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Description
In this research, construction of a model membrane system using Polyvinylidene Chloride-Co Acrylonitrile and Linde Type A zeolites is described. The systems aims to separate out flow through zeolite pores and flow through interfaces between zeolites and polymers through the use of pore filled and pore open zeolites. Permeation tests

In this research, construction of a model membrane system using Polyvinylidene Chloride-Co Acrylonitrile and Linde Type A zeolites is described. The systems aims to separate out flow through zeolite pores and flow through interfaces between zeolites and polymers through the use of pore filled and pore open zeolites. Permeation tests and salt rejection tests were performed, and the data analyzed to yield approximation of separated flow through zeolites and interfaces. This work concludes the more work is required to bring the model system into a functioning state. New polymer selections and new techniques to produce the membrane system are described for future work.
ContributorsShabilla, Andrew Daniel (Author) / Lind, Mary Laura (Thesis director) / Lin, Jerry (Committee member) / Barrett, The Honors College (Contributor) / Chemical Engineering Program (Contributor)
Created2014-05
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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
Durable, cost-effective, and environmentally friendly anti-icing methods are desired to reduce the icing hazard in many different industrial areas including transportation systems, power plants, power transmission, as well as offshore oil and gas production. In contrast to traditional passive anti-icing surfaces, this thesis work introduces an anti-icing coating that responds

Durable, cost-effective, and environmentally friendly anti-icing methods are desired to reduce the icing hazard in many different industrial areas including transportation systems, power plants, power transmission, as well as offshore oil and gas production. In contrast to traditional passive anti-icing surfaces, this thesis work introduces an anti-icing coating that responds to different icing conditions by releasing an antifreeze liquid. It consists of an outer porous superhydrophobic epidermis and a wick-like underlying dermis that is infused with the antifreeze liquid. This bi-layer coating prevents accumulation of frost, freezing fog, and freezing rain, while conventional anti-icing surfaces typically work only in one of these conditions. The bi-layer coating also delays condensation on the exterior surface at least ten times longer than identical system without antifreeze.

It is demonstrated that the significant delay in condensation onset is due to the integral humidity sink effect posed by the hygroscopic antifreeze liquid infused in the porous structure. This effect significantly alters the water vapor concentration field at the coating surface, which delays nucleation of drops and ice. It was demonstrated that with a proper design of the environmental chamber the size of the region of inhibited condensation and condensation frosting around an isolated pore, as well as periodically spaced pores, filled by propylene glycol can be quantitatively predicted from quasi-steady state water vapor concentration field. Theoretical analysis and experiments revealed that the inhibition of nucleation is governed by only two non-dimensional geometrical parameters: the pore size relative to the unit cell size and the ratio of the unit cell size to the thickness of the boundary layer. It is demonstrated that by switching the size of the pores from millimeters to nanometers, a dramatic depression of the nucleation onset temperature, as well as significantly greater delay in nucleation onset can be achieved.
ContributorsSun, Xiaoda (Author) / Rykaczewski, Konrad (Thesis advisor) / Lin, Jerry (Committee member) / Phelan, Patrick (Committee member) / Wang, Robert (Committee member) / Herrmann, Marcus (Committee member) / Wang, Liping (Committee member) / Arizona State University (Publisher)
Created2017
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Description
Many defense, healthcare, and energy applications can benefit from the development of surfaces that easily shed droplets of liquids of interest. Desired wetting properties are typically achieved via altering the surface chemistry or topography or both through surface engineering. Despite many recent advancements, materials modified only on their exterior are

