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Description
Ordered mesoporous materials have tunable pore sizes between 2 and 50 nm and are characterized by ordered pore structures and high surface areas (~1000 m2/g). This makes them particularly favorable for a number of membrane applications such as protein separation, polymer extrusion, nanowire fabrication and membrane reactors. These membranes can

Ordered mesoporous materials have tunable pore sizes between 2 and 50 nm and are characterized by ordered pore structures and high surface areas (~1000 m2/g). This makes them particularly favorable for a number of membrane applications such as protein separation, polymer extrusion, nanowire fabrication and membrane reactors. These membranes can be fabricated as top-layers on macroporous supports or as embedded membranes in a dense matrix. The first part of the work deals with the hydrothermal synthesis and water-vapor/oxygen separation properties of supported MCM-48 and a new Al-MCM-48 type membrane for potential use in air conditioning systems. Knudsen-type permeation is observed in these membranes. The combined effect of capillary condensation and the aluminosilicate matrix resulted in the highest separation factor (142) in Al-MCM-48 membranes, with a water vapor permeance of 6×10-8mol/m2Pas. The second part focuses on synthesis of embedded mesoporous silica membranes with helically ordered pores by a novel Counter Diffusion Self-Assembly (CDSA) method. This method is an extension of the interfacial synthesis method for fiber synthesis using tetrabutylorthosilicate (TBOS) and cetyltrimethylammonium bromide (CTAB) as the silica source and surfactant respectively. The initial part of this study determined the effect of TBOS height and humidity on fiber formation. From this study, the range of TBOS heights for best microscopic and macroscopic ordering were established. Next, the CDSA method was used to successfully synthesize membranes, which were characterized to have good support plugging and an ordered pore structure. Factors that influence membrane synthesis and plug microstructure were determined. SEM studies revealed the presence of gaps between the plugs and support pores, which occur due to shrinking of the plug on drying. Development of a novel liquid deposition method to seal these defects constituted the last part of this work. Post sealing, excess silica was removed by etching with hydrofluoric acid. Membrane quality was evaluated at each step using SEM and gas permeation measurements. After surfactant removal by liquid extraction, the membranes exhibited an O2 permeance of 1.65x10-6mol/m2.Pa.s and He/O2 selectivity of 3.30. The successful synthesis of this membrane is an exciting new development in the area of ordered mesoporous membrane technology.
ContributorsSeshadri, Shriya (Author) / Lin, Jerry Y. S. (Thesis advisor) / Dai, Lenore (Committee member) / Rege, Kaushal (Committee member) / Smith, David J. (Committee member) / Vogt, Bryan (Committee member) / Arizona State University (Publisher)
Created2011
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Description
Polymer and polymer matrix composites (PMCs) materials are being used extensively in different civil and mechanical engineering applications. The behavior of the epoxy resin polymers under different types of loading conditions has to be understood before the mechanical behavior of Polymer Matrix Composites (PMCs) can be accurately predicted. In many

Polymer and polymer matrix composites (PMCs) materials are being used extensively in different civil and mechanical engineering applications. The behavior of the epoxy resin polymers under different types of loading conditions has to be understood before the mechanical behavior of Polymer Matrix Composites (PMCs) can be accurately predicted. In many structural applications, PMC structures are subjected to large flexural loadings, examples include repair of structures against earthquake and engine fan cases. Therefore it is important to characterize and model the flexural mechanical behavior of epoxy resin materials. In this thesis, a comprehensive research effort was undertaken combining experiments and theoretical modeling to investigate the mechanical behavior of epoxy resins subject to different loading conditions. Epoxy resin E 863 was tested at different strain rates. Samples with dog-bone geometry were used in the tension tests. Small sized cubic, prismatic, and cylindrical samples were used in compression tests. Flexural tests were conducted on samples with different sizes and loading conditions. Strains were measured using the digital image correlation (DIC) technique, extensometers, strain gauges, and actuators. Effects of triaxiality state of stress were studied. Cubic, prismatic, and cylindrical compression samples undergo stress drop at yield, but it was found that only cubic samples experience strain hardening before failure. Characteristic points of tensile and compressive stress strain relation and load deflection curve in flexure were measured and their variations with strain rate studied. Two different stress strain models were used to investigate the effect of out-of-plane loading on the uniaxial stress strain response of the epoxy resin material. The first model is a strain softening with plastic flow for tension and compression. The influence of softening localization on material behavior was investigated using the DIC system. It was found that compression plastic flow has negligible influence on flexural behavior in epoxy resins, which are stronger in pre-peak and post-peak softening in compression than in tension. The second model was a piecewise-linear stress strain curve simplified in the post-peak response. Beams and plates with different boundary conditions were tested and analytically studied. The flexural over-strength factor for epoxy resin polymeric materials were also evaluated.
ContributorsYekani Fard, Masoud (Author) / Chattopadhyay, Aditi (Thesis advisor) / Dai, Lenore (Committee member) / Li, Jian (Committee member) / Papandreou-Suppappola, Antonia (Committee member) / Rajadas, John (Committee member) / Arizona State University (Publisher)
Created2011
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Description
Plasmon resonance in nanoscale metallic structures has shown its ability to concentrate electromagnetic energy into sub-wavelength volumes. Metal nanostructures exhibit a high extinction coefficient in the visible and near infrared spectrum due to their large absorption and scattering cross sections corresponding to their surface plasmon resonance. Hence, they can serve

