Ceramics Introduction

Ceramics Introduction
 What are Ceramics
• Ceramics are compounds of 
metals and non‐metals
• Advanced ceramic (structural, 
technical or fine): highly 
engineered, high performance 
predominantly non‐metallic 
inorganic ceramic material having 
specific functional properties
• Unique atomic bonding:  covalent 
(sharing)  and ionic (give up)
•C
Crystalline lattice structure: cubic, 
ysta e att ce st uctu e: cub c,
etc. or amorphous (glasses)

ME 355 Sp’05 W. Li 2
 DEFINITIONS
The word ceramic, derives its name from the Greek keramos, meaning "pottery", 
which in turn is derived from an older Sanskrit root, meaning "to burn". The Greeks 
used the term to mean "burnt stuff" or "burned earth". Thus the word was used to 
refer to a product obtained through the action of fire upon earthy materials 
f d b i d h h h i f fi h i l

Ceramics are inorganic and non‐metallic materials that are commonly electrical and 
th
thermal insulators, brittle and composed of more than one element (e.g., two in Al
li l t b ittl d d f th l t( t i Al2O3)   
)

They are inorganic and nonmetallic materials. Most ceramics are compounds 
between metallic and nonmetallic elements for which the interatomic bonds are 
either totally ionic, or predominantly ionic but having some covalent character.

Ceramics make up one of three large classes of solid materials. The other material 
Ceramics make up one of three large classes of solid materials. The other material
classes include metals and polymers (recently added: composites). The combination 
of two or more of these materials together to produce a new material whose 
properties would not be  attainable by conventional means is  called a composite. 
Examples of composites include steel reinforced  concrete, steel belted tyres, glass 
or carbon fibre – reinforced plastics (so called fibre‐glass resins) used for boats, 
tennis rackets, skis, And  racing bikes. 
 CERAMIC GROUPING

CERAMIC
MATERIALS

ADVANCED 
GLASSES CLAY REFRACTORIES ABRASIVES CEMENTS
CERAMICS

FIRECLAY
STRUCTURAL
GLASSES CLAY
PRODUCTS
SILICA

GLASS 
WHITEWARES BASIC
CERAMICS

SPECIAL
 Classification of Ceramics
Classification of Ceramics
Ceramic Materials

Glasses Clay 
Clay Refractories Abrasives Cements Advanced 
Advanced
products ceramics
‐optical  ‐whiteware  ‐bricks for  ‐sandpaper  ‐composites  ‐engine 
‐composite ‐structural
‐composite  high T
high T  ‐cutting
‐cutting  ‐structural rotors
rotors 
reinforce  (furnaces) ‐polishing valves 
‐containers/  Adapted from Fig. 13.1 and discussion in 
bearings
household Section 13.2‐8, Callister & Rethwisch 8e. ‐sensors

5
• Traditional ceramics bear a close relationship to those 
materials that have been developed since the earliest 
civilizations. They are pottery, structural clay products, 
and clay‐based refractories, with which we may also 
y y
group cements and concretes and glasses.
• Advanced ceramics include ceramics for electrical, 
magnetic, electronic, and optical applications
magnetic, electronic, and optical applications 
(sometimes referred to as functional ceramics) and 
ceramics for structural applications at ambient as well 
as at elevated temperatures (structural ceramics)
as at elevated temperatures (structural ceramics).
• Chemically, with the exception of carbon, ceramics are 
nonmetallic, inorganic compounds.
 Advanced Ceramics

• Advanced ceramic materials have been developed over the

past half century

• Applied as thermal barrier coatings to protect metal

structures, wearing surfaces, or as integral components by
themselves.

• Engine applications are very common for this class of

material which includes silicon nitride (Si3N4), silicon carbide
(SiC), Zirconia (ZrO2) and Alumina (Al2O3)

• Heat resistance and other desirable properties have lead to

the development of methods to toughen the material by
reinforcement with fibers and whiskers opening up more
applications for ceramics
 Advanced Ceramics Usage
Advanced Ceramics Usage
• Structural: Wear parts, bioceramics, cutting tools, 
Wear parts, bioceramics, cutting tools,
engine components, armour.
• Electrical: Capacitors, insulators, integrated circuit 
p , , g
packages, piezoelectrics, magnets and 
superconductors
• Coatings: Engine components, cutting tools, and 
industrial wear parts
• Chemical and environmental: Filters, membranes, 
catalysts, and catalyst supports
Ceramics can be classified based on chemical composition – oxides, carbides, nitrides, 
sulfides and fluorides. Or they can be grouped according to their major functions. 
f f f
Ceramics found in coatings – glazes, are ceramic coatings applied to glass objects and 
enamels are ceramic coatings applied to metallic objects. 

