CERAMIC MATRIX COMPOSITES: REACTION
BONDED
ALBERTO ORTONA
iCIMSI-SUPSI, Manno,
Switzerland
INTRODUCTION
Ceramic matrix composites (CMCs) offer unique perfor-
mances in high temperature applications because they
put together the ability of ceramics to withstand high
temperature hostile environments with the CMC struc-
tural behavior which allows to bear load beyond the
proportional limit stress (Fig. 1). Further details on CMC
mechanical properties can be found in other chapters of
this encyclopedia. The type of CMC and thus their rele-
vant manufacturing routes is mainly determined by the
type of matrices. Reaction-bonded matrices have gained
their popularity, among several well-known manufactur-
ing methods, because processing is cost effective, produces
near to net shape components, and the final product has
nearly no porosity.
REACTION BONDING
Reaction bonding (RB) is a process in which a porous
ceramic preform becomes dense through an in situ chemi-
cal reaction of two or more elements. This process was first
developed for monolithic ceramics. RB ceramics applied in
CMC matrices are silicon carbides (RBSiC) and silicon
nitrides (RBSN) which were developed around 1960.
RBSiC was obtained by infiltrating carbonaceous mate-
rial with molten Si in vacuum (10−2 mbar) at temperatures
ranging between 1450 and 1600◦ C [1]. The chemical reac-
tion between Si and C [2] is
Siliquid + Csolid = SiCsolid [H = −73 kJ/mol]
At these temperatures, molten Si infiltrates the porous
carbon body per capillarity (contact angle 20–40◦ [3]); in
CMC manufacturing, this process is usually known as melt
infiltration (MI) or liquid silicon infiltration (LSI) [4].
RBSN compact bodies with an appraisable strength
were produced by reacting nitrogen with loosely packed
Si powder preforms at temperatures between 1200 and
1400◦ C [5]. At these temperatures the associated chemical
reaction [2] is
3Sisolid + 2N2gas → Si3 N4solid [H = −744 kJ/mol]
Both reactions are exothermic and thus process condi-
tions (especially for RBSN [6]) must be carefully optimized
in order not to increase the process temperatures. What
makes this process interesting compared to others is that
it occurs without volume changes. Parts produced via RB
employs less expensive techniques and they are near to
the net shape.
Wiley Encyclopedia of Composites, Second Edition. Edited by Luigi Nicolais and Assunta Borzacchiello.
© 2012 John Wiley & Sons, Inc. Published 2012 by John Wiley & Sons, Inc.
1
SiC MATRIX COMPOSITES
RB, first adopted to produce SiC matrix CMC around 1980,
is one of the several densification techniques employed
for CMC manufacturing such as chemical vapor infiltra-
tion (CVI), polymer infiltration and pyrolysis (PIP), and
sintering by hot isostatic pressing (HIP). CVI produces
CMC with high thermo-mechanical properties and with
a crystalline SiC matrix. Processing implies expensive
equipments and highly skilled personnel making it lim-
ited to aerospace and fusion applications. PIP is a simpler
but time-consuming process because many re-infiltration
cycles must be performed to reduce the residual porosity.
SiC matrix is often amorphous and the final product still
has residual open porosity. Even so, these methods are
utilized during the MI process.
Processing
MI CMC have been produced infiltrating C [7] or SiC
[8] fiber preforms and converting fully or partially their
porous matrix into SiC.
Processing conditions are similar to that of the mono-
lithic SiC. For CMC manufacturing, since Si is highly reac-
tive during processing, fibers must be protected against it.
If molten Si reacts with the fiber material, the resulting
mechanical properties will drop [9], leading to a brittle,
low performing CMC.
Typically, MI CMCs are produced following these
steps:
Step 1. Coating fibers or bundles to protect them dur-
ing the process and to obtain a weak interphase
Step 2. Manufacturing of a porous near to net-shaped
polymeric matrix preform
Step 3. Conversion of the polymer into amorphous car-
bon (T ∼ 1000◦ C)
Step 4. Infiltration with molten Si and RB.
Fiber interphase acts as a CMC-toughening agent
because under load it promotes fiber pull out at the onset of
matrix cracking (Fig. 1). Single fibers or full bundles can be
protected via CVI or PIP. Typical interphase materials are
pyrolytic carbon and boron nitride (BN); interphase thick-
ness ranges from 0.1 to 1 μm. To avoid reaction between
Si and C or BN interphases, an additional SiC overcoating
is applied with thickness from 0.5 to 5 μm [4].
The ‘‘green’’ composite is manufactured with common
techniques employed in the Carbon Fibre reinforced Plas-
tics (CFRP) production such as for continuous fibers CMC:
autoclave processing, filament winding, and resin trans-
fer molding (RTM); for short fiber CMC: sheet molding
compound (SMC).
Articles are then pyrolyzed in an inert atmosphere
(argon, nitrogen) to convert the polymer binder into car-
bon. During its decomposition, the polymer loses mass and
shrinks, yielding amorphous carbon and, if the process is
correct, distributed open porosity. This is probably the
most critical step in the process.
2 CERAMIC MATRIX COMPOSITES: REACTION BONDED

