A vehicle flying at hypersonic speeds, i.e. at speeds greater than Mach 4, needs to be able to withstand the heat arising from friction and shock waves, which can reach temperatures of up to 3000oC. The current project focuses on producing thermal protection systems based on ultra high temperature ceramic (UHTC) impregnated carbon-carbon composites. The carbon fibres offer low mass and excellent resistance to thermal shock; their vulnerability is to oxidation above 500oC. The aim of introducing HfB2, a UHTC, as a coating on the fibre tows or as particulate reinforcement into the carbon fibre preform, was to improve this property. The objectives of this project were to: i) identify a low temperature synthesis route for group IV diborides, ii) produce a powder fine enough to reduce the difficulties associated with sintering the refractory diborides, iii) develop sol-gel coating of HfB2 onto carbon fibre tows iv) improve the solid loading of the particulate reinforcement into the carbon fibre preform, which should, in turn, increase the oxidation protection. In order to achieve the above set objectives, fine HfB2 powder was synthesized through a low temperature sol gel and boro/carbothermal reduction process, using a range of different carbon sources. Study of the formation mechanism of HfB2 revealed an intermediate boron sub-oxide and/or active boron formation that yielded HfB2 formation at 1300oC. At higher temperatures the formation of HfB2 could be via intermediate HfC formation and/or B4C formation. Growth mechanism analysis showed that the nucleated particles possessed screw dislocations which indicated that the formation of HfB2 was not only through a substitution reaction, but there could have been an element of a precipitation nucleation mechanism that lead to anisotropic growth under certain conditions. The effect of carbon sources during the boro/carbothermal reduction reaction on the size of the final HfB2 powders was analysed and it was found that a direct relation existed between the size and level of agglomeration of the carbon sources and the resulting HfB2 powders. A powder phenolic resin source led to the finest powder, with particle sizes in the range 30 to 150 nm. SPS sintering of the powder revealed that 99% theoretical density could be achieved without the need for sintering aids at 2200oC. Sol-gel coatings and slurry impregnation of HfB2 on carbon fibres tows was performed using dip coating and a 'squeeze-tube' method respectively. Crack free coatings and non-porous matrix infiltration were successfully achieved. The solid loading of the fine HfB2 into the carbon fibre preform was carried out through impregnation of a HfB2 / phenolic resin/acetone slurry using vacuum impregnation. Although the sub-micron Loughborough (LU) powders were expected to improve the solid loading, compared to the commercially available micron sized powders, due to the slurry made from them having a higher viscosity because of the fine particle size, the solids loading achieved was consequently decreased. Optimisation of the rheology of the slurry with LU HfB2 still requires more work. A comparison of the oxidation and ablation resistance of the Cf-HfB2 composites prepared with both commercial micron sized HfB2 powder and Loughborough sub-micron sized HfB2 powder, each with similar level of solid loading, was carried out using oxyacetylene torch testing. It was found that the composite containing the finer, Loughborough powders suffered a larger erosion volume than the composite with the coarser commercial powders indicating that the former offered worse ablation and oxidation resistance than the latter. A full investigation of the effect of solids loading and particle size, including the option of using mixtures of fine and coarse powders, is still required.

L'élaboration de composites à matrice céramique denses et à fibres continues multidirectionnelles par de nouveaux procédés hybrides a été étudiée. Les procédés développés reposent sur le dépôt d'interphases autour des fibres par Infiltration Chimique en phase Vapeur (CVI) puis sur l'introduction de poudres céramiques au sein de préformes fibreuses par infusion de suspensions aqueuses colloïdales concentrées et stables, et enfin sur la consolidation des préformes soit par frittage flash, soit par imprégnation réactive de métaux liquides.La consolidation des composites par frittage flash est très rapide (palier de maintien en température inférieure à 5 minutes) et permet d'obtenir des composites denses. Durant le frittage, la dégradation des fibres de carbone a pu être évitée en adaptant le cycle de pression afin de limiter l'évolution des gaz au sein du système.La densification totale des composites par imprégnation de métaux liquides a été obtenue en contrôlant attentivement les paramètres d'imprégnation afin d'éviter de piéger des espèces gazeuses au sein des préformes fibreuses.Les composites à fibres de carbone consolidés par frittage flash ou par imprégnation réactive de métaux liquide possèdent un comportement mécanique de type élastique endommageable ainsi qu'une contrainte à rupture en flexion voisine de 300 MPa. Ces composites ont montré leur capacité à s'autocicatriser dans des conditions oxydantes. Comparés aux composites à matrice céramiques élaborés par CVI, les composites densifiés par imprégnation de métaux liquide sont eux parfaitement denses et ont un comportement mécanique en traction à température ambiante similaire avec notamment une contrainte à rupture en traction de 220 MPa. / The fabrication of multidirectional continuous carbon fibers reinforced dense self healing Ceramic Matrix Composites by new short time hybrid processes was studied. The processes developed are based, first, on the deposition of fiber interphase and coating by chemical vapor infiltration, next, on the introduction of ceramic powders into the fibrous preform by Slurry Impregnation and, finally, on the densification of the composite by liquid-phase Spark Plasma Sintering (SPS) or by Reactive Melt Infiltration of silicon (RMI).The homogeneous introduction of the ceramic particles into the multidirectional fiber preforms was realized by slurry impregnation from highly concentrated (> 32 %vol.) and well dispersed aqueous colloid suspensions. The densification of the composites by spark plasma sintering was possible with a short (< 5 minutes) dwelling period in temperature. The chemical degradation of the carbon fibers during the fabrication was prevented by adapting the sintering pressure cycle to inhibit gas evolution inside the system. The composites elaborated are dense. The fully densification of the composites by RMI was realised by carefully controlling the impregnation parameters to avoid to entrap some gaseous species inside the fiber preforms. Our carbon fiber reinforced ceramic matrix composites processed by Spark Plasma Sintering or Reactive Melt Infiltration have a damageable mechanical behaviour with a room temperature bending stress at failure around 300 MPa and have shown their ability to self-healing in oxidizing conditions. Compared to the CMC processed by CVI, the composites processed with a final consolidation step by RMI are fully dense and have a similar room temperature tensile test behaviour with an ultimate tensile stress around 220 MPa.