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- Genre: Doctoral Dissertation

Description
Nanoparticle suspensions, popularly termed “nanofluids,” have been extensively investigated for their thermal and radiative properties. Such work has generated great controversy, although it is arguably accepted today that the presence of nanoparticles rarely leads to useful enhancements in either thermal conductivity or convective heat transfer. On the other hand, there are still examples of unanticipated enhancements to some properties, such as the reported specific heat of molten salt-based nanofluids and the critical heat flux. Another largely overlooked example is the apparent effect of nanoparticles on the effective latent heat of vaporization (hfg) of aqueous nanofluids. A previous study focused on molecular dynamics (MD) modeling supplemented with limited experimental data to suggest that hfg increases with increasing nanoparticle concentration.
Here, this research extends that exploratory work in an effort to determine if hfg of aqueous nanofluids can be manipulated, i.e., increased or decreased, by the addition of graphite or silver nanoparticles. Our results to date indicate that hfg can be substantially impacted, by up to ± 30% depending on the type of nanoparticle. Moreover, this dissertation reports further experiments with changing surface area based on volume fraction (0.005% to 2%) and various nanoparticle sizes to investigate the mechanisms for hfg modification in aqueous graphite and silver nanofluids. This research also investigates thermophysical properties, i.e., density and surface tension in aqueous nanofluids to support the experimental results of hfg based on the Clausius - Clapeyron equation. This theoretical investigation agrees well with the experimental results. Furthermore, this research investigates the hfg change of aqueous nanofluids with nanoscale studies in terms of melting of silver nanoparticles and hydrophobic interactions of graphite nanofluid. As a result, the entropy change due to those mechanisms could be a main cause of the changes of hfg in silver and graphite nanofluids.
Finally, applying the latent heat results of graphite and silver nanofluids to an actual solar thermal system to identify enhanced performance with a Rankine cycle is suggested to show that the tunable latent heat of vaporization in nanofluilds could be beneficial for real-world solar thermal applications with improved efficiency.
Here, this research extends that exploratory work in an effort to determine if hfg of aqueous nanofluids can be manipulated, i.e., increased or decreased, by the addition of graphite or silver nanoparticles. Our results to date indicate that hfg can be substantially impacted, by up to ± 30% depending on the type of nanoparticle. Moreover, this dissertation reports further experiments with changing surface area based on volume fraction (0.005% to 2%) and various nanoparticle sizes to investigate the mechanisms for hfg modification in aqueous graphite and silver nanofluids. This research also investigates thermophysical properties, i.e., density and surface tension in aqueous nanofluids to support the experimental results of hfg based on the Clausius - Clapeyron equation. This theoretical investigation agrees well with the experimental results. Furthermore, this research investigates the hfg change of aqueous nanofluids with nanoscale studies in terms of melting of silver nanoparticles and hydrophobic interactions of graphite nanofluid. As a result, the entropy change due to those mechanisms could be a main cause of the changes of hfg in silver and graphite nanofluids.
Finally, applying the latent heat results of graphite and silver nanofluids to an actual solar thermal system to identify enhanced performance with a Rankine cycle is suggested to show that the tunable latent heat of vaporization in nanofluilds could be beneficial for real-world solar thermal applications with improved efficiency.
ContributorsLee, Soochan (Author) / Phelan, Patrick E (Thesis advisor) / Wu, Carole-Jean (Thesis advisor) / Wang, Robert (Committee member) / Wang, Liping (Committee member) / Taylor, Robert A. (Committee member) / Prasher, Ravi (Committee member) / Arizona State University (Publisher)
Created2015

Description
The rapid progress of solution-phase synthesis has led colloidal nanocrystals one of the most versatile nanoscale materials, provided opportunities to tailor material's properties, and boosted related technological innovations. Colloidal nanocrystal-based materials have been demonstrated success in a variety of applications, such as LEDs, electronics, solar cells and thermoelectrics. In each of these applications, the thermal transport property plays a big role. An undesirable temperature rise due to inefficient heat dissipation could lead to deleterious effects on devices' performance and lifetime. Hence, the first project is focused on investigating the thermal transport in colloidal nanocrystal solids. This study answers the question that how the molecular structure of nanocrystals affect the thermal transport, and provides insights for future device designs. In particular, PbS nanocrystals is used as a monitoring system, and the core diameter, ligand length and ligand binding group are systematically varied to study the corresponding effect on thermal transport.