Alumina (Al2O3):  

Diamond (C):
Diamond (C): 

Silica (SiO2):   

Silicon carbide:  

Silicon nitride (Si3N4):  

Titanium oxide (TiO2):  

Zi
Zirconia (ZrO
i (Z O2):          
)
 Common Ceramics Types
yp
• Silicates such as kaolinite [Al2Si2O5(OH)4] and mullite (Al6Si2O13), 
• Simple oxides such as alumina (Al2O3) and zirconia (ZrO2), 
• complex oxides other than the silicates such as barium titanate
l id h h h ili h b i i
(BaTiO3), and the superconducting material YBa2Cu3O6+δ(0 ≤ δ ≤ 1).
• In addition, there are nonoxides including carbides such as silicon 
carbide (SiC) and boron carbide (B4C), nitrides such as silicon nitride 
carbide (SiC) and boron carbide (B C) nitrides such as silicon nitride
(Si3N4) and boron nitride (BN),
• borides such titanium diboride (TiB2), 
• silicides such as molybdenum disilicide
such as molybdenum disilicide (MoSi2)
• and halides such as lithium fluoride (LiF). 
• There are also compounds based on nitride–oxide or oxynitride
systems (e.g. β′‐sialons
y ( g β with the general formula Si
g 6 zAlzN8‐z
6‐z 8 zOz ,, 
where 0 < z <~ 4).
• In ceramics as well as in metals, we are concerned with 
,
two types of structure, both of which have a profound 
effect on properties. 
• The first type of structure is at the atomic scale: the 
Th fi t t f t t i t th t i l th
type of bonding and the crystal structure (for a 
crystalline ceramic) or the amorphous structure (if it is 
y ) p (f
glassy).
• The second type of structure is at a larger scale: the 
microstructure which refers to the nature quantity
microstructure, which refers to the nature, quantity, 
and distribution of the structural elements or phases in 
the ceramic (e.g., crystals, glass, and porosity).
• The intrinsic properties are determined by the 
structure at the atomic scale and are properties that 
are not susceptible to significant change by 
modification of the microstructure, properties such as 
p p
the melting point, elastic modulus, coefficient of 
thermal expansion, and whether the material is brittle, 
magnetic, ferroelectric, or semiconducting.
g g
• In contrast, many of the properties critical to the 
engineering applications of materials are strongly 
dependent on the microstructure (e g mechanical
dependent on the microstructure (e.g., mechanical 
strength, dielectric constant, and electrical 
conductivity).
• The important relationships between chemical composition, atomic 
structure, fabrication, microstructure, and properties of 
polycrystalline ceramics are illustrated in Fig 1 1
polycrystalline ceramics are illustrated in Fig. 1.1. 
• The intrinsic properties must be considered at the time of materials 
selection. 
• For example, the phenomenon of ferroelectricity
p , p y originates in the 
g
perovskite crystal structure, of which BaTiO3 is a good example. For 
the production of a ferroelectric material, we may therefore wish to 
select BaTiO3.
• The role of the fabrication process, then, is to produce 
Th l f th f b i ti th i t d
microstructures with the desired engineering properties. For 
example, the measured dielectric constant of the fabricated BaTiO3
will depend significantly on the microstructure (grain size, porosity, 
p g y (g ,p y,
and presence of any secondary phases)

(Rehmann)
• The functions of ceramic products are very 
p y
dependent on their chemicalcomposition and their 
atomic and microscale structure, which determines 
their properties. 
p p

• Compositions of ceramic products vary widely, and 
b th id
both oxide and nonoxide materials are used.
d id t i l d

• Today
Today the composition and structure of grains and 
the composition and structure of grains and
grain boundary phases and the distribution and 
structure of pores is more carefully controlled to 
achieve greater product performance and reliability
achieve greater product performance and reliability 
(Fig.1.2). 
WHY STUDY Structures and Properties 
of Ceramics?
f ?
• Some of the properties of ceramics may be 
p p y
explained by their structures. For example: 
(a) The optical transparency of inorganic glass 
materials is due in part to their noncrystallinity
materials is due, in part, to their noncrystallinity; 
(b) the hydroplasticity of clays (i.e., development of 
plasticity upon the addition of water) is related to
plasticity upon the addition of water) is related to 
interactions between water molecules and the 
clay structures and 
( ) h
(c) the permanent magnetic and ferroelectric 
i df l i
behaviors of some ceramic materials are 
p y y
explained by their crystal structures
Function Application Examples
Electrical Capacitor dielectrics
Microwave dielectrics
BaTiO3, SrTiO3, Ta2O5,
Ba2Ti9O20, Al2O3 Ba(Mg
( g1/3Ta2/3))O3,
Ba(Zn1/3Ta2/3)O3, BaTi4O9,
Conductive oxides In-doped SnO2 (ITO)
Superconductors YBa2Cu3O7-x (YBCO)
Electronic packaging Al2O3
Insulators Porcelain
Solid-oxide fuel cells ZrO2, LaCrO3
Piezoelectronic Pb(ZrxTi1-x
1 x)O3 (PZT)

