Sādhanā Vol. 28, Parts 1 & 2, February/April 2003, pp. 349–358.

© Printed in India

High performance carbon–carbon composites

LALIT M MANOCHA
Department of Materials Science, Sardar Patel University, Vallabh Vidyanagar
388 120, India

Abstract. Carbon–carbon composites rank first among ceramic composite mate-

rials with a spectrum of properties and applications in various sectors. These com-
posites are made of fibres in various directions and carbonaceous polymers and
hydrocarbons as matrix precursors. Their density and properties depend on the type
and volume fraction of reinforcement, matrix precursor used and end heat treatment
temperature. Composites made with thermosetting resins as matrix precursors pos-
sess low densities (1·55–1·75 g/cm3 ) and well-distributed microporosity whereas
those made with pitch as the matrix precursor, after densification exhibit densities
of 1·8–2·0 g/cm3 with some mesopores, and those made by the CVD technique
with hydrocarbon gases, possess intermediate densities and matrices with close
porosities. The former (resin-based) composites exhibit high flexural strength, low
toughness and low thermal conductivity, whereas the latter (pitch- and CVD-based)
can be made with very high thermal conductivity (400–700 W/MK) in the fibre
direction. Carbon–carbon composites are used in a variety of sectors requiring high
mechanical properties at elevated temperatures, good frictional properties for brake
pads in high speed vehicles or high thermal conductivity for thermal management
applications. However, for extended life applications, these composites need to be
protected against oxidation either through matrix modification with Si, Zr, Hf etc.
or by multilayer oxidation protection coatings consisting of SiC, silica, zircon etc.

Keywords. Carbon fibres; carbon–carbon composites; high temperature mate-

rials; mechanical/thermal properties.

1. Carbon–carbon concept

Carbon is a truly remarkable element existing as four allotropes, viz. diamond, graphite,
carbynes and fullerenes, each having significant scientific and technological importance. Its
most abundant allotrope, graphite, can take many forms with respect to microstructure, amor-
phous to highly crystalline structure, highly dense with density 2·2 g/cm3 to highly porous
with density 0·5 g/cm3 and different shapes. These types of graphites are called synthetic car-
bons and in technical terms, engineered carbons. Examples are cokes, graphite electrodes,
mechanical carbons, glassy carbons, carbon black, porous carbons, activated carbons, car-
bon fibres and composites etc.. Solid carbons are preferred for structural applications under
extreme environmental conditions of temperature or corrosion (liquid as well as gaseous) etc.
This is mainly because, theoretically, carbon materials with covalently bonded atoms pos-
sess very high specific strengths (40–50 GPa) and retain this strength at high temperatures

349
350 Lalit M Manocha

Current PAN-based fibres

6
Current mesophase-pitch-based fibres
(High performance)
Fibre tensile strength, GPa

1 Mesophase-pitch-based fibres
Isotropic-pitch-based fibres Figure 1. Mechanical proper-
(Textron) (General purpose)
ties of commercial PAN-based
0
0 100 200 300 400 500 600 700 800 900 1000 and mesophase pitch-based car-
Fibre modulus, GPa bon fibres.

