CHAPTER X

INTRODUCTION

The ceramic materials are, from the chemical point of view,

compounds of metals and non-metals. The first ceramic products are probably
earthenware. The process of preparing these products is quite simple. Soil that
contains organic binders (humus) is mixed with solvent (water) and shaped into
a green body. The green body is dried and fired to obtain the ceramic pots. The
next materials are glasses with silica as the major component and are shaped
into objects in the molten state. This is because, silica is the most commonly
occurring material on earth crust. Another class of materials is based on
alumina, which is also an abundantly naturally occurring material. High purity
alumina and silica based materials can be prepared by purification of natural
materials, oxidation of high purity elements, or the hydrolysis of inorganic salts
and alkoxides. Some non-oxides such as silicon carbide do exist in nature,
although they are not abundant. The methods of preparation of most modem
non-oxides have their origins in mid 1800 and research on these materials
continues (Kingery et al 1991).

Ceramic materials exhibit a number of useful properties such as

High temperature strength
Relatively low density
High Youngs Modulus
Low coefficient of thermal expansion
Outstanding corrosion and oxidation resistance
Wear and erosion resistance
High hardness
 The major disadvantage of ceramics is their lack of ductility.
However, careful design makes ceramics useful in demanding physical and
mechanical applications (Parrott 1990).

Figure 1.1 shows the condition of use of typical engineering ceramics,

such as silicon nitride (SrjN^, silicon carbide (SiC) and zirconia (Zr02). S^ty-
based ceramics with outstanding properties such as high strength, high
toughness and good corrosion resistance have already been put into practical
use in highly stressed applications, for example, cutting tools, bearing balls and
turbocharger rotors.

Mainly
SiC New materials
Increasing operating temperature

Gas
1300C Turbine rotor
It
Both Si3N4 & SiC Mainly SijN4
Glow Plug
Swirl Chamber
Piston head Valve
Mainly metals Turbocharger Rotor

Mainly
Zr02
Bearing balls
Cylinder

Increasing stress----

Figure 1.1 Stress-temperature diagram for the development of

engineering ceramics (() application of Si3N4 components)
(Yamada 1993)

Advanced ceramics are the emerging class of materials suitable for

engineering applications. Leading contenders for such applications are silicon
 3

nitride and related materials, which offer excellent combination of intrinsic

properties such as high hardness, good creep resistance and excellent resistance
to thermal shock (Katz 1992).

1.1 NON-OXIDE CERAMICS

Table 1.1 gives the properties of some common non-oxides.

1.1.1 Silicon Nitride (Si3N4)

The recorded terrestrial history of Si3N4 spans just longer than 100 years.
It must be assumed that in the earths prehistory, when the atmosphere was
chemically reducing and rich in ammonia, the crust contained large quantities
of silicon and other nitrides (according to Lord Raleighs estimates, there is far
more nitrogen in the rocks of the earths crust than in the atmosphere (Lee et al
1995)). Evidence for the natural existence of Si3N4 is seen from the detailed
analysis of particles of meteoritic rock. (Nittler et al 1995). Silicon nitride is
one of the prime materials in the field of structural ceramics. The development
of Si3N4 based ceramics as potential high temperature structural materials has
markedly accelerated in the early 1960s. This is the outcome of deliberate and
structured search for new materials with good high temperature properties like
resistance to thermal shock. When components produced from silicon nitride
are used in engines, they promote higher fuel efficiency, reduce vibration and
overall weight (Riley 2000). However, the major drawback is its high cost due
to complex processing (Das and Curlee 1992, Schoenung 1991, Winslow
1993).

The fabrication of silicon nitride products follows two methods namely

Reaction Bonded Silicon Nitride (RBSN) and Sintered Silicon Nitride (SSN).
 Table 1.1 Properties of common non-oxide ceramics (Weimer 1997)

cl
dp.
u
*3

a

>
Electical & magnetic Mechanical
Conduc
Melting Linear Magnetic Com Fracture
Non- tivity Elastic Micro Bend
Sp. or disso exp. coeff. Electrical suscepti pressive Tough
Oxide Gravity ciation (300- K modulus Poissons hardness Strength
resistivity p bility strength ness
(g/cc) (d) temp 1300K) (xlO6) x E ratio v at IN load Otr
(ohm.m) oc (MPa.
a (106/K) (W/m,K) (GPa) Hv(GPa) (MPa)
(K) (1/mol) (GPa)