Electro-optical PLZT, LiNbO3

Magnetic Recording media

Ferrofluids, credit cards,
γ-Fe2O3, CrO2(chrome cassettes)
Fe3O4
Circulators, isolators, Nickel zinc ferrite
Inductors, magnets Manganese zinc ferrite

Optical Fibre optics

Glasses
Doped SiO2
SiO2 based
Lasers Al2O3, yttrium aluminium garnate
Lighting Al2O3, glasses

Automotive Oxygen sensors, fuel cells

Catalyst support
ZrO2
Cordierite
Spark plugs Al2O3
Tires SiO
Mechanical/ Cutting tools WC-Co cermets
Silicon-aluminium-oxynitride
structural (Sialon), Al2O3
Composites SiC, Al2O3, silica glass fibres
Abrasives SiC,Al2O3, diamond,BN, ZrSiO4

Biomedical Implants
Dentistry
Hydroxyapatite
Porcelain,
l All2O3
Ultrasound imaging PZT

Construction Buildings Concrete, Glass, Sanitaryware

Others Defense
Armor materials
PZT, B4C
SnO2
Sensors UO2
Nuclear Al2O3, SiO2-based refractories
Metal processing O2 sensors, casting molds

Chemical Catalysis
Ai li
Air, liquid
id filt
filtration
ti
Oxides (Al2O3,ZrO2,ZnO,TiO2)

Sensors
Paints, rubber

D
Domestic
ti Tiles, sanitaryware
Tiles
Whiteware, kitchenware,
Clay, Al2O3, SiO2-based and glass
Clay
ceramics, diamond, ruby, cubic,
Pottery, art, jewelry zirconia
 Properties of Ceramics

Material Melting Thermal Knoop Hardness

point expansion (HK) (100 g)
(°C) coefficient (x10-
6 cm/cm)/
cm/cm)/°°C
Al2O3 2000 6.8 2100
BN 2732 0.57, -0.46 5000
SiC 2700 3.7 2500
Diamond 1.02 7000
M llit
Mullite 1810 4.5
45 _
TiO2 1840 8.8 _
Cubic 2700 10 5
10.5 _
ZrO2
 Material D(g/c T F (psi) C (psi) Y (psi) Ft
m3) (psi))
(p (psi√in)
(p √ )
Al2O3 3.98 30,000 80,000 400,000 56 x 106 5,000
SiC (sintered) 3.1 25,000 80,000 560,000 60 x 106 4,000
Si3N4 (rxn 2.5 20,000 35,000 150,000 30 x 106 3,000
bonded)
Si3N4 (hot 32
3.2 80,000
80 000 130,000
130 000 500,000
500 000 45 x 106 5,000
5 000
pressed)
Sialon 3.24 60,000 140,000 500,000 45 x 106 9,000
ZrO2 (partially 5.8 65,000 100,000 270,000 30 x 106 10,000
stabilized)
ZrO2 5.8 50,000 115,000 250,000 29 x 106 11,000
(transformation
toughened)
Tensile strength = T; Flexural strength = F; Young
Tensile strength = T; Flexural strength = F; Young’ss modulus = Y;
modulus = Y;
Compressive strength = C; Fracture toughness = Ft; Density = D.
 Properties of Ceramics
• Probabilistic properties due to 
distributions of flaws
distributions of flaws 
• ASTM standards address many 
aspects of these properties
• Low fracture toughness (<10 MPa 
√m)
• High strengths at small volumes (>1 
g g (
GPa)
• Low CTE (2‐4 x 10‐6 /°C)
• High Hardness (1 GPa)
High Hardness (1 GPa)
• High Stiffness (300‐600 GPa)

ME 355 W. Li 23
ME 355 Sp’05 W. Li 24
 Design with Ceramics

‐ Brittle materials
‐ Probabilistic methods
Probabilistic methods
‐ Strength statistics
‐ Stress raisers
‐ Reliability
‐ Volume/area effects

ME 355 W. Li 25
 Applications: Advanced Ceramics
pp

Heat Engines
Heat Engines • Disadvantages:  
g
– Brittle
• Advantages:   – Too easy to have voids‐
– Run at higher temperature weaken the engine
weaken the engine
– Excellent wear & corrosion  – Difficult to machine
resistance
– Low frictional losses
Low frictional losses
– Ability to operate without a 
cooling system
– Low density
Low density
• Possible parts – engine block, piston coatings, jet engines
Ex:  Si3N4, SiC, & ZrO2
 Applications: Advanced Ceramics

