Polymeric biomaterials have become ubiquitous in modern medical devices. ‘Smart’ materials, materials that respond to external stimuli, have been of particular interest for biomedical applications such as drug delivery. Poly(n-isopropylacrylamide) (pNIPAAm) is the best studied thermally responsive, biocompatible, ‘smart’ polymer and has been integrated into many potential drug delivery devices; however, the architectural design of the polymer in these devices is often overlooked. My research focus was the exploration of pNIPAAm architecture for biological applications. Two new biomaterials were synthesized as a result. Architectural modification of linear pNIPAAm was used to synthesize a well-defined homopolymer pNIPAAm with a sharp transition slightly above normal body temperature under isotonic conditions. This polymer required a combination of polymerization and control techniques including controlled radical polymerization, hydrogen bond induced tacticity, and end-group manipulation. The synthesis of this polymer opened up a variety of biomedical possibilities, one of which is the use of these polymers in a novel hydrogel system. Through the use of the controlled linear pNIPAAm synthesized through chain architectural modification, hydrogels with physiological transition temperatures were also synthesized. These hydrogels showed greater shrinking properties than traditional hydrogels synthesized in the same manner and showed physiological mechanical properties. Highly branched pNIPAAm was also optimized for biological applications. In this case, the branching reduced the efficacy of end-groups in transition temperature modification but increased the efficacy of certain copolymers. The resulting biomaterial was incorporated into a nanoparticle drug delivery system. By combining gold nanoparticles with highly branched pNIPAAm, which was designed to entrap small molecule drugs, a hybrid system was synthesized where heating of the nanoparticle through surface plasmon resonance can trigger drug release from the pNIPAAm. This system proved to be easy to synthesize, effective in loading, and controlled in release. As shown from the applications, architectural control of pNIPAAm can open up new possibilities with this polymer for biomedical applications. Small structural changes can lead to significant changes in the bulk properties of the polymer and should be considered in future pNIPAAm based medical devices.

This thesis was concerned with the proof of concept for mid-grade, 250-500oC, industrial waste heat recovery using a thermally regenerative electrochemical system. Proposed thermally regenerative electrochemical systems are limited to high operating temperatures (> 900oC) and suffer from poor conversion efficiencies (< 20%). As such, a single chamber design that is free of moving parts was presented in this work. The concept for this novel regenerative system relies on gravity and a liquid medium to convey dissolved sodium hydride in a hydride-borohydride solution from cold to hot regions in a continuous circuit. Such a liquid transport medium could allow for operation below 500oC while stabilizing the hydride from thermal decomposition. Investigations on this system were carried out using a custom pressure differential thermal analyzer that was able to operate above temperatures of 700oC and pressures of 2.2MPa. The results of the experiments provided valuable information concerning the phase diagrams of various hydride-borohydride mixtures. The eutectic composition of the NaH-KBH4 system was found to be 43 mole% NaH. The corresponding eutectic temperature (503oC) was determined using the differential cooling curves. Appreciable NaH decomposition was noticed in mixtures above 59.0 mole% NaH. Mixtures up to 42.5 mole% KH in KBH4 were also investigated. The eutectic composition of the KH-KBH4 binary system was determined by extrapolating the liquidus curve to intersect the solidus curve. The KH-KBH4 eutectic temperature was found to be 390oC at 66 mole% KH. The experimental work successfully demonstrates that thermally unstable hydrides can be obtained in the liquid phase below their melting points, under moderate pressures, when mixed with alkali borohydrides. This significantly lowers the achievable operating temperature of the thermally regenerative electrochemical systems currently proposed. The use of the single chamber design with a hydride-borohydride liquid medium offers numerous advantages including: reduced maintenance, reduced operating temperature, reduced system weight, reduced parasitic losses, increased voltage, and increased reliability. The viability for mid-grade industrial waste heat recovery requires construction of a prototype which optimizes power outputs and explores the hydrodynamic transport of material. / Thesis (Master, Mining Engineering) -- Queen's University, 2009-09-24 14:33:22.627

