R. Naslain

Solid-state synthesis and characterization of the ternary phase Ti3SiC2

Ti3SiC2 is the only true ternary compound in the Ti-Si-C system. It seems to exhibit promising thermal and mechanical behaviour. With the exception of its layered crystal structure, most of its properties are unknown, owing to the great difficulty of synthesis. A new procedure of solid-state synthesis with several steps is proposed, which results in Ti3SiC2 with less than 5 at % of TiC. Ti3SiC2 is stable at least up to 1300 °C. Beyond this temperature, it can decompose with formation of non-stoichiometric titanium carbide and gaseous silicon, with kinetics highly dependent on the nature of the surroundings. As an example, graphite can initiate this process by reacting with silicon, while alumina does not favour the decomposition which remains very slow. The oxidation of Ti3SiC2 under flowing oxygen starts at 400 °C with formation of anatase-type TiO2 film, as studied by TGA, XRD, SEM and AES. Between 650 and 850 °C both rutile and anatase are formed, rapidly becoming protecting films and giving rise to slow formation of SiO2 and more TiO2. The oxidation kinetics is slower than for TiC, owing to a protecting effect of silica. By increasing the temperature, both oxidation processes (i.e. direct reaction and diffusion through oxide layers) are activated and an almost total oxidation is achieved between 1050 and 1250 °C resulting in titania (rutile) and silica (cristobalite).

Conversion mechanisms of a polycarbosilane precursor into an SiC-based ceramic material

The pyrolysis of a PCS precursor has been studied up to 1600 °C through the analysis of the gas phase and the characterization of the solid residue by thermogravimetric analysis, extended X-ray absorption fine structure, electron spectrocopy for chemical analysis, transmission electron microscopy, X-ray diffraction, Raman and Auger electron spectroscopy microanalyses, as well as electrical conductivity measurements. The pyrolysis mechanism involves three main steps: (1) an organometallic mineral transition (550 < Tp < 800 °C) leading to an amorphous hydrogenated solid built on tetrahedral SiC, Si02 and silicon oxycarbide entities, (2) a nucleation of SiC (1000 < Tp < 1200 °C) resulting in SiC nuclei (less than 3 nm in size) surrounded with aromatic carbon layers, and (3) a SiC grain-size coarsening (Tp > 1400 °C) consuming the residual amorphous phases and giving rise simultaneously to a probable evolution of SiO and CO. The formation of free carbon results in a sharp insulator-quasimetal transition with a percolation effect.

The design of the fibre-matrix interfacial zone in ceramic matrix composites

Abstract Ceramic matrix composites are tough when the fibre-matrix bonding is properly controlled during processing, via the use of an interphase. The interphase is either formed in situ as the result of fibre-matrix interactions or deposited on the fibre surface prior to composite fabrication. It has several key functions, including crack deflection, load transfer, diffusion barrier and residual stress relaxation. Four types of interphase are depicted involving weak interfaces, materials with a layered crystal structure (pyrocarbon, BN, micas and phyllosiloxides, or materials with the β-alumina/magnetoplumbite structures), multilayers such as (PyC-SiC)n or (BN-SiC)n or, finally, porous materials. Achieving high mechanical properties and long lifetimes in severe environments require a subtle design of the fibre-matrix interfacial zone, which is depicted for Nicalon/glass–ceramic and Nicalon/SiC-matrix composites.

Oxidation-resistant carbon-fiber-reinforced ceramic-matrix composites

Abstract A multilayer Si–B–C ceramic matrix has been developed to improve the oxidation resistance and the lifetime in an oxygen environment of carbon-fiber-reinforced ceramic-matrix composites. This concept has been applied to a multidirectional fibrous carbon preform. The paper deals with the processing, the mechanical behaviour and the oxidation resistance of a carbon-fiber-reinforced multilayer ceramic-matrix composite. The efficiency of this matrix is compared to that of the classical anti-oxidation systems based on an external coating usually employed to reduce the oxygen permeation. The efficiency of the oxidation protection of the multilayer ceramic matrix is still evident in spite of the complex architecture of the fibrous preform and the damage of the matrix. The experimental results show that a strong improvement in the lifetime of such composites under thermomechanical loading and in an oxygen environment is obtained when a multilayer matrix is used to protect the carbon reinforcement against oxidation.

Discontinuously-reinforced aluminum matrix composites

Abstract This article reviews the literature relating to aluminum matrix composites reinforced by ceramic particles, short fibers or whiskers. The main reinforcements which have been used are presented with respect to their nature, morphology and mechanical behavior. The influence of matrix alloying elements on ceramic-metal compatibility is discussed. Most fabrication techniques which have been proposed are described and particular attention is paid to the methods suitable for large scale production. The mechanical characteristics of this kind of composite are reported and compared in relation to processing parameters. Finally, models giving a rough prediction of the mechanical behavior of the composites are discussed.

Thermal stability of a PCS-derived SiC fibre with a low oxygen content (Hi-Nicalon)

The oxygen free Si–C fibre (Hi-Nicalon) consists of β-SiC nanocrystals (≈5nm) and stacked carbon layers of 2–3nm in extension, in the form of carbon network along the fibre. This microstructure gives rise to a high density, tensile strength, stiffness and electrical conductivity. With respect to a Si–C–O fibre (Nicalon NL202), the Si–C fibres have a much greater thermal stability owing to the absence of the unstable SiOxCy phase. Despite its high chemical stability, it is nevertheless subject to a slight structural evolution at high temperatures of both SiC and free carbon phases, beginning at pyrolysis temperatures in the range 1200–1400°C and improving with increasing pyrolysis temperature and annealing time. A moderate superficial decomposition is also observed beyond 1400°C, in the form of a carbon enriched layer whose thickness increases as the pyrolysis temperature and annealing time are raised. The strength reduction at ambient for pyrolysis temperatures below 1600°C could be caused by SiC coarsening or superficial degradation. Si–C fibres have a good oxidation resistance up to 1400°C, due to the formation of a protective silica layer.

