Synthesis and processing of sub-micron hafnium diboride powders and carbon-fibre hafnium diboride composite

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.