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- Creators: Arizona State University
- Creators: Green, Matthew D.
- Member of: Theses and Dissertations
- Member of: Barrett, The Honors College Thesis/Creative Project Collection
- Resource Type: Text
Description
Of the potential technologies for pre-combustion capture, membranes offer the advantages of being temperature resistant, able to handle large flow rates, and having a relatively small footprint. A significant amount of research has centered on the use of polymeric and microporous inorganic membranes to separate CO2. These membranes, however, have limitations at high temperature resulting in poor permeation performance. To address these limitations, the use of a dense dual-phase membrane has been studied. These membranes are composed of conductive solid and conductive liquid phases that have the ability to selectively permeate CO2 by forming carbonate ions that diffuse through the membrane at high temperature. The driving force for transport through the membrane is a CO2 partial pressure gradient. The membrane provides a theoretically infinite selectivity. To address stability of the ceramic-carbonate dual-phase membrane for CO2 capture at high temperature, the ceramic phase of the membrane was studied and replaced with materials previously shown to be stable in harsh conditions. The permeation properties and stability of La0.6Sr0.4Co0.8Fe0.2O3-δ (LSCF)-carbonate, La0.85Ce0.1Ga0.3Fe0.65Al0.05O3-δ (LCGFA)-carbonate, and Ce0.8Sm0.2O1.9 (SDC)-carbonate membranes were examined under a wide range of experimental conditions at high temperature. LSCF-carbonate membranes were shown to be unstable without the presence of O2 due to reaction of CO2 with the ceramic phase. In the presence of O2, however, the membranes showed stable permeation behavior for more than one month at 900oC. LCGFA-carbonate membranes showed great chemical and permeation stability in the presence of various conditions including exposure to CH4 and H2, however, the permeation performance was quite low when compared to membranes in the literature. Finally, SDC-carbonate membranes showed great chemical and permeation stability both in a CO2:N2 environment for more than two weeks at 900oC as well as more than one month of exposure to simulated syngas conditions at 700oC. Ceramic phase chemical stability increased in the order of LSCF < LCGFA < SDC while permeation performance increased in the order of LCGFA < LSCF < SDC.
ContributorsNorton, Tyler (Author) / Lin, Jerry Y.S. (Thesis advisor) / Alford, Terry (Committee member) / Lind, Mary Laura (Committee member) / Smith, David (Committee member) / Torres, Cesar (Committee member) / Arizona State University (Publisher)
Created2013
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 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
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 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
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. 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.
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
Description
Cancer poses a significant worldwide burden where ongoing efforts are targeted towards improving patient outcomes in which a significant contribution results from cancer screening. Multi-cancer early detection tests have been introduced which measure a series of biomarkers to detect signals that may indicate carcinogenesis in its earliest stages and work in tandem with other diagnostic techniques to localize and verify tumor formation across multiple cancer types. Molecular biomarkers such as autoantibodies are promising candidates for early detection across multiple cancers. This study identifies autoantibodies that are aberrantly expressed across multiple cancer types that may be used to discriminate between healthy individuals and those with cancer from a single serum sample. Multiple datasets are integrated from prior studies to examine 8,200 sera autoantibodies from 5 cancer types including lung adenocarcinoma, basal-like breast cancer, advanced colorectal cancer, ovarian cancer, and HER2+ breast cancer. The diagnostic utility of these autoantibodies is assessed for combined cancer types by meta-receiver operating characteristic (ROC) curve analysis. A meta-analysis data processing pipeline is utilized for processing each biomarker with statistical analysis performed across ROC metrics for each meta-curve including partial area under the curve and sensitivity at a 90% specificity threshold. Results identified 26 autoantibody biomarkers that are useful for multi-cancer detection and may be developed for future clinical applications in cancer screening.
ContributorsGoeringer, Cayden Brett (Author) / Chung, Yunro (Thesis advisor) / Broatch, Jennifer (Thesis advisor) / Hart, Steven (Committee member) / Arizona State University (Publisher)
Created2024
A Meta-Analysis of Experimental Examinations of Racism in U.S. Pre-K-12th Grade Educational Contexts
Description
Racism primarily has been examined in United States (U.S.) educational contexts via survey and qualitative investigations, which reveal Black, Indigenous, and People of Colors’ (BIPOCs’) self-reported experiences of individual racism. Missing from this research is a focus on the perpetrators of racism and the institutional nature of racism in U.S. education. Experimental examinations of racism in U.S. education are efficacious in identifying perpetrators of racism and offer objective evidence of racism, which can underscore the importance of qualitative and survey findings. However, experimental examinations of racism in educational contexts are infrequent, examine a wide array of perpetrators (e.g., peers, teachers, principals) and educational domains (grading, diagnoses, liking), and reveal mixed findings. Thus, I utilized meta-analytic techniques to explore the magnitude of the effect of racism in pre-K-12th grade contexts as demonstrated by experimental examinations. In addition, I explore moderation of the effect of racism by 1) the type of experimental technique, 2) the specific perpetrator, 3) the BIPOC target, 4) the region of the US, and 5) the design of treatment assignment. Using 71 effect sizes from 57 studies, I found evidence that racism is present in U.S. pre-K-12th grade education for BIPOC [Cohen’s d=0.15, 95% CI(0.05, 0.25)]. Heterogeneity existed in the overall effect, and moderators included the U.S. region, and the level of racism (e.g., individual versus institutional) explained the heterogeneity of the effects. The findings are discussed in terms of theoretical and methodological implications and future directions for research.
