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Description
Graphene oxide membranes have shown promising gas separation characteristics specially for hydrogen that make them of interest for industrial applications. However, the gas transport mechanism for these membranes is unclear due to inconsistent permeation and separation results reported in literature. Graphene oxide membranes made by filtration, the most common synthesis

Graphene oxide membranes have shown promising gas separation characteristics specially for hydrogen that make them of interest for industrial applications. However, the gas transport mechanism for these membranes is unclear due to inconsistent permeation and separation results reported in literature. Graphene oxide membranes made by filtration, the most common synthesis method, contain wrinkles affecting their gas separation characteristics and the method itself is difficult to scale up. Moreover, the production of graphene oxide membranes with fine-tuned interlayer spacing for improved molecular separation is still a challenge. These unsolved issues will affect their potential impact on industrial gas separation applications.

In this study, high quality graphene oxide membranes are synthesized on polyester track etch substrates by different deposition methods and characterized by XRD, SEM, AFM as well as single gas permeation and binary (H2/CO2) separation experiments. Membranes are made from large graphene oxide sheets of different sizes (33 and 17 micron) using vacuum filtration to shed more light on their transport mechanism. Membranes are made from dilute graphene oxide suspension by easily scalable spray coating technique to minimize extrinsic wrinkle formation. Finally, Brodie’s derived graphene oxide sheets were used to prepare membranes with narrow interlayer spacing to improve their (H2/CO2) separation performance.

An inter-sheet and inner-sheet two-pathway model is proposed to explain the permeation and separation results of graphene oxide membranes obtained in this study. At room temperature, large gas molecules (CH4, N2, and CO2) permeate through inter-sheet pathway of the membranes, exhibiting Knudsen like diffusion characteristics, with the permeance for the small sheet membrane about twice that for the large sheet membrane. The small gases (H2 and He) exhibit much higher permeance, showing significant flow through an inner-sheet pathway, in addition to the flow through the inter-sheet pathway. Membranes prepared by spray coating offer gas characteristics similar to those made by filtration, however using dilute graphene oxide suspension in spray coating will help reduce the formation of extrinsic wrinkles which result in reduction in the porosity of the inter-sheet pathway where the transport of large gas molecules dominates. Brodie’s derived graphene oxide membranes showed overall low permeability and significant improvement in in H2/CO2 selectivity compared to membranes made using Hummers’ derived sheets due to smaller interlayer space height of Brodie’s sheets (~3 Å).
ContributorsIbrahim, Amr Fatehy Muhammad (Author) / Lin, Jerry Y.S. (Thesis advisor) / Mu, Bin (Committee member) / Lind, Mary (Committee member) / Green, Matthew (Committee member) / Wang, Qing (Committee member) / Arizona State University (Publisher)
Created2018
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Description
Alloying in semiconductors has enabled many civilian technologies in optoelectronic, photonic fields and more. While the phenomenon of alloying is well established in traditional bulk semiconductors, owing to vastly available ternary phase diagrams, the ability to alloy in 2D systems are less clear. Recently anisotropic materials such as ReS2 and

Alloying in semiconductors has enabled many civilian technologies in optoelectronic, photonic fields and more. While the phenomenon of alloying is well established in traditional bulk semiconductors, owing to vastly available ternary phase diagrams, the ability to alloy in 2D systems are less clear. Recently anisotropic materials such as ReS2 and TiS3 have been extensively studied due to their direct-gap semiconductor and high mobility behaviors. This work is a report on alloys of ReS2 & ReSe2 and TiS3 &TiSe3.

Alloying selenium into ReS2 in the creation of ReS2xSe2-x, tunes the band gap and changes its vibrational spectrum. Depositing this alloy using bottom up approach has resulted in the loss of crystallinity. This loss of crystallinity was evidenced by grain boundaries and point defect shown by TEM images.

