Lecture 8: carbon-carbon composite

 What are Carbon-Carbon Composites?

 Which Fibre and Matrix are used in Carbon-Carbon Composites?
 How to Synthesize Carbon-Carbon Composites?
 General Properties of Carbon-Carbon Composites?
 Applications of Carbon-Carbon Composites?
Composites
Composite is a material consisting of two or more distinct constituents or phases. However, this statement is
not sufficient for the complete description of a composite material. There are few more criteria which have to
be satisfied before a material can be said to be a composite.
 Both constituents have to be present in reasonable proportions, say greater than 5 %.
 The constituent phases should have different properties and the properties of the composite should
also be noticeably different from those of the constituents.
 One constituent act as continuous phase and the second constituent act as discontinuous phase.
 Both the continuous and discontinues phases retain their identity or chemical composition in the
composite. It means they do not react chemical to form the composite.
 The discontinues phase is responsible to increase the strength of the composite.
The continuous phase is also known as matrix and mostly present in larger amount as compared to
discontinuous phase.
The discontinues phases in known as fiber and present in smaller amount as compared to the continuous
phase.
So, in general we can say that Composite = Matrix + Fiber

Carbon-Carbon Composites
Carbon-Carbon Composites are those composites in which both the matrix and Fiber are made of carbon.
Carbon-Carbon (C-C) composites are the oldest and most mature of the ceramic matrix composites. They
were developed in the 1950s by the aerospace industry for use as rocket motor casings, heat shields, leading
edges, and thermal protection.
Although C-C composites are basically ceramic matrix composites because the usage and fabrication
procedures of C-C composites are similar and overlap to the matrix composites but C-C composites are often
treated as a separate material class from other ceramic matrix composites.
Carbon Fibres
Carbon has two well-known crystalline forms which are diamond and
graphite. But it also exists in quasi-crystalline and glassy states. As far as fibre
technology is concerned graphite is the most important structural form of
carbon.
Graphite structure consists of hexagonal layers in which the bonding is
covalent and strong (525 KJ/mol). These layers, which are called the basal
planes, are stacked in an ABAB sequence with interlayer bonds being weak
wan der Waals bonds (bond energy less than 10 KJ/mol). Due to this marked
difference in the intra layer and interlayer bonding the properties of
graphite are very anisotropic. The theoretical elastic modulus of graphite is
approximately 1000 GP in the basal plane and only 35 GP in the c direction
that is perpendicular to the planes.
The alignment of the basal plane parallel to the fibre axis gives stiff fibres which, because of relatively low
density of around 2 mg/m 3, have extremely high values for specific stiffness. Graphite sublimes at 3700 °C but
starts to oxidize at around 500 ° C, carbon fibers can however be used at temperatures exceeding 2500 °C if
protected from oxygen.
Carbon fibres are produced from a variety of precursors. The mechanical properties vary greatly with the
precursor used and the processing conditions employed because both the precursor used and the processing
conditions affect the perfection and the alignment of the crystals.
There are three main precursors which are used for the synthesis of carbon fibres.
 Rayon or Cellulose  Polyacrylonitrile (PAN)  Pitch

Rayon
Rayon is a polymer whose molecular structure resembles natural cellulose (polymeric glucose), but that has
been modified somewhat by chemical treatment. To produce rayon, natural cellulose is degraded, purified,
and then reconstructed. Rayon’s molecular structure closely resembles to cellulose from which it is derived.

Carbon Fibres from Rayon or Cellulose

Controlled heating of cellulose or rayon fibre converts the fibre to graphite. The decomposition is complex but
essentially loss of weight and shrinkage takes place during pyrolysis in the temperature range 200 to 400 °C as
the organic precursor decomposes to carbon. This is followed by carbonization that is gradual ordering of the
structure and finally graphitization at higher temperatures. The yield is low, only 15 to 30%, and although the
fibre is crystalline the alignment
is poor. Thus at
Molecular structure of a cellulose from which this stage the
fibres have low Rayon is derived. strength and
stiffness, the latter being of the
order of the modulus in the c direction (perpendicular to the basal planes) of the graphitic structure. However
hot stretching by up to 50% at the temperatures in the range 2700 to 3000 °C increases the modulus and
strength by developing a preferred orientation in the fibres and reducing porosity. The preferred orientation
is such that there is a tendency for the basil planes to be aligned parallel to the axis of the fibre, although the
alignment is far from perfect.
This manufacturing route is declining because of the decreasing availability of the main source of suitable
rayon, low yield and the problems involved in stretching at such high temperatures.

