Esta pesquisa tem como finalidade desenvolver implantes de alumina com núcleo denso e superfície gradualmente porosa (FGM) recobertos com materiais bioativos - hidroxiapatita e biovidro. Materiais porosos são estudados como solução para a osseointegração, porém apresenta déficit nas suas propriedades mecânicas. Estruturas bifásicas foram desenvolvidas por pesquisadores com o propósito de promover crescimento tecidual, sem afetar significativamente sua propriedade mecânica, no entanto ocorre delaminação. Neste trabalho é proposta uma estrutura em gradiente funcional que visa aprimorar as propriedades mecânicas conjugadas com a sinalização celular e com integração óssea. O tamanho, a morfologia de poros e também a porosidade são parâmetros fundamentais para boa resposta tecidual e integração do implante, pois afetam a viabilidade e a afinidade celular. Para essa finalidade a busca por uma espessura efetiva de porosidade se faz fundamental para alto desempenho do implante. Peças de alumina porosas infiltradas com materiais bioativos foram fabricadas e estudadas in vivo, em tíbias de ratos da raça Wistar durante 14, 18, 21 e 28 dias, para investigar a qualidade do crescimento de tecido ósseo. O estudo com implantes porosos recobertos foi realizado para avaliar e padronizar a superfície porosa do gradiente funcional. Os animais foram analisados com densidade mineral óssea (DMO), as tíbias foram caracterizadas na interface osso-implante e nos poros com histologia, com EDS-line-scan, com radiografias e com ensaios de cisalhamento. Implantes de alumina com 70% de porosidade foram comparados com recobrimento bioativo e sem recobrimento in vivo e ex-vivo. Nos resultados, os implantes recobertos aceleram o processo de osseointegração. Essa característica foi mais evidente no período de 28 dias de implantação com aumento de 24% na tensão de cisalhamento. Após validar uma superfície porosa e osseointegrável para a superfície do gradiente funcional, foram aplicadas técnicas diferenciadas para manufaturar peças com núcleo denso e superfície com gradiente de porosidade. As peças com FGM foram manufaturadas com a utilização de duas técnicas, dipping e co-prensagem e foram analisadas com microscopia eletrônica de varredura. Com o método de manufatura de co-prensagem foram obtidas peças com superfície gradualmente porosa, com transição de densificação contínua, sem delaminação. Os implantes de alumina em gradiente funcional com 70 % de porosidade na superfície mais externa, recobertos por bioativos apresentam potencial para aplicações em implantes ósseos ou dentários. / The present thesis reports on the development of alumina implants with dense core and gradually porous surface (FGM) covered with bioactive materials, hydroxyapatite (HA) and bioactive glass. Porous materials have been studied to provide tissue ingrowth, however they strongly affect the mechanical properties of the implant. Biphasic structures have been developed by some researchers to promote tissue growth without affecting the mechanical properties, although delamination may occur. This study proposes a functional gradient structure to improve both the mechanical properties of the material and cell signaling. The size and morphology of the pores as well as their porosity are key parameters for good tissue response and implant integration, since they affect the viability and cell affinity, and an effective porosity thickness becomes essential for a high performance of the implant. Porous alumina implants coated with bioactive materials were fabricated and studied in vivo in rat tibia for 14, 18, 21, and 28 days to investigate the quality of bone tissue growth. The study of porous coated implants was performed to evaluate and standardize the porous surface of the functional gradient. The animals were examined with bone mineral density (BMD), the tibiae were characterized in the bone-implant interface and the pores were analyzed with histology, EDS line-scan, X-ray and shear tests. Alumina with 70% porosity was compared with and without bioactive coating in vivo and ex vivo. The results showed that the covered implants accelerated the osseointegration process. This characteristic is more evident within 28 days of deployment with a 24% increase in shear stress. After validating a porous and osteointegrated surface for the surface of the functional gradient, several techniques were applied to manufacture parts with dense core and surface with gradient of porosity. The pieces were manufactured with FGM using two techniques, dipping and co-pressing and were analyzed by scanning electron microscopy. The manufacturing method of co-pressing allowed obtaining pieces with gradually porous surface and continuous transition of densification without delamination. On the outermost surface, alumina implants with functional gradient and 70% porosity and coated with bioactive materials presented potential for application to bone or dental implants.