A
lb
AIN 3.26 2572(d) 5.00 180.0 320 0.25 15.3 320 3.8 2.8

m
8
o
b
2.52 2743 5.54 28.0 427 0.19 31.5 340 6.6 3.2

OS
1
1
09

14
X
O
ro
BN 2.28 2600(d) 2.00 15.0 20 0.3 16.0

X
o
o
SiC 3.21 3103(d) 5.12 41.0 408 0.14 fO 350 6.3 3.9

Os

in
A
14
o

Z4
co

t <r>
n
8
00

3.18 2151(d) 2.60 29.5 0.27 15.0 4.4 6.0

H
es
iro
4.52 3193 4.60 24.0 9.0 31.3 541 25.5 450 5.7 6.4
610
14

TiC 4.92 3290 7.95 17.2 200.0 5.0 494 30.0 500 2.0
l

oo
O
Sf
i

o
d
CO

TiN 5.44 3223 28.9 37.0 390 19.9 260

r-
CO
t*-

WC 15.8 3073(d) 5.76 29.3 19.2 9.8 0.24 30.0 530 4.3 6.0
4
 5

Powder metallurgy techniques are used to fabricate shapes of silicon metal,

which are then fired in nitrogen atmosphere to produce a porous Si3N4 product
called reaction bonded, or reaction sintered Si3N4 (RBSN). The product is
primarily low temperature a-Si3N4 and has lower strength, lower toughness and
less oxidation resistance than the dense forms. In sintered silicon nitride (SSN),
sintering aids such as CaO, MgO, Y2O3 are blended with the pure powder to
allow densification to proceed thereby enabling the manufacture of essentially
pore-free bodies (Lences et al 1995). The price of silicon nitride powders varies
from $20/kg to $350/kg, depending on specified particle size and purity (Ault
and Yeckley 1992).

A comparison of properties of RBSN and SSN is given in Table 1.2

Table 1.2 A comparison of properties of RBSN and SSN

(Taffner et al 1991)

PROPERTIES RBSN SSN

Density (g/cm3) 2.2- 2.7 3.1 -3.3
0
Porosity (%) 30-15
Bend Strength (25C) MPa 190-230 600 - 950
100-220
Youngs Modulus (25C) GPa 260 -310
Thermal Expansion (0-1000C) x lO^/K 2.5-3.0 3.1 -3.5
Fracture Toughness MPam1/2 2.0-3.6 4.5 - 7.5
Thermal Conductivity (25C) Wrn'V 3.21 12-32

Silicon nitride occurs in two forms, alpha (a) and beta (P), with

similar hexagonal crystal structures, but different cell dimensions. The a phase

has almost twice the cell volume of P (a-phase has a = 0.775-0.777 nm and c =
0.516-0.569 nm and P-phase has a = 0.759 - 0.761 nm and c = 0.271-0.292
nm). Both phases are built up of SiN4 tetrahedra joined in a three dimensional
 6

network by sharing corners. In a-Si3N4, the bottom half of the unit cell is same
as p, but the top half relates to the bottom by the operation of c-glide plane.

Blegans calculation (Blegan 1975), based on temperature-pressure

relationships, shows that a-Sh^ is not a true nitride, but rather the oxynitride
represented by the formula Si23N3oO, with a range located between P-Si3N4 and

Si2N20. The determination of stable phases at 1327C and 1527C shows that,

at high temperatures, the only stable form is P-Si3N4 (Figurel.2). At high

temperatures, more nitrogen is required in the system to produce silicon nitride.

Low nitrogen partial pressure leads to the formation of deleterious SiC>2 or Si
metal, depending on the partial pressure of oxygen. The most recent theories
assume that a-Si3N4 is a metastable form whose formation is favoured by low
temperature and certain reaction routes in which nitrogen is available in the
atomic form (Pyzik and Hart 1995).

