CARBON FIBER

By
Maheswaran G
(07mt63)
Introduction
Carbon fiber became known to mankind
in 1879.
Edison took out a patent in Jan 1880.
Manufactured to use in electric lamps.
Importance in aerospace industry for
better light weight materials.
Successful commercial production
process was developed by William Watt
and his team in UK.
Introduction
USA are using nearly 60% of the
worlds production.
Japan almost 50% of the worlds
capacity.
Definition:
Carbon fiber has been described as a fiber
containing at least 90%of carbon obtained
by controlled pyrolysis of appropriate
fibers.
Variety of such appropriate fibers are
known as precursors.
Classification and Types:
Ranks to the ultimate fibers is not easy
task as the fibers made from a variety
of precursors.
Involving different manufacturing
routes with a very wide range of final
heat treatment temperatures.
On the basis of modulus, strength and
final heat treatment temperature the
carbon fibers were classified.
Classification and Types:
Based on modulus
Ultra high modulus
Modulus greater than 500GPa.
Type P 120
Example - union carbide
It is a mesophase pitch based fiber with
modulus 820Gpa
High modulus
Moduli between 300 500GPa
Strength to modulus ratio 5 7 * 10-3
Example - Torays M50
Classification and Types:
Intermediate modulus
Fibers with moduli up to 300GPa
Strength to modulus ratio 1 * 10-2
Example - Torays M30
Low modulus
Have modulus as low as 100GPa
Low strength value
It have isotropic structure
Classification and Types:
Based on tensile strength
Ultra high strength
Tensile strength value = greater than
5.0GPa
Strength to stiffness ratio = 2 3 * 10-2
Example - Torays T1000.
high strength
Tensile strength value = greater than
3.0GPa
Strength to stiffness ratio = 1.5 2 * 10-2
Example Hercules PAN based material AS
- 6.
Classification and Types:
Based on Heat treatment
temperature
Type I
Final heat treatment temperature should
above 2000C
Type II
Final heat treatment temperature should
above 1500C - 2000C
Type III
Final heat treatment temperature should
above 1000C - 1500C
Manufacturing Process
In the production of carbon fibers, the
most prevalent precursors are
Polyacrylonitrile
Cellulose fibers
Certain phenolic fibers
Different routes are followed to develop
carbon fibers either from fibrous
precursors or by the extrusion of pitch.
Manufacturing process:
In the production of carbon fibers, the
most prevalent precursors are PAN,
Cellulose fibers (viscose & cotton), pitch
and certain phenolic fibers.
Different routes are followed to develop
carbon fibers either from fibrous
precursors or by the extrusion of pitch.
Schematic showing the process for making carbon
fibers
Carbon fiber from Polyacrylonitrile(PAN):
High technology carbon fibers consist
mainly of nitrogen containing
dyaromatics with structural preferred
direction.
PAN based precursors has greatest
commercial interest compared to other
precursors.
There are three successive stages in the
conversion of PAN precursor in to high
performance carbon fibers.
Oxidative stabilization at 200 - 300C
Carbonization at about 1000C
Graphitization between 1500 - 3000C
Oxidative stabilization:
PAN precursors is first stretched and
simultaneously oxidized at a temperature in
the range of 200-300C.
This treatment converts thermoplastic PAN to
a non-plastic cycle or ladder compound.
Temp range of 150 - 400C for the oxidative
stabilization process is used.
Formation of ladder polymer takes place in
two steps
Cyclization
Dehydrogenation.
Oxidative stabilization:
The main reason for stretching the fiber
during oxidation is to prevent the polymer
chains from relaxing and loosing their
orientation, which becomes locked in through
cross linking.
Producing of carbon fibers from acrylic
precursors involves a rapid stabilization
process.
The improvement comprises a two stage
oxidation process to permit substantially
complete permeation of oxygen throughout
the fiber structure.
Carbonization:
After oxidation the fibers are carbonized at > 1000C
without tension in an inert atmosphere for a few
hours.
During carbonizing process the non-carbon elements
are removed as volatiles to give carbon fibers with a
yield of about 50% of the mass of the original PAN.
The carbonization process proceeds mainly in two
stages
Between 400 600C denitrogenation occurs
The elimination of nitrogen continues above
700C and reaches a maximum rate at 900C.
At 1300C the fiber has a low nitrogen content.
Heat treatment higher than 2500C improves the
ordering and orientation of the crystallites in the
direction of the fiber axis. (graphitization)
Carbon fibers from Rayon
The conversion of rayon into carbon fibers is a
complex 3 stage process.
Stage 1 = stabilization (25 to 400C)
Stage 2 = Carbonization (400 to 700C)
Stage 3 = Graphitization (700 to 2700C).
Stabilization is basically an oxidative process.
The process goes through the following three
steps
Physical desorption of water (25 to 150C)
Dehydration from the cellulosic unit (150 to 240C)
Thermal cleavage of the cyclosidic linkage and
scission of ether c-o bonds and some c-c bonds via
free radical reaction (240 to 400C) and thereafter
aromatization
Carbon fibers from Rayon
At between 400 &700C the carbonaceous
residue is converted in to graphite like layers
by aromatization.
During this process the original preferred
orientation of the cellulosic structure is
destroyed.
That is why even after graphitization of the
fibers, there appears to be no preferential
orientation of the carbon structure.
To obtain high modulus fiber, graphitization
under strain is necessary as it will help to
achieve longitudinal orientation of the planes
Carbon fibers from Mesophase Pitch
The isolation of the components from a pitch
used as precursors for various carbon
products is possible if the thermodynamics of
various hydrocarbon mixtures are known.
The extraction of pitch by using a solvent
system of specified solubility parameter can
give a fraction which is ideal for carbon fiber
production.
High molecular weight aromatic pitches ,
mainly anisotropic in nature, are called
mesophase.
Carbon fibers from Mesophase Pitch
After spinning the mesophase molecules are oriented
parallel to the fiber axis giving a thermodynamically
stable structure.
Due to this structural stability the preferred
orientation of the molecule is partially retained during
carbonization process.
Before actual conversion, pitch is spun into a
precursor fiber.
The process of producing carbon fibers from
mesophase pitch is as follows
Commercial pitch = polymerization to mesophase
Melt spinning
Stabilization in air
Carbonization
Graphitization
Carbon fibers from Mesophase Pitch
The pitch precursor is thermally treated above
350C to convert it to a mesophase pitch.
Which contains both isotropic & anisotropic
phase.
After spinning the isotropic part is made
infusible by thermosetting in air at a
temperature below its softening point.
The fiber is then carbonized up to a
temperature of 1000C.
The main advantage of this process is that no
tension is required during the stabilization or
the graphitization steps unlike the case of the
rayon or PAN precursors.
Structure:
The characterization of the carbon fiber
microstructure has mainly been performed by
X-ray scattering and electron microscopy
techniques.
In PAN based fibers the linear chain structure
is transformed to a planer structure during
oxidative stabilization and subsequent
carbonization.
X-ray studies have shown that the intensity of
the main equatorial reflection at 2 = 17
from the plane lattice is initially increased but
is followed by a continuous decreased during
stabilization.
Structure:
At higher rates of the carbonization process,
a outer layer of a fiber is carbonized rapidly
and subsequent consolidation normally occurs
from the skin inwards, which results in a
hollow core at the end of the process.
Macrostructural heterogeneities are reported
to exist between an outer sheath and the
inner core of the PAN based fibers.
The core shows a lower preferred orientation
and a lower crystallite height.
Structure:
Data obtained by using x ray diffraction
techniques could be used to determine
the parameters
Layer plane separation
Lattice order
Average pore size
Crystallite size
Stacking height
Preferred orientation
Unit Cells
Properties:
Young's modulus of a carbon fiber is an
intrinsic property and it is governed by the
orientation of the graphitic crystallites relative
to the fiber axis.
A fiber having basal planes of the crystallites
lying within35 of the fiber axis had shown
a young's modulus of 103GPa while another
sample with an orientation angle of 10 was
found to have a young's modulus of 410GPa.
On the other hand, the strength of a carbon
fiber depends on the type of precursor, the
processing condition, heat treatment temp,
and the presence of flaws and defects.
Properties:
With PAN based fibers, strength increases up
on heat treatment, reaches a maximum value
at about 1500C and decreases there after at
a higher temp treatment.
Compared with other high performance fibers
both PAN based and mesophase pitch based
carbon fibers exhibit high tensile modulus
which can be varied considerable according
to the choice of processing parameters.
A spool of carbon fibers
Applications and new developments
Aircraft and space shuttle
Automotive
Sports and recreational equipment
Marine
General engineering
Miscellaneous.
GRAPHITE FIBER:
The mineral graphite is one of the
allotropes of carbon. It was named by
Abraham Gottlob Werner in 1789 from
the Greek
To draw/write", for its use in pencils
Graphite is an electrical conductor, a
semimetal, and can be used, for
instance, in the electrodes of an arc
lamp.
Graphite holds the distinction of being
the most stable form of carbon under
standard conditions.
A sample of graphite
Types:
There are three principal types of natural
graphite, each occurring in different types of
core deposit.
(1) Crystalline flake graphite (or flake graphite for
short) occurs as isolated, flat, plate-like particles
with hexagonal edges if unbroken and when
broken the edges can be irregular or angular.
(2) Amorphous graphite occurs as fine particles
and is the result of thermal metamorphism of coal,
the last stage of coalification, and is sometimes
called meta-anthracite. Very fine flake graphite is
sometimes called amorphous in the trade;
Types:
(3) Lump graphite (also called vein graphite)
occurs in fissure veins or fractures and appears as
massive platy intergrowths of fibrous or acicular
crystalline aggregates, and is probably
hydrothermal in origin.
Highly Ordered Pyrolytic Graphite or Highly
Oriented Pyrolytic Graphite (HOPG) refers to
graphite with an angular spread of the
between the graphite sheets of less than 1.
This highest-quality synthetic form is used in
scientific research. The name "graphite fiber"
is also sometimes used to refer to carbon
fiber or carbon fiber reinforced plastic.
Structure:

graphite's unit cell side view of layer stacking

Properties:
Graphite is a layered compound. In each
layer, the carbon atoms are arranged in a
hexagonal lattice with separation of
0.142 nm, and the distance between planes is
0.335 nm.
The two known forms of graphite, alpha
(hexagonal) and beta (rhombohedral), have
very similar physical properties (except that
the graphene layers stack slightly differently).
The hexagonal graphite may be either flat or
buckled.
Properties:
Graphites that naturally occur have been
found to contain up to 30% of the beta form,
when synthetically-produced graphite only
contains the alpha form.
The alpha form can be converted to the beta
form through mechanical treatment and the
beta form reverts to the alpha form when it is
heated above 1300 C.
The layering contributes to its lower density.
Properties:
The acoustic and thermal properties of
graphite are highly anisotropic, since phonons
propagate very quickly along the tightly-
bound planes, but are slower to travel from
one plane to another.
Graphite can conduct electricity due to the
vast electron delocalization within the carbon
layers. These valence electrons are free to
move, so are able to conduct electricity.
However, the electricity is only conducted
within the plane of the layers.
Applications:
Refractories
Steelmaking
Expanded graphite
Intercalated graphite
Brake linings
Foundry facings and lubricants
Other uses
in common pencils, in zinc-carbon
batteries, in electric motor brushes.