National Textile University

Write-up on Ceramic Matrix 2/17

Composites

Submitted To; Dr. Mumtaz Hasan Malik

A Write-Up on Ceramic Matrix
By; Umer Mushtaq (09-NTU-6011)

National Textile University

Composites

(CMC)

Textile Composites (TE-671)

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1.Introduction
A composite is defined as a material containing two or more distinct phases
combined in such a way so that each remains distinct. Based on this broad
definition of composite, ceramic matrix composites (CMCs) are conveniently
separated into two categories: discontinuous reinforced and continuous fiber
reinforced CMCs. Discontinuous reinforced CMCs include particulate, platelet,
whisker, fiber and in situ reinforced composites (including nano-composites). CMCs
containing discontinuous second phases are, in general, processed by shaping
techniques commonly used for monolithic ceramics; i.e., injection molding, slip
casting, and tape casting, followed by sintering to densify the composite. By
contrast continuous fiber ceramic composites (CFCCs) have required the
development of infiltration (vapor, sol, melt, liquid pre-ceramic polymers) methods
that enable the densification of various ceramic matrices in continuous fiber lay-ups
and/or net shape woven fiber preforms. Continuous fiber reinforced CMCs are
further subdivided into carbon fiber reinforced carbon composites, a.k.a. carbon-
carbon composites and other composites.

2.Classification of composites
Composite material is a material composed of two or more distinct phases (matrix
phase and dispersed phase) and having bulk properties significantly different from
those of any of the constituents.

• Matrix phase
The primary phase, having a continuous character, is called matrix. Matrix is
usually more ductile and less hard phase. It holds the dispersed phase and
shares a load with it.

• Dispersed (reinforcing) phase

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The second phase (or phases) is embedded in the matrix in a discontinuous

form. This secondary phase is called dispersed phase. Dispersed phase is
usually stronger than the matrix, therefore it is sometimes called reinforcing
phase.

Many of common materials (metal alloys, doped Ceramics and Polymers mixed with
additives) also have a small amount of dispersed phases in their structures,
however they are not considered as composite materials since their properties are
similar to those of their base constituents (physical properties of steel are similar to
those of pure iron).

There are two classification systems of composite materials. One of them is

based on the matrix material (metal, ceramic, and polymer) and the second is
based on the material structure:

CLASSIFICATION OF COMPOSITES I (based on matrix material)

I. Metal Matrix Composites (MMC)

Metal Matrix Composites are composed of a metallic matrix (aluminum,

magnesium, iron, cobalt, copper) and a dispersed ceramic (oxides, carbides)
or metallic (lead, tungsten, molybdenum) phase.

II. Ceramic Matrix Composites (CMC)

Ceramic Matrix Composites are composed of a ceramic matrix and embedded

fibers of other ceramic material (dispersed phase).

III. Polymer Matrix Composites (PMC)

Polymer Matrix Composites are composed of a matrix from thermoset

(Unsaturated Polyester (UP), Epoxy (EP)) or thermoplastic (Polycarbonate
(PC), Polyvinylchloride, Nylon, Polystyrene) and embedded glass, carbon,
steel or Kevlar fibers (dispersed phase).
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CLASSIFICATION OF COMPOSITE MATERIALS II (based on reinforcing material

structure)

I. Particulate Composites

Particulate Composites consist of a matrix reinforced by a dispersed phase in

form of particles.

i. Composites with random orientation of particles.

ii. Composites with preferred orientation of particles. Dispersed
phase of these materials consists of two-dimensional flat platelets
(flakes), laid parallel to each other.

I. Fibrous Composites

i. Short-fiber reinforced composites. Short-fiber reinforced

composites consist of a matrix reinforced by a dispersed phase in
form of discontinuous fibers (length < 100*diameter).
a) Composites with random orientation of fibers.
b) Composites with preferred orientation of fibers.
i. Long-fiber reinforced composites. Long-fiber reinforced
composites consist of a matrix reinforced by a dispersed phase in
form of continuous fibers.
a) Unidirectional orientation of fibers.
b) Bidirectional orientation of fibers (woven).

