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- All Subjects: Materials Science
- All Subjects: Membranes (Technology)
- Status: Published
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
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
Description
Water recovery from impaired sources, such as reclaimed wastewater, brackish groundwater, and ocean water, is imperative as freshwater resources are under great pressure. Complete reuse of urine wastewater is also necessary to sustain life on space exploration missions of greater than one year’s duration. Currently, the Water Recovery System (WRS) used on the National Aeronautics and Space Administration (NASA) shuttles recovers only 70% of generated wastewater.1 Current osmotic processes show high capability to increase water recovery from wastewater. However, commercial reverse osmosis (RO) membranes rapidly degrade when exposed to pretreated urine-containing wastewater. Also, non-ionic small molecules substances (i.e., urea) are very poorly rejected by commercial RO membranes.
In this study, an innovative composite membrane that integrates water-selective molecular sieve particles into a liquid-barrier chemically resistant polymer film is synthetized. This plan manipulates distinctive aspects of the two materials used to create the membranes: (1) the innate permeation and selectivity of the molecular sieves, and (2) the decay-resistant, versatile, and mechanical strength of the liquid-barrier polymer support matrix.
To synthesize the membrane, Linde Type A (LTA) zeolite particles are anchored to the porous substrate, producing a single layer of zeolite particles capable of transporting water through the membrane. Thereafter, coating the chemically resistant latex polymer filled the space between zeolites. Finally, excess polymer was etched from the surface to expose the zeolites to the feed solution. The completed membranes were tested in reverse osmosis mode with deionized water, sodium chloride, and rhodamine solutions to determine the suitability for water recovery.
The main distinguishing characteristics of the new membrane design compared with current composite membrane include: (1) the use of an impermeable polymer broadens the range of chemical resistant polymers that can be used as the polymer matrix; (2) the use of zeolite particles with specific pore size insures the high rejection of the neutral molecules since water is transported through the zeolite rather than the polymer; (3) the use of latex dispersions, environmentally friendly water based-solutions, as the polymer matrix shares the qualities of low volatile organic compound, low cost, and non- toxicity.
In this study, an innovative composite membrane that integrates water-selective molecular sieve particles into a liquid-barrier chemically resistant polymer film is synthetized. This plan manipulates distinctive aspects of the two materials used to create the membranes: (1) the innate permeation and selectivity of the molecular sieves, and (2) the decay-resistant, versatile, and mechanical strength of the liquid-barrier polymer support matrix.
To synthesize the membrane, Linde Type A (LTA) zeolite particles are anchored to the porous substrate, producing a single layer of zeolite particles capable of transporting water through the membrane. Thereafter, coating the chemically resistant latex polymer filled the space between zeolites. Finally, excess polymer was etched from the surface to expose the zeolites to the feed solution. The completed membranes were tested in reverse osmosis mode with deionized water, sodium chloride, and rhodamine solutions to determine the suitability for water recovery.
The main distinguishing characteristics of the new membrane design compared with current composite membrane include: (1) the use of an impermeable polymer broadens the range of chemical resistant polymers that can be used as the polymer matrix; (2) the use of zeolite particles with specific pore size insures the high rejection of the neutral molecules since water is transported through the zeolite rather than the polymer; (3) the use of latex dispersions, environmentally friendly water based-solutions, as the polymer matrix shares the qualities of low volatile organic compound, low cost, and non- toxicity.
ContributorsKhosravi, Afsaneh Khosravi (Author) / Lind, Mary Laura (Thesis advisor) / Dai, Lenore (Committee member) / Green, Matthew (Committee member) / Lin, Jerry (Committee member) / Seo, Don (Committee member) / Arizona State University (Publisher)
Created2016
Description
Environmentally responsive hydrogels are one interesting class of soft materials. Due to their remarkable responsiveness to stimuli such as temperature, pH, or light, they have attracted widespread attention in many fields. However, certain functionality of these materials alone is often limited in comparison to other materials such as silicon; thus, there is a need to integrate soft and hard materials for the advancement of environmental-ly responsive materials.