Another phase of the Si-N-0 system is silicon oxynitride (Si2N20)

and is the only compound in the Si3N4-Si02 system. The formation of Si2N20
from ShN4 and SiC>2 occurs via a liquid phase provided by the eutectic
composition 98-mol% SiC>2 and 2-mol% Si3N4. The eutectic temperature is
1590C. Above 1750C, gradual decomposition of Si2N20 to P-Si3N4 (s), Si (1),
SiO (g) and N2 (g) takes place. The oxidation study of Si3N4 showed that the
outer layer consists of Si02 and Sb^O is formed as the intermediate layer. The
Si2N20 structure is built up of SiN30 tetrahedra joined by sharing comers. The
orthorhombic crystal structure consists of irregular, but parallel sheets of
covalently bonded silicon and nitrogen atoms linked by Si-O-Si bonds. Because
of the structural similarities between nitride and oxynitride, there exists some
limited solubility and a solid solution can form without a change of structure.
 7

log (Ph2)
Figure 1.2 Thermo-chemical diagram for the Si-O-N system
(Pyzik and Hart 1995)
 8

1.1.2 Silicon Carbide (SiC)

SiC is popular for decades as high quality abrasive, both in loose and
bonded grits. The original preparation of silicon carbide and the production
method devised by Acheson is unchanged since its inception. The fabrication of
commercial silicon carbide products follows one of the three ways, depending
upon the requirements of the intended use. (i) The SiC carbide powder is mixed
with a second material such as resin, glass, silicon nitride, clay or metal to form
a composite. This composite material is then fired to allow the second phase to
develop as a bond (e.g. clay-bonded silicon carbide), ii) Silicon metal powder is
mixed with carbon and formed into shapes that reaction bonded on heating
(reaction-bonded silicon carbide), (iii) Silicon carbide powder can also be
mixed with carbon and silicon metal powder. Carbon may react with silicon
vapour to form a silicon carbide bond (self-bonded). Self-bonded silicon
carbide generally contains a quantity of unreacted silicon metal in the pores. It
can be removed by refiring in vacuum or in the presence of carbon. Sintered
silicon carbide is a product made from pure silicon carbide powders with a
small quantity of sintering aid.

The commercial silicon carbide whiskers are produced by reaction of

carbon and silicon dioxide. Figure 1.3 depicts the phase diagram of the silicon
containing products of the reaction SiC>2 and C. In this figure, the equilibrium
reaction products between SiC>2 and carbon with temperature demonstrates that
silicon carbide formation begins above melting point of SiC>2 and continues up
to 2400 K. Figure 1.4 shows the equilibrium compositions of the products from
the reaction of the SiO-C-O phases at 2400 K. A maximum in silicon carbide
level is achieved when the ratio of Si02 to carbon is 6:4. For higher ratio of
SiC>2, the formation of SiC drops drastically.
 AMOUNT OF SiO

Figure 1.3 Phase diagram of the silicon containing products of the

reaction Si02 and C (Pyzik and Hart 1995)
 AMOUNT OF CARBON

Figure 1.4 Equilibrium composition of the products in the reaction

of Si02 with carbon at 2400 K (Pyzik and Hart 1995)
 11

In the presence of excess carbon, SiC is synthesised via a gaseous

intermediate phase above 1786 K according to

C + Si02-> SiO + CO (LI)

2C + SiO-SiC +CO (1.2)

Other reactions that are possible in this system include Si (s) + CO (g)
(favourable at low temperatures), or CO + SiO and C (s) + Si (s, 1, or g). These
reactions result in producing Si02 if the partial pressure of oxygen containing
species CO and SiO in the temperature range for typical SiC whisker synthesis.
The following chemical reaction gives the most commercial significance:

Si02 + 3C - SiC +2CO (T>1786 K) (1.3)

There are two types of crystalline forms of silicon carbide, namely

alpha (a) and beta ((3) SiC. The a-SiC exhibit hexagonal crystal structure and
p-SiC exhibit cubic crystal structure. The variations result due to the slightly

shifting of the basic coordinating tetrahedra of SiGj and CSLt. The fourfold
coordination of both silicon and carbon atoms is satisfied by sharing of comers.
Notations to the various types of SiC are given with respect to the stacking
sequence of the repeating unit cell. There are more than 70 different polytypes,
the most common being 2H, 3C, 4H, 6H and 15R. These five polytypes have
short-range periodicity and are the most stable forms.

The polymorphic form of silicon carbide depends on many factors

including thermal history, type and level of impurity and environment. The P

form is stable phase at low temperatures, whereas the a form is the high
 12

temperature form. There are many exceptions to the rule, as the conversion to a
from p and the converse is possible.

