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Description
Production from a high pressure gas well at a high production-rate encounters the risk of operating near the choking condition for a compressible flow in porous media. The unbounded gas pressure gradient near the point of choking, which is located near the wellbore, generates an effective tensile stress on the porous rock frame. This tensile stress almost always exceeds the tensile strength of the rock and it causes a tensile failure of the rock, leading to wellbore instability. In a porous rock, not all pores are choked at the same flow rate, and when just one pore is choked, the flow through the entire porous medium should be considered choked as the gas pressure gradient at the point of choking becomes singular. This thesis investigates the choking condition for compressible gas flow in a single microscopic pore. Quasi-one-dimensional analysis and axisymmetric numerical simulations of compressible gas flow in a pore scale varicose tube with a number of bumps are carried out, and the local Mach number and pressure along the tube are computed for the flow near choking condition. The effects of tube length, inlet-to-outlet pressure ratio, the number of bumps and the amplitude of the bumps on the choking condition are obtained. These critical values provide guidance for avoiding the choking condition in practice.
ContributorsYuan, Jing (Author) / Chen, Kangping (Thesis advisor) / Wang, Liping (Committee member) / Huang, Huei-Ping (Committee member) / Arizona State University (Publisher)
Created2013
Description
Tesla turbo-machinery offers a robust, easily manufactured, extremely versatile prime mover with inherent capabilities making it perhaps the best, if not the only, solution for certain niche applications. The goal of this thesis is not to optimize the performance of the Tesla turbine, but to compare its performance with various working fluids. Theoretical and experimental analyses of a turbine-generator assembly utilizing compressed air, saturated steam and water as the working fluids were performed and are presented in this work. A brief background and explanation of the technology is provided along with potential applications. A theoretical thermodynamic analysis is outlined, resulting in turbine and rotor efficiencies, power outputs and Reynolds numbers calculated for the turbine for various combinations of working fluids and inlet nozzles. The results indicate the turbine is capable of achieving a turbine efficiency of 31.17 ± 3.61% and an estimated rotor efficiency 95 ± 9.32%. These efficiencies are promising considering the numerous losses still present in the current design. Calculation of the Reynolds number provided some capability to determine the flow behavior and how that behavior impacts the performance and efficiency of the Tesla turbine. It was determined that turbulence in the flow is essential to achieving high power outputs and high efficiency. Although the efficiency, after peaking, begins to slightly taper off as the flow becomes increasingly turbulent, the power output maintains a steady linear increase.
ContributorsPeshlakai, Aaron (Author) / Phelan, Patrick (Thesis advisor) / Trimble, Steve (Committee member) / Wang, Liping (Committee member) / Arizona State University (Publisher)
Created2012
Description
Cyanovirin-N (CVN) is a cyanobacterial lectin with potent anti-HIV activity, mediated by binding to the N-linked oligosaccharide moiety of the envelope protein gp120. CVN offers a scaffold to develop multivalent carbohydrate-binding proteins with tunable specificities and affinities. I present here biophysical calculations completed on a monomeric-stabilized mutant of cyanovirin-N, P51G-m4-CVN, in which domain A binding activity is abolished by four mutations; with comparisons made to CVNmutDB, in which domain B binding activity is abolished. Using Monte Carlo calculations and docking simulations, mutations in CVNmutDB were considered singularly, and the mutations E41A/G and T57A were found to impact the affinity towards dimannose the greatest. 15N-labeled proteins were titrated with Manα(1-2)Manα, while following chemical shift perturbations in NMR spectra. The mutants, E41A/G and T57A, had a larger Kd than P51G-m4-CVN, matching the trends predicted by the calculations. We also observed that the N42A mutation affects the local fold of the binding pocket, thus removing all binding to dimannose. Characterization of the mutant N53S showed similar binding affinity to P51G-m4-CVN. Using biophysical calculations allows us to study future iterations of models to explore affinities and specificities. In order to further elucidate the role of multivalency, I report here a designed covalent dimer of CVN, Nested cyanovirin-N (Nested CVN), which has four binding sites. Nested CVN was found to have comparable binding affinity to gp120 and antiviral activity to wt CVN. These results demonstrate the ability to create a multivalent, covalent dimer that has comparable results to that of wt CVN.
