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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
Dry and steam NanoBonding™ are conceived and researched to bond Si-based surfaces, via nucleation and growth of a two-dimensional SiOxHy or hydrated SiOxHy interphase connecting surfaces at the nanoscale across macroscopic domains. The motivation is to create strong, long lasting, hermetically bonded sensors with their electronics for the development

Dry and steam NanoBonding™ are conceived and researched to bond Si-based surfaces, via nucleation and growth of a two-dimensional SiOxHy or hydrated SiOxHy interphase connecting surfaces at the nanoscale across macroscopic domains. The motivation is to create strong, long lasting, hermetically bonded sensors with their electronics for the development of an artificial pancreas and to bond solar cells to glass panels for robust photovoltaic technology. The first step in NanoBonding™ is to synthesize smooth surfaces with 20 nm wide atomic terraces via a precursor phase, ß-cSiO2 on Si(100) and oxygen-deficient SiOx on the silica using the Herbots-Atluri process and Entrepix’s spin etching. Smooth precursor phases act as geometric and chemical template to nucleate and grow macroscopic contacting domains where cross bridging occurs via arrays of molecular strands in the hydrated SiOxHy interphase. Steam pressurization is found to catalyze NanoBonding™ consistently, eliminating the need for direct mechanical compression that limits the size and shape of wafers to be bonded in turn, reducing the cost of processing. Total surface energy measurements via 3 Liquids Contact Angle Analysis (3L CAA) enables accurate quantitative analysis of the total surface energy and each of its components. 3L CAA at each step in the process shows that surface energy drops to 42.4 ± 0.6 mJ/m2 from 57.5 ± 1.4 mJ/m2 after the Herbots-Atluri clean of an “As Received” wafer. 3L CAA after steam pressurization Nanobonding™ shows almost complete elimination from 13.8 mJ/m2 ± 1.0 to 0.002 ±- 0.0002 mJ/m2 in the contribution of acceptors to the total free surface energy, and an increase from 0.2 ± .03 to 23.8± 1.6 mJ/m2 in the contribution of donors. This is consistent with an increase in hydroxylation of the ß-cSiO2 surface as a consistent precursor phase for cross-bridging. This research optimizes the use of glycerin, water, and α-bromo-naphtalene in the use of 3L CAA to effectively quantify the components of total free surface energy which helps to better understand the most consistent method for NanoBonding™.
ContributorsBennett-Kennett, Ross Buchanan (Author) / Culbertson, Robert (Thesis director) / Herbots, Nicole (Committee member) / Foy, Joseph (Committee member) / Barrett, The Honors College (Contributor) / Materials Science and Engineering Program (Contributor) / Department of Physics (Contributor) / School of Historical, Philosophical and Religious Studies (Contributor)
Created2013-05
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Description
Proposed and tested were three different methods to deposit important layers of Silicon heterojunction solar cells (SHJs). If there were a shortage of Silver, Aluminum could be substituted for the contacts. If there were a shortage of Indium, Yttrium Zinc Oxide could be substituted. To improve the solar cell, the

Proposed and tested were three different methods to deposit important layers of Silicon heterojunction solar cells (SHJs). If there were a shortage of Silver, Aluminum could be substituted for the contacts. If there were a shortage of Indium, Yttrium Zinc Oxide could be substituted. To improve the solar cell, the p and n type layers can be grown with hydrogenated nanocrystallline Silicon (nc-Si:H). 40% and 50% nc-Si:H has shown a maximum absorbance reduction of 5 times compared to hydrogenated amorphous Silicon (a-Si). The substitutions offer alternatives which increase the total possible amount of solar cell production, advancing toward completion of the Terrawatt challenge.
ContributorsCarpenter, Joe Victor (Author) / Alford, Terry (Thesis director) / Holman, Zachary (Committee member) / Barrett, The Honors College (Contributor) / Chemical Engineering Program (Contributor) / Materials Science and Engineering Program (Contributor)
Created2014-05
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Description
Lithium-ion batteries are one of the most widely used energy storage solutions today. As renewable energy sources proliferate to meet growth in worldwide energy consumption, it is important that lithium-ion batteries be improved to help capture this energy for use when the demand arises. One way to boost the performance

