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33. Mullen, C. K.; and Roy, P. J.: Fabrication and Properties of AVCO 3-D Carbon/Carbon Cylinder Material. Proceedings of the 17th National SAMPE Symposium, 1972, p. III-A-2.

34. Pierson, H. O.: Development and Properties of Pyrolytic Carbon Felt Composites. Advanced Techniques for Material Investigation and Fabrication, Volume 14 of Science of Advanced Materials and Process Engineering Proceedings, Soc. of Aerospace Material and Process Engineers, 1968, paper II-4B-2.

35. Stoller, H. M.; and Frye, E. R.: Processing of Carbon-Carbon Composites. Advanced Materials: Composites and Carbon, American Ceramic Soc., c.1972, pp. 165-172.

36. Guo, L.: An Investigation of the 4D Texture in Carbon-Carbon Composites and Its Behaviors. International Symposium on Composite Materials StructuresAbstracts of Papers for Work-in-Progress, T. T. Loo and C. T. Sun, eds., (Beijing, China), 1986, pp. 9-12.

37. Herrick, J. W.: Multidimensional Advanced Composites for Improved Impact Resistance. 10th National SAMPE Technical Conference, 1978, p. 38.

38. Herrick, J. W.: Multi-Directional Advanced Composites for Improved Damage Tolerance. SME Tech. Paper EM84-104, Jan. 1984.

39. Herrick, J. W.: Advanced Impact Resistant Multidimensional CompositesFinal Report. Rep. No. FR-79-1-3, Jan. 30, 1978.

40. Herrick, J. W.: Advanced Impact Resistant Multidimensional Composites. FR-79-1-3 (Contract NO0O19-77-C-O430), Fiber Materials, Inc., Jan. 1979. (Available from DTIC as AD A068 517.)

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44. Ma, C. L.; Yang. J. M.; and Chou, T. W.: Elastic Stiffness of ThreeDimensional Braided Textile Structural Composites.Composite Materials: Testing and Design, ASTM STP 983, American Soc. for Testing and Materials, 1986, pp. 404-421.

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A. Chou, T. W.; and Ko, F. K.: Textile Structural Composites. Elsevier, 1988.

B. Hearle, J. W. S.; Grosberg, P.; and Backer, S.: Structural Mechanics of Fibers, Yarns nd Fabrics. John Wiley & Sons, 1969.

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Chapter 5 Carbon-Carbon Matrix Materials

N. Murdie, C. P. Ju, J. Don, and M. A. Wright

Southern Illinois University at Carbondale

Carbondale, Illinois

Introduction 106
Carbon Fibers 108

Fabrication Methods of CC Composites 111
Liquid Phase Infiltration 112
Pitch Matrices 112
Thermoset Resin Matrices 115
Gas Phase Infiltration Process 118

Isothermal Chemical Vapor Deposition 119
Thermal-Gradient Chemical Vapor Deposition 119
Differential Pressure Chemical Vapor Deposition 120
Matrix Inhibition 121

Microstructural Characterization Techniques 123
Optical Microscopy 123
X-Ray Diffraction 124
Scanning Electron Microscopy 125
Transmission Electron Microscopy 126
Microstructure of CC Matrices 127
Pitch Matrix Composites 127
Resin Matrix Composites 135
CVI Matrix Composites 142
Influence of Matrix on Composite Properties 149

General Background 149

Elastic Modulus 150

Tensile Strength 151

Matrix Dominated Properties 154

Two-Dimensional Reinforcements 156

Three-Dimensional Reinforcements 156

Acknowledgments 157

References 158


Carbonaceous materials have been used as refractories, as electrodes in both steelmaking and aluminum production, as moderators for nuclear reactors, rocket nozzles and exhausts, as aircraft brakes, and in various chemical and electrical applications (ref. 1). Initially, the carbons used for each structure were comprised of a granular material bonded together with a carbonized resin or pitch matrix. Improvements in the mechanical properties of structural carbons were obtained by depositing carbon layers from the gas phase. Mechanical properties of this material were superior to those exhibited by the pitch- or resin-bonded material, especially so when measured parallel to the basal plane of the graphite (ref. 1).

