Ceramics- Engineering Materials

Outline
T. Udomphol

• Introduction to ceramics
• Structures of ceramics
• Processing of ceramics
• General properties and applications of ceramics
• Engineering ceramics, glass and composites

Suranaree University of Technology October 2007

 Objectives

• Students are required to understand basic structures,

properties and applications of ceramics as one of the most
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important engineering materials.

• Identification and selection of appropriate ceramic
materials for the desirable applications should be made.
• Composite materials are introduced for properties and
applications that cannot be achieved from conventional
materials.

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 References

• Smith, W.F, Hashemi, J., Foundations of material science and

engineering, 4th edition, McGraw-Hill International, ISBN 007-
125690-3.
• Callister Jr., W.D., Fundamentals of materials science and
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engineering, 2001, John Wiley&Sons, Inc., ISBN 0-471-39551-X.

• Hull, D., Clyne, T.W., An introduction to composite materials,
2nd edition, 1996, Cambridge University Press, UK, ISBN 0-512-
38855-4.

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 Chapter 1

Introduction to ceramics
and classifications
Grinding wheel
What is ceramic?
• Inorganic or non-metallic materials
• Primarily Ionic and covalent bonded
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Interesting properties

• Hard and brittle

(depending on type of bonding)
• High melting point (Refractory)
• Wear resistance
• High hot hardness
Cemented carbides

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Classification of ceramics

Ceramics can be divided into various types

Conventional ceramics www.dynacer.com

• Tableware /sanitary ware/ pottery

• Bricks / tiles
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• Glass Refractory
• Refractory
Bioceramics
• Electrical porcelain

Advanced ceramics
• Bioceramics
• Cutting tools
• Semi-conductor, superconductor
• Ferro-magnetic materials Ceramic
cutting tools
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 Chapter 1

Simple ceramic crystal structures

Simple ionic arrangement

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CN = coordinating number
Radius ratio = rcation/ranion
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 Chapter 1

Simple ceramic crystal structures

Cesium chloride (CsCl) crystal structure

+ -
• Simple ionic bonding (equal numbers of Cs and Cl ions).
• CN = 8, radius ratio = 0.94
• Ex: CsCl, CsBr, TlCl, TlBr, AgMg, LiMg, AlNi
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• Similar to BCC in metallic bonding (atomic packing factor = 0.68)

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 Chapter 1

Simple ceramic crystal structures

Example: Predict the coordinating number for the ionic solids CsCl and NaCl.
Use the following ionic radii for the prediction:
Cs+ = 0.170 nm Na+ = 0.102 nm Cl- = 0.181 nm

r (Cs + ) 0.170 nm
The radius ratio for CsCl is −
= = 0.94
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R(Cl ) 0.181 nm
Since this ratio is greater than 0.732, CsCl should
show cubic coordinator (CN = 8)

r ( Na + ) 0.102 nm
The radius ratio for NaCl is
−
= = 0.56
R(Cl ) 0.181 nm
Since this ratio is greater than 0.414, but less than
0.732, NaCl should show octahedral coordinator
(CN = 6)

Suranaree University of Technology October 2007

 Chapter 1

Simple ceramic crystal structures

Example: Calculate the ionic packing for CsCl. Ionic radii are Cs+ = 0.170 nm
and Cl- = 0.181 nm.

3a = 2r + 2 R
Let r = Cs+ and R = Cl-
3a = 2(0.170 nm + 0.181 nm)
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a = 0.405 nm
CsCl ionic packing factor
4
πr 3 (1 Cs + ion) + 43 πr 3 (1 Cl −ion)
= 3
a3
4
πr 3
( 0. 170 nm ) + 4
πr 3
(0.181nm)
= 3 3
(0.405) 3
= 0.68

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 Chapter 1

Simple ceramic crystal structures

Sodium chloride (NaCl) crystal structure

+ -
• Highly ionic bonding (equal numbers of Na and Cl ions).
• CN = 6,
• Radius ratio = 0.56
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• Ex: MgO, CaO

, NiO, FeO

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 Chapter 1

Simple ceramic crystal structures

Interstitial sites in FCC and HCP crystal lattice

• Intersitial atoms (small) fit into empty voids/spaces in the lattice.
• Two types of interstitial types : octahedral and tetrahedral
FCC-Octahedral
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4 octahedral interstitial
sites/ FCC unit cell

FCC-Tetrahedral
8 tetrahedral interstitial
sites/ FCC unit cell
At  14 , 14 , 14  type sites
Note: HCP structure is also close-packed-similar to FCC
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Simple ceramic crystal structures

Interstitial sites in FCC crystal lattice

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 Chapter 1

Simple ceramic crystal structures

Zinc Blend (ZnS) crystal structure

2+ 2-
• Equivalent of 4 Zn and 4 S atoms
• CN= 4, (80% covalent character)
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• Either Zn or S occupies lattice points

of FCC unit cell while the other occupies
haft the tetrahedral sites.
• Ex: CdS, InAs, InSb, ZnSe.

