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This dissertation provides a fundamental understanding of the impact of bulk polymer properties on the nanometer length scale modulus. The elastic modulus of amorphous organic thin films is examined using a surface wrinkling technique. Potential correlations between thin film behavior and intrinsic properties such as flexibility and chain length are

This dissertation provides a fundamental understanding of the impact of bulk polymer properties on the nanometer length scale modulus. The elastic modulus of amorphous organic thin films is examined using a surface wrinkling technique. Potential correlations between thin film behavior and intrinsic properties such as flexibility and chain length are explored. Thermal properties, glass transition temperature (Tg) and the coefficient of thermal expansion, are examined along with the moduli of these thin films. It is found that the nanometer length scale behavior of flexible polymers correlates to its bulk Tg and not the polymers intrinsic size. It is also found that decreases in the modulus of ultrathin flexible films is not correlated with the observed Tg decrease in films of the same thickness. Techniques to circumvent reductions from bulk modulus were also demonstrated. However, as chain flexibility is reduced the modulus becomes thickness independent down to 10 nm. Similarly for this series minor reductions in Tg were obtained. To further understand the impact of the intrinsic size and processing conditions; this wrinkling instability was also utilized to determine the modulus of small organic electronic materials at various deposition conditions. Lastly, this wrinkling instability is exploited for development of poly furfuryl alcohol wrinkles. A two-step wrinkling process is developed via an acid catalyzed polymerization of a drop cast solution of furfuryl alcohol and photo acid generator. The ability to control the surface topology and tune the wrinkle wavelength with processing parameters such as substrate temperature and photo acid generator concentration is also demonstrated. Well-ordered linear, circular, and curvilinear patterns are also obtained by selective ultraviolet exposure and polymerization of the furfuryl alcohol film. As a carbon precursor a thorough understanding of this wrinkling instability can have applications in a wide variety of technologies.
ContributorsTorres, Jessica (Author) / Vogt, Bryan D (Thesis advisor) / Stafford, Christopher M (Committee member) / Richert, Ranko (Committee member) / Rege, Kaushal (Committee member) / Dai, Lenore (Committee member) / Arizona State University (Publisher)
Created2011
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Description
The disordered nature of glass-forming melts results in two features for its dynamics i.e. non-Arrhenius and non-exponential behavior. Their macroscopic properties are studied through observing spatial heterogeneity of the molecular relaxation. Experiments performed in a low-frequency range tracks the flow of energy in time on slow degrees of freedom and

The disordered nature of glass-forming melts results in two features for its dynamics i.e. non-Arrhenius and non-exponential behavior. Their macroscopic properties are studied through observing spatial heterogeneity of the molecular relaxation. Experiments performed in a low-frequency range tracks the flow of energy in time on slow degrees of freedom and transfer to the vibrational heat bath of the liquid, as is the case for microwave heating. High field measurements on supercooled liquids result in generation of fictive temperatures of the absorbing modes which eventually result in elevated true bath temperatures. The absorbed energy allows us to quantify the changes in the 'configurational', real sample, and electrode temperatures. The slow modes absorb energy on the structural relaxation time scale causing the increase of configurational temperature resulting in the rise of dielectric loss. Time-resolved high field dielectric relaxation experiments show the impact of 'configurational heating' for low frequencies of the electric field and samples that are thermally clamped to a thermostat. Relevant thermal behavior of monohydroxy alcohols is considerably different from the cases of simple non-associating liquids, due to their distinct origins of the prominent dielectric loss. Monohydroxy alcohols display very small changes due to observed nonthermal effects without increasing sample temperature. These changes have been reflected in polymers in our measurements.
ContributorsPathak, Ullas (Author) / Richert, Ranko (Thesis advisor) / Dai, Lenore (Thesis advisor) / Nielsen, David (Committee member) / Arizona State University (Publisher)
Created2012
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Rotary drums are commonly used for their high heat and mass transfer rates in the manufacture of pharmaceuticals, cement, 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

Rotary drums are commonly used for their high heat and mass transfer rates in the manufacture of pharmaceuticals, cement, 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 tremendous energy savings on a global scale. This study investigates the effects of drum fill level and rotation rate on the steady-state average particle bed temperature. 3 mm silica beads and a stainless steel rotary drum were used at fill levels ranging from 10 \u2014 25 % and rotation rates from 2 \u2014 10 rpm. Four heat guns were used to heat the system via conduction and convection, and an infrared camera was used to record temperature data. A three-level, two-factor, full-factorial design of experiments was employed to determine the effects of each factor on the steady-state average bed temperature. Low fill level and high rotation rate resulted in higher steady-state average bed temperatures. A quantitative model showed that rotation rate had a larger impact on the steady-state bed temperature than fill level.
ContributorsBoepple, Brandon Richard (Author) / Emady, Heather (Thesis director) / Adepu, Manogna (Committee member) / W.P. Carey School of Business (Contributor) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2018-05
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This report investigates the effects of autolyzing, fermentation medium, fermentation temperature, and proofing medium on the growth and porosity of 50% whole wheat sourdough bread. A model was designed using a 24 statistical design of experiment with replicates to screen and quantify the individual and combined effects of the aforementioned

