Chapter 12: Structures & Properties of

Ceramics

ISSUES TO ADDRESS...
• How do the crystal structures of ceramic materials
differ from those for metals?
• How do point defects in ceramics differ from those
defects found in metals?
• How are impurities accommodated in the ceramic lattice?
• In what ways are ceramic phase diagrams different from
phase diagrams for metals?
• How are the mechanical properties of ceramics
measured, and how do they differ from those for metals?

Chapter 12 - 1
Classifications of
Ceramics

Chapter 12 -
 Atomic Bonding in Ceramics
• Bonding:
-- Can be ionic and/or covalent in character.
-- % ionic character increases with difference in
electronegativity of atoms.

Chapter 12 - 3
 Atomic Bonding in Ceramics
• Bonding:
-- Can be ionic and/or covalent in character.
-- % ionic character increases with difference in
electronegativity of atoms.
• Degree of ionic character may be large or small:

Chapter 12 - 4
 Atomic Bonding in Ceramics
• Bonding:
-- Can be ionic and/or covalent in character.
-- % ionic character increases with difference in
electronegativity of atoms.
• Degree of ionic character may be large or small:
CaF2: large
SiC: small

Chapter 12 - 5
 Ceramic Crystal Structures
Oxide structures
– oxygen anions larger than metal cations
– close packed oxygen in a lattice (usually FCC)
– cations fit into interstitial sites among oxygen ions

Chapter 12 - 6
 Ceramic Crystal Structures
Oxide structures
– oxygen anions larger than metal cations
– close packed oxygen in a lattice (usually FCC)
– cations fit into interstitial sites among oxygen ions
Mg2+

O2-

Anions (gained electrons) are usually larger than cations (gave up electrons)

Chapter 12 - 7
 Factors that Determine Crystal Structure
1. Relative sizes of ions – Formation of stable structures:
--maximize the # of oppositely charged ion neighbors (maximize the coordination number).

Chapter 12 -
 Factors that Determine Crystal Structure
1. Relative sizes of ions – Formation of stable structures:
--maximize the # of oppositely charged ion neighbors (maximize the coordination number).
For a structure to be stable the surrounding anions must be in contact with the surrounded cation

Chapter 12 -
 Factors that Determine Crystal Structure
1. Relative sizes of ions – Formation of stable structures:
--maximize the # of oppositely charged ion neighbors (maximize the coordination number).
For a structure to be stable the surrounding anions must be in contact with the surrounded cation

- - - - - -
+ + +
- - - - - -
unstable stable stable

Chapter 12 - 10
 Factors that Determine Crystal Structure
1. Relative sizes of ions – Formation of stable structures:
--maximize the # of oppositely charged ion neighbors (maximize the coordination number).
For a structure to be stable the surrounding anions must be in contact with the surrounded cation
There is thus a minimum
cation radius regarding the
- - - - - - anion one for the structure to
+ + + be stable. In the first
structure in the left the cation
- - - - - - is too small, it cannot touch
all the cations and hence
does not maximize the
unstable stable stable coordination number

Chapter 12 - 11
 Factors that Determine Crystal Structure
1. Relative sizes of ions – Formation of stable structures:
--maximize the # of oppositely charged ion neighbors (maximize the coordination number).
For a structure to be stable the surrounding anions must be in contact with the surrounded cation
There is thus a minimum
cation radius regarding the
- - - - - - anion one for the structure to
+ + + be stable. In the first
structure in the left the cation
- - - - - - is too small, it cannot touch
all the cations and hence
does not maximize the
unstable stable stable coordination number

2. Maintenance of Electroneutrality :
--Net charge in ceramic should be zero.
--Reflected in chemical formula:

Chapter 12 - 12
 Factors that Determine Crystal Structure
1. Relative sizes of ions – Formation of stable structures:
--maximize the # of oppositely charged ion neighbors (maximize the coordination number).
For a structure to be stable the surrounding anions must be in contact with the surrounded cation
There is thus a minimum
cation radius regarding the
- - - - - - anion one for the structure to
+ + + be stable. In the first
structure in the left the cation
- - - - - - is too small, it cannot touch
all the cations and hence
does not maximize the
unstable stable stable coordination number

2. Maintenance of Electroneutrality :
--Net charge in ceramic should be zero. F-
--Reflected in chemical formula:
CaF 2 : Ca 2+ +
cation anions
F-
A m Xp
m, p values to achieve electroneutrality Chapter 12 - 13
 Coordination Number and Ionic Radii
r cation
• Coordination Number increases with r
anion
To form a stable structure, how many anions can surround a cation?

