CERAMIC INDUSTRY- CH 552

Lesson –2 (Technical Ceramics)

Professor B. S. B. Karunaratne

1
 Engineering Ceramics
• As mentioned in Lesson 1, the
new ceramics are called
Advanced ceramics or
engineering ceramics or
Technical ceramics.

• New Ceramics are used in a

wide range of technologies
such as ceramic
superconductors,
semiconductors, piezoelectric
ceramics, bio-ceramics, etc.
During this lecture series we
shall study most of these
materials.
2
 Physical properties of some useful engineering materials

Material Density Melting Max Hard- Elastic Linear Thermal

(:103) Temp. Working ness Modulus Expan- Conduc-
(kg/m3) (approx) Temp. (MOHS) Y sivity tivity
(oC) (oC) (GPa) (10-6K-1) (Wm-1K-1)
Rubber 0.910 300 50 ~1 220 0.15

Nylon 1.150 150 50 1-2 2.8 100 0.25

Wood 0.650 50 ~1 12 0.15

Aluminium 2.7 630 300 2-2.9 69 25 201

Iron 7.87 1535 500 4-5 197 12 75

Ni-based 8.23 1300 700 4-5 210 10 20
Alloys
Co-based 9.13 1330- 700 8-9 220 15 25
alloys 1410
3
Material Density Melting Max Hard- Elastic Linear Thermal
(:103) Temp. Working ness Modulus Expan- Conduc-
(kg/m3) (approx) Temp. (MOHS) Y sivity tivity
(oC) (oC) (GPa) (10-6K-1) (Wm-1K-1)

Magnesia 3.75 2800 1000 4-5 207 12 4.9

(MgO)
Alumina - 3.95 2050 1200 9-10 380 7.4 10
(Al2O3) - 3.47
2-9Glass 2.5 1600 900 7-8 100 2-9 0.005
Ceramics
Zirconia 5.8 2770 1000 7-8 138 13.5 1.7
(ZrO2)
Silicon 3.17 2650 1300 9-10 414 4.0 21-23
Carbide (sublim-
(SiC) ation)
Silicon 3.19 1900 1300 9-10 304 3.0 9-30
nitride (sublim-
(Si3N4) ation)
Diamond 3.52 10 1035 Very Very 4
small small
New Ceramics: (Categories)
(1) Pure Oxide Ceramics:
Alumina(Al2O3) , Magnesia(MgO), Zirconia(ZrO2) ,Thoria(ThO2) ,
Beryllia(BeO), Titania(TiO2)

These oxide ceramics have a high state of uniformity with

outstanding properties.

(2) Electro-ceramics
(a) Electrical Insulators: Electrical porcelains
(Clay based ceramics)
(b) Conducting Ceramics: SiC, MoSi2, ZrO2

Question:
What are the possible applications of conducting ceramics where the metallic
conductors would not be able to perform.
5
Answer: High temperature Heating Elements for furnaces and kilns. Due to
oxidation and relatively low melting temperature of many metallic heating
elements, The maximum attainable temperature of metallic heating is limited to
about 1200 oC.
Observe carefully the ceramic heating elements shown below and realize the way
of obtaining the required resistance for the heating. You know that for heating you
need certain resistance.

SiC elements
– Up to about 1600oC MoSi2 elements different configurations - Up to about 1800oC
6
 Electro- optics devices
These materials can transform electrical information to
optical information.

Examples: Lithium Niobate (LiNbO3) and Lanthanum

modified lead zirconate

(PbLa) (ZrTi) O3 or PLZT

Electrical signal PLTZ Optical Function (change in

refractive inde

Question:
What are the possible engineering applications?
7
Answer: Fibre optics communications

(3) Superconducting ceramics (Examples)

YBa2Cu3O(T
7-
c = 90 K = -183 0C )

Tl-Ba-Ca-Cu-O (Tc = 125 K = -148 0C )

. .. (Tc= 153 K = -120 0C )

Hg-Ba-Ca-Cu-O etc
• Below the critical temperature Tc
superconducting materials show no
resistance to electrical conductivity.

• Additionally superconductors show

Meissner effect . The Meissner effect is the
expulsion of a magnetic field from a Variation of electrical resistivity ( )
superconductor. with temperature
8
As a result of expulsion of the magnetic field, floating or lavation of a
magnet or visa versa will occur. This levitation or floating can be
observed due to a ceramic superconductor when cooled down to the
liquid nitrogen temperature, about 90 K.

Magnet
YBa2Cu3O7-
In liquid nitrogen

Expulsion of a
magnetic field
Question:
The critical temperature of ceramic superconductors is very high
compared to that of metallic superconductors.
What are the possible applications of ceramic superconductors? 9
Answer: (See slides from 10 to 12
Applications: No Joule heating and therefore high currents are
possible through ceramic superconductors. As a result high
efficiency( high magnetic fields, etc.) can be achieved in many
electrical applications and speedy data transmission in computers. .

Power Transmission,
Strong electro magnets,
Medical Applications - Magnetic Resonance Imaging (MRI)

10
 Here's what an MRI
looks like!

A test that takes pictures of the soft tissues in the body.

