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Description
Pervaporation is a membrane separation technology that has had industrial application and which is the subject of ongoing research. Two major factors are important in judging the quality of a membrane: selectivity and permeation flux. Although many types of materials can be used for the separation layer, zeolites will be

Pervaporation is a membrane separation technology that has had industrial application and which is the subject of ongoing research. Two major factors are important in judging the quality of a membrane: selectivity and permeation flux. Although many types of materials can be used for the separation layer, zeolites will be the material considered in this thesis. A simple mathematical model has been developed to demonstrate the inter-relationships between relative permeation flux, reduced selectivity, and the relative resistance to mass transfer of the support to the zeolite layer. The model was applied to several membranes from our laboratory and to two examples from the literature. The model offers a useful way of conceptualizing membrane performance and facilitates the comparison of different membrane performances. The model predicts the effect of different supports on zeolite supported membrane performance.
ContributorsMann, Stewart (Author) / Lin, Jerry (Thesis advisor) / Lind, Mary Laura (Committee member) / Nielsen, David (Committee member) / Arizona State University (Publisher)
Created2014
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Description
Environmentally responsive microgels have drawn significant attention due to their intrinsic ability to change volume in response to various external stimuli such as pH, temperature, osmotic pressure, or electric and magnetic fields. The extent of particle swelling is controlled by the nature of the polymer-solvent interaction. This thesis focuses on

Environmentally responsive microgels have drawn significant attention due to their intrinsic ability to change volume in response to various external stimuli such as pH, temperature, osmotic pressure, or electric and magnetic fields. The extent of particle swelling is controlled by the nature of the polymer-solvent interaction. This thesis focuses on design and synthesis of environmentally responsive microgels and their composites, and encompasses methods of utilizing microgel systems in applications as vehicles for the adsorption, retention, and targeted delivery of chemical species. Furthermore, self-assembled microgel particles at ionic liquid (IL)-water interfaces demonstrate responsive colloidal lattice morphology. The thesis first reports on the fundamental aspects of synthesis, functionalization, and characteristic properties of multifunctional environmentally responsive microgels derived from poly(N-isopropylacrylamide) (PNIPAm) and other functional co-monomers. In particular, the uptake and release of active chemical species such as rheology modifiers into and from these ionic microgels is demonstrated. Moreover, a facile tunable method for the formation of organic-inorganic composites with Fe3O4 nanoparticles adsorbed and embedded within ionic microgel particles is explored. Additionally, the development of zwitterionic microgels (ZI-MG) is presented. These aqueous ZI-MG dispersions exhibit reversible parabolic swelling as a function of pH and display a minimum hydrodynamic diameter at a tunable isoelectric point (IEP). This study also elucidates the controlled uptake and release of surfactants from these particle systems. The extent of surfactant loading and the ensuing relative swelling/deswelling behaviors within the polymer networks are explained in terms of their binding interactions. The latter part of this thesis highlights the versatility of fluorescently labeled microgel particles as stabilizers for IL-water droplets. When the prepared particles form monolayers and equilibrate at the liquid-liquid interface, the colloidal lattice organization may re-order itself depending on the surface charge of these particles. Finally, it is shown that the spontaneously formed and densely packed layers of microgel particles can be employed for extraction applications, as the interface remains permeable to small active species.
ContributorsChen, Haobo (Author) / Dai, Lenore L (Committee member) / Chen, Kangping (Committee member) / Forzani, Erica (Committee member) / Lind, Mary Laura (Committee member) / Mu, Bin (Committee member) / Arizona State University (Publisher)
Created2015
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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

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.
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
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Description
The recovery of biofuels permits renewable alternatives to present day fossil fuels that cause devastating effects on the planet. Pervaporation is a separation process that shows promise for the separation of ethanol from biologically fermentation broths. The performance of thin film composite membranes of polydimethylsiloxane (PDMS) and zeolite imidazolate frameworks

