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- All Subjects: chemical engineering
- Genre: Academic theses
- Creators: Rege, Kaushal
- Member of: Theses and Dissertations
Description
Emergent environmental issues, ever-shrinking petroleum reserves, and rising fossil fuel costs continue to spur interest in the development of sustainable biofuels from renewable feed-stocks. Meanwhile, however, the development and viability of biofuel fermentations remain limited by numerous factors such as feedback inhibition and inefficient and generally energy intensive product recovery processes. To circumvent both feedback inhibition and recovery issues, researchers have turned their attention to incorporating energy efficient separation techniques such as adsorption in in situ product recovery (ISPR) approaches. This thesis focused on the characterization of two novel adsorbents for the recovery of alcohol biofuels from model aqueous solutions. First, a hydrophobic silica aerogel was evaluated as a biofuel adsorbent through characterization of equilibrium behavior for conventional second generation biofuels (e.g., ethanol and n-butanol). Longer chain and accordingly more hydrophobic alcohols (i.e., n-butanol and 2-pentanol) were more effectively adsorbed than shorter chain alcohols (i.e., ethanol and i-propanol), suggesting a mechanism of hydrophobic adsorption. Still, the adsorbed alcohol capacity at biologically relevant conditions were low relative to other `model' biofuel adsorbents as a result of poor interfacial contact between the aqueous and sorbent. However, sorbent wettability and adsorption is greatly enhanced at high concentrations of alcohol in the aqueous. Consequently, the sorbent exhibits Type IV adsorption isotherms for all biofuels studied, which results from significant multilayer adsorption at elevated alcohol concentrations in the aqueous. Additionally, sorbent wettability significantly affects the dynamic binding efficiency within a packed adsorption column. Second, mesoporous carbons were evaluated as biofuel adsorbents through characterization of equilibrium and kinetic behavior. Variations in synthetic conditions enabled tuning of specific surface area and pore morphology of adsorbents. The adsorbed alcohol capacity increased with elevated specific surface area of the adsorbents. While their adsorption capacity is comparable to polymeric adsorbents of similar surface area, pore morphology and structure of mesoporous carbons greatly influenced adsorption rates. Multiple cycles of adsorbent regeneration rendered no impact on adsorption equilibrium or kinetics. The high chemical and thermal stability of mesoporous carbons provide potential significant advantages over other commonly examined biofuel adsorbents. Correspondingly, mesoporous carbons should be further studied for biofuel ISPR applications.
ContributorsLevario, Thomas (Author) / Nielsen, David R (Thesis advisor) / Vogt, Bryan D (Committee member) / Lind, Mary L (Committee member) / Arizona State University (Publisher)
Created2011
Description
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
Description
Emission of CO2 into the atmosphere has become an increasingly concerning issue as we progress into the 21st century Flue gas from coal-burning power plants accounts for 40% of all carbon dioxide emissions. The key to successful separation and sequestration is to separate CO2 directly from flue gas (10-15% CO2, 70% N2), which can range from a few hundred to as high as 1000°C. Conventional microporous membranes (carbons/silicas/zeolites) are capable of separating CO2 from N2 at low temperatures, but cannot achieve separation above 200°C. To overcome the limitations of microporous membranes, a novel ceramic-carbonate dual-phase membrane for high temperature CO2 separation was proposed. The membrane was synthesized from porous La0.6Sr0.4Co0.8Fe0.2O3-d (LSCF) supports and infiltrated with molten carbonate (Li2CO3/Na2CO3/K2CO3). The CO2 permeation mechanism involves a reaction between CO2 (gas phase) and O= (solid phase) to form CO3=, which is then transported through the molten carbonate (liquid phase) to achieve separation. The effects of membrane thickness, temperature and CO2 partial pressure were studied. Decreasing thickness from 3.0 to 0.375 mm led to higher fluxes at 900°C, ranging from 0.186 to 0.322 mL.min-1.cm-2 respectively. CO2 flux increased with temperature from 700 to 900°C. Activation energy for permeation was similar to that for oxygen ion conduction in LSCF. For partial pressures above 0.05 atm, the membrane exhibited a nearly constant flux. From these observations, it was determined that oxygen ion conductivity limits CO2 permeation and that the equilibrium oxygen vacancy concentration in LSCF is dependent on the partial pressure of CO2 in the gas phase. Finally, the dual-phase membrane was used as a membrane reactor. Separation at high temperatures can produce warm, highly concentrated streams of CO2 that could be used as a chemical feedstock for the synthesis of syngas (H2 + CO). Towards this, three different membrane reactor configurations were examined: 1) blank system, 2) LSCF catalyst and 3) 10% Ni/y-alumina catalyst. Performance increased in the order of blank system < LSCF catalyst < Ni/y-alumina catalyst. Favorable conditions for syngas production were high temperature (850°C), low sweep gas flow rate (10 mL.min-1) and high methane concentration (50%) using the Ni/y-alumina catalyst.