The pictures are clearer than x-rays.
11
 Other applications: Motors, Dynamos, Levitated trains, etc.

High-speed trains of the future that will be levitated A MagLev train operated between
by superconducting magnets will be even faster than Birmingham International Railway Station
the TGV in France (shown here). and Birmingham International Airport.

12
(4) Magnetic ceramics
A large number of compositions have been developed.
They form the basis of magnetic memory units in large
computers and other memory devices.
Ferrites (MFe2O4 ,where M= Ni, Mn, Zn, Cu, Co or a mixture)

(5) Ceramic Nitrides

AlN, Si3N4, Si-Al-O-N (sialon), BN (Boron Nitride), TiN
(6) Ceramic Carbides
SiC, B4C (Boron Carbide), TiC
(7) Nuclear Materials
These are based on UO2. UO2 has the unique ability to
maintain its properties after long use in nuclear reactors.

13
Ceramics of major interest for high
technological applications

Al2O3, ZrO2, TiO2, BeO, Si3N4, SiAlON, BN, TiN, SiC, B4C

Alumina Ceramics
Al2O3 Aluminium Oxide
E ~380 GPa
MT ~20500 C

The O2- anions are arranged in nearly hexagonal close-

packing(HCP).

Question:
What are the possible applications of alumina ceramics?
14
Answer: (See slides from 15 to 17 )
Applications:
(1) Car spark plug insulators-
(Electrical Insulating property and high
mechanical strength against spark
corrosion).

(2) Microcircuit substrates in Electronics Industry

Al2O3 + 2.5% SiO2 , 0.75% MgO, 0.25% CaO sintered at 15500C

15
(3) Transparent Lamp envelopes (High Intensity Na-lamps)
Al2O3 + 0.25% MgO sintered in H2 at 19000C (low porosity)

16
(4) Wear parts (seals and valves) and cutting tools

Engine Seal Combustor Turbine Nozzle

Oil Pump Rotor Ring

17
(5) Composites
Al2O3 30% SiC whiskers hot-pressed at 18000C.

(6) High temperature cements.

Synthesis

Aluminium oxide(Al2O3) occurs naturally as the mineral

corundum. Gem quality crystals are known as ruby and
sapphire. Al2O3 powder is produced in large quantities from the
mineral bauxite by the Bayer process.
 Zirconia Ceramics (ZrO2)
ZrO2 exhibits three well defined polymorphs.
(I) monoclinic (ii) tetragonal (iii) cubic phases
The monoclinic is stable up to about 11100 C where it transforms
to the tetragonal phase which is stable up to 23700 C. Cubic
phase exists up to the melting point of 26800 C.
Monoclinic Tetragonal Cubic

a= 51.56 nm a= 50.94 nm a= 51.24 nm

b= 51.91 nm c= 51.77 nm
c= 53.04 nm
Angle = 98.90

Question:
Try to calculate the density of above polymorphs.
19
Answer:

Monoclinic Tetragonal Cubic

a= 51.56 nm a= 50.94 nm a= 51.24 nm

b= 51.91 nm c= 51.77 nm
c= 53.04 nm
Angle = 98.90
Density (kg m-3)
5830 6100 (calculated) 6090 (calculated)

Question:
Calculate the volume change due to the above transformations.
20
 Answer: Tetragonal Monoclinic
• Transformation is accompanied by a large volume change about (4-
5%) to cause fracture or cracking. Ceramic body becomes weaker.
• This transformation can be avoided by adding a small amount of MgO,
CaO, Y2O3. Material will stabilise in the cubic form.

Yttria-stabilized zirconia ceramics are known as YSZ.

• By doping zirconia (ZrO2 ) with Yttria (Y2O3,) some Zr4+ ions are replaced by
Y3+ ions so that oxygen vacancies are created. You may recall that this
resulting structure is imperfect or defective and can show interesting
properties compared to the un defective ZrO2 .

Question:
What are the possible applications of zirconia ceramics?
21
 Answer: Applications
(1) Cutting tool tips and Abrasive wheels

(2) Kitchen knives, blades for paper industry, surgical

instruments- corrosion resistance Hair salons- Clipper blades

Think about the advantages of ceramic cutting tools

over the traditional metal tools. 22
 Applications: …….
(3) Seals and valves in chemical and slurry pumps.
Tetragonal Zirconia polycrystalline (TZP)– commercially available.

(4) Automotive engine parts-

in particular in the diesel engine.

23
Applications: …….
(5) Refractory materials
(6) ZrO2 refractory fibres
(7) Thermal barrier coatings

Ceramic coated turbine blades

Thermal spray coatings on turbine blades increase the

efficiency of modern airplane engines.
Valves made from advanced ceramics are setting
new standards in engine construction.
24
 Applications: …….

(8) Yttria Stabilized Zirconia(YSZ)

Is used as a solid electrolyte in fuel cells-
for Energy generation

Fuel cell
(9) Oxygen monitoring devices, oxygen
sensors, control of O2 in steel making.

