MateriaIs & Design, Vol. 18, No. 1, pp. 11-15.

1997
0 1997 Elsevier Science Ltd
ELSEVIER Printed in Great Britain. All rights reserved
0261-3069/97 $17.00 + 0.00
PII: SO261-3069(97MOO24-1

Carbon-carbon composites: a summary of

recent developments and applications
Torsten Windhorst, Gordon Blount*

Coventry University, School of Engineering, Priory Street, Coventry CVI 5FB, UK

Received 4 March 1997; accepted 21 April 1997

Carbon Fibre Reinforced Carbon (CFRC), or Carbon-carbon, is a unique composite material consist-
ing of carbon fibres embedded in a carbonaceous matrix. Originally developed for aerospace
applications, its low density, high thermal conductivity and excellent mechanical properties at elevated
temperatures make it an ideal material for aircraft brakes, rocket nozzles and re-entry nose tips. It
withstands temperatures in excess of 2000°C without major deformation. The properties are very
much dependent on the manufacturing methods used for production. Although the general production
technology is known, the combination of processes to achieve specially tailored properties remains the
expertise of particular manufacturers. This paper reviews major developments of Carbon-carbon
composites and describes actual and future applications. Improved oxidation resistance and continu-
ously decreasing manufacturing costs make this family of materials more and more attractive to high
performance applications as well as for general engineering design. 0 1997 Elsevier Science Ltd

Keywords: carbon matrix composites (A); fibres and filaments (B); thermal properties (E)

Introduction commercial supersonic passenger airliner by Dunlop in

Carbon-carbon composites are a family of advanced
composite materials. They are the most advanced form
of carbon and consist of a fibre based on carbon
precursors embedded in a carbon matrix. This unique
composition gives them such properties as low density,
high thermal conductivity and shock resistance, low
thermal expansion and high modulus. Carbon-carbon
is mostly used in aerospace applications, mainly for
aircraft disc brakes, rocket re-entry nose tips and for
parts of rocket nozzles. The unique features and an
advanced manufacturing technology which leads to a
cheaper production process make this material more
and more available for industrial applications.
Carbon-carbon composites were initially developed
for the American defence and space industry, which
was funded by the American government. They were
subject on restrictions and dissemination, in particular
to foreign countries. Brennan Forcht of Chance Vought
Aircraft is generally credited as the discoverer of this
material, which was first developed in 1958. In the mid
1960s the first rayon-based materials with acceptable
tensile strength were developed. In 1969 the first high
performance and lower cost polyacrylonitrile (PAN)-
based fibres were commercialised and gradually re-
placed rayon. The material was identified as friction
material for aircraft brakes and fitted to the Concorde
*Correspondence to Prof. G. BIount. Tel.: f44
+ 44 1203 838272.
1974l. Further research led to standard installation of
carbon brakes in about 50 aircraft types. Graphitic
pitch-based carbon fibres with ultra-high moduli values
and very high thermal and electrical conductance val-
ues became available in 1982. Today, PAN-based car-
bon fibres are the dominant reinforcement used in
Carbon-carbon composites.
There are about 40 companies in the world dealing
with some form of carbon-carbon composites. The
major market share is kept by American companies
followed by French and British companies. Other coun-
tries with more focus on industrial rather than aeros-
pace and military applications are Germany and Japan*.
Manufacturing and machining
The fabrication of carbon-carbon composites consists
mainly of producing the fibre precursor and then densi-
fying this with the carbon matrix. The principles of the
manufacturing process used in laboratories are well
documented’-‘, but the technology used in production
is normally regarded as confidential. The basic routes
and precursor materials for production are the same
for all carbon-carbon materials, but details of the
techniques used are known only to the manufacturer.
The fibres are based on rayon, PAN or pitch, where
1203 838829; fax: PAN-based fibres are the most widely used. Rayon was
the first precursor to be used in carbon-carbon pro-