ContributorsAnderson, Matthew Brandon (Author) / Lin, Jerry (Thesis advisor) / Alford, Terry (Committee member) / Rege, Kaushal (Committee member) / Anderson, James (Committee member) / Rivera, Daniel (Committee member) / Arizona State University (Publisher)
Created2011
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 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/m2Pas. 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
Description
Temporary bonding-debonding of flexible plastic substrates to rigid carriers may facilitate effective substrate handling by automated tools for manufacture of flexible microelectronics. The primary challenges in implementing practical temporary bond-debond technology originate from the stress that is developed during high temperature processing predominately through thermal-mechanical property mismatches between carrier, adhesive and substrate. These stresses are relaxed through bowing of the bonded system (substrate-adhesive-carrier), which causes wafer handling problems, or through delamination of substrate from rigid carrier. Another challenge inherent to flexible plastic substrates and linked to stress is their dimensional instability, which may manifest itself in irreversible deformation upon heating and cooling cycles. Dimensional stability is critical to ensure precise registration of different layers during photolithography. The global objective of this work is to determine comprehensive experimental characterization and develop underlying fundamental engineering concept that could enable widespread adoption and scale-up of temporary bonding processing protocols for flexible microelectronics manufacturing. A series of carriers with different coefficient of thermal expansion (CTE), modulus and thickness were investigated to correlate the thermo-mechanical properties of carrier with deformation behavior of bonded systems. The observed magnitude of system bow scaled with properties of carriers according to well-established Stoney's equation. In addition, rheology of adhesive impacted the deformation of bonded system. In particular, distortion-bowing behavior correlated directly with the relative loss factor of adhesive and flexible plastic substrate. Higher loss factor of adhesive compared to that of substrate allowed the stress to be relaxed with less bow, but led to significantly greater dimensional distortion. Conversely, lower loss factor of adhesive allowed less distortion but led to larger wafer bow. A finite element model using ANSYS was developed to predict the trend in bow-distortion of bonded systems as a function of the viscoelastic properties of adhesive. Inclusion of the viscoelasticity of flexible plastic substrate itself was critical to achieving good agreement between simulation and experiment. Simulation results showed that there is a limited range within which tuning the rheology of adhesive can control the stress-distortion. Therefore, this model can aid in design of new adhesive formulations compatible with different processing requirements of various flexible microelectronics applications.
ContributorsHaq, Jesmin (Author) / Raupp, Gregory B (Thesis advisor) / Vogt, Bryan D (Thesis advisor) / Dai, Lenore (Committee member) / Loy, Douglas (Committee member) / Li, Jian (Committee member) / Arizona State University (Publisher)
Created2011
Description
Mesoporous materials that possess large surface area, tunable pore size, and ordered structures are attractive features for many applications such as adsorption, protein separation, enzyme encapsulation and drug delivery as these materials can be tailored to host different guest molecules. Films provide a model system to understand how the pore orientation impacts the potential for loading and release of selectively sized molecules. This research work aims to develop structure-property relationships to understand how pore size, geometry, and surface hydrophobicity influence the loading and release of drug molecules. In this study, the pore size is systematically varied by incorporating pore-swelling agent of polystyrene oligomers (hPS) to soft templated mesoporous carbon films fabricated by cooperative assembly of poly(styrene-block-ethylene oxide) (SEO) with phenolic resin. To examine the impact of morphology, different compositions of amphiphilic triblock copolymer templates, poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (PEO-PPO-PEO), are used to form two-dimensional hexagonal and cubic mesostructures. Lastly, the carbonization temperature provides a handle to tune the hydrophobicity of the film. These mesoporous films are then utilized to understand the uptake and release of a model drug Mitoxantrone dihydrochloride from nanostructured materials. The largest pore size (6nm) mesoporous carbon based on SEO exhibits the largest uptake (3.5μg/cm2); this is attributed to presence of larger internal volume compared to the other two films. In terms of release, a controlled response is observed for all films with the highest release for the 2nm cubic film (1.45 μg/cm2) after 15 days, but this is only 56 % of the drug loaded. Additionally, the surface hydrophobicity impacts the fraction of drug release with a decrease from 78% to 43%, as the films become more hydrophobic when carbonized at higher temperatures. This work provides a model system to understand how pore morphology, size and chemistry influence the drug loading and release for potential implant applications.