• As we mentioned earlier by doping ZrO2 with Yttria, some

Zr4+ ions are replaced by Y3+ ions so that oxygen vacancies
are created. We know that the presence of vacancies
allows oxygen ions ( O2- ) to diffuse fast in ZrO2. This will
result in oxygen ion conduction and is used for measuring
oxygen concentration. This occurs especially at high
temperatures over 650°C. Oxygen sensor
25
(10) Ceramic colours.

Colouring agents based on Zirconia are widely used in

traditional ceramic industry (tiles, tableware, sanitary ware
etc.).
 Applications: …….

Gemstone Zirconia -single crystals Colours from different

dopants; e.g: Pink Er2O3, Eu2O2, Ho2O3

Synthesis:
Zirconia is produced from zircon

(Large deposits are available in Sri Lanka-coastal areas)

750oC
ZrSiO4 + 2NaOH / KOH Zr(OH)4 + Na or K Silicates

Zirconia is also produced from the naturally occurring zirconium oxide

mineral baddeleyite.

27
Synthesis of TiO2
Ilmenite (FeTiO3) + coal 1200 °C TiO2 + Fe +CO

(Ilmenite- Large deposits are available in Sri Lanka-coastal area

• Heating Ilmenite with coal a mixture of

Fe (iron) and rutile (TiO2) is obtained.
• To separate rutile form coal treat with
chemicals to convert Fe Into rust.
• Then, rust and rutile are separated
using a wet cyclone.
• Last traces of rust are removed using
acid leaching.
This contains more than 93 % rutile. Wet cyclone.
Ti metal
Extraction of Ti
TiO2 + 2 Cl2 + 2 C ~ 900ºC TiCl4 (g)+ 2 CO

Other metallic low- volatile chloride ( Mg , Fe) are

separated by condensation and fractional distillation to
obtain extremely pure liquid TiCl4.
TiCl4(g) + 2Mg(l) 900 °C Ti(s) + MgCl2(g)

Ar- atmosphere
Synthesis method of anatase (lower density form)

• Hydrothermal method using amorphous TiO2,equeous

TiCl3, TiCl4 or TiOCl2
TiCl3(aq) + NH4OH (aq) Ti(OH)2 200 °C TiO2

TiCl4 + H2O2 = Ti(O2)Cl2 + 2HCl

2Ti(O2)Cl2 + 2H2O = TiO2 + 4HCl + O2

• Sol-gel method using titanium alkoxides
Key advantage is possibility of controlling their
microstructure and homogeneity
TiCl4 + 4 (CH3)2CHOH Ti{OCH(CH3)2}4 + 4 HCl

Ti(OC3H7)4 + 4 H2O Ti(OH)4 + 4 C3H7OH

Ti(OH)4 + Ti(OH)4 Ti2O(OH)6 + H2O

Ti2O(OH)6 2 TiO2 + 3 H2O (nano particles)

Scanning electron microscopy (SEM) of Nano
TiO2 particles (diameter <10nm) have an evenly
layer film, solid adhesion to the substrate,
densely.
Applications of titania (TiO2)

Multifunctional
TiO2 Nanofiber
Membrane for
Water Treatment
Applications of titania (TiO2)
Synthesis of titania nanotubes

Wet synthesis methods are used to synthesise the desired nanostructures. They can
be used for photocatalysts in solar cells.
Applications of titania (TiO2) Nano TiO2 air purifier(Home
Type

Nano-TiO2 (Titanium Dioxide)

GENS

photocatalyst nano-coating destroys

viruses, bacteria, odor, harmful gases,
allergens, air / water pollutants and
protects treated surfaces against growth of
algae, fungus, mold and mildew
Key Features:
TOTAL protection against
harmful pollutants and
pathogens 1.Nano TiO2
disinfection technology: With
over 95% disinfection and
TVOC (Total Volatile Organic
Compoundes)

Main Product:
Photocatalyst Nano-TiO2 Coatings
 Non Oxide Ceramics
Silicon Nitride ceramic- Si3N4 (1960's)

3Si + 2N2  Si3N4

Question :
What is the bonding type of Silicon Nitride - Si3N4 ?
Draw a schematic diagram of the structural unit to show
how Si atom is bonded to N atoms.
37
 Answer : • The structure is formed from a network of SiN4 tetrahedral
units with each having a central Si atom surrounded by four
N atoms at equal distance.

• Silicon nitride occurs in three polymorphic structures, two

hexagonal α- and β-Si3N4 modifications and a cubic (γ-
Si3N4 ) high-pressure/high temperature modification with
spinel structure.
• We shall discuss the two main crystalline structures.
Structure (Two forms -Both Hexagonal)
α – Si3N4  - Si3N4

The tetrahedra are linked together into a rigid three dimensional framework by
sharing corners. The Si-N bonds are covalent and short and they are very
strong. This strong, rigid, compact structure is responsible for many of the
important properties of Si3N4. 38
We shall now study the ways of formation of the unit cells structure by joining
SiN4 tetrahedral units together.
• Si atoms are represented by circles and N atoms represented by
triangles.
• The A layer of atoms are represented by filled circles and filled triangles.

• The B layer of atoms are represented by open circles and open triangles.

