MAT5030 Composites

Ton Peijs

4 Processing of
4.
Metal & Ceramic Matrix Composites

Content

Metal
M t l matrix
t i composites
it
Ceramic matrix composites
Carbon-carbon composites

Matrix materials
Metal
(MMCs)

Ceramic
(CMCs)

Polymer
(PMCs)

Fibre: boron; Borsic;

carbon (graphite); SiC;
alumina (Al2O3)

Fibre: SiC; alumina;

SiN
thermoplastic
Tough; high
melt viscosity;
recyclable

Matrix: aluminium;
magnesium; titanium;
copper
Fibres improve high
temp creep; thermal
expansion, wear. Little
advantage to stiffness
and strength

Matrix: SiC;
alumina; glass-ceramic;
SiN

thermoset
Brittle; low
viscosity before
cure; not
recyclable

Fibres improve
toughness. Little
advantage to stiffness

The matrix material largely determines the processing method

High temperature properties

C
Composite
it matrix
ti

U
Upper
operation
ti
ttemperature
t

polymer

300C

metal (Al)

600C

ceramic

1000C

High temperature properties

Content

Metal
M t l matrix
t i composites
it
Ceramic matrix composites
Carbon-carbon composites

Metals are tough

Metals can be cheap

High temperature properties

Comparison of the yield strength of sintered aluminum powder (SAP) composite with that of two conventional twophase high-strength aluminum alloys. The composite has benefits above about 300C. A SiC coated Boron fibrereinforced aluminum composite is shown for comparison.

Continuous fibre MMC properties

Metal matrix composites (MMC)

MMCs are made by dispersing a reinforcing material into a metal matrix. In structural applications,
the matrix is usually a lighter metal such as aluminium, magnesium or titanium, and provides
a compliant support for the reinforcement. In high temperature applications, cobalt and cobaltnickel alloy matrices are common
The reinforcement does not always serve a purely structural task (reinforcing the compound), but
is also used to change physical properties such as wear resistance, friction coefficient, or
thermal conductivity. The reinforcement can be either continuous, or discontinuous.
Discontinuous MMCs can be isotropic, and can be worked with standard metalworking techniques,
such as extrusion, forging or rolling. In addition, they may be machined using conventional
techniques, but commonly would need the use of diamond tooling. Continuous reinforcement uses
monofilament wires or fibres such as carbon fibres or silicon carbide. Because the fibres are
embedded into the matrix in a certain direction, the result is an anisotropic structure in which the
alignment of the material affects its strength. One of the first MMCs used boron filament as
reinforcement.
i f
t Discontinuous
Di
ti
reinforcement
i f
t uses whiskers,
hi k short
h t fibres,
fib
or particles.
ti l
Th mostt
The
common reinforcing materials in this category are alumina (Al2O3) and silicon carbide.
The reinforcement surface can be coated to prevent a chemical reaction with the matrix. For
example, carbon fibres are commonly used in aluminium matrix to synthesize composites showing
low density and high strength. However, carbon reacts with aluminum to generate a brittle and
water-soluble compound aluminium carbide (Al4C3) on the surface of the fibre. To prevent this
reaction, the carbon fibres are coated with nickel or titanium boride.

Types of reinforcement
Particles, flakes, whiskers, short fibres, continuous fibres & monofilaments

Types of reinforcements
Continuous fibres (f): usually delivered on bobbins of multifilament tows, each tow consisting of
many individual fibres of diameters typically in the range of 6 to 20 m.
Discontinuous reinforcement: a non-percolating constituent of a composite, taking the form of
individual elements embedded in the matrix constituent (e.g., particulates, short fibres, whiskers).
Preforms produced from discontinuous reinforcements that are mechanically stabilised by a binder
or by cold compaction are still considered discontinuous reinforcements.
Monofilaments (m): essentially endless reinforcement as continuous fibres, except for a larger
diameter, typically greater than 100 m. Monofilaments are generally produced by deposition onto
a core fibre (often of carbon or tungsten), and are delivered as individual fibres instead of tows.
Particulates (p): roughly equiaxed reinforcement or composite ingredient, usually of aspect ratio
(ratio of largest to smallest diameter) less than about 5. Particulates can be both mono- or
polycrystalline, can take various shapes (spherical, angular, plate-like) and are typically greater
than 1 m in diameter.
Platelets: flat reinforcements of an aspect ratio (diameter to thickness) greater than 2.
2 Platelets
of an aspect ratio less than 5 can be considered as a type of particulates.
Short fibres (s): cylindrical reinforcement or composite ingredient with a ratio of length to
diameter greater than 5 (but typically > 100), and with a diameter typically greater than 1 m.
Whiskers (w): elongated single crystals, typically produced with a length to diameter ratio
greater than 10 and with a diameter typically less than 1m

Types of reinforcement
Particles, flakes & fibres

Reinforcement types

Microstructure of SiC/Ti MMC

MMC applications
Carbide

drills are often made from a tough cobalt matrix with hard tungsten carbide (WC)
particles inside.
Some tank armours may be made from metal matrix composites, probably steel reinforced with
boron nitride. Boron nitride is a good reinforcement for steel because it is very stiff and it does not
dissolve in molten steel.
Some automotive disk brakes use MMCs. Modern high-performance sport cars, such as those
built by Porsche, use rotors made of carbon fibre within a silicon carbide matrix because of its high
specific heat and thermal conductivity. 3M sells a preformed aluminium matrix insert for
strengthening cast aluminium disc brake callipers, allowing them to weigh as much as 50% less
while increasing stiffness.
Ford offers an MMC driveshaft upgrade. The MMC driveshaft is made of an aluminum matrix
reinforced with boron carbide, allowing the critical speed of the driveshaft to be raised by reducing
inertia. The MMC driveshaft has become a common modification for racers, allowing the top speed
to be increased far beyond the safe operating speeds of a standard aluminium driveshaft.
Honda
H d has
h
used
d aluminium
l i i
metal
t l matrix
t i composite
it cylinder
li d liners
li
i some off their
in
th i engines.
i
Toyota has since used MMC in engine. Porsche also uses MMCs to reinforce their engine's
cylinder sleeves.
The F-16 uses monofilament silicon carbide fibres in a titanium matrix for a structural component
of the fighter jet's landing gear.
Specialized Bicycles has used aluminium MMC compounds for its top of the range bicycle
frames for several years.

