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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

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
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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
Within recent years, metal-organic frameworks, or MOF’s, have gained a lot of attention in the materials research community. These micro-porous materials are constructed of a metal oxide core and organic linkers, and have a wide-variety of applications due to their extensive material characteristic possibilities. The focus of this study is

Within recent years, metal-organic frameworks, or MOF’s, have gained a lot of attention in the materials research community. These micro-porous materials are constructed of a metal oxide core and organic linkers, and have a wide-variety of applications due to their extensive material characteristic possibilities. The focus of this study is the MOF-5 material, specifically its chemical stability in air. The MOF-5 material has a large pore size of 8 Å, and aperture sizes of 15 and 12 Å. The pore size, pore functionality, and physically stable structure makes MOF-5 a desirable material. MOF-5 holds applications in gas/liquid separation, catalysis, and gas storage. The main problem with the MOF-5 material, however, is its instability in atmospheric air. This inherent instability is due to the water in air binding to the zinc-oxide core, effectively changing the material and its structure. Because of this material weakness, the MOF-5 material is difficult to be utilized in industrial applications. Through the research efforts proposed by this study, the stability of the MOF-5 powder and membrane were studied. MOF-5 powder and a MOF-5 membrane were synthesized and characterized using XRD analysis. In an attempt to improve the stability of MOF-5 in air, methyl groups were added to the organic linker in order to hinder the interaction of water with the Zn4O core. This was done by replacing the terepthalic acid organic linker with 2,5-dimethyl terephthalic acid in the powder and membrane synthesis steps. The methyl-modified MOF-5 powder was found to be stable after several days of exposure to air while the MOF-5 powder exhibited significant crystalline change. The methyl-modified membrane was found to be unstable when synthesized using the same procedure as the MOF-5 membrane.
ContributorsAnderson, Anthony David (Author) / Lin, Jerry Y.S. (Thesis director) / Ibrahim, Amr (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05
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Description
Due to the environmental problems caused by global warming, it has become necessary to reduce greenhouse gas emissions across the planet. Biofuels, such as ethanol, have proven to release cleaner emissions when combusted. However, large scale production of these alcohols is uneconomical and inefficient due to limitations in standard separation

Due to the environmental problems caused by global warming, it has become necessary to reduce greenhouse gas emissions across the planet. Biofuels, such as ethanol, have proven to release cleaner emissions when combusted. However, large scale production of these alcohols is uneconomical and inefficient due to limitations in standard separation processes, the most common being distillation. Pervaporation is a novel separation technique that utilizes a specialized membrane to separate multicomponent solutions. In this research project, pervaporation utilizing ZIF-71/PDMS mixed matrix membranes are investigated to see their ability to recover ethanol from an ethanol/aqueous separation. Membranes with varying nanoparticle concentrations were created and their performances were analyzed. While the final results indicate that no correlation exists between nanoparticle weight percentage and selectivity, this technology is still a promising avenue for biofuel production. Future work will be conducted to improve this existing process and enhance membrane selectivity.
ContributorsHoward, Chelsea Elizabeth (Author) / Lind, Mary Laura (Thesis director) / Nielsen, David (Committee member) / Greenlee, Lauren (Committee member) / Barrett, The Honors College (Contributor) / Chemical Engineering Program (Contributor) / Materials Science and Engineering Program (Contributor)
Created2015-05
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Description
The goal of this research project is to create a mixed matrix membrane that can withstand very acidic environments but still be used to purify water. The ultimate goal of this membrane is to be used to purify urine both here on Earth and in space. The membrane would be