Materials & Design Volume 18 Number 1 1997 11

Carbon-carbon composites: T. Windhorsf and G. Blounf
Figure 1 Bi-directional woven fibres.
duction but the properties which can be achieved with
rayon are far lower than with the other precursors.
Pitch-based fibres lead to high level properties but
their use is limited by the high price and the limited
number of suppliers. Fibres are usually woven in ap-
propriate directions to tailor specific properties. Neu-
meister 3 investigated the mechanical performance of
carbon-carbon composites with different fibre archi-
tecture. The result of this research programme was
that, although unidirectional non-woven composites had
the highest tensile strength, woven material behaved
more consistently and showed less variation in proper-
ties. Figure I shows an example of a bi-directional
woven fibre. The fibre content is in the range between
20-60% by volume depending on the properties to be
achieved and the manufacturing processes used. Before
impregnation, oxidized PAN- and resin-based fibres are
carbonized at > 1000°C in an inert atmosphere (e.g.
argon) or vacuum to convert the fibres to carbon.
Matrices are carbon-containing substances which are
in the form of either liquid or gas. Liquid matrices are
either resin-based or pitch-based and three processes
for impregnation are used4:
1. Liquid Phase Impregnation (LPI)
2. Hot Isostatic Pressure Impregnation Carbonization
(HIP10
3. Hot Pressing.
Before liquid impregnation the fibres are pre-im-
pregnated with resin or pitch and carbonized at
350-850°C. A pressure of up to 100 MPa can be
applied which increases the carbon yield up to 90%.
Then the liquid impregnation processes vary signifi-
cantly.
In LPI a vacuum impregnation process adds more
pitch or resin to the composite which increases density
and interlaminar shear strength (ILSS). Intermediate
graphitization at 2200-3000°C opens the closing pores
again and further impregnation leads to higher density.
The impregnation process is typically repeated 3-6
times.
With HIPIC the material is carbonized/impregnated
at 650-1000°C at a pressure of 100 MPa. The high
pressure increases carbon yield and maintains more
volatile fractions of pitch in a condensed phase. The
composite is then graphitized at > 2000°C without
pressure. The HIPIC process produces carbon-carbon
12 Materials & Design Volume 18 Number 1 1997
composites with higher density than LPI but it is also
more expensive.
Hot Pressing (also called High Temperature Consoli-
dation) uses carbonization at either 650°C or lOOO”C,
depending on the matrix precursor. A pressure of up to
76 MPa can be applied in an inert, reducing or vacuum
atmosphere. Subsequent graphitization at 2200-3000°C
without pressure can lead to graphitization of ther-
mosetting resins, which are harder to graphitize than
pitch. The part thickness is reduced by 50% during
these processes. Figure 2 gives an overview of the
manufacturing processes used.
For impregnating carbon fibres with a matrix in the
form of gas Chemical Vapour Infiltration (CVI, or also
called Chemical Vapour Deposition, CVD> is used. At
700-2000°C hydrocarbon gas is impregnated into the
preforms, which can be prepregs (carbonized and
graphitized fibres) or dry wound fibres. Three CVI
methods are available:
1. Isothermal: the gas and sample kept at uniform
temperature; several cycles are necessary and the
surface is skinned in-between cycles
2. Temperature gradient: use of induction furnace,
deposition of carbon first inside the sample; process
is limited to one single sample per operation
3. Pressure gradient: a hydrocarbon gas impinges on
the inside surface of the sample, the gas pressure
inside the sample is higher than outside; also
limited to single sample and not widely used.
The CVI process achieves a low rate of carbon
deposition, but the carbon is harder than carbon from
pitch or resin. Most aircraft brake materials are pro-
duced by this method.
Further graphitization of the composites is possible
to enhance thermal conductivity. It will result in a
decrease in mechanical properties. The processes de-
scribed above, especially CVI, need several weeks. The
time consumption combined with the high pressures
and temperatures needed make the material relatively
expensive.
Gxidation of carbon-carbon composites is a real
problem above 320°C. It attacks the fibre-matrix inter-
face and weakens the fibre bundles. A combination of
four methods can be used to counter this5.
1. Sic coating of the outer composite surface.
2. Internal protection by oxidation inhibitors intro-
duced in the matrix during lay up and densification.
3. Glassy sealant on top of the Sic coating.
4. Sic or Si,Ni, overlayer on glassy layer.
The addition of glass-forming additives like boron,
silicon carbide and zirconium boride reduce the reac-
tivity with air.
Machining of carbon-carbon composites is a com-
plex area, especially as companies are keen to keep
their knowledge under secrecy. Turning and especially
thread cutting is a problem, as the fibres and fibre
direction result in an uneven cutting force and high
tool wear. Diamond tipped cutting tools or silicon
carbide tools are commonly used. Lubrication is nor-
mally not required, as the carbon is self-lubricating.
Other cooling liquids than water would probably influ-
 PRECURSORS