I. Laminate Composites

When a fiber reinforced composite consists of several layers with different

fiber orientations, it is called multilayer (angle-ply) composite.

1.Ceramic Matrix Composites (introduction)

According to the classification of composite materials:

Ceramic Matrix Composite (CMC) is a material consisting of a ceramic matrix

combined with a ceramic (oxides, carbides) dispersed phase. Ceramic Matrix
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Composites are designed to improve toughness of conventional ceramics, the main

disadvantage of which is brittleness.

Ceramic Matrix Composites are reinforced by either continuous (long) fibers or

discontinuous (short) fibers.

I. Short-fiber (discontinuous) composites are produced by

conventional ceramic processes from an oxide (alumina) or non-oxide (silicon
carbide) ceramic matrix reinforced by whiskers of silicon carbide (SiC),
titanium boride (TiB2), aluminum nitride (AlN), zirconium oxide (ZrO2) and
other ceramic fibers. Most of CMC are reinforced by silicon carbide fibers due
to their high strength and stiffness (modulus of elasticity). Whiskers
incorporated in a short-fiber Ceramic Matrix Composite improve its toughness
resisting to cracks propagation. However a character of failure of short-fiber
reinforced materials is catastrophic.

II.Long-fiber (continuous) composites are reinforced either by long

monofilament of long multifilament fibers. The best strengthening effect is
provided by dispersed phase in form of continuous monofilament fibers,
which are fabricated by chemical vapor deposition (CVD) of silicon carbide on
a substrate made of tungsten (W) or carbon (C) fibers. Monofilament fibers
produce stronger interfacial bonding with the matrix material improving its
toughness. Failure of long-fiber Ceramic Matrix Composites is not
catastrophic.

Typical properties of long-fiber Ceramic Matrix Composites:

 High mechanical strength even at high temperatures

 High thermal shock resistance;
 High stiffness;
 High toughness;
 High thermal stability;
 Low density;
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 High corrosion resistance even at high temperatures

Matrix material for long-fiber (continuous fiber) composite may be silicon
carbide ceramic, alumina (alumina-silica) ceramic or carbon.

I. Silicon carbide matrix composites are fabricated by chemical vapor

infiltration or liquid phase Infiltration methods of a matrix material into a
preform prepared from silicon carbide fibers. Silicon carbide matrix
composites are used for manufacturing combustion liners of gas turbine
engines, hot gas re-circulating fans, heat exchangers, rocket propulsion
components, filters for hot liquids, gas-fired burner parts, furnace pipe
hangers, immersion burner tubes.

II.Alumina and alumina-silica (mullite) matrix composites are

produced by sol-gel method, direct metal oxidation or chemical bonding.
Alumina and alumina-silica (mullite) matrix composites are used for
manufacturing heat exchangers, filters for hot liquids, thermo-photovoltaic
burners, burner stabilizers, combustion liners of gas turbine engines.

III.Carbon-Carbon Composites are fabricated by chemical vapor

infiltration or Liquid phase infiltration methods of a matrix material into a
preform prepared from carbon fibers. Carbon-Carbon Composites are used for
manufacturing high performance braking systems, refractory components,
hot-pressed dies, heating elements, turbojet engine components.

Both discontinuous reinforced and continuous fiber reinforced composites decrease

the susceptibility of ceramic components to catastrophic thermal-structural "brittle
failure". The mechanisms by which discontinuous reinforced and continuous
reinforced CMCs retard crack initiation and/or propagation are dependent on the
nature of material reinforcements (geometry, quantity, and distribution).
Understandably, the reinforcements in discontinuous and continuous CMCs give rise
to inherently different mechanical properties, different advantages, and different
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end uses. A list of the general advantages of carbon-carbon, continuous reinforced

CMCs, and discontinuous reinforced CMCs are presented in Figure 1.

Figure 1; Comparison of different CMCs

1.Fibers for Ceramic Matrix Composites

In CMCs, only fiber components are used that withstand the relatively high
temperatures required for the production of ceramics, without significant damage.

Other requirements to be met are long - term high - temperature stability, creep
resistance, and oxidation stability. The importance of each of these demands
depends on the type of application.

