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- Creators: Barrett, The Honors College
Description
Membrane-based gas separation is promising for efficient propylene/propane (C3H6/C3H8) separation with low energy consumption and minimum environment impact. Two microporous inorganic membrane candidates, MFI-type zeolite membrane and carbon molecular sieve membrane (CMS) have demonstrated excellent thermal and chemical stability. Application of these membranes into C3H6/C3H8 separation has not been well investigated. This dissertation presents fundamental studies on membrane synthesis, characterization and C3H6/C3H8 separation properties of MFI zeolite membrane and CMS membrane.
MFI zeolite membranes were synthesized on α-alumina supports by secondary growth method. Novel positron annihilation spectroscopy (PAS) techniques were used to non-destructively characterize the pore structure of these membranes. PAS reveals a bimodal pore structure consisting of intracrystalline zeolitic micropores of ~0.6 nm in diameter and irregular intercrystalline micropores of 1.4 to 1.8 nm in size for the membranes. The template-free synthesized membrane exhibited a high permeance but a low selectivity in C3H6/C3H8 mixture separation.
CMS membranes were synthesized by coating/pyrolysis method on mesoporous γ-alumina support. Such supports allow coating of thin, high-quality polymer films and subsequent CMS membranes with no infiltration into support pores. The CMS membranes show strong molecular sieving effect, offering a high C3H6/C3H8 mixture selectivity of ~30. Reduction in membrane thickness from 500 nm to 300 nm causes an increase in C3H8 permeance and He/N2 selectivity, but a decrease in the permeance of He, N2 and C3H6 and C3H6/C3H8 selectivity. This can be explained by the thickness dependent chain mobility of the polymer film resulting in final carbon membrane of reduced pore size with different effects on transport of gas of different sizes, including possible closure of C3H6-accessible micropores.
CMS membranes demonstrate excellent C3H6/C3H8 separation performance over a wide range of feed pressure, composition and operation temperature. No plasticization was observed at a feed pressure up to 100 psi. The permeation and separation is mainly controlled by diffusion instead of adsorption. CMS membrane experienced a decline in permeance, and an increase in selectivity over time under on-stream C3H6/C3H8 separation. This aging behavior is due to the reduction in effective pore size and porosity caused by oxygen chemisorption and physical aging of the membrane structure.
MFI zeolite membranes were synthesized on α-alumina supports by secondary growth method. Novel positron annihilation spectroscopy (PAS) techniques were used to non-destructively characterize the pore structure of these membranes. PAS reveals a bimodal pore structure consisting of intracrystalline zeolitic micropores of ~0.6 nm in diameter and irregular intercrystalline micropores of 1.4 to 1.8 nm in size for the membranes. The template-free synthesized membrane exhibited a high permeance but a low selectivity in C3H6/C3H8 mixture separation.
CMS membranes were synthesized by coating/pyrolysis method on mesoporous γ-alumina support. Such supports allow coating of thin, high-quality polymer films and subsequent CMS membranes with no infiltration into support pores. The CMS membranes show strong molecular sieving effect, offering a high C3H6/C3H8 mixture selectivity of ~30. Reduction in membrane thickness from 500 nm to 300 nm causes an increase in C3H8 permeance and He/N2 selectivity, but a decrease in the permeance of He, N2 and C3H6 and C3H6/C3H8 selectivity. This can be explained by the thickness dependent chain mobility of the polymer film resulting in final carbon membrane of reduced pore size with different effects on transport of gas of different sizes, including possible closure of C3H6-accessible micropores.
CMS membranes demonstrate excellent C3H6/C3H8 separation performance over a wide range of feed pressure, composition and operation temperature. No plasticization was observed at a feed pressure up to 100 psi. The permeation and separation is mainly controlled by diffusion instead of adsorption. CMS membrane experienced a decline in permeance, and an increase in selectivity over time under on-stream C3H6/C3H8 separation. This aging behavior is due to the reduction in effective pore size and porosity caused by oxygen chemisorption and physical aging of the membrane structure.