4
PrePreparation

I I I
LPI HIPIC Hot
Pressing

I Vacuum
Impregnation

/
Carbonization/
Impregnation

+
Carbonization

Carbon-Carbon Composite
Figure 2 Carbon-carbon manufacturing processes.

ence the later use of the high temperature
they contain oil.
Properties
The properties are very much dependent on the manu-
facturing processes used, on the raw materials and on
additional treatments such as fibre surface modification
or inclusion of oxidation protection. Considerable
changes in roperties can be achieved by varying these
parameters r9’. Table I shows the range of properties
that can be achieved and for comparison those of
ferritic steel and titanium alloys. The properties for
carbon-carbon are given in the fibre direction. Perpen-
dicular to the fibres, the properties are much less
superior.
Carbon-carbon composites have the capability of
structural integrity at temperatures above 1000°C.
Compared to other composite materials, carbon-carbon
has a very high thermal conductivity. The thermal and
material, as electrical conductivity are 12-15 times higher in the
fibre direction than perpendicular to the fibres.
The mechanical properties are much superior to
those of conventional graphite. In particular three-di-
mensional carbon-carbon composites can be tailored
to withstand damage and minimum delamination crack
growth under interlaminar shearing.
The tensile strength increases above 1200°C when
conventional superalloy components start to weaken;
the density is only about 1.9 g cme3 compared with 8 g
cme3 for superalloys and in the event of failure the
material does not disintegrate catastrophically, but goes
through a gradual failure that has been called graceful
failure.
Heat treatment temperature has a significant effect
on the mechanical properties. When carbonized at
1000°C upon subsequent graphitization at 2700°C the
material shows a 54% increase in the flexural strength,
a 40% decrease in the interlaminar shear strength and
a 93% increase in the flexural modulus. The choice of
the graphitization temperature affects the toughness of
the composite. The tensile and flexural properties of

Table 1 Range of properties for Carbon-carbon composites

Property Unit Carbon-carbon Ferritic steel Titanium alloys
Compressive strength MPa 100-150 240-400 130-1400
Density g cme3 1.3-2.5 7.5-7.7 4.38-4.82
Tensile strength MPa up to 900 500-800 241-1280
Thermal expansion K-1 -2-2 x 10-6 12-15 x 10-6 7.9-9.8 x lo-”
Thermal conductivity W m-’ K-’ 20-150 23-27 4-21.9
Thermal shock resistance W mm-’ 150-170 5.5 N/A
Young’s modulus GPa up to 300 200-205 95-125

