CARBON-CARBON COMPOSITES 15

John D. Buckley

15.1 INTRODUCTION n

Carbon-carbon (CC) materials are a generic

class of composites similar to the
graphite/epoxy family of polymer matrix
composites. These materials can be made in a
1-D 2-D
wide variety of forms, from one-dimensional
to n-dimensional, using unidirectional tows,
tapes, or woven cloth (Fig. 15.1). Because of
their multiformity, their mechanical properties
can be readily tailored (Table 15.1). Carbon
materials have high strength and stiffness
potential as well as high thermal and chemical
stability in inert environments. These materi- 3-D n-D
als must, however, be protected with coatings
and/or surface when used in an OXi- Fig. 15.1 Multiformity and general properties of
dizing environment. carbon-fiber and carbon-matrix composites.

The development of CC materials began in

Table 15.1 General properties of carbon-carbon 1958 and was nurtured under the US Air Force
composites space plane program, Dyna-Soar and NASA's
Apollo projects. It was not until the Space
Ultimate tensile >276 MPa >40 000 psi Shuttle Program that CC material systems
strength were intensively researched. The criteria that
Modulus of >69 GPa >lo7 psi led to the selection of CC composites as a ther-
elasticity mal protection system were based on the
Melting point >41OO0C 7412°F following requirements:
Thermal ~11.W
5 m-' K-' 6.64
conductivity h ft "F 1. maintenance of reproducible strength levels
at 1650°C (3002°F);
Linear thermal ~ 1 .x110"OC 6.1 x W7"F
expansion 2. sufficient stiffness to resist flight loads and
large thermal gradients;
Density <2990 kg m-3 186.6 lb/ft3
3. low coefficient of thermal expansion to min-
imize induced thermal stresses;
Handbook of Composites. Edited by S.T. Peters. Published 4. oxidation resistance sufficient to limit
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7 strength reduction;
334 Carbon-carbon composites
5. tolerance to impact damage;
6. manufacturing processes within the state of
the art.
Carbon-carbon composites consist of a fibrous
carbon substrate in a carbonaceous matrix.
Although both constituents are the same ele-
ment, this fact does not simplify composite
behavior because the state of each constituent
may range from carbon to graphite.
Crystallographic carbon, namely graphite,
consists of tightly bonded, hexagonal
arranged carbon layers that are held together
by weak van der Waals forces. The single crys-
tal graphite structure is illustrated in Fig. 15.2
(Bokros, 1969). The atoms within the layer
E a
Reference directions
Fig. 15.2 Tightly bonded, hexagonally arranged carbon layers held together by weak van der Waals forces.
I
LC
Fig. 15.3 Comparison of (a) carbon turbostratic structure with (b) 3-D graphite lattice (Bokros, 1969).
plane or basal plane (a-b direction) have a
covalent bond strength of =524 kJ/mol
(Kanter, 1957), while the bonding energy
between basal planes (c direction) is =7 kJ/mol
(Dienes, 1952). The result is a crystal that is
remarkable in its anisotropy, being almost
isotropic within the basal plane but with c
direction properties that differ by orders of
magnitude. On a larger scale, carbon, in addi-
tion to its two well-defined allotropic forms
(diamond and graphite), can take any number
of quasicrystalline forms ranging continu-
ously from turbostratic (amorphous, glassy
carbon) to a highly crystalline graphite (Fig.
15.3) (Bokros, 1969).
:rdo02

The anisotropy of the graphite single crystal
encompasses many structural forms of carbon.
It ranges in the degree of preferred orientation
of the crystallites and influences porosity,
among other variables. A broad range of prop-
erties is the result of this anisotropy. In CC
composites, this range of properties can
extend to both constituents. Coupled with a
variety of processing techniques that can be
used in the fabrication of CC composites, great
flexibility exists in the design of and the resul-
tant properties obtained from CC composites.
The wide range of properties of carbon
materials can be shown when comparing the
tensile modulus of commercially manufac-
tured carbon fibers that range from 27.6 GPa
(4 x 106psi) to 690 GPa (100 x lo6psi). In fabri-
cation, the fibers can be used in either
continuous or discontinuous form. The direc-
tionality of the filaments can be varied ranging
from unidirectional lay-ups to multidirec-
tional weaves. Fiber volume fraction
constitutes another variable. The higher the
volume fraction of a specific high-strength
fiber in a matrix, the greater the strength of the
composite. The matrix can be formed via two
basic approaches: (1) through the carboniza-
tion of an organic solid or liquid, such as a
resin or pitch, or (2) through the chemical
vapor deposition (CVD) of carbon from a
hydrocarbon. A range of carbon structures can
be obtained by either approach. Finally, heat
treatment of the composite material at graphi-
tization temperatures offers additional
variability to the properties that can be
obtained. Typically, there is an optimum
graphitization temperature at which the high-
est strength can be obtained for a given
composite composition of fiber and matrix
(Edie et al., 1986; Stoller et al., 1974).
15.2 CARBON FIBERS
The properties of carbon fibers can vary over a
wide range depending on the organic precur-
sor and processing conditions used. At
present, graphite fibers are produced from
Carbon fibers 335
three precursor materials: rayon, polyacryloni-
trile (PAN)and petroleum pitch. Fibers having
a low modulus (27.6 GPa (4 x 106 psi)) are
formed using a rayon precursor material that
may be chemically pretreated by a sequence of
heating steps. First, the fiber is heated to
>400"C (752°F) to allow cellulose to pyrolyze
(decomposition or chemical change during
thermal conversion of organic materials to car-
bon and graphite). Carbonization (continued
heating of organic material to >lOOO"C (1832°F)
to initiate ordering of the carbon structures
produced by pyrolysis) is completed more
rapidly at >lOOO"C (1832°F).Upon completion
of carbonization, the fiber is graphitized (con-
tinued heating of carbonized organic materials
to the 2000-3000°C (3632-5432°F) range of
produce 100% graphite-ordered crystal struc-
ture) by heating to >2000"C (3632°F);the fiber
is now, for all practical purposes, 100% carbon.
High-modulus carbon fibers from rayon pre-
cursors are obtained by the additional process
of stretching the carbon fibers at the final heat
treatment temperature. Nigh-modulus (344
GPa (50 x 106 psi)), high-strength (2.07 GPa
(300 x lo3 psi)) carbon fibers are typically
made from PAN or, in some cases, mesophase
pitch precursors. These fibers are processed
similarly in a three-stage operation (Fig. 15.4)
(Diefendorf, 1987).The PAN fibers are initially
stretched from 500-1300% and then stabilized
(cross-linked) in an oxygen atmosphere at
200°C (392°F)to 280°C (536°F) under tension.
Carbonization of the fibers is conducted
between 1000°C (1832°F)and 1600°C (2912°F).
Finally, graphitization is accomplished at
>2500"C (4532°F). Mesophase pitch fibers
undergo the same processing procedure as
PAN fibers but do not require an expensive
stretching process during heat treatment to
maintain preferred alignment of crystallites
(Fig. 15.4) (Diefendorf, 1987). Control of fiber
shape has resulted in improved fiber strength
(4.1 GPa, 600000 psi) (Cogburn et al., 1987)
when produced from melt-spun, mesophase
petroleum pitch (Fig. 15.5) (Cogburn et al.,
1987). Round fibers using the same method
336 Carbon-carbon composites