ContributorsMa, Xiaoli (Author) / Lin, Jerry (Thesis advisor) / Alford, Terry (Committee member) / Chan, Candace (Committee member) / Arizona State University (Publisher)
Created2015
Description
Emission of CO2 into the atmosphere has become an increasingly concerning issue as we progress into the 21st century Flue gas from coal-burning power plants accounts for 40% of all carbon dioxide emissions. The key to successful separation and sequestration is to separate CO2 directly from flue gas (10-15% CO2, 70% N2), which can range from a few hundred to as high as 1000°C. Conventional microporous membranes (carbons/silicas/zeolites) are capable of separating CO2 from N2 at low temperatures, but cannot achieve separation above 200°C. To overcome the limitations of microporous membranes, a novel ceramic-carbonate dual-phase membrane for high temperature CO2 separation was proposed. The membrane was synthesized from porous La0.6Sr0.4Co0.8Fe0.2O3-d (LSCF) supports and infiltrated with molten carbonate (Li2CO3/Na2CO3/K2CO3). The CO2 permeation mechanism involves a reaction between CO2 (gas phase) and O= (solid phase) to form CO3=, which is then transported through the molten carbonate (liquid phase) to achieve separation. The effects of membrane thickness, temperature and CO2 partial pressure were studied. Decreasing thickness from 3.0 to 0.375 mm led to higher fluxes at 900°C, ranging from 0.186 to 0.322 mL.min-1.cm-2 respectively. CO2 flux increased with temperature from 700 to 900°C. Activation energy for permeation was similar to that for oxygen ion conduction in LSCF. For partial pressures above 0.05 atm, the membrane exhibited a nearly constant flux. From these observations, it was determined that oxygen ion conductivity limits CO2 permeation and that the equilibrium oxygen vacancy concentration in LSCF is dependent on the partial pressure of CO2 in the gas phase. Finally, the dual-phase membrane was used as a membrane reactor. Separation at high temperatures can produce warm, highly concentrated streams of CO2 that could be used as a chemical feedstock for the synthesis of syngas (H2 + CO). Towards this, three different membrane reactor configurations were examined: 1) blank system, 2) LSCF catalyst and 3) 10% Ni/y-alumina catalyst. Performance increased in the order of blank system < LSCF catalyst < Ni/y-alumina catalyst. Favorable conditions for syngas production were high temperature (850°C), low sweep gas flow rate (10 mL.min-1) and high methane concentration (50%) using the Ni/y-alumina catalyst.
ContributorsAnderson, Matthew Brandon (Author) / Lin, Jerry (Thesis advisor) / Alford, Terry (Committee member) / Rege, Kaushal (Committee member) / Anderson, James (Committee member) / Rivera, Daniel (Committee member) / Arizona State University (Publisher)
Created2011
Description
This work demonstrates a capable reverse pulse deposition methodology to influence gap fill behavior inside microvia along with a uniform deposit in the fine line patterned regions for substrate packaging applications. Interconnect circuitry in IC substrate packages comprises of stacked microvia that varies in depth from 20µm to 100µm with an aspect ratio of 0.5 to 1.5 and fine line patterns defined by photolithography. Photolithography defined pattern regions incorporate a wide variety of feature sizes including large circular pad structures with diameter of 20µm - 200µm, fine traces with varying widths of 3µm - 30µm and additional planar regions to define a IC substrate package. Electrodeposition of copper is performed to establish the desired circuit. Electrodeposition of copper in IC substrate applications holds certain unique challenges in that they require a low cost manufacturing process that enables a void-free gap fill inside the microvia along with uniform deposition of copper on exposed patterned regions. Deposition time scales to establish the desired metal thickness for such packages could range from several minutes to few hours. This work showcases a reverse pulse electrodeposition methodology that achieves void-free gap fill inside the microvia and uniform plating in FLS (Fine Lines and Spaces) regions with significantly higher deposition rates than traditional approaches. In order to achieve this capability, systematic experimental and simulation studies were performed. A strong correlation of independent parameters that govern the electrodeposition process such as bath temperature, reverse pulse plating parameters and the ratio of electrolyte concentrations is shown to the deposition kinetics and deposition uniformity in fine patterned regions and gap fill rate inside the microvia. Additionally, insight into the physics of via fill process is presented with secondary and tertiary current simulation efforts. Such efforts lead to show “smart” control of deposition rate at the top and bottom of via to avoid void formation. Finally, a parametric effect on grain size and the ensuing copper metallurgical characteristics of bulk copper is also shown to enable high reliability substrate packages for the IC packaging industry.
