Discipline: Physics

Subject: Ceramics

Chapter/ Unit 3: Structural Ceramics

Lesson/ Module 7 : Nonoxide structural

ceramics

Quad 1 : Text

Author (CW): Dr. Dinesh C Agrawal

Professor (retired)
Materials Science ProgrammeIIT Kanpur
 Unit 3: Structural Ceramics

Module 7: Nonoxide structural ceramics

1. Introduction

Earlier we discussed two important oxide structural ceramics – alumina and

zirconia. In this module the non oxide ceramics will be discussed. These constitute
an important class of structural ceramics.

2. Silicon carbide

Silicon carbide for applications in refractories has been discussed in the unit of
refractories. As mentioned there, the two major polymorphs of silicon carbide are
-SiC which has a hexagonal structure like wurtzite and -SiC which has a zinc
blende structure like diamond. Of the two, the  phase is marginally more stable
than the  polymorph.
Because of its low thermal coefficient of expansion and high thermal
conductivity it has a very high thermal shock resistance. It retains high strength at
high temperatures and has high fracture toughness. It is inert to attack from most
chemicals and slags. It oxidizes slowly in an oxidizing atmosphere but can still be
used in air in air up to quite high temperatures (up to 1720o C under certain
e-PG Pathshala Physics Ceramics

conditions) and almost up to its dissociation temperature (2400 -2700 o C) in the

inert atmospheres.
For application in structural engineering products, silicon carbide bodies are
fabricated via two routes: (i) reaction bonding and (ii) sintering of ultrafine powder
with some dopants.
In reaction bonding or reaction sintering, a mixture of SiC and carbon are
compacted and infiltrated with liquid silicon. Firing is carried out at 1400oC.
Silicon and carbon react to form -silicon carbide which bonds the pre-existing SiC
grains. It is difficult to react the silicon totally – about 8-10% silicon remains
unreacted because of which the product can not be used above 1350oC.
In the sintering of the ultrafine powder of SiC, additives like carbon and boron
or carbon and aluminium are used. Dopants like iron, lithium and magnesium are
also used. The dopants are so selected that they do not decompose SiC during
sintering.
Carbon plays an important role during the sintering of SiC. It increases the
concentration of point defects which increases the diffusion. It also removes the
oxide film at the grain boundary which retards the transport of vacancies across the
grain boundary. The compact is sintered in an inert atmosphere between 2000 and
2100oC. A complex set of reactions takes place during sintering.
The representative properties of silicon carbide are given in Table 3.7.1.1

Table 3.7.1.1 Representative properties of silicon carbide

__________________________________________________
Property Value
__________________________________________________
Density, gm.cm-3 3.2
Young’s modulus, GPa 370
Fracture toughness, KIC, MNm-3/2 3.5
Fracture strength, MPa 390
__________________________________________________
Structural Ceramics Module 7 Nonoxide Structural Ceramics

3. Silicon nitride

The basic building block of the structure of silicon nitride is the SiN4 tetrahedron.
The tetrahedra are linked at the corners. The Si-N bonds are short and they are very
strong.
The silicon nitride powder is prepared by the following processes.
(i) Direct nitridation of silicon: This is the method most used in commercial
practice. The following reaction occurs
3 Si + 2N2  Si3N4 H = -175 Kcal.mol-1 at 1600 K (Exothermic)
The melting point of silicon is 1414oC. Silicon is very volatile at temperatures
near the melting point. Also it tends to oxidize readily. On the other hand, complete
nitridation is not possible unless the silicon is melted. Nitridation is therefore
carried out in pure nitrogen atmosphere. To reduce the silicon volatilization, the
reaction is carried out in two stages – for 25-50 hrs at 1325-1350oC followed by 10-
25 hrs at 1425-1450oC. The product consists of  and  Si3N4 phases in the ratio of
3:1 if the temperature is kept below 1410oC; the  phase increases if higher
temperatures are used.
The other three processes and the corresponding reactions are as follows
(ii) Carbothermal reduction of silica followed by nitridation

3SiO2 + 6 C(s) + 2N2 (g)  Si3N4 + 6CO; Cal.mol-1 (endothermic)