Next, a fundamental study is presented on the phase stability and solid-liquid transformation of metallic (In, Sn and Bi) colloidal nanocrystals. Although the phase change of nanoparticles has been a long-standing research topic, the melting behavior of colloidal nanocrytstals is largely unexplored. In addition, this study is of practical importance to nanocrystal-based applications that operate at elevated temperatures. Embedding colloidal nanocrystals into thermally-stable polymer matrices allows preserving nanocrystal size throughout melt-freeze cycles, and therefore enabling observation of stable melting features. Size-dependent melting temperature, melting enthalpy and melting entropy have all been measured and discussed.
In the next two chapters, focus has been switched to developing colloidal nanocrystal-based phase change composites for thermal energy storage applications. In Chapter 4, a polymer matrix phase change nanocomposite has been created. In this composite, the melting temperature and energy density could be independently controlled by tuning nanocrystal diameter and volume fractions. In Chapter 5, a solution-phase synthesis on metal matrix-metal nanocrytal composite is presented. This approach enables excellent morphological control over nanocrystals and demonstrated a phase change composite with a thermal conductivity 2 - 3 orders of magnitude greater than typical phase change materials, such as organics and molten salts.
Next, a fundamental study is presented on the phase stability and solid-liquid transformation of metallic (In, Sn and Bi) colloidal nanocrystals. Although the phase change of nanoparticles has been a long-standing research topic, the melting behavior of colloidal nanocrytstals is largely unexplored. In addition, this study is of practical importance to nanocrystal-based applications that operate at elevated temperatures. Embedding colloidal nanocrystals into thermally-stable polymer matrices allows preserving nanocrystal size throughout melt-freeze cycles, and therefore enabling observation of stable melting features. Size-dependent melting temperature, melting enthalpy and melting entropy have all been measured and discussed.
In the next two chapters, focus has been switched to developing colloidal nanocrystal-based phase change composites for thermal energy storage applications. In Chapter 4, a polymer matrix phase change nanocomposite has been created. In this composite, the melting temperature and energy density could be independently controlled by tuning nanocrystal diameter and volume fractions. In Chapter 5, a solution-phase synthesis on metal matrix-metal nanocrytal composite is presented. This approach enables excellent morphological control over nanocrystals and demonstrated a phase change composite with a thermal conductivity 2 - 3 orders of magnitude greater than typical phase change materials, such as organics and molten salts.
ContributorsLiu, Minglu (Author) / Wang, Robert Y (Thesis advisor) / Wang, Liping (Committee member) / Rykaczewski, Konrad (Committee member) / Phelan, Patrick (Committee member) / Dai, Lenore (Committee member) / Arizona State University (Publisher)
Created2015

Description
The energy crisis in the past decades has greatly boosted the search for alternatives to traditional fossil foils, and solar energy stands out as an important candidate due to its cleanness and abundance. However, the relatively low conversion efficiency and energy density strongly hinder the utilization of solar energy in wider applications. This thesis focuses on employing metamaterials and metafilms to enhance the conversion efficiency of solar thermal, solar thermophotovoltaic (STPV) and photovoltaic systems.
A selective metamaterial solar absorber is designed in this thesis to maximize the absorbed solar energy and minimize heat dissipation through thermal radiation. The theoretically designed metamaterial solar absorber exhibits absorptance higher than 95% in the solar spectrum but shows emittance less than 4% in the IR regime. This metamaterial solar absorber is further experimentally fabricated and optically characterized. Moreover, a metafilm selective absorber with stability up to 600oC is introduced, which exhibits solar absorptance higher than 90% and IR emittance less than 10%.
Solar thermophotovoltaic energy conversion enhanced by metamaterial absorbers and emitters is theoretically investigated in this thesis. The STPV system employing selective metamaterial absorber and emitter is investigated in this work, showing its conversion efficiency between 8% and 10% with concentration factor varying between 20 and 200. This conversion efficiency is remarkably enhanced compared with the conversion efficiency for STPV system employing black surfaces (<2.5%).
Moreover, plasmonic light trapping in ultra-thin solar cells employing concave grating nanostructures is discussed in this thesis. The plasmonic light trapping inside an ultrathin GaAs layer in the film-coupled metamaterial structure is numerically demonstrated. By exciting plasmonic resonances inside this structure, the short-circuit current density for the film-coupled metamaterial solar cell is three times the short-circuit current for a free-standing GaAs layer.