Plasmon resonance in nanoscale metallic structures has shown its ability to concentrate electromagnetic energy into sub-wavelength volumes. Metal nanostructures exhibit a high extinction coefficient in the visible and near infrared spectrum due to their large absorption and scattering cross sections corresponding to their surface plasmon resonance. Hence, they can serve as an attractive candidate for solar energy conversion. Recent papers have showed that dielectric core/metallic shell nanoparticles yielded a plasmon resonance wavelength tunable from visible to infrared by changing the ratio of core radius to the total radius. Therefore it is interesting to develop a dispersion of core-shell multifunctional nanoparticles capable of dynamically changing their volume ratio and thus their spectral radiative properties. Nanoparticle suspensions (nanofluids) are known to offer a variety of benefits for thermal transport and energy conversion. Nanofluids have been proven to increase the efficiency of the photo-thermal energy conversion process in direct solar absorption collectors (DAC). Combining these two cutting-edge technologies enables the use of core-shell nanoparticles to control the spectral and radiative properties of plasmonic nanofluids in order to efficiently harvest and convert solar energy. Plasmonic nanofluids that have strong energy concentrating capacity and spectral selectivity can be used in many high-temperature energy systems where radiative heat transport is essential. In this thesis,the surface plasmon resonance effect and the wavelength tuning ranges for different metallic shell nanoparticles are investigated, the solar-weighted efficiencies of corresponding core-shell nanoparticle suspensions are explored, and a quantitative study of core-shell nanoparticle suspensions in a DAC system is provided. Using core-shell nanoparticle dispersions, it is possible to create efficient spectral solar absorption fluids and design materials for applications which require variable spectral absorption or scattering.
ContributorsLv, Wei (Author) / Phelan, Patrick E (Thesis advisor) / Dai, Lenore (Committee member) / Prasher, Ravi (Committee member) / Arizona State University (Publisher)
Created2012
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Description
This work systematically investigates structure-stability relations in various polymer derived ceramic (PDC) systems and metal organic frameworks (MOFs), both of which are hybrid materials. The investigation of silicon carbides (SiC) confirms thermodynamic stabilization of PDCs with increasing mixed bonding (Si bonded to both C, O and/or N). The study of

