SiC-SiC Composites, A State of The Art Review

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ADVANCE MATERIALS

SiC/SiC composite material: A state of the art review


María Camila Belduque Correa

Aeronautical Engineering Faculty, Universidad Pontificia Bolivariana, Medellín, Colombia

ABSTR ACT

Ceramic Matrix Composite materials ‘CMCs’ are the new focus in aerospace industry,
after decades of researching they finally are getting those places in which metals and its
alloys are located, and despite some properties, as its fracture toughness, have to be
improve there are others that overcome for much the metallic ones. Among CMC’s,
SiC/SiC has shown its great capacity to fulfil the aerospace sector requirements, and today
are being a very important part in Boeing 737 and Airbus A320 aircrafts families engines.
This article presents some of those topics concerning to SiC/SiC composites that make
them one of the best choices for innovating and improving aerospace sector.

1. Introduction 500°C, an excellent corrosion resistance


[2] and other characteristics that allow a
From its earliest days the aeronautica l
combined-cycle gas turbine operate at
industry has aimed to increase engine’s
60% fuel efficiency [3].
efficiency in such a way that they save
fuel and remain in a safety condition to Not being sufficient, lighter materia ls
operate. Speaking about conventio na l that obtain higher temperatures range
materials, actually Titanium is one of the have been researched, and though
best choices for fan and compressor ceramics are brittle, they could be
blades [1], and its alloys (Ti-6Al-4V) for reinforced to satisfy the requireme nts
static and rotating components at higher demanded by aero engines. This material
temperatures, where only some super have no ductility, which involves a low
alloys (nickelbase and cobaltbase with tolerance for stress concentrations or for
almost 25% of chromium additions and high-contact stresses, but they are stiff,
lower quantities of Aluminum, Titanium hard, abrasion-resistant and more
and others) can replace them because of attractive for aerospace and aeronautica l
their capacity to maintain an industry, they offer strength above
approximately constant specific strength 1500°C while most metals start to
when temperature increases above decrease their properties almost at
SiC/SiC composite material: A state of the art review | Maria Camila Belduque Correa

800°C, figure 1 depicts this behavior. SiC, reaching temperatures up to 1500°C


[4]. and excellent creep resistance [7],

Figure 1. Strength vs Maximum service temperature of random families of


materials.

Among the ceramic’s family, the Silicon improving its electrical properties and
Carbide (SiC) is one of the most used. It positioning itself as one of the principa l
was discovered by Edward G. Acheson candidates in aeronautical industry for
while running an experiment on the structural components as gas turbine, jet
synthesis of diamonds, he was the first in engines, and heat control on surfaces [8].
synthesize it by passing and electric
In the next pages SiC/SiC composite
current through a mixture of clay and
material fabrication techniques,
carbon, and today is produced via a solid
properties, advantages and
state reaction between sand and
disadvantages will be discuss; those
petroleum coke at very high
innovative characteristics that make it
temperatures in an electric arc furnace
today as one of the most researched
[5]. Due to its high Young’s moduli,
materials in aeronautical and aerospace
hardness, thermal and chemical stability
industry.
[6], high melting point, oxidation
resistance, etc., it’s a perfect candidate 2. The SiC system
for many applications in several
Since its discovery, many SiC polytypes
industries, but it’s brittle, then for
have been found up today, they depends
increasing considerably its ductility and
on the grain orientation and the more
damage tolerance it is reinforced by
common of them are the hexagonal alpha
continuous fibers of the same material,
silicon carbide (αSi-C), which has the

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SiC/SiC composite material: A state of the art review | Maria Camila Belduque Correa

stable form at temperatures higher than SiC common forms are powder,
1700°C [9] and the cubic one, beta commonly obtained through Acheson
silicon carbide (βSi-C), which has the process, a solid-state reaction mixture of
zinc blend structure and is formed below green petroleum coke and silica sand is
1700°C; both theoretical densities of heated at more than 2500°C using two
αSi-C and βSi-C are approximate ly large graphite electrodes. Fibers, via
3.210 g/cm3, this makes the silico n pyrolysis of organosilicon polymers, it
carbide one of the few light weight consists of melt-spinning
covalently bonded ceramics. Figure 2 polycarbosilane at 300°C generally,
depicts the two major crystal structures unfusing with thermal oxidation at
[5]. 110°C-200°C and baking at 1000°C-
1500°C under a flow of inert gas. Other
forms of SiC are whiskers, coating and
single crystals that could be obtained via
Physical Vapor Transport ‘PVT’,
Chemical Vapor Deposition ‘CVD’, Sol-
gel and others. The methods of
fabrication are selected depending on the
desire form, purity level and applicatio n
[9]. Which are several in the industry,
as an abrasive material or a band gap
semiconductor for high power, high
temperature electronic devises, as
reinforcing material in Al2 O3 or in SiC
and other ceramics for decreasing their
brittleness and be used for cutting tools,
[10], high temperature applicatio ns
including gas turbines and nuclear
reactors [6].

