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Reductive dechlorination by members of the bacterial genus Dehalococcoides is a common and cost-effective avenue for in situ bioremediation of sites contaminated with the chlorinated solvents, trichloroethene (TCE) and perchloroethene (PCE). The overarching goal of my research was to address some of the challenges associated with bioremediation timeframes by improving

Reductive dechlorination by members of the bacterial genus Dehalococcoides is a common and cost-effective avenue for in situ bioremediation of sites contaminated with the chlorinated solvents, trichloroethene (TCE) and perchloroethene (PCE). The overarching goal of my research was to address some of the challenges associated with bioremediation timeframes by improving the rates of reductive dechlorination and the growth of Dehalococcoides in mixed communities. Biostimulation of contaminated sites or microcosms with electron donor fails to consistently promote dechlorination of PCE/TCE beyond cis-dichloroethene (cis-DCE), even when the presence of Dehalococcoides is confirmed. Supported by data from microcosm experiments, I showed that the stalling at cis-DCE is due a H2 competition in which components of the soil or sediment serve as electron acceptors for competing microorganisms. However, once competition was minimized by providing selective enrichment techniques, I illustrated how to obtain both fast rates and high-density Dehalococcoides using three distinct enrichment cultures. Having achieved a heightened awareness of the fierce competition for electron donor, I then identified bicarbonate (HCO3-) as a potential H2 sink for reductive dechlorination. HCO3- is the natural buffer in groundwater but also the electron acceptor for hydrogenotrophic methanogens and homoacetogens, two microbial groups commonly encountered with Dehalococcoides. By testing a range of concentrations in batch experiments, I showed that methanogens are favored at low HCO3 and homoacetogens at high HCO3-. The high HCO3- concentrations increased the H2 demand which negatively affected the rates and extent of dechlorination. By applying the gained knowledge on microbial community management, I ran the first successful continuous stirred-tank reactor (CSTR) at a 3-d hydraulic retention time for cultivation of dechlorinating cultures. I demonstrated that using carefully selected conditions in a CSTR, cultivation of Dehalococcoides at short retention times is feasible, resulting in robust cultures capable of fast dechlorination. Lastly, I provide a systematic insight into the effect of high ammonia on communities involved in dechlorination of chloroethenes. This work documents the potential use of landfill leachate as a substrate for dechlorination and an increased tolerance of Dehalococcoides to high ammonia concentrations (2 g L-1 NH4+-N) without loss of the ability to dechlorinate TCE to ethene.
ContributorsDelgado, Anca Georgiana (Author) / Krajmalnik-Brown, Rosa (Thesis advisor) / Cadillo-Quiroz, Hinsby (Committee member) / Halden, Rolf U. (Committee member) / Rittmann, Bruce E. (Committee member) / Stout, Valerie (Committee member) / Arizona State University (Publisher)
Created2013
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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
High-temperature mechanical behaviors of metal alloys and underlying microstructural variations responsible for such behaviors are essential areas of interest for many industries, particularly for applications such as jet engines. Anisotropic grain structures, change of preferred grain orientation, and other transformations of grains occur both during metal powder bed fusion additive

High-temperature mechanical behaviors of metal alloys and underlying microstructural variations responsible for such behaviors are essential areas of interest for many industries, particularly for applications such as jet engines. Anisotropic grain structures, change of preferred grain orientation, and other transformations of grains occur both during metal powder bed fusion additive manufacturing processes, due to variation of thermal gradient and cooling rates, and afterward during different thermomechanical loads, which parts experience in their specific applications, could also impact its mechanical properties both at room and high temperatures. In this study, an in-depth analysis of how different microstructural features, such as crystallographic texture, grain size, grain boundary misorientation angles, and inherent defects, as byproducts of electron beam powder bed fusion (EB-PBF) AM process, impact its anisotropic mechanical behaviors and softening behaviors due to interacting mechanisms. Mechanical testing is conducted for EB-PBF Ti6Al4V parts made at different build orientations up to 600°C temperature. Microstructural analysis using electron backscattered diffraction (EBSD) is conducted on samples before and after mechanical testing to understand the interacting impact that temperature and mechanical load have on the activation of certain mechanisms. The vertical samples showed larger grain sizes, with an average of 6.6 µm, a lower average misorientation angle, and subsequently lower strength values than the other two horizontal samples. Among the three strong preferred grain orientations of the α phases, <1 1 2 ̅ 1> and <1 1 2 ̅ 0> were dominant in horizontally built samples, whereas the <0 0 0 1> was dominant in vertically built samples. Thus, strong microstructural variation, as observed among different EB-PBF Ti6Al4V samples, mainly resulted in anisotropic behaviors. Furthermore, alpha grain showed a significant increase in average grain size for all samples with the increasing test temperature, especially from 400°C to 600°C, indicating grain growth and coarsening as potential softening mechanisms along with temperature-induced possible dislocation motion. The severity of internal and external defects on fatigue strength has been evaluated non-destructively using quantitative methods, i.e., Murakami’s square root of area parameter model and Basquin’s model, and the external surface defects were rendered to be more critical as potential crack initiation sites.
ContributorsMian, Md Jamal (Author) / Ladani, Leila (Thesis advisor) / Razmi, Jafar (Committee member) / Shuaib, Abdelrahman (Committee member) / Mobasher, Barzin (Committee member) / Nian, Qiong (Committee member) / Arizona State University (Publisher)
Created2022
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Description
Traditional public health strategies for assessing human behavior, exposure, and activity are considered resource-exhaustive, time-consuming, and expensive, warranting a need for alternative methods to enhance data acquisition and subsequent interventions. This dissertation critically evaluated the use of wastewater-based epidemiology (WBE) as an inclusive and non-invasive tool for conducting near real-time

