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ANNUAL
REVIEWS Further
1994.24:19-44
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1994 by Annual Reviews Inc.

Annu. Rev. Mater. Sci.
Copyright © All rights reserved
CARBON-CARBON COMPOSITES
J. E. Sheehan, K. W. Buesking, and B. J. Sullivan

Annu. Rev. Mater. Sci. 1994.24:19-44. Downloaded from www.annualreviews.org
MSNW, Inc., P.O. Box 865, San Marcos, California 92079
applications, constituents, fabrication, properties, oxidation

Access provided by 41.46.43.6 on 05/08/20. For personal use only.
KEY WORDS:
protection
INTRODUCTION AND BACKGROUND
Carbon-carbon (C-C) composites are composed of carbon fibers in a

carbon matrix. They are lightweight materials that can perform struc
turally at extreme temperatures and have superior thermal shock, tough
ness, ablation, and high-speed friction properties. C-C components have
been produced in the United States for over 20 years in response to
sustained aerospace and defense needs.
Constituents and Microstructure

The fibers in C-C composites can be continuous or short and can range
from the isotropic variety that have low elastic moduli and modest strengths
to highly oriented, high-performance fibers with elastic moduli over 700
GPa and strengths of 3 to 4 GPa (1). The carbon fibers are generally 7 to
10 {lm in diameter and are derived from polyacrylonitrile (PAN) resin,
petroleum pitch, or rayon.
The characteristics of the carbon matrix can vary widely depending on
the method and details of fabrication. At one extreme, the matrix carbon
can be glass-like and made up of small, randomly oriented crystallites of
poorly-graphitic or turbostratic carbon; at the other extreme, the carbon
can be strongly oriented and highly graphitized in relatively large crys
tallites. The microstructure of matrix carbons can vary continuously
between the two extremes, and the degree and direction of preferred
crystallographic orientation often vary spatially with respect to the fibers
(2�6).
The fine microstructural features of C-C composites are determined by
the type of fiber, the method by which the matrix is formed, and
19
0084-6600/94/0801-0019$05.00
20 SHEEHAN, BUESKING & SULLIVAN
parameters, such as temperature and pressure, that are used in establishing

the matrix. As shown in Figure I, the coarse microstructural features are
determined by the fiber architecture, matrix fabrication method, and the
amount of residual porosity and degree of cracking that is present in
the matrix (7, 8). Properties are determined by both the fine and coarse
microstructural features and by the nature of the interface between the
fibers and matrix.
Relatively weak interfaces usually exist between the carbon fibers and
matrix because strong covalent atomic bonding prevents carbons from
sintering, even at very high temperatures. Weak fiber-matrix interfaces
are, for the most part, mechanically advantageous because the failure
strain of the matrix carbon is usually much lower than that of the fibers.
Very strong interfaces produce composites that are brittle and have low
strengths in the fiber directions because matrix failure induces fiber failure
at low strains. Conversely, weak interfaces allow matrix cracking to occur
without crack propagation through the fibers so the fibers can continue to
carry load (9). Some properties are enhanced by strong coupling between
the matrix and fibers. For this reason, fiber treatments and variations in
matrix fabrication methods are being investigated to tailor the interfacial
strength for specific composite applications and properties requirements
(10, 11).
Fabrication
The fabrication ofC-C composites with continuous fibers initially involves
the textile processing of multifiber yarns to produce a carbon fiber preform.
The specific technique that is used depends on the required fiber archi
tecture and the component design. Typical processes include fabric
weaving, braiding, winding, and the multidirectional weaving of free
standing bodies (12, 13).
Frequently C-C fabrication requires the use of a resin to rigidize the
preform and includes a procedure in which the fibers are consolidated and
the resin is cured to form a carbon fiber-resin matrix composite. For
example, fabric laminates are made by weaving fabric from multifiber
yarns, impregnating the fabric with liquid resin, cutting and stacking the
impregnated layers (prepreg) after drying and advancing the resin, and
then compressing the prepreg layers in a press or autoclave while heat
curing the resin. Composites with discontinuous fibers can be made by
chopping resin-impregnated yarns and warm molding the chopped
prepreg. Slurry forming methods are also used to make discontinuous fiber
composites. Rigidizing resins are generally not required for freestanding
multidirectional fiber preforms.
Phenolic resins are commonly used in preforming because they are
CARBON-CARBON COMPOSITES 21
(a)
(b)
Figure 1 Polished-section light micrographs showing the coarse microstructural features of
two C-C composites: (a) short pitch-derived fibers in a matrix formed from pitch, (b) braided
multifiber yarns of continuous PAN-derived fibers with a matrix formed by CVD (both
IOOX).
inexpensive, are easily processed, and provide a relatively high yield of

carbon when decomposed by heating. Carbon-phenolic preforms are con
verted to C-C preforms by slow heating in an inert gas environment. This
initial thermal decomposition or pyrolysis step leaves carbon in place of
the resin. Afterward, the composites are porous and have poor properties,
so the pores are filled with additional carbon matrix.
Composite pore filling or densification is accomplished by either liquid
or vapor phase processing, or combinations of the two (2-6, 12, 14-16).
Liquid processing involves repeated cycles of resin or pitch impregnation
and inert gas pyrolysis and heat treatment. Vapor phase densification is
conducted in reactors at reduced pressures where a flowing hydrocarbon

gas infiltrates the composite and is thermally decomposed to deposit
carbon. This is termed densification by chemical vapor deposition (CVD)

or chemical vapor infiltration (CVI).
After C-C composites are processed to achieve the desired bulk density
or porosity level, they receive a final machining and nondestructive examin
ation (NDE). Densification procedures often include intermittent machin
ing to remove surface deposits, and NDE is often conducted early in the
fabrication process as well as at the end. NDE techniques that are useful
include X-ray radiography, ultrasonic inspection, and electrical con
ductivity measurements.
Applications and Technological Importance