WW domains are small modules consisting of 32-40 amino acids that recognize proline-rich peptides and are found in many signaling pathways. We use WW domain sequences to explore protein folding by simulations using Zipping and Assembly Method. We identified five crucial contacts that enabled us to predict the folding of WW domain sequences based on those contacts. We then designed a folded WW domain peptide from an unfolded WW domain sequence by introducing native contacts at those critical positions.
WW domains are small modules consisting of 32-40 amino acids that recognize proline-rich peptides and are found in many signaling pathways. We use WW domain sequences to explore protein folding by simulations using Zipping and Assembly Method. We identified five crucial contacts that enabled us to predict the folding of WW domain sequences based on those contacts. We then designed a folded WW domain peptide from an unfolded WW domain sequence by introducing native contacts at those critical positions.
ContributorsWoodrum, Brian William (Author) / Ghirlanda, Giovanna (Thesis advisor) / Redding, Kevin (Committee member) / Wang, Xu (Committee member) / Arizona State University (Publisher)
Created2014
Description
Spider dragline silk is an outstanding biopolymer with a strength that exceeds steel by weight and a toughness greater than high-performance fibers like Kevlar. For this reason, structural and dynamic studies on the spider silk are of great importance for developing future biomaterials. The spider dragline silk comprises two silk proteins, Major ampullate Spidroin 1 and 2 (MaSp1 and 2), which are synthesized and stored in the major ampullate (MA) gland of spiders. The initial state of the silk proteins within Black Widow MA glands was probed with solution-state NMR spectroscopy. The conformation dependent chemical shifts information indicates that the silk proteins are unstructured and in random coil conformation. 15N relaxation parameters, T1, T2 and 15N-{1H} steady-state NOE were measured to probe the backbone dynamics for MA silk proteins. These measurements indicate fast sub-nanosecond timescale backbone dynamics for the repetitive core of spider MA proteins indicating that the silk proteins are unfolded, highly flexible random coils in the MA gland. The translational diffusion coefficients of the spider silk proteins within the MA gland were measured using 1H diffusion NMR at 1H sites from different amino acids. A phenomenon was observed where the measured diffusion coefficients decrease with an increase in the diffusion delay used. The mean displacement along the external magnetic field was found to be 0.35 μm and independent of the diffusion delay. The results indicate that the diffusion of silk protein was restricted due to intermolecular cross-linking with only segmental diffusion observable.
To understand how a spider converts the unfolded protein spinning dope into a highly structured and oriented in the super fiber,the effect of acidification on spider silk assembly was investigated on native spidroins from the major ampullate (MA) gland fluid excised from Latrodectus hesperus (Black Widow) spiders. The in vitro spider silk assembly kinetics were monitored as a function of pH with a 13C solid-state Magic Angle Spinning (MAS) NMR approach. The results confirm the importance of acidic pH in the spider silk self-assembly process with observation of a sigmoidal nucleation-elongation kinetic profile. The rates of nucleation and elongation and the percentage of β-sheet structure in the grown fibers depend on pH.
The secondary structure of the major ampullate silk from Peucetia viridians (Green Lynx) spiders was characterized by X-ray diffraction (XRD) and solid-state NMR spectroscopy. From XRD measurement, β-sheet nano-crystallites were observed that are highly oriented along the fiber axis with an orientational order of 0.980. Compare to the crystalline region, the amorphous region was found to be partially oriented with an orientational order of 0.887. Further, two dimensional 13C-13C through-space and through-bond solid-state NMR experiments provide structural analysis for the repetitive amino acid motifs in the silk proteins. The nano-crystallites are mainly alanine-rich β-sheet structures. The total percentage of crystalline region is determined to be 40.0±1.2 %. 18±1 % of alanine, 60±2 % glycine and 54±2 % serine are determined to be incorporated into helical conformations while 82±1 % of alanine, 40±3 % glycine and 46±2 % serine are in the β-sheet conformation.