1.1.3 SiAION

SiAlON based products are often fabricated with alumina, aluminium

nitride and silicon nitride as raw materials. The past fifteen years has seen
considerable worldwide effort to understand the production processes for all
these forms of the material and to gain improvements in strength, fracture
toughness, creep resistance and weibull modulus (Zeng et al 1990). From phase
equilibrium point of view, these materials are all members of a silicon nitride
system (Ekstrom and Nygren 1992).

1.1.4 Boron Nitride (BN)

Boron nitride (BN) exists in several crystallographic forms. The most

common forms are hexagonal and cubic. Hexagonal boron nitride is a white
chalk like powder, sometimes called white graphite. It is very soft, plate like
and is manufactured by hot pressing (Rudolph 2000). This material exhibits
anisotropy because platelets are oriented in directions perpendicular to that of
applied pressure. It has excellent thermal shock resistance, high thermal
conductivity, low dielectric loss and good machinability. The material is not
wettable to a host of metals, viz. Al, Cu, Cd, Fe, Sb, Bi, Si, Ge and molten salts
such as cryolite. Thin walled shapes for applications such as crucibles for
special glasses may be produced by chemical vapour deposition (CVD) or a
pyrolytic method. Hexagonal BN converts to cubic at temperatures above
1300C under 5.5 GPa pressure. Cubic BN is a unique material with hardness
close to that of diamond. Cubic boron nitride is used as grinding material in grit
 13,

form or as a solid ceramic for the manufacture of metal cutting tools. The
commonly used processes to synthesis boron nitride are nitridation of boron,
carbothermal reduction and nitridation, reaction of boric oxide with ammonia
and vapour reaction of halide (BCI3) with ammonia (Morrell 1985).

1.1.5 Boron Carbide (B4C)

B4C is the third hardest material known, next to diamond and cubic
boron nitride and is currently the hardest material produced in tonnage
quantities. The most commercial boron carbide contains a small quantity of
carbon in graphitic form. The presence of second phase graphite is a major
factor that limits the strength of commercial boron carbide. The graphite exists
in the form of thin easily cleavable lamellae. The commercial boron carbide is
produced by reacting a mixture of boric oxide and carbon in an electric arc
furnace. Boron carbide is used as a thermal neutron absorber, loose abrasive
and armour.

1.1.6 Tungsten Carbide (WC)

Tungsten carbide is the earliest non-oxide ceramic material that found

widespread usage in the machinery industry for metal cutting and drilling
applications. Tungsten and carbon form two simple compounds of interest,
ditungsten carbide (W2C) and tungsten monocarbide (WC). They also form
another compound pentatungsten tricarbide, which is stable only above 2535C.
Of the two stable phases, the monocarbide is the one of primary interest.
Tungsten carbide parts, dies and cutting tools are actually composites in which
tungsten carbide grains are bonded to another metallic phase (typically cobalt).
 14

The combination of rigid carbide network and the tougher metal substructure
provides these cemented carbides outstanding properties.

Ditungsten carbide is used in combination with metals such as nickel

as a plasma spray hard facing material and as a powder filling for tubular hard
facing welding electrodes.

1.1.7 Titanium Carbide (TiC)

The hardness of titanium carbide (TiC) coupled with its resistance to

high temperatures and corrosive chemical atmospheres makes it an attractive
material for applications in pumps for transporting molten materials. It is also
used in rocket components, as a constituent in electrodes for oxyelectric cutting
of steel and as thermocouple material for use in reducing and neutral
atmospheres.

1.1.8 Titanium Diboride (TiB2)

Titanium diboride (TiB2) is used as an armour material due to its high

hardness and relatively low specific gravity. TiB2 is also used as an electrode
material and a wall material for nuclear fusion due to its high electrical
conductivity. Titanium diboride is used as crucibles for handling liquid metals
such as Al, Cu, Ag, Au, Zn, Cd, Ag, Ge, Pb, Bi and Cr.