Conventional hydrogels lack good mechanical properties and have inherently slow response time, important characteristics which must be improved before the hydrogels can be integrated with silicon. In the present dissertation work, both these important attrib-utes of a temperature responsive hydrogel, poly(N-isopropylacrylamide) (PNIPAAm), were improved by adopting a low temperature polymerization process and adding a sili-cate compound, tetramethyl orthosilicate. Furthermore, the transition temperature was modulated by adjusting the media quality in which the hydrogels were equilibrated, e.g. by adding a co-solvent (methanol) or an anionic surfactant (sodium dodecyl sulfate). In-terestingly, the results revealed that, based on the hydrogels’ porosity, there were appre-ciable differences when the PNIPAAm hydrogels interacted with the media molecules.
Next, an adhesion mechanism was developed in order to transfer silicon thin film onto the hydrogel surface. This integration provided a means of mechanical buckling of the thin silicon film due to changes in environmental stimuli (e.g., temperature, pH). We also investigated how novel transfer printing techniques could be used to generate pat-terned deformation of silicon thin film when integrated on a planar hydrogel substrate. Furthermore, we explore multilayer hybrid hydrogel structures formed by the integration of different types of hydrogels that have tunable curvatures under the influence of differ-ent stimuli. Silicon thin film integration on such tunable curvature substrates reveal char-acteristic reversible buckling of the thin film in the presence of multiple stimuli.
Finally, different approaches of incorporating visible light response in PNIPAAm are discussed. Specifically, a chemical chromophore- spirobenzopyran was synthesized and integrated through chemical cross-linking into the PNIPAAm hydrogels. Further, methods of improving the light response and mechanical properties were also demonstrat-ed. Interestingly, such a system was shown to have potential application as light modulated topography altering system
Conventional hydrogels lack good mechanical properties and have inherently slow response time, important characteristics which must be improved before the hydrogels can be integrated with silicon. In the present dissertation work, both these important attrib-utes of a temperature responsive hydrogel, poly(N-isopropylacrylamide) (PNIPAAm), were improved by adopting a low temperature polymerization process and adding a sili-cate compound, tetramethyl orthosilicate. Furthermore, the transition temperature was modulated by adjusting the media quality in which the hydrogels were equilibrated, e.g. by adding a co-solvent (methanol) or an anionic surfactant (sodium dodecyl sulfate). In-terestingly, the results revealed that, based on the hydrogels’ porosity, there were appre-ciable differences when the PNIPAAm hydrogels interacted with the media molecules.
Next, an adhesion mechanism was developed in order to transfer silicon thin film onto the hydrogel surface. This integration provided a means of mechanical buckling of the thin silicon film due to changes in environmental stimuli (e.g., temperature, pH). We also investigated how novel transfer printing techniques could be used to generate pat-terned deformation of silicon thin film when integrated on a planar hydrogel substrate. Furthermore, we explore multilayer hybrid hydrogel structures formed by the integration of different types of hydrogels that have tunable curvatures under the influence of differ-ent stimuli. Silicon thin film integration on such tunable curvature substrates reveal char-acteristic reversible buckling of the thin film in the presence of multiple stimuli.
