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Description
Membrane technology is a viable option to debottleneck distillation processes and minimize the energy burden associated with light hydrocarbon mixture separations. Zeolitic imidazolate frameworks (ZIFs) are a new class of microporous metal-organic frameworks with highly tailorable zeolitic pores and unprecedented separation characteristics. ZIF-8 membranes demonstrate superior separation performance for propylene/propane (C3) and hydrogen/hydrocarbon mixtures at room temperature. However, to date, little is known about the static thermal stability and ethylene/ethane (C2) separation characteristics of ZIF-8. This dissertation presents a set of fundamental studies to investigate the thermal stability, transport and modification of ZIF-8 membranes for light hydrocarbon separations.
Static TGA decomposition kinetics studies show that ZIF-8 nanocrystals maintain their crystallinity up to 200○C in inert, oxidizing and reducing atmospheres. At temperatures of 250○C and higher, the findings herein support the postulation that ZIF-8 nanocrystals undergo temperature induced decomposition via thermolytic bond cleaving reactions to form an imidazole-Zn-azirine structure. The crystallinity/bond integrity of ZIF-8 membrane thin films is maintained at temperatures below 150○C.
Ethane and ethylene transport was studied in single and binary gas mixtures. Thermodynamic parameters derived from membrane permeation and crystal adsorption experiments show that the C2 transport mechanism is controlled by adsorption rather than diffusion. Low activation energy of diffusion values for both C2 molecules and limited energetic/entropic diffusive selectivity are observed for C2 molecules despite being larger than the nominal ZIF-8 pore aperture and is due to pore flexibility.
Finally, ZIF-8 membranes were modified with 5,6 dimethylbenzimidazole through solvent assisted membrane surface ligand exchange to narrow the pore aperture for enhanced molecular sieving. Results show that relatively fast exchange kinetics occur at the mainly at the outer ZIF-8 membrane surface between 0-30 minutes of exchange. Short-time exchange enables C3 selectivity increases with minimal olefin permeance losses. As the reaction proceeds, the ligand exchange rate slows as the 5,6 DMBIm linker proceeds into the ZIF-8 inner surface, exchanges with the original linker and first disrupts the original framework’s crystallinity, then increases order as the reaction proceeds. The ligand exchange rate increases with temperature and the H2/C2 separation factor increases with increases in ligand exchange time and temperature.
Static TGA decomposition kinetics studies show that ZIF-8 nanocrystals maintain their crystallinity up to 200○C in inert, oxidizing and reducing atmospheres. At temperatures of 250○C and higher, the findings herein support the postulation that ZIF-8 nanocrystals undergo temperature induced decomposition via thermolytic bond cleaving reactions to form an imidazole-Zn-azirine structure. The crystallinity/bond integrity of ZIF-8 membrane thin films is maintained at temperatures below 150○C.
Ethane and ethylene transport was studied in single and binary gas mixtures. Thermodynamic parameters derived from membrane permeation and crystal adsorption experiments show that the C2 transport mechanism is controlled by adsorption rather than diffusion. Low activation energy of diffusion values for both C2 molecules and limited energetic/entropic diffusive selectivity are observed for C2 molecules despite being larger than the nominal ZIF-8 pore aperture and is due to pore flexibility.
Finally, ZIF-8 membranes were modified with 5,6 dimethylbenzimidazole through solvent assisted membrane surface ligand exchange to narrow the pore aperture for enhanced molecular sieving. Results show that relatively fast exchange kinetics occur at the mainly at the outer ZIF-8 membrane surface between 0-30 minutes of exchange. Short-time exchange enables C3 selectivity increases with minimal olefin permeance losses. As the reaction proceeds, the ligand exchange rate slows as the 5,6 DMBIm linker proceeds into the ZIF-8 inner surface, exchanges with the original linker and first disrupts the original framework’s crystallinity, then increases order as the reaction proceeds. The ligand exchange rate increases with temperature and the H2/C2 separation factor increases with increases in ligand exchange time and temperature.