1.1.9 Aluminium Nitride (AIN)

Aluminium nitride is the only stable compound in the binary system

Al-N and exists in wurtzite hexagonal crystal structure (Sheppard 1990).
 IS

Aluminium nitride (AIN) is developed as an insulating substrate for

microelectronic applications where its high thermal conductivity allows good

heat dissipation. In this regard, AIN is cheaper, non-toxic and an alternative to

beryllium oxide. AIN based substrates are manufactured from aluminium

nitride powder mixed with sinter additives such as CaO or Y2O3 by the process

of tape casting into thin sheets followed by blanking out and sintering at 1650

to 1800C in a nitrogen atmosphere (Russell et al 1991). Aluminium nitride is

also stable against molten salts such as carbonates, eutectic mixtures, chloride

and cryolite. AIN is the preferred choice for substrate packages and heat sinks

or coolers, whenever the thermo mechanical properties or power dissipation

capabilities of conventional aluminium oxide materials are insufficient. Typical

examples are highly integrated thick film and thin film components water-

cooled power converters in rail transport systems and transmitter and high

frequency diode substrates subjected to thermal cycling in satellite systems. The

mechanical properties at ambient temperatures would suggest that aluminium

nitride is not suitable for high stress applications, though some limited studies

have been carried out at temperature up to 1200C. Oxidation of AIN above

800C limits its usefulness (Mussler 2000).

1.2 ADVANCED REFRACTORIES

Many non-oxides such as SiC, carbon have made great progress in the

refractories during the last 30 years (Ian and Yiquan 1995). A survey of existing

coarse grained refractory materials show that coarse grained silicon carbide

bonded with silicon nitride, silicon oxynitride or sialon display thermo

mechanical properties and corrosion resistance significantly better than oxide

refractory systems (Jack 1986).

 16

1.2.1 Nitride and SiAION Bonded SiC Refractories

There are many types of SiC refractories such as clay bonded SiC
refractories, self-bonded SiC refractories, nitride bonded SiC refractories and
sialon-bonded SiC refractories. The main advantage of nitride-bonded
refractories is its low affinity and wettability to the slag. This results in
minimum penetration of slag and less corrosion.

Nitride bonded SiC refractories continue to lead the world production

approaching 20,000 tonnes/year. Table 1.3 gives a comparison of sialon bonded
and Si3N4 bonded SiC refractories used in blast furnaces.

Table 1.3 Comparison of properties of sialon bonded and Si3N4 bonded SiC
refractories (Zhipping et al 1993).

SiC Refractory bonded

Properties with
SiAION Si3N4
Bulk density (g/cm3) 2.7 2.72
Apparent Porosity (%) 15 15
CCS (MPa) 220 204
MOR (Mpa) at R.T. 53 51.7
at 1400C 50 57.5
Thermal conductivity (Wm^K1)
at 350C _ 18.6
at 800C 19.4 -

atl200C 16 -

Thermal expansion x 10-6 /K (20 -1200C) 5.1 4.6

Chemical composition
SiC 70 70
SiAION/ Si3N4 >20 >20
 17

1.2.2 SiAION and AION Bonded Corundum refractories

The SiAION and AION bonded corundum refractories have good

resistance to alkali slag and molten steel. The reasons may be attributed to the
trivalent nitrogen atom leading to the additional cross-linking in the Si-0
network structure. The Si-N bond in sialon has poor wettability to alkali, slag
and molten steel. Thermal shock resistance of sialon decreases as AIN.AI2O3
substitution increases. An alternative method of increasing the thermal shock
resistance is via resin bonding of ceramic grain graphite mixtures. These
materials are widely used in nozzles and slide gate plates for continuous casting
of steel. The submerged entry nozzles lined with sialon/graphite mixtures have
a beneficial effect in overcoming the nozzle blockage during casting. This
phenomenon is caused by a buildup of friable material composed
predominantly of alumina and calcium aluminates which precipitates from the
steel and adheres to the internal walls of the alumina-graphite nozzle
(Nakabayashi 1990).

Hosaka and Kato (1985) reported that AION (5AIN.9AI2O3) improved

the corrosion resistance and thermal shock resistance of the trough. It has been
shown that the addition of AIN to AI2O3-C refractories can improve life of slide
gates and corrosion resistance and spalling resistance of submerged nozzle
(Murakami et al 1986). Shimpo et al (1992) have reported that AlON-BN
composites have good erosion resistance to molten steel. Shimomura et al
(1985) observed that AI2O3-AIN composite refractories have high resistivity to
penetration and corrosion by molten Al-Mg alloy.
 18

1.3 WHISKERS

Whiskers are single crystals with aspect ratio usually over 20. The
high degree of structural perfection of whiskers which stems from their single
crystalline morphology and small diameter (usually sub micron) bestows on
them a very high Youngs modulus and a strength that approaches to the
theoretical strength of the material calculated to be

c,h = (Ey/a)m (1.4)

where E is the Youngs modulus, y is the surface energy per unit area and a- is
the equilibrium spacing of the atomic planes. Whisker diameter is also a critical
parameter in terms of its strength. The increase in diameter raises the
probability for the presence of defects and hence lowers the strength (Levitt
1970).

