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4291 12253 1 SM PDF
4291 12253 1 SM PDF
@ 1993, DESIDOC
ABSTRACT
Carbon-carbon composites are a new class of engineering materials that are ceramic in nature
but exhibit brittle to pseudoplastic behaviotir. Carbon-carbon is a unique all-carbon composite with
carbon fibre embeded in carbon matrix and is known as an inverse composite. Due to their excellent
thermo-structural properties, carbon-carbon composites are used in specialised application like
re-entry nose-tips, leading edges, rocket nozzles, and aircraft brake discs apart from.several industrial
and-biomedical applications. The multidirectional carbon-carbon product technology is versatile and
offers design flexibility. This paper describes the multidirectional preform and carbon-carbon process
technology and research and development activities within the country .Carbon-carbon product
experience at DRDL has also been discussed. Development of carbon-carbon brake discs process
technology using the liquid impregnation process is described- Further the test results on material
characterisation, thermal, mechanical and tribological properties are presented.
I. INTRODUCTION
a crude form of carbon fibre for the first electric lamp3.
Carbon is a unique element that can exhibit different Germans used graphite for the jet vanes in the V 2rocket.
properties in different forms. Sollle forms of carbon are But its application in structures was limited because of
extremely hard, like diamond, while some forms are its failure even at low strains, thermal shock sensitivity,
extremely soft and ductile. Thus, in addition to its well anisotropy and processing difficulties for large and
defined .~Iotropic forms ( diamond and graphite) , complex shapes. The advent of carbon-carbon (CC)
carbon can take any number of quasi-crystalline forms composites changed the scene drasllcally.
ranging from amorphous or glassy carbon to highly 2. CC COMPOSITES
,
crystalline gfaphitel. The latest form of carbon (C60),
CC composites are a new class of engineering
discovered re'Cently, is called Fullerene, named after
materials that are ceramic in nature but exhibit brittle
Buck-Minister Fuller, the renowned American architect
to pseudoplastic behaviour. Carbon fibre
and philosopher. Fullerene is the roundest of all round
reinforcements when embedded in carbonaceous matrix
molecules, more like a soccer ball, and has properties
material results in CC composites. As in all com~sites,
like. high strength, ferromagneti.c properties,
the aim is to combine the advantage of high specific
Superconductivity and is an excellent semiconducto~ .
Full knowledge of its properties is still not acquired. strength and stiffness of carbon fibres with the refractory
properties of carbon matrix. When the fibres are laid
The changing Defence scenario and satellite in near-net shapeswith multidirectional reinforcements,
i launchings using re-usable launch vehicles led to
the result is an ideal high temperatu-"e structure.
vigorous search for light weight, ultrahigh temperature
materials. For a long time, carbon has been known for 2.1 Unique Features
its high temperature properties and is widely used in These composites are the best among all high
heating elements. In 1879, Thomas Alva Edison used temperature materials becausethey are thermally stable
--
Received12september1993
369
)f $( VOL NO )(IOBER 1993
and do not melt up to 3000°C, have high thermal candidate material in glass industry , furnace and
conductivity and low thermal expansion (thus having semiconductor industry as well as for preventing
high resistance to thermal shock) and retain their corrosion in chemical plants4. One interesting and
mechanical strength to the end. Also, these composites innovative use is as tooling material for metallurgical
maintain good frictional properties over the entire superplastic stage forging process. Other high tech
temperature range with low wear. They have high applications are as heat exchanger tubes for helium
fracture toughness and do not fracture in a brittle cooled high-temperature '1uclear reactors, high
manner like conventional ceramics. A multimode temperature crucibles, fastners, load bearing plates,
mechanism of fracture occurs where the fibres break as rods and heating elements. Elemental carbon is "nown
well debondl.ll. The brake discs for high speed aircrafts to have the best biocompatibility with blood and soft
like Mirage 2{)()(), Concorde, Airbus-320 are Some of tissues. Thus it finds use in hi,p bone endoprosthesis,
the example where the favourable frictional properties bone plates, osteosynthesis and artificial heart valves.
were put to use. The first generation CC composites
h:ld the limitation of proneness to oxidation over long 3 CC COMPOSITES: F ABRICA TION PROCESS
exposures. However, with the advent of second AND STRUCTURAL DESIGN
generation oxidation-resistant composites, this
limitation was overcome. These unique features made 3 Fabrication Process
it the most favourite material for re- entry nosetips,
Classically, carbon ceramics are fabricated by
leading edge material for space shuttle wings, rocket
combining solid particles of pure carbon (known as
nozzles, thrust vectoring nozzles using CC ball and
primary carbon) with a preliminary binder which acts
socket joints and high performance turbojet engines.