r cation Coord. ZnS

r anion Number (zinc blende)
< 0.155 2 linear

0.155 - 0.225 3 triangular NaCl

(sodium
0.225 - 0.414 4 tetrahedral chloride)

0.414 - 0.732 6 octahedral CsCl

(cesium
chloride)
0.732 - 1.0 8 cubic

Chapter 12 - 14
 Coordination Number and Ionic Radii
r cation
• Coordination Number increases with r
anion
To form a stable structure, how many anions can surround a cation?

r cation Coord. ZnS

r anion Number (zinc blende)
< 0.155 2 linear

0.155 - 0.225 3 triangular NaCl

(sodium
0.225 - 0.414 4 tetrahedral chloride)

0.414 - 0.732 6 octahedral CsCl

(cesium
chloride)
0.732 - 1.0 8 cubic

Chapter 12 - 15
 Coordination Number and Ionic Radii
r cation
• Coordination Number increases with r
anion
To form a stable structure, how many anions can surround a cation?

r cation Coord. ZnS

r anion Number (zinc blende)
< 0.155 2 linear

0.155 - 0.225 3 triangular NaCl

(sodium
0.225 - 0.414 4 tetrahedral chloride)

0.414 - 0.732 6 octahedral CsCl

(cesium
chloride)
0.732 - 1.0 8 cubic

Chapter 12 - 16
 Coordination Number and Ionic Radii
r cation
• Coordination Number increases with r
anion
To form a stable structure, how many anions can surround a cation?

r cation Coord. ZnS

r anion Number (zinc blende)
< 0.155 2 linear

0.155 - 0.225 3 triangular NaCl

(sodium
0.225 - 0.414 4 tetrahedral chloride)

0.414 - 0.732 6 octahedral CsCl

(cesium
chloride)
0.732 - 1.0 8 cubic

Chapter 12 - 17
 Coordination Number and Ionic Radii
r cation
• Coordination Number increases with r
anion
To form a stable structure, how many anions can surround a cation?

r cation Coord. ZnS

r anion Number (zinc blende)
< 0.155 2 linear

0.155 - 0.225 3 triangular NaCl

(sodium
0.225 - 0.414 4 tetrahedral chloride)

0.414 - 0.732 6 octahedral CsCl

(cesium
chloride)
0.732 - 1.0 8 cubic

Chapter 12 - 18
 Coordination Number and Ionic Radii
r cation
• Coordination Number increases with r
anion
To form a stable structure, how many anions can surround a cation?

r cation Coord. ZnS

r anion Number (zinc blende)
< 0.155 2 linear

0.155 - 0.225 3 triangular NaCl

(sodium
0.225 - 0.414 4 tetrahedral chloride)

0.414 - 0.732 6 octahedral CsCl

(cesium
chloride)
0.732 - 1.0 8 cubic

Chapter 12 - 19
Example Problem: Predicting the Crystal Structure of FeO

• On the basis of ionic radii, what crystal structure

would you predict for FeO?
Cation Ionic radius (nm)
Al 3+ 0.053
Fe 2+ 0.077
Fe 3+ 0.069
Ca 2+ 0.100

Anion
O2- 0.140
Cl - 0.181
F- 0.133
Chapter 12 - 20
Example Problem: Predicting the Crystal Structure of FeO

• On the basis of ionic radii, what crystal structure

would you predict for FeO?
Cation Ionic radius (nm)
Al 3+ 0.053
Fe 2+ 0.077
Fe 3+ 0.069
Ca 2+ 0.100

Anion
O2- 0.140
Cl - 0.181
F- 0.133
Chapter 12 - 21
Example Problem: Predicting the Crystal Structure of FeO

• On the basis of ionic radii, what crystal structure

would you predict for FeO?
Cation Ionic radius (nm) • Answer:
Al 3+ 0.053 rcation 0.077
=
Fe 2+ 0.077 ranion 0.140
Fe 3+ 0.069
= 0.550
Ca 2+ 0.100

Anion
O2- 0.140
Cl - 0.181
F- 0.133
Chapter 12 - 22
Example Problem: Predicting the Crystal Structure of FeO