(iii) Silicon imide decomposition
(a) SiCl4 + 6NH2  Si(NH)2 + 4NH4Cl (at room temperature)
(b) 3Si(NH)2 (s)  Si3NH4(s) + 2NH3 (g) (1200-1500oC)
(iv) Gas phase synthesis
3SiCl4 + 16NH3  Si3N4 + 12 NH4Cl
To prepare sintered silicon nitride bodies, several methods are used depending
on the application. These are as follows:
(i) Reaction bonding or reaction sintering: The silicon powder is
compacted into the desired shape. It is heated to 1200oC in an
atmosphere of nitrogen or mixtures of nitrogen and hydrogen or
nitrogen and argon. Nitrogen reacts with silicon to form silicon
nitride. Initially, -Si3N4 fibres grow into the pores of the compact.
The temperature is gradually raised to 1400o C. Now mostly -Si3N4
e-PG Pathshala Physics Ceramics

forms. A density of about 85 % is achieved. The final microstructure

consists of grains of the  and the  phases.
 Hot pressed silicon nitride, HPSN: Silicon nitride powder is mixed
with some additives and hot pressed at 1700o-2000oC. Hot pressing
produces simple shapes. Very high densities and strengths can be
achieved. For complicated shapes, hot isostatic pressing is used.
(iii) Liquid phase sintered silicon nitride, LPSSN: Large amounts of
suitable additives and the silicon nitride powder is used to carry out
the liquid phase sintering. An inexpensive process, which yields
adequate properties suitable for many applications.
A large number of sintering aids are used to sinter silicon nitride.
They are mostly Y2O3 or MgO based.
(iv) Gas pressure sintered silicon nitride, GPSSN: Silicon nitride powder
with sintering aids is sintered at high temperature under a high
nitrogen pressure. The high gas pressure prevents the dissociation of
silicon nitride.
The silicon nitride microstructure has been developed over the years
to give interlocking elongated grains, a microstructure responsible for
the very high toughness of this material.
The representative properties of silicon nitride are given in Table 3.7.1.2

Table 3.7.1.2 Representative properties of silicon nitride

__________________________________________________
Property Value
__________________________________________________
Density, gm.cm-3 3.2
Young’s modulus, GPa 300
Fracture toughness, KIC, MNm-3/2 7
Fracture strength, MPa 900-1200
Weibull modulus, m 15
__________________________________________________
Structural Ceramics Module 7 Nonoxide Structural Ceramics

4. SiALONS

SiALONS are the solid solutions of Si3N4 in which part of the silicon is replaced
by aluminium and simultaneously part of the nitrogen is replaced by oxygen to
maintain the charge balance. They can be looked upon as part of the quaternary
system SiO2-Si3N4-AlN-Al2O3 (Fig. 7.3.1.1) Three types of SiALONS can be
identified which are isostructural with -Si3N4, -Si3N4 and with silicon oxynitride
respectively.
Most common are the -SiALONS which have the general formula
Si6-2AlzOzN8-z. Sintering aids such as Y2O3 or MgO or a rare earth oxide are used to
densify. More liquid is formed at lower temperature than in the case of Si 3N4 and
the densification is better. On sintering above 1700oC, elongated hexagonal -
SIALON grains grow in an oxynitride liquid phase made of the additives such as
yttria, alumina , silica and aluminium nitride. The liquid phase forms a high
temperature glass on cooling.
The -SiALONS have excellent toughness but their hardness which is 14-16
GPa is low.The -SiALON have a higher hardness of 22 GPa. This comes from

Fig. 7.3.1.1. The SiALONs can be looked upon as part of the quaternary system Si3N4-AlN-Al2O3-SiO2.
e-PG Pathshala Physics Ceramics

their longer stacking sequence (ABCD as compared to AB for the  variety). Such
a structure provides a higher resistance to dislocation motion.

4.1.1 -SiALON

The -SiALON materials produced earlier had a microstructure of fine equiaxed
grains. Consequently, the material had a low toughness. Over the years, progress
has been made to produce a microstructure with interlocking, elongated grains. This
has resulted in -SiALON material of high fracture toughness.
In -SiALON, is essentially a solid solution of -Si3N4 in which there is the
standard substitution of the Si-N bond with the Al-O bond. In addition there is
substitution of Si by Al and, simultaneously, filling of the interstitial sites by a
cation M. It has the general formula (M)m/zSi12- (m+n)Al(m+n)OnN(16-n) where M is the
interstitial cation with a valence of z.


