ASU Electronic Theses and Dissertations
This collection includes most of the ASU Theses and Dissertations from 2011 to present. ASU Theses and Dissertations are available in downloadable PDF format; however, a small percentage of items are under embargo. Information about the dissertations/theses includes degree information, committee members, an abstract, supporting data or media.
In addition to the electronic theses found in the ASU Digital Repository, ASU Theses and Dissertations can be found in the ASU Library Catalog.
Dissertations and Theses granted by Arizona State University are archived and made available through a joint effort of the ASU Graduate College and the ASU Libraries. For more information or questions about this collection contact or visit the Digital Repository ETD Library Guide or contact the ASU Graduate College at gradformat@asu.edu.
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- Creators: Mobasher, Barzin
- Creators: Dai, Lenore
Description
The disordered nature of glass-forming melts results in two features for its dynamics i.e. non-Arrhenius and non-exponential behavior. Their macroscopic properties are studied through observing spatial heterogeneity of the molecular relaxation. Experiments performed in a low-frequency range tracks the flow of energy in time on slow degrees of freedom and transfer to the vibrational heat bath of the liquid, as is the case for microwave heating. High field measurements on supercooled liquids result in generation of fictive temperatures of the absorbing modes which eventually result in elevated true bath temperatures. The absorbed energy allows us to quantify the changes in the 'configurational', real sample, and electrode temperatures. The slow modes absorb energy on the structural relaxation time scale causing the increase of configurational temperature resulting in the rise of dielectric loss. Time-resolved high field dielectric relaxation experiments show the impact of 'configurational heating' for low frequencies of the electric field and samples that are thermally clamped to a thermostat. Relevant thermal behavior of monohydroxy alcohols is considerably different from the cases of simple non-associating liquids, due to their distinct origins of the prominent dielectric loss. Monohydroxy alcohols display very small changes due to observed nonthermal effects without increasing sample temperature. These changes have been reflected in polymers in our measurements.
ContributorsPathak, Ullas (Author) / Richert, Ranko (Thesis advisor) / Dai, Lenore (Thesis advisor) / Nielsen, David (Committee member) / Arizona State University (Publisher)
Created2012
Description
Gels are three-dimensional polymer networks with entrapped solvent (water etc.). They bear amazing features such as stimuli-responsive (temperature, PH, electric field etc.), high water content and biocompatibility and thus find a lot of applications. To understand the complex physics behind gel's swelling phenomenon, it is important to build up fundamental mechanical model and extend to complicated cases. In this dissertation, a coupled large deformation and diffusion model regarding gel's swelling behavior is presented. In this model, free-energy of the total gel is constituted by polymer stretching energy and polymer-solvent mixing energy. In-house nonlinear finite element code is implemented with fast computational capability. Complex phenomenon such as buckling and healing of cracked gel by swelling are studied. Due to the wide coverage of polymeric materials and solvents, solvent diffusion in gels not only follows Fickian diffusion law where concentration map is continuous but also follows non-Fickian diffusion law where concentration map shows high gradient. Phenomenological model with viscoelastic polymer constitutive and concentration dependent diffusivity is created. The model well captures this special diffusion phenomenon such as sharp diffusion front and distinctive swollen and unswollen region.
ContributorsZhang, Jiaping (Author) / Jiang, Hanqing (Thesis advisor) / Peralta, Pedro (Committee member) / Dai, Lenore (Committee member) / Rajan, Subramaniam D. (Committee member) / Chawla, Nikhilesh (Committee member) / Arizona State University (Publisher)
Created2012
Description
This dissertation provides a fundamental understanding of the properties of mesoporous carbon based materials and the utilization of those properties into different applications such as electrodes materials for super capacitors, adsorbents for water treatments and biosensors. The thickness of mesoporous carbon films on Si substrates are measured by Ellipsometry method and pore size distribution has been calculated by Kelvin equation based on toluene adsorption and desorption isotherms monitored by Ellipsometer. The addition of organometallics cobalt and vanalyl acetylacetonate in the synthesis precursor leads to the metal oxides in the carbon framework, which largely decreased the shrink of the framework during carbonization, resulting in an increase in the average pore size. In addition to the structural changes, the introduction of metal oxides into mesoporous carbon framework greatly enhances the electrochemical performance as a result of their pseudocapacitance. Also, after the addition of Co into the framework, the contraction of mesoporous powders decreased significantly and the capacitance increased prominently because of the solidification function of CoO nanoparticles. When carbon-cobalt composites are used as adsorbent, the adsorption capacity of dye pollutant in water is remarkably higher (90 mg/g) after adding Co than the mesoporous carbon powder (2 mg/g). Furthermore, the surface area and pore size of mesoporous composites can be greatly increased by addition of tetraethyl orthosilicate into the precursor with subsequent etching, which leads to a dramatic increase in the adsorption capacity from 90 mg/g up to 1151 mg/g. When used as electrode materials for amperometric biosensors, mesoporous carbons showed good sensitivity, selectivity and stability. And fluorine-free and low-cost poly (methacrylate)s have been developed as binders for screen printed biosensors. With using only 5wt% of poly (hydroxybutyl methacrylate), the glucose sensor maintained mechanical integrity and exhibited excellent sensitivity on detecting glucose level in whole rabbit blood. Furthermore, extremely high surface area mesoporous carbons have been synthesized by introducing inorganic Si precursor during self-assembly, which effectively determined norepinephrine at very low concentrations.