A-layer

B-layer

a 39
The structures are formed from the network of SiN4 tetrahedral to result in  -
Si3N4 (ABABAB…..) and α - Si3N4 (ABCDABCD…)

A B Layer C D Layer

A B Layer A B Layer
 - Si3N4 a = 0.7608 nm, α - Si3N4 a = 0.7753 nm,
c = 0.2911 nm c = 0.5617 nm
Question: Study carefully
the staking of atoms in 
structure and in the 
structure.

What are the differences?

List them.

How many Si atoms and

how many N atoms are in

(i) α - Si3N4 unit cell and

(ii) in  - Si3N4 unit cell?

41
Answer:

• As a result of above staking, the c-axis of the  unit cell (Si12N16) is

nearly twice that of the  unit cell (Si6N8).

• The other important structural property of this stacking is the

presence of a continuous c-axis channels ( one larger channel and
three smaller channels) in the  unit cell structure.

• In contrast the  unit cell structure has two large interstitial sites
(cages) at coordinates 2/3, 1/3, 3/8 and 1/3, 2/3, 7/8 and two smaller
channels.

• The presence of this two cages are important in designing novel

materials by stuffing (doping) these two cages with appropriate
cations to give specific properties.
• The phase transition from α to β occurs between the temperatures of
1400 and 1600°C, depending on impurity (eg. alumina) concentration.

• Additions of alumina reduce the activation energy of the phase

transformation.

Silicon Nitride based structural ceramics exhibit attractive properties.

• High strength, stiffness
• Good wear and corrosion resistance.
Therefore these ceramics are considered as very appropriate materials for
many special engineering applications.

Think about some applications based on the properties.

Synthesis of silicon nitride:

(1) 3Si(s) + 2N2(g) Si3N4(s) Heat (at ~1400°C)

• Melting point of silicon (1414°C), makes the importance of temperature control during
the direct nitridation process.

• The kinetics of the direct nitridation reaction can be improved through the use of
catalysts.

• The most substantial impurity in silicon is iron, which is introduced in the milling
process. The iron impurity acts to catalyze the nitriding reaction by removal of the
SiO2 film formed on each silicon particle.
(N2 gas has a small amount of impurity oxygen and it forms a thin layer of
SiO2 film on each silicon particle). Other Possible catalysts CaF2 or BaF2
(2) Carbothermal reduction and nitridation

3SiO2 + 6C + 2N2 + Heat α-Si3N4 + 6CO

(at 1450-1500°C)

The carbothermal reduction process can be divided into three steps:

• Preparation of the raw material
• Reaction
• Carbon removal

Reaction of finely dispersed high-purity silica and carbon in nitrogen flow begins at
approximately 1250°C, and effective synthesis of α-silicon nitride was carried out
at 1500–1550°C.

(3) 3SiCl4 + 4NH3 Si3N4 + 12HCl - Very pure silicon nitride can be produce,
but small quantities.
Si3N4 -nano-products

Preparation of high-purity α-Si3N4 nano-powder

by precursor-carbothermal reduction and
nitridation.

HNO3 and CO(NH2)2 were used as reaction raw

materials, C6H12O6·H2O as carbon source and
SiO2 as silicon source.

Synthesis of α-Si3N4 nanowires by sol–gel route

Silicon nitride (Si3 N4) nanowires have been prepared by carbothermal reduction followed by
the nitridation (CTRN) of silica gel containing ultrafine excess carbon obtained by the
decomposition of dextrose over the temperature range of 1200–1350 °C. The most likely
reactions are
Different types of Silicon Nitrides
(1) Reaction Bonded silicon nitride (1960's)
70-80% dense
(1359OC) 3Si + 2N2  Si3N4  - Si3N4
(2) Pressure less sintered Si3N4

Since Silicon Nitrides is a strong covalent solid Self diffusion is very

low and solid state sintering is difficult. In order to improve the
sintering, sintering additives such as a metal oxide MgO or Y2O3 is
added.

-Si3N4 + 10 % MgO is add as a sintering aid

MgO reacts with surface oxide layer of the  - Si3N4

and forms a silicate liquid at the sintering temperature and
promotes liquid phase sintering.
Now we shall try to understand the sintering mechanism.
 - Si3N4 particle with SiO2 surface layer.
N2 gas has a small amount of impurity
oxygen and it forms a thin layer of SiO2 film
on each silicon particle).

• MgO reacts with surface oxide layer and forms a silicate liquid at the
sintering temperature.  - Si3N4 particles dissolved in this liquid and re-
precipitate as  - Si3N4 particles.

• The resulting microstructure is dense  - Si3N4 + glassy/crystalline grain

junctions and boundaries. (See the next few slides regarding this
microstructure). This sintering mechanism is known as liquid phase
sintering.

• We shall learn more about sintering mechanisms later.

Secondary electron SEM image of a plasma-etched polished surface,
showing dark  -Si3N4 grains and a bright(white), continuous intergranular
glassy phase.
 1 m

TEM showing Intergranular glassy at junctions- appear dark in Si3N4

High-resolution TEM
(HRTEM) image of an
amorphous triple-
junction phase (TP),

Grain-boundary film
and an amorphous
inter-granular grain-
boundary film (IGF)
between two
crystalline Si3N4
grains (bearing the
characteristic lattice
fringes-straight
parallel lines represent
atomic planes) atomic
structure. Thin IGF is
about 10-20 nm. Lattice fringes represent
atomic planes 51
HRTEM image of an
amorphous grain-boundary Parallel lattice fringes
Represent atomic planes
glassy film between two
crystalline grains bearing the
characteristic lattice fringes.
We know that sintering
additives are responsible for
the formation of this grain
boundary classy phase.