Si-C-N ceramics with a high microstructural stability elaborated from the pyrolysis of new polycarbosilazane precursors

Novel polycarbosilazanes (PCSZs) were prepared by stepwise synthesis and thermal crosslinking of polysilasilazane (PSSZ) copolymers. Their pyrolysis under inert gas, producing Si-C-N ceramics, was investigated up to 1600 °C by analyses performed on the solids (elemental analysis; EPMA; TGA, density; 1H, 13C and 29Si solid state NMR, i.r. XRD, electrical conductivity) and analyses of the evolved gases (gas chromatography and mass spectrometry). From 250 to 450 °C, a first strong weight loss was observed, which was due to the formation and elimination of low-boiling-point oligomers. The weight loss closely depends on the cross-linking degree of the ceramic precursor resulting from the PSSZ/PCSZ conversion. Then, the organic/inorganic transition took place between 500 and 800 °C, proceeding via evolution of gases (mainly H2 and CH4) and yielding a hydrogenated silicon carbonitride. This residue remained stable up to 1250 °C although it progressively lost its residual hydrogen as the temperature was raised. Then, crystallization occurred between 1250 and 1400 °C, yielding β-SiC crystals surrounded by free-carbon cage-like structures. Finally, above 1400 °C, the remaining amorphous Si-C-N matrix underwent a decomposition process accompanied by nitrogen evolution and a second substantial weight loss. At 1600 °C, the pyrolytic residue was a mixture of β-SiC and free carbon. So, the amorphous silicon carbonitride resulting from the pyrolysis of PCSZ precursors was found to be appreciably more thermally stable than the previously reported Si-C-O ceramic obtained by pyrolysis of polycarbosilane precursors.

SiC filament/titanium matrix composites regarded as model composites

Two types of large diameter SiC CVD filaments have been investigated on both chemical and mechanical standpoints: a 100μm filament with a tungsten core (from SNPE) and three 140μm filaments with carbon cores and surface coatings (from AVCO). On the basis of microprobe (X-ray, Auger and Raman), X-ray diffraction and SEM analyses, it appears that the former is made of a single homogeneous stoichiometric SiC deposit while the latter are mainly made of two concentric shells (the inner being a SiC+C mixture and the outer almost pure SiC). All the C-core filaments had received a surface coating (either pure pyrocarbon or SiC+C mixture) presumably to protect the brittle SiC deposit against abrasion due to handling in opposition to the W-core filament which seems to have no surface coating at all. The W-core filament, although smaller in diameter, is weaker than the C-core filaments (average UTS of 3 and 4 GPa respectively for a 40 mm gauge length). However, its strength distribution is much narrower (Weibull moduli of 7–8 and 2–5 respectively). Failures of most filaments appear to have a multimodal character.

A theoretical and experimental approach to the active-to-passive transition in the oxidation of silicon carbide: Experiments at high temperatures and low total pressures

Active-to-passive oxidation transition in chemical vapour deposited β-SiC was investigated in the temperature range 1300≤T≤1700°C under low total pressures (100≤Ptot≤800 Pa) and relatively high linear gas flow rates (10≤Vgas≤60 m s1) by thermogravimetric analysis. For given T, Ptot and Vgas, the oxygen partial pressure at the transition, PtO2, corresponds to the value where the mass-loss rate per unit area of the oxidized sample, R, is maximum. Logarithms of PtO2 are linear functions of reciprocal temperature for given Ptot, and Vgas. Vgas has a significant influence on the position of the transition log(PtO2)–T-1 line. PtO2 is also slightly affected by an increase of Ptot from 100 Pa to 800 Pa. In passive oxidation at high temperatures (>1500°C), large bubbles form in the silica film which is then disrupted leading to a loss of material. In active oxidation, R significantly depends on Vgas: the kinetics is diffusion or mass transfer controlled under the conditions investigated in the present study. In both active and passive oxidation regimes, a mass loss of the test specimen is always observed; an explanation is proposed.

Wetting improvement of carbon or silicon carbide by aluminium alloys based on a K2ZrF6 surface treatment: application to composite material casting

A surface treatment with aqueous solutions of K2ZrF6 has been carried out to improve, in dramatic manner, the wetting of carbon (or SiC)-base ceramics by liquid light alloys at low temperatures (i.e. within the 700 to 900°C range). The mechanism which is thought to be responsible for the wetting improvement involves two steps: (i) K2ZrF6 reacts with aluminium with the formation of K3AlF6, other complex fluoride species and intermetallics, (ii) K3AlF6 dissolves the alumina thin layer, coating the liquid light alloy and enables the wetting of the ceramics. The mechanism has been worked out from sessile drop experiments, solid state chemistry experiments and composite casting. The K2ZrF6 surface treatment appears to be particularly suitable for processing composite materials made of carbon (or SiC) fibrous preforms and aluminium-base matrices according to techniques directly derived from the light alloy foundry.