MMC engine parts

MMC brake disks and drum

MMC brake drum

Space shuttle fuselage

F-16 landing gear

SP aerospace developed
d
l
d a titanium
tit i
metal
t l matrix
t i composite
it (MMC) lower
l
d
drag
b
brace
f
for
th
the
landing gear on F-16. It is the first application of an MMC landing gear part. Flat MMC prepreg
sheet was produced, using monofilament fibres made by chemical vapour deposition of silicon
carbide on a carbon fibre core, combined with titanium in a plasma spray process. The prepreg
was wound onto a steel mandrel and consolidated in a hot isostatic press under fluid pressure. The
blanks were machined to final dimensions. The MMC replacement braces weighs 40 percent less
than the original, which is fabricated with high-strength steel. Additionally, the MMC material has
better corrosion and fatigue resistance than either steel or aluminium.

Fatigue life

High speed civil transport

The High Speed Civil Transport (HSCT), a supersonic airliner, was the focus of the High-Speed Research
(HSR) Program, a NASA program to develop the technology needed to design and build a supersonic transport
that would be environmentally acceptable and economically feasible. The aircraft was to be a future supersonic
passenger aircraft, able to fly Mach 2, or twice the speed of sound. The project started in 1990 and ended
during 1999. The goal was to employ up-to-date technologies. It was intended to cross the Atlantic in half the
time of a non-supersonic aircraft. It was also intended to be fuel efficient, carry 300 passengers.

High speed civil transport

Estimated HSCT structural materials (20-year service life). The potential for using these materials at the upper end
of the indicated temperature band is based on short-term experimental data. processes. This is not the case with
regard to airframe aerodynamics, the propulsion system, or integrated aircraft systems. Although those areas also
face extremely difficult technical challenges, the level of risk is essentially the same for cruise speeds between
Mach 2.0 and 2.4. thermal stability of potential

Aluminium matrix composites (AMC)

This is the widest group of MMC. AMC are usually based on Al-Si alloys and 2xxx and 6xxx alloys.
Aluminum Matrix Composites (AMC) are reinforced by:
Alumina (Al2O3) or silicon carbide (SiC) particles in amounts 15-70 vol%;
Continuous fibres of alumina, silicon carbide, carbon (long fibre reinforced composite);
Discontinuous fibres of alumina (short-fibre
(short fibre reinforced composite);
Aluminum Matrix Composites are manufactured by:
Powder metallurgy (sintering);
Stir casting;
Infiltration;
Typical properties for Aluminum Matrix Composites:
High strength even at elevated temperatures;
High stiffness;
Low density; good corrosion resistance; low thermal expansion
High thermal conductivity;
Excellent wear and abrasion resistance.
Used for manufacturing automotive parts (pistons, pushrods, brake components), bicycles, golf
clubs, cores for high voltage cables. AMCs offer potential mass savings of up to 60%, and
increases in stiffness and strength of up to 200% when compared with conventional aluminium
alloys. Furthermore, AMCs can be produced with near-zero coefficients of thermal expansion.

Magnesium matrix composites

Magnesium Matrix Composites are reinforced mainly by silicon carbide (SiC) particles (particulate
composites)
Typical properties for Magnesium Matrix Composites:
Low density;
High stiffness (modulus of elasticity);
High wear resistance;
Good strength even at elevated temperatures;
Good creep resistance
Magnesium Matrix Composites are used for manufacturing components for racing cars, lightweight
automotive brake system, aircraft parts for: gearboxes, transmissions, compressors and engine.

Titanium matrix composites

Titanium Matrix Composites are reinforced mainly by:
Continuous monofilament silicon carbide fibre (long-fibre reinforced composites);
Titanium boride (TiB2) and titanium carbide (TiC) particles (particulate composites).
Powder metallurgy (sintering)is used for fabrication of Titanium Matrix Composites.
Typical properties for Titanium Matrix Composites:
High strength;
High stiffness (modulus of elasticity);
High creep resistance;
High thermal stability;
High wear resistance.
Titanium Matrix Composites are used for manufacturing structural components of the F-16
F 16 jet
jets
s
landing gear, turbine engine components (fan blades, actuator pistons, synchronization rings,
connecting links, shafts, discs), automotive engine components, drive train parts, general machine
components.

Copper matrix composites

Copper Matrix Composites are reinforced by:

Continuous fibres of carbon, silicon carbon (SiC), tungsten (W), stainless steel 304 (long-fibre
reinforced composites);
p
);
Silicon carbide particles (particulate composites).
Powder metallurgy (sintering) and infiltration technique are used for fabrication Copper Matrix
Composites.
Typical properties for Copper Matrix Composites:
Low coefficient of thermal expansion;
High stiffness (modulus of elasticity);
Good electrical conductivity;
High thermal conductivity;
Good
G d wear resistance.
i t
Copper Matrix Composites are used for manufacturing hybride modules, electronic relays,
electrically conducting springs and other electrical and electronic components

MMC manufacturing methods

Solid state methods
Powder blending and consolidation (powder metalurgy): Powdered metal and discontinuous
reinforcement are mixed and then bonded through a process of compaction, degassing, and
thermo-mechanical treatment (possibly via hot isotactic pressing (HIP) or extrusion).
Foil diffusion bonding:
g Layers
y
of metal foil are sandwiched with long
g fibres,, and then p
pressed
through to form a matrix.
Liquid state methods
Electroplating / Electroforming: A solution containing metal ions loaded with reinforcing particles
is co-deposited forming a composite material.
Stir casting: Discontinuous reinforcement is stirred into molten metal, which is allowed to solidify.
Squeeze casting: Molten metal is injected into a form with fibres preplaced inside it.
Spray deposition: Molten metal is sprayed onto a continuous fibre substrate.
Reactive processing: A chemical reaction occurs, with one of the reactants forming the matrix
and
d the
th other
th the
th reinforcement.
i f
t
Vapour deposition
Physical vapour deposition: The fibre is passed through a cloud of vapourized metal, coating it.
In-situ fabrication technique.
Controlled unidirectional solidification of a eutectic alloy can result in a two-phase microstructure
with one of the phases, present in lamellar or fibre form, distributed in the matrix.