in the temperature range over 1500◦ C (Pierson 1993; Burchell 1999). However, the normal
bulk synthetic graphite exhibits less than 2% of the theoretical strength. Therefore, for long
there has been a quest by scientists to explore and achieve the maximum possible strength in
carbon materials. This, coupled with the requirement of high performance reinforcing fibres
for composite materials, had led to the development of carbon fibres (Fitzer 1989).
Over the past three decades, carbon fibres have proved to be the main reinforcement for
advanced composites for a wide range of applications. The majority of products still belong
to high technology space and aeronautics (Manocha 2001). Carbon fibres are a few micron
thick, light weight, very strong and stiff black synthetic fibres with long aromatic molecular
chains comprising mainly carbon. These fibres are capable of maintaining their structure and
properties under extreme conditions of temperature and pressure, fluids etc. and therefore can
be used with all types of matrices, polymer, ceramic and metal, employing different composite
processing techniques. Interest in carbon fibres as reinforcement for composites for structural
applications started with the demand from the aeronautical sector for light weight strong and
stiff material. Subsequently its application extended to civilian sector, especially in sports
goods and biomedical sectors (Edie 1998). Though major consumption of carbon fibres is for
polymer matrix composites, these are the only choice materials for special application high
temperature composites with specific high thermal and thermo-mechanical properties. This
kept alive the interest in carbon and carbon fibre research. Presently a large variety of car-
bon fibres derived from PAN (polyacrylonitrile polymers) and pitch precursors with varying
properties are available, some in the open market and some for restricted sale. Figure 1 shows
present status of these fibres. However, the properties are getting continuously upgraded.
Carbon fibre reinforced carbon matrix composites or the so called carbon–carbon (C/C)
composites have densities in the range 1·6–2·0 gm/cm3 , much lower than those of metals
and ceramics and hence make lower component weight an important consideration for aero-
vehicales (Buckley 1988; Fitzer & Manocha 1998). Some of the most important and useful
properties of carbon–carbon composites are light weight, high strength at high temperature
(3000◦ C) in non-oxidising atmospheres, low coefficient of thermal expansion, high thermal
conductivity (higher than that of copper and silver), high thermal shock resistance and low
recession in high pressure ablation environments. The mechanical strength of C/C increases
with temperature, in contrast to the strength of metal and ceramics, which decrease with
 High performance carbon–carbon composites 351

Figure 2. Variation of strength

of some engineering materials with
temperature.

increasing temperature (see figure 2). These extraordinary properties of carbon/carbon com-
posites have made these materials extremely useful right for aerospace and defence applica-
tions such as brake discs, rocket nozzles, leading edges of re-entry vehicles, furnace heat-
ing, thermal management components in space vehicles etc. to those for common man as
biomedical implants, glass and high temperature glass and ceramic industry etc. (Fitzer &
Manocha 1998). A well-known example for the practical application of C/C composites is
in the American Space shuttle, wherein the fuselage nose and the leading edge of the wings
are manufactured from C/C composites and have withstood a total of 100 missions under the
extreme re-entry condition (Kochendorfer 2001). A national programme has been launched
in India for indigenous development of carbon/carbon composite and related technologies.
These composites have been successfully developed and used as nose-tip for the Agni missile
and as brake pads for LCA.

2. Processing of carbon/carbon composites

Like carbon, carbon–carbon composites can also be manufactured by using different tech-
niques such as all solid pyrolysis using thermosetting resins, or pitch route using liquid infil-
tration carbonization route or CVD route. Fabrication method of C/C composites involves
fabrication of a 3D (three directionally reinforced) or MD porous carbon fibre preforms hav-
ing the desired shape or a porous carbon–carbon skeleton (UD, 2D or 3D) with carbon fibres
and a carbonaceous matrix followed by their densification (see figure 3). The densification
can be achieved through vapour phase infiltration (CVI) wherein the hydrocarbon gases such
as methane, propane etc. infiltrate into porous fibrous structure heated to a temperature of
1000–1400◦ C and are made to crack therein. Commercially, isothermally heated stack of com-
ponents are impregnated simultaneously in a large-size furnace. Principally, the gases should
infiltrate into the pores and interfilamentary spaces and then crack. But these gases have a ten-
dency to crack at the outer surface itself which blocks the passeges and causes closed pores.
In order to have dense composites, the surfaces are ground and the components are reinfil-
trated. CVD is a very slow process and it takes months together to get dense carbon–carbon
composites. Porous structures can also be impregnated with liquid phase pitch/phenolic resin
followed by carbonisation and high temperature heat treatment (1000–2700◦ C). Pyrolysis
of the pitch/resin matrix can be done under normal pressure or under high pressure (HIP).
352 Lalit M Manocha

Reinforcement (Carbon Fibre; 1-D, 2-D, 3-D, n-D)

Thermosetting Thermoplastic Hydrocarbon

Resin Pitch Vapour

Liquid Phase
Solid Phase Vapour Phase
Pyrolysis
Pyrolysis Pyrolysis
with/without pressure
1000-1500oC 800-1200oC
550-800oC

1-4 times
Impregnation Impregnation
Impregnation

1-4 times Carbonize

1000-1500oC
1-3 times

Heat Treatment Heat Treatment Heat Treatment

1500-2200oC 2200-2750oC 2000-2500oC

Carbon-Carbon Composite

Figure 3. Processing of carbon/carbon composites.