This grain-boundary glassy film starts softening (melting) at high temperature and
affects adversely the properties such as fracture toughness, strength, creep
resistance and oxidation resistance. Therefore, scientist considered forming
techniques without or with a small amount of sintering additives. We shall now
discuss such techniques. (Hot Pressing, Hot Isostatic Pressing, etc.)
 (3) Hot-pressed Si3N4
 - Si3N4 + 5% MgO (Less amount of additives)
hot-pressed in graphite die 1700o Liquid phase sintering
Fully dense Si3N4 + small glassy grain boundaries

Pressure

Heat

Heat

Simultaneous application of pressure and heat to a 'green' component. Pressure is applied to the heated
component along a single axis. A nitrogen atmosphere is required to prevent the component reacting
with air,
Heat can be applied directly (induction or resistance heating) or indirectly (convection or radiation).
(4) Hot-Isostatically Pressed (Pressing from all the direction)

Si3N4 (1980's) - 1700oC - 2000oC

2000 Atmospheric pressure.
Dense high grade Si3N4

Cold Isostatic
Normal Pressing (CIP)
UNIAXIAL Cold-Room Dense Si3N4 + no glassy grain
PRESSING Temperature junctions and boundaries
HRTEM image showing absence of glassy film between two
crystalline grains in HIPed materials.
(5) Gas Pressure Sintering(GPS)

(6) Spark Plasma Sintering (SPS)

The above two techniques are mainly used to fabricate nono ceramics.
 Si-Al-O-N (Sialon) Ceramics (1970)

Mainly sialon exists in two polymorphic forms, -sialon and -sialon.

-sialon is obtained by simultaneous substitution of Al for Si, and O for N in  -Si3N4,
Note that the net charge neutrality remains unchanged.

• The relationship between that of sialon and Si3N4 is similar to that between brass
and pure copper. In the case of brass, copper atoms are replaced by zinc to give a
better and stronger alloy than the mother metal.

• In the case of sialon, there is substitution for Si by Al with corresponding atomic

replacement of N by O, to satisfy valency requirements. The resulting 'solution'
(Sialon) has superior properties to the original pure solvent (silicon nitride).

• Salons are ceramic alloys based on the elements silicon (Si), aluminium (Al), oxygen
(O) and nitrogen (N) and were developed in the 1970s to solve the problem of silicon
nitride (Si3N4) being difficult to fabricate.
57
 • We see that simultaneous substitution of Al for Si and O for N in  -Si3N4,
- sialon is obtained and the net charge neutrality remains unchanged.

• Suppose we substitute two Al atom for two Si atoms, then we have to substitute
two N atom for two O atoms to maintain the charge neutrality. The resulting -
Sialon formula is Si6-2Al2O2N8-2 ( Si4Al2O2N6)

• Question (i): Suppose we substitute three Al atom for three Si atoms, then we
have to substitute three N atom for three O atoms to maintain the charge
neutrality. Write down the resulting formula.

• Question (ii) : Suppose we substitute Z number of Al atom for Z number Si

atoms, then we have to substitute Z number N atom for Z number O atoms to
maintain the charge neutrality.
What is the resulting -Sialon general formula interns of Z?
 Answer (ii):
The general formula of -Sialon is Si6-ZAlZOZN8-Z ; z- Al substitution level.
z value can be varied continuously from 0 to 4.2 as shown in the composition
diagram. Z= 4.2 is the maximum substitution level of Al and O in Si3N4. .

• You can see that in order to

Produce -Sialon you need the
main ingredients SiO2, Al2O3, and
AlN in addition to the parent
material Si3N4. These chemicals
appear in the corners of the
composition diagram.

• By changing Z vale from zero to

4.2 we can obtain a series of -
Sialon Ceramics. You can see that
Z=0 is the Si3N4. corner.
Z= 0 Z= 4.2
The chemical replacement is one of changing Si-N bonds for Al-O
bonds. The bond lengths are about the same for the two cases but the Al-
O bond strength is significantly higher than that of Si-N.

In sialon the Al is co-ordinated as AlO4 and not as AlO6 as in alumina

(Al2O3). Therefore, in Sialon the Al-O bond strength is 50% stronger
than in Al2O3. Thus Sialons intrinsically have better properties than both
Si3N4 and Al2O3.

Properties
low thermal expansion
High strength, hardness.
High thermal shock resistance.
Synthesis: ( -sialon)

Si3N4 + Al2O3 + ALN + SiO2 + N2 (1800 K ) ( -sialon)

Question : Balance the above chemical equation to produce  -sialons with

different Z values. For example Z=1 sialon or Z= 4.