PAN process

Pitch process 1
tCarbonize
z z I I Graphitize
zim

Spool Epoxy sizing Surface treatment

Fig. 15.4 Carbon fiber production using PAN and pitch processes (Diefendorfer, 1987).

Hydraulic piston

Cartridge housing
Heating collar
Melted-pitch precursor
Spinnerette

Melt-spun carbon
Melt-pressure indicator filaments

Wind-up bobbin

Fig. 15.5 Melt spinning apparatus used to produce noncircular carbon fibers (Cogbum et al., 1987).
 Carbonfibers 337

had a strength of 2.1 GPa (300 x lo3 psi) (Edie
et al., 1986).Of the shapes studied, the C-shape
and hollow fibers were found to be superior in
strength to round solid and trilobal cross sec-
tions (Edie et al., 1986; Cogburn et al., 1987).
15.2.1 CARBON FIBERS IN CARBON MATRIX
Addition of a matrix to carbon fiber, either
through the carbonization of an organic pre-
cursor or by the deposition of pyrolytic
carbon, is conducted at 800°C (1472°F) to
1500°C (2732°F).Subsequent heat treatment of
the composite material may involve tempera-
tures to 3000°C (5432°F).
15.2.2 DISCONTINUOUS FIBER COMPOSITES
Fabrication of discontinuous fiber composites
uses short carbon fibers combined with either
a pyrolytic carbon or pyrolyzed organic
matrix. This approach to CC composites gen-
erally does not have true fiber reinforcement
as an objective. Rather, discontinuous fiber
substrates have been used to:
1. increase fabrication capability of large-scale of the felt. Carbon content in the fibers is
structures;
2. achieve a more nearly isotropic material;
3. increase the composite interlaminar tensile
strength;
4. along with continuous filament substrates,
obtain a stronger composite by providing
additional nucleation sites that serve to
reduce composite porosity.
The most widely used starting materials are a
carbonized, rayon felt substrate with a
pyrolytic carbon matrix and short, chopped
fibers in a pitch-based matrix. Felt is produced
through the mechanical carding of viscous
rayon fibers to produce a continuous web of
fibers. The webs are folded one on top of
another to produce a batt. The batts are then
cut, stacked and needled to produce the
required felt. The rayon felt is subjected to a
controlled carbonization cycle in an inert
atmosphere or vacuum; the maximum temper-
ature determines such factors as shrinkage,
weight loss and chemical composition of the
felt. A maximum carbonization temperature of
1200°C (2192°F) is a nominal standard; the
length of the carbonization cycle and rate of
temperature rise are dictated by the thickness
~ 9 8 % .Carbon-arbon composites have also

Fig. 15.6 Models of fiber arrangements for four short-fiber fabrication techniques: (a) flocking lay-up, (b)
pulp molding, (c) isotropic casting, and (d) spray lay-up (Cook, Lambdin and Trent, 1970; Lambdin, Cook
and Marrow, 1969; Lambdin and Cook, 1971).
338 Carbon-carbon composites
been fabricated from short carbon fibers using
isotropic casting, flocking lay-up, spray lay-up
and pulp-molding techniques (Fig. 15.6)
(Cook, Lambdin and Trent, 1970; Lambdin,
Cook and Marrow, 1969; Lambdin and Cook,
1971.).The rationale for using these short fibers
is to reduce composite anisotropy (Lambdin,
Cook and Marrow, 1969).
15.3 CONTINUOUS FIBER COMPOSITES
Continuous filament substrates reflect the
properties of high-strength filaments or
achieve a high degree of preferred orientation
on the macroscale of the matrix. The fabrica-
tion complexity for continuous-filament
substrates is determined by two parameters:
(1)the directionality of the filaments, and (2)
the amount of layer interlocking achieved in
the substrate. Filament winding of unidirec-
tional tapes can be used to achieve a highly
Fig. 15.7 Interlocking approaches of continuous filament substrates: (a) tape wrapped, shingle; (b) filament
wound, helix; and (c) multidimensional.
oriented substrate, usually with no interlock-
ing between layers. Woven fabrics are used to
form a two-dimensional laminate with no
interlocking between layers. Helical filament
winding, which is directional, results in con-
tinuous, adjacent layer interlocking.
Multilayer locking is achieved through com-
plex weaving patterns or yarn placement
resulting in 'multidirectional' substrates (Fig.
15.7).
15.4 CHEMICAL VAPOR DEPOSITION
The CVD of carbon from a hydrocarbon gas
within a substrate is a complex process.
Various techniques have been applied to infil-
trate various fiber substrates including
isothermal thermal gradient (Pierson, 1968),
pressure gradient (Kotlensky and Pappis,
1969) and pressure pulsation (Beatty and
Kipplinger, 1970).The first two have been the
 Carbonized organic composites 339

