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Description
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
Description
Hydrogel polymers have been the subject of many studies, due to their fascinating ability to alternate between being hydrophilic and hydrophobic, upon the application of appropriate stimuli. In particular, thermo-responsive hydrogels such as N-Isopropylacrylamide (NIPAM), which possess a unique lower critical solution temperature (LCST) of 32°C, have been leveraged for membrane-based processes such as using NIPAM as a draw agent for forward osmosis (FO) desalination. The low LCST temperature of NIPAM ensures that fresh water can be recovered, at a modest energy cost as compared to other thermally based desalination processes which require water recovery at higher temperatures. This work studies by experimentation, key process parameters involved in desalination by FO using NIPAM and a copolymer of NIPAM and Sodium Acrylate (NIPAM-SA). It encompasses synthesis of the hydrogels, development of experiments to effectively characterize synthesized products, and the measuring of FO performance for the individual hydrogels. FO performance was measured using single layers of NIPAM and NIPAM-SA respectively. The values of permeation flux obtained were compared to relevant published literature and it was found to be within reasonable range. Furthermore, a conceptual design for future large-scale implementation of this technology is proposed. It is proposed that perhaps more effort should focus on physical processes that have the ability to increase the low permeation flux of hydrogel driven FO desalination systems, rather than development of novel classes of hydrogels
ContributorsAbdullahi, Adnan None (Author) / Phelan, Patrick (Thesis advisor) / Wang, Robert (Committee member) / Dai, Lenore (Committee member) / Arizona State University (Publisher)
Created2019
Description
Additive manufacturing (AM) describes an array of methods used to create a 3D object layer by layer. The increasing popularity of AM in the past decade has been due to its demonstrated potential to increase design flexibility, produce rapid prototypes, and decrease material waste. Temporary supports are an inconvenient necessity in many metal AM parts. These sacrificial structures are used to fabricate large overhangs, anchor the part to the build substrate, and provide a heat pathway to avoid warping. Polymers AM has addressed this issue by using support material that is soluble in an electrolyte that the base material is not. In contrast, metals AM has traditionally approached support removal using time consuming, costly methods such as electrical discharge machining or a dremel.
This work introduces dissolvable supports to single- and multi-material metals AM. The multi-material approach uses material choice to design a functionally graded material where corrosion is the functionality being varied. The single-material approach is the primary focus of this thesis, leveraging already common post-print heat treatments to locally alter the microstructure near the surface. By including a sensitizing agent in the ageing heat treatment, carbon is diffused into the part decreasing the corrosion resistance to a depth equal to at least half the support thickness. In a properly chosen electrolyte, this layer is easily chemically, or electrochemically removed. Stainless steel 316 (SS316) and Inconel 718 are both investigated to study this process using two popular alloys. The microstructure evolution and corrosion properties are investigated for both. For SS316, the effect of applied electrochemical potential is investigated to describe the varying corrosion phenomena induced, and the effect of potential choice on resultant roughness. In summary, a new approach to remove supports from metal AM parts is introduced to decrease costs and further the field of metals AM by expanding the design space.
This work introduces dissolvable supports to single- and multi-material metals AM. The multi-material approach uses material choice to design a functionally graded material where corrosion is the functionality being varied. The single-material approach is the primary focus of this thesis, leveraging already common post-print heat treatments to locally alter the microstructure near the surface. By including a sensitizing agent in the ageing heat treatment, carbon is diffused into the part decreasing the corrosion resistance to a depth equal to at least half the support thickness. In a properly chosen electrolyte, this layer is easily chemically, or electrochemically removed. Stainless steel 316 (SS316) and Inconel 718 are both investigated to study this process using two popular alloys. The microstructure evolution and corrosion properties are investigated for both. For SS316, the effect of applied electrochemical potential is investigated to describe the varying corrosion phenomena induced, and the effect of potential choice on resultant roughness. In summary, a new approach to remove supports from metal AM parts is introduced to decrease costs and further the field of metals AM by expanding the design space.
ContributorsLefky, Christopher (Author) / Hildreth, Owen (Thesis advisor) / Chawla, Nikhilesh (Committee member) / Azeredo, Bruno (Committee member) / Rykaczewski, Konrad (Committee member) / Nian, Qiong (Committee member) / Arizona State University (Publisher)
Created2018
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 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.