The dissertation is concluded by discussing about the future work on selective solar thermal absorbers, STPV/TPV systems and light trapping structures. Possibilities to design and fabricate solar thermal absorber with better thermal stability will be discussed, the experimental work of TPV system will be conducted, and the light trapping in organic and perovskite solar cells will be looked into.
A selective metamaterial solar absorber is designed in this thesis to maximize the absorbed solar energy and minimize heat dissipation through thermal radiation. The theoretically designed metamaterial solar absorber exhibits absorptance higher than 95% in the solar spectrum but shows emittance less than 4% in the IR regime. This metamaterial solar absorber is further experimentally fabricated and optically characterized. Moreover, a metafilm selective absorber with stability up to 600oC is introduced, which exhibits solar absorptance higher than 90% and IR emittance less than 10%.
Solar thermophotovoltaic energy conversion enhanced by metamaterial absorbers and emitters is theoretically investigated in this thesis. The STPV system employing selective metamaterial absorber and emitter is investigated in this work, showing its conversion efficiency between 8% and 10% with concentration factor varying between 20 and 200. This conversion efficiency is remarkably enhanced compared with the conversion efficiency for STPV system employing black surfaces (<2.5%).
Moreover, plasmonic light trapping in ultra-thin solar cells employing concave grating nanostructures is discussed in this thesis. The plasmonic light trapping inside an ultrathin GaAs layer in the film-coupled metamaterial structure is numerically demonstrated. By exciting plasmonic resonances inside this structure, the short-circuit current density for the film-coupled metamaterial solar cell is three times the short-circuit current for a free-standing GaAs layer.
The dissertation is concluded by discussing about the future work on selective solar thermal absorbers, STPV/TPV systems and light trapping structures. Possibilities to design and fabricate solar thermal absorber with better thermal stability will be discussed, the experimental work of TPV system will be conducted, and the light trapping in organic and perovskite solar cells will be looked into.
ContributorsWang, Hao (Author) / Wang, Liping (Thesis advisor) / Phelan, Patrick (Committee member) / Wang, Robert (Committee member) / Dai, Lenore (Committee member) / Rykaczewski, Konrad (Committee member) / Arizona State University (Publisher)
Created2016

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 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.
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

Description
Design and development of optical sensors for the detection of specific targets, e.g., ions, molecules, proteins, light polarizations, is one of the most essential research topics in the field of nanophotonics that paves the way for significant technological progressions in chemical and biomarker detections, polarimetric imaging and other sensing related applications. In this dissertation, three designs of optical sensors based on plasmonic and dielectric nanostructures are thoroughly studied for the applications in chemicals, biomarkers and light polarization detection. Firstly, a plasmonic nanoantenna structure, which is composed of complementary anisotropic nanobars and nanoapertures featuring strong localized electric field enhancement at nanogap region, demonstrates both high sensitivity refractometric detection and specific infrared fingerprint detection for chemical sensing. Specifically, the sensor can probe monolayer thin octadecanethiol with a large resonance shift of 136 nm and all four characteristic infrared fingerprints detected. Secondly, a bio-inspired double-layered metasurface structure, which is made of dielectric nanoantenna and plasmonic nanogratings, mediates strong optical chirality and enables the selection of circularly polarized light handedness (extinction ratio ≥ 35) with high transmission efficiency (≥ 80%). The structure can be further integrated on-chip with linear polarizers for highly precise full-Stokes polarimetric detection with minimum transmission loss. Lastly, a gold nanoparticle based colorimetric assay is designed for high sensitivity, specificity and rapid detection of infectious diseases related biomarkers. The complete design workflows from critical reagents productions, rapid detection protocol to assay characterizations are extensively studied. Detection of Ebola virus disease biomarker, secreted glycoprotein, within 20 minutes are experimentally demonstrated with limit of detection down to ~40 pM and a broad detection range from 10 pM to 1 µM.
The designs of the three sensors propose novel and versatile design concepts for the development of sensing devices in the detection of chemicals, biomarkers and light polarization. The efforts in the fundamental theoretical analysis and experimental demonstrations are expected to provide valuable contents to the optical sensor researches and to potentially inspire new sensor designs for broad sensing applications in the future.