Fig. 3.7.1.2 . Pseudo-binary phase diagram between -Si3N4 and M2/zO:3AlN showing the region of stability of
the -SiALON phase.
Structural Ceramics Module 7 Nonoxide Structural Ceramics

The  phase is stable only in a limited composition range. A full phase diagram
for -SiALON has to be a quaternary phase diagram involving three cations (Si,
Al, M) and two anions (N, O). However a binary phase diagram may be used to
illustrate the range of stability with the concentration of M. Such binary diagram is
between Si3N4 (m = 0, n= 0) and M2/zO:3AlN (m=2n) and is shown in Fig. 3.7.1.2.
The horizontal (composition) line in this diagram corresponds to m = 2n. In this
phase diagram the -SiALON exists as a eutectoid phase. Its lower 
solubility limit is nearly temperature independent as shown by nearly a vertical line
while the upper solubility limit increases with temperature. The range of solubility
decreases with increase in the size of the interstitial cation. The size of the
interstitial cation also has an effect on the eutectoid temperature – it decreases as
the size of the interstitial cation decreases. It becomes so low for small cations that
the kinetics of decomposition of the  phase becomes very slow and the
SiALON phase is stable down to room temperature. This material is suitable for
practical applications.
The region of stability of the -SiALON expands with decreasing size of the
interstitial cation, M. Thus when M= Nd, the stability region of -SIALON is very
small; in this case the -SiALON decomposes when held around 1400-1500oC. The
stability region is quite large for Y and Yb and so these -SiALONS are stable in
the useful temperature range.
Initially the -SiALON ceramics were fabricated using powders having more
than 90% -Si3N4. These particles provided the nucleation sites for the -SiALON
grains. This produced an equiaxed structure of -SiALON. This material had a high
strength but a low fracture toughness.
The key to produce -SiALON ceramics with elongated grains (to improve the
fracture toughness) is to have very few nuclei for the formation of the -SiALON
in the starting powders and during the heating and forming steps. It has been found
that -SiALON can be produced by starting from -Si3N4 and rare earths in the
starting powders. Thus in those compositions for which the stability of the -
SiALON phase is low, the propensity for the formation of the elongated grains is
more e.g, in the compositions containing Nd. This is because as the phase stability
is low so the driving force for nucleation is high and so very few nuclei form. In the
case of a composition denoted by Yb-1212 (m=1.2, n=1.2), which has a very high
driving force and a low nucleation rate, a two step process, as used for the
e-PG Pathshala Physics Ceramics

Fig. 7.1.1.3. Amount of seed vs. fracture toughness for -SiALON.

formation of glass ceramics, can be used. First the piece is held at low temperature
(1550oC) where the nucleation rate is very low so that only a few nuclei are formed.
Then the piece is heated to 1950oC to form elongated grains from these nuclei.
Even though it is possible to prepare -SiALON from suitable
compositions, using controlled heat treatment, the dependence of composition,
temperature and phase stability on the nucleation rate makes the process difficult to
control. An easier alternative is to use seeds of -SiALON in the starting powders.
Thus -SiALON is first prepared separately and then small amounts of the seeds of
this are used along with the starting powders. When the amount of seeds is small,
elongated grains of -SiALON are obtained. The amount of the elongated grains
and thus the fracture toughness of the material depends on the amount of seed and
can be controlled. A schematic plot of the amount of seed vs. the fracture toughness
is shown in Fig. 7.1.1.3. A maximum fracture toughness of about 11 MNm-3/2 can
be achieved in Y containing -SiALON by optimizing the amount of seed.
Structural Ceramics Module 7 Nonoxide Structural Ceramics

The ceramics described so far including Al2O3, ZrO2, SiC, Si3N4 and SiALONS
have high strengths but a fracture toughness which is far below that of metals and is
inadequate for many structural applications.

5. MAX ceramics

In 1960’s Hans Nowotney et al [1] discovered more than 100 new carbides and
nitrides including Ti3SiC2 and Ti3GeC2.No further interest was shown in these
materials until 1990s when Barsoum and El-Raghy[2] prepared large samples of
Ti3SiC4 and showed that it had unique properties which combined the properties of
metals and ceramics. Thus it had a high electrical and thermal conductivity like
metals and was oxidation resistant and thermal shock resistant like ceramics. Later
they discovered Ti4AlN3 and it became clear that these materials belonged to a
family which can be represented by the formula Mn+1AXn or MAX phases (n = 1, 2
or 3), where M is a transition element, A is an A group element and X is C or N.
The phases corresponding to n = 1, 2 and 3 are represented by 211, 312 and 413
respectively. M can be from group 3 (Sc), group 4 (Ti, Zr, Hf), 5(V, Nb, Ta) or 6
(Cr and Mo). No Max phases are known with transition elements Y or Lu from
group 3 or W from group 6.The A elements and their groups which form the MAX
phases are Cd (group 12), Al, Ga, In, Tl (group 13), Si, Ge, Sn, Pb (group 14), P,
As (group 15) and S 9grop 16).