This report investigates the effects of autolyzing, fermentation medium, fermentation temperature, and proofing medium on the growth and porosity of 50% whole wheat sourdough bread. A model was designed using a 24 statistical design of experiment with replicates to screen and quantify the individual and combined effects of the aforementioned factors on the area of a 1 cm cross-sectional cut from each loaf. Fermentation temperature had the single largest effect, with colder fermented loaves being on average 10 cm2 larger than their warmer fermented counter parts. Autolyzing had little individual effect, but the strengthened gluten network abated some of the degassing and overproofing that is a consequent handling the dough or letting it ferment too much. This investigation quantifies how to maximize gluten development and yeast growth to create the airiest whole wheat sourdough, a healthier and easier to digest bread than many commercially available.
ContributorsLay, Michael Loren (Author) / Emady, Heather (Thesis director) / Adepu, Manogna (Committee member) / School of Sustainability (Contributor) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2018-05
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Description
Membrane based technology is one of the principal methods currently in widespread use to address the global water shortage. Pervaporation desalination is a membrane technology for water purification currently under investigation as a method for processing reverse osmosis concentrates or for stand-alone applications. Concentration polarization is a potential problem in

Membrane based technology is one of the principal methods currently in widespread use to address the global water shortage. Pervaporation desalination is a membrane technology for water purification currently under investigation as a method for processing reverse osmosis concentrates or for stand-alone applications. Concentration polarization is a potential problem in any membrane separation. In desalination concentration polarization can lead to reduced water flux, increased propensity for membrane scaling, and decreased quality of the product water. Quantifying concentration polarization is important because reducing concentration polarization requires increased capital and operating costs in the form of feed spacers and high feed flow velocities. The prevalent methods for quantifying concentration polarization are based on the steady state thin film boundary layer theory. Baker’s method, previously used for pervaporation volatile organic compound separations but not desalination, was successfully applied to data from five previously published pervaporation desalination studies. Further investigation suggests that Baker’s method may not have wide applicability in desalination. Instead, the limitations of the steady state assumption were exposed. Additionally, preliminary results of nanophotonic enhancement of pervaporation membranes were found to produce significant flux enhancement. A novel theory on the mitigation of concentration polarization by the photothermal effect was discussed.
ContributorsMann, Stewart, Ph.D (Author) / Lind, Mary Laura (Thesis advisor) / Walker, Shane (Committee member) / Green, Matthew (Committee member) / Forzani, Erica (Committee member) / Emady, Heather (Committee member) / Arizona State University (Publisher)
Created2019
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Description
Electrolytes play a critical role in electrochemical devices and applications, and therefore design and development of electrolytes with tailored properties are much desired to accommodate variety of operation requirements. Extreme temperatures are considered as one of the challenging environmental conditions, especially for devices rely on liquid state electrolytes, rendering failure