ContributorsChen, Xiahui (Author) / Wang, Chao (Thesis advisor) / Zhao, Yuji (Committee member) / Wang, Liping (Committee member) / Goryll, Michael (Committee member) / Arizona State University (Publisher)
Created2021

Description
The objective of this dissertation is to study the use of metamaterials as narrow-band and broadband selective absorbers for opto-thermal and solar thermal energy conversion. Narrow-band selective absorbers have applications such as plasmonic sensing and cancer treatment, while one of the main applications of selective metamaterials with broadband absorption is efficiently converting solar energy into heat as solar absorbers.
This dissertation first discusses the use of gold nanowires as narrow-band selective metamaterial absorbers. An investigation into plasmonic localized heating indicated that film-coupled gold nanoparticles exhibit tunable selective absorption based on the size of the nanoparticles. By using anodized aluminum oxide templates, aluminum nanodisc narrow-band absorbers were fabricated. A metrology instrument to measure the reflectance and transmittance of micro-scale samples was also developed and used to measure the reflectance of the aluminum nanodisc absorbers (220 µm diameter area). Tuning of the resonance wavelengths of these absorbers can be achieved through changing their geometry. Broadband absorption can be achieved by using a combination of geometries for these metamaterials which would facilitate their use as solar absorbers.
Recently, solar energy harvesting has become a topic of considerable research investigation due to it being an environmentally conscious alternative to fossil fuels. The next section discusses the steady-state temperature measurement of a lab-scale multilayer solar absorber, named metafilm. A lab-scale experimental setup is developed to characterize the solar thermal performance of selective solar absorbers. Under a concentration factor of 20.3 suns, a steady-state temperature of ~500 degrees Celsius was achieved for the metafilm compared to 375 degrees Celsius for a commercial black absorber under the same conditions. Thermal durability testing showed that the metafilm could withstand up to 700 degrees Celsius in vacuum conditions and up to 400 degrees Celsius in atmospheric conditions with little degradation of its optical and radiative properties. Moreover, cost analysis of the metafilm found it to cost significantly less ($2.22 per square meter) than commercial solar coatings ($5.41-100 per square meter).
Finally, this dissertation concludes with recommendations for further studies like using these selective metamaterials and metafilms as absorbers and emitters and using the aluminum nanodiscs on glass as selective filters for photovoltaic cells to enhance solar thermophotovoltaic energy conversion.
This dissertation first discusses the use of gold nanowires as narrow-band selective metamaterial absorbers. An investigation into plasmonic localized heating indicated that film-coupled gold nanoparticles exhibit tunable selective absorption based on the size of the nanoparticles. By using anodized aluminum oxide templates, aluminum nanodisc narrow-band absorbers were fabricated. A metrology instrument to measure the reflectance and transmittance of micro-scale samples was also developed and used to measure the reflectance of the aluminum nanodisc absorbers (220 µm diameter area). Tuning of the resonance wavelengths of these absorbers can be achieved through changing their geometry. Broadband absorption can be achieved by using a combination of geometries for these metamaterials which would facilitate their use as solar absorbers.
Recently, solar energy harvesting has become a topic of considerable research investigation due to it being an environmentally conscious alternative to fossil fuels. The next section discusses the steady-state temperature measurement of a lab-scale multilayer solar absorber, named metafilm. A lab-scale experimental setup is developed to characterize the solar thermal performance of selective solar absorbers. Under a concentration factor of 20.3 suns, a steady-state temperature of ~500 degrees Celsius was achieved for the metafilm compared to 375 degrees Celsius for a commercial black absorber under the same conditions. Thermal durability testing showed that the metafilm could withstand up to 700 degrees Celsius in vacuum conditions and up to 400 degrees Celsius in atmospheric conditions with little degradation of its optical and radiative properties. Moreover, cost analysis of the metafilm found it to cost significantly less ($2.22 per square meter) than commercial solar coatings ($5.41-100 per square meter).
Finally, this dissertation concludes with recommendations for further studies like using these selective metamaterials and metafilms as absorbers and emitters and using the aluminum nanodiscs on glass as selective filters for photovoltaic cells to enhance solar thermophotovoltaic energy conversion.
ContributorsAlshehri, Hassan (Author) / Wang, Liping (Thesis advisor) / Phelan, Patrick (Committee member) / Rykaczewski, Konrad (Committee member) / Wang, Robert (Committee member) / Yu, Hongbin (Committee member) / Arizona State University (Publisher)
Created2018

Description
Just for a moment! Imagine you live in Arizona without air-conditioning systems!
