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Nanoparticles are ubiquitous in various fields due to their unique properties not seen in similar bulk materials. Among them, core-shell composite nanoparticles are an important class of materials which are attractive for their applications in catalysis, sensing, electromagnetic shielding, drug delivery, and environmental remediation. This dissertation focuses on the study

Nanoparticles are ubiquitous in various fields due to their unique properties not seen in similar bulk materials. Among them, core-shell composite nanoparticles are an important class of materials which are attractive for their applications in catalysis, sensing, electromagnetic shielding, drug delivery, and environmental remediation. This dissertation focuses on the study of core-shell type of nanoparticles where a polymer serves as the core and inorganic nanoparticles are the shell. This is an interesting class of supramolecular building blocks and can "exhibit unusual, possibly unique, properties which cannot be obtained simply by co-mixing polymer and inorganic particles". The one-step Pickering emulsion polymerization method was successfully developed and applied to synthesize polystyrene-silica core-shell composite particles. Possible mechanisms of the Pickering emulsion polymerization were also explored. The silica nanoparticles were thermodynamically favorable to self-assemble at liquid-liquid interfaces at the initial stage of polymerization and remained at the interface to finally form the shells of the composite particles. More importantly, Pickering emulsion polymerization was employed to synthesize polystyrene/poly(N-isopropylacrylamide) (PNIPAAm)-silica core-shell nanoparticles with N-isopropylacrylamide incorporated into the core as a co-monomer. The composite nanoparticles were temperature sensitive and could be up-taken by human prostate cancer cells and demonstrated effectiveness in drug delivery and cancer therapy. Similarly, by incorporating poly-2-(N,N)-dimethylamino)ethyl methacrylate (PDMA) into the core, pH sensitive core-shell composite nanoparticles were synthesized and applied as effective carriers to release a rheological modifier upon a pH change. Finally, the research focuses on facile approaches to engineer the transition of the temperature-sensitive particles and develop composite core-shell nanoparticles with a metallic shell.
ContributorsSanyal, Sriya (Author) / Dai, Lenore L. (Thesis advisor) / Jiang, Hanqing (Committee member) / Lind, Mary L. (Committee member) / Phelan, Patrick (Committee member) / Rege, Kaushal (Committee member) / Arizona State University (Publisher)
Created2012
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Description
The reality of smart cities is here and now. The issues of data privacy in tech applications are apparent in smart cities. Privacy as an issue raised by many and addressed by few remains critical for smart cities’ success. It is the common responsibility of smart cities, tech application makers,

The reality of smart cities is here and now. The issues of data privacy in tech applications are apparent in smart cities. Privacy as an issue raised by many and addressed by few remains critical for smart cities’ success. It is the common responsibility of smart cities, tech application makers, and users to embark on the journey to solutions. Privacy is an individual problem that smart cities need to provide a collective solution for. The research focuses on understanding users’ data privacy preferences, what information they consider private, and what they need to protect. The research identifies the data security loopholes, data privacy roadblocks, and common opportunities for change to implement a proactive privacy-driven tech solution necessary to address and resolve tech-induced data privacy concerns among citizens. This dissertation aims at addressing the issue of data privacy in tech applications based on known methodologies to address the concerns they allow. Through this research, a data privacy survey on tech applications was conducted, and the results reveal users’ desires to become a part of the solution by becoming aware and taking control of their data privacy while using tech applications. So, this dissertation gives an overview of the data privacy issues in tech, discusses available data privacy basis, elaborates on the different steps needed to create a robust remedy to data privacy concerns in enabling users’ awareness and control, and proposes two privacy applications one as a data privacy awareness solution and the other as a representation of the privacy control framework to address data privacy concerns in smart cities.
ContributorsMusafiri Mimo, Edgard (Author) / McDaniel, Troy (Thesis advisor) / Michael, Katina (Committee member) / Sullivan, Kenneth (Committee member) / Arizona State University (Publisher)
Created2022
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Description
The objective of this dissertation is to study the optical and radiative properties of inhomogeneous metallic structures. In the ongoing search for new materials with tunable optical characteristics, porous metals and nanowires provides an extensive design space to engineer its optical response based on the morphology-dependent phenomena.This dissertation firstly discusses

