Carbon-Carbon Composites

Carbon-Carbon Composites
• Carbon is a truly remarkable element existing in three
allotropic forms, namely, diamond, graphite, and fullerenes,
and each allotrope is having significant scientific and
technological importance .
• Carbon is a preferred material for structural applications,
where extreme environmental conditions such as high
temperature and corrosive liquids or gases are encountered.
• This is mainly due to its high strength, chemical inertness, and
ability to retain the strength at high temperatures above
1500°C.
• Bulk synthetic graphite has less than 2% of theoretical
strength. This requires the need for development of high
performance fibers for carbon composites which led to the
development of carbon fibers.
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 Carbon-Carbon Composites
• The judicious incorporation of these carbon fibers into
carbon matrix has led to the birth of carbon–carbon (C/C)
composite materials with improved properties.
• Carbon-based materials are one of the most promising
candidates for high-temperature applications because of
their intrinsic high thermal stability (>3000°C), low density
(<2.2 g cm−3), and increasing strength with temperature
up to 2500°C. (Closing of micro-cracks at interface).
• In its bulk form, its utility is limited for many applications
because of low strain-to-failure, high flaw sensitivity,
anisotropy (variations in properties) and difficulties in
fabricating large size, as well as complex-shaped
components.
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 Carbon-Carbon Composites
• The requirement for high-temperature mechanical properties
has led to the development of C/C composites by incorporating
carbon fibers.
• These composites generally consist of graphite fibers and
graphite matrix. The attractive properties of monolithic graphite
are combined with the high strength to create versatility of
composites in this new class of materials.
• The initial usage was limited to military applications, such as
rocket nozzles and missiles parts, due to the high cost of these
materials.
• The presence of carbon fibers in these materials makes them
stronger, tougher, and more resistant to thermal shock than
conventional graphite.
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 Carbon-Carbon Composites
• C/C composites are having high strength at high temperature
(up to 3000°C) under inert atmosphere, low coefficient of
thermal expansion (CTE), high thermal conductivity (higher
than that of copper and silver), good fatigue and creep
resistance and retain its resistance at high-temperature
ablation environments.
• The combination of low thermal expansion and high thermal
conductivity makes these composite materials resistant to
thermal shock.

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 Carbon-Carbon Composites
• The C/C composite components weight will be very low, which is
an important consideration for aerospace applications.
• The mechanical strength of C/C composites increases with
temperature, in contrast to the strength of most engineering
materials, in which the strength decreases with increasing
temperature.
• These extraordinary properties of C/C composites have made
them useful for aerospace and defense applications such as brake
disks, rocket nozzles, leading edges of re-entry vehicles, and
thermal management components in space vehicles. They are
also used in biomedical parts and glass and ceramic industries.

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 Carbon-Carbon Composites
• The variety of carbon fibers and multidirectional weaving
techniques now available allow tailoring the properties of
C/C composites to meet complex design requirements.
• The majority of applications are found in the aerospace
industry, and their application for missile nose tips, reentry
vehicle heat shields, and rocket nozzles.
• Another application that relies on their thermal
conductivity and tribological properties is aircraft brakes.

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 Carbon-Carbon Composites
• Apart from aircrafts, vehicles such as racing cars and high-speed
trains also benefit from C/C composite brakes.
• The specific applications necessitate different requirements, which
may be strength, stiffness, high thermal conductivity, low thermal
expansion, high wear resistance, or high toughness.
• These in turn influence the selection of fiber, the geometry of the
reinforcement, the choice of matrix material, and the processing
method.

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Aircraft disk brakes Car disk brakes
 Carbon-Carbon Composites
• Carbon Fiber Reinforcements
• The choice of carbon fiber (pan & pitch type), its surface
morphology and treatment, and the weave patterns are
also important and lead to a variety of processing options.
• The types of carbon fibers commercially available are
high-tensile, high-modulus, and intermediate-modulus
fibers. These fibers are prepared from pitch or
polyacrylonitrile (PAN).
• The rayon-based carbon fibers are used only in a few
specific applications, such as military or space structures.

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 Carbon-Carbon Composites
Typical multi-directional preforms for composites,
showing designed models (left) and photos of
fabricated object (right):
(a) 3D through-the-thickness interlock woven
preform
(b) 3D layer-by-layer interlock woven preform,
(c) 3D orthogonal woven preform,
(d) 3D rectangular 4-step braided preform,
(e) 3D cylindrical 4-step braided preform,
(f) 2D plain woven preform,
(g) 2D triaxial woven preform,
(h) honeycomb preform with hexagon cells, and
(i) Z-pinned sandwich preform consisting of 5
layers (top plain weave, 0° unidirectional lamina,
honeycomb with rectangular cells, 90°
unidirectional lamina, and bottom plain weave).