ContributorsGanesan, Kousik (Author) / Tasooji, Amaneh (Thesis advisor) / Manepalli, Rahul (Committee member) / Alford, Terry (Committee member) / Chan, Candace (Committee member) / Arizona State University (Publisher)
Created2018
Targeting Tumors: Inclusion of Functional Groups on Ion-Containing Block Copolymers to Combat Cancer
Description
This research attempts to determine the most effective method of synthesizing a peptide such that it can be utilized as a targeting moiety for polymeric micelles. Two melanoma-associated peptides with high in vitro and in vivo binding affinity for TNF receptors have been identified and synthesized. Matrix Assisted Laser Desorption/Ionization-Time of Flight Mass Spectrometry (MALDI-ToF) was used to help verify the structure of both peptides, which were purified using Reversed-Phase High Performance Liquid Chromatography (RP-HPLC). The next steps in the research are to attach the peptides to a micelle and determine their impact on micelle stability.
ContributorsMoe, Anna Marguerite (Author) / Green, Matthew (Thesis director) / Jones, Anne (Committee member) / Sullivan, Millicent (Committee member) / Chemical Engineering Program (Contributor) / School of International Letters and Cultures (Contributor) / Sandra Day O'Connor College of Law (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05
Description
The mechanisms of extracellular respiration in Geobacter sulfurreducens, commonly considered to be a model organism for anode respiration, are yet to be completely understood. The interplay between electron and proton transport especially could be a key to gaining further insights. One way to investigate the mechanisms of extracellular respiration under varying environmental conditions is by analyzing the electrochemical response of the biofilm with respect to pH, buffer concentrations, and acetate concentrations. I seek to increase the understanding of the electrochemical response of the G. sulfurreducens biofilm through electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) techniques in concert with chronoamperometry. I used Geobacter sulfurreducens PCA biofilms in single-chamber electrochemical cells (approximately 100 mL volume) with a small gold working electrode (3.14 mm2). I observed limitations in the initial methods used for media replacement. I tracked changes in the CV data, such as EKA (midpoint potential), as a function of pH and buffer concentration. The media replacement method developed demonstrates success in pH experiments that will be transferrable to other environmental conditions to study electron transport. The experiments revealed that the clarity of data collected is dependent on the quality of the biofilm. A high quality biofilm is characterized by a high current density and normal growth behavior. The general trends seen in these experiments are that as pH increases the potential decreases, and as buffer concentration increases the potential decreases and pH increases. Acetate-free conditions in the reactor were unable to be achieved as characterized by non-zero current densities in the acetate-free experiments.
ContributorsHolzer, Denton Gene (Author) / Torres, Cesar (Thesis director) / Popat, Sudeep (Committee member) / Yoho, Rachel (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05
Description
Lithium-ion batteries are the predominant source of electrical energy storage for most portable electronics applications, including hybrid/electric vehicles, laptops, and cellular phones. However, these batteries pose safety concerns due to their flammability and tendency to violently ignite upon short circuiting or failing. Solid electrolytes are a current research development aimed at reducing the flammability and reactivity of lithium batteries. The compound Li7La3Zr2O12, or LLZO, exhibits satisfactory ionic conductivity in the cubic phase, which is normally synthesized via doping with Al. It has recently been discovered that synthesizing nanostructured LLZO can stabilize the cubic phase without the need for doping. Here nanostructured LLZO was formed using templating on various cellulosic fibers, including cotton fibers, printer paper, filter paper, and nanocellulose fibrils followed by calcination at 700-800 °C. The effect of templating material, calcination temperature, calcination time, and heating ramp rate on LLZO phase and morphology was thoroughly investigated. Templating was determined to be an effective method for controlling the LLZO size and morphology, and most templating experiments resulted in LLZO fibers or ligaments similar in size and morphology to the original template material. A systematic study on the various experimental parameters was performed, concluding that low calcination time and low ramp rate favored smaller ligament formation. Further, it was verified that cubic phase stabilization occurred for LLZO with ligaments of less than 1 micron on average without the use of doping. This research provides more information regarding the size dependence on cubic LLZO stabilization that has not been previously investigated in detail.