The recovery of biofuels permits renewable alternatives to present day fossil fuels that cause devastating effects on the planet. Pervaporation is a separation process that shows promise for the separation of ethanol from biologically fermentation broths. The performance of thin film composite membranes of polydimethylsiloxane (PDMS) and zeolite imidazolate frameworks (ZIF-71) dip coated onto a porous substrate are analyzed. Pervaporation performance factors of flux, separation factor and selectivity are measured for varying ZIF-71 loadings of pure PDMS, 5 wt%, 12.5 wt% and 25 wt% at 60 oC with a 2 wt% ethanol/water feed. The increase in ZIF-71 loadings increased the performance of PDMS to produce higher flux, higher separation factor and high selectivity than pure polymeric films.
ContributorsLau, Ching Yan (Author) / Lind, Mary Laura (Thesis director) / Durgun, Pinar Cay (Committee member) / Lively, Ryan (Committee member) / Barrett, The Honors College (Contributor) / School of International Letters and Cultures (Contributor) / Chemical Engineering Program (Contributor)
Created2014-05
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Description
The overall goal of this project is to use metallic nanoparticles to develop a thin, ductile amorphous film at room temperature. Currently bulk metallic glasses are mainly formed via quenching, which requires very high cooling rates to achieve an amorphous molecular structure. These formations often fail in a brittle manner.

The overall goal of this project is to use metallic nanoparticles to develop a thin, ductile amorphous film at room temperature. Currently bulk metallic glasses are mainly formed via quenching, which requires very high cooling rates to achieve an amorphous molecular structure. These formations often fail in a brittle manner. The advantages of using a bottom-up approach with amorphous nanoparticles at ambient conditions is that the ductility of the metal can be improved, and the process will be less energy intensive. The nanoparticles used are iron precursors with ATMP and DTPMP ligand stabilizers and dispersed in methanol. Three forms of experimentation were applied over the course of this project. The first was a simple, preliminary data collection approach where the particles were dispersed onto a glass slide and left to dry under various conditions. The second method was hypersonic particle deposition, which accelerated the particles to high speeds and bombarded onto a glass or silicon substrate. The third method used Langmuir-Blodgett concepts and equipment to make a film. Qualitative analyses were used to determine the efficacy of each approach, including SEM imaging. In the end, none of the approaches proved successful. The first approach showed inconsistencies in the film formation and aggregation of the particles. The results from the hypersonic particle deposition technique showed that not enough particles were deposited to make a consistent film, and many of the particles that were able to be deposited were aggregated. The Langmuir-Blodgett method showed potential, but aggregation of the particles and uneven film formation were challenges here as well. Although there are ways the three discussed experimental approaches could be optimized, the next best step is to try completely new approaches, such as convective assembly and 3D printing to form the ideal nanoparticle film.
ContributorsKline, Katelyn Ann (Author) / Lind, Mary Laura (Thesis director) / Cay, Pinar (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-12
Description
Styrene, a component of many rubber products, is currently synthesized from petroleum in a highly energy-intensive process. The Nielsen Laboratory at Arizona State has demonstrated a biochemical pathway by which E. coli can be engineered to produce styrene from the amino acid phenylalanine, which E. coli naturally synthesizes from glucose.

Styrene, a component of many rubber products, is currently synthesized from petroleum in a highly energy-intensive process. The Nielsen Laboratory at Arizona State has demonstrated a biochemical pathway by which E. coli can be engineered to produce styrene from the amino acid phenylalanine, which E. coli naturally synthesizes from glucose. However, styrene becomes toxic to E. coli above concentrations of 300 mg/L, severely limiting the large-scale applicability of the pathway. Thus, styrene must somehow be continuously removed from the system to facilitate higher yields and for the purposes of scale-up. The separation methods of pervaporation and solvent extraction were investigated to this end. Furthermore, the styrene pathway was extended by one step to produce styrene oxide, which is less volatile than styrene and theoretically simpler to recover. Adsorption of styrene oxide using the hydrophobic resin L-493 was attempted in order to improve the yield of styrene oxide and to provide additional proof of concept that the flux through the styrene pathway can be increased. The maximum styrene titer achieved was 1.2 g/L using the method of solvent extraction, but this yield was only possible when additional phenylalanine was supplemented to the system.
ContributorsMcDaniel, Matthew Cary (Author) / Nielsen, David (Thesis director) / Lind, Mary Laura (Committee member) / McKenna, Rebekah (Committee member) / Barrett, The Honors College (Contributor) / Department of Chemistry and Biochemistry (Contributor) / Chemical Engineering Program (Contributor)
Created2013-05
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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
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Description
Neurological disorders are difficult to treat with current drug delivery methods due to their inefficiency and the lack of knowledge of the mechanisms behind drug delivery across the blood brain barrier (BBB). Nanoparticles (NPs) are a promising drug delivery method due to their biocompatibility and ability to be modified by