One of the successful proven approaches to increase the fracture

toughness of ceramics is the application of single crystal whiskers introduced
into the material or grown in-situ during the densification stage. The chemically
pure nature and highly ordered structure of ceramic whiskers can provide very
high tensile strengths. The toughening of ceramics by the addition of single
crystal whiskers that are different from the matrix material is the most
traditional and the best explored technology. The advantage of this method is
that a broad spectrum of ceramic composites can be prepared. Since the
whiskers are manufactured in a separate process, it is possible to control their
size, morphology and surface chemistry without affecting the matrix material.
Additionally, whiskers can undergo chemical or thermal treatment to change
their interactions with the matrix. The main disadvantage of this method is the
high manufacturing cost of whiskers.

1.3.1 Silicon Nitride Whiskers

The formation of silicon nitride whiskers is observed in different

techniques such as nitriding of metallic silicon, carbothermal reduction of silica
with simultaneous nitridation and thermal decomposition of silicon halides.

1.3.1.1 Direct Nitridation

The Direct nitridation technique is based on reaction of silicon in a

nitrogen atmosphere where

3Si + 2N2->Si3N4 (1.5)

The growth of whiskers requires specific substrate materials (mullite

or graphite) or the presence of A1 or Fe catalysts in silicon at the growth zone.
The a-type whiskers are formed in the temperature range of 1200 to 1400C.
The reaction is strongly exothermic, which causes problems in controlling the
synthesis temperature. This leads to the formation of both a and P phases.

The mechanism of whisker growth depends on the substrate used for

the reaction. For example, the Si3N4 whiskers grown on mullite substrate show
axial defects, characteristic of crystallization by screw dislocation mechanism.
In the presence of a catalyst, whisker growth occurs by means of VLS
mechanism, involving crystallization of the nitride from the drops of binary or
 20

ternary alloys of silicon with iron and aluminium. The iron and aluminium act
as solvents for silicon.

1.3.1.2 Carbotherma) Reduction

Carbothermal reduction and simultaneous nitridation of silica takes

place according to the reaction.

3SiO(g) + 3CO(g) +2N2(g) -> Si3N4+ 3C02 (1.6)

This is a potential method for producing pure silicon nitride whiskers.

Its advantage over direct nitridation is that it has better control of the processing
temperature. Several processes have been developed. According to Rahman and
Riley (1989), the decomposition of pyrolysed rice husk at a temperature ranging
from 1260 to 1450C under nitrogen atmosphere leads to the formation of a-
Si3N4 whiskers. The formation of whiskers depends on the size of the pyrolysed
rice husk grains. The ratio of the whisker to particulate in the final product
increases with increasing size of the pyrolysed grains. The most common
mechanism for whisker growth occurring in carbothermal nitridation is a solid
vapor mechanism.

1.3.1.3 Diimide Decomposition

The diimide thermal decomposition method is based on reaction of

SiCU and NH4 to synthesis silicon diimide, Si(NH)2. When the Si(NH)2 is
thermally decomposed, amorphous silicon nitride powder is produced. This is
then converted to silicon nitride whiskers when metal catalysts such as iron are
present. The Si3N4 whiskers manufactured by this process has diameter ranging
 21

from 0.1 to 0.4jnm and length from 5 to 20 pm. These whiskers grow along die

c axis by a Vapour-Liquid-Solid (VLS) mechanism (Nakamura et al 1989). The

modified diimide decomposition process uses gas mixtures of S^CL, NH3 and

H2. Amorphous whiskers are formed on quartz or graphite substrates coated

with metal catalyst. The uniqueness of this method is the ability to form

whiskers of a special shape, e.g. a coil at 1200C. All whiskers have smooth

surface and are 2 to 5 pm in diameter and have a coil diameter of about 10 to

15pm.

1.3.2 Silicon Carbide Whiskers

SiC in whisker form has been proved to be an excellent reinforcement

material in ceramic and glass matrix composites, giving better high temperature

properties and therefore improving the potential of the materials for use in high

temperature engineering applications (Yang and Stevens 1990). The main

hurdles in extending the application of SiC whiskers or short fibres are their

limited availability and prohibitive manufacturing costs.