Due to their ability to confer enhanced surface properties without compromising the properties of the substrate, coatings have become ubiquitous in heavy industrial applications for corrosion, wear, and thermal protection, among others. Kinetic Metallization (KM), a solid-state impact consolidation and coating process, is well-suited for depositing industrial coatings due to its versatility, low substrate heat input, and low cost. The ability of KM coatings to adhere to the substrate is determined by the quality of the interface. The purpose of this study is to develop a model to predict the interfacial quality of KM coatings using known coating and substrate properties. Of the various contributions to adhesion of KM coatings, research suggests that the thermodynamic Work of Adhesion (WAD) is the most fundamental. It is useful to define interfacial quality in terms of the critical strain energy release rate (GC) at which coating delamination occurs. Studies show that GC for a given interface is related to WAD. This study attempts to develop a theoretical model for calculating WAD and understand the relationship between GC and WAD. For a bimetallic interface between two transition metals, WAD can be theoretically calculated using known electronic and physical properties of each metal: the molar volume, V, the surface energy, γ, and the enthalpy of alloy formation, ΔHinterface; ΔHinterface is a function of the molar volume, V, the work function, φ, and the electron density at the boundary of the Wigner-Seitz cell, nWS.WAD for Ni-Cu and Ni-Ti interfaces were 3.51 J/m2 and 4.55 J/m2, respectively. A modified Four-point bend testing technique was used to experimentally measure GC for Ni-Cu and Ni-Ti specimens produced by KM. These tests yielded mean G­C values of 50.92 J/m2 and 132.68 J/m2 for Ni-Cu and Ni-Ti specimens, respectively. Plastic deformation and surface roughness are likely the main reasons for the large discrepancy between GC and WAD. At the 95% confidence level, the mean GC of the Ni-Ti interface is significantly higher than that of the Ni-Cu interface. Further testing is recommended to better understand the relationship between WAD and GC.

L'exfoliation en phase liquide du graphite est l'une des méthodes les plus prometteuses pour augmenter la production et la disponibilité commerciale du graphène. Le processus d'exfoliation peut être décrit, de manière conceptuelle, en quatre étapes: le contact du graphite avec le liquide, l'intercalation du solvant entre les feuillets de graphène, la dispersion du matériau à deux dimension et sa stabilisation en phase liquide. Comme les liquides ioniques peuvent être facilement obtenus avec différentes structures moléculaires et donc des propriétés physicochimiques modulables, ils ont été utilisés dans cette thèse comme milieux liquides pour l'exfoliation du graphite. Notre objectif est d'optimiser l'exfoliation du graphite à travers la compréhension des mécanismes moléculaires et des interactions impliquées dans chaque étape du processus. Les énergies interfaciale graphite-liquide ont été calculées à partir de tensions de surface et d'angles de contact mesurées entre des liquides ioniques et du graphite pour déterminer l'affinité de différents liquides à la surface du graphite. Afin d'étudier cette interface liquide - solide, des simulations en dynamique moléculaire ont été menées pour analyser l'organisation des liquides ioniques à la surface du graphite. De même, l'énergie libre nécessaire pour créer des cavités au sein du liquide ionique a été calculée.Des simulations moléculaires ont également été réalisées pour modéliser l'exfoliation d'un feuillet de graphène à partir de graphite en apportant une vue microscopique de l'intercalation des molécules de solvant. L'énergie nécessaire à l'exfoliation a pu être calculée en présence de différents liquides. Des composés polyaromatiques ont été considérés comme des modèles pour le graphène car ils peuvent être facilement obtenus purs, sans variabilité de structure, défauts ou groupes fonctionnels non contrôlés. Les enthalpies de dissolution du naphtalène, anthracène et pyrène dans différents liquides ioniques ont été mesurées par calorimétrie en solution et liées à leur solubilité. L'organisation des ions autour de ces composés modèles a été étudiée par simulation moléculaire et spectroscopie Infra-Rouge.Après l'exfoliation, les échantillons de graphène en suspension dans différents liquides ioniques ont été caractérisés expérimentalement en termes de taille de feuillets (microscopie électronique à transmission et microscopie à force atomique), nombre de couches de graphène (microscopie