• On the basis of ionic radii, what crystal structure

would you predict for FeO?
Cation Ionic radius (nm) • Answer:
Al 3+ 0.053 rcation 0.077
=
Fe 2+ 0.077 ranion 0.140
Fe 3+ 0.069
= 0.550
Ca 2+ 0.100
based on this ratio,
Anion -- coord # = 6 because
0.414 < 0.550 < 0.732
O2- 0.140
-- crystal structure is octahedral
Cl - 0.181
(like NaCl)
F- 0.133
Chapter 12 - 23
 Rock Salt Structure
Same concepts can be applied to ionic solids in general.
Example: NaCl (rock salt) structure
rNa = 0.102 nm

rCl = 0.181 nm

rNa/rCl = 0.564

 cations (Na+) prefer octahedral sites

Chapter 12 - 24
 Rock Salt Structure
Same concepts can be applied to ionic solids in general.
Example: NaCl (rock salt) structure
rNa = 0.102 nm

rCl = 0.181 nm

rNa/rCl = 0.564

 cations (Na+) prefer octahedral sites

So each Na+ has 6 neighbor chloride anions

Chapter 12 - 25
 MgO and FeO
MgO and FeO also have the NaCl structure
O2- rO = 0.140 nm

Mg2+ rMg = 0.072 nm

rMg/rO = 0.514

 cations prefer octahedral sites

So each Mg2+ (or Fe2+) has 6 neighbor oxygen atoms

Chapter 12 - 26
 AX Crystal Structures
AX–Type Crystal Structures include NaCl, CsCl, and zinc blende

Cesium Chloride structure:

r 0.170
Cs+
= = 0.939
r 0.181
Cl-

 Since 0.732 < 0.939 < 1.0,

cubic sites preferred
So each Cs+ has 8 neighbor Cl-

Chapter 12 - 27
 AX Crystal Structures
AX–Type Crystal Structures include NaCl, CsCl, and zinc blende

Cesium Chloride structure:

r 0.170
Cs+
= = 0.939
r 0.181
Cl-

 Since 0.732 < 0.939 < 1.0,

cubic sites preferred
So each Cs+ has 8 neighbor Cl-

Conclusion: It is not only the chemical formula which determines the crystal
structure but also the relative sizes of the cations and anions.
Chapter 12 - 28
 AX2 Crystal Structures
Fluorite structure
• Calcium Fluorite (CaF2)
• Ca2+ cations in cubic sites

• ZrO2 (zirconia), CeO2 (ceria), UO2, ThO2,

Chapter 12 - 29
 AX2 Crystal Structures
Fluorite structure
• Calcium Fluorite (CaF2)
• Ca2+ cations in cubic sites

• ZrO2 (zirconia), CeO2 (ceria), UO2, ThO2,

• Antifluorite structure –
positions of cations and anions reversed

Li2O

Chapter 12 - 30
 ABX3 Crystal Structures

• Perovskite structure

Ex: complex oxide BaTiO3

Chapter 12 - 31
 ABX3 Crystal Structures

• Perovskite structure

Ex: complex oxide BaTiO3

Verify the electroneutrality of this crystal

Chapter 12 - 32
 ABX3 Crystal Structures

• Perovskite structure

Ex: complex oxide BaTiO3

Verify the electroneutrality of this crystal

As we saw in the crystalline structure chapter:

Chapter 12 - 33
 ABX3 Crystal Structures

• Perovskite structure

Ex: complex oxide BaTiO3

Verify the electroneutrality of this crystal

As we saw in the crystalline structure chapter:

occupies the corners of the cube:

8 corners, 1/8 cation per corner,
1 equivalent cation per cube, valence +2 in the crystal

Chapter 12 - 34
 ABX3 Crystal Structures

• Perovskite structure

Ex: complex oxide BaTiO3

Verify the electroneutrality of this crystal

As we saw in the crystalline structure chapter:

occupies the corners of the cube:

8 corners, 1/8 cation per corner,
1 equivalent cation per cube, valence +2 in the crystal

occupies the center of the cube (like in a BCC):

1 cation per cube, valence +4 in the crystal

Chapter 12 - 35
 ABX3 Crystal Structures

• Perovskite structure

Ex: complex oxide BaTiO3

Verify the electroneutrality of this crystal

As we saw in the crystalline structure chapter:

occupies the corners of the cube:

8 corners, 1/8 cation per corner,
1 equivalent cation per cube, valence +2 in the crystal

occupies the center of the cube (like in a BCC):

1 cation per cube, valence +4 in the crystal

occupies the center of the faces cube (like in a FCC):

6 faces, 1/2 anions per face,
3 equivalent anions per cube, valence -6 in the crystal

Chapter 12 - 36
 ABX3 Crystal Structures

• Perovskite structure

Ex: complex oxide BaTiO3

Verify the electroneutrality of this crystal

As we saw in the crystalline structure chapter:

occupies the corners of the cube:

8 corners, 1/8 cation per corner,
1 equivalent cation per cube, valence +2 in the crystal

occupies the center of the cube (like in a BCC):