Depending on the densification approach, two or more densification cycles are required to get
the desired density, the number of impregnation cycles being fewer when HIP processes is
used. A new approach of intermediate graphitisation has been evolved in which the compos-
ites after certain impregnation/normal pressure carbonisation cycles are heat-treated to high
temperature and then reimpregnated. This intermediate high temperature heat treatment opens
up the pores for further infiltration. Figure 4 shows generic comparison of densification pro-
cesses. Often a combination of processing routes is used. These comprise fabrication of host
composites using a pitch or resin route followed by densification and pore sealing by CVD.

3. Structural aspects of carbon–carbon composites

Prime factors of importance in achieving tough and high thermal conductive carbon/carbon
composites are proper choice of reinforcing carbon fibres, carbon matrix microstructure,
density and macrostructure of the composites. Processing routes and the choice of carbon
precursor greatly influence the density, macrostructure (type, size and quantities of defects i.e.,
defects, pores, cracks etc.) and matrix microstructure (orientation of graphitic planes). Some
of these striking structural features of carbon/carbon composites are listed in table 1 and are
shown in the SEM micrograph of the composites (see figure 5). The voids and macrocracks are
normally fewer in pitch-derived C/C composites processed through HIP route than in those
made by CVD route or phenolic resin derived carbon route. The latter exhibit low densities.
These features also controll the thermal transport mechanism in carbon–carbon composites. In
order to have desired fibre/matrix bonding and to reduce cracking at the fibre/matrix interface,
pyrolytic carbon coatings are also used at the surface of the fibres.
 High performance carbon–carbon composites 353

g/cm3 C

1.9

B
1.8

1.7

A
1.6

1.5
Density

1.4 A - impregnation carbonisation at

normal pressure
B - intermediate graphitisation
1.3 C - pressure impregnation
carbonization

1.2

1.1
0.7
2 4 6 8 10 12 14 Figure 4. Increase in density of carbon/
Densification cycle carbon composites with densification.

The matrix microstructure (degree of graphitisation) is also an important aspect governing

the properties of carbon–carbon composites. From the strength point of view, a semicrystalline
or randomly oriented carbon matrix is desired which can arrest crack propagation whereas for
thermal and electrical properties, highly graphitic matrix is a prerequisite. The development
of crystalline carbon matrix originates from CVD route or pitch route. Thermosetting polymer
route result in amorphous carbon matrix. However, in composites made with high strength
carbon fibres or surface treated carbon fibres, due to strong fibre/matrix bonding at polymer
stage and differential pyrolysis shrinkage in fibres and matrix, thermal stresses are generated

Table 1. Micro/macrostructural features of carbon/carbon composites and their effect on

composites properties.

Nature Scale Position Effect

Micromechanical Fibre Cracking in matrix Load transfer among fibres

cracking dia scale Fibre/matrix interface Transverse properties of
fibre bundles
Minimechanical Cloth layer Fibre bundle Porosity
cracking thickness Interface between Load transfer among fibre
scale fibre bundles bundles and laminaes
Interyarn pocket of Major influence on
unreinforced matrix mechanical & thermal
Interface between fibre properties
bundle and matrix pocket
Matrix-matrix interface
354 Lalit M Manocha

Figure 5. SEM micrograph of a 2D car-

bon/carbon composite.

in the matrix which on heat treatment to 2000◦ C and above cause stress graphitisation of the
matrix (Rand 1993; Manocha 1994; Fitzer & Manocha 1998). This subject has been of great
scientific interest, especially correlating fibre/matrix bonding and resulting orientation of
graphite basic structural units in the matrix. The technological importance of this phenomenon
has been to control the fibre/matrix bonding so that low priced carbon fibres can be used for
making carbon/carbon composites for mechanical and general purpose application.