This work systematically investigates structure-stability relations in various polymer derived ceramic (PDC) systems and metal organic frameworks (MOFs), both of which are hybrid materials. The investigation of silicon carbides (SiC) confirms thermodynamic stabilization of PDCs with increasing mixed bonding (Si bonded to both C, O and/or N). The study of more complex silicon oxycarbide (SiOC) structures shows stabilization of SiOCs with increasing pyrolysis temperature (between 1200 and1500 oC), and points to dissimilarities in the stabilizing effect of different mixed bonding environments (SiO3C, SiO2C2, or SiOC3) and their relative amounts. Analyses of quaternary silicon oxycarbonitride (SiC(N)(O)) materials suggests increased stabilization with increasing N content, and superior stabilization due to SiNxC4-x compared to SiOxC4-x mixed bonds. Investigation of the energetics of metal filler (Nb, Hf, Ta) incorporation in SiOCs shows that choice of metal filler influences the composition, structural evolution, and thermodynamic stability in PDCs. Ta fillers can stabilize otherwise unstable SiO3C mixed bonds. Independent of metal incorporation or lack thereof, in SiOC systems, higher pyrolysis temperature (1200-1500 oC) forms more stable ceramics. The stabilizing effect of order/disorder of the free carbon phase is system-dependent. The work on (MOFs) highlights stabilization trends obtained from the investigation of zeolitic imidazolate frameworks (ZIFs) and boron imidazolate frameworks (BIFs) based on azolate linkers. Study of the energetics of metal (Co(II), Cu (II), and Zn (II) ) substitution in isostructural ZIFs shows that in MOFs the stabilizing effect of metal is dependent on both framework topology (diamondoid (dia) > sodalite (SOD)) and dimensionality (2D > 3D). Thermodynamic analyses of metal substitution (Ag(I), Cu(I), and Li (I)) in isostructural ii SOD and dia BIF systems confirm increase in density as a general descriptor for increased stabilization in MOFs. The study of energetics of guest-host interactions during CO2 incorporation in azolate frameworks (i.e., ZIF-8) shows strong dependence of energetics of adsorption on choice of linker and metal. Additionally, several energetically favorable reaction pathways for the formation of CO3-ZIF-8 have been identified. Both PDCs and MOFs show a complex energetic landscape, with identifiable system dependent and general structural descriptors for increased thermodynamic stabilization and tunability of the energetics of guest-host interactions.
ContributorsLeonel, Gerson J (Author) / Navrotsky, Alexandra (Thesis advisor) / Dai, Lenore (Committee member) / Thomas, Mary (Committee member) / Singh, Gurpreet (Committee member) / Friščić, Tomislav (Committee member) / Arizona State University (Publisher)
Created2023
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Description
Intelligent engineering designs require an accurate understanding of material behavior, since any uncertainties or gaps in knowledge must be counterbalanced with heightened factors of safety, leading to overdesign. Therefore, building better structures and pushing the performance of new components requires an improved understanding of the thermomechanical response of advanced materials

Intelligent engineering designs require an accurate understanding of material behavior, since any uncertainties or gaps in knowledge must be counterbalanced with heightened factors of safety, leading to overdesign. Therefore, building better structures and pushing the performance of new components requires an improved understanding of the thermomechanical response of advanced materials under service conditions. This dissertation provides fundamental investigations of several advanced materials: thermoset polymers, a common matrix material for fiber-reinforced composites and nanocomposites; aluminum alloy 7075-T6 (AA7075-T6), a high-performance aerospace material; and ceramic matrix composites (CMCs), an advanced composite for extreme-temperature applications. To understand matrix interactions with various interfaces and nanoinclusions at their fundamental scale, the properties of thermoset polymers are studied at the atomistic scale. An improved proximity-based molecular dynamics (MD) technique for modeling the crosslinking of thermoset polymers is carefully established, enabling realistic curing simulations through its ability to dynamically and probabilistically perform complex topology transformations. The proximity-based MD curing methodology is then used to explore damage initiation and the local anisotropic evolution of mechanical properties in thermoset polymers under uniaxial tension with an emphasis on changes in stiffness through a series of tensile loading, unloading, and reloading experiments. Aluminum alloys in aerospace applications often require a fatigue life of over 109 cycles, which is well over the number of cycles that can be practically tested using conventional fatigue testing equipment. In order to study these high-life regimes, a detailed ultrasonic cycle fatigue study is presented for AA7075-T6 under fully reversed tension-compression loading. The geometric sensitivity, frequency effects, size effects, surface roughness effects, and the corresponding failure mechanisms for ultrasonic fatigue across different fatigue regimes are investigated. Finally, because CMCs are utilized in extreme environments, oxidation plays an important role in their degradation. A multiphysics modeling methodology is thus developed to address the complex coupling between oxidation, mechanical stress, and oxygen diffusion in heterogeneous carbon fiber-reinforced CMC microstructures.
ContributorsSchichtel, Jacob (Author) / Chattopadhyay, Aditi (Thesis advisor) / Dai, Lenore (Committee member) / Ghoshal, Anindya (Committee member) / Huang, Huei-Ping (Committee member) / Jiao, Yang (Committee member) / Oswald, Jay (Committee member) / Arizona State University (Publisher)
Created2022
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Description
Atmospheric water extraction (AWE) is an emerging technology to tackle water resource shortage challenges. One such approach to provide fresh water utilizes stimuli-responsive hydrogel-based desiccants to capture the moisture from the air and release it into the liquid form. Typical gel desiccants are composed of a hygroscopic agent for capturing

