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International audience; SiC/BN/SiC-Si single-ply composites with Hi-Nicalon STM fibres were synthesised by chemical vapour infiltration and the liquid route. These are model composites representing the behaviour of industrial composites intended to be used as structural parts in the hot sections of aeronautical engines. Four interphases with two different degrees of crystallisation and, in each case, two different thicknesses were tested. The interfacial shear stress measured by fibre push-out test is significantly higher when the crystallisation degree of the BN interphase is low, yet in this case it decreases with the thickness of the interphase. This higher interfacial bonding is also associated, albeit less significantly, with better macromechanical properties as measured by tensile and shear tests. The cracks observed in the composite with different microscopy techniques are also less long and open. Depending on the interphases, the debonds are more or less pronounced and occur preferentially at different locations in the interfacial system.

International audience; BN interphases were synthesized by chemical vapour infiltration (CVI) from BCl3 and NH3 at 900 °C and 1200 °C within preforms made of a single 2D woven SiC fibre ply. Then CVI of a SiC matrix followed by molten silicon infiltration resulted in laboratory-made single-ply SiC/SiC-Si composites representative of similar industrial ceramic matrix composites. The interphases and interfaces were characterized by transmission electron microscopy. It has been found that, in the two cases, the interphases are mostly turbostratic BN. Those synthesized at 900 °C are very poorly crystallized and exhibit a quasi-isotropic microstructure. An equiaxed interlayer is obtained prior to the columnar CVI growth of SiC matrix. Interphases synthesized at 1200 °C exhibit high degrees of crystallization and structural anisotropy. The SiC matrix grows directly in columns on BN. For interphase thicknesses of 300 nm and more, triangular-shaped crystallites of rhombohedral BN appear in turbostratic BN and the columnar growth of SiC is disoriented.

We report on a successful attempt to introduce Al 2 O 3 and AlN nanoparticles in the matrix of a C/C composite via (i) aqueous synthesis of AlOOH nanoparticles in a predensified C/C composite preform, (ii) ceramization of AlOOH into either Al 2 O 3 or AlN, and (iii) final pyrocarbon densification. We show that we were able to synthesize a uniform and thin layer of high aspect ratio (nanoneedle) AlOOH particles at the surface of pyrocarbon coated fibers. This morphology was conserved upon transformation to alumina, however, coalescence into larger compact grains (thus discontinuous) was observed after nitridation. Nevertheless, the ceramic introduction did not alter the microstructure of the resulting composite after full densification. While most of the ceramic/carbon interfaces showed a parallel arrangement of graphene layers at the surface of the ceramic particles, characteristic of weak bonding, a carbon/AlN interface showed a perpendicular arrangement, suggesting strong covalent bonding.

Silicon carbide fibers combine structural and refractory properties making them good candidates for ceramic matrix composite reinforcement, driving their ultimate failure. The fractographic observation after tensile tests of various silicon carbide fibers, belonging to first, second or third generations, reveals the critical flaw location i.e. internal or surface. An etching treatment under pure chlorine at 500–850 °C can be used to transform the fibers surface on hundreds of nanometers and alter the surface-located flaw population. This way, first-generation SiC-based fibers successfully show an asymptotic improvement of tensile strength (up to 60%) and Weibull modulus (up to twice), when etched on 0.3–1 μm depth range. The lifetime of bundles, under static fatigue conditions at intermediate temperature, is consequently multiplied by a factor ranging from 10 to 40 with a narrower dispersion. Nevertheless, the tensile strength could neither be increased on second-generation Hi-Nicalon nor dramatically dropped on third-generation Hi-Nicalon-S fiber.

The design of Si-(B)-C materials is investigated, with detailed insight into the precursor chemistry and processing, the precursor-to-ceramic transformation, and the ceramic microstructural evolution at high temperatures. In the early stage of the process, the reaction between allylhydridopolycarbosilane (AHPCS) and borane dimethyl sulfide is achieved. This is investigated in detail through solid-state NMR and FTIR spectroscopy and elemental analyses for Si/B ratios ranging from 200 to 30. Boron-based bridges linking AHPCS monomeric fragments act as crosslinking units, extending the processability range of AHPCS and suppressing the distillation of oligomeric fragments during the low-temperature pyrolysis regime. Polymers with low boron contents display appropriate requirements for facile processing in solution, leading to the design of monoliths with hierarchical porosity, significant pore volume, and high specific surface area after pyrolysis. Polymers with high boron contents are more appropriate for the preparation of dense ceramics through direct solid shaping and pyrolysis. We provide a comprehensive study of the thermal decomposition mechanisms, and a subsequent detailed study of the high-temperature behavior of the ceramics produced at 1000 °C. The nanostructure and microstructure of the final SiC-based ceramics are intimately linked to the boron content of the polymers. B4 C/C/SiC nanocomposites can be obtained from the polymer with the highest boron content.

