Design, Fabrication, and Application of Thermostructural Composites
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Design, Fabrication, and REVIEWS Application of Thermostructural Composites (TSC) like C/C, C/SiC, and SiC/SiC Composites By François Christin* The French company Snecma Moteurs is a leading producer of high-performance composites for opera- tion under high mechanical stress and at high temperature, such as in jet engines, aircraft brake disks, or even rocket propulsion systems. The author presents the different families and generations of carbon-carbon and ceramic-matrix composites developed by Snecma, and discusses their manufacture and characteristics. 1. Introduction ability and thermomechanical cycling in oxidative environ- ments, a last step was investigated from 1980 with the devel- The main features of thermostructural composites (TSCs) opment of ceramic±ceramic composites. are their highly specific mechanical properties, high thermal conductivity, excellent behavior to thermal shocks; endurance 2. Manufacturing Process of Thermal Structural to very high temperature, and easy fabrication. They are used in thicknesses ranging from 1 mm to 200 mm. TSCs provide a Composite Materials much lighter-weight solution than refractory metals. With TSCs are made of carbon or silicon carbide (SiC) fibers (la- systematic use of high-performance composite materials, beled ªtextureº or ªpreformº), linked together by the matrix Snecma has significantly decreased the inert mass of its rocket (carbon or silicon carbide materials). Preform parameters can motors. Development of carbon±carbon thermostructural be tuned up in order to meet the mission/design require- composite materials started at SEP in 1969. At that time, the ments (fibers selection, type and composition, deformation, aim was to improve the performance and reliability of solid laying-up, etc.). These preforms can be densified using var- propellant rocket nozzles and to find replacement materials ious matrices (carbon, silicon carbide, etc.) by means of three for tungsten (too heavy), pyrographite (not suitable for mak- processes (resin pitch polymer impregnation, pyrolysis (PIP), ing large integral parts), and polycrystalline graphites (too chemical vapor infiltration (CVI), and/or any combination of brittle). The first solid-propellant rocket motor composite car- them), which allow material properties to be managed as bon±carbon (CCC) nozzle was test fired in 1972. In parallel, required (Table 1). Several combinations of textures and the potential of CCC materials for brake disks was investi- matrices have been developed for Sepcarb (trade name for gated. In 1985, in order to respond to the increasing demand CCC produced by Snecma Moteurs) for solid and liquid for these CCC brakes, a new company, Carbone Industrie, propulsion, and brake applications. was created. In 1975, the chemical vapor infiltration (CVI) of porous carbon with a silicon carbide matrix was investi- ± gated.[1] The aim was to obtain materials capable of with- [*] Dr. F. Christin standing high temperature in an oxidative environment. The Snecma Moteurs, Site de Bordeaux fundamental studies were conducted from 1975 to 1979 and Les Cinq Chemins, F-33187 Le Haillan Cedex (France) their success led to a patent being filed in 1979. For long dur- E-mail: [email protected] ADVANCED ENGINEERING MATERIALS 2002, 4, No. 12 Ó 2002 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1438-1656/02/1212-0903 $ 17.50+.50/0 903 Christin/Design, Fabrication, and Application of Thermostructural Composites Table 1. Main thermostructural materials designs. an original texture which could benefit both from the advan- tages of the multidirectional reinforcements (3D, 4D) and Reinforcements Processes Matrixes C or SiC those of 2D preforms. Novoltex is a 3D carbon non-woven Fibers C, SiC Winding Impregantion (C), A/O CVI preform construction made using automatic technology. Rods C, SiC nD construction Pitch impregnation (C) and CVI Needling consists of attaching fabric layers to each other with REVIEWS Clothes C, SiC Wrapping 2D or Resin impregnation (C), A/O CVI carbon fibers carried by hook-fitted needles (hooks are de- involute layers signed so that fibers stay where they have been carried when Novoltex C Needling - 3D Resin impregnation (C) A/O CVI the needles leave the preform). Needling is carried out after Guipex C, SiC Multilayer Weaving Resin impregnation (C), A/O CVI each layer so that, at the end, each part of the preform Braids C, SiC Weaving Resin impregnation (C), A/O CVI through the thickness has received the same amount of trans- ferred fibers: this provides Novoltex with its good through- the-thickness homogeneity (Fig. 1). For extended use oxidative environment (e.g., liquid rock- Nowadays, Snecma Group (including CCC brakes) pro- et