Le but principal de ces travaux de thèse fut la conception et la réalisation de biocapteurs par utilisation de méthodes de transduction sans marquage, comme la spectroscopie d’impédance électrochimique (EIS), pour la détection de cible d’intérêts. Pour cela, différentes architectures moléculaires, spécifiques à la molécule d’intérêt ciblée, ont été développées afin de permettre la transduction du signal issu de la reconnaissance entre le biorécepteur et son substrat, et conduire ainsi à la détection de la cible.Les systèmes mis au point reposent sur l’intégration de nanomatériaux, tels que les nanotubes de carbones ou le disulfure de tungstène, pour assurer l'immobilisation de l'entité biospécifique à la surface du capteur. L’intérêt de ces matériaux est multiple puisqu’ils permettent une très forte augmentation de la surface spécifique du système et sont également mis à contribution lors de la fonctionnalisation de la surface de l’électrode. Un des grands défis rencontré dans le développement des biocapteurs étant la stratégie d'immobilisation de l'entité biospécifique sur la surface du capteur.Ces travaux se sont donc dans un premier temps intéressés à la réalisation et à la caractérisation de films minces de ces nanomatériaux ainsi qu’à leur transfert à la surface d’une électrode. Dans ce contexte, le but est de concevoir des bioarchitectures poreuses à base de polymères fonctionnels électrogénérés autour des nanostructures de carbone permettant la pénétration de grandes biomolécules comme des anticorps pour développer des immunocapteurs de haute performance.La seconde partie de ce travail s’est donc orientée vers la conception de biocapteurs par utilisation de ces différents matériaux. La fiabilité du procédé de la construction de ces nanostructures poreuses a été validée par la conception de systèmes immunologiques pour la détection de l’anticorps de l’antitoxine du choléra et l’anticorps de la toxine de la dengue.Enfin, un dernier biocapteur enzymatique, s’appuyant sur l’utilisation de nano-bâtonnets de disulfure de tungstène, a été développé. Ce dernier permet la détection de deux molécules d’intérêts, à savoir le catéchol et la dopamine, par utilisation de la polyphénol oxydase. / The main purpose of this work was the design and the development of biosensors by using non-marking transduction methods, such as electrochemical impedance spectroscopy (EIS), for the detection of targets of interests. To this end, various molecular architectures have been developed to allow the transduction of the signal resulting from the recognition between the bioreceptor and its substrate, and thus lead to the detection of the target.The systems developed are based on the integration of nanomaterials, such as carbon nanotubes or tungsten disulfide, to ensure the immobilization of the biospecific entity at the surface of the sensor. The advantages of these materials are multiples, since they allow a very large increase in the specific surface area and are also used in the functionalization of the surface of the electrode. Indeed, one of the major challenges encountered in the development of biosensors is the strategy involved in the immobilization of the biospecific entity on the surface of the sensor.This work was initially interested in the realization and characterization of thin films of these nanomaterials as well as their transfer to the surface of an electrode. In this context, the aim is to design porous bioarchitectures based on electrogenerated functional polymers around carbon nanostructures allowing the penetration of large biomolecules such as antibodies to develop high-performance immunosensors.The second part of the work was oriented towards the design of biosensors using these different materials. The reliability of the process has been validated by the design of immunological systems for the detection of the anti-cholera toxin antibody and dengue toxin antibody.Finally, a last enzymatic biosensor, based on the use of tungsten disulfide nano-sticks, has been developed. The latter allows the detection of two molecules of interest, catechol and dopamin, by the use of polyphenol oxidase.