Synthesis: Carbothermal reduction and nitridation

3(Al2Si2O5(OH)4 ) (Kaolin-China clay ) + 15C (graphite )+ 5N2 (1800 K )

( -sialon) 2 Si3Al3O3N5 + 15CO + 6H2O

Question : What is the Z value of the above sialon? How can you produce Z=1
and Z= 4 from carbothermal reduction and nitridation reaction. Hint: You need to
add some chemicals(Oxides) to control the required Al and Si levels. What are
these chemicals? 61
The β-SiAlONs produced using yttria as a sintering aid. When
sintered above 1700°C elongated hexagonal shaped β-
SiAlON grains are precipitated and grow in the oxynitride
liquid phase formed from the sintering additives such as yttria,
alumina, silica and aluminium nitride. Subsequently, on
cooling the liquid phase forms a refractory intergranular glass.
This material, with its elongated β grains, is characterised by Polycrystalline microstructure of
high strength and toughness.  -sialons with very low grain-
boundary residue. The average
The fine beta-sialon (β) grains surround small grain size is about 1 m.
pockets of glass (g).
62
-Sialon is an another solid solution based on -Si3N4

We have seen that in -Si3N4 structure, there are two interstitial sites
per unit cell (See the two red marked cages in the next slide).
Stuffing suitable metal cations in the interstitial sites,
more Si atoms can be replaced by Al atoms. Therefore the general
formula of -Sialon is,

MV+ m/v Si12-(m+n) Alm+n On N16-n

where v is the valency of the metal cation M. The metal cation should have the
correct ionic radius to fit into the interstitial sites.
( See the next slide)
Radius  1 Å
M = Y, Ca, and some Rare Earth Elements
 A B Layer C D Layer

A B Layer A B Layer

 - Si3N4 a = 0.76 nm, c =0.29 nm α – Si3N4 a = 0.78 nm, c =0.56 nm

M = Y, Ca, and some Rare Earth Elements
 -Sialon Composition

The β -sialons are expressed by the general formula Si6-zAlzOzN8-z. We know

that we need 4 chemical compounds to synthesize beta sialon and a square
figure can be used to represent the composition diagram.

However, for  -sialons we need additional cations. We can add this cation by
oxide and nitride forms. Therefore, we can show the composition diagram by a
prism. These chemical compounds are represented at the corners. This prism is
called the Janecke Prism.

In -Sialons formula we have only one variable, Z. Hence a line representing Z

variation for Al substitution. Where as in -Sialon formula we have two
variables, m and n.
Hence the -Sialon the phase field is represented by a plane. By changing m
and n we can prepare unlimited number of -Sialons.
 The Janecke Prism showing the β line and the phase field of ά -sialon
UNLIKE in the case of -Sialons, the phase field of -Sialon is represented by a plane.

Question: Suppose you wish to prepare Y--Sialon having m = 3 and n = 1.

Mark this composition on the Janecke Prism diagram and write down the formula.
Answer: YSi8 Al4ON15

-Sialon Microstructure
• In principle you can make  sialon
ceramics composites without any
residual glass. You can exactly add
the amount of stabilizing cations just
sufficient for forming - sialon.

• So the glassy liquid at sintering

temperature will be consumed to
form - sialon and ceramic will form α-Sialon with very low grain-
without residual glass. boundary residue. We will
• This is called reactive liquid phase discuss more on this under
sintering or transient liquid phase sintering mechanisms.
sintering.
 Different types of Si-Al-O-N (Sialon)

 - sialon

Crystal Structure types Composites of  and 

 - sialon
 Composites of  and 
Materials Preparation

Si3N4 + AIN + Al2O3 + SiO2 + MO

Ball milled, sieved and dried

Sintering

M = Y, Ca, and
some Rare
Earth
Elements Elongated β-sialon (Black) α-sialon matrix (Gray)
 Self reinforce microstructure

Elongated β-sialon in α-sialon matrix with different α/β ratio by adjusting composition
70
• Doping appropriate
elements(Yb, Sm, Eu, etc.) to
form α-sialon, functional
properties such as
semiconductor, magnetic,
phospher, etc. can be obtained.

• Warm-white light-emitting
diode with yellowish orange
SiAlON ceramic phosphor

CaEuSiAlON phosphor material

and converts blue light into
white light
 Silicon Carbide SiC (1965)
Si + C   SiC

Two polymorphic forms  and  SiC Structures

 -SiC – HCP,
 SiC - Cubic Close-packed Zinc blend structure

• Silicon carbide has been the most widely used

material as a structural ceramic.
• Characteristics such as relatively low thermal
expansion, high specific modulus, high thermal
conductivity, hardness, resistance to abrasion and
corrosion, and most importantly, the
maintenance of elastic resistance at temperatures
up to 1650 ° C, have led to a wide range of uses.
• First we discuss the functional (electronic)
applications.
72
Applications- In Electronic Industry
• The Si technology is reaching the material’s theoretical limits and can not
meet all the requirements of the transportation and energy production
industries.
• New semiconductor materials called wide band gap semiconductors, such
as Silicon Carbide(SiC), is a possible material for replacing Silicon.
• As a material, SiC stands between silicon and diamond. The crystal lattice
of SiC is exactly similar to Si and diamond, but exactly half the lattice sites
are filled by Si atoms and remaining lattice sites by C atoms. This shows
SiC having better electronic properties than silicon.

