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Submicron tin oxide (SnO2) was obtained from thermal decomposition of tin oxalate (SnC2O4) precipitated at room temperature from amixture of solutions of tin (II) chloride (SnCl2) and oxalic acid (H2C2O4). Aqueous precipitation of SnC2O4 was firstly investigated by parametersvariation of starting material concentrations, addition methods and mixing times. Upon calcination, SnO2 powder tacky and subsequent grinding was found to cause nanosized SnO2 particles to agglomerate into plates. Aqueous??alcohol precipitation was then developed, based on the previously conducted aqueous precipitation Stabilisation of SnO2 suspensions was found to be better in aqueous rather than non??aqueous media, as determined by zeta potential analysis and sedimentation tests. A detailed concept of the effects of zeta potential and sedimentation (enhanced sedimentation region (ESR)) on colloidal processing, i.e., suspension stability, was introduced. Two systems, Sn??Al??O and Sn??Si??O, were investigated at their invariant temperatures and ternary phase diagrams, which haven??t been reported elsewhere, were constructed (at nine isothermal temperatures each). The binary diagram for the system SnO2??SiO2, which has not been reported in the literature, was constructed. The systems compatibilities were confirmed experimentally at 1000oC, with incidental finding of micron??sized fibres of single crystal SnO2 with preferential [110] growth direction obtained. It was also deduced that 1000oC can be used for SnO2 coatings sintering without undesired reaction or mutual solubility. Successful electrophoretic deposition (EPD) of commercial SnO2 powder on dense sapphire was obtained by the use of pH 2 SnO2 suspension, but not with pH 9 suspensions leading to a review of the basis for EPD requirements in terms of suspension properties. Thus, another conceptual approach to EPD processing and setup was proposed in terms of zeta potential, suspension stability and net particle charge. Obtained homogeneous deposition of commercial SnO2 powders contradicted the findings of published works of EPD on insulating dense substrates. Thus critical factors in the design of EPD processing on dense insulating substrates and associated mechanisms responsible for the deposition were developed. However, EPD of synthesised SnO2 powders yielded inhomogeneous coatings, even with voltage application of up to 30 V. Microcell effects, which were deduced based on localised particle leaching in the suspension, were proposed. Although deposition was relatively unsuccessful, this demonstrated possibility of aqueous EPD with the usage of high voltages without occurrence of water electrolysis which hasn??t been observed in literature.

Electrostatic Assisted Vapor Deposition method was adopted to deposit SnO2 thin films in this work using either SnCl4 or DBTDC (C12H24O4Sn) as precursors. Appropriate deposition parameters were identified for deposition of porous and dense films . A post-deposition calcination of 600¢XC/2h yielded well crystalline rutile phase. Electrical resistance measurement indicated that the most porous films ,derived from the precursor solution of ethanol solvent, were not continuous. Instead, films derived from precursor solution of mixed ethanol-carbitol solvent were less porous allowing stable resistance values to be measured. A detection sensitivity of 2.55 for 100ppm CO gas was obtained from films derived from a 30% ethanol-70% carbitol solution. A higher sensitivity of 6.55 was obtained from films derived from solutions containing Di-n-butyltin diacetate (DBTDC) as precursor.

A B S T R A C T V2O5/SnO2 solid acid catalysts have been employed for the vapour-phase Beckmann rearrangement of cyclohexanone oxime to e-caprolactam. Catalysts with different vanadia loading (3–15 wt%) were prepared by impregnation method and characterized by XRD, BET surface area, FTIR and 51V NMR techniques. The surface acidic properties were determined by temperature programmed desorption and cumene cracking reaction. Under optimized reaction conditions, catalyst with 9 wt% V2O5 gives the maximum amount of desired product (yield 78.8%). However, the catalysts are susceptible for deactivation due to the basic nature of the reaction products (50% deactivation in 5 h). A good correlation was obtained among the rearrangement activities of V2O5/SnO2 catalysts, their weak plus medium acidities (usually of the Bro¨ nsted type) and structural properties.