Also, in the creation of TiS3xSe3-x, by alloying Se into TiS3, a fixed ratio of 8% selenium deposit into TiS3 host matrix is observed. This is despite the vastly differing precursor amounts and growth temperatures, as evinced by detailed TEM, EDAX, TEM diffraction, and Raman spectroscopy measurements. This unusual behavior contrasts with other well-known layered material systems such as MoSSe, WMoS2 where continuous alloying can be attained. Cluster expansion theory calculations suggest that only limited composition (x) can be achieved. Considering the fact that TiSe3 vdW crystals have not been synthesized in the past, these alloying rejections can be attributed to energetic instability in the ternary phase diagrams estimated by calculations performed. Overall findings highlight potential means and challenges in achieving stable alloying in promising direct gap and high carrier mobility TiS3 materials.
ContributorsAgarwal, Ashutosh (Author) / Tongay, Sefaattin (Thesis advisor) / Green, Matthew (Committee member) / Zhuang, Houlong (Committee member) / Arizona State University (Publisher)
Created2018
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Description
In this study, the differences in delivery of methylated and unmethylated prokaryotic

DNA in mammalian cells was investigated. 3 plasmids, DH5-α, ER2925 and

GM272 were extracted and transformed from E. coli bacteria. DH5-α is the regular

methylated plasmid, however,ER2925 and GM272 lack Dam and Dcm enzymes which

methylate adenine and internal cytosine in prokaryotes

In this study, the differences in delivery of methylated and unmethylated prokaryotic

DNA in mammalian cells was investigated. 3 plasmids, DH5-α, ER2925 and

GM272 were extracted and transformed from E. coli bacteria. DH5-α is the regular

methylated plasmid, however,ER2925 and GM272 lack Dam and Dcm enzymes which

methylate adenine and internal cytosine in prokaryotes respectively, hence they are

unmethylated. The 3 plasmids were delivered via different delivery vectors in two

cell lines, UMUC3 and MDA-MB-231 which are human bladder cancer cell line and

human triple negative breast cancer cell line, respectively.

Luciferase and BCA assay were carried out to quantify transgene expression to

compare the efficacy of gene delivery in three aforementioned plasmids. In addition,

hydrodynamic diameter and zeta potential was measured for all delivery vectors, to

correlate with other transgene expression data. The results show that methylated

plasmid has significantly higher transgene expression in mammalian cell lines. This

can be either a result of smaller size and more positive zeta potential that the methylated

plasmid had, or a result of having Dam and Dcm enzymes which enhance binding

of DNA and transcription factors and enhance gene expression. Having smaller size

and more positive zeta potential was proven to be the case for the methylated plasmid

in this study. However the latter hypothesis should be investigated furthermore.
ContributorsMeraji, Seyedehmelika (Author) / Rege, Kaushal (Thesis advisor) / Nannegna, Brent (Committee member) / Green, Matthew (Committee member) / Arizona State University (Publisher)
Created2018
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Description
Encapsulant is a key packaging component of photovoltaic (PV) modules, which protects the solar cell from physical, environmental and electrical damages. Ethylene-vinyl acetate (EVA) is one of the major encapsulant materials used in the PV industry. This work focuses on indoor accelerated ultraviolet (UV) stress testing and characterization to investigate

Encapsulant is a key packaging component of photovoltaic (PV) modules, which protects the solar cell from physical, environmental and electrical damages. Ethylene-vinyl acetate (EVA) is one of the major encapsulant materials used in the PV industry. This work focuses on indoor accelerated ultraviolet (UV) stress testing and characterization to investigate the EVA discoloration and delamination in PV modules by using various non-destructive characterization techniques, including current-voltage (IV) measurements, UV fluorescence (UVf) and colorimetry measurements. Mini-modules with glass/EVA/cell/EVA/backsheet construction were fabricated in the laboratory with two types of EVA, UV-cut EVA (UVC) and UV-pass EVA (UVP).

The accelerated UV testing was performed in a UV chamber equipped with UV lights at an ambient temperature of 50°C, little or no humidity and total UV dosage of 400 kWh/m2. The mini-modules were maintained at three different temperatures through UV light heating by placing different thickness of thermal insulation sheets over the backsheet. Also, prior to thermal insulation sheet placement, the backsheet and laminate edges were fully covered with aluminum tape to prevent oxygen diffusion into the module and hence the photobleaching reaction.