Electrolytes play a critical role in electrochemical devices and applications, and therefore design and development of electrolytes with tailored properties are much desired to accommodate variety of operation requirements. Extreme temperatures are considered as one of the challenging environmental conditions, especially for devices rely on liquid state electrolytes, rendering failure of operations once the electrolyte systems undergo phase transitions. This work focuses on development of low-temperature iodide-containing liquid electrolyte systems, specifically designed for the molecular electronic transducer (MET) sensors in space applications. Utilizing ionic liquids, molecular liquids, and salts, multiple low-temperature liquid electrolytes were designed with enhancements in thermal, transport, and electrochemical properties. Effects of intermolecular interactions were further investigated, revealing correlations between optimization of microscopic dynamics and improvements of macroscopic characteristics. As a result, three low-temperature electrolyte systems were reported utilizing ethylammonium/water, gamma-butyrolactone/propylene carbonate, and butyronitrile as solvent with ionic liquid, 1-butyl-3-methylimidazolium iodide, and lithium iodide salt. Consequently, the liquidus range of these systems have been extended to -108 ˚C, -120 ˚C, and -152 ˚C, respectively, marking the lowest liquidus temperature of liquid electrolytes to the author’s best knowledge. Moreover, transport properties of designed systems were characterized from 25 to -75 ˚C. Effects of selected cosolvent/solvent on evolutions of transport properties were observed, revealing interplay between two governing mechanisms, ion disassociation and ion mobility, and their dominance at different temperatures. Experimental spectroscopy characterization techniques validated the hypothesized intermolecular interactions between solvent-cation and solvent-anion, complimented by computational simulation results on the complex dynamics between constituent ions and molecules. To support MET sensing technology, the essential iodide/triiodide redox were investigated in developed electrolytes. Effects of different molecular solvents on electrochemical kinetics were elucidated, and steady performances were validated under a properly controlled electrochemical window. Optimized electrolytes were tested in the MET sensor prototypes and showcased adequate functionality from calibration. The MET sensor prototype has also successfully detected real-time earthquake with low noise floor during long term testing at ASU seismology facility. The presented work demonstrates a facile design strategy for task-specific electrolyte development, which is anticipated to be further expanded to high temperatures for broader applications in the future.
ContributorsLin, Wendy Jessica (Author) / Dai, Lenore L (Thesis advisor) / Wiegart, Yu-chen Karen (Committee member) / Emady, Heather (Committee member) / Lind Thomas, MaryLaura (Committee member) / Torres, Cesar (Committee member) / Arizona State University (Publisher)
Created2022
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Description
Lithium-ion and lithium-metal batteries represent a predominant energy storage solution with the potential to address the impending global energy crisis arising from limited non-renewable resources. However, these batteries face significant safety challenges that hinder their commercialization. The conventional polymeric separators and electrolytes have poor thermal stability and fireproof properties making

Lithium-ion and lithium-metal batteries represent a predominant energy storage solution with the potential to address the impending global energy crisis arising from limited non-renewable resources. However, these batteries face significant safety challenges that hinder their commercialization. The conventional polymeric separators and electrolytes have poor thermal stability and fireproof properties making them prone to thermal runaway that causes fire hazards and explosions when the battery is subjected to extreme operating conditions. To address this issue, various materials have been investigated for their use as separators. However, polymeric, and pure inorganic material-based separators have a trade-off between safety and electrochemical performance. This is where zeolites emerge as a promising solution, offering favorable thermal and electrochemical characteristics. The zeolites are coated onto the cathode as a separator using the scalable blade coating method. These separators are non-flammable with high thermal stability and electrolyte wettability. Furthermore, the presence of intracrystalline pores helps in homogenizing the Li-ion flux at anode resulting in improved electrochemical performance. This research delves into the preparation of zeolite separators using a commercial zeolite and lab-scale zeolite to study their safety and electrochemical performance in lithium-ion batteries. At low C-rates, both zeolites exhibited excellent capacity retention and capacity density displaying their potential to advance high-performance safe lithium-ion batteries. The commercial zeolite has demonstrated remarkable capacity retention and good performance in terms of charge and discharge cycles, as well as stability. This makes it a valuable resource for the scaling up of electrode-coated separator technology. Furthermore, the previous study demonstrated the superior electrochemical performance of plate silicalite separator (also a lab-made zeolite) with both lithium-ion and lithium-metal batteries. However, the process of scaling up and achieving precise control over plate silicalite particle size, and morphology using the existing synthesis procedure has proven challenging. Thus, the modification of process conditions is studied to enhance control over particle size, aspect ratio, and yield to facilitate a more efficient scaling-up process. Incorporation of stirring during the crystallization phase enhanced yield and uniformity of particle size. Also, the increase in temperature and time of crystallization enlarged the particles but did not show any significant improvement in the aspect ratio of the particles.
ContributorsNalam, Ramasai Dharani Harika (Author) / Lin, Jerry (Thesis advisor) / Emady, Heather (Committee member) / Seo, S. Eileen (Committee member) / Arizona State University (Publisher)
Created2023
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Description
Electrospun fibrous membranes have gained increasing interest in membrane filtration applications due to their high surface area and porosity. To develop a high-performance water filtration membrane a novel zwitterionic functionalized zwitterionic Polysulfone was Electrospun to bead free fibers on Polysulfone membranes. The SBAES25 was successfully Electrospun on Polysulfone membrane and