Tin oxide (SnO2) has been investigated and used as a gas sensing material for numerous applications from the very start of the sensor industry. Most of these sensors use semiconductors (mostly SnO2) as the sensing material. In this work, SnO2 was prepared using 2 techniques: firstly the MOCVD where we dope the sample with fluorine and secondly sputtering technique where samples are undoped in our case. These samples were tested at different conditions of temperature varying from room temperature to 150 degrees C, in ambient gas atmosphere of 200 CC Nitrogen (N2). The typical thickness of the sputtered samples was 1500 A with a sheet resistance of 300; and these sputtered samples were found to be more porous. These samples when tested in room temperature showed a change of -4 [mu]A change for 10% and -9 [mu]A for 90% of H2. While at higher temperatures (150 degrees C) the current change for 10% increased from -4 [mu[A to -2 mA showing that higher ambient temperatures increased the sensitivity of the samples. The repeatability of the samples after a period of 3 days were found to be well within 10%. The samples prepared by MOCVD were fluorine doped, the samples were conductive to 1 order of magnitude more than the sputtered ones. 3 different samples of approximate thicknesses 3000, 6000 and 9000 A were prepared and tested in this work, with typical resistivity of 6 /cm and the grains in this case are typically more compact. The conductive samples showed no response at room temperature, including the 6000 and 9000 A samples. While at higher temperatures (150degreesC) the 3000 A sample showed very sensitive response to H2. Also noticed was that the response was linear compared to the sputtered samples. The samples showed very good repeatability and sensitivity.

An onset coarsening-coalescence event based on the incubation time of cylindrical mesopore formation and a significant decrease of specific surface area by 50% relative to the dry pressed samples was determined by N2 adsorption-desorption hysteresis isotherm for cassiterite SnO2 nanoparticles (rutile-type structure with bimodal size distribution). In the temperature range of 800-1100oC, the nanoparticles underwent onset sintering coupled with coarsening-coalescence without appreciable polymorphic transformation or decomposition of SnO2. The apparent activation energy of such a rapid process for SnO2 nanoparticles was estimated as 75 ¡Ó 5 kJ/mol, respectively. The minimum temperature for sintering/coarsening/coalescence of the SnO2 nanoparticles is 735oC based on the extrapolation of steady specific surface area reduction rates to null. PLA fragmentation of cassiterite SnO2 powder (rutile type, 20-50 nm in size) in water was conducted under Q-switch mode (532 nm, 400 mJ per pulse) having laser focal point fixed at 5, 10, 15 and 20 mm beneath the water level for an accumulation time of 5, 15, 20 and 30 min at 10 Hz. The 532 nm laser incidence suffered little water absorption and was effective to produce cassiterite nanocondensates as small as 5 nm in diameter and occasional nanocondensates of £\-PbO2-type structure more or less in coalescence. The combined effects of nanosize, internal compressive stress and H+ and Sn2+ co-signature in the lattice may account for a lower minimum band gap.

As propriedades físico-químicas da superfície de pós cerâmicos desempenham um papel muito importante na obtenção de produtos cerâmicos de alta qualidade, elevada performance e confiabilidade. Estas propriedades estão relacionadas com as ligações químicas superficiais e suas interações com o meio. As superfícies dos óxidos geralmente contêm grupos hidroxilas adsorvidos e as suas modificações podem ser estudadas por espectroscopia de infravermelho. Neste trabalho, pós à base de SnO2 contendo íons Fe ou Mg foram preparados pela rota química derivada do método de Pechini. Os pós foram caracterizados quanto à sua morfologia e suas propriedades superficiais. Os resultados obtidos mostraram que os aditivos segregam na superfície e modificam as bandas de infravermelho correspondentes aos grupos hidroxilas adsorvidas superficialmente. Estas modificações causaram mudanças em propriedades macroscópicas como o ponto isoelétrico das suspensões aquosas e a área de superfície específica dos pós. Os estudos quanto à sinterização destes materiais foram feitos com pastilhas conformadas por pressão uniaxial e foram submetidas à sinterização por queima rápida, apresentando densificação em tempos muito curtos de tratamento térmico. (<1 min.) Observações microestruturais mostraram que a redução da porosidade neste sistema ocorre congruente com crescimento de grãos. O aumento da área de superfície específica dos pós com a elevação da porcentagem molar dos aditivos, bem como a densificação rápida do óxido de estanho pode estar relacionada com a redução das energias de superfície quando os aditivos estão segregados na superfície dos grãos. / Surface properties of ceramic powders frequently play an important role in producing high-quality, high-performance, and reliable ceramic products. These properties are related to the surface bond types and interactions with the surroundings. Oxide surfaces generally contain adsorbed hydroxyl groups and modifications in the chemical composition of the surface may be studied by infrared spectroscopy. In this work, SnO2 containing Fe or Mg ions were prepared by organic chemical route derived from Pechini’s method. The prepared powders were characterized by means of surface properties and morphology. Results demonstrated that the studied additives segregate onto the oxide surface and modify the hydroxyl IR bands of the adsorbed hydroxyl groups. These surface modifications change some macroscopic properties of the powder such as the isoelectric point (IEP) in aqueous suspensions and the final specific surface area. The sintering behavior of these materials was studied using pellets conformed by uniaxial pressing and the sintering was made by fast firing, showing quick densification with shorts periods of time (<1 min.). A porosity reduction congruent with grain growth is observed during microestructure characterization. Both, increase of the surface area with additive concentration and quick densification are supposedly due to the reduction of surface energy of the powders when additives segregate on the powder surface.