Traditional public health strategies for assessing human behavior, exposure, and activity are considered resource-exhaustive, time-consuming, and expensive, warranting a need for alternative methods to enhance data acquisition and subsequent interventions. This dissertation critically evaluated the use of wastewater-based epidemiology (WBE) as an inclusive and non-invasive tool for conducting near real-time population health assessments. A rigorous literature review was performed to gauge the current landscape of WBE to monitor for biomarkers indicative of diet, as well as exposure to estrogen-mimicking endocrine disrupting (EED) chemicals via route of ingestion. Wastewater-derived measurements of phytoestrogens from August 2017 through July 2019 (n = 156 samples) in a small sewer catchment revealed seasonal patterns, with highest average per capita consumption rates in January through March of each year (2018: 7.0 ± 2.0 mg d-1; 2019: 8.2 ± 2.3 mg d-1) and statistically significant differences (p = 0.01) between fall and winter (3.4 ± 1.2 vs. 6.1 ± 2.9 mg d-1; p ≤ 0.01) and spring and summer (5.6 ± 2.1 vs. 3.4 ± 1.5 mg d-1; p ≤ 0.01). Additional investigations, including a human gut microbial composition analysis of community wastewater, were performed to support a methodological framework for future implementation of WBE to assess population-level dietary behavior. In response to the COVID-19 global pandemic, a high-frequency, high-resolution sample collection approach with public data sharing was implemented throughout the City of Tempe, Arizona, and analyzed for SARS-CoV-2 (E gene) from April 2020 through March 2021 (n = 1,556 samples). Results indicate early warning capability during the first wave (June 2020) compared to newly reported clinical cases (8.5 ± 2.1 days), later transitioning to a slight lagging indicator in December/January 2020-21 (-2.0 ± 1.4 days). A viral hotspot from within a larger catchment area was detected, prompting targeted interventions to successfully mitigate community spread; reinforcing the importance of sample collection within the sewer infrastructure. I conclude that by working in tandem with traditional approaches, WBE can enlighten a comprehensive understanding of population health, with methods and strategies implemented in this work recommended for future expansion to produce timely, actionable data in support of public health.
ContributorsBowes, Devin Ashley (Author) / Halden, Rolf U (Thesis advisor) / Krajmalnik-Brown, Rosa (Thesis advisor) / Conroy-Ben, Otakuye (Committee member) / Varsani, Arvind (Committee member) / Whisner, Corrie (Committee member) / Arizona State University (Publisher)
Created2022
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Description
Phase change materials (PCMs) are combined sensible-and-latent thermal energy storage materials that can be used to store and dissipate energy in the form of heat. PCMs incorporated into wall-element systems have been well-studied with respect to energy efficiency of building envelopes. New applications of PCMs in infrastructural concrete, e.g., for

Phase change materials (PCMs) are combined sensible-and-latent thermal energy storage materials that can be used to store and dissipate energy in the form of heat. PCMs incorporated into wall-element systems have been well-studied with respect to energy efficiency of building envelopes. New applications of PCMs in infrastructural concrete, e.g., for mitigating early-age cracking and freeze-and-thaw induced damage, have also been proposed. Hence, the focus of this dissertation is to develop a detailed understanding of the physic-chemical and thermo-mechanical characteristics of cementitious systems and novel coating systems for wall-elements containing PCM. The initial phase of this work assesses the influence of interface properties and inter-inclusion interactions between microencapsulated PCM, macroencapsulated PCM, and the cementitious matrix. The fact that these inclusions within the composites are by themselves heterogeneous, and contain multiple components necessitate careful application of models to predict the thermal properties. The next phase observes the influence of PCM inclusions on the fracture and fatigue behavior of PCM-cementitious composites. The compliant nature of the inclusion creates less variability in the fatigue life for these composites subjected to cyclic loading. The incorporation of small amounts of PCM is found to slightly improve the fracture properties compared to PCM free cementitious composites. Inelastic deformations at the crack-tip in the direction of crack opening are influenced by the microscale PCM inclusions. After initial laboratory characterization of the microstructure and evaluation of the thermo-mechanical performance of these systems, field scale applicability and performance were evaluated. Wireless temperature and strain sensors for smart monitoring were embedded within a conventional portland cement concrete pavement (PCCP) and a thermal control smart concrete pavement (TCSCP) containing PCM. The TCSCP exhibited enhanced thermal performance over multiple heating and cooling cycles. PCCP showed significant shrinkage behavior as a result of compressive strains in the reinforcement that were twice that of the TCSCP. For building applications, novel PCM-composites coatings were developed to improve and extend the thermal efficiency. These coatings demonstrated a delay in temperature by up to four hours and were found to be more cost-effective than traditional building insulating materials.