The characterization results showed that mini-modules with UV-cut EVA suffered from discoloration while the modules with UV-pass EVA suffered from delamination. UVf imaging technique has the capability to identify the discoloration region in the UVC modules in the very early stage when the discoloration is not visible to the naked eyes, whereas Isc measurement is unable to measure the performance loss until the color becomes visibly darker. YI also provides the direct evidence of yellowing in the encapsulant. As expected, the extent of degradation due to discoloration increases with the increase in module temperature. The Isc loss is dictated by both the regions – discolored area at the center and non-discolored area at the cell edges, whereas the YI is only determined at the discolored region due to low probe area. This led to the limited correlation between Isc and YI in UVC modules.

In case of UVP modules, UV radiation has caused an adverse impact on the interfacial adhesion between the EVA and solar cell, which was detected from UVf images and severe Isc loss. No change in YI confirms that the reason for Isc loss is not due to yellowing but the delamination.

Further, the activation energy of encapsulant discoloration was estimated by using Arrhenius model on two types of data, %Isc drop and ΔYI. The Ea determined from the change in YI data for the EVA encapsulant discoloration reaction without the influence of oxygen and humidity is 0.61 eV. Based on the activation energy determined in this work and hourly weather data of any site, the degradation rate for the encaspulant browning mode can be estimated.
ContributorsDolia, Kshitiz (Author) / Tamizhmani, Govindasamy (Thesis advisor) / Green, Matthew (Thesis advisor) / Srinivasan, Devarajan (Committee member) / Arizona State University (Publisher)
Created2018
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Description
An urgent need for developing new chemical separations that address the capture of dilute impurities from fluid streams are needed. These separations include the capture of carbon dioxide from the atmosphere, impurities from drinking water, and toxins from blood streams. A challenge is presented when capturing these impurities because the

An urgent need for developing new chemical separations that address the capture of dilute impurities from fluid streams are needed. These separations include the capture of carbon dioxide from the atmosphere, impurities from drinking water, and toxins from blood streams. A challenge is presented when capturing these impurities because the energy cost for processing the bulk fluid stream to capture trace contaminants is too great using traditional thermal separations. The development of sorbents that may capture these contaminants passively has been emphasized in academic research for some time, producing many designer materials including metal-organic frameworks (MOFs) and polymeric resins. Scaffolds must be developed to effectively anchor these materials in a passing fluid stream. In this work, two design techniques are presented for anchoring these sorbents in electrospun fiber scaffolds.

The first technique involves imbedding sorbent particles inside the fibers: forming particle-embedded fibers. It is demonstrated that particles will spontaneously coat themselves in the fibers at dilute loadings, but at higher loadings some get trapped on the fiber surface. A mathematical model is used to show that when these particles are embedded, the polymeric coating provided by the fibers may be designed to increase the kinetic selectivity and/or stability of the embedded sorbents. Two proof-of-concept studies are performed to validate this model including the increased selectivity of carbon dioxide over nitrogen when the MOF ZIF-8 is embedded in a poly(ethylene oxide) and Matrimid polymer blend; and that increased hydrothermal stability is realized when the water-sensitive MOF HKUST-1 is embedded in polystyrene fibers relative to pure HKUST-1 powder.