To understand how a spider converts the unfolded protein spinning dope into a highly structured and oriented in the super fiber,the effect of acidification on spider silk assembly was investigated on native spidroins from the major ampullate (MA) gland fluid excised from Latrodectus hesperus (Black Widow) spiders. The in vitro spider silk assembly kinetics were monitored as a function of pH with a 13C solid-state Magic Angle Spinning (MAS) NMR approach. The results confirm the importance of acidic pH in the spider silk self-assembly process with observation of a sigmoidal nucleation-elongation kinetic profile. The rates of nucleation and elongation and the percentage of β-sheet structure in the grown fibers depend on pH.
The secondary structure of the major ampullate silk from Peucetia viridians (Green Lynx) spiders was characterized by X-ray diffraction (XRD) and solid-state NMR spectroscopy. From XRD measurement, β-sheet nano-crystallites were observed that are highly oriented along the fiber axis with an orientational order of 0.980. Compare to the crystalline region, the amorphous region was found to be partially oriented with an orientational order of 0.887. Further, two dimensional 13C-13C through-space and through-bond solid-state NMR experiments provide structural analysis for the repetitive amino acid motifs in the silk proteins. The nano-crystallites are mainly alanine-rich β-sheet structures. The total percentage of crystalline region is determined to be 40.0±1.2 %. 18±1 % of alanine, 60±2 % glycine and 54±2 % serine are determined to be incorporated into helical conformations while 82±1 % of alanine, 40±3 % glycine and 46±2 % serine are in the β-sheet conformation.
ContributorsXu, Dian (Author) / Yarger, Jeffery L (Thesis advisor) / Holland, Gregory P (Thesis advisor) / Wang, Xu (Committee member) / Liu, Yan (Committee member) / Arizona State University (Publisher)
Created2015
Description
An animal's ability to produce protein-based silk materials has evolved independently in many different arthropod lineages, satisfying various ecological necessities. However, regardless of their wide range of uses and their potential industrial and biomedical applications, advanced knowledge on the molecular structure of silk biopolymers is largely limited to those produced by spiders (order Araneae) and silkworms (order Lepidoptera). This thesis provides an in-depth molecular-level characterization of silk fibers produced by two vastly different insects: the caddisfly larvae (order Trichoptera) and the webspinner (order Embioptera).
The molecular structure of caddisfly larval silk from the species Hesperophylax consimilis was characterized using solid-state nuclear magnetic resonance (ss-NMR) and Wide Angle X-ray Diffraction (WAXD) techniques. This insect, which typically dwells in freshwater riverbeds and streams, uses silk fibers as a strong and sticky nanoadhesive material to construct cocoons and cases out available debris. Conformation-sensitive 13C chemical shifts and 31P chemical shift anisotropy (CSA) information strongly support a unique protein motif in which phosphorylated serine- rich repeats (pSX)4 complex with di- and trivalent cations to form rigid nanocrystalline β-sheets. Additionally, it is illustrated through 31P NMR and WAXD data that these nanocrystalline structures can be reversibly formed, and depend entirely on the presence of the stabilizing cations.
Nanofiber silks produced by webspinners (order Embioptera) were also studied herein. This work addresses discrepancies in the literature regarding fiber diameters and tensile properties, revealing that the nanofibers are about 100 nm in diameter, and are stronger (around 500 MPa mean ultimate stress) than previous works suggested. Fourier-transform Infrared Spectroscopy (FT-IR), NMR and WAXD results find that approximately 70% of the highly repetitive glycine- and serine-rich protein core is composed of β-sheet nanocrystalline structures. In addition, FT-IR and Gas-chromatography mass spectroscopy (GC-MS) data revealed a hydrophobic surface coating rich in long-chain lipids. The effect of this surface coating was studied with contact angle techniques; it is shown that the silk sheets are extremely hydrophobic, yet due to the microstructural and nanostructural details of the silk surface, are surprisingly adhesive to water.