Organic, polymeric fiber materials cannot be used in CMCs because of their

degradation at temperatures below 500 ° C. Also conventional glass fibers, with
melting or softening points below 700 ° C, cannot be used for this purpose.

Possible candidates for the reinforcement of ceramic materials are polycrystalline or

amorphous inorganic fibers or carbon fibers. The term “Ceramic fibers” summarizes
all non - metallic inorganic fibers (oxide or non - oxide), with the exception of fibers
manufactured via solidification of glass melts.

The distinction between ceramic fibers and glass fibers has become more difficult
during the last few years, because ceramics produced via new precursor or sol – gel
routes can also be amorphous (i.e. “glassy”) in structure and the production process
can also contain a melt processing step. This means that ceramic fibers can be
either polycrystalline, partially crystalline, or amorphous. However, the expression
“glass fibers” should only be applied to fibers that are produced via solidification of
typical glass melts based on silicate systems. If these melts are produced by using
minerals such as basalt, then the fibers should be called “mineral fibers.”
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Carbon fibers can also be used under certain conditions in CMCs. Although these
fibers degrade in an oxidizing atmosphere above 450 ° C, they are stable under non
- oxidizing conditions up to temperatures of 2800 ° C. Carbon fibers have a very
good cost - performance ratio, if an environmental protection of the composite
allows the use of this fiber type. Therefore, Environmental Barrier Coatings (EBC) is
an important field of research in CMCs.

Figure 2

2.Fabrication of Ceramic Matrix Composites

A number of ceramic composites systems have reached the commercial stage of
development in which process and properties are defined and available in
commercial quantities and geometries. The different systems are described in terms
of their fabrication technology.

There are four methods to fabricate Ceramic Matrix Composite as follows;

I. Chemical Vapor Infiltration (CVI) process

II. Liquid phase Infiltration process
III. Sol-gel process
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IV. Direct Oxidation Process

1.1. Chemical Vapor Infiltration process
CVI method of Ceramic Matrix Composites fabrication is a process, in which reactant
gases diffuse into an isothermal porous preform, made of long continuous fibers,
and form a deposition. Deposited material is a result of chemical reaction occurring
on the fibers surface.

The deposition fills the space between the fibers, forming composite material in
which matrix is the deposited material and dispersed phase is the fibers of the
preform.

Chemical Vapor Infiltration (CVI) is similar to Chemical Vapor Deposition (CVD), in

which deposition forms when vapor gases react on the outer substrate surface.
Chemical Vapor Infiltration is widely used for fabrication of silicon carbide matrix
composites reinforced by silicon carbide long (continuous) fibers.

Silicon carbide (SiC) matrix is formed from a mixture of methyltrichlorosilane and

Hydrogen.

The process (isothermal CVI) is very slow because of low diffusion rate.

There are three modifications of CVI process with enhanced deposition

rate:
i. Temperature Gradient CVI (TG-CVI) is a CVI process in which
deposition rate is increased due a temperature gradient in the preform.

ii. Forced–flow CVI is a CVI process in which deposition rate is increased due
to pressure gradient forcing the reactant gases to penetrate into the preform.

iii.Pressure pulsed CVI (P-CVI) is a CVI process, which involves

application of alternating pressure of the reactant gases, resulting in
multilayer structure of the deposition.

The presented process combines both temperature gradient and pressure gradient
for reduction of densification time.
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Temperature gradient in preform is achieved by heating the top region of it when

the bottom region is cooled.

Pressure gradient is determined by the difference in the pressures of the entering

and exhausting gases. Scheme of Chemical Vapor Infiltration process is shown in
the picture below.

Figure 3; Scheme of Chemical Vapor Infiltration process

1.1.Liquid phase Infiltration process

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The methods of fabrication of Ceramic Matrix Composites, utilizing infiltration of a

liquid into long continuous fibers, are as follows:

I. Infiltration of molten ceramic

II.Slurry Infiltration Process (SIP)

III.Reactive Melt Infiltration (RMI)
IV.Polymer Infiltration and Pyrolysis (PIP)
I. Infiltration of molten ceramic

Infiltration of molten ceramic into a fiber preform is limited by low

viscosity of molten ceramics and by high temperature causing chemical
interaction between the molten matrix and the dispersed phase (fibers).
This process (similar to Liquid state fabrication of Metal Matrix
Composites) is sometimes used for fabrication glass matrix composites.