The objective of this dissertation is to study the optical and radiative properties of inhomogeneous metallic structures. In the ongoing search for new materials with tunable optical characteristics, porous metals and nanowires provides an extensive design space to engineer its optical response based on the morphology-dependent phenomena.This dissertation firstly discusses the use of aluminum nanopillar array on a quartz substrate as spectrally selective optical filter with narrowband transmission for thermophotovoltaic systems. The narrow-band transmission enhancement is attributed to the magnetic polariton resonance between neighboring aluminum nanopillars. Tuning of the resonance wavelengths for selective filters was achieved by changing the nanopillar geometry. It concludes by showing improved efficiency of Gallium-Antimonide thermophotovoltaic system by coupling the designed filter with the cell. Next, isotropic nanoporous gold films are investigated for applications in energy conversion and three-dimensional laser printing. The fabricated nanoporous gold samples are characterized by scanning electron microscopy, and the spectral hemispherical reflectance is measured with an integrating sphere. The effective isotropic optical constants of nanoporous gold with varying pore volume fraction are modeled using the Bruggeman effective medium theory. Nanoporous gold are metastable and to understand its temperature dependent optical properties, a lab-scale fiber-based optical spectrometer setup is developed to characterize the in-situ specular reflectance of nanoporous gold thin films at temperatures ranging from 25 to 500 oC. The in-situ and the ex-situ measurements suggest that the ii specular, diffuse, and hemispherical reflectance varies as a function of temperature due to the morphology (ligament diameter) change observed. The dissertation continues with modeling and measurements of the radiative properties of porous powders. The study shows the enhanced absorption by mixing porous copper to copper powder. This is important from the viewpoint of scalability to get end products such as sheets and tubes with the requirement of high absorptance that can be produced through three-dimensional printing. Finally, the dissertation concludes with recommendations on the methods to fabricate the suggested optical filters to improve thermophotovoltaic system efficiencies. The results presented in this dissertation will facilitate not only the manufacturing of materials but also the promising applications in solar thermal energy and optical systems.
ContributorsRamesh, Rajagopalan (Author) / Wang, Liping (Thesis advisor) / Azeredo, Bruno (Thesis advisor) / Phelan, Patrick (Committee member) / Yu, Hongbin (Committee member) / Rykaczewski, Konrad (Committee member) / Arizona State University (Publisher)
Created2022
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Description
District heating plays an important role in improving energy efficiency and providing thermal heat to buildings. Instead of using water as an energy carrier to transport sensible heat, this dissertation explores the use of liquid-phase thermochemical reactions for district heating as well as thermal storage. Chapters 2 and 3 present

District heating plays an important role in improving energy efficiency and providing thermal heat to buildings. Instead of using water as an energy carrier to transport sensible heat, this dissertation explores the use of liquid-phase thermochemical reactions for district heating as well as thermal storage. Chapters 2 and 3 present thermodynamic and design analyses for the proposed district heating system. Chapter 4 models the use of liquid-phase thermochemical reactions for on-site solar thermal storage. In brief, the proposed district heating system uses liquid-phase thermochemical reactions to transport thermal energy from a heat source to a heat sink. The separation ensures that the stored thermochemical heat can be stored indefinitely and/or transported long distances. The reactant molecules are then pumped over long distances to the heat sink, where they are combined in an exothermic reaction to provide heat. The product of the exothermic reaction is then pumped back to the heat source for re-use. The key evaluation parameter is the system efficiency. The results demonstrate that with heat recovery, the system efficiency can be up to 77% when the sink temperature equals 25 C. The results also indicate that the appropriate chemical reaction candidates should have large reaction enthalpy and small reaction entropy. Further, the design analyses of two district heating systems, Direct District Heating (DDH) system and Indirect District Heating (IDH) system using the solvated case shows that the critical distance is 106m. When the distance is shorter than 1000,000m, the factors related to the chemical reaction at the user side and factors related to the separation process are important for the DDH system. When the distance is longer than 106m, the factors related to the fluid mechanic become more important. Because the substation of the IDH system degrades the quality of the energy, when the distance is shorter than 106m, the efficiency of the substation is significant. Lastly, I create models for on-site solar thermal storage systems using liquid-phase thermochemical reactions and hot water. The analysis shows that the thermochemical reaction is more competitive for long-duration storage applications. However, the heat recovery added to the thermochemical thermal storage system cannot help improving solar radiation absorption with high inlet temperature of the solar panel.
ContributorsZhang, Yanan (Author) / Wang, Robert (Thesis advisor) / Milcarek, Ryan (Committee member) / Parrish, Kristen (Committee member) / Phelan, Patrick (Committee member) / Rykaczewski, Konrad (Committee member) / Arizona State University (Publisher)
Created2022
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Description
Siloxane, a common contaminant present in biogas, is known for adverse effects on cogeneration prime movers. In this work, the solid oxide fuel cell (SOFC) nickel-yttria stabilized zirconia (Ni-YSZ) anode degradation due to poisoning by siloxane was investigated. For this purpose, experiments with different fuels, different deposition substrate materials, different

