Including inherited genetic diseases, like lipoprotein lipase deficiency, and acquired diseases, such as cancer and HIV, gene therapy has the potential to treat or cure afflicted people by driving an affected cell to produce a therapeutic protein. Using primarily viral vectors, gene therapies are involved in a number of ongoing clinical trials and have already been approved by multiple international regulatory drug administrations for several diseases. However, viral vectors suffer from serious disadvantages including poor transduction of many cell types, immunogenicity, direct tissue toxicity and lack of targetability. Non-viral polymeric gene delivery vectors (polyplexes) provide an alternative solution but are limited by poor transfection efficiency and cytotoxicity. Microfluidic (MF) nano-precipitation is an emerging field in which researchers seek to tune the physicochemical properties of nanoparticles by controlling the flow regime during synthesis. Using this approach, several groups have demonstrated the successful production of enhanced polymeric gene delivery vectors. It has been shown that polyplexes created in the diffusive flow environment have a higher transfection efficiency and lower cytotoxicity. Other groups have demonstrated that charge-stabilizing polyplexes by sequentially adding polymers of alternating charges improves transfection efficiency and serum stability, also addressing major challenges to the clinical implementation of non-viral gene delivery vectors. To advance non-viral gene delivery towards clinical relevance, we have developed a microfluidic platform (MS) that produces conventional polyplexes with increased transfection efficiency and decreased toxicity and then extended this platform for the production of ternary polyplexes. This work involves first designing microfluidic devices using computational fluid dynamics (CFD), fabricating the devices, and validating the devices using fluorescence flow characterization and absorbance measurements of the resulting products. With an integrated separation mechanism, excess polyethylenimine (PEI) is removed from the outer regions of the stream leaving purified polyplexes that can go on to be used directly in transfections or be charge stabilized by addition of polyanions such as polyglutamic acid (PGA) for the creation of ternary polyplexes. Following the design portion of the research, the device was used to produce binary particle characterization was carried out and particle sizes, polydispersity and zeta potential of both conventional and MS polyplexes was compared. MS-produced polyplexes exhibited up to a 75% reduction in particle size compared to BM-produced polyplexes, while exhibiting little difference in zeta potential and polydispersity. A variety of standard biological assays were carried out to test the effects of the vectors on a variety of cell lines – and in this case the MS polyplexes proved to be both less toxic and have higher transfection efficiency in most cell lines. HeLa cells demonstrated the highest increase in transgene expression with a 150-fold increase when comparing to conventional bulk mixed polyplexes at the optimum formulation. A similar set of experiments were carried out with ternary polyplexes produced by the separation device. In this case it was shown that there were statistically significant increases in transfection efficiency for the MS-produced ternary polyplexes compared to BM-produced poyplexes, with a 23-fold increase in transfection activity at the optimum PEI/DNA ratio in MDAMB-231 cells. These MS-produced ternary polyplexes exhibited higher cell viability in many instances, a result that may be explained but the reduction in both free polymer and ghost particles.

Les matériaux à changement de phase (PCM) sont utilisés pour la réalisation de mémoire non volatile. Ces matériaux possèdent la particularité de passer d’un état cristallin à un état amorphe à l’aide d’une impulsion de chaleur, créant ainsi un processus propre au stockage de l’information. Les PCMs sont généralement basés sur des composés ternaires de type Ge-Sb-Te (GST) avec une température de transition de l’ordre de 125°C, rendent ces matériaux inutilisable dans le domaine de l’automobile et pour des applications militaires. Pour contourner cette limitation, le GST est remplacé par le composé In-Sb-Te (IST) possèdent une température de transition plus élevé et un temps de transition beaucoup plus rapide (nanoseconde). Les propriétés thermiques de l’IST et de ses interfaces au sein de la cellule PCM peuvent influencer la température de transition. C’est pourquoi la mesure de la conductivité thermique nous donnera une estimation de la valeur de cette transition.Différentes techniques ont été misent en oeuvre pour mesurer la conductivité thermique des couches minces d’IST en fonction de la concentration en Te, à savoir ; la radiométrie photo-thermique modulée (MPTR) et la méthode 3ω dans une gamme de température allant de l’ambiant jusqu'à 550°C.Les résultats obtenus par les deux techniques de caractérisation thermiques démontrent que la conductivité thermique de l'IST diminue lorsque l'on augmente la teneur en Te. L'augmentation de la teneur en Te pourrait donc conduire à un alliage thermiquement plus résistif, qui est censé apporter l'avantage d'un flux de chaleur plus confiné et limiter la cross-talk thermique dans le dispositif de mémoire à changement de phase. / Phase change memories (PCM) are typically based on compounds of the Ge-Sb-Te (GST) ternary system. Nevertheless, a major drawback of PCM devices is the failure to fulfill automotive-level or military-grade requirements (125°C continuous operation), due to the low crystallization temperature of GST. To overcome this limitation, alloys belonging to the In-Sb-Te (IST) system have been proposed, which have demonstrated high crystallization temperature, and fast switching. Thermal properties of the chalcogenide alloy and of its interfaces within the PCM cell can influence the programming current, reliability and optimized scaling of PCM devices. The two methods, namely: 3ω and Modulated Photothermal Radiometry (MPTR) technique was implemented to measure the thermal conductivity of IST thin films as well as the thermal boundary resistance at the interface with other surrounding materials (a metal and a dielectric). The experiment was carried outin situ from room temperature up to 550oC in order to investigate the intrinsic thermal properties at different temperatures and the significant structural rearrangement upon the phase transition.The results obtained from the two thermal characterization techniques demonstrate that the thermal conductivity of IST decreases when increasing the Te content. Increasing the Te content could thus lead to a more thermally resistive alloy, which is expected to bring the advantage of a more confined heat flow and limiting the thermal cross-talk in the phase change memory device.