The MAX ceramics have a layered structure. They have a hexagonal unit cell.
There are two formula units per unit cell. The unit cell consists of M6X octahedra
with layers of A element between them. In the 211 phase , two M6X layers separate
each A layer. In the 312 and the 413 phases the number of M layers separating the
A layers is 3 and 4 respectively.
In addition to the pure MAX phases, the solid solutions between them also exist.
The number of these solid solutions is quite large. The bonds in the MAX phases
are a combination of metallic, covalent and ionic bonds. The M-X is strongly
covalent like that in the MX binaries. The M-d-M-d bonding is metallic. Also the
M-A bonds are relatively weaker than the M-X bonds.
e-PG Pathshala Physics Ceramics
The MAX phases have excellent electrical conductivity with resistivity in the
range of 0.2-0.7 .m at room temperature. Many of the MAX phases are so
called “compensated conductors” in which both electrons and holes are the charge
carriers. They are also good thermal conductors. Their thermal coefficients of
expansion are relatively low in the range of 5 -10 K-1. Several of them have very
low thermoelectric or Seeback coefficients.
The MAX phases oxidize in air. But some of them form an oxide which forms a
protective oxide layer, making them resistant to oxidation. An example is T2AlC
which forms a protective Al2O3 layer on oxidation. This layer also has a good
spalling resistance making this material quite resistant to oxidation.

Most of the MAX phases have near isotropic elastic properties. Their room
temperature moduli are quite high – with Young’s and shear moduli in the range
178-362 and 80-142 GPa respectively. They also have a very low density of the
order of 4-5 g.cm-3, thus imparting them a very high specific stiffness.

Unlike the corresponding binary compounds, the MAX phases can be very
damage tolerant. Thus while TiC is brittle, damage intolerant and nonmachinable,
Ti3SiC is machinable and damage tolerant. The reason for this is the presence of a
high density of mobile dislocations in the MAX phases. The dislocations are basal
plane dislocations which are able to multiply rapidly at room temperature. Howver,
since the slip is confined only to the basal plane, the number of slip systems is less
than 5 – the number needed for good ductility. The result is that the MAX ceramics
are ductile under constrained deformation or at high temperatures but are brittle at
room temperature. The deformation occurs by shear band formation, kink
formation and by delamination.

The MAX ceramics are relatively soft materials. They have a hardness between
2-8 GPa which is higher than that of metals but lower than that of ceramics.

Their room temperature fracture toughness ranges from 5-20 MNm-3/2. They
show an R curve behaviour. The relatively high value of the fracture toughness and
the R curve behaviour is due to the formation of plastically deformable bridging
ligaments and the kink boundaries which arrest cracks.

The Max ceramics undergo a brittle to plastic transition (BPT) at a temperature

above which they are quite ductile even in tension. The BPT temperatures for many
Structural Ceramics Module 7 Nonoxide Structural Ceramics
of the MAX ceramics is found to lie between 1000-1100oC. When loaded above the
BPT temperature in air in tension, they can be deformed by as much as 25 % if
loaded slowly; at high deformation rates they fail in a brittle manner.

The MAX ceramics have an exceptional resistance to thermal shock. Unlike

other ceramics, they do not shatter on quenching from high temperatures – in some
cases their residual flexural strength after quenching is found to be higher.
Another exceptional property of MAX ceramics is their easy machinability.
They can be machined with the conventional high speed tools or even cut by a hack
saw. This is primarily because of their laminated structure.
Powders of Ti3SiC and Ti2AlC are available commercially for about $ 500 per
kg which makes them quite expensive. They can be sintered in a pressureless
manner to high density. Despite the high cost of powders, the ability to do
pressureless sintering and to be able to machine to close tolerances may make these
materials find more and more applications as the cost of the powders drops as the
demand increases.

