Ceramic Matrix composites

Ceramic matrix composites

The monolithic ceramics have reasonably high strength

and stiffness but are brittle. Thus one of the main
objectives in producing ceramic matrix composites is to
increase the toughness.
There is a concomitant improvement in strength and
stiffness.
Figure 7 compares typical stress-strain curves for
composites with that for a monolithic ceramic; the area
under the stress-strain curve is the energy of fracture of the
sample and is a measure of the toughness. It is clear from
this figure that reinforcement with particulates and
continuous fibres has lead to an increase in toughness but
that the increase is more significant for the latter.
Fig. 7 Schematic force-displacement curves for a monolithic ceramic and
CMCs illustrating the greater energy of fracture of the CMCs.
Ceramic matrix composite (CMC) development has lagged
behind other composites for two main reasons.
1. Most of the processing routes for CMCs involve high
temperatures and can only be employed with high
temperature reinforcements. It follows that it was not until
fibres and whiskers of high temperature ceramics, such
as silicon carbide, were readily available was there much
interest in CMCs. The high temperature properties of the
reinforcement are also of importance during service. A
major attribute of monolithic ceramics is that they maintain
their properties to high temperatures and this
characteristic is only retained in CMCs if the
reinforcements also have good high temperature
properties. Hence, there is only limited interest in
toughening ceramics by the incorporation of
reinforcements of materials, such as ductile metals, that
lose their strength and stiffness at intermediate
temperatures.
2. The second factor that has hindered the progress of
CMCs is also concerned with the high temperatures
usually employed for production. Differences in the
coefficients of thermal expansion, , between the matrix
and the reinforcement lead to thermal stresses on cooling
from the processing temperature as previously described
for metal matrix composites (MMCs).
Certain ceramics can be produced from slurries by shaping
using a range of methods including casting and extrusion
followed by setting at ambient or slightly elevated
temperatures. Examples are plaster of Paris, which is
obtained from gypsum CaSO4.2H2O, and AIPO4 formed
from phosphoric acid and aluminium hydroxide solutions.
The slurries of these types of ceramic are amenable to the
incorporation of particles, whiskers or chopped fibres and
the normally employed shaping techniques may be used to
produce the composite component.
Fig. 8 Simplified flow sheet for mixing as a slurry prior to shaping.
Fig. 9 Processing using a slurry and hot pressing for continuous fibre
reinforced glass or glass-ceramic. (Source Prewo, 1989).
 Slurry method for continuous fibre reinforced
composites.
The intimate mixing of continuous fibres and the glass
(parent glass in the case of a glass-ceramic) is achieved by
drawing bundles of the fibres, called tows, through a slurry
of powdered glass in water and a water soluble resin binder.
The tows, impregnated with the slurry, are wound on to a
mandrel to form a monolayer tape. The tape is cut into plies
which are stacked into the required stacking sequence, e.g.,
unidirectional, crossplied, etc., prior to burnout of the binder.
This is followed by hot pressing to consolidate the matrix. In
glass-ceramic composite production some crystallization
occurs during the hot pressing stage but an additional heat
treatment may be required to complete devitrification.
The most successful of the melt techniques is matrix transfer
moulding which was originally developed for glass matrix
composites but can also be used for glass-ceramic matrix
composites. The advantage of matrix transfer moulding is that
it permits the fabrication of components, such as tubes, which
are difficult to produce by many of the other methods. Tube
production is illustrated in Figure 10. A preform and a glass
slug are inserted into a cylindrical mould. Application of heat
and pressure forces the fluid glass into the pores in the
preform and, after cooling, the composite tube is ejected from
the mould.
Fig. 10 Matrix transfer moulding of a thin wall tube (Source: Prewo, 1989)
Sol-gel processing

A sol is a dispersion of small particles of less than 100 nm

which is usually obtained by precipitation resulting from a
reaction in solution, for example, the precipitation of
zirconium hydroxide particles from a solution of ZrOCl2 by
ammonia according to

ZrOCl2 + NH3 + 3H2O = 2NH4Cl + Zr(OH)4.