Finally, different approaches of incorporating visible light response in PNIPAAm are discussed. Specifically, a chemical chromophore- spirobenzopyran was synthesized and integrated through chemical cross-linking into the PNIPAAm hydrogels. Further, methods of improving the light response and mechanical properties were also demonstrat-ed. Interestingly, such a system was shown to have potential application as light modulated topography altering system
ContributorsChatterjee, Prithwish (Author) / Dai, Lenore L. (Thesis advisor) / Jiang, Hanqing (Thesis advisor) / Lind, Mary Laura (Committee member) / Yu, Hongyu (Committee member) / Yu, Hongbin (Committee member) / Arizona State University (Publisher)
Created2015
Description
In the United States, 95% of the industrially produced hydrogen is from natural gas reforming. Membrane-based techniques offer great potential for energy efficient hydrogen separations. Pd77Ag23 is the bench-mark metallic membrane material for hydrogen separation at high temperatures. However, the high cost of palladium limits widespread application. Amorphous metals with lower cost elements are one alternative to replace palladium-based membranes. The overall aim of this thesis is to investigate the potential of binary and ternary amorphous metallic membranes for hydrogen separation. First, as a benchmark, the influence of surface state of Pd77Ag23 crystalline metallic membranes on the hydrogen permeability was investigated. Second, the hydrogen permeability, thermal stability and mechanical properties of Cu-Zr and Ni60Nb35M5 (M=Sn, Ti and Zr) amorphous metallic membranes was evaluated.
Different heat treatments were applied to commercial Pd77Ag23 membranes to promote surface segregation. X-ray photoelectron spectroscopy (XPS) analysis indicates that the membrane surface composition changed after heat treatment. The surface area of all membranes increased after heat treatment. The higher the surface Pd/(Pd+Ag) ratio, the higher the hydrogen permeability. Surface carbon removal and surface area increase cannot explain the observed permeability differences.
Previous computational modeling predicted that Cu54Zr46 would have high hydrogen permeability. Amorphous metallic Cu-Zr (Zr=37, 54, 60 at. %) membranes were synthesized and investigated. The surface oxides may result in the lower experimental hydrogen permeability lower than that predicted by the simulations. The permeability decrease indicates that the Cu-Zr alloys crystallized in less than two hours during the test (performed at 300 °C) at temperatures below the glass transition temperature. This original experimental results show that thermal stability of amorphous metallic membranes is critical for hydrogen separation applications.
The hydrogen permeability of Ni60Nb35M5 (M=Sn, Ti and Zr) amorphous metallic membranes was investigated. Nanoindentation shows that the Young’s modulus and hardness increased after hydrogen permeability test. The structure is maintained amorphous after 24 hours of hydrogen permeability testing at 400°C. The maximum hydrogen permeability of three alloys is 10-10 mol m-1 s-1 Pa-0.5. Though these alloys exhibited a slight hydrogen permeability decreased during the test, the amorphous metallic membranes were thermally stable and did not crystalize.
Different heat treatments were applied to commercial Pd77Ag23 membranes to promote surface segregation. X-ray photoelectron spectroscopy (XPS) analysis indicates that the membrane surface composition changed after heat treatment. The surface area of all membranes increased after heat treatment. The higher the surface Pd/(Pd+Ag) ratio, the higher the hydrogen permeability. Surface carbon removal and surface area increase cannot explain the observed permeability differences.
Previous computational modeling predicted that Cu54Zr46 would have high hydrogen permeability. Amorphous metallic Cu-Zr (Zr=37, 54, 60 at. %) membranes were synthesized and investigated. The surface oxides may result in the lower experimental hydrogen permeability lower than that predicted by the simulations. The permeability decrease indicates that the Cu-Zr alloys crystallized in less than two hours during the test (performed at 300 °C) at temperatures below the glass transition temperature. This original experimental results show that thermal stability of amorphous metallic membranes is critical for hydrogen separation applications.
The hydrogen permeability of Ni60Nb35M5 (M=Sn, Ti and Zr) amorphous metallic membranes was investigated. Nanoindentation shows that the Young’s modulus and hardness increased after hydrogen permeability test. The structure is maintained amorphous after 24 hours of hydrogen permeability testing at 400°C. The maximum hydrogen permeability of three alloys is 10-10 mol m-1 s-1 Pa-0.5. Though these alloys exhibited a slight hydrogen permeability decreased during the test, the amorphous metallic membranes were thermally stable and did not crystalize.
