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Description
Alkali-activated aluminosilicates, commonly known as "geopolymers", are being increasingly studied as a potential replacement for Portland cement. These binders use an alkaline activator, typically alkali silicates, alkali hydroxides or a combination of both along with a silica-and-alumina rich material, such as fly ash or slag, to form a final product

Alkali-activated aluminosilicates, commonly known as "geopolymers", are being increasingly studied as a potential replacement for Portland cement. These binders use an alkaline activator, typically alkali silicates, alkali hydroxides or a combination of both along with a silica-and-alumina rich material, such as fly ash or slag, to form a final product with properties comparable to or better than those of ordinary Portland cement. The kinetics of alkali activation is highly dependent on the chemical composition of the binder material and the activator concentration. The influence of binder composition (slag, fly ash or both), different levels of alkalinity, expressed using the ratios of Na2O-to-binders (n) and activator SiO2-to-Na2O ratios (Ms), on the early age behavior in sodium silicate solution (waterglass) activated fly ash-slag blended systems is discussed in this thesis. Optimal binder composition and the n values are selected based on the setting times. Higher activator alkalinity (n value) is required when the amount of slag in the fly ash-slag blended mixtures is reduced. Isothermal calorimetry is performed to evaluate the early age hydration process and to understand the reaction kinetics of the alkali activated systems. The differences in the calorimetric signatures between waterglass activated slag and fly ash-slag blends facilitate an understanding of the impact of the binder composition on the reaction rates. Kinetic modeling is used to quantify the differences in reaction kinetics using the Exponential as well as the Knudsen method. The influence of temperature on the reaction kinetics of activated slag and fly ash-slag blends based on the hydration parameters are discussed. Very high compressive strengths can be obtained both at early ages as well as later ages (more than 70 MPa) with waterglass activated slag mortars. Compressive strength decreases with the increase in the fly ash content. A qualitative evidence of leaching is presented through the electrical conductivity changes in the saturating solution. The impact of leaching and the strength loss is found to be generally higher for the mixtures made using a higher activator Ms and a higher n value. Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy (ATR-FTIR) is used to obtain information about the reaction products.
ContributorsChithiraputhiran, Sundara Raman (Author) / Neithalath, Narayanan (Thesis advisor) / Rajan, Subramaniyam D (Committee member) / Mobasher, Barzin (Committee member) / Arizona State University (Publisher)
Created2012
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Description
The alkali activation of aluminosilicate materials as binder systems derived from industrial byproducts have been extensively studied due to the advantages they offer in terms enhanced material properties, while increasing sustainability by the reuse of industrial waste and byproducts and reducing the adverse impacts of OPC production. Fly ash and

The alkali activation of aluminosilicate materials as binder systems derived from industrial byproducts have been extensively studied due to the advantages they offer in terms enhanced material properties, while increasing sustainability by the reuse of industrial waste and byproducts and reducing the adverse impacts of OPC production. Fly ash and ground granulated blast furnace slag are commonly used for their content of soluble silica and aluminate species that can undergo dissolution, polymerization with the alkali, condensation on particle surfaces and solidification. The following topics are the focus of this thesis: (i) the use of microwave assisted thermal processing, in addition to heat-curing as a means of alkali activation and (ii) the relative effects of alkali cations (K or Na) in the activator (powder activators) on the mechanical properties and chemical structure of these systems. Unsuitable curing conditions instigate carbonation, which in turn lowers the pH of the system causing significant reductions in the rate of fly ash activation and mechanical strength development. This study explores the effects of sealing the samples during the curing process, which effectively traps the free water in the system, and allows for increased aluminosilicate activation. The use of microwave-curing in lieu of thermal-curing is also studied in order to reduce energy consumption and for its ability to provide fast volumetric heating. Potassium-based powder activators dry blended into the slag binder system is shown to be effective in obtaining very high compressive strengths under moist curing conditions (greater than 70 MPa), whereas sodium-based powder activation is much weaker (around 25 MPa). Compressive strength decreases when fly ash is introduced into the system. Isothermal calorimetry is used to evaluate the early hydration process, and to understand the reaction kinetics of the alkali powder activated systems. A qualitative evidence of the alkali-hydroxide concentration of the paste pore solution through the use of electrical conductivity measurements is also presented, with the results indicating the ion concentration of alkali is more prevalent in the pore solution of potassium-based systems. The use of advanced spectroscopic and thermal analysis techniques to distinguish the influence of studied parameters is also discussed.
ContributorsChowdhury, Ussala (Author) / Neithalath, Narayanan (Thesis advisor) / Rajan, Subramanium D. (Committee member) / Mobasher, Barzin (Committee member) / Arizona State University (Publisher)
Created2013
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Description
Concrete design has recently seen a shift in focus from prescriptive specifications to performance based specifications with increasing demands for sustainable products. Fiber reinforced composites (FRC) provides unique properties to a material that is very weak under tensile loads. The addition of fibers to a concrete mix provides additional ductility