The results of this work prove the feasibility of PCMs as a temperature-regulating technology. Not only do PCMs reduce and control the temperature within cementitious systems without affecting the rate of early property development but they can also be used as an auto-adaptive technology capable of improving the thermal performance of building envelopes.
ContributorsAguayo, Matthew Joseph (Author) / Neithalath, Narayanan (Thesis advisor) / Rajan, Subramaniam D. (Committee member) / Mobasher, Barzin (Committee member) / Underwood, Benjamin (Committee member) / Liu, Yongming (Committee member) / Arizona State University (Publisher)
Created2018
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Description
In order to verify the dispersive nature of transverse displacement in a beam, a deep understanding of the governing partial differential equation is developed. Using the finite element method and Newmark’s method, along with Fourier transforms and other methods, the aim is to obtain consistent results across each numerical technique.

In order to verify the dispersive nature of transverse displacement in a beam, a deep understanding of the governing partial differential equation is developed. Using the finite element method and Newmark’s method, along with Fourier transforms and other methods, the aim is to obtain consistent results across each numerical technique. An analytical solution is also analyzed for the Euler-Bernoulli beam in order to gain confidence in the numerical techniques when used for more advance beam theories that do not have a known analytical solution. Three different beam theories are analyzed in this report: The Euler-Bernoulli beam theory, Rayleigh beam theory and Timoshenko beam theory. A comparison of the results show the difference between each theory and the advantages of using a more advanced beam theory for higher frequency vibrations.
ContributorsTschetter, Ryan William (Author) / Hjelmstad, Keith D. (Thesis advisor) / Rajan, Subramaniam D. (Committee member) / Mobasher, Barzin (Committee member) / Arizona State University (Publisher)
Created2016
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Description
The need for sustainability in construction has encouraged scientists to develop novel environmentally friendly materials. The use of supplementary cementitious materials was one such initiative which aided in enhancing the fresh and hardened concrete properties. This thesis aims to explore the understanding of the early age rheological properties of such

The need for sustainability in construction has encouraged scientists to develop novel environmentally friendly materials. The use of supplementary cementitious materials was one such initiative which aided in enhancing the fresh and hardened concrete properties. This thesis aims to explore the understanding of the early age rheological properties of such cementitious systems.

The first phase of the work investigates the influence of supplementary cementitious materials (SCM) in combination with ordinary Portland cement (OPC) on the rheological properties of fresh paste with and without the effect of superplasticizers. Yield stress, plastic viscosity and storage modulus are the rheological parameters which were evaluated for all the design mixtures to fundamentally understand the synergistic effects of the SCM. A time-dependent study was conducted on these blends to explore the structure formation at various time intervals which explains the effect of hydration in conjecture to its physical stiffening. The second phase focuses on the rheological characterization of novel iron powder based binder system.

The results of this work indicate that the rheological characteristics of cementitious suspensions are complex, and strongly dependent on several key parameters including: the solid loading, inter-particle forces, shape of the particle, particle size distribution of the particles, and rheological nature of the media in which the particles are suspended. Chemical composition and reactivity of the material play an important role in the time-dependent rheological study.

A stress plateau method is utilized for the determination of rheological properties of concentrated suspensions, as it better predicts the apparent yield stress and is shown to correlate well with other viscoelastic properties of the suspensions. Plastic viscosity is obtained by calculating the slope of the stress-strain rate curve of ramp down values of shear rates. In oscillatory stress measurements the plateau obtained within the linear visco-elastic region was considered to be the value for storage modulus.

Between the different types of fly ash, class F fly ash indicated a reduction in the rheological parameters as opposed to class C fly ash that is attributable to the enhanced ettringite formation in the latter. Use of superplasticizer led to a huge influence on yield stress and storage modulus of the paste due to the steric hindrance effect.