Much of the C-C currently being pro duced is in the form of components
for missiles and military aircraft. The most important applications include
reentry bodies, rocket nozzles, and exit cones for strategic missiles, and
brake discs for military aircraft ( 1 4-17). Recently, a commercial aerospace
application, brake discs for transport aircraft, has become prominent ( 1 8).
Also notable is the coated C-C used for the nose cap and wing leading edges
on the Shuttle Orbiter vehicles ( 1 9-21). Present industrial applications for
C-C composites, such as hot glass handli ng tools and hot press dies and
pistons, are minor compared with the uses in defense and aerospace.
It is li kely that the most important near future applications for C-C
composites will be in the aerospace and defense industries. The use of
C-C brake discs on commercial transport aircraft has become a significant
business and is expected to grow. It is more difficult to predict the future
for C-C composites in 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 ( 1 7).
Commercial non-aerospace applications for C-C composites are minor
at this time because of the high cost of the material. Expanded use of
C-C 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 conductivity electronic substrates,
prosthetic devices, and components for internal combustion engines ( 14,
15, 17). More distant large-scale applications include plasma limiters for
nuclear fusion devices and inert gas ducting and heat exchangers for gas
cooled fission reactors.
MATERIALS DESIGN AND ANALYSIS
C-C composites offer a wide range of properties that can be tailored by

selection of constituent materials, fiber orientations, and the details of
fabrication. Typically, a C-C material and component are designed simul
taneously so the composite properties can be selected to enhance the
performance of the component. The following sections describe some
of the analytical methods that have been developed for calculating the
properties of C-C composites and present typical thermal and mechanical
properties.
Analytical Methods
The first step in analyzing or predicting the properties of a C-C composite
is the calculation of unidirectional (one-dimensional) composite properties
using the fiber properties, matrix properties, and fiber volume fraction.
Simple theoretical models are based on methods such as the rule of mix
tures or the Halpin-Tsai equations (22, 23). More complex models use
finite element techniques or a concentric cylinders solution (24, 25). One
of the more widely accepted techniques is the composite cylinders assem
blage in which the composite is assumed to consist of a central cylindrical
fiber surrounded by an outer cylinder of matrix (25). The ratio of fiber
diameter to matrix diameter is selected to provide the proper fiber volume
fraction. Bounding approaches are used to compute the five independent
elastic constants associated with transversely isotropic unidirectional com
posites (25). It has been shown that the bounds provide exact solutions
for all of the constants except the transverse Young's modulus. In the
analysis of C-C materials, the composite cylinders assemblage has been
extended to account for cylindrical voids and a sheath of highly oriented
matrix within the unidirectional fiber bundle.
Most C-C components are made from materials that have several direc
tions of fiber reinforcement. These include bidirectional (two-dimensional)
laminates, three-directional (three-dimensional) orthogonal weaves, and
multidirectional weaves and braids. A representative volume element or
unit cell of a three-dimensional orthogonal C-C composite is shown in
Figure 2. It includes three orthogonal unidirectional fiber bundles, two
regions of interstitial matrix material, and the characteristic microcracked
regions that occur at the interfaces between the fiber bundles and interstitial
matrix regions. Theoretical models of the behavior of this type of material
are described in the literature (WC Loomis, personal communication).
In one model, a finite element approach is used in which three-dimensional

brick elements are employed to represent the subregions of the unit cell
(WC Loomis, personal communication). This model allows crack propa

gation at the microcracked surfaces, and thus is capable of projecting non
linear shear behavior, which is a characteristic of C-C composites. The
second model is called the Degraded Composites Analysis Program
(DCAP) and has been used extensively in C-C component design studies
(27). This model is also based on a variational approach, but uses more
strictly defined displacement fields for the subregions of the unit cell.
Input to the DCAP model includes the dimensions of the unit cell,
fiber volume fraction, fiber properties, matrix properties, and information
related to porosity, matrix sheath volume fraction, and degree of subcell
microcracking. The output of the model includes orthotropic Young's
moduli, Poisson's ratios, shear moduli, thermal expansion coefficients, and
strengths as functions of temperature.
The computed strengths of a three-dimensional C-C composite are based
on the stresses carried by each subregion and the estimated strengths of
those subregions (27). Tensile failure of the composite is predicated on
tensile failure of the unidirectional fiber bundles. The strength of the fiber
bundle is estimated using the cumulative weakening theory of unidi
rectional composites (28). Compressive strength is associated with com
pressive failure of the unidirectional fiber bundle by microbuckling (29).
Treatment of shear failure has been limited to an estimate of the shear
yield strength, which is based on shear failure of the microcracked interface
between yarn bundles and interstitial matrix regions (27). The effects of
interaction among stress components and the determination of a failure
surface for C-C composites have received only limited study. It has been
hypothesized that tensile strengths will be insensitive to stress interaction
and that interactions may exist among various shear components and
among compression and shear components (27).
DCAP contains two empirical parameters that are believed to be sen
sitive to the details of fabrication and are typically set by correlations with
x
/'
y
FIBERS AND BUNDLE

MATRIX
�__ CRACKED OR DEGRADED

REGIONS
FIBERS AND
BUNDLE MATRIX
INTERSTITIAL MATRIX
Figure 2 Schematic drawing of an orthogonal three-dimensional C-C volume element.