Concrete design has recently seen a shift in focus from prescriptive specifications to performance based specifications with increasing demands for sustainable products. Fiber reinforced composites (FRC) provides unique properties to a material that is very weak under tensile loads. The addition of fibers to a concrete mix provides additional ductility and reduces the propagation of cracks in the concrete structure. It is the fibers that bridge the crack and dissipate the incurred strain energy in the form of a fiber-pullout mechanism. The addition of fibers plays an important role in tunnel lining systems and in reducing shrinkage cracking in high performance concretes. The interest in most design situations is the load where cracking first takes place. Typically the post crack response will exhibit either a load bearing increase as deflection continues, or a load bearing decrease as deflection continues. These behaviors are referred to as strain hardening and strain softening respectively. A strain softening or hardening response is used to model the behavior of different types of fiber reinforced concrete and simulate the experimental flexural response. Closed form equations for moment-curvature response of rectangular beams under four and three point loading in conjunction with crack localization rules are utilized. As a result, the stress distribution that considers a shifting neutral axis can be simulated which provides a more accurate representation of the residual strength of the fiber cement composites. The use of typical residual strength parameters by standards organizations ASTM, JCI and RILEM are examined to be incorrect in their linear elastic assumption of FRC behavior. Finite element models were implemented to study the effects and simulate the load defection response of fiber reinforced shotcrete round discrete panels (RDP's) tested in accordance with ASTM C-1550. The back-calculated material properties from the flexural tests were used as a basis for the FEM material models. Further development of FEM beams were also used to provide additional comparisons in residual strengths of early age samples. A correlation between the RDP and flexural beam test was generated based a relationship between normalized toughness with respect to the newly generated crack surfaces. A set of design equations are proposed using a residual strength correction factor generated by the model and produce the design moment based on specified concrete slab geometry.
ContributorsBarsby, Christopher (Author) / Mobasher, Barzin (Thesis advisor) / Rajan, Subramaniam D. (Committee member) / Neithalath, Narayanan (Committee member) / Arizona State University (Publisher)
Created2011
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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

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
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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

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

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
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Description
The objective of this dissertation is to study the optical and radiative properties of inhomogeneous metallic structures. In the ongoing search for new materials with tunable optical characteristics, porous metals and nanowires provides an extensive design space to engineer its optical response based on the morphology-dependent phenomena.This dissertation firstly discusses

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

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

Cellular metamaterials arouse broad scientific interests due to the combination of host material and structure together to achieve a wide range of physical properties rarely found in nature. Stochastic foam as one subset has been considered as a competitive candidate for versatile applications including heat exchangers, battery electrodes, automotive, catalyst devices, magnetic shielding, etc. For the engineering of the cellular foam architectures, closed-form models that can be used to predict the mechanical and thermal properties of foams are highly desired especially for the recently developed ultralight weight shellular architectures. Herein, for the first time, a novel packing three-dimensional (3D) hollow pentagonal dodecahedron (HPD) model is proposed to simulate the cellular architecture with hollow struts. An electrochemical deposition process is utilized to manufacture the metallic hollow foam architecture. Mechanical and thermal testing of the as-manufactured foams are carried out to compare with the HPD model. Timoshenko beam theory is utilized to verify and explain the derived power coefficient relation. Our HPD model is proved to accurately capture both the topology and the physical properties of hollow stochastic foam. Understanding how the novel HPD model packing helps break the conventional impression that 3D pentagonal topology cannot fulfill the space as a representative volume element. Moreover, the developed HPD model can predict the mechanical and thermal properties of the manufactured hollow metallic foams and elucidating of how the inevitable manufacturing defects affect the physical properties of the hollow metallic foams. Despite of the macro-scale stochastic foam architecture, nano gradient gyroid lattices are studied using Molecular Dynamics (MD) simulation. The simulation result reveals that, unlike homogeneous architecture, gradient gyroid not only shows novel layer-by-layer deformation behavior, but also processes significantly better energy absorption ability. The deformation behavior and energy absorption are predictable and designable, which demonstrate its highly programmable potential.
ContributorsDai, Rui (Author) / Nian, Qiong (Thesis advisor) / Jiao, Yang (Committee member) / Kwon, Beomjin (Committee member) / Liu, Yongming (Committee member) / Phelan, Patrick (Committee member) / Arizona State University (Publisher)
Created2021
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Description
Composites are replacing conventional materials in aerospace applications due to their light weight, non-corrosiveness, and high specific strength. This thesis aims to characterize the input data for IM7-8552 unidirectional composite to support MAT213, an orthotropic elasto-plastic damage material model and MAT_186, a mixed mode cohesive zone model used to model

Composites are replacing conventional materials in aerospace applications due to their light weight, non-corrosiveness, and high specific strength. This thesis aims to characterize the input data for IM7-8552 unidirectional composite to support MAT213, an orthotropic elasto-plastic damage material model and MAT_186, a mixed mode cohesive zone model used to model delamination. MAT_213 in conjunction with MAT_186 can be used to predict the behavior of composite under crush and impact loads including delamination. MAT_213 requires twelve sets of stress-strain curves, direction-dependent material constants, and flow rule coefficients as input. All the necessary inputs are obtained through the post-processing of a total of twelve distinct quasi-static and room temperature (QS-RT) experiments. MAT_186 is driven by a set of Mode I and Mode II fracture parameters and traction separation laws, a constitutive law that derives the relationship between stresses and relative displacements at integration points of cohesive elements. Obtaining cohesive law parameters experimentally is a tedious process as it requires close monitoring of the crack length during the test, which is a difficult task to achieve with accuracy even after using sophisticated equipment such as Digital Image Correlation (DIC). In this thesis, a numerical inverse analysis method to precisely predict these parameters by using finite element analysis with cohesive zone modeling and response surface methodology (RSM) is proposed. Three steps comprise RSM. The process in Step 1 involves calculating the root mean square error between the finite element and experimental load-displacement curves to produce the response surface. In step 2, the response surface is fitted with a second-order polynomial using the Levenberg-Marquardt algorithm. In step 3, an optimization problem is solved by minimizing the fitted function to find the optimum cohesive zone parameters. Finally, the obtained input for MAT_213 and MAT_186 material models is validated by performing a quasi-isotropic tension test simulation.
ContributorsRaihan, Mohammed (Author) / Rajan, Subramaniam (Thesis advisor) / Neithalath, Narayanan (Committee member) / Hoover, Christian (Committee member) / Yellavajjala, Ravi (Committee member) / Arizona State University (Publisher)
Created2023