4. Properties of carbon–carbon composites

Carbon/carbon composites in the true sense, cover a large range of materials with the tar-
getted properties. The properties of interest are strength and stiffness, fracture toughness,
frictional properties, thermal conductivity and resistance to oxidation at high temperatures.
The operating mechanisms for these properties are quite different, especially in such multi-
phase composite materials. The mechanical properties of the constituents and their volume
fraction, bonding, and crack propagation mechanism control the mechanical properties of
the composites, whereas thermal properties are governed by thermal transport phenomena.
Moreover, the constituents, both reinforcement and matrix, are likely to undergo a change in
properties during processing as influenced by heat treatment temperature, differential dimen-
sional changes, thermal stresses etc. All these factors influence the ultimate properties of the
composites. It is difficult to cover completely all these aspects in this article. However, a gen-
eral trend of the most fascinating properties of carbon/carbon composites are given below.

4.1 Mechanical properties of carbon–carbon composites

The strength and fracture of carbon/carbon composites are governed by the Cook–Gorden
theory for strengthening of brittle solids (Cook & Gorden 1964), which states that if the
ratio of the adhesive strength of the interface to the cohesive strength of the solid is in
the right range, a large increase in strength and toughness of otherwise brittle material is
achieved. Extensive work has been done in achieving highest possible translation of fibre
properties in carbon/carbon composites. Composites with strong fibre/matrix bonding fail
 High performance carbon–carbon composites 355

Matrix dominated Mixed mode Fibre dominated

failure failure failure
Small
Tensile strength

Large

Figure 6. Effect of heat treatment tem-

perature on strength and fracture mode
1100 1600 2100 2400 of carbon/carbon composites – a general
Heat treatment temperature (oC) view.

catastrophically without fibre pull-out while those with controlled interface fail in mixed
tensile cum shear mode exhibiting high strength (Manocha 1988, 1994). A generalised view
of the effect of processing temperature, on fracture modes and strengths of different types of
carbon/carbon composites is given in figure 6. Numerical values of the mechanical properties
of the composites are dependent on the fibre architecture and the direction of measurement
of the properties w.r.t. fibre orientation etc. as shown in figure 7. Other architectures and fibre
lay-ups (angle-plied, sandwiched) have similar effects and the values lie in-between (Fitzer &
Manocha 1998). Similarly, these composites exhibit a range of high fracture toughness (20–
100 Nm m3/2 ) and good creep and fatigue resistance. When subjected to high temperature
testing, carbon/carbon composites have been found to exhibit about 10–20% increase in
mechanical properties at 2000◦ C under inert atmosphere. However, in air, the properties drop
down to 10–20% depending on the temperature and time i.e. the weight loss. Carbon is a stable
and highly sought after material for nuclear applications. So are carbon/carbon composites.
Under neutron irradiation at low fluence levels of 1021 n/cm2 , these composites exhibit an
increase in strength and fracture toughness by 20–30% and Young’s modulus by about 30%.

4.2 Thermal properties of the composites

Carbon/carbon composites being of heterogeneous structure consisting of fibres, matrix and
pores, with the first two having a variety of microstructures, estimation of their thermal trans-

Figure 7. Strength of carbon–

carbon composites with fibre
orientation.
356 Lalit M Manocha

W/mK
300
In-plane
direction
Thermal conductivity, RT

200

100 Across-ply
direction

0 Figure 8. Thermal conducti-

Pan- Pan- Pitch- Pitch- Pan- Pan- Pitch-
resin pitch pitch cvd resin pitch pitch vity of carbon/carbon composites
with different fibre/matrix combi-
Fibre type-matrix precursor nations.

port properties becomes complex. However, carbon/carbon materials with tailored thermal
conductivities can be fabricated by proper choice of constituents, their configuration, and
processing conditions. A comparison of thermal conductivities of carbon/carbon composites
with different fibre/matrix combinations is given in figure 8. Composites having highly ori-
ented graphitic fibres or matrices or their combination, like vapour-grown carbon fibres and
matrix or mesophase pitch-based carbon fibres and matrix, exhibit very high thermal con-
ductivities of the order of 250–350 W/MK in the fibre direction. Though these composites
exhibit highly anisotropic character and low conductivities in transverse directions, there is
always scope of improvement by varying the fibre architecture and their addition in different
forms and ways. Coefficient of thermal expansion of the composites is dictated largely by
the fibre orientation. It is 0–1 ppm/◦ C in the fibre direction and 6–8 ppm/◦ C in a direction
perpendicular to the fibres.