ContributorsLai, Tianmiao (Author) / Lind, Mary Laura (Thesis advisor) / Lin, Jerry (Committee member) / Li, Jian (Committee member) / Arizona State University (Publisher)
Created2015
Description
As selenium is toxic at low levels, treatment methods to remove selenium from industrial waste waters are needed. In this work, three groups of sorbent materials were investigated in detail for their effectiveness for selenium and arsenic removal from water: 1) nanostructured carbon-based materials, 2) layered double hydroxide (LDH)-based materials, and 3) biopolymer-based sorbents. The materials were investigated in spiked de-ionized water and waters collected from different locations at Salt River Project’s (SRP) Santan Generating Station in Gilbert, AZ. The results show that nanostructured carbon-based materials removed ~80% and up to 100% selenium and arsenic, respectively in spiked DI water. Heat treated layered double hydroxides removed close to 100% removal in selenium and arsenic spiked DI water. Isotherms conducted in spiked DI water fit the Langmuir model and showed a maximum selenate adsorption capacity of 67 mg/g for the calcined LDH powder. Results from SRP waters showed that certain LDH sorbents were effective for removing the selenium, but that higher pH and existence of competing ions affected the removal efficiencies. The functionalized biopolymer sorbent from Crystal Clear Technologies: CCT-149/OCI-B showed good removal efficiencies for both selenate and selenite in DI water. Isotherms conducted in spiked DI water for CCT-149 fit the Langmuir model and showed a maximum selenate adsorption capacity of 90.9 mg/g. Column tests using spiked DI water and waters obtained from SRP wells were investigated using both LDH and CCT-149/OCI-B. Removal of sulfate using chemical pre-treatment of the water with barium chloride resulted in about three times higher selenate loading onto the granular LDH and doubled the water volume that can be treated using CCT-149/OCI-B. The results from the column tests are being used to guide the pilot testing investigating the implementation of LDH sorbents at pilot scale at the Santan plant. The good results in the cooling tower #5 blowdown water and combined discharge waste water of SRP provide valuable information about the efficacy and efficiency of adsorptive media for the removal of selenium. Composites comprising LDH nanosheets with different substrates were successfully synthesized that were able to retain the performance in removing selenate of nanosheet LDH.
ContributorsLi, Man (Author) / Chan, Candace (Thesis advisor) / Lind, Mary Laura (Committee member) / Perreault, Francois (Committee member) / Arizona State University (Publisher)
Created2017
Description
Membranes are a key part of pervaporation processes, which is generally a more
efficient process for selective removal of alcohol from water than distillation. It is
necessary that the membranes have high alcohol permeabilities and selectivities.
Polydimethylsiloxane (PDMS) based mixed matrix membranes (MMMs) have
demonstrated very promising results. Zeolitic imidazolate framework-71 (ZIF-71)
demonstrated promising alcohol separation abilities. In this dissertation, we present
fundamental studies on the synthesis of ZIF-71/PDMS MMMs.
Free-standing ZIF-71/ PDMS membranes with 0, 5, 25 and 40 wt % ZIF-71
loadings were prepared and the pervaporation separation for ethanol and 1-butanol from
water was measured. ZIF-71/PDMS MMMs were formed through addition cure and
condensation cure methods. Addition cure method was not compatible with ZIF-71
resulting in membranes with poor mechanical properties, while the condensation cure
method resulted in membranes with good mechanical properties. The 40 wt % ZIF-71
loading PDMS nanocomposite membranes achieved a maximum ethanol/water selectivity
of 0.81 ± 0.04 selectivity and maximum 1-butnaol/water selectivity of 5.64 ± 0.15.