The second technique involves the creation of a pore network throughout the fiber to increase accessibility of embedded sorbent particles. It is demonstrated that the removal of a blended highly soluble polymer additive from the spun particle-containing fibers leaves a pore network behind without removing the embedded sorbent. The increased accessibility of embedded sorbents is validated by embedding a known direct air capture sorbent in porous electrospun fibers, and demonstrating that they have the fastest kinetic uptake of any direct air capture sorbent reported in literature to date, along with over 90% sorbent accessibility.
ContributorsArmstrong, Mitchell (Author) / Mu, Bin (Thesis advisor) / Green, Matthew (Committee member) / Seo, Dong (Committee member) / Lackner, Klaus (Committee member) / Holloway, Julianne (Committee member) / Arizona State University (Publisher)
Created2018
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Description
Recently, two-dimensional (2D) materials have emerged as a new class of materials with highly attractive electronic, optical, magnetic, and thermal properties. However, there exists a sub-category of 2D layers wherein constituent metal atoms are arranged in a way that they form weakly coupled chains confined in the 2D landscape. These

Recently, two-dimensional (2D) materials have emerged as a new class of materials with highly attractive electronic, optical, magnetic, and thermal properties. However, there exists a sub-category of 2D layers wherein constituent metal atoms are arranged in a way that they form weakly coupled chains confined in the 2D landscape. These weakly coupled chains extend along particular lattice directions and host highly attractive properties including high thermal conduction pathways, high-mobility carriers, and polarized excitons. In a sense, these materials offer a bridge between traditional one-dimensional (1D) materials (nanowires and nanotubes) and 2D layered systems. Therefore, they are often referred as pseudo-1D materials, and are anticipated to impact photonics and optoelectronics fields.

This dissertation focuses on the novel growth routes and fundamental investigation of the physical properties of pseudo-1D materials. Example systems are based on transition metal chalcogenide such as rhenium disulfide (ReS2), titanium trisulfide (TiS3), tantalum trisulfide (TaS3), and titanium-niobium trisulfide (Nb(1-x)TixS3) ternary alloys. Advanced growth, spectroscopy, and microscopy techniques with density functional theory (DFT) calculations have offered the opportunity to understand the properties of these materials both experimentally and theoretically. The first controllable growth of ReS2 flakes with well-defined domain architectures has been established by a state-of-art chemical vapor deposition (CVD) method. High-resolution electron microscopy has offered the very first investigation into the structural pseudo-1D nature of these materials at an atomic level such as the chain-like features, grain boundaries, and local defects.

Pressure-dependent Raman spectroscopy and DFT calculations have investigated the origin of the Raman vibrational modes in TiS3 and TaS3, and discovered the unusual pressure response and its effect on Raman anisotropy. Interestingly, the structural and vibrational anisotropy can be retained in the Nb(1-x)TixS3 alloy system with the presence of phase transition at a nominal Ti alloying limit. Results have offered valuable experimental and theoretical insights into the growth routes as well as the structural, optical, and vibrational properties of typical pseudo-1D layered systems. The overall findings hope to shield lights to the understanding of this entire class of materials and benefit the design of 2D electronics and optoelectronics.
ContributorsWu, Kedi (Author) / Tongay, Sefaattin (Thesis advisor) / Zhuang, Houlong (Committee member) / Green, Matthew (Committee member) / Arizona State University (Publisher)
Created2018
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Description
Carbon dioxide (CO2) levels in the atmosphere have reached unprecedented levels due to increasing anthropogenic emissions and increasing energy demand. CO2 capture and utilization can aid in stabilizing atmospheric CO2 levels and producing carbon-neutral fuels. Utilizing hollow fiber membranes (HFMs) for microalgal cultivation accomplishes that via bubbleless gas-transfer,