Carbon fibers are a relatively recent development in which the basal planes of the graphite-like crystallites are arranged almost parallel to the fiber axis. This arrangement produces a fiber that exhibits a significant anisotropy of properties. The elastic modulus, strength, and electrical conductivity are large parallel to the fiber axis, while the same properties measured transverse to that direction are an order of magnitude smaller. Conversely, the thermal expansion coefficient is small parallel to the fiber axis, but much larger perpendicular to it (ref. 2).

Carbon-carbon (CC) composites are fabricated by infiltrating a carbon precursor into a preform of carbon fibers. Chemical vapor infiltration (CVI) directly produces a carbon fiber-reinforced composite at approximately 1000°C. Alternatively, similar materials can be formed by heating pitch or resin matrix composites to a temperature of about 1000°C. This process eliminates volatile elements from the matrix and "carbonizes" it. The appreciable matrix shrinkage that occurs during carbonization generates pores and cracks. Differences between the coefficient of thermal expansion of the fibers and matrix also generate internal stresses and stress cracks on cooling (ref. 3). The carbonized solid therefore exhibits a low density that must be increased to the desired level either by reinfiltration with and carbonization of additional matrix precursor or by CVI with carbon. This process is repeated until an acceptable composite density is obtained (ref. 4). Multiple cycles of CVI are also necessary in order to densify the solid. Surface machining has to be included in the process since, in most cases, a thick surface layer is formed which tends to prevent diffusion of the hydrocarbon gas into the internal regions of the preform.

If the composite is to be used at very high temperatures, the material may be graphitized by heating above 2000°C. Both the fibers and the matrix materials then exhibit increasing graphite-like properties.

The graphitic form of carbon has a hexagonal crystal structure in which each carbon atom is associated with four valence electrons, three of which form tight covalent bonds with neighboring atoms; the fourth is more loosely bound. Since each carbon atom is surrounded by three neighbors at equal distances in a single plane, a hexagonal ring structure results. The layers formed by these rings are primarily bonded together by van der Waals forces that are much weaker than the covalent bonds. Adjacent atoms in any layer are closer (1.42 A) than the spacing (3.35 A) between layers. This atomic configuration results in extreme anisotropy in the crystal structure. Graphite is unique among engineering materials in that parallel to the basal planes, its specific elastic modulus (modulus/weight ratio) is the largest known, while much lower values of the same property are recorded normal to these planes (ref. 2).

Carbon fibers, when arranged unidirectionally in any carbon matrix, produce a solid that exhibits anisotropic mechanical properties. In this case, since the fibers take most of the load, both the stiffness and strength of the composite are large when measured parallel to the fibers but are small when measured perpendicular to them. In addition, the composite becomes tough because a pseudo-plasticity is exhibited if debonding of the fibers and matrix occurs during failure. The frictional resistance of pulling the fibers out of the matrix behind the crack front then contributes to the work of fracture.

Fibers can be aligned unidirectionally, multidirectionally. or they can be present as various fiber weaves; these include braided yarns, stacked two-dimensional (2-D) fabrics, orthogonal fabrics, or multidirectional weaves. An important variable that influences the properties of CC composites is the volume fraction of fibers relative to the carbon matrix. Generally, the higher the volume fraction of strong/stiff fibers in a matrix, the greater the strength and stiffness of the composite. The type of weave can vary, with those more commonly used consisting of either a plain weave or a harness satin weave (ref. 5). The harness satin weaves allow a higher volume fraction of fibers and usually produce higher strengths due to the floating yarns (refs. 4 and 5). Carbon-carbon composites are generally considered among the most competitive materials in structures designed for use at high temperature. Unfortunately, although their stability is extremely good in nonaggressive mediums, their performance quickly degrades if oxidation occurs (refs. 6 and 7).

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