Siloxane, a common contaminant present in biogas, is known for adverse effects on cogeneration prime movers. In this work, the solid oxide fuel cell (SOFC) nickel-yttria stabilized zirconia (Ni-YSZ) anode degradation due to poisoning by siloxane was investigated. For this purpose, experiments with different fuels, different deposition substrate materials, different structure of contamination siloxane (cyclic and linear) and entire failure process are conducted in this study. The electrochemical and material characterization methods, such as Electrochemical Impedance Spectroscopy (EIS), Scanning Electron Microscope- Wavelength Dispersive Spectrometers (SEM-WDS), X-ray Photoelectron Spectroscopy (XPS), X-ray Diffraction (XRD), and Raman spectroscopy, were applied to investigate the anode degradation behavior. The electrochemical characterization results show that the SOFCs performance degradation caused by siloxane contamination is irreversible under bio-syngas condition. An equivalent circuit model (ECM) is developed based on electrochemical characterization results. Based on the Distribution of Relaxation Time (DRT) method, the detailed microstructure parameter changes are evaluated corresponding to the ECM results. The results contradict the previously proposed siloxane degradation mechanism as the experimental results show that water can inhibit anode deactivation. For anode materials, Ni is considered a major factor in siloxane deposition reactions in Ni-YSZ anode. Based on the results of XPS, XRD and WDS analysis, an initial layer of carbon deposition develops and is considered a critical process for the siloxane deposition reaction. Based on the experimental results in this study and previous studies about siloxane deposition on metal oxides, the proposed siloxane deposition process occurs in stages consisting of the siloxane adsorption, initial carbon deposition, siloxane polymerization and amorphous silicon dioxide deposition.
ContributorsTian, Jiashen (Author) / Milcarek, Ryan J. (Thesis advisor) / Muhich, Christopher (Committee member) / Wang, Liping (Committee member) / Phelan, Patrick (Committee member) / Nian, Qiong (Committee member) / Arizona State University (Publisher)
Created2022
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Description
Cellular metamaterials arouse broad scientific interests due to the combination of host material and structure together to achieve a wide range of physical properties rarely found in nature. Stochastic foam as one subset has been considered as a competitive candidate for versatile applications including heat exchangers, battery electrodes, automotive, catalyst

Cellular metamaterials arouse broad scientific interests due to the combination of host material and structure together to achieve a wide range of physical properties rarely found in nature. Stochastic foam as one subset has been considered as a competitive candidate for versatile applications including heat exchangers, battery electrodes, automotive, catalyst devices, magnetic shielding, etc. For the engineering of the cellular foam architectures, closed-form models that can be used to predict the mechanical and thermal properties of foams are highly desired especially for the recently developed ultralight weight shellular architectures. Herein, for the first time, a novel packing three-dimensional (3D) hollow pentagonal dodecahedron (HPD) model is proposed to simulate the cellular architecture with hollow struts. An electrochemical deposition process is utilized to manufacture the metallic hollow foam architecture. Mechanical and thermal testing of the as-manufactured foams are carried out to compare with the HPD model. Timoshenko beam theory is utilized to verify and explain the derived power coefficient relation. Our HPD model is proved to accurately capture both the topology and the physical properties of hollow stochastic foam. Understanding how the novel HPD model packing helps break the conventional impression that 3D pentagonal topology cannot fulfill the space as a representative volume element. Moreover, the developed HPD model can predict the mechanical and thermal properties of the manufactured hollow metallic foams and elucidating of how the inevitable manufacturing defects affect the physical properties of the hollow metallic foams. Despite of the macro-scale stochastic foam architecture, nano gradient gyroid lattices are studied using Molecular Dynamics (MD) simulation. The simulation result reveals that, unlike homogeneous architecture, gradient gyroid not only shows novel layer-by-layer deformation behavior, but also processes significantly better energy absorption ability. The deformation behavior and energy absorption are predictable and designable, which demonstrate its highly programmable potential.
ContributorsDai, Rui (Author) / Nian, Qiong (Thesis advisor) / Jiao, Yang (Committee member) / Kwon, Beomjin (Committee member) / Liu, Yongming (Committee member) / Phelan, Patrick (Committee member) / Arizona State University (Publisher)
Created2021
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Description
One type of assistive device for the blind has attempted to convert visual information into information that can be perceived through another sense, such as touch or hearing. A vibrotactile haptic display assistive device consists of an array of vibrating elements placed against the skin, allowing the blind individual to