Lithium-ion batteries are one of the most widely used energy storage solutions today. As renewable energy sources proliferate to meet growth in worldwide energy consumption, it is important that lithium-ion batteries be improved to help capture this energy for use when the demand arises. One way to boost the performance of lithium-ion batteries is to replace the electrode active materials with materials of higher specific capacity. Silicon is one material that has been widely touted as a potential replacement for the graphite used in commercial anodes with a theoretical capacity of 3500 mAh/g as opposed to graphite's 372 mAh/g. However, bulk silicon is known to pulverize after experiencing large strains during lithiation. Here, silicon clathrates are investigated as a potential structure for accommodation of these strains. Silicon clathrates consist of covalently bonded silicon host cages surrounding a guest alkali or alkaline earth metal ion. Previous work has looked at silicon clathrates for their superconducting and thermoelectric properties. In this study, electrochemical properties of type I and II silicon clathrates with sodium guest ions (NaxSi46 and NaxSi136) and type I silicon clathrates with copper framework substitution and barium guest ions (Ba8CuxSi46-x) are examined. Sodium clathrates showed very high capacities during initial lithiation (>2500 mAh/g), but rapidly lost capacity thereafter. X-ray diffraction after lithiation showed conversion of the clathrate phase to lithium silicide and then to amorphous silicon after delithiation, indicating destruction of the clathrate structure as a possible explanation for the rapid capacity fade. Ba8CuxSi46-x clathrates were found to have their structures completely intact after 50 cycles. However, they had very low reversible capacities (<100 mAh/g) and potentially might not be electrochemically active. Further work is needed to better understand exactly how lithium is inserted into clathrates and if copper impurities detected during wavelength-dispersive X-ray spectroscopy could be inhibiting lithium transport into the clathrates.
ContributorsWagner, Nicholas Adam (Author) / Chan, Candace (Thesis director) / Sieradzki, Karl (Committee member) / Barrett, The Honors College (Contributor) / Materials Science and Engineering Program (Contributor)
Created2014-05
Description
Acute Kidney Injury (AKI) may be detected through biomarkers in urine. This research is being done to develop a membrane for use in separating urine biomarkers to monitor their level. A hydrophobic membrane was treated to improve separation of the desired biomarker for colorimetric sensing. This method was tested with

Acute Kidney Injury (AKI) may be detected through biomarkers in urine. This research is being done to develop a membrane for use in separating urine biomarkers to monitor their level. A hydrophobic membrane was treated to improve separation of the desired biomarker for colorimetric sensing. This method was tested with model solutions containing the biomarker. Future work will extend to testing with real urine.
ContributorsBrown, Stephanie Ann (Author) / Lind, Mary Laura (Thesis director) / Yin, Huidan (Committee member) / Materials Science and Engineering Program (Contributor) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2017-05
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Description
Zeolite thin films and membranes are currently a promising technology for pervaporation, gas separation and water purification. The main drawback with these technologies is that the synthesis is not consistent leading to varied and unreproducible results. The Langmuir-Blodgett technique is a robust method for transferring monolayers of molecules or crystals