Carbon dioxide (CO2) levels in the atmosphere have reached unprecedented levels due to increasing anthropogenic emissions and increasing energy demand. CO2 capture and utilization can aid in stabilizing atmospheric CO2 levels and producing carbon-neutral fuels. Utilizing hollow fiber membranes (HFMs) for microalgal cultivation accomplishes that via bubbleless gas-transfer, preventing CO2 loss to the atmosphere. Various lengths and geometries of HFMs were used to deliver CO2 to a sodium carbonate solution. A model was developed to calculate CO2 flux, mass-transfer coefficient (KL), and volumetric mass-transfer coefficient (KLa) based on carbonate equilibrium and the alkalinity of the solution. The model was also applied to a sparging system, whose performance was compared with that of the HFMs. Typically, HFMs are operated in closed-end mode or open-end mode. The former is characterized by a high transfer efficiency, while the latter provides the advantage of a high transfer rate. HFMs were evaluated for both modes of operation and a varying inlet CO2 concentration to determine the effect of inert gas and water vapor accumulation on transfer rates. For pure CO2, a closed-end module operated as efficiently as an open-end module. Closed-end modules perform significantly worse when CO2-enriched air was supplied. This was shown by the KLa values calculated using the model. Finally, a mass-balance model was constructed for the lumen of the membranes in order to provide insight into the gas-concentration profiles inside the fiber lumen. For dilute CO2 inlet streams, accumulation of inert gases -- nitrogen (N2), oxygen (O2), and water vapor (H2O) -- significantly affected module performance by reducing the average CO2 partial pressure in the membrane and diminishing the amount of interfacial mass-transfer area available for CO2 transfer.
ContributorsShesh, Tarun (Author) / Rittmann, Bruce E. (Thesis advisor) / Green, Matthew (Committee member) / Torres, Cesar (Committee member) / Arizona State University (Publisher)
Created2018
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Description
The large-scale anthropogenic emission of carbon dioxide into the atmosphere leads to many unintended consequences, from rising sea levels to ocean acidification. While a clean energy infrastructure is growing, mid-term strategies that are compatible with the current infrastructure should be developed. Carbon capture and storage in fossil-fuel power plants is

The large-scale anthropogenic emission of carbon dioxide into the atmosphere leads to many unintended consequences, from rising sea levels to ocean acidification. While a clean energy infrastructure is growing, mid-term strategies that are compatible with the current infrastructure should be developed. Carbon capture and storage in fossil-fuel power plants is one way to avoid our current gigaton-scale emission of carbon dioxide into the atmosphere. However, for this to be possible, separation techniques are necessary to remove the nitrogen from air before combustion or from the flue gas after combustion. Metal-organic frameworks (MOFs) are a relatively new class of porous material that show great promise for adsorptive separation processes. Here, potential mechanisms of O2/N2 separation and CO2/N2 separation are explored.

First, a logical categorization of potential adsorptive separation mechanisms in MOFs is outlined by comparing existing data with previously studied materials. Size-selective adsorptive separation is investigated for both gas systems using molecular simulations. A correlation between size-selective equilibrium adsorptive separation capabilities and pore diameter is established in materials with complex pore distributions. A method of generating mobile extra-framework cations which drastically increase adsorptive selectivity toward nitrogen over oxygen via electrostatic interactions is explored through experiments and simulations. Finally, deposition of redox-active ferrocene molecules into systematically generated defects is shown to be an effective method of increasing selectivity towards oxygen.
ContributorsMcIntyre, Sean (Author) / Mu, Bin (Thesis advisor) / Green, Matthew (Committee member) / Lind, Marylaura (Committee member) / Arizona State University (Publisher)
Created2019
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Description
Rapid development of new technology has significantly disrupted the way radiotherapy is planned and delivered. These processes involve delivering high radiation doses to the target tumor while minimizing dose to the surrounding healthy tissue. However, with rapid implementation of these new technologies, there is a need for the detection of

Rapid development of new technology has significantly disrupted the way radiotherapy is planned and delivered. These processes involve delivering high radiation doses to the target tumor while minimizing dose to the surrounding healthy tissue. However, with rapid implementation of these new technologies, there is a need for the detection of prescribed ionizing radiation for radioprotection of the patient and quality assurance of the technique employed. Most available clinical sensors are subjected to various limitations including requirement of extensive training, loss of readout with sequential measurements, sensitivity to light and post-irradiation wait time prior to analysis. Considering these disadvantages, there is still a need for a sensor that can be fabricated with ease and still operate effectively in predicting the delivered radiation dose.