Abstract not available

<p>This thesis is a summary of five papers with focus on adsorption processes of various monocarboxylates and aminocarboxylates at the water/goethite interface. Interaction of organic acids at the water/mineral interfaces are of importance in biogeochemical processes, since such processes have potential to alter mobility and bioavailability of the acids and metal ions.</p><p>In order to determine the coordination chemistry of acetate, benzoate, cyclohexanecarboxylate, sarcosine, MIDA (methyliminediacetic acid), EDDA (ethylenediamine-N,N’-diacetic acid) and EDTA (ethylenediamine-N,N’-tetraacetic acid) upon adsorption to the goethite (alpha-FeOOH) surface, a combination of quantitative measurements with attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) was utilized.</p><p>Over the pH range studied here (pH 3- 9) all ligands, except for sarcosine, have been found to form surface complexes with goethite. In general, theses were characterized as outer sphere surface complexes i.e. with no direct interaction with surface Fe(III) metal ions. Furthermore, two types of different outer-sphere complexes were identified, the solvent-surface hydration-separated ion pair, and hydration-shared ion pair. For the monocarboxylate surface complexes distinction between these two could be made. At high pH values the solvent-surface hydration-separated ion pair was the predominating complex, while at low pH the surface complex is stabilized through the formation of strong hydrogen bonds with the goethite surface. However, it was not possible to clearly separate between the two outer-sphere complexes for coordination of the aminocarboxylates with the surface of goethite. Additionally, EDDA also formed an inner-sphere surface complex at high pH values. The EDDA molecule was suggested to coordinate to the surface by forming a five membered ring with an iron at the goethite surface, through the amine and carboxylate groups.</p><p>Contrary to the other ligands studied, EDTA significantly induced dissolution of goethite. Some of the dissolved iron, in the form of the highly stable FeEDTA- solution complex, was indicated to re-adsorb to the mineral surface as a ternary complex. Similar ternary surface complexes were also found in the Ga(III)EDTA/goethite system, and quantitative and spectroscopic studies on adsorption of Ga(III) in presence and absence of EDTA showed that EDTA considerably effects speciation of gallium at goethite surface.</p><p>The collective results in this thesis show that the affinity of these ligands for the surface of goethite is primarily governed by their chemical composition and structure, and especially important are the types, numbers and relative position of functional groups within the molecular structure.</p>