Carbon Fibres from PAN

Compared with rayon or cellulose fibres, those produced from polyacrylonitrile (PAN) have a high degree of
orientation in filament form. The PAN precursor also gives a high yield of up to 50% on conversion to carbon.
A three stage process is involved in the conversion PAN to carbon and the resulting structure is sensitive to
the rates of heating. The first stage involves stretching and oxidation. The fibres are initially stretched 500 to
1300 % improve molecular alignment and then heated in air while still under tension, to 200 to 280 °C. This
results in inter molecular rearrangement to give a ladder like polymer that is chemical cross links between the
oriented chains in three dimensions are formed so that chains can no longer bend are distort on heating.
In second stage, oxidation is carried out
where by some two- thirds of the oxygen sites
are filled slowly with the release of water
(H2O). At this stage the product is also called
oxyPAN.

In third stage, heating of oxyPAN

in nitrogen or argon at 900 to
1200 °C is carried out which produces
low modulus, high strength carbon
fibres, which have fine well
oriented crystals parallel to the fibre excess. However, they have a fair degree of porosity and the density is
only 1.74 mg/m3.
The idealized formation of the carbon ring structure is shown in figure it can be seen that there is an
operational hazard at this
stage as toxic volatile oils such
as HCN are given off.

Heating in organ upto 2800

°C causes graphitization and
produces high modulus fibres of increased density up to 2.00 mg/m the density of graphite is 2.26 mg/m3.
3

The value of the modulus increases with increasing temperature of graphitization as shown in figure.
In fact the properties can be varied over a wide range by suitable heat treatment conditions but it is difficult
to combine high
strength with high
modulus. stretched 500 to 1300 %
200 to 280 °C

PAN ladder like polymer

Carbon Fibres from Petroleum or Coal tar Pitches
Petroleum and Coal tar Pitches contain a complex mixture of high molecular weight aliphatic and aromatic
hydrocarbons; they have therefore high carbon content and thus are suitable as precursors.
The pitch is heated to above 350 °C to polymerize it to molecular weights of about 10,000. The structure of
the molecules is such that an ordered liquid crystal is or mesophase is formed. The polymer is extruded
through the holes in a hot walled metal cylinder whilst the cylinder rotates. This process, which is known as
melt spinning, orientates the hot mesophase pitch.
After oxidation to induce crosslinking, and hence prevent the fibre remelting and sticking together, the fibres
are carbonized at temperatures up to 2000 ° C giving low modulus carbon fibres. The carbon yield is high at
about 80%. The degree of graphitization is controlled by heat treatment at temperature upto 2900 ° C.
A high degree of perfection of the graphite may be obtained, together with good axial alignment of the basal
planes, and not surprisingly this lead to high density, high modulus fibres. An unusual characteristic of carbon
fibres is there very low or even slightly negative coefficients of longitudinal expansion.
As for other properties, the coefficient of thermal expansion depends on the fabrication route and hence
degree of graphitization and crystal orientation.
Ultra high modulus carbon fibres have negative coefficients of expansion of approximately -1.4 x10 -6 K-1 and
are employed in the production of polymer matrix composites with near net zero thermal expansion.
Finally it should be mentioned that although we have concentrated on the effect of graphitization and
orientation on properties. There are other structural features such as wide microcracks, surface flaws and
impurities which have to be controlled in order to obtain fibres of a consistent high quality.

Carbon Matrix for Carbon-Carbon Composites

There are two precursor types which are dominantly used to produce the matrix in Carbon-Carbon
Composites. These are thermosetting resins (Phenolic, furan and polyimide) and thermoplastic resins
(pitches). The percent yield of carbon on pyrolysis of these precursors is given the following table.

Material % Yield
Phenolic resin 45
Furan Resin 60
Polyimide 80
Poly-Phenylene 80
Pitch 50 (when processed at 1 atm)
Pitch 80 (when processed at 100 atm)