Thermally bonded nonwovens are low-price substitutes for traditional textiles. They are used in many areas including filtration, automotive and aerospace industries. Hence, understanding deformation behaviours of these materials is required to design new products tailored for specific applications in different areas. Because of their complex and random structure, numerical simulations of nonwoven materials have been a challenging task for many years. The main aim of the thesis is to develop a computational modelling tool to simulate the effect of design parameters on structural behaviour of low-density nonwoven materials by using a finite element method. The modelling procedure is carried out with a parametric modelling technique, which allows a designer to run a series of analyses with different design parameters and observe the effects of these parameters on the mechanical behaviour of nonwoven materials. The thesis also presents the study of rate dependent behaviour of nonwoven fibres. Novel test and data-interpretation procedures are proposed to determine the creep behaviour of fibres in the nonwoven structure. Some case studies are presented to demonstrate the effectiveness of the model. The developed computational tool allows macro and micro-scale structural investigation of nonwoven materials. Two additional studies are presented, performed with the developed tool. In the first study, the effect of design parameters on tensile stiffness of nonwovens was determined by performing numerical analyses with various nonwoven models. In the second one, strain distribution in fibres is studied thoroughly together with factors affecting the distribution. The models, developed in the thesis can also be employed in further studies of nonwovens, such as investigation of their damage and fracture behaviour.

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.

Submitted by Johnny Rodrigues (johnnyrodrigues@ufcg.edu.br) on 2018-03-08T20:19:59Z No. of bitstreams: 1 BRUNO BRITO DANTAS - DISSERTAÇÃO PPGEQ 2016..pdf: 1656780 bytes, checksum: eef180b8a56ee0bcd0361febde377c56 (MD5) / Made available in DSpace on 2018-03-08T20:19:59Z (GMT). No. of bitstreams: 1 BRUNO BRITO DANTAS - DISSERTAÇÃO PPGEQ 2016..pdf: 1656780 bytes, checksum: eef180b8a56ee0bcd0361febde377c56 (MD5) Previous issue date: 2016-10 / Capes / A destilação extrativa é um dos mais importantes procedimentos utilizados para a separação de misturas azeotrópicas na indústria química, porém é um método relativamente caro, tendo em vista sua alta demanda energética. As limitações dessa operação vêm estimulando durante décadas, estudos acerca de alternativas que os minimizem. A intensificação de processos por meio do acoplamento térmico entre colunas de destilação é uma opção que vem recebendo cada vez mais atenção, haja vista os bons resultados que trabalhos publicados nessa área têm apresentado. Porém, recentemente alguns estudiosos tiveram conclusões que vão de encontro à toda eficiência creditada ao acoplamento térmico, o que torna necessário ainda mais estudos a cerca dessa tecnologia. Devido a essas divergências, surgem também dúvidas a respeito do método mais adequado para a implementação de um sistema de destilação termicamente acoplado, uma vez que se observa o emprego de diversos métodos na tentativa de alcançar um design para essas configurações que nem sempre repercutem na melhor alternativa. Neste trabalho foi descrito um procedimento para a obtenção do ótimo design de sequências de destilação convencional (CS) e termicamente acoplada (TCS), além da obtenção do ótimo operacional, baseado no método de otimização desenvolvido por Figueiredo et al. (2015). A metodologia foi aplicada à simulação de dois sistemas, acetonametanol-água (M1) e acetona-metanol-DMSO (M2), e seus resultados foram comparados em termos de consumo anual total (TAC) e consumo específico de energia (SEC) com a literatura. A aplicação do procedimento de otimização alcançou reduções de até 30% e 15% do TAC das configurações CS e TCS, respectivamente, quando comparadas com a literatura, comprovando sua eficiência. Ademais, o uso de diferentes solventes nos permitiu chegar à conclusão de que nem sempre o acoplamento térmico é a melhor opção. / Extractive distillation is one of the most important procedures for the separation of azeotropic mixtures in the chemical industry, but it is a relatively expensive method, given its high energy demand. The limitations of this operation has been stimulating for decades, studies on alternatives to minimize them. The intensification process through thermal coupling between distillation columns is an option that has been receiving increasing attention, considering the good results that papers published in this area have shown. But recently some researchers presented findings that go against all efficiency credited to the thermal coupling, which makes it even more necessary studies about this technology. Due to such differences, questions arise regarding the most appropriate method for implementing a distillation system thermally coupled, as observed employing various methods in the attempt at achieving a design for those configurations that impact is not always the best alternative. This paper described a procedure for obtaining the optimal design of conventional distillation sequences (CS) and thermally coupled (TCS), in addition to obtaining the optimum operating based on the optimization method developed by Figueiredo et al. (2015). The methodology was applied to the simulation of two systems, acetone-methanol-water (M1) and acetone-methanol-DMSO (M2), and their results were compared in terms of TAC and SEC with literature. The application of the optimization procedure resulted in reductions of 30% and 15% of the TAC of the CS and TCS configurations, respectively, when compared with the literature, proving its efficiency. Futhermore, the use of different solvents has allowed us to reach the conclusion that not always the thermal coupling is the best option.