ContributorsDai, Mingzhi (Author) / Vogt, Bryan D (Thesis advisor) / La Belle, Jeffrey T (Committee member) / Dai, Lenore (Committee member) / Nielsen, David R (Committee member) / Torres, César I (Committee member) / Arizona State University (Publisher)
Created2012
Description
Ultra-concealable multi-threat body armor used by law-enforcement is a multi-purpose armor that protects against attacks from knife, spikes, and small caliber rounds. The design of this type of armor involves fiber-resin composite materials that are flexible, light, are not unduly affected by environmental conditions, and perform as required. The National Institute of Justice (NIJ) characterizes this type of armor as low-level protection armor. NIJ also specifies the geometry of the knife and spike as well as the strike energy levels required for this level of protection. The biggest challenges are to design a thin, lightweight and ultra-concealable armor that can be worn under street clothes. In this study, several fundamental tasks involved in the design of such armor are addressed. First, the roles of design of experiments and regression analysis in experimental testing and finite element analysis are presented. Second, off-the-shelf materials available from international material manufacturers are characterized via laboratory experiments. Third, the calibration process required for a constitutive model is explained through the use of experimental data and computer software. Various material models in LS-DYNA for use in the finite element model are discussed. Numerical results are generated via finite element simulations and are compared against experimental data thus establishing the foundation for optimizing the design.
ContributorsVokshi, Erblina (Author) / Rajan, Subramaniam D. (Thesis advisor) / Neithalath, Narayanan (Committee member) / Mobasher, Barzin (Committee member) / Arizona State University (Publisher)
Created2012
Description
This dissertation provides a fundamental understanding of the impact of bulk polymer properties on the nanometer length scale modulus. The elastic modulus of amorphous organic thin films is examined using a surface wrinkling technique. Potential correlations between thin film behavior and intrinsic properties such as flexibility and chain length are explored. Thermal properties, glass transition temperature (Tg) and the coefficient of thermal expansion, are examined along with the moduli of these thin films. It is found that the nanometer length scale behavior of flexible polymers correlates to its bulk Tg and not the polymers intrinsic size. It is also found that decreases in the modulus of ultrathin flexible films is not correlated with the observed Tg decrease in films of the same thickness. Techniques to circumvent reductions from bulk modulus were also demonstrated. However, as chain flexibility is reduced the modulus becomes thickness independent down to 10 nm. Similarly for this series minor reductions in Tg were obtained. To further understand the impact of the intrinsic size and processing conditions; this wrinkling instability was also utilized to determine the modulus of small organic electronic materials at various deposition conditions. Lastly, this wrinkling instability is exploited for development of poly furfuryl alcohol wrinkles. A two-step wrinkling process is developed via an acid catalyzed polymerization of a drop cast solution of furfuryl alcohol and photo acid generator. The ability to control the surface topology and tune the wrinkle wavelength with processing parameters such as substrate temperature and photo acid generator concentration is also demonstrated. Well-ordered linear, circular, and curvilinear patterns are also obtained by selective ultraviolet exposure and polymerization of the furfuryl alcohol film. As a carbon precursor a thorough understanding of this wrinkling instability can have applications in a wide variety of technologies.