II. 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

I. Reactive Melt Infiltration Process (RMI)

Reactive Melt Infiltration Process (RMI) is used primarily for fabrication of

silicon carbide (SiC) matrix composites. The process involves infiltration of
carbon (C) containing preform with molten silicon (Si). Infiltration is
usually forced by capillary action. Carbon of the impregnated preform
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reacts with liquid silicon, forming silicon carbide (SiC). Resulting matrix
consists of silicon carbide and some residual silicon.
When liquid aluminum (Al) is used for infiltration of a preform in oxidizing
atmosphere, alumina-aluminum (Al2O3 – Al) matrix is formed.
Reactive Melt Infiltration method is fast and relatively cost effective.
Materials fabricated by RMI method possess low porosity and high thermal
conductivity and electrical conductivity.

II. Polymer Infiltration and Pyrolysis (PIP)

Polymer Infiltration and Pyrolysis (PIP) involves the following operations:

• Fiber preform (or powder compact) is soaked with a soft (heated)

polymer, forming polymeric precursor.

• The polymer is cured (cross-linked) at 480 ºF (250 ºC).

• The polymer precursor is then pyrolyzed at 1100 – 1830 ºF (600

-1000 ºC). As a result of pyrolysis the polymer converts to ceramic.
Pyrolysis causes shrinkage of the matrix material and formation of
pores (up to 40 vol. %).

• The pyrolyzed polymeric cursor may be hot pressed for

densification. Hot pressing is limited by possible damage of fibers.

• Infiltration – pyrolysis cycle is repeated several times until the

desired density is achieved.

Matrices consisting of carbon, silicon carbide, silicon oxy-carbide, silicon

nitride and silicon oxy-nitride may be fabricated by PIP method.
The following materials are used as polymers in Polymer
Infiltration and Pyrolysis method:

• Thermosets (thermosetting resins);

• Pitches or other carbon-containing liquids for fabrication of carbon

matrix;
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• Poly-carbosilane, Poly-silastyrol, Dodecamethylcyclohexasilan for

fabrication of silicon carbide matrix.

Polymer Infiltration and Pyrolysis method are simple low temperature

methods, which allow production of intrinsic parts.

1.1.Direct Oxidation Process

Direct metal oxidation process (Dimox) of Ceramic Matrix Composites
fabrication involves a formation of the matrix in the reaction of a molten metal with
an oxidizing gas. Preform of dispersed phase (fibers, particles) is placed on the
surface of parent molten metal in an atmosphere of oxidizing agent (Oxygen).

Two conditions are necessary for conducting direct oxidation process:

• Dispersed phase is wetted by the formed oxide ceramic;

• Dispersed phase does not oxidize in an atmosphere of oxygen.

Liquid metal oxidizes when it is in contact with oxygen, forming a thin layer of
ceramic with some dispersed phase incorporated in it. Capillary effect forces the
melt to penetrate through the porous ceramic layer to the reaction front where the
metal reacts with the gas resulting in growing the ceramic layer.
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Figure 4

The melt advances to the reaction front continuously at a rate limited by the
oxidation reaction rate.

Ceramic growth stops when the reaction front reaches the barrier (see the picture).
Some residual metal (about 10% of the material volume) remains in the inter-
granular spaces of the ceramic matrix. The resulting materials have no pores and
impurities, which are usually present in ceramics fabricated by sintering (binders,
plasticizers, lubricants, deflocculants, water etc.).

The main disadvantage of Direct Oxidation Process is its low productivity – growth
rate is about 0.04”/hour (1mm/hour).

1.1.Sol-gel process
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The sol-gel process, also known as chemical solution deposition, is a wet-chemical

technique widely used in the fields of materials science and ceramic engineering.
Such methods are used primarily for the fabrication of materials (typically a metal
oxide) starting from a chemical solution (or sol) that acts as the precursor for an
integrated network (or gel) of either discrete particles or network polymers. Typical
precursors are metal alk-oxides and metal chlorides, which undergo various forms
of hydrolysis and poly-condensation reactions.