4.3 Frictional properties of the composites

Carbon–carbon composites have widened the scope of application of carbon-based materi-
als in wear-related applications from bearing seals and electrical brushes to brake pads for
heavy duty vehicles such as military, supersonic and civilian aircrafts to trucks and railways.
This has been due to basic tribological properties of carbon with additional high strength
and thermal conductivity contribution from the reinforcing fibres. Carbon/carbon compos-
ites exhibit low coefficient of friction µ in the fibre direction (0·3–0·5) and 0·5–0·8 in the
perpendicular direction. Wear rates also follow similar trends (0·05–0·1 and 0·1–0·3 mm).
The friction and wear mechanism of carbon/carbon composites on application of brakes is
quite complex and various factors like peak temperature, formation of debris and films on
sliding surfaces further effect the coefficient of friction etc. which is too vast to cover here.
In general, for fabricating brake discs for different vehicles, different types of fibres (PAN
and pitch-based high strength and high thermal conductivity) are used in a number of config-
urations, either alone or in combinations with carbon matrix derived from different type of
precursor, pitch or CVD. In commercial carbon–carbon brake pads, carbon fibre fabric plies
are used with fibre tows inserted in the third direction and pitch/CVD route for densifica-
tion. However, choice of the constituents and processing parameters is at the discretion of the
manufacturers.
 High performance carbon–carbon composites 357

5. Oxidation protection of carbon/carbon composites

Carbon is prone to reaction with oxygen at temperature of 450◦ C and above. For long time
application of these composites at elevated temperature in a normal environment, it is essen-
tial that these composites be protected against oxidation. Therefore studies on oxidation
protection of carbon/carbon composites are as important as the development of the compos-
ites themselves. Oxidation protection systems for carbon/carbon composites are based on (i)
modification of matrix through addition of some oxidation inhibitors (like B, Si, Zr or their
compounds) or/and (ii) deposition of ceramic coatings on the surface. These coatings are gen-
erally multilayer coatings of functionally gradient materials of carbides, nitrides and oxides
of Si, Zr, Ta, Al etc. (Mckee 1981; Fitzer & Manocha 1998)

6. Applications of carbon/carbon composites

Carbon/carbon composites, developed about three decades ago to meet the needs of the space
programme, are nowadays considered high performance engineering materials with potential
application in high temperature industries. Accordingly, steady growth also prevails in the
civil market segment. In terms of mass consumption, the main application of carbon/carbon
composites are still in high performance braking systems. New innovations still owe to
requirements from space industries. In general engineering sectors these are used in engine
components, as refractory materials, as hot-pressed dies and heating elements, as high tem-
perature fasteners, liners and protection tubes, as guides in glass industries etc. Some of the
applications are shown in figure 9. Carbon/carbon composites have great potential in energy

(a) (b)

(c) (d)

Figure 9. Carbon/carbon composite components. (a) carbon–carbon brake discs, (b) turbine rotor,
(c) resistance-heating elements, (d) protection tubes and grids.
358 Lalit M Manocha

sectors as polar plates for fuel cells, in storage batteries etc. As the technology becomes more
economical a viable, more and more applications get evolved.

7. Conclusions

With carbon fibre reinforcements in different forms and directions and thermosetting resins or
thermoplastic pitches or hydrocarbon gases as matrix precursors, these composites can attain
densities between 1·6–1·98 g/cm3 . Reinforcing fibres are more anisotropic in structure and
properties than the carbon matrix. Accordingly, the properties of carbon–carbon composites
are dependent on fibre volume content and fibre orientation. Unlike polymer matrices, car-
bon matrices contribute significantly to the ultimate properties of the composites, especially
in case of pitch and CVD-derived carbon matrices. Carbon–carbon composites are a family
of materials with choice of variation in fibre and matrix architecture, structure, microstruc-
ture, mechanical, thermal and physical properties etc. Hence these provide high performance
materials for application in a number of sectors.

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