The dissertation discusses the development of a sensor that changes color upon exposure to therapeutic levels of ionizing radiation used during routine radiotherapy. The underlying principle behind the sensor is based on the formation of gold nanoparticles from its colorless precursor salt solution upon exposure to ionizing radiation. Exposure to ionizing radiation generates free radicals which reduce ionic gold to its zerovalent gold form which further nucleate and mature into nanoparticles. The generation of these nanoparticles render a change in color from colorless to a maroon/pink depending on the intensity of incident ionizing radiation. The shade and the intensity of the color developed is used to quantitatively and qualitatively predict the prescribed radiation dose.

The dissertation further describes the applicability of sensor to detect a wide range of ionizing radiation including high energy photons, protons, electrons and emissions from radioactive isotopes while remaining insensitive to non-ionizing radiation. The sensor was further augmented with a capability to differentiate regions that are irradiated and non-irradiated in two dimensions. The dissertation further describes the ability of the sensor to predict dose deposition in all three dimensions. The efficacy of the sensor to predict the prescribed dose delivered to canine patients undergoing radiotherapy was also demonstrated. All these taken together demonstrate the potential of this technology to be translatable to the clinic to ensure patient safety during routine radiotherapy.
ContributorsSubramaniam Pushpavanam, Karthik (Author) / Rege, Kaushal (Thesis advisor) / Sapareto, Stephen (Committee member) / Nannenga, Brent (Committee member) / Green, Matthew (Committee member) / Mu, Bin (Committee member) / Arizona State University (Publisher)
Created2019
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Description
Ethylene vinyl acetate (EVA) is the most commonly used encapsulant in photovoltaic modules. However, EVA degrades over time and causes performance losses in PV system. Therefore, EVA degradation is a matter of concern from a durability point of view.

This work compares EVA encapsulant degradation in glass/backsheet and glass/glass field-aged

Ethylene vinyl acetate (EVA) is the most commonly used encapsulant in photovoltaic modules. However, EVA degrades over time and causes performance losses in PV system. Therefore, EVA degradation is a matter of concern from a durability point of view.

This work compares EVA encapsulant degradation in glass/backsheet and glass/glass field-aged PV modules. EVA was extracted from three field-aged modules (two glass/backsheet and one glass/glass modules) from three different manufacturers from various regions (cell edges, cell centers, and non-cell region) from each module based on their visual and UV Fluorescence images. Characterization techniques such as I-V measurements, Colorimetry, Different Scanning Calorimetry, Thermogravimetric Analysis, Raman spectroscopy, and Fourier Transform Infrared Spectroscopy were performed on EVA samples.

The intensity of EVA discoloration was quantified using colorimetric measurements. Module performance parameters like Isc and Pmax degradation rates were calculated from I-V measurements. Properties such as degree of crystallinity, vinyl acetate content and degree of crosslinking were calculated from DSC, TGA, and Raman measurements, respectively. Polyenes responsible for EVA browning were identified in FTIR spectra.

The results from the characterization techniques confirmed that when EVA undergoes degradation, crosslinking in EVA increases beyond 90% causing a decrease in the degree of crystallinity and an increase in vinyl acetate content of EVA. Presence of polyenes in FTIR spectra of degraded EVA confirmed the occurrence of Norrish II reaction. However, photobleaching occurred in glass/backsheet modules due to the breathable backsheet whereas no photobleaching occurred in glass/glass modules because they were hermetically sealed. Hence, the yellowness index along with the Isc and Pmax degradation rates of EVA in glass/glass module is higher than that in glass/backsheet modules.

The results implied that more acetic acid was produced in the non-cell region due to its double layer of EVA compared to the front EVA from cell region. But, since glass/glass module is hermetically sealed, acetic acid gets entrapped inside the module further accelerating EVA degradation whereas it diffuses out through backsheet in glass/backsheet modules. Hence, it can be said that EVA might be a good encapsulant for glass/backsheet modules, but the same cannot be said for glass/glass modules.
ContributorsPatel, Aesha Parimalbhai (Author) / Tamizhmani, Govindasamy (Thesis advisor) / Green, Matthew (Committee member) / Mu, Bin (Committee member) / Arizona State University (Publisher)
Created2018