Some Key features of Sources of Matrix materials

Thermosetting resins
Thermosetting resins (Phenolic, furan and polyimide) polymerize at low temperature (250 °C) to form a cross-
linked amorphous material. Higher temperatures of the order of 1000 °C are required to carbonize to a glassy,
isotropic carbon.
Multiple impregnation and carbonization cycles are necessary to obtain dense composites. A cycle may take
three days as the gases formed during pyrolysis have to be released slowly in order to avoid structural
damage, therefore the complete fabrication process is time taking. The glass carbon matrix does not
transform readily to graphite and temperature in excess of 2500 °C together with stress is needed for
graphitization to occur at reasonable rate.
Thermoplastic Resins or Piches
The pitches such as petroleum pitch used in carbon-carbon composite fabrication are mixture of polynuclear
aromatic hydrocarbon which are thermoplastic in nature. The main structural feature on heating a pitch is
the formation of small volumes (0.1µm diameter) of a highly oriented structure that is similar to liquid
crystals. These are known as mesophases. On prolonged heating they coalesce to form larger regions with an
ordered structure.
The lamellar arrangement of the ordered structure is favorable for the formation of graphite when heated at
the temperature of the order of 2500 °C. Due to a difference in the structure of carbon matrix prepared from
thermosets and the thermoplastics, composites with matrix produced form pitch (thermoplastic) have higher
density.
Lamellar arrangement is that which is formed if a number of fine sheets of a material held adjacent to one
another, in a gill-shaped structure, often with fluid in between though sometimes simply a set of 'welded'
plates. 
Synthesis Techniques for C-C Composites
Classically, carbon ceramics are fabricated by combining solid particles of pure carbon (known as
primary carbon) with a preliminary binder which acts as a precursor for secondary carbon formed
during the carbonization process. In C-C composites the carbon fibres (based on rayon/PAN/pitch) in
the form of U- D, 2-0 and multi-directional preforms are used as primary carbon rather than particulate
fillers. There are two distinct techniques used to fill the interstices between the carbon fibres. These
are (i) Gas Phase using a Chemical Vapour Deposition process, and (ii) the Liquid Phase route using
thermosetting resins or pitch (PIC). The fibres can be very stiff, highly oriented graphitic and dense
(pitch precursor) or. relatively flexible , stronger, less oriented graphitic and less dense (PAN precursor).
Conversely, the matrix can be highly oriented and graphitic if produced from pitch, either isotropic or
anisotropic if produced from CVD or usually isotropic if produced from thermosetting resin using
phenolic resin. A general rule of thumb employed by manufacturers is that the gas phase route is
adequate for thin-walled parts and the liquid phase route is preferable for thick parts. A combination
of liquid and gas phase processes is also being followed.

Gas Phase Impregnation (Chemical Vapour Deposition, CVD)

This technique uses volatile hydrocarbons such as methane, propane, benzene and other low molecular
weight units as precursors. Thermal decomposition is achieved on the heated surface of the carbon
fibre substrates resulting in a pyrolitic carbon deposit. This technique can be employed to deposit
carbon on to dry fibre preforms or to densify porous CC structures produced by the liquid
impregnation route, in which case it is referred to as chemical vapour infiltration. This process was
widely used by the Western countries for the production of thinner parts like aircraft brake discs and
nozzles.

Liquid Phase Impregnation Process

This process involves impregnation with liquid impregnates like coal tar/petroleum pitches and high
carbon-yielding thermosetting resins. The criterion for selection of impregnates is based on the
characteristics like viscosity, carbon yield, matrix microstructure and matrix crystalline structure which
are considerably influenced by the time-temperature pressure relationships during the process.
The two general categories are aromatic, ring-structured, conventional thermosetting resins such as
phenolics, furans and advanced resins like ethynyl pyrenes or pitches based on coal tar, petroleum and
their blends. The CC manufacturing process using the multiple impregnation, carbonization (1000 °C),
high pressure (1000 bars) carbonization (HIP) and graphitization (2750 ° C) is shown in Figure (at next
slide).
In atmospheric pressure carbonization, the carbon yields obtained from pitch are only around 50 per
cent i.e. approximating those from high yield thermosetting resins. Yields as high as 90 % can be
obtained by carbonizing the pitch under high pressure of 1000 bars, thus making the process more
efficient. Pressure applied during pyrolysis also affects the matrix microstructure. The higher the
pressure the more. course and isotropic will be the microstructure due to the suppression of gas
formation and escape. High pressure also helps in lowering the temperature of mesophase formation
in pitch, resulting in highly oriented crystalline structure. The HIP process is the only practical route to
lower the production cost of CC composites.

Properties of Carbon-Carbon Composites

Properties of Carbon-Carbon composite vary from composite to composite depending the precursor used,
method adopted for synthesis and design of the composite. However, in general, the properties of Carbon-
Carbon composite can enlisted as
 Excellent thermal shock resistance;
 Low Coefficient of Thermal Expansion;
 High Modulus of Elasticity (up to 29000 ksi / 200 GPa);
 High Thermal Conductivity (about 700 BTU.in/(hr*ft²*ºF) / 101 W/m*K;
 Low density 1.49 to 1.99 g/cm3
 High strength;
 Low coefficient of friction (in the fiber direction);
 Excellent heat resistance in non-oxidizing atmosphere. C/C Composites retain their mechanical
properties up to 3000 °C.
 High abrasion resistance;
 High electrical conductivity;
 Non-brittle failure.

Applications of Carbon-Carbon Composites

 High performance breaking system  Electronic heat sinks
 Refractory material
 Hot Pressed Dies (Brake pads)
 Turbo jet engine components
 Heating elements
 Missile Nose Tips
 Rocket motor throats
 Leading edges (Space shuttle, Agni missile)
 Heat Shields
 X-ray Targets
 Aircraft Braks
 Reenntry vehicles
 Biomedical implants
 Engine pistons
 Automotive and motorcycle bodies
Assignments
1. Students have to search out a research article on carbon-carbon composite published in 2020 and
prepare its summery that will include precursor used, synthesis method, properties and applications
reported in that article.