most extensively used. The isothermal tech-

nique is illustrated in Fig. 15.8. The substrate is
radiantly heated by an inductively heated sus-
ceptor so that the gas and substrate are
maintained at a uniform temperature.
Infiltration is normally accomplished at
1100°C (2012°F) and at reduced pressures
(6 kPa (50 torr)) with the flow rates primarily
determined by the substrate surface area. This
technique produces a crust on the outer sur-
faces of the substrate, thus requiring
machining and multiple infiltration cycles.
In the thermal gradient technique (Fig.
15.9), the part to be infiltrated is supported by
a mandrel that is inductively heated.
Therefore, the hottest portion of the substrate Hydrocarbon 2(-Carrier Original fiber
is the inside surface, which is in direct contact gas gas substrate
with the mandrel. The outer surface of the
low-density substrate is exposed to a cooler
environment and results in a temperature gra- Fig. 15.8 Isothermal chemical vapor deposition to
dient through the substrate thickness. Surface infiltrate fibrous carbon substrate.
crusting is eliminated because the deposition
rate is greater on the heated fibers near the
mandrel, whereas the cooler outer fibers
receive little or no deposit. Under proper infil-
tration conditions, the carbon is first deposited
on the inside surface and, in a continuous
process, progresses radially through the sub-
strate as the densified substrate itself becomes
inductively heated. Infiltration is normally
accomplished at atmospheric pressure with a
mandrel heated to approximately 1100°C
(2012°F) (Theis et al., 1970).

15.5 CARBONIZED ORGANIC COMPOSITES

Carbonized organic composites have fabrica-
tion procedures that are similar to those of
conventional fiber-reinforced, resin-laminat-
ing techniques. The starting material is usually
a prepregged fabric or yarn (a fabric impreg-
nated with a matrix material in a tacky state).
These precursor materials are staged nomi-
nally at approximately 100°C (212°F) to
achieve the desired degree of tack and flow of
the resin. A laminate is then constructed and Fig. 15.9 Thermal gradient chemical vapor deposi-
cured under pressure. Curing temperatures tion.
340 Carbon-carbon composites
AprepreK+ Cut, lay-up,
Fig. 15.10 Fabrication steps involved in manufacture of 2-D carboniarbon part impregnated with
tetraethylorthosilicate (TEOS).
normally range from 125°C (257°F) to 175°C
(347°F) with curing pressures on the order of
2.76 MPa (400 psi). The reinforced resin lami-
nate is then post-cured at 200°C (392°F) to
275°C (527°F).As pyrolysis is initiated, shrink-
ing occurs as the organic phase decomposes.
Simultaneously the release of vapors from
pyrolysis expands the composite material. A
slow release of these volatile by-products is
required to minimize structural damage to the
char. Finally, as higher temperatures are
reached, thermal expansion of the carbon char
itself occurs after pyrolysis is complete. After
the initial carbonization, the material is then
subjected to a series of reimpregnation and
carbonization cycles until the desired density
or the maximum density is achieved. The
reimpregnation process is usually conducted
under vacuum and pressure to aid in maxi-
mizing the pore filling. If graphitization is
desired, the high-temperature heat treatment
may be used after each carbonization step or at
the end of the reimpregnation and recar-
bonization cycles.
3 t o 5 times I cure I
To summarize, a typical manufacturing cycle
of a 2-D CC part is shown in Fig. 15.10.First, a
woven graphite fabric that is preimpregnated
with phenolic resin is laid up as a phenolic-
graphite laminate in a mold and is autoclave
cured. Once cured, the part is pyrolyzed to
form a carbon matrix surrounding the graphte
fibers. The part is then densified by multiple
furfural alcohol reimpregnations and pyrolyza-
tions. The resulting CC part then is ready for
use in inert or vacuum environments. This
process is very time consuming. A single pyrol-
ysis may take >70 h in a low-temperature,
inert-atmosphere furnace.
Although CC materials can withstand tem-
peratures >3000"C (5432°F) in a vacuum or in
an inert atmosphere, they oxidize and sublime
when in an oxygen atmosphere at 600°C
(1112°F). To allow for use of CC parts in an
oxidizing atmosphere, they must be com-
pounded with materials that produce
oxidation-protective coatings through thermo-
chemical reaction with oxygen at >2000"C
(3632°F) (Buckley, 1967) or they must be coated

