Elaboration de matrices céramiques par un nouveau procédé hybride : imprégnation de poudres et CVI réactive

Ceramic matrix composites were originally developed for aerospace,military aeronautics or energyapplications thanks to their good properties at high temperature. They are generally made by ChemicalVapor Infiltration (CVI). A new short hybrid process combining fiber preforms lurry impregnation ofceramic powders with an innovative Reactive CVI (RCVI) route is proposed to reduce the productiontime. This route is based on the combination of Reactive Chemical Vapour Deposition (RCVD), whichis often used to deposit coatings on fibres, with the Chemical Vapor Infiltration (CVI).In RCVD, the absence of one element of the deposited carbide in the initial gas phase involves theconsumption/conversion of the solid substrate. In this work, the RCVD growth and the associatedconsumption were studied with different parameters in the Ti-H-Cl-C chemical system. The study hasbeen completed with the chemical products analysis, combining XRD, XPS and FTIR. Then, the partialconversion of sub-micrometer carbon powders into titaniumcarbide and the consolidation of greenbodies by RCVI from H2/TiCl4 gaseous infiltration were studied. The residual porosity and the final TiCcontent were measured in the bulk of the infiltrated powders by image analysis from scanning electronmicroscopy. Depending on temperature, few hundred micrometers-depth infiltrations are obtained.Finally, the results have been transposed to the RCVI into CMC-type preforms. Despite aminimalTiC content of 25% in the overall preform, the results shown a bad homogeneity of the infiltration anda poor cohesion of fibres with RCVI consolidated powder of their environment.Les composites à matrice céramique ont initialement été développés pour des applications aérospatiales, aéronautiques militaires ou énergétiques en raison de leurs bonnes propriétés à haute température. Ils sont généralement fabriqués par le procédé CVI (Chemical Vapour Infiltration). Un nouveau procédé hybride combinant l’imprégnation de poudre au sein de préformes, suivie de la CVI Réactive(RCVI), est proposé afin de réduire les temps de production. Cette voie est basé sur l’adaptation du procédé RCVD à l’infiltration en milieu poreux. En RCVD, l’absence d’une partie des éléments du dépôt de carbure dans la phase gazeuse implique une consommation/conversion du substrat solide. Dans cette étude, la croissance et la consommation associée ont été étudiées en fonction de divers paramètres dans le système chimique Ti-H-Cl-C. Cette étude est accompagnée d’analyses (DRX, XPS, IRTF) des produits issus de la réaction chimique de formation du TiC. Ensuite, la conversion partielle d’une poudre de carbone submicronique enTiC et la consolidation des zones compactes de poudre par l’infiltration RCVI utilisant le mélange gazeux H2/TiCl4 a été étudiée. La porosité résiduelle et la teneur en TiC ont été mesurées par analyse d’image à différentes distance de la surface des matériaux. Selon la température, plusieurs centaines de micromètres infiltrés ont été obtenus. Finalement, les résultats ont été transposés à l’infiltration RCVI de préformes type CMC. Malgré une teneur minimale de 25% de TiC dans l’ensemble de la préforme, les résultats montrent une mauvaise homogénéité d’infiltration et une mauvaise cohésion des blocs de poudre consolidés avecles fibres de leurs environnements

Non-centrosymmetric Na3Nb4As3O19

A new non-centrosymmetric compound, tris­odium tetra­niobium triarsenic nona­deca­oxide, Na3Nb4As3O19, has been synthesized by a solid-state reaction at 1123 K. The structure consists of AsO4 tetra­hedra and NbO6 octa­hedra sharing corners to form a three-dimensional framework containing two types of tunnels running along the c axis, in which the sodium ions are located. Na+ cations occupying statistically several sites, respectively, are surrounded by seven, six and four O atoms at distances ranging from 2.08 (1) to 2.88 (4) Å. The title structure is compared with those containing the same groups, viz. M 2XO13 and M 2 X 2O17 (M = transition metal, and X = As or P)

La variété β-NaMoO2(AsO4)

The title compound, sodium dioxidomolybdenum(VI) arsenate(V), β-NaMoO2AsO4, was prepared by solid-state reaction at 953 K. In the crystal structure, the AsO4 tetra­hedra and MoO6 octa­hedra (both with m symmetry) share corner atoms to form a three-dimensional framework that delimits cavities parallel to [010] where disordered six-coordinated sodium cations (half-occupation) are located. Structural relationships between the different orthoarsenates of the AMoO2AsO4 series (A = Ag, Li, Na, K and Rb) are discussed

K0.8Ag0.2Nb4O9AsO4

The title compound, potassium silver tetra­niobium nona­oxide arsenate, K0.8Ag0.2Nb4O9AsO4, was prepared by a solid-state reaction at 1183 K. The structure consists of infinite (Nb2AsO14)n chains parallel to the b axis and cross-linked by corner sharing via pairs of edge-sharing octa­hedra. Each pair links together four infinite chains to form a three-dimensional framework. The K+ and Ag+ ions partially occupy several independent close positions in the inter­connected cavities delimited by the framework. K0.8Ag0.2Nb4O9AsO4 is likely to exhibit fast alkali-ion mobility and ion-exchange properties. The Wyckoff symbols of special positions are as follows: one Nb 8e, one Nb 8g, As 4c, two K 8f, one Ag 8f, one Ag 4c, one O 8g, one O 4c

AgNa2Mo3O9AsO4

The title compound, silver disodium trimolybdenum(VI) nonaoxide arsenate, AgNa2Mo3O9AsO4, was prepared by a solid-state reaction at 808 K. The structure consists of an infinite (Mo3AsO13)n ribbon, parallel to the c axis, composed of AsO4 tetra­hedra and MoO6 octa­hedra sharing edges and corners. The Na and Ag ions partially occupy several independent close positions, with various occupancies, in the inter-ribbon space delimited by the one-dimensional framework. The composition was refined to Ag1.06(1)Na1.94(1)Mo3O9AsO4