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Description
The increased emphasis on the detrimental effects of the production of construction materials such as ordinary portland cement (OPC) have driven studies of the alkali activation of aluminosilicate materials as binder systems derived from industrial byproducts. They have been extensively studied due to the advantages they offer in terms of

The increased emphasis on the detrimental effects of the production of construction materials such as ordinary portland cement (OPC) have driven studies of the alkali activation of aluminosilicate materials as binder systems derived from industrial byproducts. They have been extensively studied due to the advantages they offer in terms of enhanced material properties, while increasing sustainability by the reuse of industrial waste and reducing the adverse impacts of OPC production. Ground granulated blast furnace slag is one of the commonly used materials for their content of calcium and silica species. Alkaline activators such as silicates, aluminates etc. are generally used. These materials undergo dissolution, polymerization with the alkali, condensation on particle surfaces and solidification under the influence of alkaline activators. Exhaustive studies exploring the effects of sodium silicate as an activator however there is a significant lack of work on exploring the effect of the cation and the effect of liquid and powder activators. The focus of this thesis is hence segmented into two topics: (i) influence of liquid Na and K silicate activators to explore the effect of silicate and hydroxide addition and (ii) influence of powder Na and K Silicate activators to explore the effect of cation, concentration and silicates. Isothermal calorimetric studies have been performed to evaluate the early hydration process, and to understand the reaction kinetics of the liquid and powder alkali activated systems. The reaction kinetics had an impact on the early age behavior of these binders which can be explained by the compressive strength results. It was noticed that the concentration and silica modulus of the activator had a greater influence than the cation over the compressive strength. Quantification of the hydration products resultant from these systems was performed via thermo gravimetric analysis (TGA). The difference in the reaction products formed with varying cation and silicate addition in these alkali activated systems is brought out. Fourier transform infrared (FTIR) spectroscopy was used to investigate the degree of polymerization achieved in these systems. This is indicative of silica and alumina bonds in the system. Differences in the behavior of the cation are attributable to size of the hydration sphere and polarizing effect of the cation which are summarized at the end of the study.
ContributorsDakhane, Akash (Author) / Neithalath, Narayanan (Thesis advisor) / Subramaniam, Dharmarajan (Committee member) / Mobashar, Barzin (Committee member) / Arizona State University (Publisher)
Created2013
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Description
Dwindling energy resources and associated environmental costs have resulted in a serious need to design and construct energy efficient buildings. One of the strategies to develop energy efficient structural materials is through the incorporation of phase change materials (PCM) in the host matrix. This research work presents details of a

Dwindling energy resources and associated environmental costs have resulted in a serious need to design and construct energy efficient buildings. One of the strategies to develop energy efficient structural materials is through the incorporation of phase change materials (PCM) in the host matrix. This research work presents details of a finite element-based framework that is used to study the thermal performance of structural precast concrete wall elements with and without a layer of phase change material. The simulation platform developed can be implemented for a wide variety of input parameters. In this study, two different locations in the continental United States, representing different ambient temperature conditions (corresponding to hot, cold and typical days of the year) are studied. Two different types of concrete - normal weight and lightweight, different PCM types, gypsum wallboard's with varying PCM percentages and different PCM layer thicknesses are also considered with an aim of understanding the energy flow across the wall member. Effect of changing PCM location and prolonged thermal loading are also studied. The temperature of the inside face of the wall and energy flow through the inside face of the wall, which determines the indoor HVAC energy consumption are used as the defining parameters. An ad-hoc optimization scheme is also implemented where the PCM thickness is fixed but its location and properties are varied. Numerical results show that energy savings are possible with small changes in baseline values, facilitating appropriate material design for desired characteristics.
ContributorsHembade, Lavannya Babanrao (Author) / Neithalath, Narayanan (Thesis advisor) / Rajan, Subramaniam D. (Thesis advisor) / Mobasher, Barzin (Committee member) / Arizona State University (Publisher)
Created2012
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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
Buildings consume a large portion of the world's energy, but with the integration of phase change materials (PCMs) in building elements this energy cost can be greatly reduced. The addition of PCMs into building elements, however, becomes a challenge to model and analyze how the material actually affects the energy

Buildings consume a large portion of the world's energy, but with the integration of phase change materials (PCMs) in building elements this energy cost can be greatly reduced. The addition of PCMs into building elements, however, becomes a challenge to model and analyze how the material actually affects the energy flow and temperatures in the system. This research work presents a comprehensive computer program used to model and analyze PCM embedded wall systems. The use of the finite element method (FEM) provides the tool to analyze the energy flow of these systems. Finite element analysis (FEA) can model the transient analysis of a typical climate cycle along with nonlinear problems, which the addition of PCM causes. The use of phase change materials is also a costly material expense. The initial expense of using PCMs can be compensated by the reduction in energy costs it can provide. Optimization is the tool used to determine the optimal point between adding PCM into a wall and the amount of energy savings that layer will provide. The integration of these two tools into a computer program allows for models to be efficiently created, analyzed and optimized. The program was then used to understand the benefits between two different wall models, a wall with a single layer of PCM or a wall with two different PCM layers. The effect of the PCMs on the inside wall temperature along with the energy flow across the wall are computed. The numerical results show that a multi-layer PCM wall was more energy efficient and cost effective than the single PCM layer wall. A structural analysis was then performed on the optimized designs using ABAQUS v. 6.10 to ensure the structural integrity of the wall was not affected by adding PCM layer(s).
ContributorsStockwell, Amie (Author) / Rajan, Subramaniam D. (Thesis advisor) / Neithalath, Narayanan (Thesis advisor) / Mobasher, Barzin (Committee member) / Arizona State University (Publisher)
Created2013
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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
Manufacture of building materials requires significant energy, and as demand for these materials continues to increase, the energy requirement will as well. Offsetting this energy use will require increased focus on sustainable building materials. Further, the energy used in building, particularly in heating and air conditioning, accounts for 40 percent