ContributorsTorres, Jessica (Author) / Vogt, Bryan D (Thesis advisor) / Stafford, Christopher M (Committee member) / Richert, Ranko (Committee member) / Rege, Kaushal (Committee member) / Dai, Lenore (Committee member) / Arizona State University (Publisher)
Created2011
Description
Current economic conditions necessitate the extension of service lives for a variety of aerospace systems. As a result, there is an increased need for structural health management (SHM) systems to increase safety, extend life, reduce maintenance costs, and minimize downtime, lowering life cycle costs for these aging systems. The implementation of such a system requires a collaborative research effort in a variety of areas such as novel sensing techniques, robust algorithms for damage interrogation, high fidelity probabilistic progressive damage models, and hybrid residual life estimation models. This dissertation focuses on the sensing and damage estimation aspects of this multidisciplinary topic for application in metallic and composite material systems. The primary means of interrogating a structure in this work is through the use of Lamb wave propagation which works well for the thin structures used in aerospace applications. Piezoelectric transducers (PZTs) were selected for this application since they can be used as both sensors and actuators of guided waves. Placement of these transducers is an important issue in wave based approaches as Lamb waves are sensitive to changes in material properties, geometry, and boundary conditions which may obscure the presence of damage if they are not taken into account during sensor placement. The placement scheme proposed in this dissertation arranges piezoelectric transducers in a pitch-catch mode so the entire structure can be covered using a minimum number of sensors. The stress distribution of the structure is also considered so PZTs are placed in regions where they do not fail before the host structure. In order to process the data from these transducers, advanced signal processing techniques are employed to detect the presence of damage in complex structures. To provide a better estimate of the damage for accurate life estimation, machine learning techniques are used to classify the type of damage in the structure. A data structure analysis approach is used to reduce the amount of data collected and increase computational efficiency. In the case of low velocity impact damage, fiber Bragg grating (FBG) sensors were used with a nonlinear regression tool to reconstruct the loading at the impact site.
ContributorsCoelho, Clyde (Author) / Chattopadhyay, Aditi (Thesis advisor) / Dai, Lenore (Committee member) / Wu, Tong (Committee member) / Das, Santanu (Committee member) / Rajadas, John (Committee member) / Papandreou-Suppappola, Antonia (Committee member) / Arizona State University (Publisher)
Created2011
Description
Mesoporous materials that possess large surface area, tunable pore size, and ordered structures are attractive features for many applications such as adsorption, protein separation, enzyme encapsulation and drug delivery as these materials can be tailored to host different guest molecules. Films provide a model system to understand how the pore orientation impacts the potential for loading and release of selectively sized molecules. This research work aims to develop structure-property relationships to understand how pore size, geometry, and surface hydrophobicity influence the loading and release of drug molecules. In this study, the pore size is systematically varied by incorporating pore-swelling agent of polystyrene oligomers (hPS) to soft templated mesoporous carbon films fabricated by cooperative assembly of poly(styrene-block-ethylene oxide) (SEO) with phenolic resin. To examine the impact of morphology, different compositions of amphiphilic triblock copolymer templates, poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (PEO-PPO-PEO), are used to form two-dimensional hexagonal and cubic mesostructures. Lastly, the carbonization temperature provides a handle to tune the hydrophobicity of the film. These mesoporous films are then utilized to understand the uptake and release of a model drug Mitoxantrone dihydrochloride from nanostructured materials. The largest pore size (6nm) mesoporous carbon based on SEO exhibits the largest uptake (3.5μg/cm2); this is attributed to presence of larger internal volume compared to the other two films. In terms of release, a controlled response is observed for all films with the highest release for the 2nm cubic film (1.45 μg/cm2) after 15 days, but this is only 56 % of the drug loaded. Additionally, the surface hydrophobicity impacts the fraction of drug release with a decrease from 78% to 43%, as the films become more hydrophobic when carbonized at higher temperatures. This work provides a model system to understand how pore morphology, size and chemistry influence the drug loading and release for potential implant applications.