Table 1. Typical CMC Properties at RT (Otherwise

Marked) Obtained by Si Melt Infiltration on Weaved
Fibersa
Ultimate strength
Fiber/Matrix C–C/–SiC C/SiC SiC/SiC
Density [g/cm3 ] 1.9–2.0 2 2.8
Vf % 55–65 — 20–25
Porosity % 2–5 2 <2
Stress

Tensile strength [MPa] 80–190 110 321

Strain to % 0.15–0.35 0.3 0.89
failure
Proportional limit
Young’s modulus [GPa] 50–70 65 285
Compression [MPa] 210–320 470 —
strength
Flexural strength [MPa] 160–30 190 —
ILSS [MPa] 28–33 — 135

CTE = [10−6 /K] −1 to 2.5b −0.3 3.57c

Strain to failure ⊥
2.5–7b −0.03 to 1.36d 4.07c
Strain Thermal
conductivity = [W/mK] 17.0–22.6e 23–12f 33.8c
Figure 1. Typical in-plane tensile stress–strain behavior for a ⊥
continuous fiber-reinforced RB CMC. 7.5–10.3e — 24.7c
Specific heat [J/kg K] 690–1550 — 710c
a Ref. 4.
b RT– 1500◦ C.
c RT.
d 200– 1200◦ C.
e 200– 1650◦ C.
f ◦
20– 1200 C.

depending on the process, residual (5–15% vol) metallic

silicon (Fig. 2). That allow to realize a dense material, but
limits the maximum CMC working temperature.
For applications such as turbine engines characterized
by large vibrational loads at high temperatures, fatigue
and creep tests have been conducted with promising
results [10].

Applications

Figure 2. C fibers (C and SiC coated by CVI) with a matrix
containing SiC powder (gray) and MI Si (white).
The last step consists in placing the article in contact
with Si grains into a vacuum furnace, bringing it above the
melting point of Si (1420◦ C) and allowing the infiltration.
Many preforms contain also SiC powder into the matrix
(Fig. 2), to mitigate the exothermic reaction. Since the
transformation into SiC leads to a volume increase, pore
channels can close leading to residual internal porosity.
Properties
MI CMCs are well known for their good thermo-mechanical
properties. As produced MI CMC mechanical properties
are summarized in Table 1. Properties can vary depending
on the fibers employed, the manufacturing methods, and
the evaluation method. A direct comparison thus cannot
be made. Table 1 reports the values of CMC produced
by DLR (D) [4], SGL Carbon Group (D) [4] and General
Electric (USA) [4,10]. MI leads to a CMC which has,
Owing to their unique specific properties, CMC have been
developed for aircraft/spacecraft thermal protection struc-
tures (TPS). C/SiC composites were developed for reusable
TPS of the BURAN from the former USSR and also on the
NASA X38, developed by DLR. Coated C/SiC CMCs have
also been employed in military rocket motors. SiC/SiC
materials have been employed for long-term applications
such as gas turbine engines. Coated SiC/SiC have been
mounted on gas turbine from GE and solar turbines, the
real challenge of this application is the long SiC/SiC stabil-
ity since the minimum required service for a gas turbine
is of 30,000 h. The most successful industrial applica-
tion of C/SiC CMC is in the friction sector, following the
impressive research work done around 1990 [11,12]. These
materials stand between carbon/carbon and gray cast iron
because they take advantage of stable dynamic and static
coefficients of friction; high wear stability; low weight;
design freedom (e.g., for internal cooling ducts, attach-
ments), and low life-cycle costs [13]. CMC brakes are now
commercialized (Brembo SGL Carbon Ceramic Brakes,
Schunk, and DaimlerChrysler) for sport cars (Porsche,
Ferrari, and DaimlerChrysler).
 CERAMIC MATRIX COMPOSITES: REACTION BONDED 3

