No description available.

Doctor of Philosophy / Department of Chemical Engineering / Mary E. Rezac / Membrane reactor is a device that simultaneously carrying out reaction and membrane-based separation. The advantageous transport properties of the membranes can be employed to selectively remove undesired products or by-products from the reaction mixture, to break the thermodynamic barrier, and to selectively supply the reactant. In this work, membrane reactor technology has been exploited with robust H₂ selective polymeric membranes in the process of hydrogenation and dehydrogenation. A state-of-the-art 3-phase catalytic membrane contactor is utilized in the processes of soybean hydrogenation and bio-oil hydro-deoxygenation, where the membrane functions as phase contactor, H₂supplier, and catalytic support. Intrinsically skinned asymmetric Polyetherimide (PEI) membranes demonstrated predominant H₂permeance and selectivity. By using the PEI membrane in the membrane contactor, soybean oil is partially hydrogenated efficiently at relatively mild reaction conditions compared with a conventional slurry reactor. In the hydroprocessing of bio-oil using the same system, the membrane successfully removed water, an undesired component from bio-oil by pervaporation. The more industrially feasible membrane-assisted reactor is studied in the alkane dehydrogenation process. Viable polymeric materials and their stability in elevated temperatures and organic environment are examined. The blend polymeric material of Matrimid® 5218 and Polybenzimidazole (PBI) remained H₂permeable and stable with the presence of hydrocarbons, and displayed consistent selectivity of H2/hydrocarbon, which indicated the feasibility of using the material to fabricate thermally stable membrane for separation. The impact of membrane-assisted reactor is evaluated using finite parameter process simulation in the model reaction of the dehydrogenation of methylcyclohexane (MCH). By combining tested catalyst performance, measured transport properties of the material and hypothetical membrane configuration, by using a membrane assisted packed-bed reactor, the thermodynamic barrier of the reaction is predicted to be broken by the removal of H₂. The overall dehydrogenation conversion can be increased by up to 20% beyond equilibrium. The predicted results are justified by preliminary experimental validation using intrinsically skinned asymmetric Matrimid/PBI blend membrane. The conversions at varied temperatures partially exceeded equilibrium, indicating successful removal of H₂by the blend membrane as well as decent thermal stability of the membrane at elevated temperatures with the presence of hydrocarbons. The successful outcome of membrane contactor and membrane-assisted reactor using robust polymeric membranes shows the effectiveness and efficiency of membrane reactors in varied application. The future work should be focusing on two direction, to further develop durable and efficient membranes with desired properties; and to improve the reactor system with better catalytic performance, more precise control in order to harvest preferable product and greater yield.

abstract: In this research, our goal was to fabricate Josephson junctions that can be stably processed at 300°C or higher. With the purpose of integrating Josephson junction fabrication with the current semiconductor circuit fabrication process, back-end process temperatures (>350 °C) will be a key for producing large scale junction circuits reliably, which requires the junctions to be more thermally stable than current Nb/Al-AlOx/Nb junctions. Based on thermodynamics, Hf was chosen to produce thermally stable Nb/Hf-HfOx/Nb superconductor tunnel Josephson junctions that can be grown or processed at elevated temperatures. Also elevated synthesis temperatures improve the structural and electrical properties of Nb electrode layers that could potentially improve junction device performance. The refractory nature of Hf, HfO2 and Nb allow for the formation of flat, abrupt and thermally-stable interfaces. But the current Al-based barrier will have problems when using with high-temperature grown and high-quality Nb. So our work is aimed at using Nb grown at elevated temperatures to fabricate thermally stable Josephson tunnel junctions. As a junction barrier metal, Hf was studied and compared with the traditional Al-barrier material. We have proved that Hf-HfOx is a good barrier candidate for high-temperature synthesized Josephson junction. Hf deposited at 500 °C on Nb forms flat and chemically abrupt interfaces. Nb/Hf-HfOx/Nb Josephson junctions were synthesized, fabricated and characterized with different oxidizing conditions. The results of materials characterization and junction electrical measurements are reported and analyzed. We have improved the annealing stability of Nb junctions and also used high-quality Nb grown at 500 °C as the bottom electrode successfully. Adding a buffer layer or multiple oxidation steps improves the annealing stability of Josephson junctions. We also have attempted to use the Atomic Layer Deposition (ALD) method for the growth of Hf oxide as the junction barrier and got tunneling results. / Dissertation/Thesis / Ph.D. Materials Science and Engineering 2013