1 cation per cube, valence +4 in the crystal

occupies the center of the faces cube (like in a FCC):

6 faces, 1/2 anions per face,
3 equivalent anions per cube, valence - 6 in the crystal

The crystal (and hence the ceramics) is electroneutral

Chapter 12 - 37
Silicate Ceramics

A large percentage of ceramics is

based on combinations of Silicon,
Aluminum and Oxygen, the three
most abundant elements in the earth
crust (rocks, soils, clays, sand)
 Silicate Ceramics

A large percentage of ceramics is

based on combinations of Silicon,
Aluminum and Oxygen, the three
most abundant elements in the earth
crust (rocks, soils, clays, sand)

• Basic building block: SiO44- tetrahedron.

• Si-O bonding is largely covalent.
•Note: each SiO4 unit carries with it a net
negative charge of -4.
 Silicate Ceramics

A large percentage of ceramics is

based on combinations of Silicon,
Aluminum and Oxygen, the three
most abundant elements in the earth
crust (rocks, soils, clays, sand)

• Basic building block: SiO44- tetrahedron.

• Si-O bonding is largely covalent.
•Note: each SiO4 unit carries with it a net
negative charge of -4.
- This does not violate our previous rule
about charge neutrality because isolated
SiO4 tetrahedra do not exist.
• Different ways to arrange SiO44- blocks
→ Various silicate structures
 Silicate Ceramics: Silica
SiO2 (silica) polymorphic forms are quartz, crystobalite, & tridymite

Those are complex structures yet based in the

Chapter 12 -
 Silicate Ceramics: Silica
SiO2 (silica) polymorphic forms are quartz, crystobalite, & tridymite

Those are complex structures yet based in the

quartz
cristobalite

Chapter 12 -
 Silicate Ceramics: Silica
SiO2 (silica) polymorphic forms are quartz, crystobalite, & tridymite

Those are complex structures yet based in the

quartz
cristobalite
Both quartz and cristobalite are built upon the silicate tetrahedron 𝑆𝑖𝑂44− but are denoted 𝑆𝑖𝑂2 . Why and how?

Chapter 12 -
 Silicate Ceramics: Silica
SiO2 (silica) polymorphic forms are quartz, crystobalite, & tridymite

Those are complex structures yet based in the

quartz
cristobalite
Both quartz and cristobalite are built upon the silicate tetrahedron 𝑆𝑖𝑂44− but are denoted 𝑆𝑖𝑂2 . Why and how?

As the crystal must be electroneutral, the tetrahedra will organize themselves in a complex 3-D layered
structure, so that each “individual” tetrahedron share oxygen anions with other tetrahedra.

Chapter 12 -
 Silicate Ceramics: Silica
SiO2 (silica) polymorphic forms are quartz, crystobalite, & tridymite

Those are complex structures yet based in the

quartz
cristobalite
Both quartz and cristobalite are built upon the silicate tetrahedron 𝑆𝑖𝑂44− but are denoted 𝑆𝑖𝑂2 . Why and how?

As the crystal must be electroneutral, the tetrahedra will organize themselves in a complex 3-D layered
structure, so that each “individual” tetrahedron share oxygen anions with other tetrahedra.

The two blue rectangles in the two pictures surround 4 Si cations and 8 oxygen anions: 𝑆𝑖𝑂2

Chapter 12 -
 Silicate Ceramics: Silica
SiO2 (silica) polymorphic forms are quartz, crystobalite, & tridymite

Those are complex structures yet based in the

quartz
cristobalite
Both quartz and cristobalite are built upon the silicate tetrahedron 𝑆𝑖𝑂44− but are denoted 𝑆𝑖𝑂2 . Why and how?

As the crystal must be electroneutral, the tetrahedra will organize themselves in a complex 3-D layered
structure, so that each “individual” tetrahedron share oxygen anions with other tetrahedra.