• Ceramic Armor
Ceramic Armor
– Al2O3, B4C, SiC & TiB2
– Extremely hard materials 
Extremely hard materials
• shatter the incoming projectile
• energy absorbent material underneath
energy absorbent material underneath
 Applications: Advanced Ceramics
Electronic Packaging
• Chosen to securely hold microelectronics & provide heat 
transfer
• Must match the thermal expansion coefficient of the 
microelectronic chip & the electronic packaging material. 
Addi i
Additional requirements include:
l i i l d
– good heat transfer coefficient
– poor electrical conductivity

• Materials currently used include:
• Boron nitride (BN)
• Silicon Carbide (SiC)
Silicon Carbide (SiC)
• Aluminum nitride (AlN)
– thermal conductivity 10x that for Alumina
– good expansion match with Si
 Ceramic Armour

• Ceramic armour systems are used to protect military

personnel and equipment.

• Advantage: low density of the material can lead to weight-

efficient armour systems.

• Typical ceramic materials used in armour systems include

alumina, boron carbide, silicon carbide, and titanium
diboride.

• The ceramic material is discontinuous and is sandwiched

between a more ductile outer and inner skin.

• The outer skin must be hard enough to shatter the projectile.

 Advanced Ceramics: 
M
Materials for Ceramic Armor
i l f C i A

Components:
‐‐ Outer facing plates
‐‐ Backing sheet

Properties/Materials:
‐‐ Facing plates ‐‐ hard and brittle
— fracture high
fracture high‐velocity
velocity projectile
projectile
— Al2O3, B4C, SiC, TiB2
‐‐ Backing sheets ‐‐ soft and ductile
— deform and absorb remaining energy
— aluminum, synthetic fiber laminates 
l i h i fib l i

30
• Most of the impact
p energy
gy is absorbed byy the fracturing
g of
the ceramic and any remaining kinetic energy is
absorbed by the inner skin, that also serves to contain
the fragments of the ceramic and the projectile
preventing severe impact with the personnel/equipment
being protected.

• Alumina ceramic/Kevlar composite system in sheets

about 20mm thick are used to protect key areas of
Hercules aircraft (cockpit crew/instruments and
loadmaster station).

• This lightweight solution provided an efficient and

removable/replaceable armour system
system. Similar systems
used on Armoured Personnel Carrier’s.
Ceramic ‐ Composite Armor
Ceramic  Composite Armor

Ceramic-
Outer hard Discontinuous
skin

Projectile

Personnel
and
Equipment

Inner
ductile
skin

C
Ceramic
i AArmor S
System
t
 Ceramics Application: Sensors
Ceramics Application:  Sensors
•  Example: ZrO2 as an oxygen sensor
Ca 2+
•  Principle: Increase diffusion rate of oxygen 
to produce rapid response of sensor signal to 
d id f i l
change in oxygen concentration
•  Approach: A substituting Ca2+ ion 
Add Ca impurity to ZrO2: removes a Zr 4+ ion and 
an O2‐ ion.   
‐‐ increases O2‐ vacancies
‐‐ increases O2‐ diffusion rate
•  Operation:
‐‐ voltage difference produced when  sensor
O2‐ ions diffuse from the external  gas with an  reference 
unknown higher
unknown, higher  gas at fixed 
t fi d
surface through the sensor to the 
f h h h h oxygen content O 2‐
oxygen content
reference gas surface. diffusion
‐‐ magnitude of voltage difference 
∝ partial pressure of oxygen at the 
partial pressure of oxygen at the
+ ‐
external surface voltage difference produced!
33
Figure 1.3 Bar‐chart of room temperature density values for various
metals, ceramics, polymers, and composite materials.
Figure 1.4 Bar‐chart of room temperature stiffness (i.e., elastic 
modulus) values for various metals, ceramics, polymers, and
composite materials.
Figure 1.5 Bar‐chart of room temperature strength (i.e., tensile 
strength) values for various metals, ceramics, polymers, and
composite materials.
Figure 1.6 Bar‐chart of room‐temperature resistance to fracture (i.e., 
fracture toughness) for various metals, ceramics, polymers, and composite 
materials. (Reprinted from Engineering Materials 1: An Introduction to 
Properties, Applications and Design, third edition, M. F. Ashby
and D. R. H. Jones, pages 177 and 178,
Figure 1.7 Bar‐chart of room temperature electrical conductivity ranges
for metals, ceramics, polymers, and semiconducting Materials (Fig.1.3‐1.7 
, ,p y , g ( g
from Callister)
Comparison metals v ceramics
Comparison metals v ceramics

Metals Ceramics