Concerning to SiC as matrix in a


composite material, there are random
ceramics options that can be used as
reinforcement for improving its
properties for ultra-high temperature
Figure 2. SiC Crystal Structures. The figure
above shows βSi-C, called 3C too. And lower
services, such as Zirconium Carbide
figure the αSi-C, the majority of its phases are (ZrC), is a refractory carbide which
6H. The crystalline polytypes has a number
for the number of layers in the unit cell,
melting point is 3540°C approximate ly
followed by a letter suffix that designates the and has a low density of 6.7 g/cm3 , it is
crystal symmetry. In this case, “C” for cubic
and “H” for hexagonal. The more common
used, e.g., for reducing the active
are the 3C, 4H and 6H. oxidation mode that SiC presents above

3
SiC/SiC composite material: A state of the art review | Maria Camila Belduque Correa

1650°C [11], it occurs after a passive of the SEVIRI instrument on the


oxidation mode, where a protective film Meteosat Second Generation (MSG)
is generated, in the active mode a spacecraft, figure 3 shows its mechanic a l
volatile sub-oxide is formed and can lead design [14], other applications include
to rapid material consumption[12 ]; microelectronics or calibration of
Alumina (Al2 O3 ) is an oxide material dimensional control tools; in aerospace
with a thermal conductivity of 17.5 sector has been applied for leading
W/m*K at room temperature, employed edges, nose-skirt panels and body flap
as an additive in the fabrication process control surfaces in the NASA X-38
of SiC to promote its sintered (which Keraman, a reentry vehicle [15].
presents strict and complex pressing,
temperature and vacuum requireme nts)

Figure 3. The mechanical design of the 80cm x 50cm elliptical ULS M


and one of the polished mirror blanks. It weights 7kg [14].

without decreasing its heat capacity and It has to be noticed that the lower matrix
lead to a composite with good thermal porosity the higher thermal conductivity
storage and other excellent properties and creep resistance in multip le
named before [13]. Carbon (C), the directions, that means to operate above
C/SiC composite has been studied as a 1300°C, to get this depends on the
candidate for the telescope mirrors used manufacturing process, Chemical Vapor
in the satellite mission ‘SPICA’, Space Infiltration ‘CVI’ and Polymer
Infrared Telescope for Cosmology and Infiltration and Pyrolysis ‘PIP’ and Melt
Astrophysics [43], and for the Ultra- Infiltration ‘MI’ are the best choicest, but
Lightweight Scanning Mirror ‘ULSM’

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SiC/SiC composite material: A state of the art review | Maria Camila Belduque Correa

the lower porosity (±5%) is achieve by 3.1. Properties


CVI [16].
SiC/SiC presents a strong embrittle me nt
SiC properties are summarized in Table and fracture when are exposed to
1, its density is nearly the half of oxidizing environments at 700°C -900°C
conventional materials used in aero under stresses that are below their
engines (Ni alloys= 8.83-8.95 mg/m3 , Ti ultimate strength, above or below this
Alloys= 4.4-4.8 mg/m3) but its fracture temperature range the embrittlement is
toughness definitely is too low in slower [7], this material degradation
comparison with the same materials (Ni occurs mainly due to the propagation of
alloys= 80-110 Mpa*m1/2 , Ti Alloys= the premature fracture of the SiO 2 layer
14-120 Mpa*m1/2 ) [4]. [20, 21]; to improve the fracture

Table 1. SiC properties

3. The SiC/SiC system resistance an interfacial or multip le


layers -pyrolytic carbon, hexagonal BN
As the Al2O3, ZrC, C and other
or alternating C/SiC layers- between the
ceramics, SiC can be used as a fiber-
fiber and the matrix can be produced, this
reinforcement and improve in a
will weaken the fiber-matrix bonding,
considerably way the SiC matrix
and the fracture toughness will increase
properties by receiving a part of the
from 5Mpa m1/2 to 20-30Mpa.m1/2 [22].
mechanical stresses applied to it. This
Zirconia ‘ZrO 2 ’, being a refractory oxide
Properties can varying depending on the
has been used as interphase to achieve
geometry and concentration of the
the same purpose, the outcome with this
constituents and the manufactur ing
multilayered coating is a ductile fracture;
processes: ‘CVI’ [17], Chemical Vapor
but the interphase thick affects those
Deposition ‘CVD’ [18], Hot Pressing
results, a very thick interphase will
‘HP’, Reaction Sintering ‘RS’, Liquid
decrease mechanical properties owing to
Phase Sintering ‘LPS’ [19].
the lower load transfer at the same; while
a too thin interphase will induce a brittle