and sealed to protect them (Strife and Sheehan,
1988). For applications such as the Space
Shuttle CC leading edges and nose caps, sur-
faces are converted to silicon carbide in a
high-temperature diffusion-coating process
(Fig. 15.10). Because of differences in thermal
expansion between the silicon carbide and the
CC part, the coating develops microcracks
when the part is cooled from the coating tem-
perature. To maintain oxidation protection on
space vehicles such as the Space Shuttle, cracks
are impregnated with tetraethylorthosilicate
(TEOS).The TEOS process leaves silica in all of
the microcracks, greatly enhancing the oxida-
tion protection of the CC substrate. Current
improvements being developed for oxidation
protection of the CC Space Shuttle components
are additions of low-temperature glass formers
that enhance the sealing capability of the exist-
ing coating-TEOS system.
15.6 MANUFACTURING
The fabrication process of the Space Shuttle
Orbiter nose cap and wing leading edge com-
ponents (Fig. 15.11) (Curry, Scott and Webster,
1979) is a multi-step process typical of the
technology used to produce CC composites.
The process steps are illustrated in Figs.
15.12-15.16.
Initial material lay-up is similar to conven-
tional practices with fiberglass-reinforced
plastic parts. Square-weave graphite fabric
impregnated with phenolic resin is laid-up in
an epoxy/fiberglass mold cavity shaped to the
desired configuration (Fig. 15.12) (Curry, Scott
and Webster, 1979).Lay-up thickness for these
components varies from 19 plies in the exter-
nal skin and web areas to 38 plies in the
attachment locations. Upon completion of lay-
up, the part is vacuum-bagged and cured in an
autoclave to 150°C (300°F) for 8 h (Fig. 15.12).
The cured part is rough trimmed, X-rayed and
ultrasonically inspected for irregularities fol-
lowing the cure cycle. Post-cure of the
component involves placing the part in a
graphite restraint fixture loading it into the
Manufacturing 341
RCC Seal strips
(22) LH
(22) RH Wing L.E. RCC panels
Nose cap (1)
RCC Seal strip
(1) LH, (1) RH and
(3) Lower
RCC ExDansion seal
(1) LH, (1) RH and
(3) Lower
Fig. 15.11 Leading edge structural subsystem
(Curry, Scott and Webster, 1979).
furnace and submitting it to a 7-day cycle dur-
ing which it is taken to 260°C (500°F) very
slowly to avoid distortion and delamination
(Fig. 15.12).
The next step is initial pyrolysis as shown in
Fig. 15.13 (Curry, Scott and Webster, 1979).
Pyrolysis tooling composed of graphite
restraining fixtures containing the part are
loaded into a steel retort that is packed with
calcined coke. The retort and its contents then
undergo a 70 h pyrolysis cycle at 815°C
(1500°F)converting the phenolic resin to a car-
bon state. During pyrolyzation, the resin forms
a network of interconnected porosity for the
escape of volatile matter. This stage is
extremely critical since, during controlled char-
ring of the cured resin matrix, the parts are
weak and delamination can easily occur if ade-
quate escape paths and time are not ensured.
After this initial pyrolysis cycle, the carbon is
342 Carbon-carbon composites

2250
I
1650

w 1100
0
j
2 540 ,
I

2 485 ;
g%
:
u1 320
I
I

UJ 260 ;
8 200
z r , h
I\
I:
150' n I

MATERIAL CUT & 0 BAG (MYLAR) 0 AUTOCLAVE 0 REMOVE BAG LOAD IN POST CURE
COLD I LAY.UP 0 APPLYVACUUM CURE 0 ROUGH T R I M RESTRAIN-
STORAGE I CLOTH 0 CHECK FOR DRILLHOLES ING
j PLIES LEAKS 0 X.RAY AND/OR FIXTURE
I & ULTRASONIC
I DEBULK

Fig. 15.12 Lay-up and cure cycle (Curry, Scott and Webster, 1979).

2205
- 2250

1650

g iioc
540
F 485
5 430
0 370
320
~ 260
a zw
x
C3 150
95
40
-2c

LOAD IN AUTOCLAVE CURE msi CURE j

VACUUM
LOADIN PYROLYSIS 0 CLEAN I CHAMBER
RETORT INSPECT IMPREG WITH
PACK WITH FURFURYL
GRAPHITE ALCOHOL
CALCINED COKE
IMPREGNATION CYCLE
ITMREE 131 TIMESI

Fig. 15.13 Initial pyrolysis (Curry, Scott and Fig. 15.14 Densification impregnation and cure
Webster, 1979). (Curry, Scott and Webster, 1979).
 Manufacturing 343

designated reinforced carbon-carbon-0

(RCC-0), a state in which the material is 2250
extremely light and porous with a flexure w 1650 ,
J I
I

strength of 21-24 MPa (3000-3500 psi).

P
F
540

15.6.1 DENSIFICATION
5 485
430
370
w 320
a
Densification for these shuttle parts is accom-
plished in three impregnation and pyrolysis
s 260
200
150
95
40
cycles (Fig. 15.14) (Curry, Scott and Webster, -20