ContributorsLabiano, Alpha (Author) / Vogt, Bryan (Thesis advisor) / Rege, Kaushal (Committee member) / Dai, Lenore (Committee member) / Potta, Thrimoorthy (Committee member) / Arizona State University (Publisher)
Created2011
Description
Cancer diseases are among the leading cause of death in the United States. Advanced cancer diseases are characterized by genetic defects resulting in uncontrollable cell growth. Currently, chemotherapeutics are one of the mainstream treatments administered to cancer patients but are less effective if administered in the later stages of metastasis, and can result in unwanted side effects and broad toxicities. Therefore, current efforts have explored gene therapy as an alternative strategy to correct the genetic defects associated with cancer diseases, by administering genes which encode for proteins that result in cell death. While the use of viral vectors shows high level expression of the delivered transgene, the potential for insertion mutagenesis and activation of immune responses raise concern in clinical applications. Non-viral vectors, including cationic lipids and polymers, have been explored as potentially safer alternatives to viral delivery systems. These systems are advantageous for transgene delivery due to ease of synthesis, scale up, versatility, and in some cases due to their biodegradability and biocompatibility. However, low efficacies for transgene expression and high cytotoxicities limit the practical use of these polymers. In this work, a small library of twenty-one cationic polymers was synthesized following a ring opening polymerization of diglycidyl ethers (epoxides) by polyamines. The polymers were screened in parallel and transfection efficacies of individual polymers were compared to those of polyethylenimine (PEI), a current standard for polymer-mediated transgene delivery. Seven lead polymers that demonstrated higher transgene expression efficacies than PEI in pancreatic and prostate cancer cells lines were identified from the screening. A second related effort involved the generation of polymer-antibody conjugates in order to facilitate targeting of delivered plasmid DNA selectively to cancer cells. Future work with the novel lead polymers and polymer-antibody conjugates developed in this research will involve an investigation into the delivery of transgenes encoding for apoptosis-inducing proteins both in vitro and in vivo.
ContributorsVu, Lucas (Author) / Rege, Kaushal (Thesis advisor) / Nielsen, David (Committee member) / Sierks, Michael (Committee member) / Arizona State University (Publisher)
Created2011
Description
A low temperature amorphous oxide thin film transistor (TFT) backplane technology for flexible organic light emitting diode (OLED) displays has been developed to create 4.1-in. diagonal backplanes. The critical steps in the evolution of the backplane process include the qualification and optimization of the low temperature (200 °C) metal oxide process, the stability of the devices under forward and reverse bias stress, the transfer of the process to flexible plastic substrates, and the fabrication of white organic light emitting diode (OLED) displays. Mixed oxide semiconductor thin film transistors (TFTs) on flexible plastic substrates typically suffer from performance and stability issues related to the maximum processing temperature limitation of the polymer. A novel device architecture based upon a dual active layer enables significant improvements in both the performance and stability. Devices are directly fabricated below 200 ºC on a polyethylene naphthalate (PEN) substrate using mixed metal oxides of either zinc indium oxide (ZIO) or indium gallium zinc oxide (IGZO) as the active semiconductor. The dual active layer architecture allows for adjustment in the saturation mobility and threshold voltage stability without the requirement of high temperature annealing, which is not compatible with flexible colorless plastic substrates like PEN. The device performance and stability is strongly dependent upon the composition of the mixed metal oxide; this dependency provides a simple route to improving the threshold voltage stability and drive performance. By switching from a single to a dual active layer, the saturation mobility increases from 1.2 cm2/V-s to 18.0 cm2/V-s, while the rate of the threshold voltage shift decreases by an order of magnitude. This approach could assist in enabling the production of devices on flexible substrates using amorphous oxide semiconductors.