Types of composites

mechanical
property

processability

Powder metallurgy

The powder metallurgy technique usually employs particles, whiskers or short fibres of the
reinforcing materials. These are mixed with the matrix powder and then pressed to consolidate
the matrix. This may or may not be followed by sintering to improve matrix density. A major
problem when using powder metallurgy is the elimination of porosity. Materials are vacuumdegassed prior to consolidation to minimise voids, surface oxidation and contamination. There is
also difficulty in obtaining alignment of the reinforcing material.

Foil diffusion bonding

In this method, alternate layers of matrix foil and properly spaced and oriented reinforcing fibres
are laid down until the necessary amount of material for the desired final thickness is assembled.
Then, by a combination of heat, pressure and time in a vacuum, the matrix is caused to flow
around the fibres and bond to the next layer of matrix and at the same time grip the reinforcing
fibre very tightly.

Electroplating or forming

Copper coating at the surface of graphite fibre

Electroforming is especially used to prepare composites of boron in aluminum matrix. A

continuous filament is on a mandrel is immersed in a solution. Aluminum or other metal is
continuously plated from this bath as the filament is wound.

Stir casting

Microstructures of aluminium MMC made

by stir casting, showing agglomerates

Extrusion fibre alignment

Squeeze casting infiltration

High-quality casting at pressurise to 1000-2000 atm during solidification, which collapses porosity
and increases thermal contact with unheated die wall resulting in rapid solidification rate. High
capital facility and tooling costs.

Squeeze casting infiltration

Squeeze Casting Infiltration is a forced infiltration method of liquid phase fabrication of MMC, using
a movable mould part (ram) for applying pressure on the molten metal and forcing it to penetrate
into a performed dispersed phase, placed into the lower fixed mould part. Squeeze Casting
Infiltration method is similar to the technique used for metal alloys casting.
Squeeze Casting Infiltration process has the following steps:
A preform of dispersed phase (particles, fibres) is placed into the lower fixed mould half.
A molten metal in a predetermined amount is poured into the lower mould half.
The upper movable mould moves downwards and forces the liquid metal to infiltrate the preform.
The infiltrated material solidifies under the pressure.
The part is removed from the mould by means of the ejector pin.
The method is used for manufacturing simple small parts (automotive engine pistons from
aluminum alloy reinforced by alumina short fibres).

Squeeze casting infiltration

Squeeze casting of Al6061/SiC/50p

Metal infiltration
Infiltration is a liquid state method of composite materials fabrication, in which a preformed
dispersed phase (ceramic particles, fibres, woven) is soaked in a molten matrix metal, which fills
the space between the dispersed phase inclusions. The motive force of an infiltration process may
be either capillary
p
y force of the dispersed
p
phase ((spontaneous
p
p
infiltration)) or an external p
pressure
(gaseous, mechanical, electromagnetic, centrifugal or ultrasonic) applied to the liquid matrix phase
(forced infiltration). Infiltration is one of the methods of preparation of tungsten-copper composites.
The principal steps of the technology are as follows:
Tungsten powder preparation with average particle size of about 1-5 mkm.
Optional step: Coating the powder with nickel. Total nickel content is about 0.04%.
Mixing the tungsten powder with a polymer binder.
Compacting the powder by a moulding method (metal injection moulding, die pressure, isostatic
pressing). Compaction should provide the predetermined porosity level (apparent density) of the
t
tungsten
t structure.
t t
Solvent debinding.
Sintering the green compact at 1200-1300C) in hydrogen atmosphere for 2 hrs.
Placing the sintered part on a copper plate (powder) in the infiltration/sintering furnace.
Infiltration of the sintered tungsten sceleton porous structure with copper at 1100-1250C) in
either hydrogen atmosphere or vacuum for 1 h.

Liquid pressure forming (LPF)

Pressure die infiltration

Similar to RTM with molten metal fed into an evacuated fibre-filled mould from below by pressure.
Gases and volatiles vented from mould top. High pressures of 10-15 atm for Saffil preforms. 70
atm for 50 v/o carbon fibre, high clamping loads, massive dies for heat retention, long
solidification times.

Gas pressure infiltration casting (PIC)

Is a forced infiltration method of liquid phase fabrication of Metal Matrix Composites, using a
pressurized gas for applying pressure on the molten metal and forcing it to penetrate into a
preformed dispersed phase. Gas Pressure Infiltration method is used for manufacturing large
composite parts and low cost tooling. The method allows using non-coated fibres due to short
contact time of the fibres with the hot metal. In contrast to the methods using mechanical force,
Gas Pressure Infiltration results in low damage of the fibres.

Spray deposition

Physical vapour deposition (PVD)

SiC fibre coated with Ti6Al4V

Ti composite (Vf=67%)

Vapour deposition is a process where the reinforcement, particularly monofilaments or whiskers

are coated by the matrix material from the deposition of its compounds. Extrusion process is
finally employed for orienting the whiskers parallel to the extrusion axis.

Plasma spray deposition

MMC p
prepared
p
via vacuum diffusion
bonding of plasma sprayed monolayers

This is a combination of a powder process and liquid process and also involves hot pressing. A
layer of fibres is laid up on a rotating mandrel, the metal is deposited on the fibres by plasma
spraying, a second layer of fibres is put on, and the operations are repeated until the desired
thickness and the number of layers is attained.