ContributorsJames, Joshua B. (Author) / Lin, Jerry Y.S. (Thesis advisor) / Emady, Heather (Committee member) / Lind, Mary Laura (Committee member) / Mu, Bin (Committee member) / Seo, Dong (Committee member) / Arizona State University (Publisher)
Created2017
Description
In material science, microstructure plays a key role in determining properties, which further determine utility of the material. However, effectively measuring microstructure evolution in real time remains an challenge. To date, a wide range of advanced experimental techniques have been developed and applied to characterize material microstructure and structural evolution on different length and time scales. Most of these methods can only resolve 2D structural features within a narrow range of length scale and for a single or a series of snapshots. The currently available 3D microstructure characterization techniques are usually destructive and require slicing and polishing the samples each time a picture is taken. Simulation methods, on the other hand, are cheap, sample-free and versatile without the special necessity of taking care of the physical limitations, such as extreme temperature or pressure, which are prominent
issues for experimental methods. Yet the majority of simulation methods are limited to specific circumstances, for example, first principle computation can only handle several thousands of atoms, molecular dynamics can only efficiently simulate a few seconds of evolution of a system with several millions particles, and finite element method can only be used in continuous medium, etc. Such limitations make these individual methods far from satisfaction to simulate macroscopic processes that a material sample undergoes up to experimental level accuracy. Therefore, it is highly desirable to develop a framework that integrate different simulation schemes from various scales
to model complicated microstructure evolution and corresponding properties. Guided by such an objective, we have made our efforts towards incorporating a collection of simulation methods, including finite element method (FEM), cellular automata (CA), kinetic Monte Carlo (kMC), stochastic reconstruction method, Discrete Element Method (DEM), etc, to generate an integrated computational material engineering platform (ICMEP), which could enable us to effectively model microstructure evolution and use the simulated microstructure to do subsequent performance analysis. In this thesis, we will introduce some cases of building coupled modeling schemes and present
the preliminary results in solid-state sintering. For example, we use coupled DEM and kinetic Monte Carlo method to simulate solid state sintering, and use coupled FEM and cellular automata method to model microstrucutre evolution during selective laser sintering of titanium alloy. Current results indicate that joining models from different length and time scales is fruitful in terms of understanding and describing microstructure evolution of a macroscopic physical process from various perspectives.
issues for experimental methods. Yet the majority of simulation methods are limited to specific circumstances, for example, first principle computation can only handle several thousands of atoms, molecular dynamics can only efficiently simulate a few seconds of evolution of a system with several millions particles, and finite element method can only be used in continuous medium, etc. Such limitations make these individual methods far from satisfaction to simulate macroscopic processes that a material sample undergoes up to experimental level accuracy. Therefore, it is highly desirable to develop a framework that integrate different simulation schemes from various scales
to model complicated microstructure evolution and corresponding properties. Guided by such an objective, we have made our efforts towards incorporating a collection of simulation methods, including finite element method (FEM), cellular automata (CA), kinetic Monte Carlo (kMC), stochastic reconstruction method, Discrete Element Method (DEM), etc, to generate an integrated computational material engineering platform (ICMEP), which could enable us to effectively model microstructure evolution and use the simulated microstructure to do subsequent performance analysis. In this thesis, we will introduce some cases of building coupled modeling schemes and present
the preliminary results in solid-state sintering. For example, we use coupled DEM and kinetic Monte Carlo method to simulate solid state sintering, and use coupled FEM and cellular automata method to model microstrucutre evolution during selective laser sintering of titanium alloy. Current results indicate that joining models from different length and time scales is fruitful in terms of understanding and describing microstructure evolution of a macroscopic physical process from various perspectives.
ContributorsChen, Shaohua (Author) / Jiao, Yang (Thesis advisor) / Wang, Qinghua (Committee member) / Emady, Heather (Committee member) / Gel, Aytekin (Committee member) / Arizona State University (Publisher)
Created2018
Description
Granulation is a process within particle technology where a liquid binding agent is added to a powder bed to create larger granules to modify bulk properties for easier processing. Three sets of experiments were conducted to screen for which factors had the greatest effect on granule formation, size distribution, and morphological properties when wet granulating microcrystalline cellulose and water. Previous experiments had identified the different growth regimes within wet granulation, as well as the granule formation mechanisms in single-drop granulation experiments, but little research has been conducted to determine how results extracted from single drop experiments could be used to better understand the first principles that drive high shear granulation. The experiment found that under a liquid solid ratio of 110%, the granule growth rate was linear as opposed to the induction growth regime experienced at higher liquid solid ratios. L/S ratios less than 100% led to a bimodal distribution comprised of large distributions of ungranulated powder and large irregular granules. Insufficient water hampered the growth of granules due to lack of enough water bridges to connect the granules and powder, while the large molecules continued to agglomerate with particles as they rotated around the mixer. The nozzle end was augmented so that drop size as well as drop height could be adjusted and compared to single-drop granulation experiments in proceeding investigations. As individual factors, neither augmentation had significant contributions to granule size, but preliminary screens identified that interaction between increasing L/S ratio and decreasing drop size could lead to narrower distributions of particles as well as greater circularity. Preliminary screening also identified that decreasing the drop height of the nozzle could increase the rate of particle growth during the 110% L/S trials without changing the growth mechanisms, indicating a way to alter the rate of steady-state particle growth. This paper screens for which factors are most pertinent to associating single-drop and wet granulation in order to develop granulation models that can ascertain information from single-drop granulations and predict the shape and size distribution of any wet granulation, without the need to run costly wet granulation experiments.
