CARBON CARBON COMPOSITES

ASSIGNMENT # 2…SEMESTER SPRING-2019

Submission Date (May 15,2019)

BY
Group # 4

18120807-007
18120807-008
18120807-024
18120807-037
18120807-040
18120807-041
18120807-054
CHEM-347 (Basic Applied Chemistry-II)
MSc-II

Submitted To

Dr. Muhammad Zubair

Department Of Chemistry

UNIVERSITY OF GUJRAT
 Table of contents
Contents Page No.

Introduction of composite…………………………………………………2
Properties of carbon-carbon composites……………………………..……3
Manufacturing of c-c composites…………………………………………7
Methods for preparation……………………………………………….….8
Fabrication of c-c composites by CVD method………………………….10
Fabrication of C-C composites by liquid phase infiltration method……...11 Commented [m1]:

Oxidation protection of c-c composites………………………………......11

Applications and technological importance…………………………..…...12
Design and optimization of c-c composites…………………….………….17
References ………………………………………..……………………….18

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 CARBON CARBON COMPOSITES

INTRODUCTION:

A composite is formed when two or more different materials are combined together to create a superior
material. It is made up of matrix and fiber.

Phases in Composite:

 Continuous phase – Matrix / binder

 Dispersed phase – Reinforcement / filler
 Interphase – An interphase between matrix and filler

Carbon-Carbon Composites:

Carbon-carbon composites are also known as Carbon fiber – reinforced carbon composite (CFRCC) in
which carbon matrix reinforced by graphitic carbon fibers.

 These were first developed in 1958, but not intensively researched until the space shuttle program.
 Carbon-carbon composites are those special composites in which both the reinforcing fibers and
the matrix material are both pure carbon.
 These are actually woven mesh of carbon fibers.
 These are used for their high strength and modulus of rigidity.
 These are light weight material which can withstand temperatures upto 3000°C.
 Carbon-carbon composite’s structure can be tailored to meet requirements.

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  Carbon carbon composite is aerospace ceramic material, and is used in heat shields for re-entry
spacecraft, liners and nozzles for rocket engines, and brake pads for aircraft.
 Reinforced carbon carbon composites is a composite material consisting of carbon fiber
reinforcement in a matrix of graphite.
 It was developed for the nose cones of intercontinental ballistic missiles, and is most widely
known as the material of the nose cone and wing leading edges of the Space Shuttle Orbiter.
 Carbon-carbon brake disc and brake pad have been the standard component of the brake systems
of Formula one racing cars since 1976.

Carbon-carbon is well suited to structural applications at high temperatures, or where thermal shock
resistance or co-efficient of thermal expansion is needed. It is less brittle than many other ceramics, it lacks
impact resistance.

Carbon-carbon composite are typical examples of a brittle-matrix composites. Its mechanical behavior is
highly dependant on the interface properties. On the other hand, variations in fiber type and matrix precursor
allows to vary the microstructure and thus properties of carbon-carbon composites interface in broad
intervals. If to exclude chemical bonding in composites obtained by chemical vapour infiltration of a 2-D
skeleton of fibre with no surface treatment, then a composite with purely mechanical bonding will be
obtained. In contrast the composites obtained by resin infiltration route have amorphous carbon interfacial
layer which do not provide strong bonding. As a consequence, the former composites have high binding
strength and poor fracture toughness, the latter ones have lower strength and higher fracture toughness.

Properties of Carbon-Carbon Composites:

 Excellent thermal shock resistance (Over 2000°C)

 Low co-efficient of thermal expansion
 High modulus of elasticity
 High thermal conductivity
 Low density ( 1830 Kg/m3)
 High strength
 Low co-efficient of friction
 Thermal resistance in non-oxidizing atmosphere
 High abrasion resistance
 High electrical conductivity
 Non-brittle failure

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Continuous carbon fibres (rather than short whiskers) are used as the reinforcement to maximize strength
and toughness. Similarly to polymer matrix laminates, the tailored arrangement of carbon fibres in selected
orientations within a continuous carbon matrix is used to achieve the desired properties. The fibre
architectures include unidirectional, bidirectional, three dimensional orthogonal weaves, or multidirectional
weaves and braids.