ContributorsMarrs, Michael (Author) / Raupp, Gregory B (Thesis advisor) / Vogt, Bryan D (Thesis advisor) / Allee, David R. (Committee member) / Arizona State University (Publisher)
Created2011
Description
Gene therapy is a promising technology for the treatment of various nonheritable and genetically acquired diseases. It involves delivery of a therapeutic gene into target cells to induce cellular responses against diseases. Successful gene therapy requires an efficient gene delivery vector to deliver genetic materials into target cells. There are two major classes of gene delivery vectors: viral and non-viral vectors. Recently, non-viral vectors such as cationic polymers have attracted more attention than viral vectors because they are versatile and non-immunogenic. However, cationic polymers suffer from poor gene delivery efficiency due to biological barriers. The objective of this research is to develop strategies to overcome the barriers and enhance polymer-mediated transgene expression. This study aimed to (i) develop new polymer vectors for gene delivery, (ii) investigate the intracellular barriers in polymer-mediated gene delivery, and (iii) explore new approaches to overcome the barriers. A cationic polymer library was developed by employing a parallel synthesis and high-throughput screening method. Lead polymers from the library were identified from the library based on relative levels of transgene expression and toxicity in PC3-PSMA prostate cancer cells. However, transgene expression levels were found to depend on intracellular localization of polymer-gene complexes (polyplexes). Transgene expression was higher when polyplexes were dispersed rather than localized in the cytoplasm. Combination treatments using small molecule chemotherapeutic drugs, e.g. histone deacetylase inhibitors (HDACi) or Aurora kinase inhibitor (AKI) increased dispersion of polyplexes in the cytoplasm and significantly enhanced transgene expression. The combination treatment using polymer-mediated delivery of p53 tumor-suppressor gene and AKI increased p53 expression in PC3-PSMA cells, inhibited the cell proliferation by ~80% and induced apoptosis. Polymer-mediated p53 gene delivery in combination with AKI offers a promising treatment strategy for in vivo and clinical studies of cancer gene therapy.
ContributorsBarua, Sutapa (Author) / Rege, Kaushal (Thesis advisor) / Dai, Lenore (Committee member) / Meldrum, Deirdre R. (Committee member) / Sierks, Michael (Committee member) / Voelkel-Johnson, Christina (Committee member) / Arizona State University (Publisher)
Created2011
Description
Cancer is the second leading cause of death in the United States and novel methods of treating advanced malignancies are of high importance. Of these deaths, prostate cancer and breast cancer are the second most fatal carcinomas in men and women respectively, while pancreatic cancer is the fourth most fatal in both men and women. Developing new drugs for the treatment of cancer is both a slow and expensive process. It is estimated that it takes an average of 15 years and an expense of $800 million to bring a single new drug to the market. However, it is also estimated that nearly 40% of that cost could be avoided by finding alternative uses for drugs that have already been approved by the Food and Drug Administration (FDA). The research presented in this document describes the testing, identification, and mechanistic evaluation of novel methods for treating many human carcinomas using drugs previously approved by the FDA. A tissue culture plate-based screening of FDA approved drugs will identify compounds that can be used in combination with the protein TRAIL to induce apoptosis selectively in cancer cells. Identified leads will next be optimized using high-throughput microfluidic devices to determine the most effective treatment conditions. Finally, a rigorous mechanistic analysis will be conducted to understand how the FDA-approved drug mitoxantrone, sensitizes cancer cells to TRAIL-mediated apoptosis.
ContributorsTaylor, David (Author) / Rege, Kaushal (Thesis advisor) / Jayaraman, Arul (Committee member) / Nielsen, David (Committee member) / Kodibagkar, Vikram (Committee member) / Dai, Lenore (Committee member) / Arizona State University (Publisher)
Created2013