The molecular structure of caddisfly larval silk from the species Hesperophylax consimilis was characterized using solid-state nuclear magnetic resonance (ss-NMR) and Wide Angle X-ray Diffraction (WAXD) techniques. This insect, which typically dwells in freshwater riverbeds and streams, uses silk fibers as a strong and sticky nanoadhesive material to construct cocoons and cases out available debris. Conformation-sensitive 13C chemical shifts and 31P chemical shift anisotropy (CSA) information strongly support a unique protein motif in which phosphorylated serine- rich repeats (pSX)4 complex with di- and trivalent cations to form rigid nanocrystalline β-sheets. Additionally, it is illustrated through 31P NMR and WAXD data that these nanocrystalline structures can be reversibly formed, and depend entirely on the presence of the stabilizing cations.
Nanofiber silks produced by webspinners (order Embioptera) were also studied herein. This work addresses discrepancies in the literature regarding fiber diameters and tensile properties, revealing that the nanofibers are about 100 nm in diameter, and are stronger (around 500 MPa mean ultimate stress) than previous works suggested. Fourier-transform Infrared Spectroscopy (FT-IR), NMR and WAXD results find that approximately 70% of the highly repetitive glycine- and serine-rich protein core is composed of β-sheet nanocrystalline structures. In addition, FT-IR and Gas-chromatography mass spectroscopy (GC-MS) data revealed a hydrophobic surface coating rich in long-chain lipids. The effect of this surface coating was studied with contact angle techniques; it is shown that the silk sheets are extremely hydrophobic, yet due to the microstructural and nanostructural details of the silk surface, are surprisingly adhesive to water.
ContributorsAddison, John Bennett (Author) / Yarger, Jeffery L (Thesis advisor) / Holland, Gregory P (Thesis advisor) / Wang, Xu (Committee member) / Ros, Robert (Committee member) / Arizona State University (Publisher)
Created2014
Description
Nanostructured materials show signicant enhancement in the thermoelectric g-
ure of merit (zT) due to quantum connement eects. Improving the eciency of
thermoelectric devices allows for the development of better, more economical waste
heat recovery systems. Such systems may be used as bottoming or co-generation
cycles in conjunction with conventional power cycles to recover some of the wasted
heat. Thermal conductivity measurement systems are an important part of the char-
acterization processes of thermoelectric materials. These systems must possess the
capability of accurately measuring the thermal conductivity of both bulk and thin-lm
samples at dierent ambient temperatures.
This paper discusses the construction, validation, and improvement of a thermal
conductivity measurement platform based on the 3-Omega technique. Room temperature
measurements of thermal conductivity done on control samples with known properties
such as undoped bulk silicon (Si), bulk gallium arsenide (GaAs), and silicon dioxide
(SiO2) thin lms yielded 150 W=m􀀀K, 50 W=m􀀀K, and 1:46 W=m􀀀K respectively.
These quantities were all within 8% of literature values. In addition, the thermal
conductivity of bulk SiO2 was measured as a function of temperature in a Helium-
4 cryostat from 75K to 250K. The results showed good agreement with literature
values that all fell within the error range of each measurement. The uncertainty in
the measurements ranged from 19% at 75K to 30% at 250K. Finally, the system
was used to measure the room temperature thermal conductivity of a nanocomposite
composed of cadmium selenide, CdSe, nanocrystals in an indium selenide, In2Se3,
matrix as a function of the concentration of In2Se3. The observed trend was in
qualitative agreement with the expected behavior.
i
ure of merit (zT) due to quantum connement eects. Improving the eciency of
thermoelectric devices allows for the development of better, more economical waste
heat recovery systems. Such systems may be used as bottoming or co-generation
cycles in conjunction with conventional power cycles to recover some of the wasted
heat. Thermal conductivity measurement systems are an important part of the char-
acterization processes of thermoelectric materials. These systems must possess the
capability of accurately measuring the thermal conductivity of both bulk and thin-lm
samples at dierent ambient temperatures.