Carbon-carbon composites are expensive to fabricate. A major drawback of these materials is their high
cost which makes them prohibitively expensive for many aerospace applications. The manufacturing
process involves impregnating fibrous carbon fabric with an organic resin such as phenolic. The material
is pyrolysed at high temperature to convert the resin matrix to carbon. The material which is soft and porous,
is impregnated with more resin and pyrolysed several more times until it form a complex, stiff and strong
composite.The material properties of carbon-carbon composites, as for fibre polymers are anisotropic. The
stiffness, strength and thermal conductivity is highest along the fibre axis and lowest normal to the fibre
direction. The properties also depend upon fibre direction, type of carbon fibre, fibre architecture and
processing cycle.

Carbon carbon composites in the true sense, cover a large range of materials with the targeted 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 multiphase composite materials.

The mechanical properties of the constituents and their volume fraction, boding, 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
dimensional 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 general trend of
the most fascinating properties of carbon/carbon composites are given below.

1.Chemical Properties of carbon-carbon composites:

1-Carbon-Carbon (C-C) composites are fire resistance nonflammable materials that can be used in
applications requiring high heat resistance such as gas tank and some medical devices.
2-Carbon-Carbon (C-C)have high resistant to corrosion and oxidation ,because they are completely inert
materials even in severe environmental conditions.
3-The properties above are important factors to be considered in most of the applications.

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2.Physical properties of carbon-carbon composites:

1-Carbon-Carbon (C-C)composites are designed in ideal thermal expansion and heat conductivity to be
similar to surrounding structures to reduce the thermal stress to the lowest value.
2-Carbon-Carbon (C-C)composites are structured to absorbing or transmitting magnetic and electrical
energy.
Some military aircrafts are made out of carbon composites absorb radar signals.

3.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, 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 fiber
properties in carbon/carbon composites. Composites with strong fiber/matrix bonding fail catastrophically
without fiber pull-out while those with controlled interface fail in mixed tensile cum shear mode exhibiting
high strength. Numerical values of the mechanical properties of the composites are dependent on the fiber
architecture and the direction of measurement of the properties w.r.t. fiber orientation etc.

Strength of carbon-carbon composites with fibre orientation

Other architecture and fibre lay-ups have similar effects and the values lie in-between. Similarly, these
composites exhibit a range of high fracture toughness and good creep and fatigue resistance. When

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subjected to high temperature testing, carbon/carbon composites have been found to exhibit about 10-20%
increase in mechanical properties at 2000C under inert atmosphere. However, in air, the properties drop
down to 10-20% depending on the temperature and time e.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%.
The strength of carbon-carbon with unidirectional reinforcement fibres is upto 700 MPa. Carbon-carbon
materials retain their properties above 2000°C. This temperature may be exceeded with the help of
protective coatings to prevent oxidation. The material has a density between 1.6 – 1.98 g/cm3.

4.Thermal properties of the carbon carbon composites:

Carbon/carbon composites being of heterogeneous structure consisting of fibers, matrix and pores, with the
first two having a variety of microstructures, estimation of their thermal transport 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 fiber/matrix combinations.
Composites having highly thermal conductivity of CC composite with different fiber-matrix combinations
oriented graphitic fibers or matrices or their combination, like vapour-grown carbon fibers and matrix or
mesophase pitch-based carbon fibers and matrix, exhibit very high thermal conductivities of the order of
250-350 W/M.K in the fiber direction.Though these composites exhibit highly anisotropic character and
low conductivities in transverse directions, there is always scope of improvement by varying the fiber
architecture and their addition in different forms and ways. Coefficient of thermal expansion of the
composites is dictated largely by the fiber orientation. It is 0-1 ppm/C in the fiber direction and 6-8 ppm/C
in a direction perpendicular to the fibers.

Thermal conductivities of C-C composites with different fibre-matrix combinations

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5.Manufacturing Properties of carbon-carbon composites:

The desirable application cannot be achieved unless the manufacturing processes are finished in the right
way. The following points should be considered:
1-Formability it is easily formed into complex shapes (ductility) and flexibility.
2-Casting is a process by which carbon-carbon composites are shaped by pouring into a mold that contains
the negative impression of a desired shape. This process allows the composites to absorb any forceful or
impact loads.
3-Weldability and machinability very important in service life (durability) even in harsh operating
environments

FIG: Manufacturing process of carbon-carbon composite

Production of Carbon-Carbon Composites:

Carbon-Carbon composites is made in three stages:

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First, material is made up in intended final shape , with carbon filament and surrounded by an organic
binder such as plastic or pitch. Often, Coke or some other fine carbon aggregate is added to the binder
mixture.