à force atomique, spectroscopie Raman), concentration totale (spectroscopie UV-visible) et pureté du matériau exfolié (spectroscopie de photoélectrons~X). Vingt liquides ioniques différents à base de cations imidazolium, pyrrolidinium et ammonium et d'anions bis (trifluorométhylsulfonyl)imide, triflate, dicyanamide, tricyanométhanide et méthylsulfate ont été testés. Les interactions moléculaires permettant d'établir de règles de conception pour les liquides ioniques capables d'exfolier les matériaux carbonés ont été identifiées. Le cation pyrrolidinium a montré des résultats prometteurs dans toutes les étapes du processus d'exfoliation, par rapport au cation imidazolium ou ammonium. La sélection d'un grand anion flexible a réduit l'énergie interfaciale avec le graphite, dispersé les nanocarbones en augmentant l'entropie du système et stabilisé le graphite exfolié en plus grande quantité. Un petit anion tel que le triflate semble être favorable à l'obtention de graphène, même si la taille des couches et leur quantité sont réduites. Un liquide ionique ayant une partie apolaire importante facilitera l'insertion et la dispersion du nanomatériau de carbone. Pour la stabilisation du graphite, les interactions alkyle-π et π- π sont décisives. / The liquid-phase exfoliation of graphite is one of the most promising methods to increase production and commercial availability of graphene. The exfoliation process can be conceptually described in four steps: the contact of the graphite with liquid, the intercalation of the solvent between layers, the dispersion of the two dimensional material, and its stabilization in the liquid-phase. Because ionic liquids can be easily obtained with chosen molecular structures and tunable physicochemical properties, they were used in this study as liquid media for the exfoliation of graphite. Our aim is to optimize the exfoliation of graphite through the understanding of the molecular mechanisms and of the interactions involved in each step of the process.The liquid-graphite interfacial energies from measured surface tensions and contact angles, between ionic liquids and pristine graphite surface, were used to determine the affinity of different liquids at the surface of graphite. In order to investigate this interface, molecular dynamics simulations were conducted to analyse the ordering of ionic liquids at the surface of graphite. The free energies necessary to create cavities inside the bulk ionic liquid have also been studied.Molecular simulations were also used to study the exfoliation of one graphene layer from a stack of graphite and hence provide a microscopic view of the intercalation of solvent molecules. The energies involved in the process have been calculated.Polyaromatic compounds were regarded as models for graphene as they can be easily obtained pure, without structure variability, defects or uncontrolled functional groups. Enthalpies of dissolution of polyaromatic hydrocarbons (naphthalene, anthracene and pyrene) in different ionic liquids were measured by solution calorimetry and related with their solubility. The ordering of the ions around this model compounds were studied by molecular simulation and spectroscopy Infra-Red.After exfoliation, samples of suspended graphene in different ionic liquids have been characterized experimentally in terms of flake size (using transmission electron microscopy and atomic force microscopy), number of layers (atomic force microscopy, spectroscopy Raman), total concentration (UV-visible spectroscopy) and purity of the exfoliated material (X-ray photoelectron spectrometry).Twenty different ionic liquids based on imidazolium, pyrrolidinium and ammonium cations and on bis(trifluoromethylsulfonyl)imide, triflate, dicyanamide, tricyanomethanide, and methyl sulfate have been tested. The molecular interactions have been identified thus allowing the establishment of design rules for ionic liquids capable of exfoliating carbon materials. The pyrrolidinium cation has shown promising results in all the steps of exfoliation process, compared to the imidazolium or ammonium cation. Selecting a large and flexible anion reduced the interfacial energy with graphite, dispersed the nanocarbons by increasing the entropy of the system and stabilized the exfoliated graphite in larger quantity. A small anion such as triflate appears to be favorable for obtaining graphene, whereas the size of the layers and their quantity is reduced. An ionic liquid having an important apolar portion will facilitate the insertion and dispersion of graphene layers. For the stabilization of graphite, the alkyl-π et π -π interactions are decisive.