Air-conditioning and refrigeration systems are one of the most crucial systems in anyone’s house and car these days. Energy resources are becoming more scarce and expensive. Most of the currently used refrigerants have brought an international concern about global warming. The search for more efficient cooling/refrigeration systems with environmental friendly refrigerants has become more and more important so as to reduce greenhouse gas emissions and ensure sustainable and affordable energy systems. The most widely used air-conditioning and refrigeration system, based on the vapor compression cycle, is driven by converting electricity into mechanical work which is a high quality type of energy. However, these systems can instead be possibly driven by heat, be made solid-state (i.e., thermoelectric cooling), consist entirely of a gaseous working fluid (i.e., reverse Brayton cycle), etc. This research explores several thermally driven cooling systems in order to understand and further overcome some of the major drawbacks associated with their performance as well as their high capital costs. In the second chapter, we investigate the opportunities for integrating single- and double-stage ammonia-water (NH3–H2O) absorption refrigeration systems with multi-effect distillation (MED) via cascade of rejected heat for large-scale plants. Similarly, in the third chapter, we explore a new polygeneration cooling-power cycle’s performance based on Rankine, reverse Brayton, ejector, and liquid desiccant cycles to produce power, cooling, and possibly fresh water for various configurations. Different configurations are considered from an energy perspective and are compared to stand-alone systems. In the last chapter, a new simple, inexpensive, scalable, environmentally friendly cooling system based on an adsorption heat pump system and evacuated tube solar collector is experimentally and theoretically studied. The system is destined as a small-scale system to harness solar radiation to provide a cooling effect directly in one system.
Air-conditioning and refrigeration systems are one of the most crucial systems in anyone’s house and car these days. Energy resources are becoming more scarce and expensive. Most of the currently used refrigerants have brought an international concern about global warming. The search for more efficient cooling/refrigeration systems with environmental friendly refrigerants has become more and more important so as to reduce greenhouse gas emissions and ensure sustainable and affordable energy systems. The most widely used air-conditioning and refrigeration system, based on the vapor compression cycle, is driven by converting electricity into mechanical work which is a high quality type of energy. However, these systems can instead be possibly driven by heat, be made solid-state (i.e., thermoelectric cooling), consist entirely of a gaseous working fluid (i.e., reverse Brayton cycle), etc. This research explores several thermally driven cooling systems in order to understand and further overcome some of the major drawbacks associated with their performance as well as their high capital costs. In the second chapter, we investigate the opportunities for integrating single- and double-stage ammonia-water (NH3–H2O) absorption refrigeration systems with multi-effect distillation (MED) via cascade of rejected heat for large-scale plants. Similarly, in the third chapter, we explore a new polygeneration cooling-power cycle’s performance based on Rankine, reverse Brayton, ejector, and liquid desiccant cycles to produce power, cooling, and possibly fresh water for various configurations. Different configurations are considered from an energy perspective and are compared to stand-alone systems. In the last chapter, a new simple, inexpensive, scalable, environmentally friendly cooling system based on an adsorption heat pump system and evacuated tube solar collector is experimentally and theoretically studied. The system is destined as a small-scale system to harness solar radiation to provide a cooling effect directly in one system.
ContributorsAlelyani, Sami M (Author) / Phelan, Patrick E (Thesis advisor) / Wang, Liping (Committee member) / Stechel, Ellen B (Committee member) / Calhoun, Ronald J (Committee member) / Alalili, Ali R (Committee member) / Arizona State University (Publisher)
Created2018

Description
Droplet-structure interactions play a pivotal role in many engineering applications as droplet-based solutions are evolving. This work explores the physical understanding of these interactions through systematic research leading to improvements in thermal management via dropwise condensation (DWC), and breathable protective wearables against chemical aerosols for better thermoregulation.
In DWC, the heat transfer rate can be further increased by increasing the nucleation and by optimally ‘refreshing’ the surface via droplet shedding. Softening of surfaces favor the former while having an adverse effect on the latter. This optimization problem is addressed by investigating how mechanical properties of a substrate impact relevant droplet-surface interactions and DWC heat transfer rate. The results obtained by combining droplet induced surface deformation with finite element model show that softening of the substrates below a shear modulus of 500 kPa results in a significant reduction in the condensation heat transfer rate.