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SiC/SiC composite material: A state of the art review | Maria Camila Belduque Correa

fracture [17, 23]. Different coatings are and a near stoichiometric SiC
employed to mitigate negative effects composition with low porosity and be
and improve coating properties, or commercially available , figure 6 depicts
fabricate the composite with a process the strength and stiffness retention
with which a high crystallinity can be during service at high temperatures [16],
obtained, then, the mechanical properties it has to be taken into account that their
will not subject to the interphase mechanical properties can chance
thickness effect [17, 24] . Figures 4 and according to the volume fraction, their
5 depicts the results when coating SiC coating, or architecture. The porosity and
fibers with ZrO 2. transverse stress wave interactions can
cause interlaminar delamination, then,
interlaminar properties as shear and
tension strengths will be affected in the
whole composite [26].

Figure 4. a) SiC/SiC with uncoated fibers


shows no fiber pullout.

Figure 6. Creep strain behavior of SiC fiber


types in single fiber form.

Generally this fibers are found in a


volume fraction of 20% to 40%, and
depending of the architecture, UD, 2D-
woven (more common) and 3D woven,
Figure 5. b) Fibers with multilayered coatings, its E can vary from 125 to 305 GPa and
the fibers are pulled out of the matrix. One of
the design concepts for the interaction its Ultimate Tensile Strength ‘UTS’ from
between fiber and matrix in CMCs is a weak 204 to 480 MPa [17, 26, 27].
interface: the fibers are coated to reduce
adhesion to the matrix, then, during the
Some studies have shown results of how
fracture fibers are pulled out of the matr i x
and absorb fracture energy [23, 25]. this and foreign objects velocities
The fibers more commonly used are Hi- (specifically from 100m/s on, at room
Nicalon, TyrannoT M and Sylramic [17]; temperature and 1316°C) may start to
according to the NASA, for aero-engine cause front damage in a 2D woven
applications, SiC/SiC grains have to SiC/SiC composite of an E= 220GPa, the
present a sizes that not exceed 500nm back side damage starts with higher

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SiC/SiC composite material: A state of the art review | Maria Camila Belduque Correa

velocities than 350m/s. Concerning to conductivity in the direction


how the strength is affected, figure 7 perpendicular to the fibers because of the
depicts a comparison of normalized post- porosity in the manufacturing processes,
impact strength between the SiC/SiC it’s about 73 W/m*K at room
composite (one specific in that temperature and 35 W/m*K at 1000°C
experiment) and the silicon nitride used [22].
in gas turbine, the composite exhibits a
3.2. Manufacturing Processes
greater FOD tolerance than its
monolithic counterparts, which have a
 Chemical Vapor Infiltration ‘CVI’
fracture toughness of 5.5 and 8.1 MPa
m1/2 respectively [28]. Among the SiC/SiC manufactur ing
processes this is the more common. Has
the advantages of an excellent control
interphase formation, low toxicity, low
thermal and mechanical stresses and
high crystallinity, purity and density are
achieved. But presents the disadvanta ges
of high cost, complexity and high
fabrication time [17].

It’s a method used for producing


Figure 7. Comparison of normalized post- continuous fiber ceramic by introduc ing
impact strength between the SiC/SiC
composite of this study and the AS800 and
reactants on the internal surface of a
SN282 silicon nitrides (2-mm thick) in full porous preform via diffusion or forced
support at ambient temperature. Vc, critical
impact velocity. convection. As infiltration occurs, the
reactants thick grows and after a certain
It should be noticed that the SiC/SiC
time fills the voids in the matrix [30].
performance is better than the monolithic
One of the precursors for the deposition
ceramics but given the catastrophica lly
of SiC is methyltrichlorosilane ‘MTS’.
damage that can cause a FOD on a gas
[18]
turbine this feature still needs to be
improved.  Liquid Phase Sintering ‘LPS’