abstract: In this research, our goal was to fabricate Josephson junctions that can be stably processed at 300&deg;C or higher. With the purpose of integrating Josephson junction fabrication with the current semiconductor circuit fabrication process, back-end process temperatures (>350 &deg;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 &deg;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 &deg;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

A thorough study on the distribution of defect-related active energy levels has been performed on nanocrystalline TiO2. Films have been deposited on thick-alumina printed circuit boards equipped with electrical contacts, heater and temperature sensors, to carry out a detailed thermally stimulated currents analysis on a wide temperature range (5-630 K), in view to evidence contributions from shallow to deep energy levels within the gap. Data have been processed by numerically modelling electrical transport. The model considers both free and hopping contribution to conduction, a density of states characterized by an exponential tail of localized states below the conduction band and the convolution of standard Thermally Stimulated Currents (TSC) emissions with gaussian distributions to take into account the variability in energy due to local perturbations in the highly disordered network. Results show that in the low temperature range, up to 200 K, hopping within the exponential band tail represents the main contribution to electrical conduction. Above room temperature, electrical conduction is dominated by free carriers contribution and by emissions from deep energy levels, with a defect density ranging within 10(14)-10(18) cm(-3), associated with physio- and chemi-sorbed water vapour, OH groups and to oxygen vacancies.

La séparation de phase au sein d'un système polymère/solvant est la méthode la plus couramment utilisée pour élaborer une membrane polymère poreuse. Les principales méthodes d'inversion de phase nécessitent l'usage de solvants organiques qui génèrent des problèmes environnementaux (traitement des bains de coagulation) et sanitaires (sécurité des installations industrielles). Cette étude porte sur le développement d'une nouvelle membrane polymère poreuse à partir d'un polymère biosourcé et hydrosoluble, l'hydroxypropylcellulose (HPC), permettant de s'affranchir de l'usage de solvants organiques. La propriété de thermosensibilité de l'HPC, caractérisé par une température critique basse en solution dans l'eau (LCST) de l'ordre de 40 °C, a par ailleurs permis de développer un procédé original d'élaboration de membranes HPC par séparation de phase induite par augmentation de la température au-delà de la LCST. Ce travail vise un triple objectif : (i) déterminer la formulation idoine permettant de former une membrane poreuse insoluble dans l'eau à partir d'HPC, (ii) appréhender et comprendre les mécanismes de structuration de la matrice polymère à travers l'interaction des mécanismes interdépendants de séparation de phase par décomposition spinodale, de réticulation chimique et d'extraction du solvant par évaporation et enfin (iii) caractériser l'aptitude des membranes à la filtration d'une solution aqueuse sous pression. Le suivi en ligne de la dynamique de séparation de phase d'un système HPC/eau/réticulant ± porogène (PEG200) par microscopie optique en contraste de phase, de la réticulation par rhéologie et de l'évaporation de l'eau par thermogravimétrie a ainsi permis de mettre en évidence l'impact de la formulation et des paramètres de conduite du procédé d'inversion de phase sur les propriétés morphologiques et d'usage des membranes. La porosité membranaire et le caractère symétrique de la morphologie ont notamment été corrélés à la vitesse des phénomènes concomitants de réticulation et d'évaporation de l'eau, donc à la vitesse de montée en température du procédé TIPS-LCST. La caractérisation de la perméabilité à l'eau des membranes HPC a confirmé l'efficacité de la réticulation et la résistance structurale des membranes au cours de plusieurs filtrations continues à l'eau. En raison du caractère thermosensible de l'HPC, ces membranes ont montré une aptitude remarquable à la filtration de solutions aqueuses à température élevée (60 °C). Par ailleurs, il a été montré que la perméabilité des membranes pouvait être en partie contrôlée par la température et la pression transmembranaire appliquée. / Phase separation of polyer/solvent system is the most widespread industrial process to manufacture membranes. Large solvent quantity is usually used whatever the process, hence leading to environmental (coagulation and washing baths treatment) and health (industrial and plant safety) problems.This study focuses on the development of new porous membranes made from hydroxypropylcellulose (HPC), a water soluble polymer, avoiding the use of any organic solvent. Moreover, the thermo-sensitive character of this polymer, characterized by a Lower Critical Solution Temperature (LCST) in water of about 40 °C, enabled to design an original thermally induced phase separation process by temperature increase above the LCST. This study aims (i) to find the ideal polymer solution composition to produce insoluble HPC membrane, (ii) to approach and understand the link between phase separation mechanism by spinodal decomposition, crosslinkig reaction and water extraction by evaporation, (iii) characterize pure water permeability under pressure. On-line monitoring of phase sepration dynamics by phase contrast optical microscopy, crosslinking reaction by rheology and water evaporation by thermogravimetric analysis of the system HPC/water/cross-linking agent ± porogen (PEG200) allowed an understanding of simultaneous and related mechanisms occurring during elaboration (phase separation / cross-linking / water evaporation) and a correlation with HPC membrane morphologies and characteristics in relation with phase separation process parametres. Pure water permeability characterization demonstrated the efficiency of cross-linking and structural strength during several filtration cycles. Furthermore, it has been shown that water permeability of HPC membranes could be controlled in part by the temperature and the applied pressure.

