Matching Items (11)
Description
Concrete is the most widely used infrastructure material worldwide. Production of portland cement, the main binding component in concrete, has been shown to require significant energy and account for approximately 5-7% of global carbon dioxide production. The expected continued increased use of concrete over the coming decades indicates this is an ideal time to implement sustainable binder technologies. The current work aims to explore enhanced sustainability concretes, primarily in the context of limestone and flow. Aspects such as hydration kinetics, hydration product formation and pore structure add to the understanding of the strength development and potential durability characteristics of these binder systems. Two main strategies for enhancing this sustainability are explored in this work: (i) the use of high volume limestone in combination with other alternative cementitious materials to decrease the portland cement quantity in concrete and (ii) the use of geopolymers as the binder phase in concrete. The first phase of the work investigates the use of fine limestone as cement replacement from the perspective of hydration, strength development, and pore structure. The nature of the potential synergistic benefit of limestone and alumina will be explored. The second phase will focus on the rheological characterization of these materials in the fresh state, as well as a more general investigation of the rheological characterization of suspensions. The results of this work indicate several key ideas. (i) There is a potential synergistic benefit for strength, hydration, and pore structure by using alumina and in portland limestone cements, (ii) the limestone in these systems is shown to react to some extent, and fine limestone is shown to accelerate hydration, (iii) rheological characteristics of cementitious suspensions are complex, and strongly dependent on several key parameters including: the solid loading, interparticle forces, surface area of the particles present, particle size distribution of the particles, and rheological nature of the media in which the particles are suspended, and (iv) stress plateau method is proposed for the determination of rheological properties of concentrated suspensions, as it more accurately predicts apparent yield stress and is shown to correlate well with other viscoelastic properties of the suspensions.
ContributorsVance, Kirk (Author) / Neithalath, Narayanan (Thesis advisor) / Rajan, Subramaniam D. (Committee member) / Mobasher, Barzin (Committee member) / Chawla, Nikhilesh (Committee member) / Marzke, Robert (Committee member) / Arizona State University (Publisher)
Created2014
Description
The central theme of this dissertation is to understand the chemical processing science of advanced ceramic materials for biomedicine, including therapy and imaging. The secondary component focuses on the chemical processing of energy materials.
Recently, layered double hydroxide (LDH) nanoparticles (NPs) with various intercalated compounds (e.g. fluorescent molecules, radio-labeled ATP, vitamins, DNA, and drugs) have exhibited versatility and promise as a combined therapeutic and diagnostic (i.e. theranostic) vector. However, its eventual acceptance in biomedicine will be contingent on understanding the processing science, reproducibly synthesizing monodispersed NPs with controlled mean particle size (MPS), and ascertaining the efficacy of the NPs for drug delivery and imaging. First, statistical design of experiments were used to optimize the wet chemistry synthesis of (Zn, Al)-LDH NPs. A synthesis model, which allows the synthesis of nearly monodispersed NPs with controlled MPS, was developed and experimentally verified. Also, the evolution of the nanostructure was characterized, from coprecipitation to hydrothermal treatment, to identify the formation mechanisms. Next, the biocompatibility, cellular uptake and drug delivery capability of LDH NPs were studied. In an in vitro study, using cultured pancreatic adenocarcinoma BXPC3 cells, valproate-intercalated LDH NPs showed an improved efficacy (~50 fold) over the sodium valproate alone. Finally, Gd(DTPA)-intercalated LDH NPs were synthesized and characterized by proton (1H) nuclear magnetic resonance. The longitudinal relaxivity (r1) of 28.38 s-1 mM-1, which is over 6 times higher than the clinically approved contrast agent, Gd(DTPA), demonstrated the potential of this vector for use in magnetic resonance imaging.
Visible light-transparent single metal-semiconductor junction devices, which convert ultraviolet photon energy into high open circuit voltage (Voc>1.5-2 V), are highly desirable for transparent photovoltaics that can potentially power an electrochromic stack for smart windows. A Schottky junction solar cell, comprised of sputtered ZnO/ZnS heterojunction with Cr/Au contacts, was fabricated and an Voc of fî1.35 V was measured. Also, a low-cost route to form ZnO/ZnS heterojunctions by partial sulfurization of solution-grown ZnO thin films (350 nm-5 fÝm thick; conductivity comparable to phosphorus-doped Si) was demonstrated. A final study was on a cathode material for Li-ion batteries. Phase-pure LiFePO4 powders were synthesized by microwave-assisted sol-gel method and characterized.