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 Chapter 1

Simple ceramic crystal structures

Calcium Fluoride (CaF2) crystal structure

2+ -
• Consists of 4 Ca and 8 F atoms
• CN= 4, (80% covalent character)
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• Either Ca occupies lattice points of

FCC unit cell while F occupies eight of
the tetrahedral sites.
• Ex: UO2, BaF2, AuAl2.

Note: unoccupied octahedral interstitial UO2 is used as nuclear fuel.

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Simple ceramic crystal structures

Anti fluorite crystal structure

2-
• Consists of anions (O ) occupying
+
4 FCC unit sites and cations (Li )
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occupying 8 tetrahedral sites.

• Ex: Li2O, Na2O, K2O, Mg2Si.

Li O

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Simple ceramic crystal structures

Corundum (Al2O3) crystal structure

• O locating at the lattice sites

of hexagonal close-packed
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unit cell.
• Al occupying 2/3 of
octahedral sites to balance
electrical neutrality
give
some distortion

Note: There are only 2 Al 3+ for 3 O 2-

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Simple ceramic crystal structures

O red, Al blue, Mg yellow;

Spinel (MgAl2O4) crystal structure tetrahedral and octahedral coordination

• Typical for oxides (AB2O4).

• Oxygen ions form an FCC lattice
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• A= metal ion (2+) and B= metal ion

(3+) occupying tetrahedral and
octahedral sites, depending of particular
type of spinel.
• Normally used for non-metallic
magnetic materials, electronic
applications.

som.web.cmu.edu/structures/S060-MgAl2O4_web.jpg

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 Chapter 1

Simple ceramic crystal structures

Perovskite (CaTiO3) crystal structure

• Ca2+ (corners) and O2- (face centre) form and FCC lattice
• Ti4+ locating at octahedral sites at the centre of the unit cell.
• Typical for piezoelectric materials.
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• Ex: SrTiO3, CaZrO3, SrZrO3, LaAlO3

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 Chapter 1

Simple ceramic crystal structures

Carbon and its allotropes

• Graphite

Carbon atoms form layers of strongly
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covalent bonded hexagonal array and

weak secondary bonded across layers.

Anisotropic property- good thermal and
electrical conductivity on the basal plane.

Density 2.26 g/cm3.

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Simple ceramic crystal structures

Carbon and its allotropes

• Diamond

Cubic structure (covalent bond)
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Isotropic

Density 3.51 g/cm3

High thermal conductivity but
very low electrical conductivity
(insulator)

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Simple ceramic crystal structures

Carbon and its allotropes

• Buckminster Fullerene (Bucky ball)

Made up of 12 pentagons and 20 hexagons (look like football)

Contain 60 carbons covalently bonded, therefore C60.
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Possible applications in electronics industries, fuel cells, lubricants and

superconductors.

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 Chapter 1

Simple ceramic crystal structures

Carbon and its allotropes

• Carbon nanotube
•Hexagonal patterns on the tube
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and pentagonal on the end cap.

• 20x stronger than steels (45 GPa).
• Can form ropes, fibres and thin
films
• Applications: chemical sensors,
fibre materials for composites,
electron producing cathode.

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Simple ceramic crystal structures

Silicate structures

• Mainly consist of silicon and oxygen.

• Ex, glass, clay, feldspar, micas.
• Cheap, abundant on earth’s crust.
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• Important for engineering construction materials.

Basic structure
• Strong bonding of Silicate (SiO44-) tetrahedron
• 50% covalent 50% ionic

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Simple ceramic crystal structures

Silicate structures Island, chain and ring structures of silicates

• Strong bonding of silicate (SiO44-)

tetrahedron
• 50% covalent 50% ionic
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• Each oxygen has one electron

available
can bond with other
positive ions.
• Ex: (Mg, Fe)2SiO4.
• Forming chains (MgSiO3)
• Forming rings (SiO32-)
(Be3Al2(SiO3)2)

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Simple ceramic crystal structures

Silicate structures Sheet structure of silicates

• Three corners are bonded together with other three.