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
Description
This study analyzes the thermoelectric phenomena of nanoparticle suspensions, which are composed of liquid and solid nanoparticles that show a relatively stable Seebeck coefficient as bulk solids near room temperature. The approach is to explore the thermoelectric character of the nanoparticle suspensions, predict the outcome of the experiment and compare the experimental data with anticipated results. In the experiment, the nanoparticle suspension is contained in a 15cm*2.5cm*2.5cm glass container, the temperature gradient ranges from 20 °C to 60 °C, and room temperature fluctuates from 20 °C to 23°C. The measured nanoparticles include multiwall carbon nanotubes, aluminum dioxide and bismuth telluride. A temperature gradient from 20 °C to 60 °C is imposed along the length of the container, and the resulting voltage (if any) is measured. Both heating and cooling processes are measured. With three different nanoparticle suspensions (carbon nano tubes, Al2O3 nanoparticles and Bi2Te3 nanoparticles), the correlation between temperature gradient and voltage is correspondingly 8%, 38% and 96%. A comparison of results calculated from the bulk Seebeck coefficients with our measured results indicate that the Seebeck coefficient measured for each suspension is much more than anticipated, which indicates that the thermophoresis effect could have enhanced the voltage. Further research with a closed-loop system might be able to affirm the results of this study.
ContributorsZhu, Moxuan (Author) / Phelan, Patrick (Thesis advisor) / Trimble, Steve (Committee member) / Prasher, Ravi (Committee member) / Arizona State University (Publisher)
Created2010
Description
Hydrogen is considered one of the most potential fuels due to its highest gravimetric energy density with no pollutant emission during the energy cycle. Among several techniques for hydrogen generation, the promising photoelectrochemical water oxidation is considered a long-term solar pathway by splitting water. The system contains a photoanode and a cathode immersed in an aqueous electrolyte where charge separation takes place in the bulk of the semiconducting material on light absorption, leading to water oxidation/reduction at the surface of the photoelectrodes/cathode. It is imperative to develop materials that demonstrate high light absorption in the wide spectrum along with photoelectrochemical stability. N-type Monoclinic scheelite bismuth vanadate (BiVO4) is selected due to its incredible light absorption capabilities, direct bandgap (Eg ∼ 2.4-2.5 eV) and relatively better photoelectrochemical stability. However, BiVO4 encounters huge electron-hole recombination due to smaller diffusion lengths and positive conduction bands that cause slow charge dynamics and sluggish water oxidation kinetics. In order to improve the illustrated drawbacks, four strategies were discussed. Chapter 1 describe the fundamental understanding of photoelectrochemical cell and BiVO4. Chapter 2 illustrates details of the experimental procedure and state-of-the-art material characterization. Chapter 3 provide the impact of alkali metal placement in the crystal structure of BiVO4 systematically that exhibited ~20 times more performance than intrinsic BiVO4, almost complete bulk charge separation and enhancement in the diffusion length. Detailed characterization determined that the alkali metal getting placed in the interstitial void of BiVO4 lattice and multiple interbands formation enhanced the charge dynamics. Chapter 4 contains stoichiometric doping of Y3+ or Er3+ or Yb3+ at the Bi3+ site, leading to an extended absorption region, whereas non-stoichiometric W6+ doping at the V5+ site minimizes defects and increased charge carriers. To further enhance the performance, type-II heterojunction with WO3 along p-n junction with Fe:NiO enhance light absorption and charge dynamics close to the theoretical performance. Chapter 5 provides a comprehensive study of a uniquely developed sulfur modified Bi2O3 interface layer to facilitate charge dynamics and carrier lifetime improvement by effectively passivating the WO3/BiVO4 heterojunction interface. Finally, chapter 6 summarized the major findings, conclusion and outlook in developing BiVO4 as an efficient photoanode material.