Recently, layered double hydroxide (LDH) nanoparticles (NPs) with various intercalated compounds (e.g. fluorescent molecules, radio-labeled ATP, vitamins, DNA, and drugs) have exhibited versatility and promise as a combined therapeutic and diagnostic (i.e. theranostic) vector. However, its eventual acceptance in biomedicine will be contingent on understanding the processing science, reproducibly synthesizing monodispersed NPs with controlled mean particle size (MPS), and ascertaining the efficacy of the NPs for drug delivery and imaging. First, statistical design of experiments were used to optimize the wet chemistry synthesis of (Zn, Al)-LDH NPs. A synthesis model, which allows the synthesis of nearly monodispersed NPs with controlled MPS, was developed and experimentally verified. Also, the evolution of the nanostructure was characterized, from coprecipitation to hydrothermal treatment, to identify the formation mechanisms. Next, the biocompatibility, cellular uptake and drug delivery capability of LDH NPs were studied. In an in vitro study, using cultured pancreatic adenocarcinoma BXPC3 cells, valproate-intercalated LDH NPs showed an improved efficacy (~50 fold) over the sodium valproate alone. Finally, Gd(DTPA)-intercalated LDH NPs were synthesized and characterized by proton (1H) nuclear magnetic resonance. The longitudinal relaxivity (r1) of 28.38 s-1 mM-1, which is over 6 times higher than the clinically approved contrast agent, Gd(DTPA), demonstrated the potential of this vector for use in magnetic resonance imaging.
Visible light-transparent single metal-semiconductor junction devices, which convert ultraviolet photon energy into high open circuit voltage (Voc>1.5-2 V), are highly desirable for transparent photovoltaics that can potentially power an electrochromic stack for smart windows. A Schottky junction solar cell, comprised of sputtered ZnO/ZnS heterojunction with Cr/Au contacts, was fabricated and an Voc of fî1.35 V was measured. Also, a low-cost route to form ZnO/ZnS heterojunctions by partial sulfurization of solution-grown ZnO thin films (350 nm-5 fÝm thick; conductivity comparable to phosphorus-doped Si) was demonstrated. A final study was on a cathode material for Li-ion batteries. Phase-pure LiFePO4 powders were synthesized by microwave-assisted sol-gel method and characterized.
ContributorsSun Zhou, Xiao Di (Author) / Dey, Sandwip K (Thesis advisor) / Krause, Stephen (Committee member) / Nagaraj, Vinay J (Committee member) / Marzke, Robert (Committee member) / Arizona State University (Publisher)
Created2014
Description
The studies on aluminosilicate materials to replace traditional construction materials such as ordinary Portland cement(OPC) to reduce the effects caused has been an important research area for the past decades. Many properties like strength have already been studied and the primary focus is to learn about the reaction mechanism and the effect of the parameters on the formed products. The aim of this research was to explore the structural changes and reaction product analysis of geopolymers (Slag & Fly Ash) using Fourier transform infrared spectroscopy (FTIR) and deconvolution
techniques. Spectroscopic techniques give valuable information at a molecular level but not all methods are economic and simple. To understand the mechanisms of alkali activated aluminosilicate materials, attenuated total reflectance (ATR) FTIR has been used where the effect of the parameters on the reaction products have been analyzed. To analyze complex systems like geopolymers using FTIR, deconvolution techniques help to obtain the properties of a particular peak attributed to a certain molecular vibration.
Time and temperature dependent analysis were done on slag pastes to understand the polymerization of reactive silica in the system with time and temperature variance. For time dependent analysis slag has been activated with sodium and potassium silicates using two different `n'values and three different silica modulus [Ms- (SiO2 /M2O)] values. The temperature dependent analysis was done by curing the samples at 60C and 80C. Similarly fly ash has been studied by activating with alkali hydroxides and alkali silicates. Under the same curing conditions the fly ash samples were evaluated to analyze the effects of added silicates for alkali activation.