Sol-Gel process of a fabrication of Ceramic Matrix Composites involves preparation

of the matrix from a liquid colloidal suspension of fine ceramic particles (sol), which
soaks a preform and then transforms to solid (gel).

Colloidal suspension is formed as a result of chemical reaction when very small

particles with radii up to 100 nm (nano-particles) precipitate within a liquid (water
or organic solvent).

Alumina matrix ceramic composites may be prepared from alumina gel, which
forms in hydrolysis (decomposition as a result of reaction with water) of aluminum
alk-oxides.

Liquid sol having low viscosity easily penetrates into a preform. The infiltrated
preform is then dried. Drying operation causes shrinkage of matrix material and
formation of pores, therefore infiltration-drying cycle is repeated several times until
the desired density is achieved. The resulting material is fired and hot pressed.

Parts of intrinsic shape may be produced by Sol-Gel method

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Figure 5

2.Applications of CMCs
Discontinuous CMCs are experiencing the largest market growth in the commercial
sector. Sales of whisker and second phase particulate reinforced ceramic cutting
tools are expanding at 45% per year. A wide range of abrasive and corrosive wear
applications are emerging for these types of composites. Protective sleeves for
molten Al mixer shafts, hot gas filters, fire proof floor tiles and a host of other
applications are emerging.

Applications for which non carbon-carbon continuous fiber reinforced CMCs are
being considered are listed in Figure 6. Most of these applications are thermal-
structural environments in turbine and rocket engines where metallic alloys cannot
meet the performance and/or durability requirements and where carbon-carbon
composites would ablate due to oxidation. The afterburner divergent flaps and seals
for fighter aircraft turbine engines and divert propulsion and attitude control nozzles
for exo-atmospheric interceptor missile rocket engines are prime examples.
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Figure 6

The next generation reusable launch vehicle will likely use CMCs for the thrust cells
and the ramp of the Aero spike engine. CMCs are presently being evaluated for
leading edges, nose section, inlet cowlings, and the nozzle of future hypersonic
vehicles. Future turbine engine applications may include combustors, shrouds,
stators, vanes, and other augmenter components for turbine engines. Heat shields
to protect metallic structures are also being considered in many aircraft
applications. Industrial applications include porous radiant burner tubes, immersion
heater tubes, heat exchangers, tube hangers for oil refining, brakes for racing
motorcycles, diesel engine valve guides, and/or corrosion resistant containment
shells for chemical pumps.

Carbon-carbon composites are a mature technology. The graphite-like matrix

maintains its strength to exceptionally high temperatures of 4000°F (2204°C) in
non-oxidizing environments. The historical use of carbon-carbon composites can be
traced to ICBM rocket nozzles over three decades ago. Over the past decade and a
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half, carbon-carbon brakes for military and commercial aircraft have developed into
the largest single market for CMCs. The lightweight and high-temperature stiffness-
to-weight properties of carbon-carbon have continued to spur funding of military
demonstration projects such as solar array, radar antenna and mirror support
structures, heat shields, and radiators for spacecraft. Turbine engine components,
reentry vehicle nose tips, and hypersonic leading edge articles have also received
demonstration funding.

The next large dual-use market on the horizon for carbon-carbon composites is
electronic packaging. The development of very high conductivity carbon fibers
coupled with lower cost matrix densification techniques offer promise as printed
wiring board or multichip module substrates, thermal planes and other heat
dissipation components. Many of these applications are summarized in Figure 7.

Figure 7

3.References
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I. http://www.substech.com/dokuwiki/doku.php?id=composites

II.Fibers for Ceramic Matrix Composites Bernd Clau ß

III.Lee , S.M. ( 1993 ) Handbook of Composite Reinforcements , Wiley - VCH

Verlag GmbH , Weinheim .

IV.DEPARTMENT OF DEFENSE HANDBOOK COMPOSITE MATERIALS HANDBOOK

VOLUME 5. CERAMIC MATRIX COMPOSITES Volume 5 of 5 17 JUNE 2002