Second, the lay-up is heated, so that the pyrolysis transforms the binder to relatively pure carbon. The
binder loses volume in the process, causing voids to form; the addition of aggregate reduces this problem,
but does not eliminate it.

Third, the voids are gradually filled by forcing a carbon forming gas such as acetylene through the material
at high temperature, over the course of several days. This long heat treatment allows the carbon to form
into larger graphite crystals and is the major reason for the material’s high cost. Carbon-carbon is a hard
material that can be made highly resistant to thermal expansion, temperature gradients, thermal cycling,
depending on how the fiber scaffold is laid up and the quality of the filler.

Carbon carbon composites such as CNTs (carbon nano tubes) can be prepared by several methods. Amongst
the most common are

 arc discharge

 laser ablation

 chemical vapor deposition (CVD) from hydrocarbons

 High pressure conversion of carbon monoxide (HiPco) .

The production of Carbon nano tubes with high purity and uniformity, low cost, and at a large scale is still
a major concern of the scientific community and the industry.

Arc Discharge method:

Arc discharge was the method used in 1991 to prepare carbon nano tubes.

In this method, a Direct Current arc plasma is generated between two carbon electrodes under an inert
atmosphere, as depicted in Fig. 1. As the anode is consumed, a soft fibrous deposit containing carbon
nanotubes and other carbon particles is formed on the cathode.The electrodes are doped with a suitable
catalyst, such as Ni-Co, Co-Y or Ni-Y. The tubes produced by this method are usually tangled and of varied
length and diameter.

However, the Carbon nano tubes are of high quality, with low incidence of defects.

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 Fig. Schematic illustration of arc discharge method

Laser Ablation

Laser ablation was first used for the synthesis of fullerenes. In this method, a graphite target is vaporized
by laser irradiation under flowing inert atmosphere at temperatures near 1200 ⃘ C as shown in Fig. The laser
vaporization produces carbon species, which are swept by the owing gas and accumulate on a water-cooled
collector. SWCNTs remarkably uniform in diameter can be produced when the graphite target is doped
with a small amount of transition metals such Ni and Co.

FIG. Schematic illustration of laser ablation method

Chemical Vapor Deposition method :

Chemical vapor deposition (CVD) has been used to produce carbon filaments and fibers since the 1960s.
In this method, preparation of C/C fiber pre form of desired shape and structure takes place. This process
gives high strength and modulus of elasticity

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 Fig. Schematic illustration of CVD method

Here if a carbon-containing gas is decomposed on a substrate in the presence of catalyst metal particles at
high temperatures ( 600 ⃘C or higher) as illustrated in fig. The lower temperatures used in this method reduce
production costs. In addition, the deposition of catalysts on the substrate allows the formation of novel
structures.

Fabrication of Carbon-Carbon Composites by Chemical Vapor Deposition process

 Preparation of carbon/graphite fiber preform of the desired structure and shape.
 Densification of the composites by chemical vapour deposition (CVD) technique.
 The CVD process involves infiltration of the preform with a pressurized hydrocarbon gas (propane,
methane, propylene, acetylene, benzene) at 1800-2200ºF (982-1204ºC). The gas is pyrolyzed
forming carbon deposition on the fiber surface. The process duration is determined by the thickness of
the preform, through which the gas diffuses.
 Graphitization heat treatment. At this stage amorphous carbon is transformed into crystalline graphite.
The temperature of the treatment may vary within the range 2700-5400°F (1500-3000°C). Typical
graphitization temperature is 4530°F (2500°C). Graphitization of carbon-carbon composites results in
increase of Modulus of elasticity and strength of the composite.
Fabrication of Carbon-Carbon Composites by Chemical Vapor Deposition process results in higher (as
compared to Liquid phase infiltration technique) elasticity modulus and mechanical strength.
Limitations of CVD technique:

Sometimes cracks get appear on the outer surface of material synthesized and gases like hydrocarbons get
deposit on outer cracks and leave lot of pores on it.

Reinfiltration and densification is required for this process.

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And it is a month long process (for specific applications).