Cette étude est dédiée à l’optimisation de capteurs chimiques de gaz de type résistifs à base de dioxyde d’étain (SnO2) pour l’application en ligne d’échappement automobile. Les capteurs sont élaborés par la technique de sérigraphie qui permet la production en masse de capteurs robustes sur substrat alumine. En vue de l’application automobile visée, les capteurs ont été optimisés par l’ajout d’une couche protectrice poreuse déposée sur l’élément sensible de SnO2. Le comportement de ces capteurs a été étudié en fonction de différents paramètres, comme la température et la vitesse des gaz, représentatifs de conditions d’échappement automobile. De plus, une modélisation « simple » de la réponse électrique des capteurs en fonction de la concentration d’un ou plusieurs gaz polluants cibles a été proposée. / This study is dedicated to the optimization of chemical gas sensors based on resistive type tin dioxide (SnO2) for automotive exhaust application. The sensors were produced by screen-printing technique which allows mass production of robust sensors on alumina substrate. In regards of the automotive application, the sensors were optimized by adding a porous protective layer deposited on the sensing element SnO2. The behaviour of this type of gas sensors was studied depending on gas parameters such as gas temperature and velocity, representative of real operation conditions. In addition, a “simple” modelisation of the electrical response of sensors depending on the concentration of one or more gaseous targets is proposed.

Dans le domaine stratégique des biocapteurs sans marquage, la détection de l'élément biologique est directement liée à la variation d'un paramètre physique donné du composé sensible (transducteur). Dans le cas de la détection de l'hybridation de l'ADN par spectroscopie d'impédance électrochimique non faradique (sans label redox), la détection se base sur le changement de conductivité de l'élément sensible. Celui-ci est généralement un matériau semi-conducteur. La présence sur sa surface, de charges électriques amenées par des biomolécules chargées, comme les brins d'ADN, induit, par un phénomène connu d' »effet de champ électrique », la création d'une zone de charge d'espace subsurfacique. Celle-ci se caractérise par la courbure vers la surface des niveaux énergétiques. En conséquence de quoi, l'impédance de l'interface électrolyte/ADN/semi-conducteur varie. Antérieurement, nous avions démontré la faisabilité de l'utilisation de films d'oxydes semi conducteurs, tels CdIn204, SnO2 pur ou dopé, présentant des surfaces denses 2D en tant qu'éléments sensibles dans des capteurs à ADN basés sur la détection par spectroscopie d'impédance électrochimique non faradique. Les résultats avaient montré que, si CdIn204 présentait une sensibilité supérieure à celle de SnO2, cet oxyde était en revanche très fragilisé durant les étapes de fonctionnalisation, ce qui n'est pas le cas de SnO2 qui est un oxyde stable et robuste chimiquement. L'objectif du présent travail a été (i) d'améliorer les performances des capteurs à base de SnO2 en utilisant cette fois des films nanostructurés (1 ou 3D) afin de développer la surface spécifique, et (ii) d'étudier comment la topologie de surface influe sur le signal de détection de l'hybridation de l'ADN. Dans un premier temps, différentes nanostructures de SnO2 ont été élaborées par la technique d'électrodéposition que nous avons montée et mise au point de façon à obtenir des films reproductibles. La morphologie désirée des films –nanofils 1D ou matrice nanoporeuse 3D- a été obtenue en modifiant la procédure et les paramètres de dépôt. Leurs caractéristiques microstructurales, morphologiques, chimiques et électriques ont été déterminées par DRX, MEB, XPS et spectroscopie d'impédance. Puis, en vue du greffage covalent d'ADN, un procédé de fonctionnalisation multi-étape a été réalisé. Enfin, dans un troisième temps, la détection de l'hybridation d'ADN sans marquage, réalisée par spectroscopie d'impédance électrochimique sur les deux types de films nanostructurés, a été réalisée. En parallèle, afin de valider l'hybridation de l'ADN, la détection par microscopie à fluorescence, soit en mode épifluorescence, soit en mode confocal, a été menée. En comparaison des surfaces denses 2D de SnO2 (étude antérieure), les résultats ont montré une sensibilité supérieure, avec une limite de détection observée d'ADN de 2 nM, montrant l'importance d'avoir une surface développée. La structuration en nanofils est plus favorable que la matrice nanoporeuse en terme de sensibilité. Par ailleurs, en utilisant des ADN cibles, soit non complémentaires, soit possédant une ou deux mutations, nous avons pu montrer le caractère hautement sélectif de notre capteur dans le cas des deux types de nanostructures. Ce travail fortement expérimental a aussi permis de montrer l'importance de l'organisation structurale et morphologique du matériau sensible sur la réponse du signal à l'hybridation d'ADN. En effet, dans le cas des nanofils, comme dans celui des films denses avec surface 2D, le signal de réponse donne systématiquement une augmentation d'impédance. Cela s'explique par le phénomène d'effet de champ explicité plus haut. En revanche, dans le cas de la matrice naporeuse de SnO2, l'hybridation d'ADN entraine une diminution de l'impédance ... / For environmental in situ diagnostic, as well as for medical point of care diagnostic, quick andaffordable sensing devices are of importance. Label-free biosensors based on electrical orelectrochemical detection methods can provide such features. In previous studies, we havedemonstrated for the first time the feasibility of using semiconductive SnO2 2D dense films fornon-faradic electrochemical impedance DNA detection. The aim of the present study is (i) toimprove the sensing performances by using SnO2 nanostructures in order to benefit from highspecific surface, and (ii) to study the influence of the morphology and microstructure on theimpedimetric DNA detection signal.We performed the cathodic electrodeposition of SnO2 nanostructures. By changing relevantprocessing parameters, two kinds of nanostructures were deposited: 3D nanoporous films and 1Dnanowires. Both nanostructures have been characterized in terms of morphology, microstructureand electrochemical properties.Our results emphasize the importance of both the microstructural and morphological organizationson the impedimetric signal upon DNA hybridization. Opposite tendencies are found. DNAhybridization induces a decrease of the impedance in the case of 3D-nanoporous films, whereasan increase of impedance is obtained in the case of 1D NWs. Indeed, following the dimensionalityof the nanostructures, either external cause - ion transport - or internal cause - field effectphenomenon - can contribute to the impedance variation.The performances of the sensors have also been analyzed, namely: sensitivity, selectivity andreusability. Compared to the 2D dense and 3D nanoporous films, the 1D SnO2 nanowires are morefavorable in term of sensitivity, showing a detection limit of 2 nM.