The peak shifts in the FTIR explains the changes in the structural nature of the matrix and can be identified using the deconvolution technique. A strong correlation is found between the concentrations of silicate monomer in the activating position of the main Si-O-T (where T is Al/Si) stretching band in the FTIR spectrum, which
gives an indication of the relative changes in the Si/Al ratio. Also, the effect of the cation and silicate concentration in the activating solution has been discussed using the Fourier self deconvolution technique.
techniques. Spectroscopic techniques give valuable information at a molecular level but not all methods are economic and simple. To understand the mechanisms of alkali activated aluminosilicate materials, attenuated total reflectance (ATR) FTIR has been used where the effect of the parameters on the reaction products have been analyzed. To analyze complex systems like geopolymers using FTIR, deconvolution techniques help to obtain the properties of a particular peak attributed to a certain molecular vibration.
Time and temperature dependent analysis were done on slag pastes to understand the polymerization of reactive silica in the system with time and temperature variance. For time dependent analysis slag has been activated with sodium and potassium silicates using two different `n'values and three different silica modulus [Ms- (SiO2 /M2O)] values. The temperature dependent analysis was done by curing the samples at 60C and 80C. Similarly fly ash has been studied by activating with alkali hydroxides and alkali silicates. Under the same curing conditions the fly ash samples were evaluated to analyze the effects of added silicates for alkali activation.
The peak shifts in the FTIR explains the changes in the structural nature of the matrix and can be identified using the deconvolution technique. A strong correlation is found between the concentrations of silicate monomer in the activating position of the main Si-O-T (where T is Al/Si) stretching band in the FTIR spectrum, which
gives an indication of the relative changes in the Si/Al ratio. Also, the effect of the cation and silicate concentration in the activating solution has been discussed using the Fourier self deconvolution technique.
ContributorsMadavarapu, Sateesh Babu (Author) / Neithalath, Narayanan (Thesis advisor) / Rajan, Subramaniam D. (Committee member) / Marzke, Robert (Committee member) / Arizona State University (Publisher)
Created2014
Description
This thesis describes several experiments based on carbon nanotube nanofludic devices and field-effect transistors. The first experiment detected ion and molecule translocation through one single-walled carbon nanotube (SWCNT) that spans a barrier between two fluid reservoirs. The electrical ionic current is measured. Translocation of small single stranded DNA oligomers is marked by large transient increases in current through the tube and confirmed by a PCR (polymerase chain reaction) analysis. Carbon nanotubes simplify the construction of nanopores, permit new types of electrical measurement, and open new avenues for control of DNA translocation. The second experiment constructed devices in which the interior of a single-walled carbon nanotube field-effect transistor (CNT-FET) acts as a nanofluidic channel that connects two fluid reservoirs, permitting measurement of the electronic properties of the SWCNT as it is wetted by an analyte. Wetting of the inside of the SWCNT by water turns the transistor on, while wetting of the outside has little effect. This finding may provide a new method to investigate water behavior at nanoscale. This also opens a new avenue for building sensors in which the SWCNT functions as an electronic detector. This thesis also presents some experiments that related to nanofabrication, such as construction of FET with tin sulfide (SnS) quantum ribbon. This work demonstrates the application of solution processed IV-VI semiconductor nanostructures in nanoscale devices.
ContributorsCao, Zhai (Author) / Lindsay, Stuart (Thesis advisor) / Vaiana, Sara (Committee member) / Ros, Robert (Committee member) / Marzke, Robert (Committee member) / Shumway, John (Committee member) / Arizona State University (Publisher)
Created2011
Description
The behaviors of various amorphous materials are characterized at high pressures to deduce phase transitions, coordination changes, densification, and other structural or electronic alterations in the system. Alongside, improvements on high pressure techniques are presented to measure equations of state of glassy materials and probe liquids using in-situ high resolution nuclear magnetic resonance (NMR) spectroscopy. 27Al NMR is used to quantify coordination changes in CaAl2O4 glass pressure cycled to 16 GPa. The structure and coordination environments remain unchanged up to 8 GPa at which 93% of the recovered glass exists as 4-fold Al, whereas the remaining population exists as [5,6]Al. Upon densification, [5,6]Al comprise nearly 30% of observed Al, most likely through the generation of 3-coordinated oxygen. A method to determine the volumetric equation of state of amorphous solids using optical microscopy in a diamond anvil cell is also described. The method relies on two dimensional image acquisition and analysis to quantify changes in the projected image area with compression. The area analysis method is used to determine the compression of cubic crystals, yielding results in good agreement with diffraction and volumetric measurements. A NMR probe capable of reaching 3 GPa is built to understand the nature of magnetic field gradients and improve upon the resolution of high pressure studies conducted in a diamond anvil cell. Field gradients in strength up to 6 G/cm are caused largely by mismatches in the magnetic susceptibility between the sample and gasket, which is proven to shift the chemical shift distribution by use of several different metallic gaskets. Polyamorphic behavior in triphenyl phosphite is studied at pressures up to 0.7 GPa to elucidate the formation of the glacial phase at high pressures. A perceived liquid-liquid phase transition is shown to follow a positive Clapeyron slope, and closely follows the predicted glass transition line up to 0.4 GPa and temperatures below 270 K. A drastic change in morphology is indicative of a transformation from liquid I to liquid II and followed by optical microscopy.