Stir casting
Stir casting is a liquid state method of composite materials fabrication, in which a dispersed phase
(particles, short fibres) is mixed with a molten matrix metal by means of mechanical stirring. Stir
Casting is the simplest and the most cost effective method of liquid state fabrication. The liquid
composite material is then cast by conventional casting methods and may also be processed by
conventional technologies.
g
Stir Casting is characterized by the following features:
Content of dispersed phase is limited (usually not more than 30 vol.%).
Distribution of dispersed phase throughout the matrix is not perfectly homogeneous:
1. There are local clouds (clusters) of the dispersed particles (fibres);
2. There may be gravity segregation of the dispersed phase due to a difference in the densities of
the dispersed and matrix phase.
Th technology
The
t h l
i relatively
is
l ti l simple
i l and
d low
l
cost.
t
Distribution of dispersed phase may be improved if the matrix is in semi-solid condition.
The method using stirring metal composite materials in semi-solid state is called rheocasting. High
viscosity of the semi-solid matrix material enables better mixing of the dispersed phase.

Secondary processing of MMC

Extrusion, forging, rolling, stamping

Superplastic forming
Machining with superhard cutting and grinding tools
AJM: abrasive waterjet cutting
CHM: chemical milling
EBM: electron beam machining
EDM: electro-discharge machining
LBM: laser beam machining
PAM: plasma arc machining
USM: ultrasonic machining

Superplastic sheet forming

Blow-forming superplastic forming process in cross section. (a) Start. (b) 20% (c) 50% (d) 100% formed

Superplastic sheet forming

Movable-tool forming process involving two different concepts. (a) The sheet form is forced into the
configurational die. (b) In a complex sequence, the sheet in place in step 1 is billowed with gas pressure (step
2), the movable die is moved into the billowed sheet (step 3), and the gas pressure is imposed on the top side
of the sheet, causing the sheet to form onto the movable tool (step 4).

Superplastic sheet forming

Mechanical properties of AMC

Al - 20% SiC particles
Property
Density
Modulus of
elasticity

Al - 60% Al2O3 continuous fibre

Value in metric unit

2.85 *10
10
kg/m
kg/m
102

GPa

Tensile
strength

300

MPa

Yield strength

275

MPa

Elongation

0.4

Hardness

78

HRB

Thermal
expansion

19.0*10-6

Thermal
conductivity

132

W/(m*K)

Property
Density

Value in metric unit

3.4 *10

kg/m

Modulus of
elasticity
(long.)

240

GPa

Modulus of
elasticity
(trans.)

130

GPa

Tensile
strength
(long.)

1600

MPa

Compressive
strength
(long.)

1700

MPa

Nature makes tough ceramics

Nacre Mother of Pearl

Laminated and tabular nanocomposites of
sea shells.
Tablets are held together with protein.
The protein layers (i) Serve as the
nucleation template for inorganic phase, (ii)
Serve as the glue holding the tablets
together
Toughness increase of 3000% compared
to monolithic calcium carbonate

Toughness of nacre

Toughness of nacre

Large strain comes from distributed deformation

Natural vs Man-made composite

RoM: Pc = Pf Vf + Pm Vm

Nature:
N
t
matrix = interface
High Vf
High organization
Self-assembly

Man-made:
matrix = easy processing
Low Vf
Low organization
Mixing

But nature is slow

Bioinspired MMC
Nacre

MMC

Berkeley Lab scientists developed a MMC that mirrors the intricate structure of nacre, which is a
finely layered substance found in some mollusk shells, such as oysters and abalone. Scientists
have long sought to duplicate nacre's strength and lightness in ceramic materials, but nacre's
architecture varies at several length scales, from micrometers to nanometers. Replicating all of
these scales -- each of which contributes to the overall performance of nacre -- in a synthetic
substance is extremely difficult. The Berkeley Lab researchers used sea ice as a template to
create a brick and mortar structure which could be used to infuse by liquid metal.

Bioinspired MMC
Hierarchical structure of natural nacre and bioinspired composite

Bioinspired MMC

Ice templating

Pattern formation and particle segregation during freeze casting of ceramic slurries.
The ice platelets grow in a direction perpendicular to the c-axis of hexagonal ice. The
wavelength of the structure is defined by .

Ice templating

Ice templating

Schematic of the experimental apparatus employed to directionally freeze the ceramic

slurries while controlling the speed of the freezing front. The ceramic slurry is poured into a
Teflon mold placed between two copper cold fingers whose temperature is controlled by
liquid nitrogen baths and ring heaters.

Why few commercial successes ?

In spite of the obvious need for improved material properties and the significant investments
made in technology and capital, why are there only a few success stories? It certainly isnt
because MMCs dont have superior properties; they do.
do It isnt because the need has
evapourated; the need for lighter, more efficient structures is greater than ever. Why then?
One often underestimates the problems and complexity of the MMC systems and most
programs were simply abandoned before completion. It was not because they didnt offer
great potential; in fact most programs completed the prototype stage and demonstrated the
structural and weight efficiency of the component. But when customers said, Great, lets
start production! they were told, Well, we made one part in the lab, but now we need to
spend a few million more to develop an affordable manufacturing process and then to build a
factory.. That usually ended the program.
factory

Content

Metal
M t l matrix
t i composites
it
Ceramic matrix composites
Carbon-carbon composites

Toughness of materials
Typical Fracture
Toughness (Klc)
Material

Klc, MPam1/2
Polymers
y

Polyethylene
Nylon
Epoxy, polyester

1-2
3
0.5
Metals

Aluminum alloys
Titanium alloys
Low carbon steel
Cast iron

20-50
50-100
50
4-10
4
10
Ceramics

Glass
Magnesium oxide
Silicon Carbide
Silicon nitride

0.5-1
3
2-4
3-5

Ceramics are brittle

High use temperature

Ceramic matrix composites (CMC)

Ceramic matrix composites (CMCs) are a subgroup of composite materials as well as a subgroup of technical
ceramics. They consist of ceramic fibres embedded in a ceramic matrix, thus forming a ceramic fibre
reinforced ceramic (CFRC) material. The matrix and fibres can consist of any ceramic material, whereby
carbon fibres can also be considered a ceramic material.