Neurological disorders are difficult to treat with current drug delivery methods due to their inefficiency and the lack of knowledge of the mechanisms behind drug delivery across the blood brain barrier (BBB). Nanoparticles (NPs) are a promising drug delivery method due to their biocompatibility and ability to be modified by cell penetrating peptides, such as transactivating transciptor (TAT) peptide, which has been shown to increase efficiency of delivery. There are multiple proposed mechanisms of TAT-mediated delivery that also have size restrictions on the molecules that can undergo each BBB crossing mechanism. The effect of nanoparticle size on TAT-mediated delivery in vivo is an important aspect to research in order to better understand the delivery mechanisms and to create more efficient NPs. NPs called FluoSpheres are used because they come in defined diameters unlike polymeric NPs that have a broad distribution of diameters. Both modified and unmodified 100nm and 200nm NPs were able to bypass the BBB and were seen in the brain, spinal cord, liver, and spleen using confocal microscopy and a biodistribution study. Statistically significant differences in delivery rate of the different sized NPs or between TAT-modified and unmodified NPs were not found. Therefore in future work a larger range of diameter size will be evaluated. Also the unmodified NPs will be conjugated with scrambled peptide to ensure that both unmodified and TAT-modified NPs are prepared in identical fashion to better understand the role of size on TAT targeting. Although all the NPs were able to bypass the BBB, future work will hopefully provide a better representation of how NP size effects the rate of TAT-mediated delivery to the CNS.
ContributorsCeton, Ricki Ronea (Author) / Stabenfeldt, Sarah (Thesis director) / Sirianni, Rachael (Committee member) / Harrington Bioengineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05
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Description
Freshwater as the resource for the survival of humans and all lives on earth is very precious but scarce. The shortage of the original freshwater resources and the interfering activities by human and other natural factors form this issue together. To reduce the water supply pressure and deterioration of freshwater

Freshwater as the resource for the survival of humans and all lives on earth is very precious but scarce. The shortage of the original freshwater resources and the interfering activities by human and other natural factors form this issue together. To reduce the water supply pressure and deterioration of freshwater systems (for example, river, wetland, and groundwater), the quantity-increase and the quality-increase strategies should be implemented at the same time. Therefore, corresponding membrane technologies have been developed to achieve water purification with high efficiency and low cost. For desalinating seawater and other types of saline water, pervaporation has been proved that has the potential to complete desalination with salt rejection rate over 99 % when dealing with high salinity water that reverse osmosis (RO) cannot handle. In this dissertation, except the discussion of commonly used materials to synthesize pervaporation membranes, two types of novel pervaporation desalination membranes (nanophotonic-enhanced membrane and free-standing sulfonated membrane) have been presented and discussed. The novel membranes were tested to see the potential of pervaporation to desalinate seawater and saline water with more complex ionic composition, and the possibility of achieving zero liquid discharge in the desalination field when having pervaporation as the assistance. For mitigating polluted water that is caused by human activities, especially agricultural activities, electrodialysis is an effective method to remove specific ions from water, and it does not require extra chemical cost or regeneration. A type of anion exchange membranes inspired by ion exchange resins was synthesized and tested, and the performance on nitrate removal has been evaluated in this dissertation.
ContributorsLi, Yusi (Author) / Lind, Mary Laura (Thesis advisor) / Perreault, Francois (Thesis advisor) / Forzani, Erica (Committee member) / Seo, S. Eileen (Committee member) / Walker, W. Shane (Committee member) / Arizona State University (Publisher)
Created2023