On the other hand, interactions between droplet and polymer leading to polymer swelling can be used to develop breathable wearables for use in chemically harsh environments. Chemical aerosols are hazardous and conventional protective measures include impermeable barriers which limit the thermoregulation. To solve this, a solution is proposed consisting of a superabsorbent polymer developed to selectively absorb these chemicals and closing the pores in the fabric. Starting from understanding and modeling the droplet induced swelling in elastomers, the extent and topological characteristic of swelling is shown to depend on the relative comparison of the polymer and aerosol geometries. Then, this modeling is extended to a customized polymer, through a simplified characterization paradigm. In that, a new method is proposed to measure the swelling parameters of the polymer-solvent pair and develop a validated model for swelling. Through this study, it is shown that for this polymer, the concentration-dependent diffusion coefficient can be measured through gravimetry and Poroelastic Relaxation Indentation, simplifying the characterization effort. Finally, this model is used to design composite fabric. Specifically, using model results, the SAP geometry, base fabric design, method of composition is optimized, and the effectiveness of the composite fabric highlighted in moderate-to-high concentrations over short durations.
In DWC, the heat transfer rate can be further increased by increasing the nucleation and by optimally ‘refreshing’ the surface via droplet shedding. Softening of surfaces favor the former while having an adverse effect on the latter. This optimization problem is addressed by investigating how mechanical properties of a substrate impact relevant droplet-surface interactions and DWC heat transfer rate. The results obtained by combining droplet induced surface deformation with finite element model show that softening of the substrates below a shear modulus of 500 kPa results in a significant reduction in the condensation heat transfer rate.
On the other hand, interactions between droplet and polymer leading to polymer swelling can be used to develop breathable wearables for use in chemically harsh environments. Chemical aerosols are hazardous and conventional protective measures include impermeable barriers which limit the thermoregulation. To solve this, a solution is proposed consisting of a superabsorbent polymer developed to selectively absorb these chemicals and closing the pores in the fabric. Starting from understanding and modeling the droplet induced swelling in elastomers, the extent and topological characteristic of swelling is shown to depend on the relative comparison of the polymer and aerosol geometries. Then, this modeling is extended to a customized polymer, through a simplified characterization paradigm. In that, a new method is proposed to measure the swelling parameters of the polymer-solvent pair and develop a validated model for swelling. Through this study, it is shown that for this polymer, the concentration-dependent diffusion coefficient can be measured through gravimetry and Poroelastic Relaxation Indentation, simplifying the characterization effort. Finally, this model is used to design composite fabric. Specifically, using model results, the SAP geometry, base fabric design, method of composition is optimized, and the effectiveness of the composite fabric highlighted in moderate-to-high concentrations over short durations.
ContributorsPhadnis, Akshay (Author) / Rykaczewski, Konrad (Thesis advisor) / Wang, Robert (Committee member) / Wang, Liping (Committee member) / Oswald, Jay (Committee member) / Burgin, Timothy (Committee member) / Arizona State University (Publisher)
Created2019

Description
The use of nanoparticle-in-matrix composites is a common motif among a broad range of nanoscience applications and is of particular interest to the thermal sciences community. To explore this morphological theme, crystalline inorganic composites were synthesized by mixing colloidal CdSe nanocrystals and In2Se3 metal chalcogenide complex (MCC) precursor in hydrazine solvent and then thermally transform the MCC precursor into a crystalline In2Se3 matrix. The volume fraction of CdSe nanocrystals was varied from 0 to ~100% .Rich structural and chemical interactions between the CdSe nanocrystals and the In2Se3 matrix were observed. The average thermal conductivities of the 100% In2Se3 and ~100% CdSe composites are 0.32 and 0.53 W/m-K, respectively, which are remarkably low for inorganic crystalline materials. With the exception of the ~100% CdSe samples, the thermal conductivities of these nanocomposites are insensitive to CdSe volume fraction.This insensitivity is attributed to competing effects rise from structural morphology changes during composite formation.
Next, thermoelectric properties of metal chalcogenide thin films deposited from precursors using thiol-amine solvent mixtures were first reported. Cu2-xSeyS1-y and Ag-doped Cu2-xSeyS1-y thin films were synthesized, and the interrelationship between structure, composition, and room temperature thermoelectric properties was studied. The precursor annealing temperature affects the metal:chalcogen ratio, and leads to charge carrier concentration changes that affect Seebeck coefficient and electrical conductivity. Incorporating Ag into the Cu2-xSeyS1-y film leads to appreciable improvements in thermoelectric performance. Overall, the room temperature thermoelectric properties of these solution-processed materials are comparable to measurements on Cu2-xSe alloys made via conventional thermoelectric material processing methods.