Fabrication of Carbon-Carbon Composites by Liquid Phase Infiltration process

 Through this method also Preparation of carbon/graphite fiber preform of the desired structure and
shape.
 Infiltration of the preform with a liquid precursor: petroleum pitch/phenolic resin /coal tar.
 Pyrolysis/carbonization (chemical decomposition by heat in the absence of oxygen) of
the polymer precursor at 1000-1830ºF (538-1000ºC) under normal or high pressure.
 Infiltration – pyrolysis cycle is repeated several (3-10) times until the desired density is achieved.
 Graphitization heat treatment. At this stage amorphous carbon is transformed into crystalline graphite.
The temperature of the treatment may vary within the range 2700-5400°F (1500-3000°C).

Fig. Liquid phase infiltration

 Typical graphitization temperature is 4530°F (2500°C). Graphitization of carbon-carbon composites

results in increase of Modulus of Elasticity and strength of the composite.

Oxidation Protection of Carbon-Carbon composites :

 The main disadvantage of carbon-carbon composites is their low oxidation resistance. Carbon materials
reacts with oxygen at temperature above 400 ⃘C.
For oxidation protection the protection coatings like ceramic coating (commonly multi layer) of
carbides, nitrides and oxides. Protection coatings may be deposited by chemical vapour deposition,
physical vapour deposition or plasma spraying method.
Impregnation of oxidation inhibitors: inorganic salts, borate and silicate glasses, phosphates , boron
oxides and halogen compounds .

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 Replacement of the matrix material from carbon to SiC. C-SiC composites possess excellent oxidation
resistance.

Applications

1.Applications and Technological Importance:

Many of the Carbon-Carbon (C-C) composites currently being produced are in the form of components for
missiles and military aircraft. The most important applications include reentry bodies, rocket nozzles, exit
cones for strategic missiles, and brake discs for military aircraft.

Recently, a commercial aerospace application, where brake discs for transport aircraft twill be coated, has
become prominent.

Carbon-Carbon (C-C) composites are used for the nose tip and wing leading edges on the Shuttle Orbiter
vehicles. Present industrial applications for Carbon-Carbon (C-C) composites, such as hot glass handling
tools and hot press dies and pistons, are minor compared with the uses in defense and aerospace. The use
of Carbon-Carbon (C-C) composites brake discs on commercial transport aircraft has become a significant
business, and is expected to grow in the coming years.
It is more difficult to predict the future for (C-C) composites especially in the advanced military
applications, because the materials are developmental and the projected systems must continue to receive
government funding.
Specific advanced military applications include hot section components for limited-life missile engines,
exhaust parts for new fighter aircraft, hypersonic vehicle fuselage and wing components, and structures for
space defense satellites. Commercial non-aerospace applications for Carbon-Carbon (C-C) composites are
minor at this time because of the high cost of the material. Expanded use of Carbon-Carbon (C-C)
composites in industries other than defense and aerospace will likely require the development of methods
that reduce cost and yet maintain properties that provide performance advantages.

Potential near-term uses that have been identified are high-speed train and special automobile brakes and
clutches, forging dies and molding crucibles, corrosive chemical reactors and heat exchangers, fuel cells,
high thermal 11 conductivity electronic substrates, prosthetic devices, and components for internal
combustion engines.

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More distant large-scale applications include plasma limiters for nuclear fusion devices and inert gas
ducting and heat exchangers for gas- cooled fission reactors.

Aircraft Brakes:

Almost 63% of the produced carbon-carbon composites are used in aircraft brakes all over the world. The
brake discs are required to provide the fractional torque which stops the aircraft.

The heat generated is very high and acting as a structural component, the surface and frictional temperature
between the rotor and stationary disc are 500°C, 2000°C respectively.

Carbon-carbon composite is the only material that can be selected because of its high thermal
conductivity and very low thermal co-efficient.The heat capacity of C-C composite brake are 2.5 times
greater than steel.

Main advantage is that the Brakes are 300kgs lighter than steel and these are more stronger because of
usage of carbon-carbon composites.

Fig: C/C composites in brake discs

Carbon-Carbon (C-C) composites used in braking systems:

1. Carbon fabric laminates.

2. Semi-random chopped carbon fibers (Hitco).
3. Laminated carbon fiber felts with cross reinforcement (SEP).

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The two methods to prevent oxidation during braking:

1. It is a achieved by applying a trowel glass forming block to the active sides on non-rubbing surfaces.
2. Adding an inhibitor during fabrication

Racing Car Brakes

These kinds of brakes are used in sport cars. Carbon -carbon (C-C) composite brakes were introduced into
formula 1. The brakes are operated by hydraulic calipers pressing the Carbon-Carbon C-C) pads against the
ventilated disc.
There are some conditions that must be considered when operated these brakes:
1- Each disc required at least 70 cm of air.
2- To avoid the thermal problems the bell must be made of titanium or aluminum alloy 2618,and its
surface to enhancement of hardness and resistance to the high temperature.