ContributorsLay, Michael (Author) / Emady, Heather (Thesis advisor) / Muhich, Christopher (Committee member) / Holloway, Julianne (Committee member) / Arizona State University (Publisher)
Created2019
Description
Rotary drums are commonly used for their high heat and mass transfer rates in the manufacture of cement, pharmaceuticals, food, and other particulate products. These processes are difficult to model because the particulate behavior is governed by the process conditions such as particle size, particle size distribution, shape, composition, and operating parameters, such as fill level and rotation rate. More research on heat transfer in rotary drums will increase operating efficiency, leading to significant energy savings on a global scale.
This research utilizes infrared imaging to investigate the effects of fill level and rotation rate on the particle bed hydrodynamics and the average wall-particle heat transfer coefficient. 3 mm silica beads and a stainless steel rotary drum with a diameter of 6 in and a length of 3 in were used at fill levels of 10 %, 17.5 %, and 25 %, and rotation rates of 2 rpm, 6 rpm, and 10 rpm. Two full factorial designs of experiments were completed to understand the effects of these factors in the presence of conduction only (Case 1) and conduction with forced convection (Case 2). Particle-particle friction caused the particle bed to stagnate at elevated temperatures in Case 1, while the inlet air velocity in Case 2 dominated the particle friction effects to maintain the flow profile. The maximum heat transfer coefficient was achieved at a high rotation rate and low fill level in Case 1, and at a high rotation rate and high fill level in Case 2. Heat losses from the system were dominated by natural convection between the hot air in the drum and the external surroundings.
This research utilizes infrared imaging to investigate the effects of fill level and rotation rate on the particle bed hydrodynamics and the average wall-particle heat transfer coefficient. 3 mm silica beads and a stainless steel rotary drum with a diameter of 6 in and a length of 3 in were used at fill levels of 10 %, 17.5 %, and 25 %, and rotation rates of 2 rpm, 6 rpm, and 10 rpm. Two full factorial designs of experiments were completed to understand the effects of these factors in the presence of conduction only (Case 1) and conduction with forced convection (Case 2). Particle-particle friction caused the particle bed to stagnate at elevated temperatures in Case 1, while the inlet air velocity in Case 2 dominated the particle friction effects to maintain the flow profile. The maximum heat transfer coefficient was achieved at a high rotation rate and low fill level in Case 1, and at a high rotation rate and high fill level in Case 2. Heat losses from the system were dominated by natural convection between the hot air in the drum and the external surroundings.
ContributorsBoepple, Brandon (Author) / Emady, Heather (Thesis advisor) / Muhich, Christopher (Committee member) / Holloway, Julianne (Committee member) / Arizona State University (Publisher)
Created2019
Description
The Basilisk lizard is known for its agile locomotion capabilities on granular and aquatic media making it an impressive model organism for studying multi-terrain locomotion mechanics. The work presented here is aimed at understanding locomotion characteristics of Basilisk lizards through a systematic series of robotic and animal experiments. In this work, a Basilisk lizard inspired legged robot with bipedal and quadrupedal locomotion capabilities is presented. A series of robot experiments are conducted on dry and wet (saturated) granular media to determine the effects of gait parameters and substrate saturation, on robot velocity and energetics. Gait parameters studied here are stride frequency and stride length. Results of robot experiments are compared with previously obtained animal data. It is observed that for a fixed robot stride frequency, velocity and stride length increase with increasing saturation, confirming the locomotion characteristics of the Basilisk lizard. It is further observed that with increasing saturation level, robot cost of transport decreases. An identical series of robot experiments are performed with quadrupedal gait to determine effects of gait parameters on robot performance. Generally, energetics of bipedal running is observed to be higher than quadrupedal operation. Experimental results also reveal how gait parameters can be varied to achieve different desired velocities depending on the substrate saturation level. In addition to robot experiments on granular media, a series of animal experiments are conducted to determine and characterize strategies
exhibited by Basilisk lizards when transitioning from granular to aquatic media.
exhibited by Basilisk lizards when transitioning from granular to aquatic media.