An experimental study of phase transitions of long-chain n-alkanes induced by the effect of interfaces is described. ¶ The phase behaviour of long-chain n-alkanes (carbon number 14, 16, 17, 18) adsorbed at isolated mica surfaces and confined between two mica surfaces has been studied in the vicinity of and down to several degrees below the bulk melting points, Tm. Using the Surface Force Apparatus we have measured the thickness of alkane films adsorbed from vapour (0.97 [equal to or greater-than] p/p[subscript o] [equal to or greater-than] 0.997), studied capillary condensation transition, subsequent growth of capillary condensates between two surfaces, and phase transitions in both the adsorbed films and the condensates. By measuring the growth rate of the capillary condensates we have identified a transition in the lateral mobility of molecules in the adsorbed films on isolated mica surfaces. This transition to greater mobility occurs slightly above Tm for n-hexadecane, n-heptadecane and n-octadecane but several degrees below Tm for n-tetradecane, and is accompanied by a change in wetting behaviour and a measurable decrease in adsorbed film thickness for n-heptadecane and n-octadecane. Capillary condensates that form below Tm remain liquid, but may freeze if the degree of confinement is reduced by separation of the mica surfaces. An increase in the area of the liquid-vapour interface relative to that of the liquid-mica interface facilitates freezing in the case of the long-chain alkanes, which show surface freezing at the liquid-vapour interface. ¶ Although thermodynamic properties of the surface freezing transition have been rather well documented, the kinetics involved in formation of such ordered monolayers has so far received very little attention. We studied the surface tension of n-octadecane as a function of temperature in the vicinity of Tm, using the static Wilhelmy plate and the dynamic maximum bubble pressure methods. The two methods give different results on cooling paths, where nucleation of the surface ordered phase is involved, but agree on heating paths, where both methods measure properties of the equilibrium surface phase. On cooling paths, the surface of bubbles may supercool below the equilibrium surface freezing temperature. The onset of surface freezing is marked by a sharp drop in the surface tension. The transition is accompanied by an increased stability of the films resulting in longer bubble lifetimes at the liquid surface, which suggests that the mechanical properties of the surfaces change from liquid-like to solid-like. Our results suggest occurrence of supercooling of the monolayer itself.

Cette thèse est dédiée à l'étude de problèmes de couplage en espace entre différents modèles d'écoulements compressibles. Nous considérons des formulations monodimensionnelles où l'interface de couplage est mince, fixe et séparant deux régions de l'espace correspondant aux deux modèles à coupler. L'objectif de notre travail consiste à définir une condition de couplage à l'interface et à résoudre numériquement le problème de couplage muni de cette condition. Après un état de l'art non exhaustif sur le couplage de systèmes hyperboliques de lois de conservation, nous proposons une nouvelle formulation de condition de couplage basée sur l'ajout d'un terme source mesure agissant exactement sur l'interface de couplage. Nous supposons, dans un premier temps, que le poids associé à ce terme source est connu et constant. Deux solveurs de Riemann sont développés dont une approche par relaxation préservant les solutions équilibres du problème de couplage. Cette méthode par relaxation est reprise par la suite dans le cadre d'un problème d'optimisation sous contraintes pour déterminer un poids dynamique en temps selon différentes motivations de transmission à l'interface. Dans une seconde partie, nous développons un solveur de Riemann approché pour un modèle bifluide à deux pressions dans le cas d'un écoulement diphasique isentropique par phase. Le modèle en question a pour particularité de comprendre des termes non conservatifs que l'on réécrit alors sous la forme de termes sources mesures. L'approche par relaxation établie dans la partie précédente est alors étendue au cas du modèle bifluide, moyennant une estimation a priori des contributions non conservatives. Cette méthode nous permet, dans un dernier chapitre, de résoudre numériquement le problème de couplage interfacial entre un modèle bifluide à deux pressions et un modèle de drift-flux grâce à l'approche dite du modèle père.