experimental data. These are the subcell efficiency, which is a measure of

the microcracking at the interfaces between fiber bundles and interstitial
matrix regions, and the sheath content, which represents the volume frac
tion of matrix that is highly oriented around the filaments. Theoretical
projections of modulus are sensitive to the sheath content and little affected
by the choice of subcell efficiency. Conversely, theoretical estimates of
composite thermal expansion are controlled more by subcell efficiency
than by sheath content. Therefore, the sheath content can be established
by comparing the computed room-temperature modulus with a measured
value from a tensile stress-strain curve. Similarly, the subcell efficiency can
be identified by comparing the predicted thermal strains with measured

thermal strains in one direction. Once the empirical parameters are
obtained, the model can be used to compute a consistent set of orthotropic

properties and to investigate the cffeets of alternate weave designs.
C-C composites are often configured as two-dimensional laminates in
which the reinforcement is provided by layers of fabric or unidirectional
fiber bundles. Such materials are analyzed using c1assical laminated plate
theory (25, 30). Laminated plate theory does not explicitly account for the
microcracking and pores that are present within C-C composites, thus
properties are predicted by using degraded matrix properties. The effective
matrix properties are determined by comparing measured properties with
computed properties and adjusting the matrix moduli and thermal expan
sion coefficients to bring the model predictions into agreement with experi
mental data.
In addition to the two- and three-dimensional materials described above,
C-C composites are also made with multidirectional reinforcements. An
example is the architecture shown in Figure 3. Such materials are
modeled using two similar techniques in which a representative volume
element of the composite is employed to define the orientations and volume
fractions of the unidirectional fiber bundles (31, 32). The properties of
the unidirectional fiber bundles are computed based on the constituent
properties and fiber volume fraction using the composite cylinders assem
blage (25). The stiffness matrix of each fiber bundle is then transformed
into its proper orientation within the representative volume element using
standard tensor transformations. The representative volume element is'
assumed to be in a state of uniform strain, which allows the stiffness of
the oriented fiber bundles to be combined to determine the effective stiffness
of the composite.
The multidirectional composite models have not explicitly accounted
for the microcracking within the composite because of the complex
geometry of the interstitial matrix regions. The microcracking is accounted
for by using degraded matrix properties that are determined by correlations
Figure 3 Schematic drawing of a five-dimensional fiber architecture.
with composite test data. In practice, the effective matrix properties are
found to be similar to those estimated for the two-dimensional C-C com
posites discussed previously.
Strengths are computed in multidirectional composites by analytically
imposing an external stress on the composite and computing the strain in
the representative volume elements. Because the strain is assumed to be
uniform, the strain in the principal direction of each oriented fibcr bundle
can be determined from the appropriate tensor transformation. The prin
cipal strains can be used to compute local stresses, which are then employed
in a variety of unidirectional composite failure criteria, the most common
of which is maximum stress.
Mechanical and Thermal Properties

High-performance C-C composites contain continuous fibers with highly
oriented crystallites that are derived from mesophase pitch or PAN resin.
Fibers of this type, which have been thermally stabilized for normal high-
temperature C-C processing, have strengths up to about 2.5 GPa and

elastic moduli in the 350 to 450 GPa range. The C-C properties listed in
Tables I and 2 and plotted in Figure 4 are for composites containing such
fibers in one-, two-, and three-dimensional arrays. Table I also contains
data for a two-dimensional C-C material made from isotropic rayon
precursor fibers.
Examination of the data shows that C-C composites can have highly
attractive mechanical and thermal properties. Elastic modulus in a prin
cipal fiber direction usually reflects the fiber modulus according to the law
of-mixtures. Strength utilization of the fibers is 25 to 50%, depending on
the fiber architecture and processing specifics. As with all fiber composites,
shear properties are often a major issue and frequently have a strong
influence on design and materials selection. In general, the shear strengths

and shear moduli of C-C composites are low compared with other
materials. The same limitations exist for tensile properties in one- and two
dimensional composites in directions normal to the fiber directions. These
low properties are the result of processing that creates less than optimum
bonding between the matrix and fibers to avoid brittleness and low fracture
strengths along the fiber directions.
A principal reason for the structural attractiveness of C-C composites
is that, although brittle, they can exhibit relatively high values of fracture
toughness. C-C materials belong to a special group of composites in which
the failure strain of the matrix is much lower than that of the fibers. As a
result, strong bonding between the matrix and fibers produces composites
that are both brittle and low in strength. This is because strong bonds
promote failure of the fibers at the low strains where the matrix fails.
Conversely, relatively weak bonds allow matrix cracking to occur without
crack propagation through the fibers (9).
Matrix cracking can occur during C-C processing because of thermal
expansion mismatch between the fibers and matrix and matrix shrinkage
during pyrolysis. Matrix cracking can also occur when the composite is
loaded in service. Strong bonding can result in fiber damage during pro
cessing and this, combined with strong bonding that persists in the final
product, can result in weak and brittle composites. In contrast, weak bonds
leave fibers undamaged and, when placed in service, allow the matrix to
crack and transfer the load to the fibers, thereby utilizing their high
strength. Shear displacement of the matrix relative to the fibers and even
tual fracture of the fibers at points away from the primary zone of matrix
failure create the fibrous pullout fracture surfaces indicative of toughness
(10).
One method of comparing the fracture toughness of a material relative
to another material is the notched beam work-of-fracture test. This simple
Table 1 Tensile and thermal properties of C-C composites with high-performance and isotropic fibers
Room
Room ternpefa ture RT-1650°C
temperature tensile thermal 800°C
tensile elastic expansion thermal
Fiber volume strength modulus coefficient conductivity
( l0-6OC-1) 'm-1O -1
Construction fraction (MPa) (GPa) (W C )
Direction x y z x z x z x z x z
Unidirectional 0.65 0 0 650--1000 2.0 240-2

