Matching Items (13)
Filtering by
- All Subjects: chemical engineering
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
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
Lithium ion batteries have emerged as the most popular energy storage system, but they pose safety issues under extreme temperatures or in the event of a thermal runaway. Lithium ion batteries with inorganic separators offer the advantage of safer operation. An inorganic separator for lithium ion battery was prepared by an improved method of blade coating α-Al2O3 slurry directly on the electrode followed by drying. The improved separator preparation involves a twice-coating process instead of coating the slurry all at once in order to obtain a thin (~40 µm) and uniform coat. It was also found that α-Al2O3 powder with particle size greater than the pore size in the electrode is preferable for obtaining a separator with 40 µm thickness and consistent cell performance. Unlike state-of-the-art polyolefin separators such as polypropylene (PP) which are selectively wettable with only certain electrolytes, the excellent electrolyte solvent wettability of α-Al2O3 allows the coated alumina separator to function with different electrolytes. The coated α-Al2O3 separator has a much higher resistance to temperature effects than its polyolefin counterparts, retaining its dimensional integrity at temperatures as high as 200ºC. This eliminates the possibility of a short circuit during thermal runaway. Lithium ion batteries assembled as half-cells and full cells with coated α-Al2O3 separator exhibit electrochemical performance comparable with that of polyolefin separators at room temperature. However, the cells with coated alumina separator shows better cycling performance under extreme temperatures in the temperature range of -30°C to 60°C. Therefore, the coated α-Al2O3 separator is very promising for application in safe lithium-ion batteries.
ContributorsSharma, Gaurav (Author) / Lin, Jerry Y.S. (Thesis advisor) / Chan, Candace (Committee member) / Kannan, Arunachala (Committee member) / Arizona State University (Publisher)
Created2016
Description
Organic optoelectronics include a class of devices synthesized from carbon containing ‘small molecule’ thin films without long range order crystalline or polymer structure. Novel properties such as low modulus and flexibility as well as excellent device performance such as photon emission approaching 100% internal quantum efficiency have accelerated research in this area substantially. While optoelectronic organic light emitting devices have already realized commercial application, challenges to obtain extended lifetime for the high energy visible spectrum and the ability to reproduce natural white light with a simple architecture have limited the value of this technology for some display and lighting applications. In this research, novel materials discovered from a systematic analysis of empirical device data are shown to produce high quality white light through combination of monomer and excimer emission from a single molecule: platinum(II) bis(methyl-imidazolyl)toluene chloride (Pt-17). Illumination quality achieved Commission Internationale de L’Éclairage (CIE) chromaticity coordinates (x = 0.31, y = 0.38) and color rendering index (CRI) > 75. Further optimization of a device containing Pt-17 resulted in a maximum forward viewing power efficiency of 37.8 lm/W on a plain glass substrate. In addition, accelerated aging tests suggest high energy blue emission from a halogen-free cyclometalated platinum complex could demonstrate degradation rates comparable to known stable emitters. Finally, a buckling based metrology is applied to characterize the mechanical properties of small molecule organic thin films towards understanding the deposition kinetics responsible for an elastic modulus that is both temperature and thickness dependent. These results could contribute to the viability of organic electronic technology in potentially flexible display and lighting applications. The results also provide insight to organic film growth kinetics responsible for optical, mechanical, and water uptake properties relevant to engineering the next generation of optoelectronic devices.
ContributorsBakken, Nathan (Author) / Li, Jian (Thesis advisor) / Dai, Lenore (Thesis advisor) / Adams, James (Committee member) / Alford, Terry (Committee member) / Lind, Mary (Committee member) / Arizona State University (Publisher)
Created2017
Description
Lithium ion batteries prepared with a ceramic separator, have proven to possess improved safety, reliability as well as performance characteristics when compared to those with polymer separators which are prone to thermal runaway. Purely inorganic separators are highly brittle and expensive. The electrode-supported ceramic separator permits thinner separators which are a lot more flexible in comparison. In this work, it was observed that not any α-alumina could be used by the blade coating process to get a good quality separator on Li4Ti5O12 (LTO) electrode. In this work specifically, the effect of particle size of α-alumina, on processability of slurry was investigated. The effect of the particle size variations on quality of separator formation was also studied. Most importantly, the effect of alumina particle size and its distribution on the performance of LTO/Li half cells is examined in detail. Large-sized particles were found to severely limit the ability to fabricate such separators. The α-alumina slurry was coated onto electrode substrate, leading to possible interaction between α-alumina and LTO substrate. The interaction between submicron sized particles of α-alumina with the substrate electrode pores, was found to affect the performance and the stability of the separator. Utilizing a bimodal distribution of submicron sized particles with micron sized particles of α-alumina to prepare the separator, improved cell performance was observed. Yet only a specific ratio of bimodal distribution achieved good results both in terms of separator formation and resulting cell performance. The interaction of α-alumina and binder in the separator, and its effect on the performance of substrate electrode was investigated, to understand the need for bimodal distribution of powder forming the separator.