ContributorsAmin, Samrat A (Author) / Yarger, Jeffery L (Thesis advisor) / Wolf, George (Committee member) / Marzke, Robert (Committee member) / Arizona State University (Publisher)
Created2012
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
Microwave hydrolysis of egg-white lysozyme was optimized using 1H liquid-state nuclear magnetic resonance (NMR) spectroscopy experiments for amino acid analysis (AAA). Time held under microwave hydrolysis was arrayed for 2, 4, 6, 8, 10, and 15 minutes. Correlations from gCOSY 2D NMR experiments combined with 1H assignments in the one-dimensional chemical shift spectra identified 18 of the 20 amino acids found in lysozyme. Comparison with Uniprot database amino acid composition values revealed the optimal microwave hydrolysis time lies between 4 and 6 minutes. Identification of lysozyme was confirmed with the ExPASy online database search tool AACompIdent. The microwave hydrolysis procedure presented is a simple analytical technique allowing quick and reliable sample preparation in less than one hour that requires no separation or derivation of amino acids residues prior to detection.
ContributorsEdwards, Maximillian Ashur (Author) / Yarger, Jeff (Thesis director) / Marzke, Robert (Committee member) / Barrett, The Honors College (Contributor) / School of Mathematical and Statistical Sciences (Contributor) / Department of Chemistry and Biochemistry (Contributor)
Created2015-05
Description
Sustainable materials and methods have achieved a pivotal role in the research plethora of the new age due to global warming. Cement production is responsible in contributing to 5% of global CO2 emissions. Complete replacement of cement by alkaline activation of aluminosilicate waste materials such as slag and fly ash is a major advancement towards reducing the adverse impacts of cement production. Comprehensive research has been done, to understand the optimized composition and hydration products. The focus of this dissertation is to understand the multiscale behavior ranging from early age properties, fundamental material structure, fracture and crack resistance properties, durability responses and alternative activation methods to existing process.
The utilization of these materials has relied primarily on the dual benefits of reduced presence in landfills and cost. These have also proven to yield a higher service life as opposed to conventional ordinary portland cement (OPC) concrete due to an enhanced microstructure. The use of such materials however has not been readily acceptable due to detrimental early age behavior. The influence of design factors is studied to understand the reaction mechanism. Silicon polymerization at the molecular level is studied to understand the aluminosilicate interactions which are responsible for prevention of any leaching of ions. A comparative study between fly ash and slag binders is carried out to evaluate the stable states of sodium, aluminum and silicon in both these binders, since the likelihood of the sodium ions leaching out is high.
Compressive and flexural strength have been reported in previous literature, but the impact of crack resistance was unevaluated from an approach of characterizing the fracture process zone. Alternative routes of activation are explored with an intent to reduce the high alkalinity by use of neutral salts such as sodium sulfate. High volume OPC replacement by both class C and F fly ash is performed to evaluate the differences in hydration phase formation responsible for its pore refinement and strength. Spectroscopic studies have also allowed to study the fundamental material structure. Durability studies are also performed on these samples to understand the probability external sulfate attacks as opposed to OPC mixes.
