Matching Items (457)
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
This research investigated deionized water contact angle measurement reliability with alumina powder using the Washburn method. This method relates the capillary rise of a liquid through a column of packed powder to the contact angle of the system. A reference liquid that is assumed to be perfectly wetting, such as hexane due to the low surface energy, must be used to compare to the tested liquid. Consistency was hypothesized to be achieved with more powder structure and consistency of packing between reference and test trials. The three types of packing structures explored in this study were unstructured, visually-structured (user tapped), and machine-structured tapping. It was also hypothesized that similar contact angle results would be found for different packing methods of the same powder and liquid. However, the average contact angle for unstructured packing was found to be 32.9°, while the angle for the tapped structure was only 11.7°. This large deviation between types of packing shows that there are more inconsistencies with the use of this method than just the regulation of the packing structure. There were two similar glass chromatography columns used, but the second column experienced an unknown interference that led to a delay in the hexane uptake into the powder, which then led to invalid contact angle calculations. There was no discernible relationship between the packing structure and the standard deviation between trials, so the more structured packing does not seem to affect the consistency of results. It is recommended to perform more experiments on a single packing type with different apparatuses and a narrower particle size range.
ContributorsConvery, Brittany Alexis (Author) / Emady, Heather (Thesis director) / Vajrala, Spandana (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2017-12
Description
The wettability of powders is an important characteristic for both industry and academia and is often described by the powder’s contact angle with a certain liquid. While there exist many ways to measure contact angle, it is a portion of the powder technology field that is not fully understood and requires more investigation and research. This study investigates two methods for measuring contact angle, the sessile drop method and the Washburn method, and looks to compare results to determine which method offers the most reliable data in terms of accuracy and repeatability. Two powders - microcrystalline cellulose and aluminum oxide - and three liquids - water, 50 cSt silicone oil, and 350 cSt silicone oil - were used to study the differences between the two measurement techniques as well as the effects of varying fluid viscosity on the measurements. It was found that the sessile drop method proved to be an ineffective method for measuring contact angle when liquid penetration into the powder occurred, as the contact angle changed while the drop penetrated. Initial results showed the contact angle for silicone oil on the powders to be greater than 90°, indicating nonwetting of the surface which was inconsistent with observations. The results from the Washburn method align better with other values in similar studies, but more study is needed to confirm the results gathered in this research.
ContributorsSmith, Bryan Alexander (Author) / Emady, Heather (Thesis director) / Rykaczewski, Konrad (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05
Description
In the development of personalized medicine and many other clinical studies, biospecimen integrity serves as the prerequisite for not only the accurate derivation of patient- and disease-specific molecular data from biological specimens but the meaningful downstream validation of biomarkers. However, a large number of preanalytical variables may influence the quality of biospecimens in an undesired way and ultimately render the samples unsuitable for molecular analysis. The limited ability to directly reduce discrepancies caused by preanalytical variables gives rise to the need for development and retrospective application of appropriate tests for assessment of biospecimen integrity. Nevertheless, the most standard approaches to assessing biospecimen integrity involve nontrivial procedures. Thus, the need for quality control tools or tests that are readily applicable and can produce results in a straightforward way becomes critical. As one of the major ex vivo biomolecular degradation mechanisms, oxidation that occurs when blood plasma and serum samples are exposed to thawed states during storage and processing is hard to forestall and detect. In an attempt to easily detect and monitor the degree of oxidation, the technique of Fluorescence Resonance Energy Transfer (FRET) was examined to determine whether this concept could be employed to monitor exposure of samples to thawed conditions when controlled by spontaneous oxidative disulfide bonding. The intended mode of usage was envisioned as a fluorescence liquid being stored in a separate compartment but within the same test tube as archived plasma and serum samples. This would allow the assessment of sample integrity by direct visualization of fluorescence under a hand-held black light. The fluorescent dynamic range as well as kinetic control of the reaction were studied. While the addition of Cu(II) proved to facilitate excellent dynamic range with regard to fluorescence quenching, the kinetics of the reaction were too rapid for practical use. Further investigation revealed that the fluorescence quenching mechanism might have actually occurred via Intramolecular Charge Transfer (ICT) rather than FRET mediated by oxidative disulfide bond formation. Introduction of Cu(II) via copper metal slowed fluorescence quenching to the point of practical utility; facilitating demonstration that storing at room temperature, refrigerating or freezing the samples delayed fluorescence quenching to different extents. To establish better kinetic control, future works will focus on establishing controlled, thoroughly understood kinetic release of Cu(II) from copper metal.
ContributorsZhang, Zihan (Author) / Borges, Chad (Thesis director) / Emady, Heather (Committee member) / Williams, Peter (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2018-12
Description
The role of robotics mobility is essential in the world of research because it allows humans to perform jobs that are dull, dirty, or dangerous without being physically present. A typical robot environment is one that is smooth and predictable. Screw-powered vehicles (SPV's) have commonly been used in these predictable environment situations such as terrestrial applications like mud and snow. However, a gap remains in SPV's traversing complex environments, particularly debris and granular material. The goal is to study the characteristics of how a SPV might move and generate force in such a granular environment for Earth and space. In our study, the chosen granular environment is soda-lime glass beads for easy characterization. This study with glass beads focuses on two separate approaches. The first approach is using a single screw rotating while the apparatus remains static and analyzing the forces that impact the screw. The second approach includes using a full body craft with two double helix screws and analyzing the translational velocity of the craft. This study presents both experimental and computational results using simulations with Multi-Body Dynamics (MBD) and Discrete Element Method (DEM) software packages to investigate the trends of SPV's in a granular environment.
ContributorsRamirez, Sierra Monique (Author) / Marvi, Hamid (Thesis director) / Emady, Heather (Committee member) / Thoesen, Andrew (Committee member) / Mechanical and Aerospace Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2018-05
Description
In industrial applications, rotary drums are poorly understood and preform suboptimally when used to process particulates. In order to better understand how these drums work, a statistical experiment was designed to measure the effects of the fill level and rotation rate on the final temperature of the particle bed. A steel rotary drum was set up to be headed by three external heat guns, simulating the conditions under which standard rotary drums are operated. By measuring the bed temperature at steady state, and recording the combination of factors in each run, a regression analysis was run to determine the factor's effects. Fill level was seen to have a small positive effect, rotation rate was seen to have a small negative effect, and the interaction of the two was shown to have a large positive effect. This led the team to conclude that the flow profile of the bed may be the most important factor in heat transfer, and that further research should be done to isolate and study the effect of the flow profile.
ContributorsBeairsto, Cole James (Author) / Emady, Heather (Thesis director) / Adepu, Manogna (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2018-05