Synthesis:
14000C
SiO2 + 2C SiC + CO2
14000C
(Mullite) 3 Al2O3. 2SiO2 + 6C 2SiC + 3Al2O3 + 4CO 73
 SiC Synthesis:

Silicon Carbide (SiC) is a synthetic mineral most commonly

produced in electrical resistance furnaces, by the Acheson process,
named after the American E.G. Acheson who invented it in 1891. In
an Acheson furnace, a mixture of carbon material (usually petroleum
coke) and a silica or quartz sand is reacted chemically at high
temperatures in the range of 1700 – 2500°C resulting in the formation
of α-SiC following the main reaction:

14000C
SiO2 + 2C SiC + CO2
TiC
• Black Powder,
• Sp. Density= 4.93,
• Melting temp.= 31600C, Very hard
material; Mohs scale 9.5 Crystal
Structure-Cubic
• Similar to the NaCl structure.
• Titanium carbide's main uses are in
the production of wear-resistant
instruments, slicing instruments,
abrasive steel bearings, wear-
resistant tools, improving
conductivity, and as a nucleating
agent.
 TiN
•Appearance:
•Coating of golden color
•Density: 5.40 g/cm3
•Melting point: 2930 °C
•Crystal structure: Cubic Titanium Nitride Powder

Question 15: Write down the chemical reactions corresponding to

the synthesis of TiC and TiN from TiO2.
 Applications collectively for
Si3N4, Sialon and SiC ceramics
Heat engines - gas turbine-blades
Piston engines - piston rings and cylinders
Melting temperature of metals super alloys(Ni, Co based alloys) is about
1400o C. However, Creep, oxidation, low high temperature strength are
some of the problems with alloys.
 Therefore metallic Heat engines require water or air cooling.
By using ceramic components, operating temperature of the heat engine can
be increased. Efficiency can be increased.

The maximum service temperature of cast iron is

less than 6000 C, that of steel is less than 5000 C and that of
aluminum alloys is less than 3000 C.
Metal engines suffer from relatively low combustion
efficiencies. 78
Turning alloys using Sialon Cutting Tips.
No coolant is used.

79
Other applications:
Extrusion and wire drawing dies ,
Nozzles, seals , Sand blasting nozzles,
Metallurgical and Chemical industries,
Extrusion and
Molten metal containers and pipes)
wire drawing dies
Si3N4 and Sialon bearings

These bearing useful where

lubrication is either limited or not
possible and also where the
temperature is beyond the limit of
metal bearings.
Added Advantages
• High elastic modulus- less deformation of the bearings
• Low density -Less centrifugal force- mr2 –
• less deformation – Hence less friction-Less heating and less
wear and tear-Long life –wind mill bearing applications. 80
Other Applications of Ceramic Materials
1. Ceramic Armour
Military Vehicle (Cars, tanks, helicopters)
armour and personal armour.

The requirements: Light weight and capability to defeat small

arms.
Example: Boron carbide(B4C). Density- 2.4 –2.5 g cm-3.
Optically transparent armour includes pure alumina and
various glasses.
2. Ceramics are used in high powered
laser.
Examples: Cr doped alumina (Ruby),
yttrium aluminum garnet (YAG), non-
oxide ceramics, and some composite
ceramics. 81
Piezoelectric ceramics
• Polarisation occurs in single crystals of some materials
when strain is applied. One side of the crystal derives
a net positive charge and the opposite side derives a
net negative charge.

• This effect is referred to as piezoelectric effect. The

Greek term piezoelectricity translates literally to
pressure electricity.
• Application of pressure results in a measurable
electrical potential. Conversely, application of an
electric field results in a very small amount of
mechanical deformation. 82
Directionality of polarization in a piezoelectric material
Stress

+
+ - + -
-
-
- + - +
+

+
+ - + -

-
Stress
(a) (b) (c) +++++++++++
Stress Piezoelectric
material
-------------

(a) Unstressed material showing no polarization, (b) Stressed

material showing deformation but no polarization, and (c)
Stressed material showing deformation plus polarization.
Application of an alternating Conversely, application of an
force (vibration) results in an AC electric field results in
AC voltage. vibration of the crystal. These
crystal vibration frequencies
are very high and are in the
ultrasound range. Wavelength
of the generated frequency is
related to the thickness of the
crystal.

84
 Piezoelectric materials and applications
Quartz (used to give vibration sources in watch), lithium
sulphate, cadmium sulphide.
• Barium titanate (BaTiO3 ) ,
TiO2 + BaCO3 BaTiO3 + CO2

Multi-layer ceramic capacitors,

Microelectronic discrete capacitors,
Capacitance laminates for printed wiring board,
Embedded capacitance materials,
Insulator rings for high power surge arrestors

• lead zirconate titanate (PZT)

Several types are available (PZT-4, PZT-5A etc.).

Question 12: What are the possible applications of

Piezoelectric materials? 85
 Answer 12: Applications ( Slides 47 and 48)
Uses of piezoelectric ceramics

Transducers in ultrasonic devices

Microphones/ Earphones
Phonograph pickups
Accelerometers
Electronic balances /Strain gauges
Sonar devices,
Ultrasound (US) generators
and detectors for medical scanners, etc..