This paper discusses the construction, validation, and improvement of a thermal
conductivity measurement platform based on the 3-Omega technique. Room temperature
measurements of thermal conductivity done on control samples with known properties
such as undoped bulk silicon (Si), bulk gallium arsenide (GaAs), and silicon dioxide
(SiO2) thin lms yielded 150 W=m􀀀K, 50 W=m􀀀K, and 1:46 W=m􀀀K respectively.
These quantities were all within 8% of literature values. In addition, the thermal
conductivity of bulk SiO2 was measured as a function of temperature in a Helium-
4 cryostat from 75K to 250K. The results showed good agreement with literature
values that all fell within the error range of each measurement. The uncertainty in
the measurements ranged from 19% at 75K to 30% at 250K. Finally, the system
was used to measure the room temperature thermal conductivity of a nanocomposite
composed of cadmium selenide, CdSe, nanocrystals in an indium selenide, In2Se3,
matrix as a function of the concentration of In2Se3. The observed trend was in
qualitative agreement with the expected behavior.
i
ContributorsJaber, Abbas (Author) / Wang, Robert (Thesis advisor) / Wang, Liping (Committee member) / Rykaczewski, Konrad (Committee member) / Arizona State University (Publisher)
Created2014
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
Glycosaminoglycans (GAGs) are a class of complex biomolecules comprised of linear, sulfated polysaccharides whose presence on cell surfaces and in the extracellular matrix involve them in many physiological phenomena as well as in interactions with pathogenic microbes. Decorin binding protein A (DBPA), a Borrelia surface lipoprotein involved in the infectivity of Lyme disease, is responsible for binding GAGs found on decorin, a small proteoglycan present in the extracellular matrix. Different DBPA strains have notable sequence heterogeneity that results in varying levels of GAG-binding affinity. In this dissertation, the structures and GAG-binding mechanisms for three strains of DBPA (B31 and N40 DBPAs from B. burgdorferi and PBr DBPA from B. garinii) are studied to determine why each strain has a different affinity for GAGs. These three strains have similar topologies consisting of five α-helices held together by a hydrophobic core as well as two long flexible segments: a linker between helices one and two and a C-terminal tail. This structural arrangement facilitates the formation of a basic pocket below the flexible linker which is the primary GAG-binding epitope. However, this GAG-binding site can be occluded by the flexible linker, which makes the linker a negative regulator of GAG-binding. ITC and NMR titrations provide KD values that show PBr DBPA binds GAGs with higher affinity than B31 and N40 DBPAs, while N40 binds with the lowest affinity of the three. Work in this thesis demonstrates that much of the discrepancies seen in GAG affinities of the three DBPAs can be explained by the amino acid composition and conformation of the linker. Mutagenesis studies show that B31 DBPA overcomes the pocket obstruction with the BXBB motif in its linker while PBr DBPA has a retracted linker that exposes the basic pocket as well as a secondary GAG-binding site. N40 DBPA, however, does not have any evolutionary modifications to its structure to enhance GAG binding which explains its lower affinity for GAGs. GMSA and ELISA assays, along with NMR PRE experiments, confirm that structural changes in the linker do affect GAG-binding and, as a result, the linker is responsible for regulating GAG affinity.
ContributorsMorgan, Ashli M (Author) / Wang, Xu (Thesis advisor) / Allen, James (Committee member) / Yarger, Jeffery (Committee member) / Arizona State University (Publisher)
Created2015
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
This dissertation will investigate two of the most promising high-capacity anode
materials for lithium-based batteries: silicon (Si) and metal lithium (Li). It will focus on
studying the mechanical behaviors of the two materials during charge and discharge and
understanding how these mechanical behaviors may affect their electrochemical
performance.