Other properties very named are its good It provides a high density and superior
thermal stability, excellent irradiatio n crystalline for monolithic SiC and
tolerance and low tritium permeability SiC/SiC composites due to the
[29]; transformation of additive materials into
some eutectoids; in comparison with
Chemically, SiC fibers have good
those solid state manufactur ing
resistance to oxidation at higher
processes, it has lower sintering
temperatures than 1300°C. And
temperature and time requirements [19].
thermally, SiC/SiC has a low thermal

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SiC/SiC composite material: A state of the art review | Maria Camila Belduque Correa

 Melt Infiltration Process ‘MI’ being used in reusable launch vehicles


under the Next Generation Launch
This process offers high density, a
Technology (NGLT) Program,
thermal conductivity about 50W/m*K,
more than the offered by CVI and PIP specifically as heat exchanger panels
processes, low cost production [31] and turbine blades, vanes, combustors,
enhance to fabricate a SiC/SiC net- bearings and tubular casing pumps [15,
shapes. It’s about a molten silico n
16, 36]; the aim is arise engines
infiltrated into a porous carbon preform
for an in-situ formation of SiC ; It has the efficiency by increasing the turbine inlet
disadvantages of degrade the matrix and temperature and decrease the cooling
induce and extensive debonding due to needed in the components named before.
the thermal exposure; the MI-SiC/SiC
Under NASA’s High-Speed Research
allow a flexural strength of 330Mpa at
room temperature, which decrease at Enabling Propulsion Materials
temperatures higher than 1100ºC [32]. (HSR/EPM) and Ultra Efficient Engine
 Hot Pressing ‘HP’ Technology ‘UEET’ programs, a vane,
showed in figure 8, was fabricated and
Is a method that combines powder
probed at 1315°C and the outcome was
pressing and sintering into a single
operation for densifying materials. It is that this can successfully withstand the
conducted by placing a compacted hard environmental conditions at which
preform into a die, of graphite generally, an engine is undergo for up to 1000h
then, uniaxial pressure is applied to the
[37], other good results can be found in
entire system, which previously was
heated at 2000°C (for SiC) by resistance reference 43.
or by induction temperature method.
Finally, the mold is cold slowly under
pressure and with a controlled
temperature for avoiding the material
oxidation [33, 34]. The general
composition includes SiC Nano-powder
> 95%, 1%-2% free carbon and 1%-1.5%
oxygen [35].
Other common processes to obtain
SiC/SiC are Sol-gel, ‘PIP’, CVD and
chemical vapor reaction [22]. Figure 8. SiC/SiC turbine stator vane fabricated
by NASA's UEET Program.

3.3. Applications
Because of the properties named before, In aeronautical industry, figure 9
SiC/SiC is been investigated to be used shows the more recent innovatio n
in nuclear applications, e.g., differe nt carried out by General Electric
core structures of Sodium Fast Reactor Aviation, IHI Corporation (Japan)
‘SFR’ [29]. But actually its major and Techspace Aero (Safran, France),
application is in both aerospace and this three companies have invested
aeronautical sectors, SiC/SiC as C/SiC is more than $1 billion to fabricate the

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SiC/SiC composite material: A state of the art review | Maria Camila Belduque Correa

Figure 9. The GE9X has 15 CMC parts, among them, the combustor and the
high pressure turbine are SiC/SiC composite [39].

new engine GE9X, which was air to enhance the lean-burn


certificated in 2015 after combustion process, adding to that
accumulating more than 2000 hours the reduction in mass density and a
an cycles on ground in flight testing, 27:1 pressure ratio, the biggest than
and fulfil with FAA nose and any other engine in commercia l
emissions requirements without any aviation can has until moment. [41].
problem [40], for entering in service Now, the challenge is to understand in
this year on Boeing 747X, Airbus a deep way the SiC/SiC behavior and
A320 aircraft and Bombardier’s improve its durability, at the moment
Global 7000 and 8000 ultra-long- large safety factors, lifetimes and
range twinjets. Among its other operational limitations must be
characteristics, the combustors and used [42].
high pressure turbines material is the
most remarkable because those are
made in SiC/SiC, improving its
durability and requiring less cooling

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SiC/SiC composite material: A state of the art review | Maria Camila Belduque Correa

4. Conclusions of High-temperature Structural


Because of its high properties CMCs are Composites for Ship - Naval Univers ity
of Engineering, Science and Technology
marking a new age in materials and
on Advanced Ceramic Fibers and
thereby in applications, industries are Composites Laboratory - National
investment every day more money, time University of Defense Technology.
and effort for improving the systems China; 2015.
already settled, in the aeronautica l
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