ContributorsJanssen, Jayley (Author) / Seaton, Eleanor (Thesis advisor) / Miller, Cindy F (Committee member) / Causadias, Jose (Committee member) / Jager, Justin (Committee member) / Arizona State University (Publisher)
Created2023
Description
The rate of urbanization has been impacted by global economic growth. A strong economy results in more people moving to already crowded urban centers to take advantage of increased employment opportunities often resulting in sprawling of the urban area. More natural land resources are being exploited to accommodate these anthropogenic activities. Subsequently, numerous natural land resources such as green areas or porous soil, which are less flood-prone and more permeable are being converted into buildings, parking lots, roads and underground utilities that are less permeable to stormwater runoff from rain events. With the diminishing of the natural landscape that can drain stormwater during a rainfall event, urban underground drainage systems are being designed and built to tackle the excess runoff resulting from urbanization. However, the construction of a drainage system is expensive and usually involves massive land excavations and tremendous environmental disturbances. The option for constructing an underground drainage system is even more difficult in dense urban environments due to the complicated underground environments, creating a need for low footprint solutions. This need has led to emerging opportunities for low impact development (LID) methods or green infrastructures, which are viewed as an environmentally friendly alternative for dealing with stormwater runoff. LID mimics the pre-development environment to retain the stormwater runoff through infiltration, retention, detention and evaporation. Despite a significant amount of prior research having been conducted to analyze the performance of runoff volume reduction and peak flow decrement of various green infrastructures, little is known about the economic benefits of using LID practices.
This dissertation fills the gap in the knowledge regarding the life-cycle-cost effectiveness of green infrastructure in current urban developments. This study’s two research objectives are:
(1) Develop a life cycle cost calculation template to analyze the cost benefits of using LID compared to the traditional drainage system
(2) Quantify the cost benefits based on the real-world construction projects
A thorough literature review led to the data collection of the hydrological benefits of using LIDs in conjunction with overviewing three real-world construction projects to quantify the cost benefits of LIDs.
This dissertation fills the gap in the knowledge regarding the life-cycle-cost effectiveness of green infrastructure in current urban developments. This study’s two research objectives are:
(1) Develop a life cycle cost calculation template to analyze the cost benefits of using LID compared to the traditional drainage system
(2) Quantify the cost benefits based on the real-world construction projects
A thorough literature review led to the data collection of the hydrological benefits of using LIDs in conjunction with overviewing three real-world construction projects to quantify the cost benefits of LIDs.
ContributorsZhang, Pengfei (Author) / Ariaratnam, Samuel T (Thesis advisor) / Vivoni, Enrique R (Committee member) / Bearup, Wylie (Committee member) / Arizona State University (Publisher)
Created2019
Description
There is a need to reinvent evidence-based interventions (EBIs) for pediatric anxiety problems to better address the demands of real-word service delivery settings and achieve public health impact. The time- and resource-intensive nature of most EBIs for youth anxiety has frequently been noted as a barrier to the utilization of EBIs in community settings, leading to increased attention towards exploring the viability of briefer, more accessible protocols. Principally, this research reports between-group effect sizes from brief-interventions targeting pediatric anxiety and classifies each as well-established, probably efficacious, possibly efficacious, experimental, or questionable. brief interventions yielded an overall mean effect size of 0.19 on pediatric anxiety outcomes from pre to post. Effect sizes varied significantly by level of intervention: Pre to post-intervention effects were strongest for brief-treatments (0.35), followed by brief-targeted prevention (0.22), and weakest for brief-universal prevention (0.09). No participant or other intervention characteristic emerged as significant moderators of effect sizes. In terms of standard of evidence, one brief intervention is well-established, and five are probably efficacious, with most drawing on cognitive and behavioral change procedures and/or family systems models. At this juncture, the minimal intervention needed for clinical change in pediatric anxiety points to in-vivo exposures for specific phobias (~3 hours), cognitive-behavioral therapy (CBT) with social skills training (~3 hours), and CBT based parent training (~6 hours, eight digital modules with clinician support). This research concludes with a discussion on limitations to available brief EBIs, practice guidelines, and future research needed to capitalize on the viability of briefer protocols in enhancing access to, and impact of, evidence-based care in the real-world.