Fig: Carbon-carbon composites In racing brakes

3- To achieve the high performance temperature must be between 400Co and
600Co.Temperaturesbelow 400 Co would increased the friction coefficient and cause low
performance, temperature higher than 600 Co would cause excessive oxidation.
4- Brakes must warm up to develop an optimum friction surface.
5- The braking system of many modern cars is also equipped with fibre-reinforced ceramic
brakes. The ceramic material's composite structure is made up firstly of silicon carbide.
The high-strength carbon fibres are then embedded in the base material to absorb the
stresses that occur in it.

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Other braking applications:

There are many advantages of using Carbon-Carbon (C-C) composites as braking materials such as light
weight applications, inertness with other materials, and high thermo mechanical performance. Carbon-
Carbon(C-C)composite brakes have an ability to absorb much energy in a short period of time compared
with other materials such as a metal or organic brakes. Aircrafts, trains, and racing cars prefer Carbon -
Carbon(C-C) composites are a metal alternative because Carbon-Carbon (C-C) composites reduce friction
by using materials that perform at lower weight. Also the low density of Carbon-Carbon (C-C) coupled
with tendency towards lower cost make it ideal for applications in transport or machinery. Carbon-Carbon
(C-C) composite brakes have the most improved air portability and give high efficient distribution of the
vehicle’s weight into the area.
These emergency brakes are particularly effective, especially in high momentum situations, when stopping
large trucks or trains over short distances and when avoiding injury and damage because of the failure of
lifting gears in mean shafts. There are some disadvantages of using Carbon-Carbon (C-C) composites in
the braking materials, such as the cost, which; can be considered prohibitive for use in domestic vehicles;
oxidation, which occurs preferentially in the matrix phase; and its inherence to all Carbon-Carbon (C-C)
applications.One of the most well-known composite applications in sports is the so-called "carbon bike".
The frame consists of carbon fibre-reinforced epoxy which makes the frame very stiff and lightweight.

Winning carbon fibre bike at the Olympics

2004

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BMC, the Swiss high-tech bicycle brand, and Easton Sports have developed the "Pro Machine" for the Tour
de France with a carbon fibre frame weighing less than 1 kg.

Carbon fibre bikes were also used by the British cycling team in the Athens olympics (Greece, 2004). The
bikes were designed and built by the Advanced Composites Group (ACG).
There are also a lot of experiments with Carbon NanoTubes (CNT) in composites for sports applications.
These carbon nano tubes are very small carbon particles having size about one ten-thousand of a millimeter
that are added to polymer resin to increase it toughness and stiffness.
By the remarkable usage of carbon nanotube technology different companies have been able to make
baseball bats and hockey sticks.

Fig: Hockey stick with carbon nano technology

Composite materials are very attractive for all kinds of sports activities. In many sports applications, weight
reduction is the primary reason to move to composites.

Carbon NanoTubes (CNT) in tennis racquet frame

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 Composite sandwich material is used in the manufacturing of loudspeakers. The composite material fulfils
both requirements of maximum sensitivity and damping, by the combination of the stiff carbon fibres and
low density foam these type of products can be synthesized. The high mechanical performance of the
material strongly reduces the deformations normally encountered in traditional cone materials under loads
and so prevents sounds colouration. The loudspeakers are also used in the most prominent places.

Sony's carbon fibre VAIO notebook Composite sandwich material for

Acer's first carbon fibre notebook Bowers & Wilkins (B&W)
loudspeakers

Design and optimization of C-C friction members:

There are four major classifications for preferred fiber orientation within C-C brake disc, it’s determined
by heat flow:
1. Diffuses or discharges the heat away from friction surface and inside the brake disc.
2. Heat can discharge radially.
3. The slot disc must withstand shear force.
4. The effectiveness of the drive slot could reduce to minimum.

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References:

 http://en.m.wikipedia.org
 http://www.sciencedirect.com
 http://www.libertexts.com
 www.cmcarbon.com
 http://www.composites.ugent.be/home_made_composites/composites_in_da
ily_life.html#C_sports
 https://www.sciencedirect.com/science/article/pii/S0008622313002686

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