Zeolite thin films and membranes are currently a promising technology for pervaporation, gas separation and water purification. The main drawback with these technologies is that the synthesis is not consistent leading to varied and unreproducible results. The Langmuir-Blodgett technique is a robust method for transferring monolayers of molecules or crystals to a solid substrate. By measuring the surface pressure and controlling the area, reliable results can be achieved by transferring monolayers to different solid substrates. It has been shown previously that various types of zeolites can be functionalized and dispersed on the top of water. This is done by using an alcohol to form a hydrophobic coating on the surface of zeolite. The Langmuir-Blodgett can be used to create thin, compact films of zeolites for synthesizing and growing zeolite films. For the first reported time, cubic LTA Zeolites monolayers have been assembled with the Langmuir-Blodgett technique with multiple solvents and different sizes of zeolites. These films were characterized with Scanning Electron Microscopy and Pressure-Area Isotherms generated from the Langmuir-Blodgett. It was found that linoleic acid is a required addition to the zeolite dispersions to protect the mechanical stability during agitation. Without this addition, the LTA zeolites are broken apart and lose their characteristic cubic structure. This effect is discussed and a theory is presented that the interparticle interactions of the long alkane chain of the linoleic acid help reduce the shear stress on the individual zeolite particles, thus preventing them from being broken. The effect of size of the zeolites on the monolayer formation was also discussed. There seemed to be little correlation between the monolayer quality and formation as size was changed. However, to optimize the process, different concentrations and target pressures are needed. Lastly, the effect of the solvent was explored and it was found that there is a different between monolayer formations for different solvents likely due to differing interparticle interactions. Overall, LTA zeolites were successfully fabricated and the important factors to consider are the zeolite size, the solvent, and the amount of surfactant stabilizer added.
ContributorsDopilka, Andrew Michael (Author) / Lind, Mary Laura (Thesis director) / Cay, Pinar (Committee member) / Materials Science and Engineering Program (Contributor) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-12
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Description
Metal-organic frameworks (MOFs) are a new set of porous materials comprised of metals or metal clusters bonded together in a coordination system by organic linkers. They are becoming popular for gas separations due to their abilities to be tailored toward specific applications. Zirconium MOFs in particular are known for their

Metal-organic frameworks (MOFs) are a new set of porous materials comprised of metals or metal clusters bonded together in a coordination system by organic linkers. They are becoming popular for gas separations due to their abilities to be tailored toward specific applications. Zirconium MOFs in particular are known for their high stability under standard temperature and pressure due to the strength of the Zirconium-Oxygen coordination bond. However, the acid modulator needed to ensure long range order of the product also prevents complete linker deprotonation. This leads to a powder product that cannot easily be incorporated into continuous MOF membranes. This study therefore implemented a new bi-phase synthesis technique with a deprotonating agent to achieve intergrowth in UiO-66 membranes. Crystal intergrowth will allow for effective gas separations and future permeation testing. During experimentation, successful intergrown UiO-66 membranes were synthesized and characterized. The degree of intergrowth and crystal orientations varied with changing deprotonating agent concentration, modulator concentration, and ligand:modulator ratios. Further studies will focus on achieving the same results on porous substrates.
ContributorsClose, Emily Charlotte (Author) / Mu, Bin (Thesis director) / Shan, Bohan (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-12
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Description
One of the grand challenges of engineering is to provide access to clean water because it is predicted that by 2025 more than two thirds of the world’s population will face severe water shortages. To combat this global issue, our lab focuses on creating a novel composite membrane to

One of the grand challenges of engineering is to provide access to clean water because it is predicted that by 2025 more than two thirds of the world’s population will face severe water shortages. To combat this global issue, our lab focuses on creating a novel composite membrane to recover potable water from waste. For use as the water-selective component in this membrane design Linde Type A zeolites were synthesized for optimal size without the use of a template. Current template-free synthesis of zeolite LTA produces particles that are too large for our application therefore the particle size was reduced in this study to reduce fouling of the membrane while also investigating the nanoparticle synthesis mechanisms. The time and temperature of the reaction and the aging of the precursor gel were systematically modified and observed to determine the optimal conditions for producing the particles. Scanning electron microscopy, x-ray diffraction, and energy dispersive x-ray analysis were used for characterization. Sub-micron sized particles were synthesized at 2 weeks aging time at -8°C with an average size of 0.6 micrometers, a size suitable for our membrane. There is a limit to the posterity and uniformity of particles produced from modifying the reaction time and temperature. All results follow general crystallization theory. Longer aging produced smaller particles, consistent with nucleation theory. Spinodal decomposition is predicted to affect nucleation clustering during aging due to the temperature scheme. Efforts will be made to shorten the effective aging time and these particles will eventually be incorporated into our mixed matrix osmosis membrane.
ContributorsKing, Julia Ann (Author) / Lind, Mary Laura (Thesis director) / Durgun, Pinar Cay (Committee member) / Chemical Engineering Program (Contributor) / Materials Science and Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05