- 80 3.4 I.l 10.1 125 10 (j
(one-dimensional) >
::c
Fabric laminate 0.31 0.30 0 300--350 2.8-5.0 110--125 4.1 1.3 6.1 95 4 t:C
0
(two-dimensional) Z
Woven orthogonal 0.13 0.13 0.21 170 300 55 96 1.3 1.3 57 80 A
>
(three-dimensional) ::c
t:C
Fabric laminate 0.25 0.25 0 41 5.0 14 3.6 4.9 6 0
Z
(two-dimensional)
(j
isotropic fibers 0
�
'"C
0
'i!l
..,
tTl
en
N
'-0
Table 2 High-performance C-C composite room temperature in-plane shear and com
pression properties
Shear Compressive
Shear elastic Compressive elastic
Fiber volume strength modulus strength modulus
Construction fraction (MPa) (GPa) (MPa) (GPa)
Direction x y z x-y x-y x x

Unidirectional 0.65 0 0 7-14 4-7 620 250
(one-dimensional)
0.31 0.30 0 7-14 4-7 150 100
Fabric laminate
(two-dimensional)
z z
0.13 0.13 0.21 21-27 1.4-2.1 140 90

Woven orthogonal
(three-dimensional)
test measures the energy required to move a tensile crack through the
material in a controlled fashion. Work-of-fracture tests on strong, fully
densified C-C specimens containing high-performance fibers have given
fracture energy values of about 2 x 104 J'm-2 for a one-dimensional
material and 3 x 103 J'm-2 for a two-dimensional fabric laminate when
cracks were propagated across the fibers (33, 34). For comparison, plastics
give values of 103 to 104 J'm-2, wood exhibits values of about 104 J'm-2,
and ductile metals are over 105 J'm 2. At the other end of the spectrum
technical-grade ceramics and premium-grade graphites show values less
than 102 J·m-2.
In general, carbon materials are unique in their retention of mechanical
properties at high temperatures. Figure 5 summarizes the effects of tem
perature on the mechanical properties of high-performance C-C
composites. The increasing tensile strength and decreasing elastic modulus
with increasing temperature in the principal fiber directions are charac
teristic of the carbon fibers (35). Conversely, the behavior of the matrix
and how the matrix is bonded to the fibers play a large role in determining
the effect of temperature on the shear, cross-fiber tensile, and compressive
strengths. In general, the carbon matrix is cracked by thermal expansion
mismatch with the highly oriented' fibers. Cracking is extensive at room
temperature, and cracks tend to close as temperature increases, which
provides a more coherent and, p'erhaps, adherent matrix. This accounts
for the increases in shear and cross-fiber tensile strengths with increasing
temperature and, along with increasing fiber strengths, is consistent with
increasing compressive strength. Moduli decrease or increase with tem
perature depending on the influence of matrix cracking relative to the basic
thermal reductions in modulus of the constituents. This appears to depend
on fiber architecture and specifics of the C-C processing.
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TEMPERATURE (Oe)
Figure 4 Representative high-performance C-C composite thermal properties in principal
fiber directions.
The creep or high-temperature time-dependent deformation of C-C

composites has received only limited study (36-38). Tests on small, single
yarn unidirectional composite specimens at 231 O°C and 770 MPa showed
an initial transient creep in the direction of the fibers of about 2% over
the first 2 hr and then a steady-state rate of about 0.37°kh-' (36, 37). For
perspective, this steady-state creep rate is comparable to that observed for
high-density polycrystalline sintered (l SiC at I 800°C and 179 MPa (39).
When the creep rates of carbon fibers are compared with those of a wide
range of po!ycrystalline ceramics in the same ranges of temperature and
stress, projected C-C steady-state creep rates are at least four orders of
magnitude lower than the most creep-resistant ionic and covalent tech
nical-grade ceramics (I).
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0 400 800 1200 1600 2000 2400
TEMPERATURE (Ge)
Figure 5 C-C composite high·temperature mechanical property trends.
OXIDATION PROTECTION
Exceptional thermal stress resistance and the retention of useful properties

at extreme temperatures make C-C composites attractive for many pro-
pulsion, aerodynamic heating, and energy generation and dissipation
applications. Versatile fabrication methods and the development of C-C
composites of excellent mechanical integrity present many opportunities
for high-temperature structural C-C components, but the lack of reliable
oxidation protection has been a serious limitation.
The principal difficulties associated with providing consistently accept
able levels of oxidation protection for structural high-performance C-C
composites are (a) a total absence of self-protection, and (b) thermal
expansion and elastic characteristics that are unique and difficult to match
with appropriate coating materials. External coatings are the most direct
and, in many cases, the most effective method of protecting materials from
chemical attack. Because the oxides of carbon are gases and provide no
physical barrier to the progression of oxidation, an external coating that

greatly inhibits contact with oxidizing species is essential to C-C oxidation
protection at all but the lowest temperatures.
The thermal expansion characteristics of C-C composites made with
high-performance fibers make establishing and maintaining coherent and
adherent external coatings extremely difficult. Furthermore, even if satis
factory thermal expansion matching could be achieved, coating defects
that are practically unavoidable both during processing and in service often
require that mechanisms for coating self-healing and internal protection of
the carbon constituents be provided.
External Coatings
In the selection of external coatings for C-C oxidation protection, it is
instructive to first consider the ideal case where the coating is unflawed
and totally envelops the component. Here the rate of carbon oxidation
can be represented by
kM
R= ' 1.
pxt

where R is the carbon oxidation rate in %'h-I, k is a constant, M is the

rate of diffusive oxygen permeation through the coating, p is the density
of the C-C, x is half the C-C section thickness, and t is the coating thickness.
In Equation I, k is the product of the weight of carbon removed per weight
of reacting oxygen, which is 0.75 for CO formation, and 3.6 x 103 s·h-I
and 100 for conversion to %. This gives a value for k of 2.7 x 105• M is
given in g·cm-I·s-\ p can be taken as 1.75 g'cm-\ a representative x
is 0.25 cm, and a reasonable maximum coating thickness is 0.02 cm (200