Electrospun fibrous membranes have gained increasing interest in membrane filtration applications due to their high surface area and porosity. To develop a high-performance water filtration membrane a novel zwitterionic functionalized zwitterionic Polysulfone was Electrospun to bead free fibers on Polysulfone membranes. The SBAES25 was successfully Electrospun on Polysulfone membrane and thermal pressed at above Tg to improve the properties of membrane. The aim of this work is to study Electrospun zwitterionic Polysulfone nanofiber membrane with different characterization methods. The electrospinning method was studied using different polymer concentrations and electrospinning conditions. Scanning Electron Microscopy was used to study the porosity and diameter size of the fiber. TGA-ASSAY method was used to study the difference in water uptake ratio of Polysulfone membrane with and without the Electrospun fiber. A goniometer was used to test the water contact angle of the membrane. Tensile tests were performed to study the improvements in mechanical properties.
ContributorsErravelly, Nitheesh Kumar (Author) / Green, Matthew (Thesis advisor) / Emady, Heather (Committee member) / Seo, Eileen S (Committee member) / Arizona State University (Publisher)
Created2023
Description
This thesis analyzed Canon GPR-30 Black Standard Yield Toner in hopes to gain better understanding of the additives and plastic used in a popular photocopier toner formulation. By analyzing the toner’s composition from the perspective of its recyclability and potential to be manufactured using recycled plastic, this thesis hoped to

This thesis analyzed Canon GPR-30 Black Standard Yield Toner in hopes to gain better understanding of the additives and plastic used in a popular photocopier toner formulation. By analyzing the toner’s composition from the perspective of its recyclability and potential to be manufactured using recycled plastic, this thesis hoped to fill a gap in current literature regarding how toner fits into a circular economy. While the analysis of the selected toner was ultimately inconclusive, three hypotheses about the toner’s composition are put forth based upon data from differential scanning calorimetry (DSC), solubility analysis, and Fourier Transform Infrared (FTIR) spectroscopy experimentation. It is hypothesized that the toner is most likely composed of either polymethyl methacrylate (PMMA) or polyethylene terephthalate (PET). Both of these polymers have characteristic FTIR peaks that were exhibited in the toner spectra and both polymers exhibit similar solubility behavior to toner samples. However, the glass transition temperature and melting temperature of the toner sampled were 58℃ and 74.5℃ respectively, both of which are much lower than that of PMMA and PET. Thus, a third hypothesis that would better support DSC findings is that the toner is primarily composed of nylon 6,6. While DSC data best matches this polymer, FTIR data seems to rule out nylon 6,6 as an option because its characteristic peaks were not found in experimental data. Thus, the Canon GPR-30 Black Standard Yield Toner is probably made from either PMMA or PET. Both PMMA and PET are 100% recyclable plastics which are commonly repurposed at recycling facilities, however, unknowns regarding toner additives make it difficult to determine how this toner would be recycled. If the printing industry hopes to move towards a circular economy in which plastic can be recycled to use towards toner manufacturing and toner can be “unprinted” from paper to be recycled into new toner, it is likely that monetary incentives or government regulations will need to be introduced to promote the sharing of toner formulations for recycling purposes.
ContributorsChase, Jasmine (Author) / Green, Matthew (Thesis director) / Emady, Heather (Committee member) / Barrett, The Honors College (Contributor) / School of Mathematical and Statistical Sciences (Contributor) / Mechanical and Aerospace Engineering Program (Contributor)
Created2023-05
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The purpose of this study was to comprehend the global warming potential (GWP), cost variability, and competitiveness of steel with rising carbon taxes. Aluminum, glass fiber composite, and carbon fiber composite were chosen as competing materials. In order to compare the aforementioned factors, the GWP of several processes to produce

The purpose of this study was to comprehend the global warming potential (GWP), cost variability, and competitiveness of steel with rising carbon taxes. Aluminum, glass fiber composite, and carbon fiber composite were chosen as competing materials. In order to compare the aforementioned factors, the GWP of several processes to produce steel, aluminum, and fiber composites was examined. Cost analyses of various methods were also carried out to determine their viability. Energy consumption data for each of the paths under consideration were taken from the literature for the study. To get the consistent GWP for traditional and decarbonized scenarios, the required energy is multiplied with corresponding energy source (natural gas or electricity). Even after accounting for the carbon tax and the weight-reduction factor, the results show that steel still has the lowest production costs, followed by aluminum, while fiber composites remain the most costly. EAF- steel and secondary aluminum has least GWP followed by H2-DRI (Hydrogen- Direct Reduced Iron)steel and NG-DRI (Natural Gas- Direct Reduced Iron) steel with carbon capture and storage (CCS). The state of art technology for glass fiber reinforced composite also emits less carbon dioxide but the cost of production is still high. Carbon fiber reinforced composite emits most carbon dioxide and is least economical.
ContributorsRajulwar, Vaishnavi Vijay (Author) / Seetharaman, Sridhar (Thesis advisor) / Emady, Heather (Committee member) / Nian, Qiong (Committee member) / Arizona State University (Publisher)
Created2023