1979).Each part is loaded in a vacuum cham-

ber impregnated with furfural alcohol
followed by a 2-hour cure period in the auto-
clave at approximately 150°C (300"F),
followed by a post-cure for 32 h to 200°C
(400°F). This cycle is followed by a 70-hour
815°C (1500°F) pyrolyzation that is shown in
Fig. 15.13.After three impregnation/pyrolyza-
tion cycles, the material is designated RCC-3
with an increased flexure strength of =124
MPa (18000 psi) at room temperature.
15.6.2 COATING
To allow for use of CC composites at elevated
temperatures above 2000°C (3632°F) in an oxi-
dizing atmosphere, it is necessary to apply
protective coatings to structural components.
The oxidation inhibition process consists of
two steps: (1)diffusion coating the CC compo-
nent and (2) applying a sealer to the surface.
The coating process (Fig. 15.15) (Curry, Scott
and Webster, 1979) used in protecting the CC
shuttle components starts with the blending of
the constituent powders: 10% alumina, 30%
silicon and 60% silicon carbide. This mix is
packed around the CC structural component
in a graphite retort and loaded into a vacuum
furnace where it undergoes a 16-hour cycle
that includes drying at 315°C (600°F) and the
coating reaction to 1650°C (=3000"F) in an
argon atmosphere. The powder characteris-
tics, constituents, formulations and the
manner in which the powders are packed
around the part are important factors that gov-
ern the chemical reactions at the high
processing temperatures, the degree of consol-
:
CLEAN COATING
PREPARATION
' CLEAN
INSPECT 1
, -X.RRY INRETORT SURFACE -X.RAY
! -ULTRASONIC COATING - ULTRASONIC
:e FINALTRIMIDRILL - DIMENSIONAL
.1 DIM. INWECT I
Fig. 15.15 Coating cycle (Curry, Scott and Webster,
1979).
idation and sintering of the powders. During
the process, the outer layers of the CC sub-
strate are converted to silicon carbide. The
silicon carbide-coated CC composite part is
removed from the retort, cleaned and
inspected. During cool down from 1650°C
(3000"F), the silicon carbide coating contracts
slightly more than the carbon substrate, caus-
ing crazing (coating fissures). This crazing
together with the inherent material porosity
provides paths for oxygen to reach the carbon
substrate. To obtain increased useful life of this
CC structural component, it is necessary to
add an additional oxidation inhibitor. The
final process used to provide oxidation protec-
tion to this type of CC structure involves
impregnating (Fig. 15.16) (Curry, Scott and
Webster, 1979)this component with TEOS. The
part is covered with a mesh, placed in a vac-
uum bag and the bag is filled with liquid
TEOS. A 5-cycle TEOS impregnation is then
performed with the bagged part. After the fifth
TEOS cycle, the part is removed from the bag
344 Carbon-carbon composites

W
9 320
9 260
5 200
8 150
w 95
W
U 40
8 -20

45 45 45 45 2 .5 IHRS
TO TO TO TO TO HRS
6 o w m 6 a 2%
MIN MIN MIN MIN HRS

.
F I V E CYCLES
EVACUATE
AND
COATED WEIGHT/ COVER INSTALL CONNECT- BACKFILL REMOVE 0 CURE NDE
PART RECORD wlm - VACUUM VACUUMAND WITHTEOS BAG - % HR @ W ' F - X.RAY
PERSPEC VERIFY MESH FITTINGS F I L L LINES MIX CLEAN - 6HR B W F - EDDY
206.741 -SRi -FILL MIXTEOS OVEN CURE PART CURRENT
- PRi TUEES ILIWIDI 225" + 5O'F -ULTRASONIC
COVER A N D FILL I 4 5 6 0 MINI 0 WEIGH/
WITH MESH RESERVOIR FEED TEOS RECORD
VACUUM M I X A5 R E Q D
BAG TO COVER
5 T H CYCLE CURE
U TO 2x H R MlNl
COOL T O 1WoF

Fig. 15.16 TEOS impregnation (Curry, Scott and Webster, 1979).

and oven cured at 315°C (600"F), liberating all labeled Space Shuttle material, is the strength
of the hydrocarbons. This procedure leaves sil- level of the reusable carbon-carbon (RCC)
ica (SiO,) in all of the microcracks and fissuresmaterial used in the Space Shuttle thermal
greatly enhancing the oxidation protection of protection system. Even though this material
the CC structure. is made with low-strength carbon fibers, its
strength efficiency is superior to both superal-
loys -and ceramics at >lOOO°C (1832°F).
15.7 MECHANICAL PROPERTIES
Development of advanced carbon-carbon
The extreme thermomechanical requirements (ACC) composites has produced a material
of the Space Shuttle have been the impetus for that is twice as strong as the CC composite
evaluating properties of low-density CC. The first put on the Space Shuttle. The ACC mate-
use of CC on the nose cap and leading edges of rial is made using woven carbon cloth. When
the Space Shuttle makes it imperative to know unidirectional carbon fiber tapes are interplied
as much as possible about all the characteris- with woven cloth to create a hybrid ACC,
tics of this material. The effect of temperature strength in at least one direction can be
on the ratio of tensile strength to density for increased by >345 MPa (>50 000 psi). Current
several classes of high-temperature materials data on thermomechanical and thermochemi-
is shown in Fig. 15.17. The major advantage of cal properties of some of the advanced CC
CC materials for high-temperature applica- systems show that material composition, oxi-
tions is that they do not lose strength as the dation resistance, processing, joining and fiber
use temperature is increased. This property is architecture are producing noticeable
in contrast to other materials such as superal- improvements in CC materials and structures
loys and ceramics. Figure 15.17 shows three (Curry, Scott and Webster, 1979; Buch, 1984;
levels of CC strength efficiency. The first, Rummler and Sawyer, 1984; Ransone and
 Thermal properties 345

Temperature, OC
0 ,550 1100 1650
I I I **%O
-
High-strengthcarbon-carbon <- 160

800 1600 2400 3200 4000

Temperature, OF

Fig. 15.17 Strength-to-density ratio for several classes of high-temperature materials.