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 Carbon-Carbon Composites
• According to the loading conditions in different
directions, the C-fibers can be suitably aligned. However,
for cost-effective manufacturing, carbon fabrics are often
used, since they are now commercially available with
different weaving patterns.
• The transverse mechanical properties are low for the
composites fabricated using 2-D fabrics and thereby
limiting the load-bearing capacity in the transverse
direction, they are more commonly used than 3-D fiber
architectures.
• 3-D reinforcement architectures are mainly used in a few
critical applications in space or military structures.
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 Carbon-Carbon Composites
• The preform cost increases with the increasing number of desired
fiber directions. Therefore, commercially made C/C composites are
mostly based on 2-D fiber reinforcements.

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 Carbon-Carbon Composites
• Matrix Systems
• The carbon matrix in C/C composites has to effectively transfer the
mechanical loads to the fiber reinforcements, and the mechanical
strength of the matrix appears to be unimportant.
• However, the matrix is also a vitally important element as the
reinforcement in the C/C composites. It acts as a binder to maintain
the alignment of the fibers and fiber bundles and at the same time
isolates the fibers from one another.
• In particular, the failure behavior of the composite strongly depends
on the matrix microstructure.
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 Carbon-Carbon Composites
• Carbon matrix can exhibit a wide range of structures and textures
ranging from near amorphous to fully graphitic structure.
• These are controlled by the nature of the precursor material,
processing conditions, and the ultimate heat treatment temperature.
• The three types of matrix precursors used for C/C composites are
thermosetting resins, thermoplastics, and gaseous hydrocarbons.

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 Carbon-Carbon Composites
• Processing of C/C Composites
• Methods of introducing the carbon matrix into the preform include
impregnation with carbon organic liquid followed by pyrolysis and
CVI of carbon from a hydrocarbon precursor gas.
• In general, C/C composites are processed by any one of the
following three routes.
• CVI process
• Impregnation and pyrolysis using thermosetting resin precursors
• Impregnation and pyrolysis using thermoplastic pitch precursors
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 Carbon-Carbon Composites
• Generally the CVI process is carried out in the temperature range of 800°C–
1500°C, and the pyrolysis of the resin and pitch precursors is also carried out in
the same temperature range. Subsequent (final) heat treatment may involve
temperatures up to 3000°C.
• The CVI process lays down the carbon directly onto the fibers, whereas the
carbon is produced in the void between the fibers after a heat treatment from
the polymer precursors.
• The CVI process involves gas-phase pyrolysis of a hydrocarbon, such as methane,
propane, or natural gas. In this process, the gaseous hydrocarbon infiltrates into
the porous fiber preform heated to a temperature of 1000°C–1400°C and
deposits carbon on the fiber surface.

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Carbon-Carbon Composites

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 Carbon-Carbon Composites
• This CVI process can be carried out under isothermal and thermal
gradient or differential pressure conditions.
• At present C/C composites are produced commercially by the CVI
process, in which isothermally heated stack of components are
impregnated simultaneously in a large furnace.
• In principle, the gaseous reactants should infiltrate into the interfiber
space completely and then coat fiber preform.

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 Processing of Carbon-Carbon Composites

* Matrix material carried by the gas

↑ Carrier gas
Here, the gases and matrix material enter the reactor from the feed system at the bottom of
the reactor. The fibrous preform undergoes a chemical reaction at high temperature with the
matrix material and thus the latter infiltrates in the fiber or preform crevices. as the reaction
between fibre surface and the matrix material takes place, a coating of matrix is formed on the
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fibre surface.
Processing of Carbon-Carbon Composites

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Processing of Carbon-Carbon Composites

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Processing of Carbon-Carbon Composites