Fish oil is an excellent source of long chain polyunsaturated fatty acids (LC-PUFA), which can reduce the risk of cardiovascular disease in addition to other health benefits. However, the average intake of LC-PUFA in the Western diet is much lower than the recommended levels. Fish oil is prone to oxidative deterioration when exposed to oxygen and thus must be protected in order to be used in food products. Microencapsulation is one possibility that is already applied by the industry to protect fish oil. However, most of the conventional microencapsulation techniques suffer from shortcomings such as harsh processing conditions or the use of numerous chemicals. The main objective of this thesis was to develop a novel spray process to microencapsulate fish oil based on supercritical fluid (SCF) technology using supercritical carbon dioxide (SC-CO2) and CO2-expanded ethanol (CX EtOH). Fundamental physicochemical properties essential for optimal process design were lacking in the literature; therefore, density, interfacial tension (IFT) and viscosity of fish oil in the form of triglycerides and fatty acid ethyl esters were determined at different temperatures and pressures. Fish oil when equilibrated with SC-CO2 at elevated pressure expanded by up to about 40% in volume and increased in density by up to about 5%. Furthermore, IFT of fish oil in contact with SC-CO2 decreased substantially by an order of magnitude with an increase in CO2 pressure. When fish oil was in contact with CX EtOH, IFT decreased to ultra low levels at pressures of less than 10 MPa. Viscosity of fish oil equilibrated with SC-CO2 decreased substantially with pressure but increased with shear rate. Based on the physicochemical properties determined in this research, a novel process to produce micro- and nano-sized particles containing fish oil was developed based on a SCF spray-drying method. Key processing parameters have been evaluated and can be further optimized to improve encapsulation efficiency. Determination of physicochemical properties contributed to the fundamental understanding of the behavior of the fish oil+CO2 system with and without ethanol under high pressure conditions. The new microencapsulation process shows great potential for the delivery of bioactives in various product applications. / Bioresource and Food Engineering

A pair of studies investigating the deposition and surface chemical properties of ultrathin metal films were pursued: (i) Pt-Co alloys on Mo(110); and (ii) Pd on Pt(111). Experimental measurement was based on a combination of electron spectroscopy (low energy ion scattering spectroscopy, X-ray photoelectron spectroscopy, Auger electron spectroscopy, and low energy electron diffraction) and electrochemistry (voltage efficiency, voltammetry, and coulometry). Mixed-metal preparation of Pt-Co films by thermal vapor deposition (TVD) resulted in a thin-film binary alloy. Careful analysis revealed a substantial divergence between the composition at the interface and that in the interior. This outcome was observed for all compositions and allowed for the construction of a ?surface phase diagram?. The proclivities of the alloys of pre-selected compositions towards enhanced catalysis of the oxygen-reduction reaction were assessed in terms of their voltage efficiencies, as manifested by the open-circuit potential (OCP) in O2-saturated dilute sulfuric acid electrolyte. The particular alloy surface, Pt3Co (XPt=3,XCo=1), whether from the thin film or a bulk single crystal, exhibited the highest OCP, a significant improvement over pure Pt but still appreciably lower than the thermodynamic limit. Under test conditions, the degradation of thusly-prepared films was primarily due to Co corrosion. Ultrathin Pd films on well-defined Pt(111) surfaces, with coverages from 0.5 to 8 monolayers (ML), were prepared by surface-limited redox replacement reaction (galvanic exchange) of underpotentially deposited Cu. Spectroscopic data revealed that films prepared in this manner are elementally pure, pseudomorphic to the substrate, and stable, independent of the surface coverage (?) of palladium. Analysis of the voltammetric profiles in the hydrogen evolution region revealed unique properties of hydrogen adsorption unseen in bulk electrodes. Notably, at 1 ML coverage, a step-free film was produced that did not exhibit hydrogen absorption. At higher coverages, digital (layer-by-layer) deposition gave way to 3D islands in a Stranski- Krastanov growth mode; under these conditions, onset of bulk-like behavior was observed. This method makes possible the synthesis of well-ordered noble-metal films in the absence of high-temperature treatment