<p>The function of titanium- and nickel-silicides is to lower the series resistance and contact resistivity in gate, source and drain contacts of an integrated circuit transistor. </p><p>With decreasing dimensions, the low resistivity C54 TiSi₂ is not formed and stays in its high resistivity phase C49. It was found that a layer of niobium interposed between titanium and silicon, which is supposed to promote the C54 phase, led to the formation of the high resistivity C40 (Ti,Nb)Si₂ in both small and large contacts. </p><p>Increased interest in Si_1-xGe_x layers led to the inclusion of the Ni-Si-Ge system in this project. The interaction between nickel and poly-Si_0.42Ge_0.58 was found to be different from nickel and poly-silicon in the meaning of the phases formed during high temperature annealing. High-resistivity NiSi₂ was formed at 750°C, but nickel and Si_0.42Ge_0.58 formed no disilicide. A massive out-diffusion of germanium from the NiSi_1-uGe_u resulted in agglomeration at lower temperatures than for NiSi. This was ascribed to the larger enthalpy of formation for nickel reacting with silicon than with germanium. Ternary phase diagrams, with and without the disilicide phase, were calculated. According to the tie lines, NiSi_1-uGe_u will be in thermodynamic equilibrium with Si_1-xGe_x when u is smaller than x. This was confirmed experimentally, where a balanced germanium concentration in NiSi_1-uGe_u and Si_1-xGe_x, stabilized the germanosilicide. When nickel interacted with strained and relaxed silicon-germanium it was established that a strained substrate led to a morphologically unstable NiSi_1-uGe_u. The germanosilicide was highly textured on both (001) and (111) substrates. The texturing was explained by the absence of Ni(SiGe)₂ which forced NiSiGe to reorient so as not to resemble a digermanosilicide at the film/substrate interface. NiSi_0.82Ge_0.18 formed on p⁺-Si_0.82Ge_0.18 in CBKs grew laterally under the SiO₂, defining the contact hole. The contact resistivity extracted by 3D modelling was 5×10^-8 Ωcm².</p>

Among the obstacles for the commercialization of the MoltenCarbonate Fuel Cell (MCFC), the dissolution of thestate-of-the-art lithiated NiO cathode is considered as aprimary lifetime limiting constraint. Development ofalternative cathode materials is considered as a main strategyfor solving the cathode dissolution problem. LiFeO2and LiCoO2had earlier been reported as the most promisingalternative materials; however, they could not satisfactorilysubstitute the lithiated NiO. On the other hand, ternarycompositions of LiFeO2, LiCoO2and NiO are expected to combine some desirableproperties of each component. The aim of this work was todevelop alternative cathode materials for MCFC in the LiFeO2-LiCoO2-NiO ternary system. It was carried out byinvestigating electronic conductivity of the materials, firstin the form of bulk pellets and then in ex-situ sinteredporous-gas-diffusion cathodes, and evaluating theirelectrochemical performance by short-time laboratory-scale celloperations. Materials in the LiFeO2-NiO binary system and five ternary sub-systems,each with a constant molar ratio of LiFeO2:NiO while varying LiCoO2content, were studied. Powders withcharacteristics appropriate for MCFC cathode fabrication couldbe obtained by the Pechini method. The particle size of LiFeO2-LiCoO2-NiO powders considerably depends on thecalcination temperature and the material composition. Theelectrical conductivity study reveals the ability of preparingLiFeO2-LiCoO2-NiO materials with adequate electricalconductivity for MCFC cathode application. A bimodal pore structure, appropriate for the MCFC cathode,could be achieved in sintered cathodes prepared usingporeformers and sub-micron size powder. Further, this studyindicates the nature of the compromise to be made between theelectrical conductivity, phase purity, pore structure andporosity in optimization of cathodes for MCFC application. Cellperformance comparable to that expected for the cathode in acommercial MCFC could be achieved with cathodes prepared from20 mole% LiFeO2- 20 mole% LiCoO2- 60 mole% NiO ternary composition. It shows aniR-corrected polarization of 62 mV and a iR-drop of 46 mV at acurrent density of 160 mAcm-2at 650 °C. Altogether, this study revealsthe possibility of preparing LiFeO2-LiCoO2-NiO cathode materials suitable for MCFCapplication. Keywords: molten carbonate fuel cell (MCFC), MCFC cathode,LiFeO2-LiCoO2-NiO ternary compositions, electrical conductivity,porous gas diffusion electrodes, polarization, electrochemicalperformance, post-cell characterization.