as a precursor for secondary carbon formed during the
carbonisation process. In CC composites the carbon
2.2 International Status of CC Composites fibres (based on rayon/P AN/pitch) in the form of U- D ,
CC composites have their origin in the jet vanes 2-0 and multi-directional preforms are used as primary
used in the German V 2 rockets. The jet vanes were carbon rather than particulate fillers. There are two
made of graphite which eroded rapidly and had limited distinct techniques used to fill the interstices between
the carbon fibres. These are (i) gas phase using a
life. Subsequently. pyrolitic graphite. A TJ graphites
were used. which when reinforced with carbon fibres chemical vapour deposition process, and (ii) the liquid
gave birth to CC composites. Major work is going on phase route using thermosetting resins or pitch (PIC).
in USA. France and former Russia. There is a great The fibres can be very stiff, highly oriented graphitic
and dense (pitch precursor) or. relatively flexihle ,
demand for CC brake discs for aircrafts. trains. trucks
stronger, less oriented graphitic and less dens.e (P AN
and even racing cars. The pioneers in this field are
Bendix in USA and Dunlop in UK. Nigrafitc. Moscow, precursor). Conversely, the matrix can be highly
oriented and graphitic if produced from pitch, either
is the leading organisation in former USSR. Little is
isotropic or anisotropic if produced from CVO or
known about its products, while Germany and Japan
usually isotropic if produced from thermosetting resin
are in the race for industrial applications. Israel. Taiwan.
and Egypt were reported to have initiated some R&D using phenolic resin~.A general rule of thumb cmployed
by manufacturers is that the gas phase route is adequate
activities. A study conducted by Dr Robert A; Meyer
for thin-wallcd parts and the liquid phasc route is
on CC composite research in the Fa! East indicates
prcferablc for thick partsn. A combination of liquid and
that, apart from India. as many as 18 institutions in
gas phase processes is also being followcd. Fig. I givcs
Japan, 4 in China. 3 in Taiwan, 3 in Korea, 2 in Australia
the general process flow sheet.
are carrying ()ut active research on different aspects of
CC technology. His assessment indicates that the
3.2 Multidirectionally Reinforced Preforms
coJlective research efforts in Japan and other Asian
countries will improve and, in time. surpass the research The main advantage of multidirectional CC
activities in the United States if the present financial composites is the freedom to orient selected fibres and
support trend continues. Internationally. the stress is amounts to accommodate the design loads of the final
on industrial applications. CC composites are a structural component and make them virtually
17()
ROHINI DEVI & RAMA RAO: CARBON-CARBON COMPOSITES
3-DIRECTIONAl ARRAY
5-D4R£CnONAl ARRAY
I
Thermal, mechanical and p.hysical properties of the Figure 3. 3-0, 4-0, and 5-0 arrays,
composites can be controlled by the appropriate design
preform. These characteristics are calculated 'for a
of substrate parameters such as fibre orientation,
typical unit cell in the preform. Several weave
volume fraction of fibres in the required direction 7.
modifications to the basic 3-0 orthogonal designs are
Preform weaving technology provides the ideal
possible as shown in Fig. 3, to form a more isotropic
approach to tailor the structural composites. The
structure in 4-0,5-0,7-0 and 11-0. To enhance the
simplest type of multidirectional structure is based on
composite properties between the planes, diagonal
a three directional (3-D) orthogonal construction as
yarns are introduced. The multidirectional preform
shown in Fig. 2, consisting of multiple yarn bundles
technology, also known as the fibre architecture,
located within the structure described in cartesian
employs multidisciplinary approaches of structural
co-ordinates. In any direction, fibre bundles are straight
engineering, mechanical engineering and textile
in order to obtain the maximum structural capability of
technology to develop preforms in simple blocks,
fibre. The type of fibre, the number of fibre bul,u,~s
cylinders, cones, contours, surfaces of revolution and
per site, the fibre bundle spacings, volume fraction
complex geometries and shapes. The techniques
distributions, the woven bulk densities characterise the
employed are conventional weaving with dry yarns,
pierced fabrics, assembly of pre-cured rods, on manual,
semiautomated and automatic loom set-ups and 3-0
braiding anc 3-0 knitting. Countries like USA, France
where this technology was pioneered, have kept this
technology closely guarded due to its immediate
adaptability to strategic products. With relentless efforts
and innovation, OROL has developed the
multidirection311y reinforced prefor:m technology for
3-0,4-0,5-0 and 6-D preforms in blocks and cylinders
with varying weave parameters. The technology and
facilities are established to develop multidirectional
preforms using, manual and semi-automated looms.