Atmospheric water extraction (AWE) is an emerging technology to tackle water resource shortage challenges. One such approach to provide fresh water utilizes stimuli-responsive hydrogel-based desiccants to capture the moisture from the air and release it into the liquid form. Typical gel desiccants are composed of a hygroscopic agent for capturing and a hydrophilic gel matrix for storage. The desorption process can be completed by elevating the temperature above the upper or lower critical solution temperature point to initiate the volume phase transition of either thermo-responsive or photothermal types. This thesis focuses on investigating the structural effect of hydrogels on moisture uptake. Firstly, the main matrix of gel desiccant, poly(N-isopropylacrylamide) hydrogel, was optimized via tuning synthesis temperature and initial monomer concentration. Secondly, a series of hydrogel-based desiccants consisting of a hygroscopic material, vinyl imidazole, and optimized poly(N-isopropylacrylamide) gel matrix were synthesized with different network structures. The moisture uptake result showed that the gel desiccant with an interpenetrating polymeric network (IPN) resulted in the best-performing moisture capturing. The gel desiccant with the best performance will be used as a primary structural unit to evaluate the feasibility of developing a light-responsive gel desiccant to materialize light-trigger moisture desorption for AWE technology in the future.
ContributorsZhao, Xingbang (Author) / Dai, Lenore (Thesis advisor) / Westerhoff, Paul (Committee member) / Jiao, Yang (Committee member) / Arizona State University (Publisher)
Created2021
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Description
A new type of electronics was envisioned, namely edible electronics. Edible electronics are made by Food and Drug Administration (FDA) certified edible materials which can be eaten and digested by human body. Different from implantable electronics, test or treatment using edible electronics doesn’t require operations and perioperative complications.

This dissertation

A new type of electronics was envisioned, namely edible electronics. Edible electronics are made by Food and Drug Administration (FDA) certified edible materials which can be eaten and digested by human body. Different from implantable electronics, test or treatment using edible electronics doesn’t require operations and perioperative complications.

This dissertation bridges the food industry, material sciences, device fabrication, and biomedical engineering by demonstrating edible supercapacitors and electronic components and devices such as pH sensor.

Edible supercapacitors were fabricated using food materials from grocery store. 5 of them were connected in series to power a snake camera. Tests result showed that the current generated by supercapacitor have the ability to kill bacteria. Next more food, processed food and non-toxic level electronic materials were investigated. A “preferred food kit” was created for component fabrication based on the investigation. Some edible electronic components, such as wires, resistor, inductor, etc., were developed and characterized utilizing the preferred food kit. These components make it possible to fabricate edible electronic/device in the future work. Some edible electronic components were integrated into an edible electronic system/device. Then edible pH sensor was introduced and fabricated. This edible pH sensor can be swallowed and test pH of gastric fluid. PH can be read in a phone within seconds after the pH sensor was swallowed. As a side project, an edible double network gel electrolyte was synthesized for the edible supercapacitor.
ContributorsXu, Wenwen (Author) / Jiang, Hanqing (Thesis advisor) / Dai, Lenore (Committee member) / Green, Matthew (Committee member) / Mu, Bin (Committee member) / Yu, Hongbin (Committee member) / Arizona State University (Publisher)
Created2019
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Description
Among the alternative processes for the traditional distillation, adsorption and membrane separations are the two most promising candidates and metal-organic frameworks (MOFs) are the new material candidate as adsorbent or membrane due to their high surface area, various pore sizes, and highly tunable framework functionality. This dissertation presents an investigation