Another advantage of MI CMC is that they can be Table 2. The Room Temperature Physical
combined with organic and sinter metallic pads. Tests and Mechanical Properties of SiC/RBSN Compositesa
operated on a comparable lifetime of a car (300,000 km) Property Reinforcement
showed the decisive role of the combination CMC/pad on
1-D 2-D
the coefficients of friction and thus on the tribological
behavior. Other friction applications include high speed Physical
trains, aircraft (civil and military), and emergency brakes Fiber content % 24–30 24–30
for elevators and cranes. Density [g/c3 ] 2.2–2.4 2.2–2.4
Porosity % 30–40 30–40
Mechanical
Si3 N4 MATRIX COMPOSITES
Elastic modulus [GPa] 186 ± 20 118 ± 15
Ultimate tensile strength [MPa] 690 ± 138 316 ± 62
RBSN CMC where developed to conjugate their thermo-
Ultimate tensile strain % 1 0.6
dynamical stable behavior at temperatures up to 1700◦ C Poisson’s ratio 0.21 NA
with high specific mechanical properties. Their reinforce- Shear modulus, [GPa] 31 ± 3 NA
ments are generally composed of C or SiC continuous fibers Interfacial shear strength [MPa] 11 ± 7 NA
coated with pyrolytic carbon or BN interphases and over- (fiber push-out method)
coated with SiC to protect them during processing and to Interlaminar shear strength [MPa] 40 ± 4 NA
improve CMC toughness under load. (double notch shear)
Silicon nitride matrices can be placed within the fibers, Fracture toughness [MPa(m)1/2 ] 13 NA
by CVI (using ammonia and silicon precursors), by PIP a Ref. 15.
(where a Si3 N4 pre-ceramic polymer is infiltrated and
pyrolyzed), by hot pressing (HP), HIP, and by RB.
Table 3. Thermal Properties of 1-D RBSN CMC in
Nitrogena
Processing Property Temperature [◦ C]
RBSN CMC are produced by heating a preform containing 25 600 1000 1400
coated fibers and porous Si powder in nitrogen-rich atmo- Thermal expansion
sphere at high temperatures (below the Si melting point)
In-plane [10−6 /◦ C] NA 3.1 3.6 3.8
to react with silicon and form silicon nitride. Through the thickness [10−6 /◦ C] NA 2.9 3.2 3.7
Preform preparation follows more or less steps 1–3 Specific heat [J/kg K] 675 1250 1312 1330
described in the previous paragraph. During step 4, nitro- Thermal diffusivity
gen diffuses from the outer surfaces to the core of the
In-plane, [106 m2 /s] 7 3.3 2.8 2.5
composite. With a proper fiber coating, if gases diffusion
Through the thickness [106 m2 /s] 2.5 1.8 1.8 1.8
is maintained slow, the porous Si matrix converts into
Thermal conductivity
Si3 N4 with no shrinking and distortion of the CMC compo-
nent. The process of converting silicon to Si3 N4 is highly In-plane [W/m K] 10 9.0 8.0 7.0
exothermic and difficult to control. Heat management is Through the Thickness [W/m K] 4.5 4.5 4.5 4.5
very important because overheating will modify Si3 N4 a Ref. 15.

matrix microstructure and phase chemistry. To allow a

continuous gas diffusion and reaction in all the CMCs, its
preform porosity must open. There is a optimum between
the final CMC densification and a fully converted matrix:
typically preform porosity values range from 20 to 40%
[15].
Properties
Because RBSN employs gaseous reactants, the RBSN
CMC materials are characterized by an open and intercon-
nected porosity. In an RBSN matrix, open porosity reduces
thermal conductivity and the elastic modulus but facili-
tates load transfer to reinforcement and lowers thermal
stresses. Residual open porosity is detrimental because of
composite oxidation. If RBSN CMCs are not coated with
environmental barriers, oxidation can lead to internal
stresses which may cause premature matrix cracking and
fiber delamination. Mechanical and thermal properties
of RBSN CMC have been extensively measured [14–16],
values are reported in Tables 2 and 3.
Applications
Because of their high specific modulus, strength, tough-
ness, and low thermal conductivity, RBSN CMC employ-
ment is foreseen in aero engine components such as
inter-turbine ducts, combustor liners, nozzle vanes, diver-
gent and convergent flaps, and blades. To protect them
against oxidation RBSN CMC components must be coated.
Other aerospace applications include radomes and exhaust
nozzles.
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