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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
This study details the construction and operation of a dry-jet wet spinning apparatus for extruding hollow fiber membranes (HFMs). The main components of the apparatus are a spinneret, a coagulation bath, and an automatic collection reel. Continuous fiber formation was achieved using two syringe pumps simultaneously delivering polymer dope and

This study details the construction and operation of a dry-jet wet spinning apparatus for extruding hollow fiber membranes (HFMs). The main components of the apparatus are a spinneret, a coagulation bath, and an automatic collection reel. Continuous fiber formation was achieved using two syringe pumps simultaneously delivering polymer dope and bore fluid to the spinneret. Based on apparatus runs performed with Polysulfone (PSF) dopes dissolved in N,N-Dimethylacetamide and supporting rheological analysis, the entanglement concentration, ce, was identified as a minimum processing threshold for creating HFMs. Similarly, significant increases in the ultimate tensile strength, fracture strain, and Young's modulus for extruded HFMs were observed as polymer dope concentration was increased at levels near ce. Beyond this initial increase, subsequent tests at higher PSF concentrations yielded diminishing changes in mechanical properties, suggesting an asymptotic approach to a point where the trend would cease. Without further research, it is theorized that this point falls on a transition from the semidiute entangled to concentrated concentration regimes. SEM imaging of samples revealed the formation of grooved structures on the inner surface of samples, which was determined to be a result of the low flowrate and polymer dope concentrations used in processing the HFMs during apparatus runs. Based on continued operation of the preliminary apparatus design, many areas of improvement were noted. Namely, these consisted of controlling the collector speed, eliminating rubbing of nascent fibers against the edge of the coagulation bath by installing an elevated roller, and replacing tygon tubing for the polymer line with a luer lock adapter for direct syringe attachment to the spinneret.
ContributorsBridge, Alexander Thomas (Author) / Green, Matthew D. (Thesis director) / Lin, Jerry Y. S. (Committee member) / School of Mathematical and Statistical Sciences (Contributor) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2017-05
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Description
Metal-organic frameworks (MOFs) are a new set of porous materials comprised of metals or metal clusters bonded together in a coordination system by organic linkers. They are becoming popular for gas separations due to their abilities to be tailored toward specific applications. Zirconium MOFs in particular are known for their

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

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

The following thesis documents a two-fold approach to investigate challenges pertaining to water purification, first through a meta-analysis of ionic liquid toxicity, then through experimentation aimed at developing water pre-treatment membranes. Ionic liquids (ILs) are salts with low melting points, typically liquid at room temperature. Several extraordinary physical attributes, e.g. low viscosity, high conductivity, low to no vapor pressure, etc., and seemingly unlimited combinations available, have pushed IL research to the forefront of many research fronts. Concerns are raised as ionic liquids are rushed into commercial production without sufficient environmental regulation. Research has shown that the chemicals are in fact toxic, yet have developed a reputation for being “green” chemicals due to select physical attributes and applications. The meta-analysis discussed focuses on industry perception of ionic liquid toxicity through a patent review, and considers toxicity of ILs comparatively against other chemical families with well-established toxicity. The meta-analysis revealed that the total patent literature pertaining to ILs (n=3358) resulted in 112 patents that addressed the toxicity of ILs, and notably few (n=17) patents defined ILs as toxic, representing only 0.51% of the evaluated body of work on intellectual property claims. Additionally, toxicity of ionic liquids is comparable to that of other chemical families.
The objective of the experimentation was to explore the effect of crosslinker chain length on the morphology of nanofiber mats. Specifically, poly(vinyl alcohol (PVA) was electrospun into nanofiber mats and poly(ethylene) glycol bis(carboxylic acid) (PEG diacid) was used as the crosslinking agent. As-spun fibers had average fiber diameter of 70 ± 30 nm with an average pore size of 0.10 ± 0.16 μm^2. The fiber diameter for the mats crosslinked with the shorter PEG diacid (Mn = 250) increased to 110 ± 40 nm with an average pore size of 0.11 ± 0.04 μm^2. The mats crosslinked with the longer PEG diacid (Mn = 600) had fiber diameters of 180 ± 10 nm with an average pore size 0.01 ± 0.02 μm^2.
ContributorsRomero, Felicia Navidad (Author) / Green, Matthew D. (Thesis director) / Lind, Mary Laura (Committee member) / Long, Timothy E. (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05