Types of ceramic matrix composites with process parameters

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 Properties of C/C Composites
• The main properties of interest in C/C composites are strength, stiffness, fracture toughness, wear
resistance, thermal conductivity, and resistance to oxidation at high temperatures.
• The mechanical properties of the constituents and their volume fraction, bonding, fiber orientation,
microstructure, and crack propagation mechanism control the mechanical properties of C/C composites.
• Whereas the thermal properties are mainly governed by thermal transport phenomena.
• Moreover, the fiber reinforcements are likely to undergo a change in properties during processing at
high temperatures. This change will also influence the ultimate properties of C/C composites.
Mechanical Properties:
• The type of fiber and matrix precursor, fiber architecture, and processing method will all determine the
mechanical properties of C/C composites. As a result of the large number of variables involved, C/C
composites have a wide range of properties.
• The stiffness and strength of C/C composites are dominated by the fibers, and consequently the specific
arrangement of fibers in the composite has a strong influence on these properties.
 Properties of C/C Composites
• The C/C composites are very complex as a result of the physical and chemical changes that can
occur during processing. Hence, the mechanical properties are dependent on a whole lot of factors,
among which the most important are.
1. Carbon fiber type (rayon, PAN, pitch, high strength, high modulus)
2. Fiber architecture (weaved fabric stack, pierced fabric, knitted preform, braided preform)
3. Fiber directions (1-D, 2-D, 3-D, etc.)
4. Fiber volume fraction
5. Matrix precursor (resin, pitch, gaseous hydrocarbons)
6. Final density of the composite
• There are some other factors, which will also influence the mechanical properties, but they are
difficult to quantify. They are change in fiber properties during heat treatment, fiber damage
during construction and densification, fiber–matrix bonding, and difference in thermal expansion
between fiber and matrix.
Properties of C/C Composites
 Properties of C/C Composites
• It is generally accepted that the maximum service temperature of carbon is limited to ∼2000°C
because of the onset of creep.
• C/C composites were developed for defense/aerospace applications to push this limit to higher
temperatures.
• It has been reported that the high-temperature creep of C/C composites is characterized by an
initial transient creep followed by steady-state creep rate, which increases progressively with
increasing temperature in the range of 2060°C–2600°C.
 Properties of C/C Composites
Thermal Properties:
• The bulk thermal expansion and thermal conductivity are highly anisotropic in the UDCs but
approximately isotropic in the 3-D fiber composites. The CTE of C/C composites tends to
decrease with increasing processing temperature.
• There is considerable interest in developing C/C composites with high thermal conductivity.
• A very large number of processing permutations are possible with the availability of a wide
variety of fiber and matrix materials.
• This wide range of options means that a wide range of thermal conductivities is possible, and
also there are opportunities to tailor the thermal conductivity of carbon-based materials.
• In graphite, the thermal conductivity within the layer planes is more than 200 times higher than
the out-of-plane thermal conductivity, which means that graphite is very a good thermal
conductor in two directions and virtually an insulator in the third direction.
• Hence, the thermal conductivity of any graphite assembly, such as C/C composite, is critically
dependent on the orientation of the layer planes.
 Properties of C/C Composites
• When carbon fibers are incorporated into a carbon matrix, the resultant thermal conductivity is not
only influenced by the fiber architecture but also by the geometry of pores.
• The orientation effects are important, and it is possible to manipulate the thermal conductivity by
the appropriate selection of matrix precursor and processing conditions, particularly the
graphitization temperature, since more graphitic carbon is associated with higher thermal
conductivity.
• For thermoset resin-based C/C composites, it is generally considered that fibers will dominate the
thermal conductivity because of the low thermal conductivity of the non-graphitizable carbon
matrix.
• Pitch-derived matrices are considered to be highly graphitizable and expected to show better
thermal conductivity.
• C/C composites with tailored thermal conductivities can be made by proper choice of fibers,
matrix precursors, fiber configuration, and processing conditions. Typical thermal conductivities
of C/C composites with different fiber/matrix combinations are shown in Figure.
 Properties of C/C Composites
• The combination of good strength, relatively high thermal conductivity, and low thermal
expansion makes C/C composites resistant to severe thermal shock.
 Properties of C/C Composites
Tribological Properties of C/C Composites:
C/C composites have widened the scope of application of carbon-based materials for wear-resistant
components from bearing seals and electrical brushes to brake pads for military and civilian aircrafts,
sports cars, and high-speed trains.
This has been due to the inherent tribological properties of graphite with additional strength and
thermal conductivity contribution from the reinforcing carbon fibers.
C/C composites exhibit low coefficient of friction in the fiber direction (∼0.3) and moderate in the
perpendicular direction (0.5–0.8).
The friction and wear mechanism of C/C composites is quite complex because of the complex
microstructural features.
Various factors like peak temperature, and the formation of debris and transfer films on surfaces
further affect the frictional properties.
 Properties of C/C Composites
• Oxidation Protection of C/C Composites:
• The most severe drawback inhibiting the widespread use of C/C composites is their susceptibility
to oxidation above 500°C under normal atmospheric conditions.
• This becomes progressively more severe with increasing temperature and the rate of oxidation is
limited only by the diffusion of oxygen through the surrounding gas to the specimen surface.
• Carbon is oxidized according to the following chemical reactions:
 Properties of C/C Composites
• The second reaction is predominant at higher temperatures, whereas CO2 is formed at lower
temperatures.
• The oxidation attack starts on the atoms present at the edge of the material, which means
crystalline defects in the carbon structure.
• Therefore, the carbon matrix is more sensitive to oxidation than the reinforcing C-fibers, since the
defects are more common in the matrix.
• Oxidation rate at low temperatures can be reduced by increasing the crystallinity and purity of the
carbon matrix by subjecting it to higher graphitization temperatures.
• The oxidation of composites preferentially occurs at the sites of high energy such as fiber–matrix
interfaces. The rate of oxidation increases with increasing operating temperature but reduces by
the increase in heat treatment temperature of the C/C composite.
Properties of C/C Composites
Properties of C/C Composites
Properties of C/C Composites
Processing of Carbon-Carbon Composites
Sol-Gel ceramic composite processing
• Sol-gel and polymer pyrolysis techniques, which have been used
to make conventional ceramic materials, can also be used to make
ceramic matrix materials in the interstices of a fibrous preform.
• A solution containing metal compounds, e.g., a metal alkoxide,
acetate , or halide, is reacted to form a sol.
• The sol is converted to a gel, which in tum is subjected to
controlled heating to produce the desired end product: a glass, a
glass-ceramic, or a ceramic.
• The sol-gel technique allows processing via liquids of low viscosity
such as the ones derived from alkoxides. Covalent ceramics, for
example, can be produced by pyrolysis of polymeric precursors at
temperatures as low as 1400°C and with yields greater than those
in CVD processes.
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Processing of Carbon-Carbon Composites
• Generally, repeated impregnations are required to
produce a substantially dense matrix.
• In filament winding, fiber tows or rovings are passed
through a tank containing the sol, and the impregnated
tow is wound on a mandrel to a desired shape and
thickness.
• Then the sol is converted to gel and the structure is
removed from the mandrel. A final heat treatment then
converts the gel to a ceramic or glass matrix.
• The sol-gel technique can also be used to prepare
prepregs by the slurry infiltration method. The sol in the
slurry acts as a binder and coats fibers and glass particles.