J.lm). Substituting these values in Equation I gives
2.
Based on experience, a weight loss of about I % is a tolerable limit. With

a minimum useful performance period of 100 hr, a maximum allowable
oxidation rate is O.Ol%·h-l. Therefore, by Equation 2 the maximum
oxygen permeability for the coating is about 3 x 10-10 g·cm -1·S-I.
Oxygen permeability data for some common refractory oxides are given
in Figure 6 (40-43). Values of 3 x 10-10 g'cm-I's-I are expected for a
number of oxides in the 1000 to 1400°C range, but only Si02 and Al203
T (Oc)
1900 1650 1400 1200 1000 800 600

-6.0
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01 ____ B 0
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>-
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-12.0
"-
- -
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0
EXTRAPOLATION
-'
-13.0
-14.0
-15.0
-16.0
l-
,
~ T �1 T
5.0 6.0 7.0 8.0 9.0 10.0 11.0 lZ.0
T-1 (10
-4
K-1)
Figure 6 Oxygen permeabilities of refractory oxides in air.

exhibit permeabilities low enough t o provide the necessary protection for

extended periods at higher temperatures.
A potentially effective approach for achieving higher temperature pro
tection is to start with a nonoxide coating that must first oxidize before
oxygen can diffuse to the underlying carbon. For example, it has been
shown that HfB2 forms a protective oxide and oxidizes parabolically so
that about 200 /-tm of oxide would form in 100 hr at 1500°C (44). Adding
SiC to the HfB2 considerably enhances the oxidation resistance of HfB2,
an d calculations show this could push the 200 /-tm oxidation in 100 hr to
almost 1600°C (45).
Because Si02 has a low oxygen permeability compared with the other
oxides, silicon-based ceramics reprcsent the ultimatc in oxidation resist
ance. For example, only about 10 /-tm of oxide would be expected to form
on high purity SiC or Si3N4 coatings in 100 hr at 1650°C (46). It should
be mentioned that because of their ultralow permeabilities at very high
temperatures, the platinum group metals, iridium and rhodium, have been
considered as coatings (47). However, extremely high cost, volatile oxide
formation , and high thermal ex p ansi on strongly detract from the utility
of these materials.
From the discussion above, it is clear that SiC and Si3N4 are the preferred
external coatings for C-C oxidation protection from the standpoint of
providing inherently low oxygen permeation. The temperature limitatiops
of SiC and Si3N4 are not based on the rate of oxide formation, but
rather on the ability of the oxide to release gaseous oxidation products.
Thermodynamic and transport calculations, which have been confirmed
experimentally, show that depending on the detailed material chemistry , the
protective Si02 that forms on SiC and Si3N4 at lower temperatures is disrupted
by gaseous reaction products in the 1500 to 1800°C range (48-51). This leads
to the rapid destruction of thin coatings by the accelerated formation of
frothed and nonprotective Si02 and by material loss caused by the production
of gaseous SiO. A similar compromise of the protective Al203 layer on AIN
by cracking and bubble formation occurs at 1500 to 1600°C (40).
The problem of oxide disruption on ceramics that forms gases during
oxidation points to a general consideration for coatings on C-c. Once
oxygen penetrates the coating and CO is generated by carbon oxidation,
pressure will build up rapidly beneath the coating, and the CO must be
released either by diffusion through the coating or coating disruption. The
fact that intact Si02 and Al203 layers are formed on SiC, Si3N4, and AIN
below certain temperatures means that the CO and N2 generated during
oxidation can diffuse out sufficiently rapidly through the oxides to prevent
disruption. In general, nondisruptive diffusive release of CO is more easily
accommodated by vitreous materials like Si02 and B203, in which bulk
molecular diffusion can occur, than in crystalline oxides where grain

boundary diffusion is the only possible and limited mechanism.
Based on intrinsic oxygen permeability and oxide stability consider
ations, the use of Si02 as an oxygen barrier, in the form of SiC or Si3N4
outer coatings, appears to be a sound approach for C-C oxidation pro
tection at temperatures up to about 1 800°C. A method for making use of
the potentially low oxygen permeability of Si02 at even higher tem
peratures by enveloping a silicate glass layer between coatings of low
expansion refractory crystalline oxide has been proposed (52).
The problem of thermal expansion mismatch between external coatings
and the underlying C-C is shown in Figure 7 wherein the thermal expansion
characteristics of prominent coating candidates and those of a high
performance fabric laminate C-C composite are compared (53-55). The

laminate C-C presents two difficulties. These are (a) a very low average
thermal expansion coefficient (CTE) along the fibers, and (b) expansion
across the fibers that is much greater than along the fibers. This extreme
anisotropy can be avoided by the use of multidirectional weaves, but this
adds cost, detracts from in-plane strength and stiffness, and still leaves the
problem of a low CTE . Figure 7 shows that several ultralow expansion
oxides, including Si02, match the CTE of C-C along the fibers fairly well,
while SiC and Si3N4 exhibit thermal expansion characteristics that fall
b etween the C-C extremes. D epositi on of SiC and Si3 N4 coati n gs at high
temperatures, and then cooling, results in compression in the direction
across the fibers and tensile cracking in the directions along the fibers. On
the other hand, an ultralow expansion coating on a fabric laminate C-C
would most likely spall because of excessive compression in the direction
across the fibers.
The discussion given above suggests that relief from thermal expansion
induced cracking or spallation could be achieved by the use of low-expan
sion, low-permeability silicate coatings on C-C composites with multi
directional weaves. Although such coatings would be expected to have
modest strengths, their inherently low elastic moduli and some degree of
plastic compliance at high temperatures could prevent cracking during
service despite the relatively high primary tensile strains often specified in
the design of structural C-C components.
Most of the work involving C-C oxidation protection has dealt with the
problems associated with using SiC or Si3N4 coatings on fabric laminate
C-C materials. As discussed earlier, these coating materials were selected
because of the inherently low oxygen permeability of their oxidation pro
duct, Si02, and average CTE values that are intermediate between the
extremes of the C-c. The concept that appears to have the best potential
for providing protection while accommodating the inevitable coating
z.o
1.8
1.6
1.4
1.2
�
z
�
SiC
""
til
z
1.0
x
'"
Co.
3A1 0 ·2Si0
2 3 2
«
::E
...J
a:
0.8
'"
:r
t-
0.6
c-c
ALONG
0.4
MAS 225 FIBERS
Ta O
z S
LAS
0.2
Al 0 ·TiO 114
z 3 z
a 200 400 600 800 1000 1200 1400 1600 1800 2000
TEMPERATURE (Oc)
Figure 7 Thermal expansion characteristics of a high-performance fabric laminate C-C and