The goal of this research project is to create a mixed matrix membrane that can withstand very acidic environments but still be used to purify water. The ultimate goal of this membrane is to be used to purify urine both here on Earth and in space. The membrane would be able to withstand these harsh conditions due the incorporation of a resilient impermeable polymer layer that will be cast above the lower hydrophilic layer. Nanoparticles called zeolites will act as a water selective pathway through this impermeable layer and allow water to flow through the membrane. This membrane will be made using a variety of methods and polymers to determine both the cheapest and most effective way of creating this chemical resistant membrane. If this research is successful, many more water sources can be tapped since the membranes will be able to withstand hard conditions. This document is primarily focused on our progress on the development of a highly permeable polymer-zeolite film that makes up the bottom layer of the membrane. Multiple types of casting methods were investigated and it was determined that spin coating at 4000 rpm was the most effective. Based on a literature review, we selected silicalite-1 zeolites as the water-selective nanoparticle component dispersed in a casting solution of polyacrylonitrile in N-methylpyrrolidinone to comprise this hydrophilic layer. We varied the casting conditions of several simple solution-casting methods to produce thin films on the porous substrate with optimal film properties for our membrane design. We then cast this solution on other types of support materials that are more flexible and inexpensive to determine which combination resulted in the thinnest and most permeable film.
ContributorsHerrera, Sofia Carolina (Author) / Lind, Mary Laura (Thesis director) / Khosravi, Afsaneh (Committee member) / Hestekin, Jamie (Committee member) / Barrett, The Honors College (Contributor) / Chemical Engineering Program (Contributor)
Created2015-05
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Description
Ethanol is a widely used biofuel in the United States that is typically produced through the fermentation of biomass feedstocks. Demand for ethanol has grown significantly from 2000 to 2015 chiefly due to a desire to increase energy independence and reduce the emissions of greenhouse gases associated with transportation. As

Ethanol is a widely used biofuel in the United States that is typically produced through the fermentation of biomass feedstocks. Demand for ethanol has grown significantly from 2000 to 2015 chiefly due to a desire to increase energy independence and reduce the emissions of greenhouse gases associated with transportation. As demand grows, new ethanol plants must be developed in order for supply to meet demand. This report covers some of the major considerations in developing these new plants such as the type of biomass used, feed treatment process, and product separation and investigates their effect on the economic viability and environmental benefits of the ethanol produced. The dry grind process for producing ethanol from corn, the most common method of production, is examined in greater detail. Analysis indicates that this process currently has the highest capacity for production and profitability but limited effect on greenhouse gas emissions compared to less common alternatives.
ContributorsSchrilla, John Paul (Author) / Kashiwagi, Dean (Thesis director) / Kashiwagi, Jacob (Committee member) / Barrett, The Honors College (Contributor) / Chemical Engineering Program (Contributor)
Created2015-05
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Description
Calcium hydroxide carbonation processes were studied to investigate the potential for abiotic soil improvement. Different mixtures of common soil constituents such as sand, clay, and granite were mixed with a calcium hydroxide slurry and carbonated at approximately 860 psi. While the carbonation was successful and calcite formation was strong on

Calcium hydroxide carbonation processes were studied to investigate the potential for abiotic soil improvement. Different mixtures of common soil constituents such as sand, clay, and granite were mixed with a calcium hydroxide slurry and carbonated at approximately 860 psi. While the carbonation was successful and calcite formation was strong on sample exteriors, a 4 mm passivating boundary layer effect was observed, impeding the carbonation process at the center. XRD analysis was used to characterize the extent of carbonation, indicating extremely poor carbonation and therefore CO2 penetration inside the visible boundary. The depth of the passivating layer was found to be independent of both time and choice of aggregate. Less than adequate strength was developed in carbonated trials due to formation of small, weakly-connected crystals, shown with SEM analysis. Additional research, especially in situ analysis with thermogravimetric analysis would be useful to determine the causation of poor carbonation performance. This technology has great potential to substitute for certain Portland cement applications if these issues can be addressed.
ContributorsHermens, Stephen Edward (Author) / Bearat, Hamdallah (Thesis director) / Dai, Lenore (Committee member) / Mobasher, Barzin (Committee member) / Barrett, The Honors College (Contributor) / Chemical Engineering Program (Contributor)
Created2015-05
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Description
Carbon capture is an essential way to reduce greenhouse gas emissions. One way to decrease the emissions is through the use of adsorbents such as zeolites. Dr. Dong-Kyun Seo’s group (School of Molecular Sciences, Arizona State University) synthesized the nanostructured faujasite (NaX). The zeolite was characterized using Scanning Electron Microscopy