The effects of synthesis time, temperature, and reactant ratio on ZIF-71 particle
size and the effect of particle size on membrane performance were studied. Temperature
had the greatest effect on ZIF-71 particle size as the synthesis temperature varied from -
20 to 35 ºC. The ZIF-71 synthesized had particle diameters ranging from 150 nm to 1
μm. ZIF-71 particle size is critical in ZIF-71/PDMS composite membrane performance
for alcohol removal from water through pervaporation. The membranes made with
micron sized ZIF-71 particles showed higher alcohol/water selectivity than those with
smaller particles. Both alcohol and water permeability increased when larger sized ZIF-
71 particles were incorporated.
ZIF-71 particles were modified with four ligands through solvent assisted linker
exchange (SALE) method: benzimidazole (BIM), 5-methylbenzimidazole (MBIM), 5,6-
dimethylbenzimidazole (DMBIM) and 4-Phenylimidazole (PI). The morphology of ZIF-
71 were maintained after the modification. ZIF-71/PDMS composite membranes with 25
wt% loading modified ZIF-71 particles were made for alcohol/water separation. Better
particle dispersion in PDMS polymer matrix was observed with the ligand modified ZIFs.
For both ethanol/water and 1-butanol/water separations, the alcohol permeability and
alcohol/water selectivity were lowered after the ZIF-71 ligand exchange reaction.
efficient process for selective removal of alcohol from water than distillation. It is
necessary that the membranes have high alcohol permeabilities and selectivities.
Polydimethylsiloxane (PDMS) based mixed matrix membranes (MMMs) have
demonstrated very promising results. Zeolitic imidazolate framework-71 (ZIF-71)
demonstrated promising alcohol separation abilities. In this dissertation, we present
fundamental studies on the synthesis of ZIF-71/PDMS MMMs.
Free-standing ZIF-71/ PDMS membranes with 0, 5, 25 and 40 wt % ZIF-71
loadings were prepared and the pervaporation separation for ethanol and 1-butanol from
water was measured. ZIF-71/PDMS MMMs were formed through addition cure and
condensation cure methods. Addition cure method was not compatible with ZIF-71
resulting in membranes with poor mechanical properties, while the condensation cure
method resulted in membranes with good mechanical properties. The 40 wt % ZIF-71
loading PDMS nanocomposite membranes achieved a maximum ethanol/water selectivity
of 0.81 ± 0.04 selectivity and maximum 1-butnaol/water selectivity of 5.64 ± 0.15.
The effects of synthesis time, temperature, and reactant ratio on ZIF-71 particle
size and the effect of particle size on membrane performance were studied. Temperature
had the greatest effect on ZIF-71 particle size as the synthesis temperature varied from -
20 to 35 ºC. The ZIF-71 synthesized had particle diameters ranging from 150 nm to 1
μm. ZIF-71 particle size is critical in ZIF-71/PDMS composite membrane performance
for alcohol removal from water through pervaporation. The membranes made with
micron sized ZIF-71 particles showed higher alcohol/water selectivity than those with
smaller particles. Both alcohol and water permeability increased when larger sized ZIF-
71 particles were incorporated.
ZIF-71 particles were modified with four ligands through solvent assisted linker
exchange (SALE) method: benzimidazole (BIM), 5-methylbenzimidazole (MBIM), 5,6-
dimethylbenzimidazole (DMBIM) and 4-Phenylimidazole (PI). The morphology of ZIF-
71 were maintained after the modification. ZIF-71/PDMS composite membranes with 25
wt% loading modified ZIF-71 particles were made for alcohol/water separation. Better
particle dispersion in PDMS polymer matrix was observed with the ligand modified ZIFs.
For both ethanol/water and 1-butanol/water separations, the alcohol permeability and
alcohol/water selectivity were lowered after the ZIF-71 ligand exchange reaction.
ContributorsYin, Huidan (Author) / Lind, Mary Laura (Thesis advisor) / Mu, Bin (Committee member) / Nielsen, David (Committee member) / Seo, Don (Committee member) / Lin, Jerry (Committee member) / Arizona State University (Publisher)
Created2017