external coating candidates.
cracks from CTE mismatch and primary in-service stresses is to seal the
cracks with a compliant glass. Borate glasses appear to havc viscosity and
wetting characteristics that are appropriate, and perhaps uniquely suited,
for this task (50, 52, 56--58).
An effective and convenient method for sealing the cracks in SiC and
Si3N4 coatings is to use a nonoxide inner coating that has a high boron
content (50, 52, 59, 60). Oxidation of the inner coating through the cracks
in the outer coating produces sealant glass that can flow into the outer
coating cracks. Crack sealing in such a system is shown in the polished
section scanning electron micrograph of Figure 8. Because no coating will
ever be totally unflawed, it is likely that even if CTE and elastic property
matching between the primary coating and the C-C could be achieved,
some mechanism of sealing such as shown in Figure 8 would be required
for reliable oxidation protection.
An estimate of the effectiveness of ideal B203 crack sealing can be
obtained using Equation I and a projected 1000°C oxygen permeability
for B203 of 8.6 x lO-llg·cm-l·s-l. Limiting the B203 thickness to 0.01 cm
x 1O- %·h-l, or a 1% average

3
(100 11m) gives an oxidation rate of 4.5
oxidation beneath the cracks in about 200 hr. Because the cracks in a SiC
or Si3N4 coating only constitute 0.1 to 0.2% of the total coating area (and
keeping in mind that CTE mismatch cracks close at temperatures above
the 1000°C coating temperature), projected useful lifetimes of up to 1000
hr seem appropriately conservative (61).
Figure 8 Polished-section scanning electron micrograph showing outer CVD SiC and inner
CVD boron carbide coatings on a C-C composite that contains particulate boron-rich
oxidation inhibitors. The thermal expansion mismatch cracks in the coatings are filled with
borate sealant glass ( lOOX).
Internal Modijications
External coatings and coating sealants are never perfect. Therefore, to

extend the useful life of coated C-C materials and to prevent catastrophic
failure in the case of a major breach in the coating system, some sort
of internal protection is advisable. This is pa rticularly important if the
component is intended for long-term duty. Internal protection can take
three forms. These are (a) chemical species that inhibit the oxidation
reaction, (b) internal coatings that act as oxygen diffusion barriers, and (c)
additiv es that oxidize to form nonvolatile oxides and therefore tie up or
getter the oxygen.
While many elements and compounds are known to catalyze the oxi
dation of carbon, the oxides of boron and phosphorous have the opposite
effect and inhibit carbon oxidation even when present in very small quan
tities (62, 63). This inhibition seems to be caused by segregation of the
chemical species to active oxidation sites on carbon internal surfaces. True
chemical inhibition is an important factor below about 600°C, but is
overwhelmed at the higher temperatures projected for the sustained oper
ation of structural C-C components.
Small scale greatly limits the effectiveness of internal coatings on indi
vidual carbon fibers and matrix pores unless these diffusion barriers are
combined with oxygen gettering, e.g. consider an ideal Si02 coating on a
carbon fiber in air at1000°C. Using Equation I and values of 3.2 x 10-15
g·cm-I·s-I for M, 5 x1O- cm (5 !lm) for x, and 2 x 10-5 cm (0.2 !lm) for
4
t, the oxidation rate is calculated to be about 5x 1O- %·h-1• Thus 1%

2
oxidation would occur in about 20 hr with a perfect Si02 coating, and
much more rapidly with other types of oxide coatings. With the use of
nonoxides, a 10-5 cm (0.1 !lm) thick SiC coating would require about 50
hr under these conditions for full conversion to Si02• Here it is assumed
that the oxygen partial pressure inside the C-C is that of air at 0.21
atm. It can be shown that without gettering, enough oxygen would enter
through an intact coating system with B 203 sealed cracks at 1000°C in 50
to 100 hr to establish this pressure. Destructive gettering by oxidation of
the carbon matrix would lower the oxygen pressure and make the fiber
coatings more effective, but this would only accelerate removal of the
matrix. Therefore, a gettering agent that oxidizes to mitigate carbon attack
and forms a condensed product must be included in the matrix. Starting
the process with a nonoxide fiber coating such asSiC instead ofSi02 would
also contribute to the gettering.
Matrix additives of fine elemental boron or B4C powders have been used
successfully for the internal oxidation protection of C-C composites (52,
58, 64-69). Fine powders rich in boron oxidize readily for effective getter-
ing, and the B203 glass that is produced wets the carbon and flows to form
protective self-healing internal coating layers on both the fibers and matrix.
Although B203 has a low viscosity and cannot be considered a structural
constituent, it contributes to composite coherency and its presence is
preferable to lost carbon. Clearly, Si02 has a much lower oxygen per
meability than B203, but a Si02 precursor such as SiC is greatly inferior
to B203 as a matrix additive because of its resistance to oxidation and the
high viscosity and poor wetting characteristics of Si02 (52). Fiber coatings
of SiC provide the advantage of low oxygen permeability, but are not self
healing and are susceptible to defects. Coatings of B4C and BN bear
consideration because of the ability of B203 to protect both the fibers and
matrix.
Composite Oxidation Performance