Membrane-based acid gas (e.g., CO2) separation, gas dehydration and humidification, as well as solvent dehydration are important to the energy and process industries. Fixed carrier facilitated transport membranes can enhance the permeation without compromising the selectivity. The development of suitable fixed carrier membranes for CO2 and water permeation, and understanding of the transport mechanism were the main objectives of this thesis. Poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) composite membranes were developed using microporous polysulfone (PSF) or polyacrylonitrile (PAN) substrates. The PDMAEMA layer was crosslinked with p-xylylene dichloride via quaternization reaction. Fourier transform infrared, scanning electron microscopy, adsorption tests, and contact angle measurements were conducted to analyze the chemical and morphological structure of the membrane. It was shown that the polymer could be formed into thin dense layer on the substrates, while the quaternary and tertiary amino groups in the side chains of PDMAEMA offered a high polarity and hydrophilicity. The solid-liquid interfacial crosslinking of PDMAEMA led to an asymmetric crosslinked network structure, which helped minimize the resistance of the membrane to the mass transport. The interfacially formed membranes were applied to CO2/N2 separation, dehydration of CH4, gas humidification and ethylene glycol dehydration. The membranes showed good permselectivity to CO2 and water. For example, a CO2 permeance of 85 GPU and a CO2/N2 ideal separation factor of 50 were obtained with a PDMAEMA/PSF membrane at 23oC and 0.41 MPa of CO2 feed pressure. At 25oC, the permeance of water vapor through a PDMAEMA/PAN membrane was 5350 GPU and the water vapor/methane selectivity was 4735 when methane was completely saturated with water vapor. On the other hand, the relative humidity of outlet gas was up to 100 % when the membrane was used as a hydrator at 45oC and at a carrier gas flow rate of 1000 sccm. For used for dehydration of ethylene glycol at 30oC, the PDMAEMA/PSF membrane showed a permeation flux of ~1 mol/(m2.h) and a permeate concentration of 99.7 mol% water at 1 mol% water in feed. This work shows that the quaternary and tertiary amino groups can be used as carriers for CO2 transport through the membrane based on the weak acid-base interaction. In the presence of water, water molecules in the membrane tend to form a water "path" or water "bridge" which also help contribute to the mass transport though the membrane. In addition, CO2 molecules can be hydrated to HCO3-, which reaction can be catalyzed by the amino groups, the hydrated CO2 molecules can transport through the water path as well as the amino groups in the membrane. On the other hand, for processes involving water (either vapor or liquid) permeation, the amino groups in the membrane are also helpful because of the hydrogen bonding effects.

The goal of this thesis is on improving the understanding of mechanical and tribological mechanisms in microelectronic wire bonding. In particular, it focusses on the development and application of quantitative models of ultrasonic (US) friction and interfacial wear in wire bonding. Another objective of the thesis is to develop a low-stress Cu ball bonding process that minimizes damage to the microchip. These are accomplished through experimental measurements of in situ US tangential force by piezoresistive microsensors integrated next to the bonding zone using standard complementary metal oxide semiconductor (CMOS) technology. The processes investigated are thermosonic (TS) Au ball bonding on Al pads (Au-Al process), TS Cu ball bonding on Al pads (Cu-Al process), and US Al wedge-wedge bonding on Al pads (Al-Al process). TS ball bonding processes are optimized with one Au and two Cu wire types, obtaining average shear strength (SS) of more than 120 MPa. Ball bonds made with Cu wire show at least 15% higher SS than those made with Au wire. However, 30% higher US force induced to the bonding pad is measured for the Cu process using the microsensor, which increases the risk of underpad damage. The US force can be reduced by: (i) using a Cu wire type that produces softer deformed ball results in a measured US force reduction of 5%; and (ii) reducing the US level to 0.9 times the conventionally optimized level, the US force can be reduced by 9%. It is shown that using a softer Cu deformed ball and a reduced US level reduces the extra stress observed with Cu wire compared to Au wire by 42%. To study the combined effect of bond force (BF) and US in Cu ball bonding, the US parameter is optimized for eight levels of BF. For ball bonds made with conventionally optimized BF and US settings, the SS is ≈ 140 MPa. The amount of Al pad splash extruding out of bonded ball interface (for conventionally optimized BF and US settings) is between 10–12 µm. It can be reduced to 3–7 µm if accepting a SS reduction to 50–70 MPa. For excessive US settings, elliptical shaped Cu bonded balls are observed, with the major axis perpendicular to the US direction. By using a lower value of BF combined with a reduced US level, the US force can be reduced by 30% while achieving an average SS of at least 120 MPa. These process settings also aid in reducing the amount of splash by 4.3 µm. The US force measurement is like a signature of the bond as it allows for detailed insight into the tribological mechanisms during the bonding process. The relative amount of the third harmonic of US force in the Cu-Al process is found to be five times smaller than in the Au-Al process. In contrast, in the Al-Al process, a large second harmonic content is observed, describing a non-symmetric deviation of the force signal waveform from the sinusoidal shape. This deviation might be due to the reduced geometrical symmetry of the wedge tool. The analysis of harmonics of the US force indicates that although slightly different from