Materials & Design Volume 18 Number 1 1997 13

Carbon-carbon composites: T. Windhorst and G. Bfount
carbon-carbon composites are fibre-dominated,
whereas the compression behaviour is mainly affected
by density and matrix morphologies. The effect of
surface treatment is significant on the mechanical
properties of the resulting composites. Surface-treated
fibres that have strong bonding with the polymer ex-
hibit high flexural strength in polymer composites, but
result in carbonized composites of poor flexural
strength. For graphitized composites, the flexural
strength increases monotonically with increasing treat-
ment time.
Carbon-carbon composites with high thermal con-
ductivity are important for first wall components for
nuclear fusion reactors, hypersonic aircraft, missiles
and spacecraft, thermal radiator panels and electronic
heat sinks. The thermal conductivity at > 1000°C in-
creases with the heat treatment temperature, particu-
larly above 28OO”C, as more graphitic carbon is associ-
ated with a higher thermai conductivity.
There is one major drawback, however, and that is its
susceptibility to oxidation above 500°C which becomes
progressively more severe as the temperature rises
until, at about BOOC, the rate of oxidation is limited
only by the diffusion rate of oxygen through the sur-
rounding gas to the carbon surface. In certain ‘one-off
applications like rocket motors this is not very impor-
tant; however, in space plane and as turbine engine
material the development of extended lifetimes of
around 100 h is required.
Recyclability of carbon-carbon composites is an-
other problem that manufacturers are dealing with. In
many cases it is possible to re-use material that is
wasted during the manufacturing process, but there is
no method to recycle material that has been in service.
Some research programmes focus on more common
materials like thermoplastic matrix composites, but up
to now there is no method to recycle carbon-carbon
composites.
Applications
Although the specific strength and thermal properties
of carbon-carbon make it the ideal material for high
temperature applications, its use has been restricted by
two major factors: the high costs and the susceptibility
to oxidation. With more than 60% by volume, aircraft
disc brakes are the main application. Compared to a
steel brake, carbon-carbon has a 2.5 higher heat capac-
ity, reduces the weight by 40% and doubles the service
life. Other main applications are re-entry heat shields
for space vehicles and missiles and rocket nozzles.
Since the first use of carbon-carbon in aircraft brakes
in 1974, major research programmes have led to new
applications, of which some are:
1. Racing car brakes and clutches*
2. Hot glass transfer elements
3. Protective shielding
4. Vacuum/inert gas furnace insulation
5. Hot pressing moulds
6. Metal sintering trays
14 Materials & Design Volume 18 Number 1 1997
7. Electronic circuit board thermal planes
8. Semiconductor manufacturing components.
Although the load bearing ability of carbon-carbon at
room temperature is not as high as that of metals, it is
superior at high temperatures. This makes it the first
choice for high temperature mechanical fasteners,
where this material also saves weight. In braking appli-
cations it is not the frictional behaviour that is of major
interest but the ability to absorb and conduct large
quantities of heat in a very short period of time without
damaging the brake assembly.
For biomedical devices carbon-carbon is used for
prosthetic implants such as hip joint replacements and
it has been tested in artificial hearts for animals. It is
considered to be ‘bio-active’, as it is compatible with
blood, bones and soft tissue and properties can be
tailored to be close to those of bones. Other future
applications where this material can be considered are
protective shielding against X-ray and laser, and parts
in gas turbine engines such as flaps, seals, liners, vanes
and tailcones. Its high purity and its resistance to heat
and ionising radiation make it a possible material for
the nuclear industry, it is already being used in the JET
(Joint European Torus) fusion reactor.
Due to the secrecy and price of carbon-carbon com-
posites, applications have been mainly restricted to
military and aerospace use. This is about to change as
improved manufacturing facilities and the increased
amount of applications reduce the price permanently.
The price varies significantly with the manufacturing
methods and precursor materials and can be con-
sidered currently at around &300 per kg for a medium
priced material. Most manufacturers who exclusively
served the military market are now expanding their
knowledge into the civilian market. This offers new
possibilities in major industries such as car manufactur-
ing, where carbon-carbon could be used as a brake
material or for engine pistons.
Conclusions
Carbon-carbon composites are an advanced composite
with superior thermal properties. It is currently the
ultimate material for brakes and other high perfor-
mance applications. The manufacturing process is very
cost intensive as high temperatures and high pressures
are required. The main factors influencing the quality
are:
. the quality of polymer matrix composite from which
carbon-carbon is made
. the choice of pitch as it affects carbon yield
l the use of resin
. the choice of carbon fibre
. the microstructure of mesophase (pitch-based)
. the weave pattern of carbon fabric
. fibre matrix bond strength
. carbonization method/medium
. surface treatment of carbon fibres.
 Carbon-carbon composites: T. Windhorst and G. Blount

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Materials & Design Volume 18 Number 1 1997 15