Oxidation tests performed on oxidation-protected C-C composites range
from isothermal tests on small coupons to tests on prototype components
using conditions that simulate the complex thermal cycling, primary
stresses, and gas chemical environments to be encountered in actual engine
and aerodynamic heating applications. Most materials development pro
grams target specific components and systems, thus coupon screening
often involves cyclic oxidation tests that are appropriate for the intended
use. The development of oxidation protection for structural C-C com
posites has been driven by defense needs so the distribution of much of
the detailed information on applications, test conditions, material charac
teristics, and test results is restricted.
In general, it has been found that the most effective way to deal with
external coating cracks caused by CTE mismatch and in-service loading
is to seal the cracks with borate glasses. A simple demonstration of this
using high-performance C-C specimens with CVD Si3N4 coatings was
reported several years ago (50). Isothermal oxidation tests of 5 hr duration
for a limited-life application were run at 871, 1093, 1315, 1538, and 1760°C.
No oxidation damage was detected in specimens run at 1315°C and above
because these temperatures were near or above the temperature of coating
application and the CTE-mismatch cracks were closed and could be sealed
by Si02 formation on the Si3N4• However, oxidative attack of the C-C was
obvious at 871 and 1093°C because the cracks in the Si3 N4 were open. In
contrast, identical specimens treated with a borate glass sealant that filled
the cracks exhibited no damage at the lower temperatures.
Applications that require long-term performance usually involve exten
sive thermal cycling between room temperature and 1200 to 1500°C. Here
the sealing of cracks in outer coatings is best accomplished using a coating
system with an inner boron-rich coating as shown in Figure 8. This

arrangement provides a continuous supply of sealant glass to compensate
for vapor losses that can occur over long periods at high temperatures. A
comparison of the cyclic oxidation resistance of boron-modified high
performance C-C specimens with single CVD Si3N4 coatings and coatings
composed of an outer CVD Si3N4 coating and an inner CVD boron carbide
layer was recently reported (60). Cycling in air between room temperature
and 1400°C with intermediate holds at 1093, 816, and 649°C produced a
7% weight loss in 60 hr for the specimens with the single coating, but
essentially no weight change after 100 hr for the specimens with the boron
carbide inner coating.

Recent cyclic oxidation test data for boron-modified high-performance
C-C specimens with single CVD SiC coatings and CVD SiC outer coatings
over CVD boron carbide inner coatings are plotted in Figure 9 (H Dietrich,
personal communication). Two air test schedules were used. The first
schedule involved four rapid heating and cooling excursions between room
temperature and 1200°C, and then a hold at 650°C. The second schedule
was of the same type with the high temperature at 1370°C and the hold
temperature 980°C. In each case, the duration of a full cycle was about
25 hr.
Figure 9 shows that four cycles or 100 hr of oxidation testing produced
little weight change in the specimens that had the inner boron carbide layer
because in both test schedules, the cracks in the outer SiC coating were
sealed with glass. On the other hand, the specimens with the single SiC
coating experienced significant weight losses from oxidation of the C-C
through the coating cracks. The lower-temperature oxidation schedule was
more severe because the CTE-mismatch cracks were wider at 650°C than
at 980°C.
Difficulties that have been encountered with crack sealing using the
configuration shown in Figure 8 appear to be associated with identifying
and reproducibly fabricating inner coatings with characteristics that pro
vide optimum quantities of glass. Dense coatings that oxidize slowly fail
to produce enough glass for effective sealing. Porous coatings generally
oxidize rapidly, and this can result in either an excess of glass or the
unconfined glass flowing into the C-C away from the outer coating cracks
leaving a poorly bonded and unsealed coating.
Too much glass can compromise the integrity of the outer coating by
fluxing the protective Si02 and rendering the SiC or Si3N4 susceptible to
destructive oxidation (50, 52, 58). The moisture sensitivity of B203 and
most borate glasses is always a concern, but it becomes an overriding issue
with excessive glass formation. Hydrolysis enhances the volatility of the
1 .0
1 370/980 CYCLE
S i C/BORON CARB I DE COAT I NG
0.0
1 200/650 CYCLE
S i C/BORON CARB I DE COAT I NG
-1 .0
1 370/980 CYCLE
S i C COAT I NG
-2 . 0
�
-3.0
-4.0
-5.0
1 200/650 CYCLE
-6.0 S i C COAT I N G
- 7. 0 I
-8.0 t
a
I
10 20 30
I
40
I
50 60 70 80 90 1 00
T I ME (h)
F�qure 9 Oxidation performance of boron-modified high-performance C-C specimens with

single CVD SiC coatings and CVD SiC coatings over CVD boron carbide inner coatings.
glass, and degradation of large amounts of glass residing beneath the outer
by the
coating can result in significant losses of sealant, coating disruption
rapid release of moisture, and poor coating adherence due to the low
integrity of the boric acid hydrolysis product ( 1 9, 50, 52, 58). The de
trimental effects of moisture exposure have been demonstrated in cyclic
oxidation tests on C-C specimens with coatings that contained large
amounts of borate glass (1 9). The general problem of coating spallation
as related to coating thickness and C-C surface preparation has also been
investigated in cyclic oxidation tests (71 ).
CARBON-cARBON COMPOSITES 43
Any Annual Review chapter, as well as any article cited in an Annual Review chapter,
may be purchased from the Annual Reviews Preprints and Reprints service.
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ANNUAL
REVIEWS Further
Quick links to online content
Annual Review of Materials Science
Volume 24, 1994
CONTENTS
MATERIALS SCIENCE AND ENGINEERING, AN EDUCATIONAL

