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Photocurable poly(ethylene glycol) diacrylate resins with variable loadings of functionalized silica nanoparticles

Description

Photocurable nanocomposites have great potential within advanced manufacturing, multifunctional materials, and most specifically tissue engineering. The properties and characteristics of these nanocomposites can be tailored to mimic those of various tissues and/or cartilage, allowing the bio-inspired synthetic materials to replace

Photocurable nanocomposites have great potential within advanced manufacturing, multifunctional materials, and most specifically tissue engineering. The properties and characteristics of these nanocomposites can be tailored to mimic those of various tissues and/or cartilage, allowing the bio-inspired synthetic materials to replace them. This project investigates the effect of methacrylate-functionalized (MA-SiO2) and vinyl-functionalized (V-SiO2) silica nanoparticle loading content on the thermal, mechanical, physical, and morphological characteristics of PEG nanocomposites. It was discovered that both V-SiO2 and MA-SiO2 did not considerably impact the glass-transition temperature or hydrophilicity of the material. The gel fraction of composites containing V-SiO2 decreases with the initial addition of 3.8 wt%, but then displays an increase with further addition (>7.4 wt%) until it reaches a plateau at 10.7 wt%. Whereas, the MA-SiO2 induced no significant changes in gel fraction with increased loading. An increase in mechanical properties was also observed with increasing concentration for both sets of series. However, due to the higher crosslink density, MA-SiO2 reached its ultimate mechanical stress threshold at a lower concentration of 7.4 wt%, while V-SiO2 maxed out at 10.7 wt%. Scanning electron microscopy coupled with transmission electron microscopy revealed that V-SiO2 displayed a bimodal size distribution, while MA-SiO2 displayed only one.

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Date Created
2020-05

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Construction and Operation of a Hollow Fiber Membrane Spinning Apparatus

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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

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.

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Date Created
2017-05

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Bi-phase Synthesis of the Zirconium Metal-Organic Framework, UiO-66

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

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.

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Date Created
2016-12

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Ionic Liquids to Lab: Investigating an Emerging Water Filtration Challenge to Engineering Nanofiber Polymer Membranes as Next-Generation Solutions for Water Purification

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,

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.

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Date Created
2016-05