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In this study tools consisting of a 5mm cylindrical pin and a 12mm shoulder held by a simple tool holder were used to compare the wear of 11 tooling materials. The objective was to determine if using these tools in a spot welding configuration to simulate friction stir welding could differentiate the potential performance of tooling materials. All tools were made of varying percentages of polycrystalline cubic boron nitride (PCBN), tungsten (W) and rhenium (Re). The materials are referred to herein as GV1, GV2, G1, G2, G3, G4, G5, G6, G7, G8 and G9.The tools were run to 205 welds if they did not fracture first. The grades averaged the following quantities of welds before fracture failure GV-1:0; GV-2:200; G1:82; G2:204; G3:205; G4:205; G5:96; G7:102.73; G8:21.2; G9:38.5. Of the tools that ran the full 205 welds without chipping, the average calculated volume loss, which was the best indication of wear, was as follows G2:1.83%; G3:2.53%; G4:2.41%; G5:1.93%; and G7:2.30%.The study showed that G2 had the least wear and G6 had the most wear, of those tools that completed all 205 spot welds. Fracture was the failure mode of all grades with over 70% CBN content. It was found that small CBN grain size was not correlated to better wear performance, as has been seen in a prior study.

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The major part of the present work, deals with the reduction kinetics of Cu2O powder and a Cu2O-WO3 powder mixture by hydrogen gas, studied by ThermoGravimetric Analysis (TGA). The reduction experiments were carried out both isothermally and non-isothermally on thin powder beds over different temperature intervals. During the experiments, the reductant gas flow rate was kept just above the starvation rate for the reaction to ensure that chemical reaction was the rate-controlling step. The activation energy for the reactions was evaluated from isothermal as well as non-isothermal reduction experiments. In the case of the reduction of Cu2O, the impact of the stability of the copper oxide on the activation energy for hydrogen reduction under identical experimental conditions is discussed. A closer investigation of additions of Ni or NiO to Cu2O did not have a perceptible effect on the kinetics of reduction. In the case of the reduction of the Cu2O-WO3 mixture, the reaction mechanism was found to be affected in the temperature range 923-973 K, which is attributed to the reaction/transformation in the starting oxide mixture. At lower temperatures, Cu2O was found to be preferentially reduced in the early stages, followed by the reduction of the tungsten oxide. At higher temperatures, the reduction kinetics was strongly affected by the formation of a complex oxide from the starting materials. It was found that the Cu2O-WO3 mixture underwent a reaction/transformation which could explain the observed kinetic behavior. The composition and microstructures of both the starting material and the reaction products were analyzed by X-ray diffraction (XRD) as well as by microprobe analysis. vi Kinetic studies of reduction indicated that, the mechanism changes significantly at 923 K and the product formed had unusual properties. The structural studies performed by XRD indicated that, at 923 K, Cu dissolved in W forming a metastable solid solution, in amorphous/nanocrystalline state. The samples produced at higher as well as lower temperatures, on the other hand, showed the presence two phases, pure W and pure Cu. The SEM results were in conformity with the XRD analysis and confirmed the formation of W/Cu alloy. TEM analysis results confirmed the above observations and showed that the particle sizes was about 20 nm. The structure of the W/Cu alloy produced in the present work was compared with those for pure copper produced from Cu2O produced by hydrogen reduction under similar conditions. It indicated that the presence of W hinders the coalescence of Cu particles and the alloy retains its nano-grain structure. The present results open up an interesting process route towards the production of intermetallic phases and composite materials under optimized conditions. / QC 20101222

Layered transition metal dichalcogenides (TMDs) are potentially ideal semiconducting materials due to their in-plane carrier transport and tunable bandgaps, which are favorable properties for electrical and optoelectronic applications. However, the ability to make p-n junctions is the foundation of semiconductor devices, and therefore the ability to achieve reproducible p- and n-type doping in TMD semiconducting materials is critical. In this work, p-type substitutional doping of pulsed laser deposited WS2 films with niobium is reported. The synthesis technique of the PLD target with dopant incorporation which also ensures host material stoichiometry is presented. Hall electrical measurements confirmed stable p-type conductivity of the grown films. Structural characterization revealed that there was no segregation phase of niobium in the fabricated films and x-ray phtoelectron spectroscopy (xps) characterization suggest that the p-type doping is due to Nb4+ which results in p-type behavior. Stable hole concentrations as high as 10E21(cm-3) were achieved. The target fabrication and thin film deposition technique reported here can be used for substitutional doping of other 2D materials to obtain stable doping for device applications.

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