Among the alternative processes for the traditional distillation, adsorption and membrane separations are the two most promising candidates and metal-organic frameworks (MOFs) are the new material candidate as adsorbent or membrane due to their high surface area, various pore sizes, and highly tunable framework functionality. This dissertation presents an investigation of the formation process of MOF membrane, framework defects, and two-dimensional (2D) MOFs, aiming to explore the answers for three critical questions: (1) how to obtain a continuous MOF membrane, (2) how defects form in MOF framework, and (3) how to obtain isolated 2D MOFs. To solve the first problem, the accumulated protons in the MOF synthesis solution is proposed to be the key factor preventing the continuous growth among Universitetet I Oslo-(UiO)-66 crystals. The hypothesis is verified by the growth reactivation under the addition of deprotonating agent. As long as the protons were sufficiently coordinated by the deprotonating agent, the continuous growth of UiO-66 is guaranteed. Moreover, the modulation effect can impact the coordination equilibrium so that an oriented growth of UiO-66 film was achieved in membrane structures. To find the answer for the second problem, the defect formation mechanism in UiO-66 was investigated and the formation of missing-cluster (MC) defects is attributed to the partially-deprotonated ligands. Experimental results show the number of MC defects is sensitive to the addition of deprotonating agent, synthesis temperature, and reactant concentration. Pore size distribution allows an accurate and convenient characterization of the defects. Results show that these defects can cause significant deviations of its pore size distribution from the perfect crystal. The study of the third questions is based on the established bi-phase synthesis method, a facile synthesis method is adopted for the production of high quality 2D MOFs in large scale. Here, pyridine is used as capping reagent to prevent the interplanar hydrogen bond formation. Meanwhile, formic acid and triethylamine as modulator and deprotonating agent to balance the anisotropic growth, crystallinity, and yield in the 2D MOF synthesis. As a result, high quality 2D zinc-terephthalic acid (ZnBDC) and copper-terephthalic acid (CuBDC) with extraordinary aspect ratio samples were successfully synthesized.
ContributorsShan, Bohan (Author) / Mu, Bin (Thesis advisor) / Forzani, Erica (Committee member) / Dai, Lenore (Committee member) / Lin, Jerry (Committee member) / Liu, Jingyue (Committee member) / Arizona State University (Publisher)
Created2019
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Description
Hydrogel polymers have been the subject of many studies, due to their fascinating ability to alternate between being hydrophilic and hydrophobic, upon the application of appropriate stimuli. In particular, thermo-responsive hydrogels such as N-Isopropylacrylamide (NIPAM), which possess a unique lower critical solution temperature (LCST) of 32°C, have been leveraged for

Hydrogel polymers have been the subject of many studies, due to their fascinating ability to alternate between being hydrophilic and hydrophobic, upon the application of appropriate stimuli. In particular, thermo-responsive hydrogels such as N-Isopropylacrylamide (NIPAM), which possess a unique lower critical solution temperature (LCST) of 32°C, have been leveraged for membrane-based processes such as using NIPAM as a draw agent for forward osmosis (FO) desalination. The low LCST temperature of NIPAM ensures that fresh water can be recovered, at a modest energy cost as compared to other thermally based desalination processes which require water recovery at higher temperatures. This work studies by experimentation, key process parameters involved in desalination by FO using NIPAM and a copolymer of NIPAM and Sodium Acrylate (NIPAM-SA). It encompasses synthesis of the hydrogels, development of experiments to effectively characterize synthesized products, and the measuring of FO performance for the individual hydrogels. FO performance was measured using single layers of NIPAM and NIPAM-SA respectively. The values of permeation flux obtained were compared to relevant published literature and it was found to be within reasonable range. Furthermore, a conceptual design for future large-scale implementation of this technology is proposed. It is proposed that perhaps more effort should focus on physical processes that have the ability to increase the low permeation flux of hydrogel driven FO desalination systems, rather than development of novel classes of hydrogels
ContributorsAbdullahi, Adnan None (Author) / Phelan, Patrick (Thesis advisor) / Wang, Robert (Committee member) / Dai, Lenore (Committee member) / Arizona State University (Publisher)
Created2019
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Description
Origami and Kirigami are two traditional art forms in the world. Origami, from

‘ori’ meaning folding, and ‘kami’ meaning paper is the art of paper folding. Kirigami, from ‘kiri’ meaning cutting, is the art of the combination of paper cutting and paper folding. In this dissertation, Origami and kirigami concepts were

Origami and Kirigami are two traditional art forms in the world. Origami, from

‘ori’ meaning folding, and ‘kami’ meaning paper is the art of paper folding. Kirigami, from ‘kiri’ meaning cutting, is the art of the combination of paper cutting and paper folding. In this dissertation, Origami and kirigami concepts were successively utilized in making stretchable lithium ion batteries and three-dimensional (3D) silicon structure which both provide excellent mechanical characteristics.
ContributorsSong, Zeming (Author) / Jiang, Hanqing (Thesis advisor) / Dai, Lenore (Committee member) / Yu, Hongbin (Committee member) / He, Ximin (Committee member) / Arizona State University (Publisher)
Created2016