bretherton analyzed the rise of a single long air bubble at a very small Capillary number under the effect of gravity in a vertical tube filled with common liquids with a thick and stable film. However, Bretherton equation cannot accurately predict the rate of the rise of the slow-moving long bubble in the vertical tube in nanofluids because it is valid only for very thick films and uses the bulk viscosity of the fluid. But, we demonstrate that the Bretherton equation can indeed be used for predicting the rate of the rise of the long single bubble through the vertical tube filled with the nanofluids by simply replacing the bulk viscosity with the proper structural nanofilm viscosity of the fluid.
Ph.D. in Chemical Engineering, May 2018
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NANOMATERIALS FOR ADVANCED BATTERY CATHODES
Title
NANOMATERIALS FOR ADVANCED BATTERY CATHODES
Creator
Moazzen, Elahe
Date
2020
Description
Cathode materials are key components that directly determine the power density of a battery. One of the most effective ways of developing high...
Show moreCathode materials are key components that directly determine the power density of a battery. One of the most effective ways of developing high power density cathodes is bringing them into the nano-scale world, which results in many expected and unexpected properties. Some of the desired characteristics include faster charge/discharge kinetics, improved capacity retention and structural stability due to the higher surface to volume ratio and shorter ion diffusion paths. In this dissertation a number of uniquely designed nano-sized cathode materials and nanocomposites are developed and investigated for alkaline aqueous and lithium ion battery applications. Nickel hydroxide (Ni(OH)2), which is one of the most important cathode materials in alkaline batteries, suffers from low conductivity, which usually leads to inefficient discharge and incomplete utilization of the material. A series of Ni(OH)2/Co(OH)2 core/shell nanoplatelets were synthesized and systematically investigated as cathode materials. Structure-property correlations revealed that electrochemical behavior and reversibility of Co(OH)2 redox conversion depended non-linearly on the average shell thickness, with the best performance (99.6% of theoretical capacity of the composite material) achieved at shell thickness of 1.9 ± 0.3 nm. Two fundamental phenomena were suggested to be responsible for the superior performance: templated shell deposition and galvanic coupling of core and shell materials.Manganese (IV) oxide (MnO2), which is another practical cathode that has a great potential to be utilized for a variety of energy storage systems, still has some major challenges including reversible cycling in rechargeable batteries. One of the most crucial challenges is the fact that polymorphs of MnO2 have different electrochemical activities as aqueous and Li-ion battery cathodes. However, most synthetic samples contain a mixture of polymorphs, which makes the structure-property correlations more complicated. This dissertation reports on systematic studies correlating synthesis, thermal and mechanical processing, and composite formation with polymorph composition, electrochemical performance and ion intercalation mechanisms. Among all the results, several main conclusions were reached: 1) Through control of the synthesis parameters and post-processing, desired phase compositions and nanoparticle morphologies, which optimize MnO2 performance in aqueous alkaline electrolyte, can be achieved. Nanoparticles with higher fraction of the akhtenskite polymorph showed higher reversible capacities in LiOH electrolyte (~210 mAh g-1), with stable performance for over 50 cycles. The effects of sub-nanoparticle organization of MnO2 polymorphs by thermal treatment without any morphology change on cycling performance, phase activation, and charge/discharge mechanisms in LiOH electrolyte as well as the detailed mechanism of the polymorph conversion during annealing were studied and for the first time, demonstrating that the electrochemical activity of MnO2 material strongly depends not only on the lattice structure of individual polymorphs but also on the sub-nanoparticle polymorph architecture and interphases.2) Several processing strategies, including thermal and mechanical processing, and composite fabrication were utilized to develop functional MnO2 cathodes for Li-ion batteries. Improvements in capacity and cycling performance were correlated to the presence of the pyrolusite phase of MnO2 and the crystallite size. Composite fabrication by graphene oxide wrapping also provided significant performance improvements through polymorph composition control and improved conductivity.
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DEVELOPMENT OF FULLY BIOCOMPATIBLE HYDROGEL NANOPARTICLE FORMULATIONS FOR CONTROLLED-RELEASE DELIVERY OF A WIDE VARIETY OF BIOMOLECULES
Title
DEVELOPMENT OF FULLY BIOCOMPATIBLE HYDROGEL NANOPARTICLE FORMULATIONS FOR CONTROLLED-RELEASE DELIVERY OF A WIDE VARIETY OF BIOMOLECULES
Creator
Borges, Fernando Tancredo Pereira
Date
2020
Description
In recent years, our group has focused on the production of PEGDA-based hydrogel scaffolds and nanoparticles for drug delivery of small...
Show moreIn recent years, our group has focused on the production of PEGDA-based hydrogel scaffolds and nanoparticles for drug delivery of small molecules. However, with recent advances in modern therapeutic treatments, such as protein and genetic engineering, there is an increasing need for the development of drug delivery devices that would be able encapsulate larger molecules. Therefore, the goal of this thesis work was to develop a systematic way to produce fully biocompatible PEGDA-based hydrogel nanoparticle formulations that would be able to encapsulate any size molecule, ranging from small ionic molecules, to peptides and proteins, all the way to large nucleic acids, and deliver it in a controlled manner.The first of part of this work consisted of developing a stable and reproducible process for the production of hydrogel PPi-NPs. Initial studies were done in order to assess the influence of phosphate salts in the polymerization system and it was found that both monophosphate and polyphosphate salts significantly damper the NVP homo-polymerization kinetics, but do not affect the co-polymerization of NVP and PEGDA. Then, emulsion stability studies were done to determine whether phosphate salts affected the stability of the minimeulsion system used in the production of the nanoparticles. Cloud point measurements and droplet size screening measurements showed that by transitioning from a Pi-loaded emulsion system to a PPi-loaded emulsion system, the required HLB of the emulsion shifts by 1.5 points. Upon correction for that shift, a reproducible process for production of PPi-loaded nanoparticles was obtained. A parametric study was then performed to see how the different process parameters affected the different properties of the produced particles. The second part of the work consisted in developing a platform for encapsulation of large to very-large molecules within these hydrogel systems. A new set of equations was developed for better estimation of the interstitial space, available for encapsulation of molecules, of crosslinked polymers that used very high molecular weight crosslinkers and/or high amounts of crosslinker. Upon development of this new set of equations, hydrogel discs were made via photopolymerization in order to validate the equations. By introducing a third monomer, EGA, and varying the molecular weight and concentration of the crosslinker, hydrogels with a wide range of mesh dimensions from 25 to 700 were achieved. These gels were then used to encapsulate 4 different sample molecules of varying molecular weights and size. A new heuristic was developed for encapsulation of non-spherical molecules, where the aspect ratios of the molecule and of the polymer network are considered. By varying the size of the ratios of the dimensions of the hydrogel network to the dimensions of the molecule, significantly different release profiles of small molecules, peptides and oligonucleotides were obtained. Finally, in order to explore different administration routes, the process was transitioning into being fully biocompatible. The organic solvent previously used in the emulsion system was replaced by soybean oil and the surfactants were replaced by a food-grade surfactant, PGPR, to form Bio-Compatible Nanoparticle Emulsions (BCNEs). Qualitative release from the BCNEs was shown. A new method for quantitative measuring of release from BCNE was developed. Release from QK-BCNE was observed up to 46 days, which is unprecedented for sustained-release and revolutionary for the field. A BCNE spreadable ointment formulation was also developed.
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