ContributorsKanhere, Narayan Vishnu (Author) / Lin, Jerry Y. S. (Thesis advisor) / Kannan, Arunachala (Committee member) / Chan, Candace (Committee member) / Arizona State University (Publisher)
Created2017
Description
Of the potential technologies for pre-combustion capture, membranes offer the advantages of being temperature resistant, able to handle large flow rates, and having a relatively small footprint. A significant amount of research has centered on the use of polymeric and microporous inorganic membranes to separate CO2. These membranes, however, have limitations at high temperature resulting in poor permeation performance. To address these limitations, the use of a dense dual-phase membrane has been studied. These membranes are composed of conductive solid and conductive liquid phases that have the ability to selectively permeate CO2 by forming carbonate ions that diffuse through the membrane at high temperature. The driving force for transport through the membrane is a CO2 partial pressure gradient. The membrane provides a theoretically infinite selectivity. To address stability of the ceramic-carbonate dual-phase membrane for CO2 capture at high temperature, the ceramic phase of the membrane was studied and replaced with materials previously shown to be stable in harsh conditions. The permeation properties and stability of La0.6Sr0.4Co0.8Fe0.2O3-δ (LSCF)-carbonate, La0.85Ce0.1Ga0.3Fe0.65Al0.05O3-δ (LCGFA)-carbonate, and Ce0.8Sm0.2O1.9 (SDC)-carbonate membranes were examined under a wide range of experimental conditions at high temperature. LSCF-carbonate membranes were shown to be unstable without the presence of O2 due to reaction of CO2 with the ceramic phase. In the presence of O2, however, the membranes showed stable permeation behavior for more than one month at 900oC. LCGFA-carbonate membranes showed great chemical and permeation stability in the presence of various conditions including exposure to CH4 and H2, however, the permeation performance was quite low when compared to membranes in the literature. Finally, SDC-carbonate membranes showed great chemical and permeation stability both in a CO2:N2 environment for more than two weeks at 900oC as well as more than one month of exposure to simulated syngas conditions at 700oC. Ceramic phase chemical stability increased in the order of LSCF < LCGFA < SDC while permeation performance increased in the order of LCGFA < LSCF < SDC.
ContributorsNorton, Tyler (Author) / Lin, Jerry Y.S. (Thesis advisor) / Alford, Terry (Committee member) / Lind, Mary Laura (Committee member) / Smith, David (Committee member) / Torres, Cesar (Committee member) / Arizona State University (Publisher)
Created2013
Description
ABSTRACT
Large-pore metal-organic framework (MOF) membranes offer potential in a number of gas and liquid separations due to their wide and selective adsorption capacities. A key characteristic of a number of MOF and zeolitic imidazolate framework (ZIF) membranes is their highly selective adsorption capacities for CO2. These membranes offer very tangible potential to separate CO2 in a wide array of industrially relevant separation processes, such as the separation from CO2 in flue gas emissions, as well as the sweetening of methane.
By virtue of this, the purpose of this dissertation is to synthesize and characterize two linear large-pore MOF membranes, MOF-5 and ZIF-68, and to study their gas separation properties in binary mixtures of CO¬2/N2 and CO2/CH4. The three main objectives researched are as follows. The first is to study the pervaporation behavior and stability of MOF-5; this is imperative because although MOF-5 exhibits desirable adsorption and separation characteristics, it is very unstable in atmospheric conditions. In determining its stability and behavior in pervaporation, this material can be utilized in conditions wherein atmospheric levels of moisture can be avoided. The second objective is to synthesize, optimize and characterize a linear, more stable MOF membrane, ZIF-68. The final objective is to study in tandem the high-pressure gas separation behavior of MOF-5 and ZIF-68 in binary gas systems of both CO2/N2 and CO2/CH4.
Continuous ZIF-68 membranes were synthesized via the reactive seeding method and the modified reactive seeding method. These membranes, as with the MOF-5 membranes synthesized herein, both showed adherence to Knudsen diffusion, indicating limited defects. Organic solvent experiments indicated that MOF-5 and ZIF-68 were stable in a variety of organic solvents, but both showed reductions in permeation flux of the tested molecules. These reductions were attributed to fouling and found to be cumulative up until a saturation of available bonding sites for molecules was reached and stable pervaporation permeances were reached for both. Gas separation behavior for MOF-5 showed direct dependence on the CO2 partial pressure and the overall feed pressure, while ZIF-68 did not show similar behavior. Differences in separation behavior are attributable to orientation of the ZIF-68 membranes.
Large-pore metal-organic framework (MOF) membranes offer potential in a number of gas and liquid separations due to their wide and selective adsorption capacities. A key characteristic of a number of MOF and zeolitic imidazolate framework (ZIF) membranes is their highly selective adsorption capacities for CO2. These membranes offer very tangible potential to separate CO2 in a wide array of industrially relevant separation processes, such as the separation from CO2 in flue gas emissions, as well as the sweetening of methane.