• Unit formula (Si2O52-)
• Can form kaolinite. Si2O52− + Al2 (OH ) 24+ → Al2 (OH ) 4 Si2O5
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• Ex: Talc.

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 Chapter 1

Simple ceramic crystal structures

Silicate structures Silicate networks

• Silica (SiO2 network)
• All four corners of SiO44- share
oxygen atoms.
• Three basic silica structures,
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quartz, tridymite and crystobalite

www.dreamtime.bz/quartz Quartz

573oC 867oC 1470oC 1710oC

Low quartz High quartz tridymite crystoballite Silica liquid

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 Chapter 1

Simple ceramic crystal structures

Silicate structures Silicate networks

• Feldspar
• Industrially important
• Three dimensional silicate network
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• Al3+ replaces some of Si4+ and the

charge is balanced by Na+, K+, Ca2+ ,
Ba2+ at the interstitial sites.

K 2O. Al2O3 .6 SiO2

Na2O. Al2O3 .6 SiO2
geology.about.com
CaO. Al2O3 .6 SiO2
Potassium feldspar
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Simple ceramic crystal structures

Silicate mineral composition

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 Chapter 1

Processing of ceramics

Ceramic particles are normally mixed with binders or

lubricants in the dry, plastic or liquid to form into shapes.

Forming Thermal treatments

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• Pressing • Drying
• Isostatic pressing • Sintering
• Extrusion • Vitrification
• Casting

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 Chapter 1

Processing of ceramics

Pressing • Ceramic particulates can be pressed in the dry, plastic

or wet condition in the die to form shaped products.
• Refractory
Dry pressing
• Rapid, uniform and good tolerance
• Ex: alumina, titanate, ferrite
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Filling

Pressing

Ejection

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 Chapter 1

Processing of ceramics

Isostatic pressing
/www.sintec-keramik.com

• Powder is placed within a deformable container

and subjected to hydrostatic pressure.
• Simultaneous densification, low porosity.
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• Near net shape process
100% material

utilization.
• High operating cost.

Hot isostatic pressing (HIP).

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 Chapter 1

Processing of ceramics

Hot Isostatic Pressing (HIP)

• Components are loaded
into furnace, which is placed
into pressure vessel.
• Temperature and pressure
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are raised simultaneously

and held.
• Cooling is carried out as
the gas is released.
• Components are removed
from the furnace.

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Processing of ceramics

Cold Isostatic Pressing

• Powder is sealed in a flexible

mould (or ‘bag’), of for example
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polyurethane and then subjected

to a uniform hydrostatic
pressure.
• Ex: refractories, bricks, spark
plug insulator, carbide tools,
crucible, bearings

CIP graphite blocks

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 Chapter 1

Processing of ceramics

Example of isostatic pressing of spark plug insulator

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Mould

a) Pressed blank
b) Turned insulator
c) Fired insulator
d) Glazed and decorated

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 Chapter 1

Processing of ceramics

Slip casting

• Forming thin-wall complex

shapes of uniform thickness.
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• Can be done in vacuum.

Main steps

1. Slip preparation
2. Slip casting
3. Draining
4. Trimming, removing
and finishing

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 Chapter 1

Processing of ceramics

Extrusion • Plastic state forming under high pressure

• Producing refractory bricks, sewer pipes, hallow tiles,
technical ceramics, electrical insulators.
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Suranaree University of Technology October 2007

 Chapter 1

Processing of ceramics

Thermal treatments Important state in making ceramics stronger

• Drying
• Sintering Drying • To remove water (and organic
binders) before firing
• Vitrification
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• Improving green strength

• Carried out at 100-300oC.

www.ceramic-drying.co.uk
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 Chapter 1

Processing of ceramics

Sintering Small particles are bonded together by solid state diffusion

T < Tm
Porous Denser, more coherent
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• Atomic diffusion takes place

at the area of contact to form
necking
• Particles get larger and
material is denser with
sintering time.
• Providing equilibrium grains.
• Lowered surface energy
Ex: Alumina, beryllia, ferrite and titanates
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Processing of ceramics

Example of MgO sintering at 1430oC in air at various times

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Sintering temp Porosity

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 Chapter 1

Processing of ceramics

Vitrification • The glass phase liquifies and fill the pores in the material.
• Then solidifies to form a vitreous matrix that bonds the
unmelted materials upon cooling.
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Ex: Porcelain, structural clay products, electronic components

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