ContributorsLabiano, Alpha (Author) / Vogt, Bryan (Thesis advisor) / Rege, Kaushal (Committee member) / Dai, Lenore (Committee member) / Potta, Thrimoorthy (Committee member) / Arizona State University (Publisher)
Created2011
Description
Increased priority on the minimization of environmental impacts of conventional construction materials in recent years has motivated increased use of waste materials or bi-products such as fly ash, blast furnace slag with a view to reduce or eliminate the manufacturing/consumption of ordinary portland cement (OPC) which accounts for approximately 5-7% of global carbon dioxide emission. The current study explores, for the first time, the possibility of carbonating waste metallic iron powder to develop carbon-negative sustainable binder systems for concrete. The fundamental premise of this work is that metallic iron will react with aqueous CO2 under controlled conditions to form complex iron carbonates which have binding capabilities. The compressive and flexural strengths of the chosen iron-based binder systems increase with carbonation duration and the specimens carbonated for 4 days exhibit mechanical properties that are comparable to those of companion ordinary portland cement systems. The optimal mixture proportion and carbonation regime for this non-conventional sustainable binder is established based on the study of carbonation efficiency of a series of mixtures using thermogravimetric analysis. The pore- and micro-structural features of this novel binding material are also evaluated. The fracture response of this novel binder is evaluated using strain energy release rate and measurement of fracture process zone using digital image correlation (DIC). The iron-based binder system exhibits significantly higher strain energy release rates when compared to those of the OPC systems in both the unreinforced and glass fiber reinforced states. The iron-based binder also exhibits higher amount of area of fracture process zone due to its ability to undergo inelastic deformation facilitated by unreacted metallic iron particle inclusions in the microstructure that helps crack bridging /deflection. The intrinsic nano-mechanical properties of carbonate reaction product are explored using statistical nanoindentation technique coupled with a stochastic deconvolution algorithm. Effect of exposure to high temperature (up to 800°C) is also studied. Iron-based binder shows significantly higher residual flexural strength after exposure to high temperatures. Results of this comprehensive study establish the viability of this binder type for concrete as an environment-friendly and economical alternative to OPC.
ContributorsDas, Sumanta (Author) / Neithalath, Narayanan (Thesis advisor) / Rajan, S.D. (Committee member) / Mobasher, Barzin (Committee member) / Marzke, Robert (Committee member) / Chawla, Nikhilesh (Committee member) / Stone, David (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
Materials with unprecedented properties are necessary to make dramatic changes in current and future aerospace platforms. Hybrid materials and composites are increasingly being used in aircraft and spacecraft frames; however, future platforms will require an optimal design of novel materials that enable operation in a variety of environments and produce known/predicted damage mechanisms. Nanocomposites and nanoengineered composites with CNTs have the potential to make significant improvements in strength, stiffness, fracture toughness, flame retardancy and resistance to corrosion. Therefore, these materials have generated tremendous scientific and technical interest over the past decade and various architectures are being explored for applications to light-weight airframe structures. However, the success of such materials with significantly improved performance metrics requires careful control of the parameters during synthesis and processing. Their implementation is also limited due to the lack of complete understanding of the effects the nanoparticles impart to the bulk properties of composites. It is common for computational methods to be applied to explain phenomena measured or observed experimentally. Frequently, a given phenomenon or material property is only considered to be fully understood when the associated physics has been identified through accompanying calculations or simulations.
The computationally and experimentally integrated research presented in this dissertation provides improved understanding of the mechanical behavior and response including damage and failure in CNT nanocomposites, enhancing confidence in their applications. The computations at the atomistic level helps to understand the underlying mechanochemistry and allow a systematic investigation of the complex CNT architectures and the material performance across a wide range of parameters. Simulation of the bond breakage phenomena and development of the interface to continuum scale damage captures the effects of applied loading and damage precursor and provides insight into the safety of nanoengineered composites under service loads. The validated modeling methodology is expected to be a step in the direction of computationally-assisted design and certification of novel materials, thus liberating the pace of their implementation in future applications.
The computationally and experimentally integrated research presented in this dissertation provides improved understanding of the mechanical behavior and response including damage and failure in CNT nanocomposites, enhancing confidence in their applications. The computations at the atomistic level helps to understand the underlying mechanochemistry and allow a systematic investigation of the complex CNT architectures and the material performance across a wide range of parameters. Simulation of the bond breakage phenomena and development of the interface to continuum scale damage captures the effects of applied loading and damage precursor and provides insight into the safety of nanoengineered composites under service loads. The validated modeling methodology is expected to be a step in the direction of computationally-assisted design and certification of novel materials, thus liberating the pace of their implementation in future applications.
ContributorsSubramanian, Nithya (Author) / Chattopadhyay, Aditi (Thesis advisor) / Dai, Lenore (Committee member) / Jiao, Yang (Committee member) / Liu, Yongming (Committee member) / Rajadas, John (Committee member) / Arizona State University (Publisher)
Created2018