The formation of silicon carbide whiskers can occur through one of

three general methods namely, vapour-solid (VS), chemical vapour deposition

(CVD) and vapour-liquid-solid (VLS). The morphology of whiskers resulting

from these processes show more than one form of whisker morphology present

in a single synthesis batch.

1.3.2.1 Vapour-Solid (VS) Method

A straightforward mechanism for whisker growth is the vapour-solid

mechanism in which the SiO (g) reacts with carbon substrate surface.
 22

Temperature affects the growth kinetics as do vapour concentrations and

impurity levels. Metal impurities can increase the formation of whisker
morphologies, although there is argument as to the exact mechanism that
occurs. An example of VS mechanism is the thermal decomposition of rice
husk first reported by Lee and Cutler (1975) and Sharma et al (1984). They
took waste rice husk that contained cellulose as the major component, but had a
very high residual ash content (approximately 15 to 30 wt%). The ash
chemistry was >95% Si(>2, with small amounts of alkalis and trace impurities.
The procedure to form silicon carbide from rice husk consists of driving the
volatile organics from the material at about 700C in the absence of air with

further treatment in a CO atmosphere up to 1500C. Some fraction of the

materials is in the form of whiskers. However, the addition of catalyst such as
iron stimulates the formation of whisker. The whiskers produced by the
decomposition of rice husk have sub micron diameters with aspect ratio of one
hundred or more. A variety of morphologies is also seen in the whisker product
by the VS method so that other mechanisms may also play a role in the growth

patterns.

1.3.2.2 Chemical Vapour Deposition (CVD) Method

CVD techniques are well known for a variety of applications from

coating to particulate synthesis. A range of silicon-based materials can be
utilized as feeds to produce silicon carbide in a variety of forms. In all cases,
the morphology of the deposited silicon carbide depends on two major factors:
the degree of super saturation and the temperature at which the deposition is
made. When the super saturation is low, the growth is slower and this leads to
the formation of larger crystals. When the temperature of deposition is higher,
the tendency to form whiskers is stronger.
 23
1.3.2.3 Vapour-Liquid-Solid (VLS) Method

Milewski et al (1985) proposed the refined VLS technique for

growing p-SiC whiskers. The term used in the process title, refer to the physical
states of three phases that interact to form the SiC whisker. Vapour refers to the
form of the gaseous silicon feed materials. Liquid refers to the intermediate
catalyst that dissolves silicon into the melt and reprecipitates out the silicon
carbide product, which is solid. The crystals grow at the solid-liquid interface
due to supersaturation in the liquid. The presence of the liquid catalyst is unique
to this process and allows the crystallization of uniform single crystal silicon
carbide whiskers.

1.4 ADVANCED COMPOSITES

The two central issues for increased applicability of advanced

ceramics are improving reliability and reducing costs. The types of composites
are Ceramic Matrix Composites (CMC), Metal Matrix Composites (MMC) and
Polymer Matrix Composites (PMC).

1.4.1 Ceramic Matrix Composites (CMC)

One method of improving the fracture toughness of a ceramic is to

incorporate a second phase, forming a ceramic matrix composite (CMC) (Evans
1990).

Various approaches demonstrate the formation of CMCs (Campbell

et al 1990) such as
 24

1. Introduction of ceramic whiskers, e.g., SiC, into a ceramic matrix.

2. Incorporation of a second ceramic phase that undergoes a phase
transition on application of a stress field (such as that near a crack
tip) (Evans and Heuer 1980).
3. Incorporation of strong fibres in the ceramic matrix (Schioler and
Stiglich 1986).
4. Introduction of ductile metal phase to impart toughness by crack
tip blunting.

CMCs have entered the market place in cutting tool inserts for
machining nickel based super alloys, precision dies for forming aluminium
beverage cans and advanced armour. CMC applications under development
include various automotive and aerospace components. Alumina reinforced
with silicon carbide whiskers (SiCw) replaces tungsten carbide (WC) cutting
tool inserts for machining Ni-based super alloys (Claussen 1999).

Knives and scissors made from Zirconia toughened alumina is used

for cutting ceramic sheets and ceramic fibre products. In automotive engines,
SiC reinforced lithium aluminium silicate is widely tested for potential
applications. Other materials of interest are SiaN4 matrix composites, which
have good high temperature strength, Z1O2 based materials having low
coefficient of thermal expansion for insulation applications, AI2O3 reinforced
aluminium titanate for application as exhaust port liners etc.