The utilization of these materials has relied primarily on the dual benefits of reduced presence in landfills and cost. These have also proven to yield a higher service life as opposed to conventional ordinary portland cement (OPC) concrete due to an enhanced microstructure. The use of such materials however has not been readily acceptable due to detrimental early age behavior. The influence of design factors is studied to understand the reaction mechanism. Silicon polymerization at the molecular level is studied to understand the aluminosilicate interactions which are responsible for prevention of any leaching of ions. A comparative study between fly ash and slag binders is carried out to evaluate the stable states of sodium, aluminum and silicon in both these binders, since the likelihood of the sodium ions leaching out is high.
Compressive and flexural strength have been reported in previous literature, but the impact of crack resistance was unevaluated from an approach of characterizing the fracture process zone. Alternative routes of activation are explored with an intent to reduce the high alkalinity by use of neutral salts such as sodium sulfate. High volume OPC replacement by both class C and F fly ash is performed to evaluate the differences in hydration phase formation responsible for its pore refinement and strength. Spectroscopic studies have also allowed to study the fundamental material structure. Durability studies are also performed on these samples to understand the probability external sulfate attacks as opposed to OPC mixes.
ContributorsDakhane, Akash (Author) / Neithalath, Narayanan (Thesis advisor) / Rajan, Subramaniam D. (Committee member) / Mobasher, Barzin (Committee member) / Marzke, Robert (Committee member) / Das, Sumanta (Committee member) / Arizona State University (Publisher)
Created2016
Description
Alkali-activated slag concretes are being extensively researched because of its potential sustainability-related benefits. For such concretes to be implemented in large scale concrete applications such as infrastructural and building elements, it is essential to understand its early and long-term performance characteristics vis-à-vis conventional ordinary portland cement (OPC) based concretes. This paper presents a comprehensive study of the property and performance features including early-age isothermal calorimetric response, compressive strength development with time, microstructural features such as the pore volume and representative pore size, and accelerated chloride transport resistance of OPC and alkali-activated binder systems. Slag mixtures activated using sodium silicate solution (SiO2-to-Na2O ratio or Ms of 1–2) to provide a total alkalinity of 0.05 (Na2O-to-binder ratio) are compared with OPC mixtures with and without partial cement replacement with Class F fly ash (20 % by mass) or silica fume (6 % by mass). Major similarities are noted between these binder systems for: (1) calorimetric response with respect to the presence of features even though the locations and peaks vary based on Ms, (2) compressive strength and its development, (3) total porosity and pore size, and (4) rapid chloride permeability and non-steady state migration coefficients. Moreover, electrical impedance based circuit models are used to bring out the microstructural features (resistance of the connected pores, and capacitances of the solid phase and pore-solid interface) that are similar in conventional OPC and alkali-activated slag concretes. This study thus demonstrates that performance-equivalent alkali-activated slag systems that are more sustainable from energy and environmental standpoints can be proportioned.
ContributorsVance, Kirk (Author) / Aguayo, Matthew (Author) / Dakhane, Akash (Author) / Ravikumar, Deepak (Author) / Jain, Jitendra (Author) / Neithalath, Narayanan (Author) / Ira A. Fulton Schools of Engineering (Contributor)
Created2014-12-01
Description
This paper reports the influence of activator type and concentration on the rheological properties of alkali-activated fly ash suspensions. A thorough investigation of the rheological influences (yield stress and plastic viscosity) of several activator parameters, including: (i) the cation type and concentration of alkali hydroxide and (ii) the alkali-to-binder ratio (n) and silica modulus (Ms), and (iii) the volume of the activation solution, on the suspension rheology is presented. The results indicate a strong dependence on the cation and its concentration in the activation solution. The viscosity of the activation solution and the volumetric solution-to-powder ratio are shown to most strongly influence the plastic viscosity of the suspension. The suspension yield stress is predominantly influenced by the changes in fly ash particle surface charge and the ionic species in the activator. A shift from non-Newtonian to Newtonian flow behavior is noted in the case of silicate-based suspensions for Ms ≤ 1.5. This behavior, which is not observed at higher MS values, or when the fly ash is dispersed in hydroxide solutions or pure water, is hypothesized to be caused by colloidal siliceous species present in this system, or surface charge effects on the fly ash particles. Comparisons of the rheological response of alkali-activated suspensions to that of portland cement-water suspensions are also reported.
ContributorsVance, Kirk (Author) / Dakhane, Akash (Author) / Sant, Gaurav (Author) / Neithalath, Narayanan (Author) / Ira A. Fulton Schools of Engineering (Contributor)
Created2014-11-01