each other, stick-slip friction is an important mechanism in all these wire bonding variants. A friction power theory is used to derive the US friction power during Au-Al, Cu-Al, and Al-Al processes. Auxiliary measurements include the current delivered to the US transducer, the vibration amplitude of the bonding tool tip in free-air, and the US tangential force acting on the bonding pad. For bonds made with typical process parameters, several characteristic values used in the friction power model such as the ultrasonic compliance of the bonding system and the profile of the relative interfacial sliding amplitude are determined. The maximum interfacial friction power during Al-Al process is at least 11.5 mW (3.9 W/mm²), which is only about 4.8% of the total electrical power delivered to the US transducer. The total sliding friction energy delivered to the Al-Al wedge bond is 60.4 mJ (20.4 J/mm²). For the Au-Al and Cu-Al processes, the US friction power is derived with an improved, more accurate method to derive the US compliance. The method uses a multi-step bonding process. In the first two steps, the US current is set to levels that are low enough to prevent sliding. Sliding and bonding take place during the third step, when the current is ramped up to the optimum value. The US compliance values are derived from the first two steps. The average maximum interfacial friction power is 10.3 mW (10.8 W/mm²) and 16.9 mW (18.7 W/mm²) for the Au-Al and Cu-Al processes, respectively. The total sliding friction energy delivered to the bond is 48.5 mJ (50.3 J/mm²) and 49.4 mJ (54.8 J/mm²) for the Au-Al and Cu-Al processes, respectively. Finally, the sliding wear theory is used to derive the amount of interfacial wear during Au-Al and Cu-Al processes. The method uses the US force and the derived interfacial sliding amplitude as the main inputs. The estimated total average depth of interfacial wear in Au-Al and Cu-Al processes is 416 nm and 895 nm, respectively. However, the error of estimation of wear in both the Au-Al and the Cu-Al processes is ≈ 50%, making this method less accurate than the friction power and energy results. Given the error in the determination of compliance in the Al-Al process, the error in the estimation of wear in the Al-Al process might have been even larger; hence the wear results pertaining to the Al-Al process are not discussed in this study.

Membrane-based acid gas (e.g., CO2) separation, gas dehydration and humidification, as well as solvent dehydration are important to the energy and process industries. Fixed carrier facilitated transport membranes can enhance the permeation without compromising the selectivity. The development of suitable fixed carrier membranes for CO2 and water permeation, and understanding of the transport mechanism were the main objectives of this thesis. Poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) composite membranes were developed using microporous polysulfone (PSF) or polyacrylonitrile (PAN) substrates. The PDMAEMA layer was crosslinked with p-xylylene dichloride via quaternization reaction. Fourier transform infrared, scanning electron microscopy, adsorption tests, and contact angle measurements were conducted to analyze the chemical and morphological structure of the membrane. It was shown that the polymer could be formed into thin dense layer on the substrates, while the quaternary and tertiary amino groups in the side chains of PDMAEMA offered a high polarity and hydrophilicity. The solid-liquid interfacial crosslinking of PDMAEMA led to an asymmetric crosslinked network structure, which helped minimize the resistance of the membrane to the mass transport. The interfacially formed membranes were applied to CO2/N2 separation, dehydration of CH4, gas humidification and ethylene glycol dehydration. The membranes showed good permselectivity to CO2 and water. For example, a CO2 permeance of 85 GPU and a CO2/N2 ideal separation factor of 50 were obtained with a PDMAEMA/PSF membrane at 23oC and 0.41 MPa of CO2 feed pressure. At 25oC, the permeance of water vapor through a PDMAEMA/PAN membrane was 5350 GPU and the water vapor/methane selectivity was 4735 when methane was completely saturated with water vapor. On the other hand, the relative humidity of outlet gas was up to 100 % when the membrane was used as a hydrator at 45oC and at a carrier gas flow rate of 1000 sccm. For used for dehydration of ethylene glycol at 30oC, the PDMAEMA/PSF membrane showed a permeation flux of ~1 mol/(m2.h) and a permeate concentration of 99.7 mol% water at 1 mol% water in feed. This work shows that the quaternary and tertiary amino groups can be used as carriers for CO2 transport through the membrane based on the weak acid-base interaction. In the presence of water, water molecules in the membrane tend to form a water "path" or water "bridge" which also help contribute to the mass transport though the membrane. In addition, CO2 molecules can be hydrated to HCO3-, which reaction can be catalyzed by the amino groups, the hydrated CO2 molecules can transport through the water path as well as the amino groups in the membrane. On the other hand, for processes involving water (either vapor or liquid) permeation, the amino groups in the membrane are also helpful because of the hydrogen bonding effects.