DISCIPLINE, Morris E. Fine and Harris L. Marcus
C> CARBON-CARBON COMPOSITES, J. E. Sheehan, K. W. Buesking,

and B. J. Sullivan 19
THE PROBLEM OF DOPING IN II-VI SEMICONDUCTORS, D. J. Chadi 45

C> POLYMER COMPOSITES, F. J. McGarry 63
C> WHISKER TOUGHENING OF CERAMICS: Toughening Mechanisms,

Fabrication and Composite Properties, Murat Bengisu and
Osman T. Inal 83
ION IMPLANTATION OF OPTICAL MATERIALS, Ch. Buchal,
S. P. Withrow, C. W. White, and D. B. Poker 125
ELECTRODEPOSITED MULTILAYER THIN FILMS, C. A. Ross 159
C> TECHNOLOGY OF SELF-REINFORCED SILICON NITRIDE, A. J. Pyzik
and D. F. Carroll 189
SURFACE AND INTERFACE STRESSES, Robert C. Cammarata and
Karl Sieradzki 215
CARBON NANOTUBES, Thomas W. Ebbesen 235
NEUTRON-DIFFRACTION DETERMINATION OF RESIDUAL STRESSES
IN ADVANCED COMPOSITES, D. S. Kupperman 265
C> FRACTURE MECHANICS FOR FAILURE OF CONCRETE, S. P. Shah
and C. Ouyang 293
C> PLASTIC FLOW IN SIC/ AL COMPOSITES-STRENGTHENING AND
DUCTILITY, N. Shi and R. J. Arsenault 321
C> PROGRESS IN TRANSFORMATION TOUGHENING OF CERAMICS,
M. V. Swain and R. H. J. Hannink 359
C> ORDERED INTERMETALLICS, E. P. George, M. Yamaguchi,
K. S. Kumar, and C. T. Liu 409
STRONGLY GEOMETRICALLY FRUSTRATED MAGNETS,
A. P. Ramirez 453
PLASTIC AND ELASTIC PROPERTIES OF COMPOSITIONALLY
MODULATED THIN FILMS, Scott A. Barnett and
Meenam Shinn 481
(continued) VB

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ANNUAL

1994 by Annual Reviews Inc.

J. E. Sheehan, K. W. Buesking, and B. J. Sullivan

MSNW, Inc., P.O. Box 865, San Marcos, California 92079

applications, constituents, fabrication, properties, oxidation

INTRODUCTION AND BACKGROUND

Carbon-carbon (C-C) composites are composed of carbon fibers in a

Constituents and Microstructure

parameters, such as temperature and pressure, that are used in establishing

inexpensive, are easily processed, and provide a relatively high yield of

conducted in reactors at reduced pressures where a flowing hydrocarbon

carbon. This is termed densification by chemical vapor deposition (CVD)

Applications and Technological Importance

MATERIALS DESIGN AND ANALYSIS

C-C composites offer a wide range of properties that can be tailored by

In one model, a finite element approach is used in which three-dimensional

(WC Loomis, personal communication). This model allows crack propa­

FIBERS AND BUNDLE

�__ CRACKED OR DEGRADED

Figure 2 Schematic drawing of an orthogonal three-dimensional C-C volume element.

experimental data. These are the subcell efficiency, which is a measure of

be identified by comparing the predicted thermal strains with measured

obtained, the model can be used to compute a consistent set of orthotropic

Figure 3 Schematic drawing of a five-dimensional fiber architecture.

Mechanical and Thermal Properties

temperature C-C processing, have strengths up to about 2.5 GPa and

influence on design and materials selection. In general, the shear strengths

Unidirectional 0.65 0 0 650--1000 2.0 240-2

Direction x y z x-y x-y x x

0.13 0.13 0.21 21-27 1.4-2.1 140 90

o 400 800 uoo 1600 2000 2400

The creep or high-temperature time-dependent deformation of C-C

Exceptional thermal stress resistance and the retention of useful properties

physical barrier to the progression of oxidation, an external coating that

where R is the carbon oxidation rate in %'h-I, k is a constant, M is the

is 0.25 cm, and a reasonable maximum coating thickness is 0.02 cm (200

Based on experience, a weight loss of about I % is a tolerable limit. With

1900 1650 1400 1200 1000 800 600

00;- -9.0 '-

Figure 6 Oxygen permeabilities of refractory oxides in air.

exhibit permeabilities low enough t o provide the necessary protection for

molecular diffusion can occur, than in crystalline oxides where grain

performance fabric laminate C-C composite are compared (53-55). The

MAS 225 FIBERS

Figure 7 Thermal expansion characteristics of a high-performance fabric laminate C-C and

x 1O- %·h-l, or a 1% average

External coatings and coating sealants are never perfect. Therefore, to

t, the oxidation rate is calculated to be about 5x 1O- %·h-1• Thus 1%

Composite Oxidation Performance

system with an inner boron-rich coating as shown in Figure 8. This

carbide inner coating.

F�qure 9 Oxidation performance of boron-modified high-performance C-C specimens with

Westport, CT: Technomic. 1 24 pp.

4. Plastic Composites, ed. RT Schwartz,

Gao F, Patrick JW, Walker A. 199 3 .

Carbon 22: 507- 1 1

Tech. Rep. ML-TDR-64- 1 73 . Dayton, 66. Ehrburger P, Baranne P, Lahaye J. 1 986.

66 Ohlhorst CW, Martin RH. 1 989. In

MATERIALS SCIENCE AND ENGINEERING, AN EDUCATIONAL

C> CARBON-CARBON COMPOSITES, J. E. Sheehan, K. W. Buesking,

THE PROBLEM OF DOPING IN II-VI SEMICONDUCTORS, D. J. Chadi 45

C> WHISKER TOUGHENING OF CERAMICS: Toughening Mechanisms,

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(WC Loomis, personal communication). This model allows crack propa