Ceramic matrix composites (CMC)

The motivation to develop CMCs was to overcome the problems associated with conventional technical
ceramics like alumina, silicon carbide, aluminium nitride, silicon nitride or zirconia they fracture easily under
mechanical or thermo-mechanical loads because of cracks initiated by small defects or scratches. The crack
resistance is like in glass very low. To increase the crack resistance or fracture toughness particles (socalled monocrystalline whiskers or platelets) are embedded into the matrix. However, the improvement is
li i d and
limited,
d the
h products
d
h
have
f
found
d application
li i only
l in
i some ceramic
i cutting
i tools.
l So
S far
f only
l the
h integration
i
i
of continuous fibres has drastically increased the crack resistance, elongation and thermal shock resistance,
and resulted in several new applications.
Carbon(C), special silicon carbide (SiC), alumina (Al2O3) and mulite (Al2O3SiO2) fibres are most commonly
used for CMCs. The matrix materials are usually the same, that is C, SiC, alumina and mullite. Generally, CMC
names include a combination of type of fibre/type of matrix. For example, C/C stands for carbon-fibre-reinforced
carbon (carbon/carbon), or C/SiC for carbon-fibre-reinforced silicon carbide. Sometimes the manufacturing
process is included, and a C/SiC composite manufactured with the liquid polymer infiltration (LPI) process (see
below) is abbreviated as LPI-C/SiC.
The important commercially available CMCs are C/C, C/SiC, SiC/SiC and Al2O3/Al2O3. They differ from
conventional ceramics in the following properties, presented in more detail below:

Strain to break up to 1% (compared to 0.05% for monolithic ceramics)

Strongly increased fracture toughness
Extreme thermal shock resistance
Improved dynamical load capability
Anisotropic properties following the orientation of fibres

Crack deflection mechanism

Interaction between the matrix and the reinforcing fibres provides higher toughness of a ceramic
composite as compared to the matrix material in the monolithic state. Such effect is a result of cracks
deflection at the matrix-fibre interface. When a crack propagating through the matrix reaches a fibre,
the relatively weak bonding (debonding) between the matrix and the fibre at their interface allows their
relative sliding, which prevents the fibre to fracture. The fibre bridges the cracked matrix.. The effect of
the crack deflection mechanism is determined by the matrix-fibre bonding strength. If the it is too great
the fibres are not capable to slide in the matrix therefore the crack passes through the fibres breaking
them. The fracture of the composite is brittle like in the monolithic ceramic.

Toughening of CMC

Toughening of CMC

Pull-out and crack bridging

Toughening of CMC

Toughening of CMC

Stress-strain behaviour of CMC

Curves of toughness measurements of

various ceramic composites and
SiSiC. Legend: SiSiC: conventional
SiSiC, SiCSiC(CVI) and CSiC(CVI):
SiC/SiC and C/SiC manufactured in
CVI
processes,
CSiC(95)
und
CSiC(93): C/SiC manufactured by the
LPI-method, Ox(PP): oxide ceramic
composite,
CSiC(Si):
C/SiC
manufactured via the LSI process

Tensile tests of CMCs usually show nonlinear stress-strain curves, which look as if the material deforms
plastically. It is called quasi-plastic, because the effect is caused by the microcracks, which are formed and
bridged with increasing load. Since the Youngs modulus of the load-carrying fibres is generally lower than
that of the matrix, the slope of the curve decreases with increasing load.

Stress-strain behaviour of CMC

The high fracture toughness or crack resistance of CMC is a result of the following mechanism: under load the
ceramic matrix cracks, like any ceramic material, at an elongation of about 0.05%. In CMCs the embedded
fibres bridge and deflect these cracks. This mechanism works only when the matrix can slide along the
fibres, which means that there must be a weak bond between the fibres and matrix. This can be achieved by
depositing a thin layer of pyrolytic carbon or boron nitride on the fibres, which weakens the bond at the
fibre/matrix interface (sometimes "interface"), leading to the fibre pull-out at crack surfaces. In oxide-CMCs,
the high porosity of the matrix is sufficient to establish the weak bond

Mechanical properties of particulate CMC

Type of
material

Al2O3

CVI-C/SiC

LPI-C/SiC

LSI-C/SiC

SiC

Porosity
(%)

<1

12

12

<1

D
Density
it
(g/cm3)

3.9

2.1

1.9

1.9

3.1

Tensile
strength
(MPa)

250

310

250

190

200

Elongation
(%)

0.1

0.75

0.5

0.35

0.05

Young's
modulus
((GPa))

400

95

65

60

395

Flexural
strength
(MPa)

450

475

500

300

400

CVI (chemical vapour infiltration), LPI (liquid polymer infiltration), and LSI (liquid
silicon infiltration) denote the manufacturing process of the C/SiC-material. Data
of the oxide CMC and SiC are taken from manufacturer data sheets.

Mechanical properties of particulate CMC

Applications of CMC

Applications of CMC
CMC materials overcome the major disadvantages of conventional technical ceramics,
namely brittle failure and low fracture toughness, and limited thermal shock resistance.
Therefore, their applications are in fields requiring reliability at high-temperatures (beyond
the capability of metals) and resistance to corrosion and wear. These include:
Heat shield systems for space vehicle, which are needed during the re-entry phase,
where high temperatures, thermal shock conditions and heavy vibration loads take place.
Components for high-temperature gas-turbines such as combustion chambers, stator
vanes and turbine blades.
Components for burners, flame holders and hot gas ducts, where the use of oxide
CMCs has found its way.
Brake disks and brake system components, which experience extreme thermal shock
(greater than throwing a glowing part of any material into water).
Components
C
t for
f slide
lid bearings
b
i
under
d heavy
h
l d requiring
loads
ii
hi h corrosion
high
i
and
d wear
resistance.
In addition to the foregoing, CMCs can be used in applications, which employ conventional
ceramics or in which metal components have limited lifetime due to corrosion or high
temperatures.