L’objectif de cette thèse était de concevoir denouveaux matériaux polymères hydrophobes pour la protectionde composants semi-conducteurs, résistants à hautetempérature, aux forts champs électriques et aux atmosphèresagressives. Dans ce contexte, les polyimides d’addition sontapparus comme la famille de polymères la mieux adaptée pourl’application envisagée. La synthèse de l’encapsulant étantréalisée directement dans les boîtiers des modules, elle ne peutdonc pas contenir de solvant organique exogène. Ainsi, nousavons développé de nouvelles voies de synthèse sans solvantde poly(aminobismaléimide)s et de poly(bismaléimide)s.Dans un premier temps, différentes diamines aliphatiques ontété utilisées comme solvant réactif lors de la synthèse depoly(aminobismaléimide)s à une température bien inférieure à latempérature de fusion du bismaléimide utilisé (Tf > 300 °C). Unepremière série de 3 nouveaux poly(aminobismaléimide)sréticulés de 70 à 95 % a ainsi été réalisée. A partir de cespremières synthèses, 10 nouveaux poly(aminobismaléimide)sont été élaborés. Pour 9 d’entre eux, des diamines aromatiquesont été utilisées et, pour le dernier, une diamine siloxane. Cesrésultats démontrent la possibilité de généraliser ce procédé desynthèse.Dans un second temps, des poly(bismaléimide)s ont étésynthétisés, toujours sans solvant. Pour cela, les synthèses dequatre nouveaux bismaléimides liquides à température ambianteont été mises au point. Ces composés ont une structurealiphatique ou siloxane dans laquelle un motif pyroméllitique aété, ou pas, introduit. Leur polymérisation amorcée avecl’amorceur radicalaire ad hoc, conduit à la formation desmatériaux sans l’usage de solvant.Selon le choix des réactifs, des matériaux thermodurcissablesou élastomères sont obtenus. Ces derniers semblent mieuxadaptés à l’application souhaitée car, d’une part, la faibleviscosité des mélanges réactionnels permet leur applicationsans difficulté dans un module de puissance et, d’autre part, leurcaractère hydrophobe est plus marqué. L’un d’eux présente unestabilité thermique à 250 °C particulièrement intéressante et unetempérature de relaxation mécanique quasi hors gamme detempérature de fonctionnement. Ce matériau peut doncvraisemblablement être utilisé comme encapsulant. / The aim of this work is to develop new hydrophobicpolymeric materials for the protection of semi-conductorcomponents. These materials must withstand high temperature,strong electric fields and aggressive atmospheres such asmoisture. In this context, addition polyimides emerged as themost suitable polymers for the intended application. Thesynthesis of the encapsulant being made directly in the powermodules, it must be solvent free. Thus, we have developed newsolvent free synthesis routes of poly(aminobismaleimide)s andpoly(bismaleimide)s.First of all, different aliphatic diamines were used as a reactivesolvent in the synthesis of poly(aminobismaleimide)s to atemperature well below the melting point of the usedbismaleimide (m.p. > 300 °C). A first series of 3 newpoly(aminobismaleimide)s, crosslinked from 70 to 95 %, hasthus been made. From these first syntheses, 10 newpoly(aminobismaleimide)s have been developed. For 9 of them,aromatic diamines were used and, for the latter, a siloxanediamine. These results demonstrate that this process can begeneralized.Secondly, poly(bismaleimide)s were synthesized, still withoutany solvent. In order to do so, the syntheses of four newbismaleimides, liquid at room temperature, have beendeveloped. These compounds have an aliphatic or siloxanestructure in which a pyromellitic pattern has been or notintroduced. Their polymerization initiated with the suitable radicalinitiator leads to the formation of materials without the use of anysolvent.Depending on the choice of reagents, thermosetting materials orelastomers are obtained. These latter seem more suitable for thedesired application because, on one hand, the low viscosity ofthe reaction mixtures enables their application in a powermodule without any difficulty and, on the other hand, theirhydrophobic behaviour is stronger. One of them has aparticularly attractive thermal stability at 250 ° C and amechanical relaxation temperature almost out of the workingtemperature range. Therefore, this material may be used asencapsulant.

Lignin-derived precursors were used in the synthesis of bio-based high-performance polymers. The project consisted of synthesizing a series of poly(ester amide)s (PEAs) from lignin building blocks and natural amino acids. In particular, the amino acid moieties were incorporated into the PEAs’ architecture to explore the effect of the side-chain size on the thermal properties and the crystallinity of the resulting materials. The polymers, which were prepared by melt polycondensation, all possessed high thermal stability in nitrogen and air with onsets of thermal degradation (Td onset) exceeding 330 °C and glass transition temperatures (Tg) ranging from 136 °C – 238 °C. It is worth noting that the Tg greatly depended on the size of the pendant R-group on the amino acid. Remarkably, the thermal stability was mostly maintained even after subjecting the polymers to various pH media (pH 1, 4 and 8) for 1 week at 50 °C. Furthermore, wide-angle X-ray scattering experiments revealed semi-crystalline polymers with identical diffraction patterns and percent crystallinity ranging from 21 – 37%. To probe the impact of chirality on the thermal properties, a meso polymer of DL-alanine was prepared and compared to the chiral version. A slight drop in the Td onset and Tg of the DL-alanine-containing polymer relative to the L-alanine counterpart occurred, signifying moderate thermal stability resulting from the chiral group. Overall, these characteristics make these bio-based PEAs potential candidates for further investigation as alternatives to petrochemical-derived thermoplastics for high-performance materials.