86
Piezoelectric effect and green energy

• A corridor in Heathrow A wind farm without turbines . Waving

Terminal 3 - an interactive piezoelectric trees produce electricity.
walkway.
• There are 51-tiles
(piezoelectric) array in the
corridor.
• Travellers became a part of the
airport infrastructure by
illuminating coloured lighting
on an adjacent wall with each
footstep, demonstrating that Why not charging your
not a step is wasted. mobile phone while walking
87
Bio-medical applications
Advantages:

* Inert, Non-toxic
*Compatible with bone/tissue
*Capability for bone in growth/adsorption
*Light weight
Applications: Medical and Dental devices
*Bone repair (appetite) - Ca5(OH,F)(PO4)3
*Replacement of joints (Hip) - Al2O3

BEFORE AFTER 88
Bioceramics:
Use of ceramic materials for bone repairs was initiated
by Hulbert and Hench in 1960.

A wide range of ceramic and glass materials are being

used in biomedical applications.

Two types of Bioceramics are available

1. Bioinert ceramics and
2. Bioactive ceramics
1 Bioinert ceramic materials

They are chemically neutral materials and enable

ceramics to preserve their properties after
implantation in the body and thus avoid rejection.

E.g.: Alumina(Al2O3), zirconia(ZrO2), and carbon

2 Bioactive ceramics
• Integrates perfectly into the bony environment.
• Ceramic materials capable of positively
interacting with the surrounding tissues.
• Ability for bone in growth/adsorption

E.g.: Hydroxyapatite (HA) and β-tricalcium

phosphate (β-TCP), Bioactive Glass, etc.
Advantages of Using Ceramics:
* Inert, Non-toxic
* Compatible with bone/tissue
* Capability for bone in growth/adsorption
• Light weight
• Low wear rate leads to long life-times, typically
over 20 years for ceramic
• Generates less polyethylene particulate debris
unlike in polyethylene and metal systems.

• No possible side effects due to metal ion release

when metal implants are used
• Patients recover quicker, which is good for the
patient and more cost-effective for the hospital
A titanium hip prosthesis, with a ceramic head
and polyethylene
acetabular cup,
Ceramic-on-Ceramic
Artificial Joint Systems
• Femoral heads with alumina.
Ceramic acetabular (cup) components

• Ceramic-on-ceramic’ systems have been developed to

eliminate the problems associated with polyethylene and metal
systems.

• Such systems have the lowest wear rate. Ceramic-on-

ceramic system is ideal for younger and more active patients.
Artificial Joint Systems
• The international golfer Jack Nicklaus has a
replacement ceramic hip.

Jack opted for a ceramic-on-

ceramic implant in 1999 as
he wanted a prosthesis that
would suit his active life style.
After his recovery from
surgery he became an public
advocate for hip replacement
surgery.
1. Hydroxyapatite [HAp, Ca.10(PO4).6(OH)2] is one of the
most attractive materials for bone implant due to its
compositional and biological similarity to bone materials.
It has unique biocompatibility feature among phosphate
groups.

2. However, due to lower strength of pure HAp, it has been

difficult to use it as bone implant.
 Hydroxyapatite bone implant cell growth

A human long bone cell growing on the surface of a hydroxyapatite ceramic foam. The
presence of microporosity allows the cell processes to attach more readily
 Ceramic materials for Thermal Protection System
(TPS) of the space shuttle
• One of the most fascinating high-temperature
applications of ceramic materials is the design of
a Thermal Protection System (TPS) for the Space
Shuttle Orbiter.
• As this application is very stimulating we shall
discuss various technical aspects in detail.
• NASA had to overcome a large number of
challenges when they were designing the
Thermal Protection System .

Question 11: What are the required

characteristics properties of the material
for the Thermal Protection System (TPS) ? Winged space shuttle
99
 Answer: Characteristics of requirements
• Low thermal conductivity, with high thermal stability at
elevated temperatures and high resistance against thermal
shock. An appropriate material to meet these requirements
is a ceramic. As such, much of the shuttle was covered with
tiles made out of amorphous silica fibers. These silica tiles
were such poor heat conductors that one could hold a tile
by the edges while it was still red- hot.

Lightweight: A lightweight Thermal Protection System (TPS) was crucial.

Reusable: Previous spacecrafts used ablative heat shields which burned off during re-entry.
By contrast, the reusable shuttle required a reusable thermal protection system.
Compatibility: The TPS had to integrate with other subsystems, such as the cryogenic fuels,
liquid hydrogen, liquid oxygen, etc. NASA decided to bond the Orbiter’s thermal protection
directly to its aluminum skin, which presented an additional challenge of structural integrity
during the launch.
100
Problems with ceramics Remedial Action
1. Brittleness (ceramic 1. Ceramic composites
composites
2. Difficulty Fabrication , 2. New Fabrication , forming
forming and sintering of and sintering methods.
ceramics 3. Improved synthetic
3. Machining is difficult and diamond tools, etc.
expensive
4. Joining- normal welding 4. Research studies to
methods can not be explore novel welding
applied.
techniques.

END
101