By virtue of this, the purpose of this dissertation is to synthesize and characterize two linear large-pore MOF membranes, MOF-5 and ZIF-68, and to study their gas separation properties in binary mixtures of CO¬2/N2 and CO2/CH4. The three main objectives researched are as follows. The first is to study the pervaporation behavior and stability of MOF-5; this is imperative because although MOF-5 exhibits desirable adsorption and separation characteristics, it is very unstable in atmospheric conditions. In determining its stability and behavior in pervaporation, this material can be utilized in conditions wherein atmospheric levels of moisture can be avoided. The second objective is to synthesize, optimize and characterize a linear, more stable MOF membrane, ZIF-68. The final objective is to study in tandem the high-pressure gas separation behavior of MOF-5 and ZIF-68 in binary gas systems of both CO2/N2 and CO2/CH4.
Continuous ZIF-68 membranes were synthesized via the reactive seeding method and the modified reactive seeding method. These membranes, as with the MOF-5 membranes synthesized herein, both showed adherence to Knudsen diffusion, indicating limited defects. Organic solvent experiments indicated that MOF-5 and ZIF-68 were stable in a variety of organic solvents, but both showed reductions in permeation flux of the tested molecules. These reductions were attributed to fouling and found to be cumulative up until a saturation of available bonding sites for molecules was reached and stable pervaporation permeances were reached for both. Gas separation behavior for MOF-5 showed direct dependence on the CO2 partial pressure and the overall feed pressure, while ZIF-68 did not show similar behavior. Differences in separation behavior are attributable to orientation of the ZIF-68 membranes.
ContributorsKasik, Alexandra Marie (Author) / Lin, Jerry (Thesis advisor) / Tasooji, Amaneh (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2015
Description
Soft materials are matters that can easily deform from their original shapes and structures under thermal or mechanical stresses, and they range across various groups of materials including liquids, foams, gels, colloids, polymers, and biological substances. Although soft materials already have numerous applications with each of their unique characteristics, integrating materials to achieve complementary functionalities is still a growing need for designing advanced applications of complex requirements. This dissertation explores a unique approach of utilizing intermolecular interactions to accomplish not only the multifunctionality from combined materials but also their tailored properties designed for specific tasks. In this work, multifunctional soft materials are explored in two particular directions, ionic liquids (ILs)-based mixtures and interpenetrating polymer network (IPN).
First, ILs-based mixtures were studied to develop liquid electrolytes for molecular electronic transducers (MET) in planetary exploration. For space missions, it is challenging to operate any liquid electrolytes in an extremely low-temperature environment. By tuning intermolecular interactions, the results demonstrated a facile method that has successfully overcome the thermal and transport barriers of ILs-based mixtures at extremely low temperatures. Incorporation of both aqueous and organic solvents in ILs-based electrolyte systems with varying types of intermolecular interactions are investigated, respectively, to yield optimized material properties supporting not only MET sensors but also other electrochemical devices with iodide/triiodide redox couple targeting low temperatures.
Second, an environmentally responsive hydrogel was synthesized via interpenetrating two crosslinked polymer networks. The intermolecular interactions facilitated by such an IPN structure enables not only an upper critical solution temperature (UCST) transition but also a mechanical enhancement of the hydrogel. The incorporation of functional units validates a positive swelling response to visible light and also further improves the mechanical properties. This studied IPN system can serve as a promising route in developing “smart” hydrogels utilizing visible light as a simple, inexpensive, and remotely controllable stimulus.
Over two directions across from ILs to polymeric networks, this work demonstrates an effective strategy of utilizing intermolecular interactions to not only develop multifunctional soft materials for advanced applications but also discover new properties beyond their original boundaries.
First, ILs-based mixtures were studied to develop liquid electrolytes for molecular electronic transducers (MET) in planetary exploration. For space missions, it is challenging to operate any liquid electrolytes in an extremely low-temperature environment. By tuning intermolecular interactions, the results demonstrated a facile method that has successfully overcome the thermal and transport barriers of ILs-based mixtures at extremely low temperatures. Incorporation of both aqueous and organic solvents in ILs-based electrolyte systems with varying types of intermolecular interactions are investigated, respectively, to yield optimized material properties supporting not only MET sensors but also other electrochemical devices with iodide/triiodide redox couple targeting low temperatures.
Second, an environmentally responsive hydrogel was synthesized via interpenetrating two crosslinked polymer networks. The intermolecular interactions facilitated by such an IPN structure enables not only an upper critical solution temperature (UCST) transition but also a mechanical enhancement of the hydrogel. The incorporation of functional units validates a positive swelling response to visible light and also further improves the mechanical properties. This studied IPN system can serve as a promising route in developing “smart” hydrogels utilizing visible light as a simple, inexpensive, and remotely controllable stimulus.
Over two directions across from ILs to polymeric networks, this work demonstrates an effective strategy of utilizing intermolecular interactions to not only develop multifunctional soft materials for advanced applications but also discover new properties beyond their original boundaries.
ContributorsXu, Yifei (Author) / Dai, Lenore L. (Thesis advisor) / Forzani, Erica (Committee member) / Holloway, Julianne (Committee member) / Jiang, Hanqing (Committee member) / Zhuang, Houlong (Committee member) / Arizona State University (Publisher)
Created2020