Many defense, healthcare, and energy applications can benefit from the development of surfaces that easily shed droplets of liquids of interest. Desired wetting properties are typically achieved via altering the surface chemistry or topography or both through surface engineering. Despite many recent advancements, materials modified only on their exterior are still prone to physical degradation and lack durability. In contrast to surface engineering, this thesis focuses on altering the bulk composition and the interior of a material to tune how an exterior surface would interact with liquids. Fundamental and applied aspects of engineering of two material systems with low contact angle hysteresis (i.e. ability to easily shed droplets) are explained. First, water-shedding metal matrix hydrophobic nanoparticle composites with high thermal conductivity for steam condensation rate enhancement are discussed. Despite having static contact angle <90° (not hydrophobic), sustained dropwise steam condensation can be achieved at the exterior surface of the composite due to low contact angle hysteresis (CAH). In order to explain this observation, the effect of varying the length scale of surface wetting heterogeneity over three orders of magnitude on the value of CAH was experimentally investigated. This study revealed that the CAH value is primarily governed by the pinning length which in turn depends on the length scale of wetting heterogeneity. Modifying the heterogeneity size ultimately leads to near isotropic wettability for surfaces with highly anisotropic nanoscale chemical heterogeneities. Next, development of lubricant-swollen polymeric omniphobic protective gear for defense and healthcare applications is described. Specifically, it is shown that the robust and durable protective gear can be made from polymeric material fully saturated with lubricant that can shed all liquids irrespective of their surface tensions even after multiple contact incidences with the foreign objects. Further, a couple of schemes are proposed to improve the rate of lubrication and replenishment of lubricant as well as reduce the total amount of lubricant required in making the polymeric protective gear omniphobic. Overall, this research aims to understand the underlying physics of dynamic surface-liquid interaction and provides simple scalable route to fabricate better materials for condensers and omniphobic protective gear.
ContributorsDamle, Viraj (Author) / Rykaczewski, Konrad (Thesis advisor) / Phelan, Patrick (Committee member) / Lin, Jerry (Committee member) / Herrmann, Marcus (Committee member) / Wang, Robert (Committee member) / Wang, Liping (Committee member) / Arizona State University (Publisher)
Created2017
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Description
Amine-modified solid sorbents and membrane separation are promising technologies for separation and capture of carbon dioxide (CO2) from combustion flue gas. Amine absorption processes are mature, but still have room for improvement. This work focused on the synthesis of amine-modified aerogels and metal-organic framework-5 (MOF-5) membranes for CO2 separation. A

Amine-modified solid sorbents and membrane separation are promising technologies for separation and capture of carbon dioxide (CO2) from combustion flue gas. Amine absorption processes are mature, but still have room for improvement. This work focused on the synthesis of amine-modified aerogels and metal-organic framework-5 (MOF-5) membranes for CO2 separation. A series of solid sorbents were synthesized by functionalizing amines on the surface of silica aerogels. This was done by three coating methods: physical adsorption, magnetically assisted impact coating (MAIC) and atomic layer deposition (ALD). CO2 adsorption capacity of the sorbents was measured at room temperature in a Cahn microbalance. The sorbents synthesized by physical adsorption show the largest CO2 adsorption capacity (1.43-1.63 mmol CO2/g). An additional sorbent synthesized by ALD on hydrophilic aerogels at atmospheric pressures shows an adsorption capacity of 1.23 mmol CO2/g. Studies on one amine-modified sorbent show that the powder is of agglomerate bubbling fluidization (ABF) type. The powder is difficult to fluidize and has limited bed expansion. The ultimate goal is to configure the amine-modified sorbents in a micro-jet assisted gas fluidized bed to conduct adsorption studies. MOF-5 membranes were synthesized on α-alumina supports by two methods: in situ synthesis and secondary growth synthesis. Characterization by scanning electron microscope (SEM) imaging and X-ray diffraction (XRD) show that the membranes prepared by both methods have a thickness of 14-16 μm, and a MOF-5 crystal size of 15-25 μm with no apparent orientation. Single gas permeation results indicate that the gas transport through both membranes is determined by a combination of Knudsen diffusion and viscous flow. The contribution of viscous flow indicates that the membranes have defects.
ContributorsRosa, Teresa M (Author) / Lin, Jerry (Thesis advisor) / Pfeffer, Robert (Thesis advisor) / Dai, Lenore (Committee member) / Nielsen, David (Committee member) / Arizona State University (Publisher)
Created2010
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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.

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.
ContributorsKasik, Alexandra Marie (Author) / Lin, Jerry (Thesis advisor) / Tasooji, Amaneh (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2015