No description available.

This dissertation explores the different ways to create thin film-based biosensors that are capable of rapid and label-free detection of cortisol, a non-specific biomarker closely linked to stress, within the physiological range of 10pM to 10 uM. Increased cortisol levels have been linked to stress-related diseases, such as chronic fatigue syndrome, irritable bowel syndrome, and post-traumatic stress disorder. It also plays a role in the suppression of the immune system as well. Therefore, accurate measurement of cortisol in saliva, serum, plasma, urine, sweat, and hair, is clinically significance to predict physical and mental diseases. In this dissertation, thin film-based electrochemical immunosensors were fabricated using a self-assembled monolayer (SAM) functionalized by cortisol specific antibodies to detect cortisol at 10 pM level sensitivities in the presence of a redox probe. The fabricated electrochemical cortisol immunosensors were able to detect cortisol in human saliva samples and the outcomes were validated using the standard Enzyme Linked Immuno Sorbent Assay (ELISA) technique. With the aim of improving signal amplification and label-free cortisol detection, copper nanoparticles were incorporated on screen-printed carbon electrodes (SPCE) for the fabrication of electrochemical cortisol immunosensor. This SPCE-based sensor showed a sensitivity of 4.21µA/M and the limit of detection 6.6nM. Both the SAM and SPCE-based immunosensors were not thermally stable due to the instability of antibodies at room temperature. To address this issue, an antibody-free immunosensor was fabricated. Molecular Imprinted Polymer (MIP) was used to template the target cortisol molecule. The MIP-based sensing platform was prepared using polypyrrole, a thermally stable conducting polymer. The conductivity of the polymer ensured good electrical performance. The polypyrrole-based MIP was synthesized by means of electrochemical polymerization and was used to detect cortisol within the physiological range at room temperature. MIP-based sensors exhibited the detection limit of 1 pM, and were cost-effective, easy to fabricate, temperature stable, and reusable. The sensing performance of the resulting sensors was comparable to those of commercially available technologies, such as ELISA. Aiming to perform cortisol sensing at point-of-care (POC), an Extended Gate Field Effect Transistor (EGFET) was integrated with a developed MIP cortisol sensor. The as developed MIP-EGFET sensor was used to detect the cortisol concentration in the range of 1 pM to 100 nM. A few of the major advantages of the developed sensor are its ability to provide a direct readout and simpler electronic systems, which are necessary for miniaturized Point of Care devices.

Tailored fluoropolymers remain the leading choice for a wide variety of advanced high-performance applications, including electronic/optical and energy conversion, owing to their unique blend of complementary high-performance properties. Amorphous semi-fluorinated polymers exhibit improved solubility and melt processability when compared to traditional perfluoropolymers. A leading class of semi-fluorinated aryl ether polymers includes perfluorocyclobutyl (PFCB), perfluorocycloalkenyl (PFCA), and fluoroarylene vinylene ether (FAVE) polymers. Monomers containing aromatic trifluorovinyl ethers (TFVE) are used to synthesize PFCB polymers via radical-mediated [2+2] cyclodimerization. On the other hand, FAVE and PFCA polymers are polymerized via base-mediated nucleophilic addition/elimination of bisphenols with TFVE monomers and decafluorocyclohexene respectively. The use of different monomer cores (aromatic, aliphatic, contorted, and renewable) should help to develop general structure/property relationships for this versatile and expanding approach to semi-fluorinated aryl ether polymers. The enchainment of polycyclic aromatic hydrocarbon (PAH) cores with functional fluorocarbon groups (or segments) recently afforded a new class of semi- fluorinated polymers in the continuing quest for novel organic materials for potential applications in optoelectronic, gas-separation, and advanced composites. Chapter 2 details the incorporation of commercially available acenaphthenequinone was achieved to afford PFCB aryl ether polymers with excellent solubility, high thermal stability, and film-forming capability. Chapter 3 represents base-promoted nucleophilic addition/elimination of commercial bisphenols with TFVE-triphenylene monomers affording FAVE aryl ether polymers possessing excellent solution processability, high thermal stability and photostability. In addition, triphenylene-enchained FAVE polymers exhibit extreme thermal-oxidative photostability and emit blue light after heating in air at 250 °C for 24 h. Further, time-dependent density functional theory (TD-DFT) computations were performed to understand electronic polymer structures. In one case, post-polymerization Scholl coupling converted the central triphenylene core to afford a hexabenzocoronene containing semi-fluorinated polymer with new optoelectronic properties. Chapter 4 demonstrates synthesis and characterization of renewable semi-fluorinated polymers obtained using aliphatic diol isosorbide. This renewable diol readily polymerizes with bis-TFVE derivatives of bisphenol A and 6F to provide high molecular weight thermoplastics exhibiting excellent solubility and tough, transparent film-forming capability. Finally, Chapter 5 presents synthesis of TFVE enchained corannulene which gave blue-light emission and outstanding processability. Synthesis and characterization, including the new materials' optical, thermal, and electronic properties, is presented.