Figure 4 shows the possible material variants to
preforming8. The weaving tcchnology and defect
figure 2 .\-dimen~ional array. characterisation techniques are developed to realise
371
~
ROHINI DEVI & RAMA RAO: CARBON-CARBON COMPOSITES
4. CC PROCESSING TECHNOLOGY
The CC .densification process inv()lves in-depth
deposition of secondary carbon from different GRAPHITISATION
r ~---,
precursors using either gas phase impregnation or the I
I
I
I
373
DEF SCI J, VOL 43, NO 4. OcrOBER 1993
374
ROHINI DEVI & RAMA RAO: CARBON-CARBON COMPOSITES
l.J
~ 10 6. CC PRODUCT DEVELOPMENT EXPERIENCE
i=
l.J
u. DRDL has initiated research and development
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activities in different aspects of CC technology for
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u. realising several hi-tech CC products. The main thrust
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of the effort is to establish the CC composite process
0.1 technology and the study of the influence of: (i) different
types of carbon fibres in various fibre architectures,
(ii) impregnants, and (iii) process parameters of
UNPROTECTED SIliCON MULTILAYER MULTlLAYER impregnation, carbonisation, high pressure carbo-
CARBON CARBON CARBIDE COATED PlUS
COATED INHIBITOR
nisation and graphitisation, on microstructure, physical,
Figure 8. Process in oxidation protection research.
thermal, mechanical, thermo-structural and tribological
performance of CC composites. DRDL has pioneered
composites constitute a diverse class of materials with the challenging tasks of design, development and
a wide range of mechanical, thermal and morphological qualification of full scale prodocts like 3-D and 4-D CC
properties. Selection of appropriate fibre, preform composites and CC aircraft brake discs. Research is
fabrication technique, matrix precursor and under active progress for biomedical products like CC
densification processing method is essential if good bone implants and heart valves. Collaborative research
oxidation resistance as well as physico-chemical with NPL includes development of pitch impregnants
compatibility between substrate and coating is to be and oxidation-resistant CC composites. Extensive
achieved. The progress on research on oxidation process and material characterisation data have been
protection is illustrated by the bar chart shown in Fig. 8. generated during the development of the above
mentioned products. While in multidirectional CC
5.2 Higher Oxidation Resistance composites, preforming with multidirectional
Introduction of a ceramic matrix like SiC instead of reinforcements is a complicated and challenging task,
carbon matrix in the carbon fibre preform gives higher in bi-directional composites densification is a complex
oxidation resistance than that of oxidation-resistant CC. process involving optimum selection ~f process
These composites known as ClSiC composites provide parameters like heating rates, temperatures, pressures
a good trade off between the high temperature and pressure gradients to avoid delamination due to
capability of carbon fibres and the high oxidation evolution of pyrolysis gases, shrinkage and thermal
resistanceof ceramic matrices. Extensive work has been stresses.DRDL has conducted systematic and planned
carried out by SEP FRANCE on ClSiC composites for experimentation to establish densification process
liquid propellant rocket and air breathing engines, parameters to get delamination-free 2-D composites.
thrust vectonng no1Zles, hot gas valves and tubes and Development experience of CC composite brake discs
space plane thermal structures. The third family of is chosen to discuss some of the process and test data
thermo-structural composites, viz. SiCISiC, employ generated.
ceramic fibres (SiC) and ceramic matrix (SiC). These
composites provide an excellent oxidation resistance for 6.1 Development of CC Brake Discs
long durations and capable of withstanding thermal cc composites are used in aircraft ~rakes as
cycling for re-usable structures. SiCISiC composites are thermostructural, frictional and as heat sink materials.
used for liquid propellant rocket engine chambers, jet Aircraft wheel brakes, in addition to producing the
engines, gas turbine components and space thermal required drag by generating frictional torque, have to
structures. However, SiCISiC composites start losing absorb large quantities of energy in the form of heat.
the mechanical strength beyond 12000Cunlike carbon CC composites have been developed to meet these
375
DEF SCI J. VOL 43. NO 4. OcrOBER 1993
THERMO-STRUCTURAL COMPOSITES
PERFORMANCE PROFILE
1(XXX)-
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,z 1000
E
SIC/sk: \
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100
~ CAR~
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, 00 200 300 400 500 , 000 2000 3(XX)
ro.PERA~C
property requirements. CC brake discs offer significant Table 2. Properties of different di!ic material!i
376
~
ROHINI DEVI & RAMA RAO: CARBON-CARBON COMPOSITES
: 0.03
of fibres and matrix, pore distribution, isotropy and
anisotropy of matrix formation and filling of cracks and
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extent of damage during either processing or testing.