Ohlhorst, 1984; Webb, 1985; Gray and Engle,
1985; Johnson and Finley, 1985; Sawyer and
Moses, 1985; Maahs and Ransone, 1985;
Ohlhorst and Ransone, 1985).
CC components on the Space Shuttle are
required to have adequate strength at design
temperatures to withstand the aerodynamic
loads of flight and to continue to do so for the
operational life of the component. Minimum
mechanical properties are guaranteed through
statistical analysis of a data sampling having
at least 99% probability and 95% confidence.
The primary variables affecting the structural
design allowables are temperature, material
thickness, coating thickness, biaxial stress con-
ditions and substrate mass loss due to
oxidation through the mission life of the com-
ponent (Table 15.2) (Curry, Scott and Webster,
1979).
Figure 15.18 (Curry, Scott and Webster,
1979) illustrates the typical effect of ply thick-
ness on the allowable stress values for tension,
bending, compression and shear used for
design. As fabricated, room temperature mod-
ulus values for the TEOS material are shown
in Fig. 15.19 (Curry, Scott and Webster, 1979).
The effect of temperature on the as-fabricated
tension strength properties is shown in Fig.
15.20 (Curry, Scott and Webster, 1979). As
shown in Figs 15.17 and 15.20, the strength of
CC composite material does not decrease sig-
nificantly with temperature. Typically, above
1425°C (2600°F) there is an increase in
strength.
The effect of substrate mass loss through
oxidation on tensile strength is shown in Fig.
15.21 (Curry, Scott and Webster, 1979). Mass
loss results in a significant reduction in design
allowable stress, emphasizing the value of the
additional oxidation protection provided by
the TEOS treatment.
15.8 THERMAL PROPERTIES
15.8.1 THERMAL OXIDATION
A critical requirement when using CC com-
posites is the ability to withstand numerous
346 Carbon-carbon composites

Table 15.2

Mechanical properties test Non-TEOS TEOS

-. __
as fabricated conditioned as fabricated conditioned
Flexure 201 221 40 24
Tension 196 80 52 34
Compression 170 57 46 28
Shear 192 79 17 17
Comer flexure 20 - 3 3
Interlaminar tension 20 50 5 5
Interlaminar shear 30 19 - -
Coefficient of thermal expansion 10 6 9 6
Impact, etc. 20 10 - -

Simultaneous cycling - - 3 18
Mission cycling
Tension 3 36 - -
Flexure 3 24 - -

Compression 3 27 - -

Total 868 609 175 135

COMPRESSION

NOTE
BREAK
IN
SCALE TENSION 7

IN-PLANE SHEAR

14 I I 1 I 1 I
15 20 25 30 35 40
NUMBER OF PLIES

Fig. 15.18 Design allowables at room temperature as-fabricated (Curry, Scott and Webster, 1979).
 Thermal properties 347

35 r T V P I C A L SECANT HOOVLUS

E
Y
14
t
7.0 1 Gw
3.5 1 1 I 1 1 I 1
I5 10 25 30 35 4a
NUMBER OF PLIES

Fig. 15.19 Design allowables at room temperature as-fabricated (Curry, Scott and Webster, 1979).

thermal and thermomechanical loads during
re-entries of the Space Shuttle into the earth's
atmosphere. Although CC Space Shuttle com-
ponents have an oxidation-inhibiting silicon
carbide coating, they can lose mass over an
extended temperature range without apparent
surface recession. Photomicrographs of CC
specimen surfaces show minute fissures and
thermal microcracks, some of which terminate
at the coating substrate interface. Specimens
exposed to convective and radiant heat trans-
fer tests micrographically have shown the
presence of voids at the coating substrate sur-
face. Tests to characterize the effects of these
flaws were performed over a wide range of
pressures and temperatures in both plasma arc
jets and radiant-heating test facilities. Arc jet
tests on CC specimens ranged in temperature
from 815°C (1500°F) to 1870°C (3400°F) and
atmospheric pressures from 0.01 Pa to 0.10 Pa.
Radiant-test conditions ranged from 420°C
(800°F)to 1425°C (2600°F)and pressures rang-
ing from 0.01 Pa to 1.0 Pa. Mass-loss data for
the CC shuttle specimens exposed to the arc jet
and radiant-heating tests are presented in Figs
15.22 and 15.23. Figure 15.22 (Curry, Scott and
Webster, 1979) shows mass loss at 980°C
(1800°F)and 0.05 Pa as a function of exposure

z0 . ---_______________---------
___- 28 PLY
111 P L V
2
Y

E 35
.
2
0 -
v)
2
w
I-

28 -
m
ss -
2 ur
< 2 1 - I I . I I I I I 1

Fig. 15.20 Design allowables as-fabricated (Curry, Scott and Webster, 1979).
348 Carbon-carbon composites

38 PLY
28 PLY
25 P L Y

1s P L Y

3
c
UJ 1.4

I 1 I 1 J
0 4.9 9.8 14.7 1U.6 24.5
MASS LOSS - kdm’x 1P

Fig. 15.21 Design allowables conditioned (Curry, Scott and Webster, 1979).

P n
z 19.6 -
n 39.0

NONTEOS \ /
/ -
-i
.x
W

- /
d/
/
/
P
9
I 14.7
v)
8/
v)
P,
s N O N TEOS
’ /
/

$ 9.8 - ,
4
I ,

- 9 . 8 W I T1
H TEOS 1
4.9 - d / ,’ &--e---
B
8 \WITH TEOS
I I I I 1
a 2 4 6 8 10 0 2 4 6 8 10
EXPOSURE TIME HOURS EXPOSURE T I M E HOURS

Fig. 15.22 Mass loss comparison plasma arc jet Fig. 15.23 Mass loss comparison radiant environ-
environment (Curry, Scott and Webster, 1979). ment (Curry, Scott and Webster, 1979).