Finally, a new route to make soluble metal chalcogenide precursors by reacting organic dichalcogenides with metal in different solvents was reported. By this method, SnSe, PbSe, SnTe and PbSexTe1-x precursors were successfully synthesized, and phase-pure and impurity-free metal chalcogenides were recovered after precursor decomposition. Compared to the hydrazine and diamine-dithiol route, the new approach uses safe solvent, and avoids introducing unwanted sulfur into the precursor. SnSe and PbSexTe1-x thin films, both of which are interesting thermoelectric materials, were also successfully made by solution deposition. The thermoelectric property measurements on those thin films show a great potential for future improvements.
Next, thermoelectric properties of metal chalcogenide thin films deposited from precursors using thiol-amine solvent mixtures were first reported. Cu2-xSeyS1-y and Ag-doped Cu2-xSeyS1-y thin films were synthesized, and the interrelationship between structure, composition, and room temperature thermoelectric properties was studied. The precursor annealing temperature affects the metal:chalcogen ratio, and leads to charge carrier concentration changes that affect Seebeck coefficient and electrical conductivity. Incorporating Ag into the Cu2-xSeyS1-y film leads to appreciable improvements in thermoelectric performance. Overall, the room temperature thermoelectric properties of these solution-processed materials are comparable to measurements on Cu2-xSe alloys made via conventional thermoelectric material processing methods.
Finally, a new route to make soluble metal chalcogenide precursors by reacting organic dichalcogenides with metal in different solvents was reported. By this method, SnSe, PbSe, SnTe and PbSexTe1-x precursors were successfully synthesized, and phase-pure and impurity-free metal chalcogenides were recovered after precursor decomposition. Compared to the hydrazine and diamine-dithiol route, the new approach uses safe solvent, and avoids introducing unwanted sulfur into the precursor. SnSe and PbSexTe1-x thin films, both of which are interesting thermoelectric materials, were also successfully made by solution deposition. The thermoelectric property measurements on those thin films show a great potential for future improvements.
ContributorsMa, Yuanyu (Author) / Wang, Robert (Thesis advisor) / Newman, Nathan (Committee member) / Wang, Liping (Committee member) / Hildreth, Owen (Committee member) / Arizona State University (Publisher)
Created2016

Description
In this dissertation, two types of passive air freshener products from Henkel, the wick-based air freshener and gel-based air freshener, are studied for their wicking mechanisms and evaporation performances.The fibrous pad of the wick-based air freshener is a porous medium that absorbs fragrance by capillary force and releases the fragrance into the ambient air. To investigate the wicking process, a two-dimensional multiphase flow numerical model using COMSOL Multiphysics is built. Saturation and liquid pressure inside the pad are solved. Comparison between the simulation results and experiments shows that evaporation occurs simultaneously with the wicking process. The evaporation performance on the surface of the wicking pad is analyzed based on the kinetic theory, from which the mass flow rate of molecules passing the interface of each pore of the porous medium is obtained. A 3D model coupling the evaporation model and dynamic wicking on the evaporation pad is built to simulate the entire performance of the air freshener to the environment for a long period of time. Diffusion and natural convection effects are included in the simulation. The simulation results match well with the experiments for both the air fresheners placed in a chamber and in the absent of a chamber, the latter of which is subject to indoor airflow.
The gel-based air freshener can be constructed as a porous medium in which the solid network of particles spans the volume of the fragrance liquid. To predict the evaporation performance of the gel, two approaches are tested for gel samples in hemispheric shape. The first approach is the sessile drop model commonly used for the drying process of a pure liquid droplet. It can be used to estimate the weight loss rate and time duration of the evaporation. Another approach is to simulate the concentration profile outside the gel and estimate the evaporation rate from the surface of the gel using the kinetic theory. The evaporation area is updated based on the change of pore size. A 3D simulation using the same analysis is further applied to the cylindrical gel sample. The simulation results match the experimental data well.
ContributorsYuan, Jing (Author) / Chen, Kangping (Thesis advisor) / Herrmann, Marcus (Committee member) / Huang, Huei-Ping (Committee member) / Wang, Liping (Committee member) / Jiao, Yang (Committee member) / Arizona State University (Publisher)
Created2021