A gel is a sol that has lost some liquid and hence has an
increased viscosity. Currently there is much interest in sol-
gel processing of ceramics and this will undoubtedly extend
into the field of CMCs.
With the exception of the production of zirconia-toughened
alumina, sol-gel processing of CMCs is still in the
experimental stage. If a sol is poured over a preform it will
infiltrate because of the fluidity of the sol (Figure 11(a)). The
sol is then dried in a subsequent heat treatment. The
processing temperature is normally low, thus reducing the
risk of damage to the preform, and complex shapes can be
produced. However there are the disadvantages of high
shrinkage and low yield
Fig. 11 Sol-gel processing: (a) infiltration of a preform; (b) mixing
reinforcement in a sol or a gel.
In CVD chemical reactions in the gaseous state lead to the
deposition of a solid on to the surface of a heated substrate.
In composite technology CVD is used to produce fibres (e.g.,
boron and SiC fibres), to coat fibres and to infiltrate porous
preforms to form the matrix. In the latter case the process is
also called chemical vapour infiltration, CVI, and it is CVI that
we will now discuss.
Fig. 12 Simplified diagram of the stages in a chemical vapour infiltration
(CVI) process
Lanxide process and in situ techniques

The Lanxide process involves the formation of a ceramic

matrix by the reaction between a molten metal and a gas,
e.g., molten aluminium reacting with oxygen to form
alumina. Growth of the ceramic occurs outwards from the
original metal surface and through a preform as shown in
Figure 13 (a).

The rate of growth is constant as it is controlled by the rate

of the chemical reaction and not transport of the reacting
species.
Fig. 13 Lanxide process: (a) infiltration of preform; (b) wicking of liquid
metal along grain boundaries.
With suitable combinations of temperature and pressure,
carbon may be deposited in a desirable form by CVI
involving the thermal decomposition of a hydrocarbon.
In CVI the structure of the carbon and the effectiveness of
the infiltration process depend critically not only on the
temperature and pressure but also on the characteristics of
the substrate such as surface roughness, surface area, pore
morphology and size. Concerning the latter, there must be an
open, permeable pore structure and the pore size must be
small for successful densification in a reasonable time scale.

There are essentially three main CVI methods for carbon

production:
a) Isothermal method: The gas and the substrate are
maintained at a constant temperature of around 1100°C. n a
reasonable time scale.
The infiltration is carried out at a reduced pressure of 0.6-6
kPa (5-50 torr) and the flow is mainly determined by the
surface area and pore morphology of the substrate. The
major problem with this method is that there is a tendency
for preferential deposition on the exterior surfaces of the
substrate resulting in the formation of an impermeable
crust. This crust has to be repeatedly removed by
machining to permit further infiltration. However it has the
advantages that it is relatively simple and a number of
substrates may be processed at the same time.

b) Thermal gradient method: the hottest part of the

substrate is the interior and the outer surface is cooler. This
is achieved by supporting the substrate on a susceptor
which is inductively heated (Figure 14(b)).
Surface crusting is eliminated as the deposition rate is less at
the cooler outer surface of the substrate and deposition
proceeds radially outwards from the interior. The normal
processing conditions are atmospheric pressure and an
interior temperature of 1100°C. The thermal gradients have
to be carefully controlled and consequently the method is
only used for single work-pieces.

c) pressure gradient method: It is also only suitable for

single work-pieces but is not as extensively used as the other
CVI methods. In this method the precursor gas is forced into
the interior of the substrate in order to obtain a more
homogeneous deposit than by the isothermal method.
Fig. 14 Chemical vapour infiltration (CVI) methods: (a) isothermal; (b)
thermal gradient; (c) pressure gradient. (Source: Savage, 1988).
Application of CMCs
Ceramic matrix composites find applications in many areas.
A convenient classification of the applications of CMCs is
aerospace and nonaeraospace. Materials-related drivers
for applications of CMCs in the aerospace field are:

High specific stiffness and strength leading to a weight

reduction, and consequently, decreased fuel consumption.
Reduction in fabrication and maintenance cost.
Higher operating temperatures leading to a greater thermal
efficiency.
Longer service life.
Signature reduction.