Applications of CMC

Particulate MMC Cemented carbide (Cermets)

WC-20%
WC
20% Co cermet (x1000)

Cemented carbides are commonly used as inserts for cutting tool inserts and are an example of regular
particulate MMCs. Co-WC cermets are produced by pressing Co and W powders into compacts, which are
heated above the melting point of Co. On cooling the WC particles become embedded in the solidified Co, which
act as a tough matrix for the WC particles. In addition to its strength and toughness, Co is also selected because
it wets the carbide particles to give a strong bond. Other ceramics such as TaC and TiC are also used to make
Cermets.

Turbine components

GE Aviation (Evendale, Ohio) introduced durable, lightweight composite components into the hot section of a
jet engine. The GE Rolls-Royce Fighter Engine Teams F136 developmental engine for the Joint Strike Fighter
(JSF) contains third-stage, low-pressure turbine vanes made by GE from ceramic matrix composites (CMC),
which are capable of handling the extreme temperatures. The work was the first commercial use of CMCs in a
jet engines combustor and turbine areas when an F136-powered JSF began flight testing in 2010.

Turbine components
The use of CMCs in gas turbines would permit higher turbine inlet temperatures, which would
improve turbine efficiency. Because of the complex shape of stator vanes and turbine blades, the
development was first focused on the combustion chamber. In the US, a combustor made of
SiC/SiC with a special SiC fibre of enhanced high-temperature
high temperature stability was successfully tested for
15,000 hours. SiC oxidation was substantially reduced by the use of an oxidation protection
coating consisting of several layers of oxides. The engine collaboration between General Electric
and Rolls-Royce is studying the use of CMC stator vanes in the hot section of the F136 turbofan
engine, an engine which failed to beat the Pratt and Whitney F-135 for use in the Joint Strike
Fighter. This engine joint venture, is also considering the use of CMC parts to reduce weight in its
Leap-X demonstrator engine program, which is aimed at providing next-generation turbine
engines for narrow-body airliners. CMC parts are also being studied for stationary applications in
both the cold and hot sections of the engines, since stresses imposed on rotating parts would
require further development effort. Generally, a successful application in turbines still needs a lot
of technical and cost reduction work for all high-temperature components to justify the efficiency
gain. Furthermore, cost reduction for fibres, manufacturing processes and protective coatings is
essential

Carbon-SiC exhaust nozzle

Carbon-SiC exhaust nozzle

Ceramic matrix composites (CMC)

Space shuttle thermal protection system

C/C is used in the nose cap, the chin area between the nose cap and nose landing gear doors, the arrowhead of
the nose landing gear door, and the wing leading edges. Used where reentry temperature exceeds 1250 C. Hightemperature reusable surface insulation (HRSI) tiles are used on the orbiter underside. Made of coated silica
ceramics and used where reentry temperature is below 1250 C.

Space shuttle thermal protection system

High-temperature reusable surface insulation (HRSI)

HRSI tiles (black in color) provide protection against temperatures up to 1250C. There are 20,548 HRSI tiles which cover the landing
gear doors, external tank umbilical connection doors, and the rest of the orbiter's under surfaces. They are used in areas on the upper
forward fuselage, parts of the orbital maneuvering system pods, vertical stabilizer leading edge, trailing edges, and upper body flap
surface as well. They vary in thickness from 2.5 to 13 cm, depending upon the heat load encountered during reentry. Except for
closeout areas, these tiles are normally 15 by 15 cm squares. The HRSI tile is composed of high purity silica fibers. Ninety percent of
the volume of the tile is empty space giving it a very low density (140 kg/m3) making it light enough for spaceflight. The uncoated tiles
are bright white in appearance and look more like a solid ceramic than the foam-like material that they are.

X-37

X-38

Pair of steering flaps for the NASA-space vehicle X-38. Size: 1.51.50.15 m, mass: 68 kg each,
various components are mounted using more than 400 CVI-C/SiC screws and nuts

HERMES heat shield

During the re-entry phase of space vehicles, the heat shield system is exposed to temperatures
above 1500 C for a few minutes. Only ceramic materials are able to survive such conditions
without significant damage, and among ceramics only CMCs can adequately handle thermal
shocks The development of CMC
shocks.
CMC-based
based heat shield systems promises the following advantages:

Reduced weight
Higher load carrying capacity of the system
Reusability for several re-entries
Better steering during the re-entry phase with CMC flap systems

In these applications the high temperatures preclude the use of oxide fibre CMCs, because under
the expected loads the creep would be too high. Amorphous silicon carbide fibres lose their
strength due to recrystalization at temperatures above 1250 C. Therefore carbon fibres in a
silicon carbide matrix (C/SiC) are used in development programs for these applications. The
European program HERMES of ESA started in the 1980s and for financial reasons abandoned in
1992, has produced first results. Several follow-up programs focused on the development,
manufacture, and qualification of nose cap, leading edges and steering flaps for the NASA space
vehicle X-38.

2D woven fabric CMC

A scanning electron microscope image of a composite composed of carbon fibres (in

blue) and silicon carbide (in brown).

3D woven fabric CMC

3D woven fabrics provide reinforcement in the out-of-plane (z-direction) of the laminates

CMC manufacturing methods

The manufacturing processes usually consist of the following three steps:
Lay-up and fixation of the fibres, shaped as the desired component
Infiltration of the matrix material
Final machining and, if required, further treatments like coating or impregnation of the intrinsic
porosity.
p
y The first and the last step
p are almost the same for all CMCs:
In step one, the fibres - often named rovings - are arranged and fixed using techniques used in
fibre-reinforced plastic materials, such as lay-up of fabrics, filament winding, braiding and knitting.
The result of this procedure is called fibre-preform or simply preform.
For the second step, four methods are used to introduce the ceramic matrix:
Deposition out of a gas mixture
Pyrolysis of a pre-ceramic polymer
Chemical reaction of elements
Sintering
Si t i att a relatively
l ti l low
l
t
temperature
t
i the
in
th range 10001200
1000 1200 C
Procedures one, two and three find applications with non-oxide CMCs, whereas the fourth one is
used for oxide CMCs; combinations of these procedures are also practiced. All procedures have
sub-variations, which differ in technical details. All procedures yield a porous material.
The third step of machining, - grinding, drilling, lapping or milling has to be done with diamond
tools. CMCs can also be processed with a water jet or laser.