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Processing of Carbon-Carbon Composites

• The binder burnout step is thus eliminated because the

binder, being of the same composition as the matrix,
becomes part of the glass matrix. An advantage of this
sol-gel-based slurry method is that consolidation can be
done at lower temperatures.
• Among the problems, it is mentioned that the coating
layer on the fiber is porous, carbon-rich, and nonuniform.

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Processing of Carbon-Carbon Composites
• Sol-Gel process of a fabrication of Ceramic Matrix
Composites involves preparation of the matrix from a liquid colloidal
suspension of fine ceramic particles (sol), which soaks a preform and
then transforms to solid (gel).
• Colloidal suspension is formed as a result of chemical reaction when
very small particles with radii up to 100 nm (nanoparticles)
precipitate within a liquid (water or organic solvent).
• Liquid sols have a low viscosity therefore they easily infiltrate into the
preform. At elevated temperatures sols containing organometallic
compounds (e.g. alkoxides) undergo cross-linking (polymerization) by
either the polycondensation or hydrolysis mechanism.
• Polymerization converts sol into gel – a polymer structure containing
liquid. Gels may be transformed into Ceramics at relatively low
temperature, which reduces the probability of the reinforcing
fiber damage.
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Sol-Gel process

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Processing of Carbon-Carbon Composites
A sol is a colloidal suspension in which the individual particles are so
small (generally in the nm range) that they show no sedimentation.
A gel, on the other hand , is a suspension in which the liquid
medium has become viscous enough to behave more or less like a
solid. The sol-gel process of making a fiber involves a conversion of
fibrous gels, drawn from a solution at a low temperature, into
glass or ceramic fibers at several hundred degrees Celsius. The
maximum heating temperature in this process is much lower than
that in conventional glass fiber manufacture. The sol-gel method
using metal alkoxides consists of preparing an appropriate
homogeneous solution, changing the solution to a sol, gelling the
sol, and converting the gel to glass by heating. The sol-gel
technique is a very powerful technique for making glass and
ceramic fibers. The 3M Company produces a series of alumina and
silica-alumina fibers, called the Nextel fibers, from metal alkoxide
solutions (see Sect. 2.6). 43