ContributorsPrasad, Umesh (Author) / Kannan, Arunachala Mada (Thesis advisor) / Azeredo, Bruno (Committee member) / Chan, Candace (Committee member) / Segura, Sergio Garcia (Committee member) / Arizona State University (Publisher)
Created2021
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 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
Description
Applications such as heat exchangers, surface-based cellular structures, rotating blades, and waveguides rely on thin metal walls as crucial constituent elements of the structure. The design freedom enabled by laser powder bed fusion has led to an interest in exploiting this technology to further the performance of these components, many of which retain their as-built surface morphologies on account of their design complexity. However, there is limited understanding of how and why mechanical properties vary by wall thickness for specimens that are additively manufactured and maintain an as-printed surface finish. Critically, the contributions of microstructure and morphology to the mechanical behavior of thin wall laser powder bed fusion structures have yet to be systematically identified and decoupled. This work focuses on elucidating the room temperature quasi-static tensile and high cycle fatigue properties of as-printed, thin-wall Inconel 718 fabricated using laser powder bed fusion, with the aim of addressing this critical gap in the literature. Wall thicknesses studied range from 0.3 - 2.0 mm, and the effects of Hot Isostatic Pressing are also examined, with sheet metal specimens used as a baseline for comparison. Statistical analyses are conducted to identify the significance of the dependence of properties on wall thickness and Hot Isostatic Pressing, as well as to examine correlations of these properties to section area, porosity, and surface roughness. A thorough microstructural study is complemented with a first-of-its-kind study of surface morphology to decouple their contributions and identify underlying causes for observed changes in mechanical properties. This thesis finds that mechanical properties in the quasi-static and fatigue framework do not see appreciable declines until specimen thickness is under 0.75 mm in thickness. The added Hot Isostatic Pressing heat treatment effectively closed pores, recrystallized the grain structure, and provided a more homogenous microstructure that benefits the modulus, tensile strength, elongation, and fatigue performance at higher stresses. Stress heterogeneities, primarily caused by surface defects, negatively affected the thinner specimens disproportionately. Without the use of the Hot Isostatic Pressing, the grain structure remained much more refined and benefitted the yield strength and fatigue endurance limit.
ContributorsParadise, Paul David (Author) / Bhate, Dhruv (Thesis advisor) / Chawla, Nikhilesh (Committee member) / Azeredo, Bruno (Committee member) / Jiao, Yang (Committee member) / Arizona State University (Publisher)
Created2022
Description
Polymer composite has been under rapid development with advancements in polymer chemistry, synthetic fibers, and nanoparticles. With advantages such as lightweight, corrosion resistance, and tunable functionalities, polymer composite plays a significant role in various applications such as aerospace, wearable electronics, energy storage systems, robotics, biomedicine, and microelectronics. In general, polymer composite can be divided into particulate-filled, fiber-filled, or network-filled types depending on the manufacturing process and internal structure. Over the years, fabrication processes on the macro- and micro-scales have been extensively explored. For example, lamination, fiber tow steering, and fiber spinning correspond to meter, millimeter, and micrometer scales, respectively. With the development of nanoparticles and their exceptional material properties, polymer nanoparticle composite has shown promising material property enhancements. However, the lack of economical solutions to achieve nanoscale nanoparticle morphology control limits the reinforcement efficiency and industrial applications. This dissertation focuses on utilizing additive manufacturing as a tooling method to achieve nanoparticle morphology control in polymer nanocomposite fibers. Chapter 1 gives a thorough background review regarding fiber composite, additive manufacturing, and the importance of nanoparticle orientation. Two types of nozzle designs, concentrical and layer-by-layer, are 3D printed and combined with the dry-jet-wet fiber spinning method to create continuous fibers with internal structures. Chapters 2 to 5 correspond to four stages of my research, namely, (2) multi-material fiber spinning, (3) interfacial-assisted nanoparticle alignment, (4) microscale patterning, and (5) nanoscale patterning. The achieved feature resolution also improves from 100 µm, 10 µm, 2 µm, to 170 nm, respectively. The process-structural-property relationship of polymer nanocomposite fibers is also investigated with applications demonstrations including sensors, electrically conductive fibers, thermally conductive fibers, and mechanically reinforced fibers. At last, Chapter 6 gives a summary and some future perspectives regarding fiber composites.
ContributorsXu, Weiheng (Author) / Song, Kenan (Thesis advisor) / Chen, Xiangfan (Committee member) / Kwon, Beomjin (Committee member) / Azeredo, Bruno (Committee member) / Arizona State University (Publisher)
Created2022
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 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
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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