One type of assistive device for the blind has attempted to convert visual information into information that can be perceived through another sense, such as touch or hearing. A vibrotactile haptic display assistive device consists of an array of vibrating elements placed against the skin, allowing the blind individual to receive visual information through touch. However, these approaches have two significant technical challenges: large vibration element size and the number of microcontroller pins required for vibration control, both causing excessively low resolution of the device. Here, I propose and investigate a type of high-resolution vibrotactile haptic display which overcomes these challenges by utilizing a ‘microbeam’ as the vibrating element. These microbeams can then be actuated using only one microcontroller pin connected to a speaker or surface transducer. This approach could solve the low-resolution problem currently present in all haptic displays. In this paper, the results of an investigation into the manufacturability of such a device, simulation of the vibrational characteristics, and prototyping and experimental validation of the device concept are presented. The possible reasons of the frequency shift between the result of the forced or free response of beams and the frequency calculated based on a lumped mass approximation are investigated. It is found that one of the important reasons for the frequency shift is the size effect, the dependency of the elastic modulus on the size and kind of material. This size effect on A2 tool steel for Micro-Meso scale cantilever beams for the proposed system is investigated.
ContributorsWi, Daehan (Author) / SODEMANN, ANGELA A (Thesis advisor) / Redkar, Sangram (Committee member) / McDaniel, Troy (Committee member) / Arizona State University (Publisher)
Created2019
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Description
Soft polymer composites with improved thermal conductivity are needed for the thermal management of electronics. Interfacial thermal boundary resistance, however, prevents the efficient use of many high thermal conductivity fill materials. Magnetic alignment of ferrous fill material enforces percolation of the high thermal conductivity fill, thereby shifting the governing boundary

Soft polymer composites with improved thermal conductivity are needed for the thermal management of electronics. Interfacial thermal boundary resistance, however, prevents the efficient use of many high thermal conductivity fill materials. Magnetic alignment of ferrous fill material enforces percolation of the high thermal conductivity fill, thereby shifting the governing boundary resistance to the particle- particle interfaces and increasing the directional thermal conductivity of the polymer composite. Magnetic alignment maximizes the thermal conductivity while minimizing composite stiffening at a fill fraction of half the maximum packing factor. The directional thermal conductivity of the composite is improved by more than 2-fold. Particle-particle contact engineering is then introduced to decrease the particle- particle boundary resistance and further improve the thermal conductivity of the composite.

The interface between rigid fill particles is a point contact with very little interfacial area connecting them. Silver and gallium-based liquid metal (LM) coatings provide soft interfaces that, under pressure, increase the interfacial area between particles and decrease the particle-particle boundary resistance. These engineered contacts are investigated both in and out of the polymer matrix and with and without magnetic alignment of the fill. Magnetically aligned in the polymer matrix, 350nm- thick silver coatings on nickel particles produce a 1.8-fold increase in composite thermal conductivity over the aligned bare-nickel composites. The LM coatings provide similar enhancements, but require higher volumes of LM to do so. This is due to the rapid formation of gallium oxide, which introduces additional thermal boundaries and decreases the benefit of the LM coatings.

The oxide shell of LM droplets (LMDs) can be ruptured using pressure. The pressure needed to rupture LMDs matches closely to thin-walled pressure vessel theory. Furthermore, the addition of tungsten particles stabilizes the mixture for use at higher pressures. Finally, thiols and hydrochloric acid weaken the oxide shell and boost the thermal performance of the beds of LMDs by 50% at pressures much lower than 1 megapascal (MPa) to make them more suitable for use in TIMs.
ContributorsRalphs, Matthew (Author) / Rykaczewski, Konrad (Thesis advisor) / Wang, Robert Y (Thesis advisor) / Phelan, Patrick (Committee member) / Wang, Liping (Committee member) / Devasenathipathy, Shankar (Committee member) / Arizona State University (Publisher)
Created2019
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Description
First, in a large-scale structure, a 3-D CFD model was built to simulate flow and temperature distributions. The flow patterns and temperature distributions are characterized and validated through spot measurements. The detailed understanding of them then allows for optimization of the HVAC configuration because identification of the problematic flow patterns