ContributorsJayanetti, Vidu (Author) / Marvi, Hamid (Thesis advisor) / Emady, Heather (Committee member) / Lee, Hyunglae (Committee member) / Arizona State University (Publisher)
Created2018
Description
The inherent risk in testing drugs has been hotly debated since the government first started regulating the drug industry in the early 1900s. Who can assume the risks associated with trying new pharmaceuticals is unclear when looked at through society's lens. In the mid twentieth century, the US Food and Drug Administration (FDA) published several guidance documents encouraging researchers to exclude women from early clinical drug research. The motivation to publish those documents and the subsequent guidance documents in which the FDA and other regulatory offices established their standpoints on women in drug research may have been connected to current events at the time. The problem of whether women should be involved in drug research is a question of who can assume risk and who is responsible for disseminating what specific kinds of information. The problem tends to be framed as one that juxtaposes the health of women and fetuses and sets their health as in opposition. That opposition, coupled with the inherent uncertainty in testing drugs, provides for a complex set of issues surrounding consent and access to information.
ContributorsMeek, Caroline Jane (Author) / Maienschein, Jane (Thesis director) / Brian, Jennifer (Committee member) / School of Life Sciences (Contributor) / Sanford School of Social and Family Dynamics (Contributor) / Barrett, The Honors College (Contributor)
Created2018-05
Description
Social-emotional learning (SEL) methods are beginning to receive global attention in primary school education, yet the dominant emphasis on implementing these curricula is in high-income, urbanized areas. Consequently, the unique features of developing and integrating such methods in middle- or low-income rural areas are unclear. Past studies suggest that students exposed to SEL programs show an increase in academic performance, improved ability to cope with stress, and better attitudes about themselves, others, and school, but these curricula are designed with an urban focus. The purpose of this study was to conduct a needs-based analysis to investigate components specific to a SEL curriculum contextualized to rural primary schools. A promising organization committed to rural educational development is Barefoot College, located in Tilonia, Rajasthan, India. In partnership with Barefoot, we designed an ethnographic study to identify and describe what teachers and school leaders consider the highest needs related to their students' social and emotional education. To do so, we interviewed 14 teachers and school leaders individually or in a focus group to explore their present understanding of “social-emotional learning” and the perception of their students’ social and emotional intelligence. Analysis of this data uncovered common themes among classroom behaviors and prevalent opportunities to address social and emotional well-being among students. These themes translated into the three overarching topics and eight sub-topics explored throughout the curriculum, and these opportunities guided the creation of the 21 modules within it. Through a design-based research methodology, we developed a 40-hour curriculum by implementing its various modules within seven Barefoot classrooms alongside continuous reiteration based on teacher feedback and participant observation. Through this process, we found that student engagement increased during contextualized SEL lessons as opposed to traditional methods. In addition, we found that teachers and students preferred and performed better with an activities-based approach. These findings suggest that rural educators must employ particular teaching strategies when addressing SEL, including localized content and an experiential-learning approach. Teachers reported that as their approach to SEL shifted, they began to unlock the potential to build self-aware, globally-minded students. This study concludes that social and emotional education cannot be treated in a generalized manner, as curriculum development is central to the teaching-learning process.