SiC reinforced SisN4 composites demonstrate increased reliability due

to good thermal conductivity in applications such as heat exchangers and heat
transfer tubes in furnaces. They are useful in mechanical seals, papermaking,
machinery components and valves due to good wear resistance. Good corrosion
 25

resistance and chemical resistance make them useful as the reaction tubes of
chemical reactors, pumps, nozzles, immersion heaters and various components
used in high temperature corrosion fluids. In high temperature engine
applications, they are useful because of their high temperature strength
properties. They combine the virtues of both SiC and S^N,}. They are emerging
as new engineering materials of study and use (Perera et al 1994).

1.4.2 Metal Matrix Composites (MMC)

In some applications, the lack of toughness of ceramics or CMCs

prohibits their use. Typically, MMCs have discrete ceramic particulate or fibre
reinforcement contained within a metal matrix. In comparison to CMCs, MMCs
tend to be more workable and more easily formed, less brittle and more flaw
tolerant (Shee et al 1998). These gains come primarily at the expense of a loss
of high temperature mechanical properties and chemical stability offered by
CMCs. These materials thus offer an intermediate set of properties between
metals and ceramics, though somewhat closer to metals than ceramics or CMCs
(Claussen 1999).

MMCs have entered the market place in lightweight brake rotors,

brake drums and drive shafts, high efficiency diesel pistons and various
recreational applications including bicycle frames golf clubs and horseshoes.
Applications under development includes lightweight tank, track shoes missile
structures and advanced engine components. In MMCs, the matrix should bond
strongly with the reinforcement and should be inert to adverse chemical
reactions (Hexemer and Pierce 2000).
 26

1.4.3 Polymer Matrix Composites (PMC)

Most composites in industrial use are based on polymeric matrices

such as thermosets and thermoplastics. These are usually reinforced with
aligned ceramic fibres such as glass or carbon. When bundles of fibres are
reinforced with resin matrix, the composite becomes strong. Here the strong
and stiff fibres are able to carry most of the stress whereas the matrix distributes
the external load to all the fibres as well as affording protection and preventing
fibre buckling under compressive forces. Glass reinforced plastics (GRP) is
now very popular for various land and sea transport applications (Smith 1990).

1.5 STATEMENT OF PROBLEM

There are many natural resources such as rice husk, coconut fibres,
diatomaceous earth from which silicon nitride and silicon carbide can be
synthesised. Among these natural precursors, rice husk have the advantage of
Si02 and carbon in intimate contact with one another. In this thesis, the
possibilities of utilizing rice husk in an effective manner to produce silicon
nitride and silicon carbide whiskers and incorporation of pyrolysed rice husk as
a secondary phase in several systems are explored.

1.5.1 Objective of theWork

Silicon nitride and silicon carbide whiskers, as a reinforcing material

cannot be incorporated in any system very easily because of its cost factor.

In chapter two, the synthesis and characterization of silicon nitride and

silicon carbide whiskers from rice husk are discussed. Silicon carbide whiskers
 27

are also synthesized from silicon nitride powders. In the third chapter, the effect
of addition of pyrolysed rice husk to the formation of porous silicon nitride and
silicon carbide-silicon nitride and sialon compacts is discussed. In the fourth
chapter, the property evaluation of ULCC castables with additions of pyrolysed
rice husk is discussed. In the fifth chapter, synthesis and characterization of sol-
gel derived silica and boehmite, and the effect of addition of pyrolysed rice
husk are studied. In the sixth chapter, conclusions are drawn.

1.6 CONCLUSIONS

In this chapter, an overview of ceramic materials has been presented

to serve as background information for better appreciation of the investigations
undertaken in the present study. A short introduction on the ceramic materials is
followed by a brief discussion on properties and applications of some non-oxide
materials. The role of non-oxides as refractory materials is also briefly
discussed. The importance of whiskers, the propeities of silicon nitride and
silicon carbide whiskers are briefly discussed. A general discussion of the types
of composites, properties and applications have been covered with a view that
composites are now a real solution to partially overcome the problems
associated with monolithic components. This is followed by the objective of the
present study of utilizing rice husk in an effective manner to produce silicon
nitride and silicon carbide whiskers and incorporation of pyrolysed rice husk in
several systems have been explored.