14.5 7
11.1-
'F ai.
B
E
1
8
i'
5'8'
2.9.
-THERMAL
a
f
-0
-28(1
+T
-OTAL
-18
TEMPERATURE "C
Fig. 15.24 Reinforced carbon-carbon thermal properties (Curry, Scott and Webster, 1979).
thermal conductivity is dependent upon the
mass loss experienced by the CC composite,
resulting from subsurface oxidation.
Results of thermal conductivity studies for
shuttle CC composite shuttle materials are
shown in Fig. 15.24 (Curry, Scott and Webster,
1979).To simplify thermal modeling, no differ-
entiation has been made for conductivity
variation resulting from the number of plies in
the substrate. Results for conditioned speci-
mens having a mass loss of 0-5 Pa (0.1 lb/ft2)
suggest that thermal conductivity decreases
with mass loss. Figure 15.24 also shows that
neither specific heat nor emittance was
affected by material or mass loss conditioning.
15.9 APPLICATIONS
An example of the state of the art in CC com-
posite applications is a one-piece, bladed
turbine rotor that, in service, is coated to pre-
vent oxidation. The rotor offers higher
temperature performance without cooling;
low weight and use of low-cost, non-strategic
materials (Miller and Grimes, 1982).Other gas
turbine engine applications using CC compos-
ites include exhaust nozzle flaps and seals,
augmenters, combustors and acoustic panels.
Applications 349
,- SPECIFIC HEAT
THERMAL CONDUCTIVITY
\
PARALLEL TO PLY
CONDUCTIVITY PERPENDICULAR
TO PLY
280
EMISSIVITY
538
818 1094
-
1372 16sO
CC material systems using coatings, TEOS
and additions to the basic CC recipe have
improved the oxidation resistance of products
made of CC composites by an order of magni-
tude. These composites are being used in
products such as the nozzle in the F-100 jet
engine afterburner, turbine wheels operating
at >40 000 rpm, nonwetting crucibles for
molten metals, nose caps and leading edges
for missiles and for the Space Shuttle, wind-
tunnel models and racing car and commercial
disk brakes (Klein, 1986).
Pushing the state of the art in CC compos-
ites is the piston for internal combustion
engines (Miller and Grimes, 1982; Taylor,
1985). The CC piston (Fig. 15.25) would per-
form the same way as any piston in a
reciprocating internal combustion engine
while reducing weight and increasing the
mechanical and thermal efficiencies of the
engine. The CC piston concept features a low
piston-to-cylinder wall clearance; this clear-
ance is so low, in fact, that piston rings and
skirts are unnecessary. These advantages are
made possible by the negligible coefficient of
thermal expansion of this kind of CC (0.54 x
/OF). (Carbon-carbon composites can
have a range of thermal expansion coefficients,
350 Carbon-carbon composites
Fig. 15.25 Carbon+arbon automotive piston.
depending on the processing techniques.) CC
material maintains its strength at elevated
temperatures allowing the piston to operate at
higher temperatures and pressures than those
of a comparable metal piston. The high emit-
tance and low thermal conductivity of the CC
piston should improve the thermal efficiency
of the engine because less heat energy is lost to
the piston and cooling system. The elimination
of rings reduces friction, thus improving
mechanical efficiency.
Besides being lighter than conventional pis-
tons, the CC piston can produce cascading
effects that could reduce the weight of other
reciprocating components such as the crank-
shaft, connecting rods, flywheels and
balances, thus improving specific engine per-
formance (Taylor, 1985).
ACKNOWLEDGEMENTS
The author acknowledges Mr. D.M. Curry of
NASA Johnson Space Center and H.C. Scott
and C.N. Webster of the Vought Corporation
for the data, as referenced, on which a portion
of the present paper is based.
Acknowledgement is also given to Mrs. H.A.
Coombs for her valuable contribution in
assisting in the formatting of this paper.
REFERENCES
Beatty, R.T. and Kipplinger, D.V., 1970, Gas pulse
impregnation of graphite with carbon. Nuclear
Application and Technology, 8(6):488495.
Bokros, J.C., 1969, Deposition, Structure and
Properties of Pyrolytic Carbon. Chemistry and
Physics of Carbon-A Series of Advances, (ed.
Philip L. Walker, Jr.) pp. 1-118. Marcel Dekker,
InC.
Buch, J.D., 1984, Graphite Crystals - A General
Model for Diverse Carbon Forms. Metal Matrix,
Carbon and Ceramic Matrix Composites, (ed. John
D. Buckley) NASA CP-2357, pp. 119-135.
Buckley, J.D., 1967, Statis, Subsonic and Supersonic
Oxidation of JT Graphite Composites, NASA TLN
D-4231.
Cogbum, J.W., Fain, C.C., Edie, D.D. and Leigh,
H.D., 1987, Processing C-Shape Pitch-Based
Carbon Fibers. Metal Matrix, Carbon and Ceramic
Matrix Composites, (ed. John D. Buckley) NASA
(2-2482, pp. 185-200.
Cook, J.L., F. Lambdin and P.E. Trent, 1970,
Discontinuous Carbon/Carbon Composite
Fabrication. Carbon Composite Technology - With
Special Emphasis on Carbon/Carbon Systems. Proc
10th Ann. Symp. New Mexico Section of ASME
and University of New Mexico, pp. 143-171.
Curry, D.M., Scott, H.C. and Webster, C.N., 1979,
Material Characteristics of Space Shuttle
Reinforced Carbon-Carbon. Paper read at the
24th National SAMPE Symposium, 1-9 May,
1979, at San Francisco, CA.
Diefendorf, R.J., 1987, Carbon/Graphite Fibers.
Engineered Materials Handbook 1: 49-53.
Dienes, G.J., 1952, Mechanism for Self-Diffusion in
Graphite. Applied Physics 23(11): 1194-1200.
Edie, D.D., Fox, N.K., Barnett, B.C. and Fain, C.C.,
1986, Melt-Spun Non-Circular Carbon Fibers.
Carbon 24(4): 477482.
Gray, P.E. and Engle, G.B., 1985, Wettability of
Carbon/Carbon Composites and Carbon Fibers
by Glass Sealants Used in Oxidation Inhibition.
Metal Matrix, Carbon and Ceramic Matrix
Composites, (ed. John D. Buckley) NASA
0-2406, pp. 149-162.
Johnson, A.C. and Finley, J.W., 1985,
Carbodcarbon Composites for Advanced
Spacecraft. Metal Matrix, Carbon and Ceramic
Matrix Composites, (ed. John D. Buckley) NASA
(3-2406, pp. 175-190.
Kanter, M.A., 1957, Diffusion of Carbon Atoms in
Natural Graphite Crystals. Physics Review 107
(3):655-663.