This thesis investigated a new group of poly(Bd)/poly(Bd-co-MAA) core-shell particles that were ionically crosslinked and cast as nanostructured ionomer films from aqueous dispersions. The new group of poly(Bd)/poly(Bd-co-MAA) core-shell particles were studied for structure-property relationships and morphology. The covalent crosslinking content in the core and the shell were varied at constant ionic crosslinking. Stress-strain data showed control of the nanostructured films. The chain transfer agent used during the preparation of the nanoparticles core-shells was shown to independently tune the mechanical properties of the films.

The rapidly expanding of the global population in the 21st-century forces people facing two serious problems: water scarcity and energy shortage. Enormous continuous studies focus on providing enough fresh water and energy in a sustainable way. This thesis aims at exploring novel membrane processes based on thermally responsive ionic liquids with the upper critical solution temperature (UCST ILs) for water desalination and energy conversion from low-grade heat energy to electricity. A UCST IL protonated betaine bis(trifluoromethylsulfonyl)imide ([Hbet][Tf2N]) was first experimentally studied as a novel draw solute in a thermal forward osmosis (FO). A 3.2 M [Hbet][Tf2N] solution can be obtained via spontaneous phase separation from an IL and water mixture at room temperature. By heating and maintaining the temperature above 56°C, this solution can draw water from high-salinity solution up to 3.0 M, 5 times salty as the sea water. The IL draw solution can be easily regenerated by phase separation. Conducting the FO process at higher temperatures can also increase the water flux. According to the different choices of the freshwater polishing step, the electric energy consumption in this novel process was estimated as 26.3% to 64.2% of conventional one-step sea water reverse osmosis. Two UCST ILs with better performance, [Hbet][Tf2N] and choline bis(trifluoromethylsulfonyl)imide ([Choline][Tf2N]), were selected as the agents in a novel closed-loop thermally responsive IL osmotic heat engine (TRIL-OHE) to convert low-grade thermal energy to electricity. The specific energies of the [Hbet][Tf2N] system and the [Choline][Tf2N] system are 2500 kJ/t and 3700 kJ/t, which are 2.7 and 4.0 times of the seawater and river water system, respectively. The maximum power density measured from a commercial FO membrane is 1.5 W/m2 for the [Hbet][Tf2N] system and 2.3 W/m2 for the [Choline][Tf2N] system, leaving a big room to improve if highly permeable membranes are used. Another notable advantage of the TRIL-OHE is the heat released from the cooling stage can be largely recovered. A rigorous energy balance showed with a 70% heat recovery, the energy efficiency could be increased from around 20% to 70% of the Carnot efficiency in both UCST ILs systems.