Polymer infiltration and pyrolysis (PIP)

Polymer infiltration and pyrolysis (PIP).

Hydrocarbon polymers shrink during pyrolysis, and upon outgassing form carbon with an amorphous, glass-like
structure, which by additional heat treatment can be changed to a more graphite-like structure. Other special
polymers, where some carbon atoms are replaced by silicon atoms, the so-called polycarbosilanes, yield
amorphous silicon carbide. A large variety of such SiC-, SiNC-, or SiBNC-producing precusrors already exist and
more are being developed. To manufacture a CMC material, the fibre preform is infiltrated with the chosen
polymer. Subsequent curing and pyrolysis yield a highly porous matrix, which is undesirable for most
applications. Further cycles of polymer infiltration and pyrolysis are performed until the final and desired quality is
achieved. Usually five to eight cycles are necessary. The process is called liquid polymer infiltration (LPI), or
polymer infiltration and pyrolysis (PIP). Here also a porosity of about 15% is common due to the shrinkage.

Polymer infiltration and pyrolysis (PIP)

Polymer Infiltration and Pyrolysis (PIP) is the method of fabrication of CMCs comprising an
infiltration of a low viscosity polymer into the reinforcing ceramic structure (e.g. fabric)
followed by pyrolysis: heating the polymer precursor in the absence of oxygen when it
decomposes and converts into a ceramic.
ceramic The ceramics produced from polymers by pyrolysis are
called polymer derived ceramics.
Molecules of preceramic polymers are commonly contain carbon (C) and/or silicon (Si) but may
also contain nitrogen (N), oxygen (O),boron (B), aluminum (Al), titanium (Ti).
Polymer Infiltration and Pyrolysis (PIP) technique is used mainly for fabrication composites with
silicon carbide (SiC) matrices from polycarbosilanes (silicon derived polymer precursors):
polymethylsilane (PMS) and allhydridopolycarbosilane. The yield of SiC of the precursors is about
65%. Polysilazane may be converted into SiCN or Si3N4 with ceramic yield up to 90%.
Carbon-carbon composites are fabricated by pyrolysis of either thermosetting resins
(phenolics, ruran resin, oxidized polystyrene, polyvinyl alcohol) or thermoplastic resins (pitches or
coal tar). The carbon yield of these resins is 50-60%.

Liquid silicon infiltration (LSI)

Liquid silicon infiltration (LSI)

Liquid Silicon Infiltration (LSI) process is a type of Reactive Melt Infiltration (RMI) technique, in
which the ceramic matrix forms as a result of chemical interaction between the liquid
infiltrated into a porous reinforcing preform and the substance (either solid or gaseous)
surrounding the melt.
Liquid Silicon Infiltration (LSI) is used for fabrication of silicon carbide (SiC) matrix composites.
The process involves infiltration of carbon (C) microporous preform with molten silicon (Si) at a
temperature exceeding its melting point 1400C).
The liquid silicon wets the surface of the carbon preform. The melt soaks into the porous
structure driven by the capillary forces. The melt reacts with carbon forming silicon carbide
according to the reaction:
Si (liquid) + C (solid) SiC (solid)
SiC produced in the reaction fills the preform pores and forms the ceramic matrix. Since the
molar volume of SiC is less than the sum of the molar volumes of silicon and carbon by 23%, the
soaking of liquid silicon continues in course of the formation of silicon carbide. The initial pore
volume fraction providing complete conversion of carbon into silicon carbide is 0.562. If the initial
pore volume fraction is lower than 0.562 the infiltration results in entrapping residual free silicon.
Commonly at least 5% of residual free silicon is left in silicon carbide matrix.

Chemical vapour infiltration (CVI)

Chemical vapour deposition (CVD) is well suited for this purpose. In the presence of a fibre preform, CVD takes
place
l
i between
in
b t
th fibres
the
fib
and
d their
th i individual
i di id l filaments
fil
t and
d therefore
th f
i called
is
ll d chemiocal
h i
l vapour infiltration
i filt ti
(CVI). One example is the manufacture of C/C composites: a C-fibre preform is exposed to a mixture of argon
and a hydrocarbon gas (methane, propoane, etc.) at a pressure of around or below 100 kPa and a temperature
above 1000C. The gas decomposes depositing carbon on and between the fibres. Another example is the
deposition of silicon carbide, which is usually conducted from a mixture of hydrogen and methyltrichlorosilane (MTS, CH3SiCl3; it is also common in silicon production). Under defined condition this gas
mixture deposits fine and crystalline silicon carbide on the hot surface within the preform. This CVI
procedure leaves a body with a porosity of about 1015%, as access of reactants to the interior of the preform is
increasingly blocked by deposition on the exterior.

Chemical vapour infiltration (CVI)

CVI is a method of Ceramic Matrix Composites fabrication is a process, in which reactant gases diffuse into an
isothermal porous preform made of long continuous fibres and form a deposition. Deposited material is a result of
chemical reaction occurring on the fibres surface. The infiltration of the gaseous precursor into the fibre preform is
driven by either diffusion process or an imposed external pressure.
p
fills the space
p
between the fibres, forming
g composite
p
material in which matrix is the deposited
p
The deposition
material. Chemical Vapour Infiltration (CVI) is similar to Chemical Vapour Deposition (CVD), in which deposition
the forms when the reactant gases react on the outer substrate surface. Chemical Vapour Infiltration is widely
used for fabrication of silicon carbide matrix composites reinforced by silicon carbide long (continuous) fibres.
Commonly the vapour reagent is supplied to the preform in a stream of a carrier gas (H2, Ar, He). SiC matrix is
formed from a mixture of methyltrichlorosilane (MTS) as the precursor and hydrogen as the carrier gas.
Methyltrichlorosilane is decomposed according to the reaction

CH3Cl3Si SiC + 3HCl

The gaseous hydrogen chloride (HCl) is removed from the preform by the diffusion or forced out by the carrier
stream. Carbon matrix is formed from a methane precursor (CH4).
The ceramic deposition is continuously growing as long as the diffusing vapour is reaching the reaction surface.
The porosity of the material is decreasing being filled with the formed solid ceramic. However in the course of the
CVI process the accessibility of the inner spaces of the preform is getting more difficult due to filling the vapour
paths with the forming ceramic matrix. The precursor transportation is slowing down. The growing solid phase
separates the spaces in the material from the percolating network of the vapour precursor. Such inaccessible
pores do not decrease any longer forming the residual porosity of the composite.
The final residual porosity of the ceramic composites fabricated by CVI method may reach 10-15%.