First, in a large-scale structure, a 3-D CFD model was built to simulate flow and temperature distributions. The flow patterns and temperature distributions are characterized and validated through spot measurements. The detailed understanding of them then allows for optimization of the HVAC configuration because identification of the problematic flow patterns and temperature mis-distributions leads to some corrective measures. Second, an appropriate form of the viscous dissipation term in the integral form of the conservation equation was considered, and the effects of momentum terms on the computed drop size in pressure-atomized sprays were examined. The Sauter mean diameter (SMD) calculated in this manner agrees well with experimental data of the drop velocities and sizes. Using the suggested equation with the revised treatment of liquid momentum setup, injection parameters can be directly input to the system of equations. Thus, this approach is capable of incorporating the effects of injection parameters for further considerations of the drop and velocity distributions under a wide range of spray geometry and injection conditions. Lastly, groundwater level estimation was investigated using compressed sensing (CS). To satisfy a general property of CS, a random measurement matrix was used, the groundwater network was constructed, and finally the l-1 optimization was run. Through several validation tests, correct estimation of groundwater level by CS was shown. Using this setup, decreasing trends in groundwater level in the southwestern US was shown. The suggested method is effective in that the total measurements of registered wells can be reduced down by approximately 42 %, sparse data can be visualized and a possible approach for groundwater management during extreme weather changes, e.g. in California, was demonstrated.
ContributorsLee, Joon Young (Author) / Lee, Taewoo (Thesis advisor) / Huang, Huei-Ping (Committee member) / Lopez, Juan (Committee member) / Phelan, Patrick (Committee member) / Chen, Kangping (Committee member) / Arizona State University (Publisher)
Created2015
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Description
The proposed research mainly focuses on employing tunable materials to achieve dynamic control of radiative heat transfer in both far and near fields for thermal management. Vanadium dioxide (VO2), which undergoes a phase transition from insulator to metal at the temperature of 341 K, is one tunable material being applied.

The proposed research mainly focuses on employing tunable materials to achieve dynamic control of radiative heat transfer in both far and near fields for thermal management. Vanadium dioxide (VO2), which undergoes a phase transition from insulator to metal at the temperature of 341 K, is one tunable material being applied. The other one is graphene, whose optical properties can be tuned by chemical potential through external bias or chemical doping.

In the far field, a VO2-based metamaterial thermal emitter with switchable emittance in the mid-infrared has been theoretically studied. When VO2 is in the insulating phase, high emittance is observed at the resonance frequency of magnetic polaritons (MPs), while the structure becomes highly reflective when VO2 turns metallic. A VO2-based thermal emitter with tunable emittance is also demonstrated due to the excitation of MP at different resonance frequencies when VO2 changes phase. Moreover, an infrared thermal emitter made of graphene-covered SiC grating could achieve frequency-tunable emittance peak via the change of the graphene chemical potential.

In the near field, a radiation-based thermal rectifier is constructed by investigating radiative transfer between VO2 and SiO2 separated by nanometer vacuum gap distances. Compared to the case where VO2 is set as the emitter at 400 K as a metal, when VO2 is considered as the receiver at 300 K as an insulator, the energy transfer is greatly enhanced due to the strong surface phonon polariton (SPhP) coupling between insulating VO2 and SiO2. A radiation-based thermal switch is also explored by setting VO2 as both the emitter and the receiver. When both VO2 emitter and receiver are at the insulating phase, the switch is at the “on” mode with a much enhanced heat flux due to strong SPhP coupling, while the near-field radiative transfer is greatly suppressed when the emitting VO2 becomes metallic at temperatures higher than 341K during the “off” mode. In addition, an electrically-gated thermal modulator made of graphene covered SiC plates is theoretically studied with modulated radiative transport by varying graphene chemical potential. Moreover, the MP effect on near-field radiative transport has been investigated by spectrally enhancing radiative heat transfer between two metal gratings.
ContributorsYang, Yue (Author) / Wang, Liping (Thesis advisor) / Phelan, Patrick (Committee member) / Wang, Robert (Committee member) / Tongay, Sefaattin (Committee member) / Rykaczewski, Konrad (Committee member) / Arizona State University (Publisher)
Created2016