The convective drying of thin layers of multicomponentliquid mixtures into an inert gas, and the influence ofdifferent process controlling mechanisms on drying selectivityis studied. Drying experiments under gas-phase-controlledconditions are performed by low intensity evaporation, fromfree liquid surfaces, of ternary mixtures without non-volatilesolutes. Liquid-side-controlled experiments are carried out bydrying a multicomponent polymeric solution containing twovolatile components, one non-volatile polymer and an optionalnonvolatile softening substance. Mathematical models to describe gas- andliquid-side-controlled drying based on interactive diffusion inboth liquid and gas phases as the main mechanisms for masstransfer are developed. For gas-phase-controlled drying, astability analysis of the ordinary differential equations thatdescribes the evaporation process is performed. Isothermal andnon-isothermal drying processes are considered in batch andcontinuous modes. The mathematical model to describe thecomposition profiles during batch drying of the polymeric film,considering liquid resistance, is solved numerically. Due tothe lack of experimental data, properties for this polymericsystem are estimated by using established methods. Ananalytical solution of the diffusion equation, by assuming anisothermal drying process and a constant matrix ofmulticomponent diffusion coefficients is developed. For thecontinuous case, liquid-side resistance is studied by modellingevaporation of a multicomponent falling liquid film into aninert gas including indirect heating. The results of the gas-phase-controlled model are in goodagreement with experimental results. For the polymeric film,the agreement is only qualitative since the model does notaccount for a membrane that develops on the film surface. Thestability analysis permits the prediction of trajectories andfinal state of a liquid mixture in a gas-phase-controlleddrying process. For isothermal evaporation of ternary mixturesinto pure gas, the solutions are trajectories in the phaseplane represented by a triangular diagram of compositions. Thepredicted ternary dynamic azeotropic points are unstable orsaddle. On the other hand, binary azeotropes are stable whenthe combination of the selectivities of the correspondingcomponents is negative. In addition, pure component singularpoints are stable when they are contained within theirrespective isolated negative selectivity zones. Undernon-isothermal conditions, maximum temperature valuescharacterise stable azeotropes. Incremental loading of the gaswith one or more of the components leads to a node-saddlebifurcation, where a saddle azeotrope and a stable azeotropecoalesce and disappear. For continuous drying, the singularpoints are infinite and represent dynamic equilibrium pointswhose stability is mainly dependent on the ratio of inletgas-to-liquid flow rates. As long as the process isgas-phasecontrolled, these results also apply to a porous solidcontaining a liquid mixture. In general, liquid-side control makes the drying processless selective but it is difficult to maintain this conditionduring the whole process. Under the influence of its owndynamics, a process starting as liquid-side-controlled tendstowards a gas-phase-controlled process. The presence ofnon-volatile components and indirect heating may delay thisdevelopment. Considering the evolution of the processcontrolling steps and its influence on selectivity, a modelaimed at describing the complete trajectory of a drying orevaporation process must include the coexistence of allrelevant mechanisms. Keywords:ternary mixture, falling film, diffusionequation, gas-phase control, liquid-phase control, selectivity,stability analysis, polymeric solution, evaporation, azeotrope,batch drying, continuous drying.

The function of titanium- and nickel-silicides is to lower the series resistance and contact resistivity in gate, source and drain contacts of an integrated circuit transistor. With decreasing dimensions, the low resistivity C54 TiSi2 is not formed and stays in its high resistivity phase C49. It was found that a layer of niobium interposed between titanium and silicon, which is supposed to promote the C54 phase, led to the formation of the high resistivity C40 (Ti,Nb)Si2 in both small and large contacts. Increased interest in Si1-xGex layers led to the inclusion of the Ni-Si-Ge system in this project. The interaction between nickel and poly-Si0.42Ge0.58 was found to be different from nickel and poly-silicon in the meaning of the phases formed during high temperature annealing. High-resistivity NiSi2 was formed at 750°C, but nickel and Si0.42Ge0.58 formed no disilicide. A massive out-diffusion of germanium from the NiSi1-uGeu resulted in agglomeration at lower temperatures than for NiSi. This was ascribed to the larger enthalpy of formation for nickel reacting with silicon than with germanium. Ternary phase diagrams, with and without the disilicide phase, were calculated. According to the tie lines, NiSi1-uGeu will be in thermodynamic equilibrium with Si1-xGex when u is smaller than x. This was confirmed experimentally, where a balanced germanium concentration in NiSi1-uGeu and Si1-xGex, stabilized the germanosilicide. When nickel interacted with strained and relaxed silicon-germanium it was established that a strained substrate led to a morphologically unstable NiSi1-uGeu. The germanosilicide was highly textured on both (001) and (111) substrates. The texturing was explained by the absence of Ni(SiGe)2 which forced NiSiGe to reorient so as not to resemble a digermanosilicide at the film/substrate interface. NiSi0.82Ge0.18 formed on p+-Si0.82Ge0.18 in CBKs grew laterally under the SiO2, defining the contact hole. The contact resistivity extracted by 3D modelling was 5×10-8 Ωcm2.