International audience; Carbon coatings have been formed on the surface of free carbon containing Tyranno ZMI and Nicalon SiC-based fibers by reaction with chlorine gas (chlorination) in the temperature range 550-675 °C. The kinetics and growth mechanisms have been investigated for both fibers. Results have shown that, for similar experimental conditions, the reactivity of both fibers displayed noticeable discrepancies. It has thus been observed that the Nicalon fiber was more prone to chlorine-based treatment and displayed a thicker carbon coating than the ZMI fiber. These results have also revealed that, in both case, these thicknesses can be closely monitored by physical parameters such as temperature and aging duration. The nature of the obtained coating has also been investigated by various experimental devices. AES, SEM and TEM analyses have thus evidenced that these carbon coatings were uniform and well adherent whereas AFM showed that the chlorine-based treatments resulted in a nanometer-range roughness at the fiber surface. Adsorption gas analyses also revealed a microporosity coupled with a high specific surface area. The chemical composition of the final products was determined by XPS and Mass Spectroscopy. Finally, the oxidation behaviour which was investigated by thermogravimetric analysis revealed that oxidation occurs at a quite low temperature (225°C).

Ex-rayon carbon yarns have been prepared according to an original route characterized by a fast pyrolysis step in the presence of an organosilicon compound. The evolution of the mechanical and physicochemical properties of the fibres throughout the transformation of cellulose into carbon showed that the organosilicon additive was necessary to obtain carbon yarns exhibiting satisfactory mechanical behaviour and to improve significantly the fracture properties of the ex-rayon carbon fibres.

International audience; Novel two-dimensional carbon-carbon composites made of carbon nanofibers (CNFs) supported on a carbon preform were functionalized by non thermal plasma treatment (room temperature, atmospheric pressure, humid air), before being used as supports for metallic cobalt nanoparticles. It was shown that the degree of functionalization of the carbon nanofibers depends on the plasma power input, the treatment time and the CNF loading. The size of the cobalt nanoparticles generated after subsequent reduction of the Co-containing plasma treated CNF/C composites under hydrogen flow seems to be independent of the amount of supported cobalt. Changes in surface characteristics were analyzed using thermogravimetric analyses coupled to a mass spectrometer, X-ray photoelectron spectroscopy analyses and Raman spectroscopy. Transmission electron microscopy was used to complementary characterize the final size, dispersion and location of the so generated Co nanoparticles

Rayon fibres were pyrolysed under inert gas flows up to 1200 °C. Changes in the mechanical properties of the fibres at various stages of the thermal treatment were studied and correlated with structural analyses of the char by CP/MAS 13 C NMR and DRIFT spectroscopies. The force/displacement curve of fibres pyrolysed at 500 °C is non-linear but reversible within the deformation, which is approximately 10% at ultimate failure.

The aim of the present work was to investigate the high temperature reaction between Si- C-O fibres and Cl2, and to correlate the carbon layer growth kinetics with their initial composition and structure. Large disparities have been observed between the various materials reaction rates. If a large amount of mixed silicon atom environments increases the reactivity of Si-O-C materials with Cl2, this sole feature does not explain all the experimental results. Traces of heteroelements (Ti, Zr, Al…) or percolated free carbon both appear to bear on the reaction rate. For a better understanding of the fibres reaction behaviour, this study was extended to other model materials (oxycarbide glasses, oxygen-free Si-C fibres, SiC).

International audience; Treatment of cellulose yarns by a polysiloxane followed by a fast pyrolysis step gave carbon fibres exhibiting strong enhancement of their mechanical resistance. To account for the beneficial effect of the polysiloxane, an investigation of the pyrolysis mechanisms was performed on a model system based on cellobiose and a polysiloxane resin. A chemical interaction between cellobiose and the resin (e.g. grafting of siloxane fragments onto the cellobiose) was established by using various physicochemical analysis techniques: nuclear magnetic resonance (NMR), photoelectron spectrometry (XPS), electronic paramagnetic resonance (EPR), Flash pyrolysis–gas chromatography–mass spectrometry (FP/GC/MS) and IR.