Carbon capture is an essential way to reduce greenhouse gas emissions. One way to decrease the emissions is through the use of adsorbents such as zeolites. Dr. Dong-Kyun Seo’s group (School of Molecular Sciences, Arizona State University) synthesized the nanostructured faujasite (NaX). The zeolite was characterized using Scanning Electron Microscopy (SEM) and the physisorption properties were determined using ASAP 2020. ASAP 2020 tests of the nano-zeolite pellets at 77K in a liquid N2 bath determined the BET surface area of 547.1 m2/mol, T-plot micropore volume of 0.2257 cm3/g, and an adsorption average pore width of 5.9 Å. The adsorption isotherm (equilibrium) of CH4, N2, and CO2 were measured at 25ºC. Adsorption isotherm experiments concluded that the linear isotherm was the best fit for N2, and CH4 and the Sips isotherm was a better fit than the Langmuir and Freundlich isotherm for CO2. At 25ºC and 1 atm the zeolite capacity for CO2 is 4.3339 mmol/g, 0.1948 mmol/g for CH4, and 0.3534 mmol/g for N2. The zeolite has a higher CO2 capacity than the conventional NaX zeolite. Breakthrough experiments were performed in a fixed bed 22in, 0.5 in packing height and width at 1 atm and 298 K with nano-zeolite pellets. The gas chromatographer tested and recorded the data every two minutes with a flow rate of 10 cm3/min for N2 and 10 cm3/min CO2. Breakthrough simulations of the zeolite in a fixed bed adsorber column were conducted on MATLAB utilizing varying pressures, flow rates, and fed ratios of various CO2, N2 and CH4. Simulations using ideal adsorbed solution theory (IAST) calculations determined that the selectivity of CO2 in flue gas (15% CO2 + 85% N2) is 571.79 at 1 MPa, significantly higher than commercial zeolites and literature. The nanostructured faujasite zeolite appears to be a very promising adsorbent for CO2/N2 capture from flue gas and the separation of CO2/N2.
ContributorsClark, Krysta D. (Author) / Deng, Shuguang (Thesis director) / Green, Matthew (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2018-05
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Description
The recovery of biofuels permits renewable alternatives to present day fossil fuels that cause devastating effects on the planet. Pervaporation is a separation process that shows promise for the separation of ethanol from biologically fermentation broths. The performance of thin film composite membranes of polydimethylsiloxane (PDMS) and zeolite imidazolate frameworks

The recovery of biofuels permits renewable alternatives to present day fossil fuels that cause devastating effects on the planet. Pervaporation is a separation process that shows promise for the separation of ethanol from biologically fermentation broths. The performance of thin film composite membranes of polydimethylsiloxane (PDMS) and zeolite imidazolate frameworks (ZIF-71) dip coated onto a porous substrate are analyzed. Pervaporation performance factors of flux, separation factor and selectivity are measured for varying ZIF-71 loadings of pure PDMS, 5 wt%, 12.5 wt% and 25 wt% at 60 oC with a 2 wt% ethanol/water feed. The increase in ZIF-71 loadings increased the performance of PDMS to produce higher flux, higher separation factor and high selectivity than pure polymeric films.
ContributorsLau, Ching Yan (Author) / Lind, Mary Laura (Thesis director) / Durgun, Pinar Cay (Committee member) / Lively, Ryan (Committee member) / Barrett, The Honors College (Contributor) / School of International Letters and Cultures (Contributor) / Chemical Engineering Program (Contributor)
Created2014-05
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Description
In this research, construction of a model membrane system using Polyvinylidene Chloride-Co Acrylonitrile and Linde Type A zeolites is described. The systems aims to separate out flow through zeolite pores and flow through interfaces between zeolites and polymers through the use of pore filled and pore open zeolites. Permeation tests

In this research, construction of a model membrane system using Polyvinylidene Chloride-Co Acrylonitrile and Linde Type A zeolites is described. The systems aims to separate out flow through zeolite pores and flow through interfaces between zeolites and polymers through the use of pore filled and pore open zeolites. Permeation tests and salt rejection tests were performed, and the data analyzed to yield approximation of separated flow through zeolites and interfaces. This work concludes the more work is required to bring the model system into a functioning state. New polymer selections and new techniques to produce the membrane system are described for future work.
ContributorsShabilla, Andrew Daniel (Author) / Lind, Mary Laura (Thesis director) / Lin, Jerry (Committee member) / Barrett, The Honors College (Contributor) / Chemical Engineering Program (Contributor)
Created2014-05