In the first part, amorphous Si anode will be studied. Despite many existing studies
on silicon (Si) anodes for lithium ion batteries (LIBs), many essential questions still exist
on compound formation, composition, and properties. Here it is shown that some
previously accepted findings do not truthfully reflect the actual lithiation mechanisms in
realistic battery configurations. Furthermore the correlation between structure and
mechanical properties in these materials has not been properly established. Here, a rigorous
and thorough study is performed to comprehensively understand the electrochemical
reaction mechanisms of amorphous-Si (a-Si) in a realistic LIB configuration. In-depth
microstructural characterization was performed and correlations were established between
Li-Si composition, volumetric expansion, and modulus/hardness. It is found that the
lithiation process of a-Si in a real battery setup is a single-phase reaction rather than the
accepted two-phase reaction obtained from in-situ TEM experiments. The findings in this
dissertation establish a reference to quantitatively explain many key metrics for lithiated a
Si as anodes in real LIBs, and can be used to rationally design a-Si based high-performance
LIBs guided by high-fidelity modeling and simulations.
In the second part, Li metal anode will be investigated. Problems related to dendrite
growth on lithium metal anodes such as capacity loss and short circuit present major
barriers to the next-generation high-energy-density batteries. The development of
successful mitigation strategies is impeded by the incomplete understanding of the Li
dendrite growth mechanisms. Here the enabling role of plating residual stress in dendrite
initiation through novel experiments of Li electrodeposition on soft substrates is confirmed,
and the observations is explained with a stress-driven dendrite growth model. Dendrite
growth is mitigated on such soft substrates through surface-wrinkling-induced stress
relaxation in deposited Li film. It is demonstrated that this new dendrite mitigation
mechanism can be utilized synergistically with other existing approaches in the form of
three-dimensional (3D) soft scaffolds for Li plating, which achieves superior coulombic
efficiency over conventional hard copper current collectors under large current density.
materials for lithium-based batteries: silicon (Si) and metal lithium (Li). It will focus on
studying the mechanical behaviors of the two materials during charge and discharge and
understanding how these mechanical behaviors may affect their electrochemical
performance.
In the first part, amorphous Si anode will be studied. Despite many existing studies
on silicon (Si) anodes for lithium ion batteries (LIBs), many essential questions still exist
on compound formation, composition, and properties. Here it is shown that some
previously accepted findings do not truthfully reflect the actual lithiation mechanisms in
realistic battery configurations. Furthermore the correlation between structure and
mechanical properties in these materials has not been properly established. Here, a rigorous
and thorough study is performed to comprehensively understand the electrochemical
reaction mechanisms of amorphous-Si (a-Si) in a realistic LIB configuration. In-depth
microstructural characterization was performed and correlations were established between
Li-Si composition, volumetric expansion, and modulus/hardness. It is found that the
lithiation process of a-Si in a real battery setup is a single-phase reaction rather than the
accepted two-phase reaction obtained from in-situ TEM experiments. The findings in this
dissertation establish a reference to quantitatively explain many key metrics for lithiated a
Si as anodes in real LIBs, and can be used to rationally design a-Si based high-performance
LIBs guided by high-fidelity modeling and simulations.
In the second part, Li metal anode will be investigated. Problems related to dendrite
growth on lithium metal anodes such as capacity loss and short circuit present major
barriers to the next-generation high-energy-density batteries. The development of
successful mitigation strategies is impeded by the incomplete understanding of the Li
dendrite growth mechanisms. Here the enabling role of plating residual stress in dendrite
initiation through novel experiments of Li electrodeposition on soft substrates is confirmed,
and the observations is explained with a stress-driven dendrite growth model. Dendrite
growth is mitigated on such soft substrates through surface-wrinkling-induced stress
relaxation in deposited Li film. It is demonstrated that this new dendrite mitigation
mechanism can be utilized synergistically with other existing approaches in the form of
three-dimensional (3D) soft scaffolds for Li plating, which achieves superior coulombic
efficiency over conventional hard copper current collectors under large current density.
ContributorsWang, Xu (Author) / Jiang, Hanqing (Thesis advisor) / Yu, Hongbin (Thesis advisor) / Chan, Candace (Committee member) / Wang, Liping (Committee member) / Qiong, Nian (Committee member) / Arizona State University (Publisher)
Created2018