Manufacture of building materials requires significant energy, and as demand for these materials continues to increase, the energy requirement will as well. Offsetting this energy use will require increased focus on sustainable building materials. Further, the energy used in building, particularly in heating and air conditioning, accounts for 40 percent of a buildings energy use. Increasing the efficiency of building materials will reduce energy usage over the life time of the building. Current methods for maintaining the interior environment can be highly inefficient depending on the building materials selected. Materials such as concrete have low thermal efficiency and have a low heat capacity meaning it provides little insulation. Use of phase change materials (PCM) provides the opportunity to increase environmental efficiency of buildings by using the inherent latent heat storage as well as the increased heat capacity. Incorporating PCM into concrete via lightweight aggregates (LWA) by direct addition is seen as a viable option for increasing the thermal storage capabilities of concrete, thereby increasing building energy efficiency. As PCM change phase from solid to liquid, heat is absorbed from the surroundings, decreasing the demand on the air conditioning systems on a hot day or vice versa on a cold day. Further these materials provide an additional insulating capacity above the value of plain concrete. When the temperature drops outside the PCM turns back into a solid and releases the energy stored from the day. PCM is a hydrophobic material and causes reductions in compressive strength when incorporated directly into concrete, as shown in previous studies. A proposed method for mitigating this detrimental effect, while still incorporating PCM into concrete is to encapsulate the PCM in aggregate. This technique would, in theory, allow for the use of phase change materials directly in concrete, increasing the thermal efficiency of buildings, while negating the negative effect on compressive strength of the material.
ContributorsSharma, Breeann (Author) / Neithalath, Narayanan (Thesis advisor) / Mobasher, Barzin (Committee member) / Rajan, Subramaniam D. (Committee member) / Arizona State University (Publisher)
Created2013
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Description
Being a remarkably versatile and inexpensive building material, concrete has found tremendous use in development of modern infrastructure and is the most widely used material in the world. Extensive research in the field of concrete has led to the development of a wide array of concretes with applications ranging from

Being a remarkably versatile and inexpensive building material, concrete has found tremendous use in development of modern infrastructure and is the most widely used material in the world. Extensive research in the field of concrete has led to the development of a wide array of concretes with applications ranging from building of skyscrapers to paving of highways. These varied applications require special cementitious composites which can satisfy the demand for enhanced functionalities such as high strength, high durability and improved thermal characteristics among others.

The current study focuses on the fundamental understanding of such functional composites, from their microstructural design to macro-scale application. More specifically, this study investigates three different categories of functional cementitious composites. First, it discusses the differences between cementitious systems containing interground and blended limestone with and without alumina. The interground systems are found to outperform the blended systems due to differential grinding of limestone. A novel approach to deduce the particle size distribution of limestone and cement in the interground systems is proposed. Secondly, the study delves into the realm of ultra-high performance concrete, a novel material which possesses extremely high compressive-, tensile- and flexural-strength and service life as compared to regular concrete. The study presents a novel first principles-based paradigm to design economical ultra-high performance concretes using locally available materials. In the final part, the study addresses the thermal benefits of a novel type of concrete containing phase change materials. A software package was designed to perform numerical simulations to analyze temperature profiles and thermal stresses in concrete structures containing PCMs.

The design of these materials is accompanied by material characterization of cementitious binders. This has been accomplished using techniques that involve measurement of heat evolution (isothermal calorimetry), determination and quantification of reaction products (thermo-gravimetric analysis, x-ray diffraction, micro-indentation, scanning electron microscopy, energy-dispersive x-ray spectroscopy) and evaluation of pore-size distribution (mercury intrusion porosimetry). In addition, macro-scale testing has been carried out to determine compression, flexure and durability response. Numerical simulations have been carried out to understand hydration of cementitious composites, determine optimum particle packing and determine the thermal performance of these composites.
ContributorsArora, Aashay (Author) / Neithalath, Narayanan (Thesis advisor) / Rajan, Subramaniam D. (Committee member) / Mobasher, Barzin (Committee member) / Chawla, Nikhilesh (Committee member) / Hoover, Christian G (Committee member) / Arizona State University (Publisher)
Created2018
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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 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.
ContributorsMadavarapu, Sateesh Babu (Author) / Neithalath, Narayanan (Thesis advisor) / Rajan, Subramaniam D. (Committee member) / Marzke, Robert (Committee member) / Arizona State University (Publisher)
Created2014
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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

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.
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