In the study of iron based binder systems, metakaolin had comparatively higher influence than fly ash on the rheology due to its tendency to agglomerate as opposed to the ball bearing effect observed in the latter. Iron increment above 60% resulted in a decrease in all the parameters of rheology discussed in this thesis. In the OPC-iron binder, the iron behaved as reinforcements yielding higher yield stress and plastic viscosity.
ContributorsInbasekaran, Aditya (Author) / Neithalath, Narayanan (Thesis advisor) / Rajan, Subramaniam D. (Committee member) / Mobasher, Barzin (Committee member) / Arizona State University (Publisher)
Created2016
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Description
As the demand of sustainable construction materials increases, use of fibers and textiles as partial or full reinforcement in concrete members present a tremendous opportunity. Proper characterization techniques and design guides for hybrid materials are therefore needed. This dissertation presents a comprehensive study on serviceability-based design of strain softening and

As the demand of sustainable construction materials increases, use of fibers and textiles as partial or full reinforcement in concrete members present a tremendous opportunity. Proper characterization techniques and design guides for hybrid materials are therefore needed. This dissertation presents a comprehensive study on serviceability-based design of strain softening and strain hardening materials. Multiple experimental procedures are developed to document the nature of single crack localization and multiple cracking mechanisms in various fiber and fabric reinforced cement-based composites. In addition, strain rate effects on the mechanical properties are examined using a high speed servo-hydraulic tension test equipment.

Significant hardening and degradation parameters such as stiffness, crack spacing, crack width, localized zone size are obtained from tensile tests using digital image correlation (DIC) technique. A tension stiffening model is used to simulate the tensile response that addresses the cracking and localization mechanisms. The model is also modified to simulate the sequential cracking in joint-free slabs on grade reinforced by steel fibers, where the lateral stiffness of slab and grade interface and stress-crack width response are the most important model parameters.

Parametric tensile and compressive material models are used to formulate generalized analytical solutions for flexural behaviors of hybrid reinforced concrete (HRC) that contains both rebars and fibers. Design recommendations on moment capacity, minimum reinforcement ratio etc. are obtained using analytical equations. The role of fiber in reducing the amount of conventional reinforcement is revealed. The approach is extended to T-sections and used to model Ultra High Performance Concrete (UHPC) beams and girders.

The analytical models are extended to structural members subjected to combined axial and bending actions. Analytical equations to address the P-M diagrams are derived. Closed-form equations that generate the interaction diagram of HRC section are presented which may be used in the design of multiple types of applications.

The theoretical models are verified by independent experimental results from literature. Reliability analysis using Monte Carlo simulation (MCS) is conducted for few design problems on ultimate state design. The proposed methodologies enable one to simulate the experiments to obtain material parameters and design structural members using generalized formulations.
ContributorsYao, Yiming (Author) / Mobasher, Barzin (Thesis advisor) / Underwood, Benjamin (Committee member) / Neithalath, Narayanan (Committee member) / Rajan, Subramaniam D. (Committee member) / Liu, Yongming (Committee member) / Arizona State University (Publisher)
Created2016
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Description
The main objective of this study is to investigate the behaviour and applications of strain hardening cement composites (SHCC). Application of SHCC for use in slabs of common configurations was studied and design procedures are prepared by employing yield line theory and integrating it with simplified tri-linear model developed in

The main objective of this study is to investigate the behaviour and applications of strain hardening cement composites (SHCC). Application of SHCC for use in slabs of common configurations was studied and design procedures are prepared by employing yield line theory and integrating it with simplified tri-linear model developed in Arizona State University by Dr. Barzin Mobasher and Dr. Chote Soranakom. Intrinsic material property of moment-curvature response for SHCC was used to derive the relationship between applied load and deflection in a two-step process involving the limit state analysis and kinematically admissible displacements. For application of SHCC in structures such as shear walls, tensile and shear properties are necessary for design. Lot of research has already been done to study the tensile properties and therefore shear property study was undertaken to prepare a design guide. Shear response of textile reinforced concrete was investigated based on picture frame shear test method. The effects of orientation, volume of cement paste per layer, planar cross-section and volume fraction of textiles were investigated. Pultrusion was used for the production of textile reinforced concrete. It is an automated set-up with low equipment cost which provides uniform production and smooth final surface of the TRC. A 3-D optical non-contacting deformation measurement technique of digital image correlation (DIC) was used to conduct the image analysis on the shear samples by means of tracking the displacement field through comparison between the reference image and deformed images. DIC successfully obtained full-field strain distribution, displacement and strain versus time responses, demonstrated the bonding mechanism from perspective of strain field, and gave a relation between shear angle and shear strain.
ContributorsAswani, Karan (Author) / Mobasher, Barzin (Thesis advisor) / Dharmarajan, Subramaniam (Committee member) / Neithalath, Narayanan (Committee member) / Arizona State University (Publisher)
Created2014