Fundamentals of Liquid Metal Foams and Emulsions

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Description
Gallium based room-temperature liquid metals (LMs) have special properties such as metal-like high thermal conductivity while in the liquid state. They are suitable for many potential applications, including thermal interface materials, soft robotics, stretchable electronics, and biomedicine. However, their high

Gallium based room-temperature liquid metals (LMs) have special properties such as metal-like high thermal conductivity while in the liquid state. They are suitable for many potential applications, including thermal interface materials, soft robotics, stretchable electronics, and biomedicine. However, their high density, high surface tension, high reactivity with other metals, and rapid oxidation restrict their applicability. This dissertation introduces two new types of materials, LM foams, and LM emulsions, that address many of these issues. The formation mechanisms, thermophysical properties, and example applications of the LM foams and emulsions are investigated.LM foams can be prepared by shear mixing the bulk LM in air using an impeller. The surface oxide layer is sheared and internalized into the bulk LM as crumpled oxide flakes during this process. After a critical amount of oxide flakes is internalized, they start to stabilize air bubbles by encapsulating and oxide-bridging. This mechanism enables the fabrication of a LM foam with improved properties and better spreadability. LM emulsions can be prepared by mixing the LM foam with a secondary liquid such as silicone oil (SO). By tuning a few factors such as viscosity of the secondary liquid, composition, and mixing duration, the thermophysical properties of the emulsion can be controlled. These emulsions have a lower density, better spreadability, and unlike the original LM and LM foam, they do not induce corrosion of other metals. LM emulsions can form by two possible mechanisms, first by the secondary liquid replacing air features in the existing foam pores (replacement mechanism) and second by creating additional liquid features within the LM foam (addition mechanism). The latter mechanism requires significant oxide growth and therefore requires presence of oxygen in the environment. The dominant mechanism can therefore be distinguished by mixing LM foam with the SO in air and oxygen-free environments. Additionally, a comprehensive analysis of foam-to-emulsion density change, multiscale imaging and surface wettability confirm that addition mechanism dominates the emulsion formation. These results provide insight into fundamental processes underlying LM foams and emulsions, and they set up a foundation for preparing LM emulsions with a wide range of fluids and controllable properties.
Date Created
2023
Agent

Experimental and Simulation Study on Novel Adsorbents for Carbon Capture, Oxygen Sorption, and Methane Recovery

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Description
Global warming resulted from greenhouse gases emission has received widespread attention. Meanwhile, it is required to explore renewable and environmentally friendly energy sources due to the severe pollution of the environment caused by fossil fuel combustion. In order to realize

Global warming resulted from greenhouse gases emission has received widespread attention. Meanwhile, it is required to explore renewable and environmentally friendly energy sources due to the severe pollution of the environment caused by fossil fuel combustion. In order to realize a substantial adsorption process to resolve the environmental issues, the development of new adsorbents with improved properties has become the most critical issue. This dissertation presents the work of four individual but related studies on systematic characterization and process simulations of novel adsorbents with superior adsorption properties.

A perovskite oxide material, La0.1Sr0.9Co0.9Fe0.1O3-δ (LSCF1991), was investigated first for high-temperature air separation. The oxygen sorption/desorption behavior of LSCF1991 was studied by thermogravimetric analysis (TGA) and fixed-bed breakthrough experiments. A parametric study was performed to design and optimize the operating parameters of the high-temperature air separation process by pressure swing adsorption (PSA). The results have shown great potential for applying LSCF1991 to the high-temperature air separation due to its excellent separation performance and low energy requirement.

Research on using nanostructured zeolite NaX (NZ) as adsorbents for CO2 capture was subsequently conducted. The CO2/N2 adsorption characterizations indicated that the NZ samples lead to enhanced adsorption properties compared with the commercial zeolites (MZ). From the two-bed six-step PSA simulation, NZ saved around 30% energy over MZ for CO2 capture and recovery while achieving a higher CO2 purity and productivity.

A unique screening method was developed for efficient evaluation of adsorbents for PSA processes. In the case study, 47 novel adsorbents have been screened for coal bed methane (CBM) recovery. The adsorbents went through scoring-based prescreening, PSA simulation, and optimization. The process performance indicators were correlated with the adsorption selectivity and capacities, which provides new insights for predicting the PSA performance.

A new medium-temperature oxygen sorbent, YBaCo4O7+δ (YBC114), was investigated as an oxygen pumping material to facilitate solar thermochemical fuel production. The oxygen uptake and release attributes of YBC114 were studied by both TGA and a small-scale evacuation test. The study proved that the particle size has a significant effect on the oxygen pumping behavior of YBC114, especially for the uptake kinetics.
Date Created
2020
Agent

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

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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.
Date Created
2020-05
Agent

Investigation of Water Permeation through Molecular Sieve Particles in Thin Film Nanocomposite Membranes

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Description
Nanoporous materials, with pore sizes less than one nanometer, have been incorporated as filler materials into state-of-the-art polyamide-based thin-film composite membranes to create thin-film nanocomposite (TFN) membranes for reverse osmosis (RO) desalination. However, these TFN membranes have inconsistent changes

Nanoporous materials, with pore sizes less than one nanometer, have been incorporated as filler materials into state-of-the-art polyamide-based thin-film composite membranes to create thin-film nanocomposite (TFN) membranes for reverse osmosis (RO) desalination. However, these TFN membranes have inconsistent changes in desalination performance as a result of filler incorporation. The nano-sized filler’s transport role for enhancing water permeability is unknown: specifically, there is debate around the individual transport contributions of the polymer, nanoporous particle, and polymer/particle interface. Limited studies exist on the pressure-driven water transport mechanism through nanoporous single-crystal nanoparticles. An understanding of the nanoporous particles water transport role in TFN membranes will provide a better physical insight on the improvement of desalination membranes.

This dissertation investigates water permeation through single-crystal molecular sieve zeolite A particles in TFN membranes in four steps. First, the meta-analysis of nanoporous materials (e.g., zeolites, MOFs, and graphene-based materials) in TFN membranes demonstrated non-uniform water-salt permselectivity performance changes with nanoporous fillers. Second, a systematic study was performed investigating different sizes of non-porous (pore-closed) and nanoporous (pore-opened) zeolite particles incorporated into conventionally polymerized TFN membranes; however, the challenges of particle aggregation, non-uniform particle dispersion, and possible particle leaching from the membranes limit analysis. Third, to limit aggregation and improve dispersion on the membrane, a TFN-model membrane synthesis recipe was developed that immobilized the nanoparticles onto the support membranes surface before the polymerization reaction. Fourth, to quantify the possible water transport pathways in these membranes, two different resistance models were employed.

The experimental results show that both TFN and TFN-model membranes with pore-opened particles have higher water permeance compared to those with pore-closed particles. Further analysis using the resistance in parallel and hybrid models yields that water permeability through the zeolite pores is smaller than that of the particle/polymer interface and higher than the water permeability of the pure polymer. Thus, nanoporous particles increase water permeability in TFN membranes primarily through increased water transport at particle/polymer interface. Because solute rejection is not significantly altered in our TFN and TFN-model systems, the results reveal that local changes in the polymer region at the polymer/particle interface yield high water permeability.
Date Created
2018
Agent

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

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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,

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.
Date Created
2016-05
Agent

Construction and Operation of a Hollow Fiber Membrane Spinning Apparatus

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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

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.
Date Created
2017-05
Agent