Slurry infiltration process (SIP)

Slurry Infiltration Process (SIP) involves the following operations:

Passing fibers (tow, tape) through a slurry containing particles of the ceramic matrix;
Winding the fibers infiltrated by the slurry onto a drum and drying;
Stack of the slurry impregnated fibers in a desired shape;
Consolidation of the matrix by hot pressing in graphite die at high temperature.

Slip & tape casting

The principle of slip casting is that a slurry of the powder is poured into a porous mould, usually made of
gypsum, which absorbs the liquid carrier causing the powder to be drawn to the mould walls. This method is
mostly used for production of traditional ceramics and is ideal for preparation of large, thin-walled, hollow
components. Recent developments in powder preparation have extended its use to advanced ceramics.
For optimum casting, the slurry or slip should be a stable suspension with as high solid contend as possible
but with low viscosity. A process related to slip casting is tape casting in which thin layers of slurry are cast
onto a substrate of thin plastic film. Both slip casting and tape casting are suitable for short-fibre composites,
tending to produce a two-dimensionally random fibre orientation.

Slip casting

Tape casting

Hot-pressing & sintering

Spark plasma sintering (SPS) or pulsed electric current sintering (PECS) utilizes uniaxial force and a pulsed
(on-off) direct electrical current (DC) to perform high speed consolidation.
Since most ceramic fibres can not withstand normal sintering temperatures of above 1600 C, special precursor
liquids are used to infiltrate the preform of oxide fibres. These precursors allow sintering - a ceramic-forming
process - at temperatures of 10001200 C. They are, for example, based on mixtures of alumina powder with
liquids tetra-ethyl-orthosilicate (as Si donor) and aluminium-butylate (as Al donor). Other techniques, such as
sol-gel chemistry, are also used. CMCs obtained with this process usually have a high porosity of about 20% but
the new spark plasma sintering process can lead to very short sintering times and low porosities.

Injection moulding

Injection moulding involves mixing of the ceramic powder with a sufficient amount of polymer or other soft
binder to produce a mouldable dough. This is then injected under pressure into a mould.
With appropriate flow properties and strength, the mix can be moulded to complex and intricate shapes.
It is desirable to produce mixes with as high ceramic powder contend as possible in order to minimise the
subsequent binder removal that is necessary to achieve a high green density. However, the powder content
is limited to a critical volume fraction above which the viscosity of the mix increases sharply. The limit is set
approximately by the point at which particles begin to develop skeletal contact and thus the process is very
sensitive to particle shape and particle size distribution. Injection moluding has the potential for the fabrication
of short-fibre reinforced composites. Particular interest is the possibility of controlling fibre orientation through
control of the flow of the mix trough the mould. The main problem is the limit to fibre fraction set by packing
geometry. Injection moluding is used mostly in the production of large series of components with complex
shape. A related process, extrusion is suitable for producing rod and strip with constant cross-sections.

Injection moulding

Content

Metal
M t l matrix
t i composites
it
Ceramic matrix composites
Carbon-carbon composites

Carbon-carbon composites (C/C)

Fabrication of Carbon-Carbon composites by liquid or gas phase Infiltration.

Preparation of carbon fibres preform of the desired structure and shape.
shape
Infiltration of preform with a liquid precursor: petroleum pitch/phenolic resin/coal tar. Alternatively a CVD
process may be used to infiltrate the preform with a pressurized hydrocarbon gas (propane, methane,
propylene, acetylene, benzene) at 1000-1200C). Gas is pyrolyzed forming carbon deposition on the fibre surface.
Pyrolysis/carbonization (chemical decomposition by heat in the absence of oxygen of the polymer precursor
at (500-1000C) under normal or high pressure.
Infiltration pyrolysis cycle is repeated several (3-10) times until the desired density is achieved.
Graphitization heat treatment. At this stage amorphous carbon is transformed into crystalline graphite. The
temperature of the treatment may vary within the range 1500-3000C. Typical temperature is 2500C.

Carbon-carbon composites

Carbon-carbon composite brake disk & clutch plate

Carbon-carbon composite brake disks

Carbon-carbon discs and pads are more abrasive than steel and dissipate heat better making them
advantageous. Steel brakes as used in CART are heavier and have disadvantages in distortion and heat
transfer. Metal brake discs weigh about 3 Kg, carbon systems typically 1.4 Kg. You can often see the brake
discs glowing during a race, this is due to the high temperatures in the disc, with the normal operating
temperature around 800 degrees Celsius.

High performance brake components

Carbon-carbon (C/C) materials have found their way into the disk brakes of racing cars, high
speed trains and airplanes, and C/SiC brake disks manufactured by the LSI process were
qualified and are commercially available for luxury vehicles. The advantages of these C/SiC
disks are:
Very little wear, resulting in lifetime use for a car with a normal driving load of 300,000 km.
No fading is experienced, even under high load.
No surface humidity effect on the friction coefficient shows up, as in C/C brake disks.
The corrosion resistance, for example to the road salt, is much better than for metal disks.
The disk mass is only 40% of a metal disk, translating into less unsprung and rotating mass.
The weight reduction improves shock absorber response, road-holding comfort, agility, fuel
economy, and thus driving comfort.
The SiC-matrix of LSI has a very low porosity, which protects the carbon fibres quite well.
Brake disks usually do not experience temperatures above 500 C for more than a few hours
in their lifetime (in F1 they only last one race). Oxidation is therefore not a problem in this
application. The reduction of manufacturing costs will decide the success of this application for
middle-class cars.