ContributorsStoll, Ryan (Author) / Pina, Armando A. (Thesis advisor) / Gonzales, Nancy (Committee member) / MacKinnon, David (Committee member) / Perez, Marisol (Committee member) / Arizona State University (Publisher)
Created2019
Description
The occurrence of micro-and nanoplastic (MNP) debris in the environment is a research area of considerable public health concern. Various combinations of methods for extraction, isolation, and quantification of MNP have been applied but literature studies evaluating the appropriateness and efficacy of these protocols are lacking. A meta-analysis of the literature (n=134; years 2010-2017) was conducted to inventory and assess the appropriateness of methodologies employed. Some 30.6% of studies employed visual identification only, which carried a calculated misidentification error of 25.8-74.2%. An additional 6.7% of studies reported counts for particles smaller than the cutoff value of the selected collection pore size, and 9.7% of studies utilized extraction solution densities which exclude some of the polymers commonly occurring in the environments investigated. A composite value of data vulnerability of 43.3% was determined for the sample, indicating considerable weaknesses in the robustness of information available on MNP occurrence and type. Additionally, the oxidizing solutions documented in the literature frequently were deemed unsuccessful in removing interfering organic matter. Whereas nanoplastics measuring <1 µm in diameter are likely principal drivers of health risk, polymer fragments reported on in the literature are much larger, measuring 10+ µm in diameter due to lack of standardized methods. Thus, current inventories of MNP in the environmental MNP feature data quality concerns that should be addressed moving forward by using more robust and standardized techniques for sampling, processing and polymer identification to improve data quality and avoid the risk of misclassification.
ContributorsCook, Cayla R (Author) / Halden, Rolf U. (Thesis advisor) / Hamilton, Kerry (Committee member) / Mascaro, Giuseppe (Committee member) / Arizona State University (Publisher)
Created2018
Description
Dielectrophoresis (DEP) is a technique that influences the motion of polarizable particles in an electric field gradient. DEP can be combined with other effects that influence the motion of a particle in a microchannel, such as electrophoresis and electroosmosis. Together, these three can be used to probe properties of an analyte, including charge, conductivity, and zeta potential. DEP shows promise as a high-resolution differentiation and separation method, with the ability to distinguish between subtly-different populations. This, combined with the fast (on the order of minutes) analysis times offered by the technique, lend it many of the features necessary to be used in rapid diagnostics and point-of-care devices.
Here, a mathematical model of dielectrophoretic data is presented to connect analyte properties with data features, including the intercept and slope, enabling DEP to be used in applications which require this information. The promise of DEP to distinguish between analytes with small differences is illustrated with antibiotic resistant bacteria. The DEP system is shown to differentiate between methicillin-resistant and susceptible Staphylococcus aureus. This differentiation was achieved both label free and with bacteria that had been fluorescently-labeled. Klebsiella pneumoniae carbapenemase-positive and negative Klebsiella pneumoniae were also distinguished, demonstrating the differentiation for a different mechanism of antibiotic resistance. Differences in dielectrophoretic behavior as displayed by S. aureus and K. pneumoniae were also shown by Staphylococcus epidermidis. These differences were exploited for a separation in space of gentamicin-resistant and -susceptible S. epidermidis. Besides establishing the ability of DEP to distinguish between populations with small biophysical differences, these studies illustrate the possibility for the use of DEP in applications such as rapid diagnostics.
Here, a mathematical model of dielectrophoretic data is presented to connect analyte properties with data features, including the intercept and slope, enabling DEP to be used in applications which require this information. The promise of DEP to distinguish between analytes with small differences is illustrated with antibiotic resistant bacteria. The DEP system is shown to differentiate between methicillin-resistant and susceptible Staphylococcus aureus. This differentiation was achieved both label free and with bacteria that had been fluorescently-labeled. Klebsiella pneumoniae carbapenemase-positive and negative Klebsiella pneumoniae were also distinguished, demonstrating the differentiation for a different mechanism of antibiotic resistance. Differences in dielectrophoretic behavior as displayed by S. aureus and K. pneumoniae were also shown by Staphylococcus epidermidis. These differences were exploited for a separation in space of gentamicin-resistant and -susceptible S. epidermidis. Besides establishing the ability of DEP to distinguish between populations with small biophysical differences, these studies illustrate the possibility for the use of DEP in applications such as rapid diagnostics.
ContributorsHilton, Shannon (Author) / Hayes, Mark A. (Thesis advisor) / Borges, Chad (Committee member) / Herckes, Pierre (Committee member) / Arizona State University (Publisher)
Created2019