engine exit cones, combustion chambers) the company has duces several ten thousands of Novoltex preforms per year. developed Ceramic Matrix Composites (CMC) since the mid The production cost has been dramatically reduced, making [2] 70's. Their trade names are Sepcarbinox or Cerasep, and they CCC and CMC composites cost-efficient materials overall. are based on carbon fiber or ceramic fiber reinforcements For the ceramic±ceramic materials, and mainly the SiC±SiC of respectively. which the manufacturing processes have been industrialized at Le Haillan, the preform is obtained in the traditional man- ner by preparing a stack of SiC woven-fabric layers. This stack is then compacted in a special machine, so as to obtain a 2.1. Fiber Arrangement: The Preforms preform with a fiber volume fraction compatible with the The carbon fibers are obtained by carbonization and gra- procedure of gaseous processing of the silicon carbide matrix. phitization of an organic precursor made from rayon or Poly- This fiber volume fraction is generally 40±45 %. AcriloNitril (PAN) and different types of fibers arrangement can be used (2D, 2.5D, 3D, nD,...). At the end of the seventies, Snecma Moteurs used to design solid rocket motor (SRM) nozzles, taking advantage of available CCCs: hot exit cones were based on 2D reinforced CCC, and nozzle throats were made of 4D reinforced CCC. The main advantages of 2D tex- tures, usually flat or involute, rely on their ability to process thin preforms using standard techniques. For the throat insert, which is a thick part, multi-direction («nD») reinforced CCC is generally used for high performance, as the high level of thermally induced stresses in this critical component requires high strength and high strain material capabilities. However, 2D CCC suffers from poor thermal-stress capabili- ty, as well as low delaminating and shear resistance. Besides, they are actually even more inclined to delaminate or crack during fabrication, as the preforms are thick. That is why the company decided, at the end of 70's, to develop ªNovoltexº, Fig. 1. Novoltex reinforcementÐa three-dimensional carbon fiber structure. François Christin is programme engineer CMC manager at Snecma Propulsion Solide (SPS) in Le Hail- lan (close to Bordeaux, France). He graduated in 1975 from the engineering school of chemistry in Tou- louse (ENSCT), and in 1979 he obtained his Ph.D. at the UniversitØ de Bordeaux (1 No. 641). Subject of his Ph.D. was "Les composites carbone±carbone±carbure de silicium: une nouvelle famille de matØriaux destinØs à des applications à haute tempØratureº. After graduation he joined industry, and over a period of 10 years he was in charge of the development and industrialization of new processes (Furnaces Scales from 50 mm to 3.5 m in diameter). He continued as a manager for research and development of compos- ite materials for 10 years and developed with his team a new materials family, and optimized character- ization methods and models. Mr. Christin is currently responsible for the research and technology program at Snecma moteurs (aeronautic and space engines). 904 ADVANCED ENGINEERING MATERIALS 2002, 4, No. 12 Christin/Design, Fabrication, and Application of Thermostructural Composites 2.2. Caron and SiC Sensification: The Matrix l A combination of great interest has been found using liq- REVIEWS uid densification and CVI processes, making CMC com- 2.2.1. Carbon Matrix posites cost-efficient materials. This combined process The matrix is obtained either by gas infiltration (CVI), by takes the advantages of the liquid route (shape, simplified resin impregnation combined with pyrolysis treatment (PIP), tooling) and of the CVI route (mechanical characteristics or by pitch impregnation combined with high isostatic pres- and thermal stability of the pure SiC matrix). It is suitable sure (HIP) carbonization (Fig. 2). to manufacture components such as flaps for aircraft en- l CVI (Chemical Vapor Infiltration). gines and the thermal protection system (TPS) and hot The carbon matrix is deposited in the pores of the fibrous structures for re-entry vehicles. carbon structures in the vapor phase by cracking of methane at a controlled temperature and low pressure. This process is the most used because it provides a carbon matrix (pyrocar- 3. Part Design bon) with good mechanical properties, and is very suitable for industrial applications such as brake yields, nozzle, and TSC system or part design is a new discipline with few sol- nozzle extension manufacturing. id bases, but our expertise and mastery have now reached l Pitch matrix process and resin matrix process. new levels where some methodologies can be settled. As for The densification of the carbon structures is achieved by any problem, the alternative between an analytical and an pitch or resin impregnation followed