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1&1 Microstructure of carbon-carbon composites has been
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studied using optical and scanning electron microscopes
(SEM). Composite samples made with different types
0
2 J of fibres and matrices are studied at various stages of
tEAT SN< LOAOt4G IMJ/k91
processing and also after subjecting to friction testing.
Figure 10. Comparativewear rates of brake disc materials. Figure 11 shows the optical micrograph of
advantages of CC composites over conventional brake carbon/phenolic sample in transverse (TS) and
disc materials in terms of wear . longitudinal (LS) directions. Bulk phenolic resin matrix
is seen between the layers and between carbon fibre
CC brake materials usually comprise different types
tows (Fig. 11(a». Bulk matrix has micropores which
of carbons each of which exhibits different friction and
are produced during the curing of phenolic resin because
wear characteristics. For example, carbon fibre
of volatile evolution. Figure 11(b) shows the
reinforcement may be from P AN, rayon or pitch
accumulation of resin near the tows crossove:r points,
precursors in different fibre architectures to meet the
of fabric weave.
thermostructuraJ and tribological performance.
377
DEF SCI J. VOL 43. NO 4. OCTOBER 1993
(a)
378
ROHINI DEVI & RAMA RAO: CARBON-CARBON COMPOSITES
ROSO-II
AFTER
TESTING
0-7
1500x
AIR
EXPOSEO
SURFACE
(a) (a)
0-7
11x
(b) (b)
figure 15 SEM micrograph or air-exposed surface of Figure 16. SEM micrograph of friction surface of dynamometer
dynamometertested CC disc samples. tested CC brake disc '.
379
DEF SCI J. VOL 43, NO 4, OcrOBER 1993
pressure carbon;sation, intermediate graphitisation and Atmospheric pressure carbonisation, it takes 15-17
machining. The stages involved iD the processing of densification cycles to get a density of 1.7 g/cc. In high
discs are: (i) skeleton formation, and (ii) densification pressure carbonisation process, it was possible to
using multiple pitch impregnation, carbonisation achieve this density just in there densification cycles
(atmospheric pressure/high pressure) and after process optimisation. Figure 17 shows the
graphitisation. In the case of skeleton formation with differences in the densification by the various processes,
resin, first carbonisation is very important. Optimised viz. atmospheric carbonisation, high pressure
cycle is to be followed to avoid the delaminations. carbonisation and an optimised densification sequence.
Heating rates as low as 4°C/hr are to be used in the Graphitisation is another important step in the
pertinent zones. Selection of cycle parameters is highly development of brake discs, which changes the
dependent on product shape and size. A carbonisation microstructure of amorphous carbon to graphite like
cycle optimised for a small product cannot be directly structure. The extent of graphitisation depends on the
used for larger discs. Delamination during skeleton precursor used. Oelaminations during graphitisation
formation was the main problem during the was a major problem during the initial development.
development of full scale products. This was solved by This problem was solved by choosing appropriate
using appropriate heating rates during different stages heating cycle. Not only the heating rates but also the
of pyrolysis and loading methods. For the densification ultimate temperature has considerable bearing on the
of skeletons, two options are available for final thermal, mechanical and tribological properties of
carbonisation: (i) atmospheric pressure carbonisation, .;le composites. Graphitisation temperature affects the
and (ii) high pressure carbonisation. properties of resin carbon and pitch carbon to different
extents.
1.8
1.7
-1.6
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>- 1.5
t-
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1.3
1.l
B( (1 01 D2 03 Dl. OS 06 07 D8 09 D10 011 012 013 011. 015 016
DENSIFICATION CYClES
380
ROHINI DEVI & RAMA RAO: CARBON-CARBON COMPOSITES
3-DCC 4-DCC
l:j Fibre type Rayon Pan
:..