ContributorsBucker, Delaney Sue (Author) / Carrese, Susan (Thesis director) / Barab, Sasha (Committee member) / School of Life Sciences (Contributor, Contributor) / School of Civic & Economic Thought and Leadership (Contributor) / School of International Letters and Cultures (Contributor) / Barrett, The Honors College (Contributor)
Created2020-05
Description
As of 2019, 30 US states have adopted abortion-specific informed consent laws that require state health departments to develop and disseminate written informational materials to patients seeking an abortion. Abortion is the only medical procedure for which states dictate the content of informed consent counseling. State abortion counseling materials have been criticized for containing inaccurate and misleading information, but overall, informed consent laws for abortion do not often receive national attention. The objective of this project was to determine the importance of informed consent laws to achieving the larger goal of dismantling the right to abortion. I found that informed consent counseling materials in most states contain a full timeline of fetal development, along with information about the risks of abortion, the risks of childbirth, and alternatives to abortion. In addition, informed consent laws for abortion are based on model legislation called the “Women’s Right to Know Act” developed by Americans United for Life (AUL). AUL calls itself the legal architect of the pro-life movement and works to pass laws at the state level that incrementally restrict abortion access so that it gradually becomes more difficult to exercise the right to abortion established by Roe v. Wade. The “Women’s Right to Know Act” is part of a larger package of model legislation called the “Women’s Protection Project,” a cluster of laws that place restrictions on abortion providers, purportedly to protect women, but actually to decrease abortion access. “Women’s Right to Know” counseling laws do not directly deny access to abortion, but they do reinforce key ideas important to the anti-abortion movement, like the concept of fetal personhood, distrust in medical professionals, the belief that pregnant people cannot be fully autonomous individuals, and the belief that abortion is not an ordinary medical procedure and requires special government oversight. “Women’s Right to Know” laws use the language of informed consent and the purported goal of protecting women to legitimize those ideas, and in doing so, they significantly undermine the right to abortion. The threat to abortion rights posed by laws like the “Women’s Right to Know” laws indicates the need to reevaluate and strengthen our ethical defense of the right to abortion.
ContributorsVenkatraman, Richa (Author) / Maienschein, Jane (Thesis director) / Brian, Jennifer (Thesis director) / Abboud, Carolina (Committee member) / Historical, Philosophical & Religious Studies (Contributor) / School of Life Sciences (Contributor, Contributor) / Barrett, The Honors College (Contributor)
Created2020-05
Description
Turbidity is a known problem for UV water treatment systems as suspended particles can shield contaminants from the UV radiation. UV systems that utilize a reflective radiation chamber may be able to decrease the impact of turbidity on the efficacy of the system. The purpose of this study was to determine how kaolin clay and gram flour turbidity affects inactivation of Escherichia coli (E. coli) when using a UV system with a reflective chamber. Both sources of turbidity were shown to reduce the inactivation of E. coli with increasing concentrations. Overall, it was shown that increasing kaolin clay turbidity had a consistent effect on reducing UV inactivation across UV doses. Log inactivation was reduced by 1.48 log for the low UV dose and it was reduced by at least 1.31 log for the low UV dose. Gram flour had a similar effect to the clay at the lower UV dose, reducing log inactivation by 1.58 log. At the high UV dose, there was no change in UV inactivation with an increase in turbidity. In conclusion, turbidity has a significant impact on the efficacy of UV disinfection. Therefore, removing turbidity from water is an essential process to enhance UV efficiency for the disinfection of microbial pathogens.
ContributorsMalladi, Rohith (Author) / Abbaszadegan, Morteza (Thesis director) / Alum, Absar (Committee member) / Fox, Peter (Committee member) / School of Human Evolution & Social Change (Contributor) / School of Life Sciences (Contributor) / Barrett, The Honors College (Contributor)
Created2020-05
Description
Aquatic macroinvertebrates are important for many ecological processes within river ecosystems and, as a result, their abundance and diversity are considered indicators of water quality and ecosystem health. Macroinvertebrates can be classified into functional feeding groups (FFG) based on morphological-behavioral adaptations. FFG ratios can shift due to changes in normal disturbance patterns, such as changes in precipitation, and from human impact. Due to their increased sensitivity to environmental changes, it has become more important to protect and monitor aquatic and riparian communities in arid regions as climate change continues to intensify. Therefore, the diversity and richness of macroinvertebrate FFGs before and after monsoon and winter storm seasons were analyzed to determine the effect of flow-related disturbances. Ecosystem size was also considered, as watershed area has been shown to affect macroinvertebrate diversity. There was no strong support for flow-related disturbance or ecosystem size on macroinvertebrate diversity and richness. This may indicate a need to explore other parameters of macroinvertebrate community assembly. Establishing how disturbance affects aquatic macroinvertebrate communities will provide a key understanding as to what the stream communities will look like in the future, as anthropogenic impacts continue to affect more vulnerable ecosystems.
ContributorsSainz, Ruby (Author) / Sabo, John (Thesis director) / Grimm, Nancy (Committee member) / Lupoli, Christina (Committee member) / School of Life Sciences (Contributor, Contributor) / Barrett, The Honors College (Contributor)
Created2020-05