6. Summary

Silicon carbide (SiC), silicon nitride (Si3N4) and SiALONs are the nonoxide
structural ceramics which have been most widely studies and used. Two major
polymorphs of SiC are -SiC which has a wurtzite structure and -SiC which has a
zinc blende structure. The silicon carbide bodies are fabricated either by reaction
bonding or by sintering of ultra fine powder of silicon carbide with some dopants.
In reaction bonding a green body is made by compacting the SiC powder with
carbon and the body is infiltrated with liquid silicon which reacts with carbon
forming -SiC which bonds the preexisting SiC grains. In the second route, dopants
such as iron, lithium and magnesium are used in addition to additives carbon and
boron. Carbon increases the concentration of vacancies and removes the oxide film
at the grain boundary, thus helping in sintering.
e-PG Pathshala Physics Ceramics
Silicon carbide has a very high thermal shock resistance and can be used to very
high temperatures, up to 1750oC under certain conditions, in air and to nearly its
decomposition temperature in the inert atmospheres.
The silicon nitride powders are prepared commercially by the direct nitridation
of silicon. Other methods are carbothermal reduction of silica followed by
nitridation, by silicon imide decomposition and gas phase synthesis using silicon
tetrachloride and ammonia.

The silicon nitride bodies are prepared by several methods. In reaction sintering,
a compact made from silicon powder is heated in a nitrogen atmosphere. About
80% density is achieved. In gas pressure sintering, a high pressure of nitrogen is
used during sintering. Silicon nitride can also be sintered by liquid phase sintering
using additives such as Y2O3 and MgO. Hot pressed silicon nitride is made by hot
pressing of bodies made of silicon nitride powder and some additives. Very high
density and strengths can be achieved. For complicated shapes hot isostatic
pressing is used.
The silicon nitride microstructure has been developed over the years to give
interlocking elongated grains, a microstructure responsible for the very high
toughness of this material.
SiALONS are the solid solutions of Si3N4 in which part of the silicon is
replaced by aluminium and simultaneously part of the nitrogen is replaced by
oxygen to maintain the charge balance. Three types of SiALONS can be identified
which are isostructural with -Si3N4, -Si3N4 and with silicon oxynitride
respectively. Most common are the -SiALONS which have the general formula
Si6-2AlzOzN8-z. The -SiALONS have excellent toughness but their hardness which
is 14-16 GPa is low. The -SiALON have a higher hardness of 22 GPa. This comes
from their longer stacking sequence (ABCD as compared to AB for the  variety).
Such a structure provides a higher resistance to dislocation motion.
The -SiALON materials produced earlier had a microstructure of fine
equiaxed grains. Consequently, the material had a low toughness. Over the years,
progress has been made to produce a microstructure with interlocking, elongated
grains. This has resulted in -SiALON material of high fracture toughness. This is
accomplished by having very few nuclei for the formation of the -SiALON in the
Structural Ceramics Module 7 Nonoxide Structural Ceramics
starting powders and during the heating and forming steps. Another route is to use
separately prepared seeds of -SiALON in the starting powders.
MAX ceramics belong to a family which can be represented by the formula
Mn+1AXn (n = 1, 2 or 3), where M is a transition element, A is an A group element
and X is C or N. The MAX ceramics have a layered structure. They have a
hexagonal unit cell. There are two formula units per unit cell. The unit cell consists
of M6X octahedra with layers of A element between them. In the 211 phase , two
M6X layers separate each A layer. In the 312 and the 413 phases the number of M
layers separating the A layers is 3 and 4 respectively. These materials have unique
properties which combine the properties of metals and ceramics. Thus they have a
high electrical and thermal conductivity like metals and oxidation resistance and
thermal shock resistance like ceramics. Their room temperature moduli are quite
high – with Young’s and shear moduli in the range 178-362 and 80-142 GPa
respectively. They also have a very low density of the order of 4-5 g.cm-3, thus
imparting them a very high specific stiffness. These ceramics are also machinable
and damage tolerant. This is due to the presence of a high density of mobile
dislocations in the basal plane. However, as the slip is confined to the basal plane –
they do not have the minimum number of slip systems (5) for polycrystalline
ductility. The MAX ceramics are ductile under constrained deformation or at high
temperatures but are brittle at room temperature. The deformation occurs by shear
band formation, kink formation and by delamination. Their room temperature
fracture toughness ranges from 5-20 MNm-3/2. They show an R curve behaviour




Further reading

1. Nowotney, H.,(1971) Progress in Solid State Chem. 5: pp. 27.

2. Barsoum, M.W. and T. El-Raghy,(79) J. Am. Ceram. Soc. 1996: pp. 1953.