The problem of inaccurate measurement techniques for quantifying isothermal solidification kinetics during transient liquid phase (TLP) bonding in binary and ternary systems; and resulting uncertainty in the accuracy of analytical and numerical models has been addressed by the development of a new technique using differential scanning calorimetry (DSC). This has enabled characterization of the process kinetics in binary and ternary solid/liquid diffusion couples resulting in advancement of the fundamental theoretical understanding of the mechanics of isothermal solidification. The progress of isothermal solidification was determined by measuring the fraction of liquid remaining after an isothermal hold period of varying length. A 'TLP half sample', or a solid/liquid diffusion couple was setup in the sample crucible of a DSC enabling measurement of the heat flow relative to a reference crucible containing a mass of base metal. A comparison of the endotherm from melting of an interlayer with the exotherm from solidification of the residual liquid gives the fraction of liquid remaining. The Ag-Cu and Ag-Au-Cu systems were employed in this study. Metallurgical techniques were used to compliment the DSC results. The effects of sample geometry on the DSC trace have been characterized. The initial interlayer composition, the heating rate, the reference crucible contents, and the base metal coating must be considered in development of the experimental parameters. Furthermore, the effects of heat conduction into the base metal, baseline shift across the initial melting endotherm, and the exclusion of primary solidification upon cooling combine to systematically reduce the measured fraction of liquid remaining. These effects have been quantified using a modified temperature program, and corrected using a universal factor. A comparison of the experimental results with the predictions of various analytical solutions for isothermal solidification reveals that the moving interface solution can accurately predict the interface kinetics given accurate diffusion data. The DSC method has been used to quantify the process kinetics of isothermal solidification in a ternary alloy system, with results compared to a finite difference model for interface motion. The DSC results show a linear relationship between the interface position and the square root of the isothermal hold time. While the numerical simulations do not agree well with the experimental interface kinetics due to a lack of accurate thermodynamic data, the model does help develop an understanding of the isothermal solidification mechanics. Compositional shift at the solid/liquid interface has been measured experimentally and compared with predictions. The results show that the direction of tie-line shift can be predicted using numerical techniques. Furthermore, tie-line shift has been observed in the DSC results. This study has shown that DSC is an accurate and valuable tool in the development of parameters for processes employing isothermal solidification, such as TLP bonding.

The problem of inaccurate measurement techniques for quantifying isothermal solidification kinetics during transient liquid phase (TLP) bonding in binary and ternary systems; and resulting uncertainty in the accuracy of analytical and numerical models has been addressed by the development of a new technique using differential scanning calorimetry (DSC). This has enabled characterization of the process kinetics in binary and ternary solid/liquid diffusion couples resulting in advancement of the fundamental theoretical understanding of the mechanics of isothermal solidification. The progress of isothermal solidification was determined by measuring the fraction of liquid remaining after an isothermal hold period of varying length. A 'TLP half sample', or a solid/liquid diffusion couple was setup in the sample crucible of a DSC enabling measurement of the heat flow relative to a reference crucible containing a mass of base metal. A comparison of the endotherm from melting of an interlayer with the exotherm from solidification of the residual liquid gives the fraction of liquid remaining. The Ag-Cu and Ag-Au-Cu systems were employed in this study. Metallurgical techniques were used to compliment the DSC results. The effects of sample geometry on the DSC trace have been characterized. The initial interlayer composition, the heating rate, the reference crucible contents, and the base metal coating must be considered in development of the experimental parameters. Furthermore, the effects of heat conduction into the base metal, baseline shift across the initial melting endotherm, and the exclusion of primary solidification upon cooling combine to systematically reduce the measured fraction of liquid remaining. These effects have been quantified using a modified temperature program, and corrected using a universal factor. A comparison of the experimental results with the predictions of various analytical solutions for isothermal solidification reveals that the moving interface solution can accurately predict the interface kinetics given accurate diffusion data. The DSC method has been used to quantify the process kinetics of isothermal solidification in a ternary alloy system, with results compared to a finite difference model for interface motion. The DSC results show a linear relationship between the interface position and the square root of the isothermal hold time. While the numerical simulations do not agree well with the experimental interface kinetics due to a lack of accurate thermodynamic data, the model does help develop an understanding of the isothermal solidification mechanics. Compositional shift at the solid/liquid interface has been measured experimentally and compared with predictions. The results show that the direction of tie-line shift can be predicted using numerical techniques. Furthermore, tie-line shift has been observed in the DSC results. This study has shown that DSC is an accurate and valuable tool in the development of parameters for processes employing isothermal solidification, such as TLP bonding.