,
~ based based
"6
~
Fibre volume
'4
~
fraction (0;0)
(J Total 44 38
iA:
(3 Z direction 27.7 13.8
111
IL
1/1
X- y direction 8.14
Eaeh
U, v, W direction 8.0
Pbysical properties
(i) Density (g/cc) 1.80 1.816
(ii) Porosity (% ) 7.498 11.90
thermal conductivity as well as specific heat of the Reinforcement type PAN(HS) PAN(HS) PAN(HM) PAN(HS)
composite, the increase being more pronounced in case Typeoflay-up Plain Plain Plain Plain
of P+p composites; it is 2-3 times higher when heat Type of matrix Resin! All Resin! Resin/
treatment temperature is raised from 2000 to 2600°C. pitch pitch pitch pitch
6.1.3 Physical Thermal and Mechanical Properties Density (g!cc) 1.64 1.74 1.65 1.73
Open porosity (%) 7.80 7.23 6.69 7.42
Table 4 lists the physical, thermal & mechanical Flexural strength (MPa) 214 206 149 191
properties measured on the multidirectional composite ILSS(MPa) II 14 11
samples, The test data on 2-0 CC composites made Tensile strength (MPa) 105 120 132
with P AN-based high-strength and high-modulus Compression strength 126 109 127
carbon fibres, are presented in Table 5. (MPa)
381
DEF SCI J, VOL 43. NO 4, OcrOBER 1993
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128
TEST CONDITIONS
TEST PLAN
R.T.O
WHEEL
1196 1250 1250
RPM
MASS
INERTIA 136 174 276
2
kgf/s
BRAKE 90 1038 157
PRESSURE
382
~
ROHINI DEVI & RAMA RAO: CARBON-CARBON COMPOSITES
OV£R
lOADOO6YST" Composite Brake Disc Technology' and also the Vikram
Lo.s
1000-j
/ Sarabhai Space Ce-ntre (VSSC), Trivandrum for
\ , \.~ LAY-II'It'ROvm i
800-1
I extending the-support for thermal characterisation.
-I '\, .,
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-- REFERENCES
« I
~ I , --.:::.><
---~
1,00-1
I ~.~~'-,
,,...
-s--
~.--
.;::
, .--, ...
0.2
1 Fitzer, Erich. The future of carbon-carbon
I
I composites. Carbon, 1987, 25(2), 163-90.
200-J ~11'/ 0.1
2 Singh, Himmat.New generation carbon materials.
Paper presented in National Workshop on Newer
oJ.- I I .., -r-!-
1200 1000 800 600 400 200 0 Carbon Products -Indian Scenario, held in
SPEED (rpll) Bangalore, 9-10 October 1992.
3 Delmonte, John. Technology of carbon and
Figure 21 Variation of torque and coefficient of friction
typical brake runs.
graphite fibre composites, Van Nostrand Reinhold
Company, New York, 1981. pp. 388-419.
In the case of rosette lay-up, coefficient of friction
4 International symposium on carbon 1990
was in the range 0.20-0.26 and wear was 8
(Tsukuba). .
microns/face/stop. In the case of plain lay-up, coefficient
~ Wright, Maurice A. Materially speaking.
of friction was in the range 0.13-0.18 and wear was on
the higher side. Figure 21 shows the torque recorded Materials Technology Center, Southern 1Iiionis
University, 1990. ,
as a function of speed during typical normal and
overload stops, it also incorporates the variation of the 6. Appell, Y .F .New composite materials for
coefficient of friction during a typical run carried out aerospace motor nozzles and their applications in
with rosette and plain lay-up discs. Analysis of the total the aircraft industry. French Aerospace Seminar
test data in relation to the material characterisation held in Bangalore, 1981.
pointed to the need for certain improvements with 7 Mcallister, L.E. Multidirectional carbon-carbon
respect to degree of graphitisation, thermal conductivity composites. In Hand book of composites, 1983,
and the fibre volume. Vo14, pp. 109-75.
To improve the thermal conductivity, toughness and 8, Choury, J .J .Thermostructural composite
tribological properties, a new batch of discs are materials in aeronautics and space application
processed and successfully tested in the dynu...vmeter French Aerospace 1989 (Aeronautical and Space
simulating normal, overload and rejected take off Conference) 15-17 Febuary 1989, Delhi.
conditions. Coefficient of friction was consistent in all
9 Klein, Allen J. Corbon-carbon composites:
the 30 normal energy stops and the value is 0.22-0.33
advanced materials and processes.Metal Progress.
with a stop time of 22.5-32.5 seconds. Figure 21 shows
1986, 130(5),64-68.
the coefficient of friction recorded during a typical run
of the improved material. 10. W..:bb, Richard D. Oxidation resistant
carbon-carbon material. Research Project abstract
ACKNOWLEDGEMENTS by A VCO Systems USA.
The authors wish to thank; the Aeronautical Huttner, W. Carbon-carbon--an inverse
Development Agency (ADA), Bangalore for composite structure. Z. Werkstofftch, 1985, 16,
sponsoring the project on 'Development of CC 430-35.
383