Klein, J., 1986, Carbon-Carbon Composites.
Advanced Materials and Processes 130 (5):64-68.
Kotlensky, W.V. and Pappis, J., 1969, Mechanical
Properties of CVD Infiltrated Composites. Proc.
95th Biennial Conf.Carbon Defense Ceramic
Information Center, Compilers, pp. 76-80.
Lambdin, F. and Cook, J.L., 1971, Fabrication of
Carbon-Carbon Composites Electrostatic Fiber
Deposition (Flocking). Y-1786 (Contract No.
W-7405-eng-26), Y-12 Plant, Union Carbide
Corp.
Lambdin, F., Cook, J.L. and Marrow, G.B., 1969,
Fiber-Reinforced Graphite Composite Fabrication
and Evaluation. Doc. Y-1684, "ID4500 (Contract
W-7405-eng-26), Nuclear Division, Union
Carbide Corp.
Maahs, H.G. and Ransone, P.O., 1985, Mechanical
Property Evaluation of 2-D Carbon-Carbon
Panels Fabricated From a Specialty-Weave
Fabric. Metal Matrix, Carbon and Ceramic Matrix
Composites, (ed. John D. Buckley) NASA
CP-2406, pp. 261-276.
Miller, T.J. and Grimes, H.H., 1982, Research on
Ultra-High-Temperature Materials-Monolithic
Ceramics, Ceramic Matrix Composites and
Carbon/Carbon Composites. Advanced
Materials Technology, (eds. Charles P.
Blankenship and Louis A. Teichman) NASA
CP-2251, pp. 275-291.
Ohlhorst, C.W. and Ransone, P.O., 1985, Effects of
Thermal Cycling on Thermal Expansion and
Mechanical Properties of Advanced
Carbon-Carbon Composites. Metal Matrix,
Carbon and Ceramic Matrix Composites, (ed. John
D. Buckley) NASA (3-2406, pp. 289-303.
Pierson, H.O., 1968, Development and Properties of
Pyrolytic Carbon Felt Composites. Advanced
Techniques for Material Investigatioiz and
Fabrication 14, National Symposium and
Exhibit, Society of Aerospace Material and
Process Engineers, Paper II4B-2.
References 351
Ransone, P.O. and Maahs, H.G., 1985, Effect of
Processing on Microstructure and Mechanical
Properties of 3-D Carbon-Carbon. Metal Matrix,
Carbon and Ceramic Matrix Composites, (ed. John
D. Buckley) NASA CP-2406, pp. 289-303.
Ransone, P.O. and Ohlhorst, C.W., 1984, Interlaminar
Shear and Out-of-Plane Tensile Properties of
Thin 3-D Carbon-Carbon. Metal Matrix, Carbon
and Ceramic Matrix Composites, (ed. John D.
Buckley) NASA CP-2357, pp. 137-148.
Rummler, D.R. and Sawyer, J.W., 1984, Properties
and Potential of Advanced Carbon-Carbon for
Space Structures. Metal Matrix, Carbon and
Ceramic Matrix Composites, (ed. John D. Buckley)
NASA (3-2357, pp. 149-170.
Sawyer, J.W. and Moses, P.L., 1985, Effect of Holes
and Impact Damage on Tensile Strength of Two-
Dimensional Carbon-Carbon Composites.
Metal Matrix, Carbon and Ceramic Matrix
Composites, (ed. John D. Buckley) NASA
(3-2406, pp. 245-260.
Stoller, H.M., Butler, B.L., Theis, J.D. and Lieberman,
M.L., 1974, Carbon Fiber Reinforced-Carbon
Matrix Composites. Composites: A State of the Art,
(eds. J.W. Weeton and E. Scala) Metallurgical
Society of the American Institute of Mining,
Metallurgical and Petroleum Engineers, Inc., pp.
69-136.
Strife, J.R. and Sheehan, J.E., 1988, Ceramic Coatings
for Carbon-Carbon Composites. Ceramic Bulletin
67(2):369-374.
Taylor, A.H., 1985, Carbon-Carbon Pistons for
Internal Combustion Engines. NASA Tech
Briefs 9 (4):156-157.
Theis, J.D., Jr., Taylor, A.J., Rayner, R.M. and Frye,
E.R., 1970, Filament Wound Carbon/Carbon
Heatshield SC-11FW-Y12-7, A Process Histoy.
SC-DR-70425, Sandia Labs.
Webb, R.D., 1985, Oxidation-Resistant
Carbon-Carbon Materials. Metal Matrix, Carbon
and Ceramic Matrix Composites, (ed. John D.
Buckley) NASA CP-2406, pp. 149-162.