ContributorsGordon, Zachary Daniel (Author) / Chan, Candace K. (Thesis director) / Lin, Jerry (Committee member) / Barrett, The Honors College (Contributor) / School of Mathematical and Statistical Sciences (Contributor) / Chemical Engineering Program (Contributor)
Created2015-05
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 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
Description
In our modern world the source of for many chemicals is to acquire and refine oil. This process is becoming an expensive to the environment and to human health. Alternative processes for acquiring the final product have been developed but still need work. One product that is valuable is butanol. The normal process for butanol production is very intensive but there is a method to produce butanol from bacteria. This process is better because it is more environmentally safe than using oil. One problem however is that when the bacteria produce too much butanol it reaches the toxicity limit and stops the production of butanol. In order to keep butanol from reaching the toxicity limit an adsorbent is used to remove the butanol without harming the bacteria. The adsorbent is a mesoporous carbon powder that allows the butanol to be adsorbed on it. This thesis explores different designs for a magnetic separation process to extract the carbon powder from the culture.
ContributorsChabra, Rohin (Author) / Nielsen, David (Thesis director) / Torres, Cesar (Committee member) / Barrett, The Honors College (Contributor) / Chemical Engineering Program (Contributor)
Created2015-05
Description
One of the primary bottlenecks to chemical production in biological organisms is the toxicity of the chemical. Overexpression of efflux pumps has been shown to increase tolerance to aromatic compounds such as styrene and styrene oxide. Tight control of pump expression is necessary to maximize titers and prevent excessive strain on the cells. This study aimed to identify aromatic-sensitive native promoters and heterologous biosensors for construction of closed-loop control of efflux pump expression in E. coli. Using a promoter library constructed by Zaslaver et al., activation was measured through GFP output. Promoters were evaluated for their sensitivity to the addition of one of four aromatic compounds, their "leaking" of signal, and their induction threshold. Out of 43 targeted promoters, 4 promoters (cmr, mdtG, yahN, yajR) for styrene oxide, 2 promoters (mdtG, yahN) for styrene, 0 promoters for 2-phenylethanol, and 1 promoter for phenol (pheP) were identified as ideal control elements in aromatic bioproduction. In addition, a series of three biosensors (NahR, XylS, DmpR) known to be inducible by other aromatics were screened against styrene oxide, 2-phenylethanol, and phenol. The targeted application of these biosensors is aromatic-induced activation of linked efflux pumps. All three biosensors responded strongly in the presence of styrene oxide and 2-phenylethanol, with minor activation in the presence of phenol. Bioproduction of aromatics continues to gain traction in the biotechnology industry, and the continued discovery of aromatic-inducible elements will be essential to effective pathway control.
ContributorsXu, Jimmy (Author) / Nielsen, David (Thesis director) / Wang, Xuan (Committee member) / School of Life Sciences (Contributor) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2018-05
Description
Asymmetric polystyrene-gold composite particles are successfully synthesized alongside core-shell composite particles via a one-step Pickering emulsion polymerization method. Unlike core-shell particles which form in the droplet phase of a stabilized Pickering emulsion, asymmetric particles form via a seeded growth mechanism. These composite particles act as catalysts with higher recyclability than pure gold nanoparticles due to reduced agglomeration. With the addition of N-isopropylacrylamide (NIPAAM) monomers, temperature-responsive asymmetric and core-shell polystyrene/poly(N-isopropylacrylamide)-gold composite particles are also synthesized via Pickering emulsion polymerization. The asymmetric particles have a greater thermo-responsiveness than the core-shell particles due to the increased presence of NIPAAM monomers in the seeded-growth formation. Poly(N-isopropylacrylamide) (PNIPAM)-containing asymmetric particles have tunable rheological and optical properties due to their significant size decrease above the lower critical solution temperature (LCST).
ContributorsRabiah, Noelle Ibrahim (Author) / Dai, Lenore (Thesis director) / Torres, Cesar (Committee member) / Zhang, Mingmeng (Committee member) / Barrett, The Honors College (Contributor) / Chemical Engineering Program (Contributor)
Created2014-05