Des investigations ont été menées concernant la caractérisation des céramiques semi-conductrices à matrice SnO2, en particulier dans des domaines de densités de courant et de champs électriques élevés. L’ensemble du procédé d’élaboration a été analysé et optimisé, de manière à obtenir des composés aux propriétés électriques aptes à l’application varistance. L’addition de plusieurs dopants a été étudiée, et deux éléments ont donné lieu à un comportement électrique remarquable. Le dopage des grains de SnO2 par l’aluminium (III) permet d’accroître leur conductivité apparente et de ce fait, d’obtenir des composants dont la plage de fonctionnement est équivalente à celle observée pour des varistances ZnO. Le silicium apparaît aux joints de grains dans la microstructure des céramiques. Il réduit fortement la surface effective des joints de grains, entrainant une diminution importante de la zone de fonctionnement des varistances. Simultanément, la caractéristique courant-tension est quasi-idéale avec des coefficients de non-linéarité supérieurs à 100 et des profils de variation similaires à ceux observés pour les diodes Zener. La modélisation du mécanisme de conduction au niveau d’un joint de grain SnO2-SnO2 suggère que ces céramiques présentent un potentiel théorique supérieur aux céramiques à base de ZnO du fait d’une largeur de bande interdite plus importante. Enfin, un comparatif technico-économique succinct a ensuite été proposé, afin d’illustrer la compétitivité des deux matériaux pour l’application varistance / Many investigations have been conducted on semiconductive ceramics with a tin dioxide matrix, particularly in the high electric field and high current density ranges. The sintering process has been optimized, in order to obtain compounds with electrical properties compatible with the varistor application. Among the many dopants studied, two elements produced a remarkable electrical behavior. By doping SnO2 grains with Aluminium (III) allows an increase of their apparent conductivity and hence, widens the working range of tin oxide based compounds, up to the ZnO varistors ones. It appears that the silicium is located on the grain boundaries in the ceramic microstructure. This element reduces strongly the effective surface of the grain boundaries and causes an important diminution of the varistors working range. Simultaneously, the current-voltage behavior appears to be like those observed for a Zener diode, with non-linearity coefficients higher than 100 and nearly ideal variation profiles. The conduction modelling in the SnO2-SnO2 grain boundary area reflects that these ceramics present theoretically a higher potential than ZnO based ceramics, due to a wider SnO2 bandgap. A brief technico-economical comparison has been proposed in order to highlight the competitiveness between the two materials for the varistor applications