The two blue rectangles in the two pictures surround 4 silicon cations and 8 oxygen anions: 𝑆𝑖𝑂2

This illustrates the crucial importance of electroneutrality in ceramics structures Chapter 12 -

Although already complex structures, silica is the simplest silicate structure. Thanks to the
high strength Si-O covalent bonds, it is insoluble in water and also in most acids, except HF

Chapter 12 -
Although already complex structures, silica is the simplest silicate structure. Thanks to the
high strength Si-O covalent bonds, it is insoluble in water and also in most acids, except HF

Silicate Ceramics: other forms of structures

Bonding of adjacent SiO44- accomplished by the sharing of common corners edges,
or faces therefore yielding different and more complex structures. Examples:

Chapter 12 -
Although already complex structures, silica is the simplest silicate structure. Thanks to the
high strength Si-O covalent bonds, it is insoluble in water and also in most acids, except HF

Silicate Ceramics: other forms of structures

Bonding of adjacent SiO44- accomplished by the sharing of common corners edges,
or faces therefore yielding different and more complex structures. Examples:

𝑆𝑖𝑂44− 𝑆𝑖𝑂44−
𝑆𝑖𝑂44−

𝑆𝑖𝑂44−
𝑆𝑖𝑂44−

𝑆𝑖𝑂44− is the base brick of most silicate ceramics

Chapter 12 -
Although already complex structures, silica is the simplest silicate structure. Thanks to the
high strength Si-O covalent bonds, it is insoluble in water and also in most acids, except HF

Silicate Ceramics: other forms of structures

Bonding of adjacent SiO44- accomplished by the sharing of common corners edges,
or faces therefore yielding different and more complex structures. Examples:

Presence of cations such as Ca2+, Mg2+, Ba2+, Al3+, …

1. maintains charge neutrality, and
2. ionically bond SiO44- to one another

Chapter 12 -
Although already complex structures, silica is the simplest silicate structure. Thanks to the
high strength Si-O covalent bonds, it is insoluble in water and also in most acids, except HF

Silicate Ceramics: other forms of structures

Bonding of adjacent SiO44- accomplished by the sharing of common corners edges,
or faces therefore yielding different and more complex structures. Examples:

Presence of cations such as Ca2+, Mg2+, Ba2+, Al3+, …

1. maintains charge neutrality, and
2. ionically bond SiO44- to one another

Mg2SiO4 Ca2MgSi2O7 BaTiSi3O9

Chapter 12 -
Although already complex structures, silica is the simplest silicate structure. Thanks to the
high strength Si-O covalent bonds, it is insoluble in water and also in most acids, except HF

Silicate Ceramics: other forms of structures

Bonding of adjacent SiO44- accomplished by the sharing of common corners edges,
or faces therefore yielding different and more complex structures. Examples:

Presence of cations such as Ca2+, Mg2+, Ba2+, Al3+, …

1. maintains charge neutrality, and
2. ionically bond SiO44- to one another

Mg2SiO4 Ca2MgSi2O7 BaTiSi3O9

(forsterite) (akermanite) (benitoite)

Chapter 12 -
 Layered Silicates
• Layered silicates (e.g., clays, mica, talc)
– SiO4 tetrahedra connected
together to form 2-D plane

• A net negative charge is associated

with each (Si2O5)2- unit

• Negative charge balanced by

adjacent plane rich in positively
charged cations

Chapter 12 - 53
 Layered Silicates (cont)
• Kaolinite clay alternates (Si2O5)2- layer with Al2(OH)42+ layer

Note: Adjacent sheets of this type are loosely bound to one another by van der Waal’s forces.

Chapter 12 - 54
 Silica Glasses

Silica exists in either a crystalline state

(discussed previously) or in a disordered
(amorphous, or vitreous, or glassy) state.

Chapter 12 -
 Silica Glasses

Silica exists in either a crystalline state

(discussed previously) or in a disordered
(amorphous, or vitreous, or glassy) state.

Note that the SiO44- tetrahedra form

different networks like the ones
shown in the figure; consequently,
SiO2 and related ceramics are called
“network formers”.

Chapter 12 -
 Silica Glasses

Silica exists in either a crystalline state

(discussed previously) or in a disordered
(amorphous, or vitreous, or glassy) state.

Note that the SiO4 tetrahedra form

different networks like the ones
shown in the figure; consequently,
SiO2 and related ceramics are called
“network formers”.

Fused silica: glass with no impurities

Chapter 12 -
 Silica Glasses

•Most of our common commercial glasses

consist of a silica network, to which various
other oxide ceramics such as CaO and Na2O
have been added.
•These oxides themselves do not form networks,
but rather modify the networks.
- Consequently, such additives are called
network modifiers

Chapter 12 -
 Silica Glasses

•Most of our common commercial glasses

consist of a silica network, to which various
other oxide ceramics such as CaO and Na2O
have been added.
•These oxides themselves do not form networks,
but rather modify the networks.
- Consequently, such additives are called
network modifiers

Chapter 12 -
 Silica Glasses

•Most of our common commercial glasses

consist of a silica network, to which various
other oxide ceramics such as CaO and Na2O
have been added.
•These oxides themselves do not form networks,
but rather modify the networks.
- Consequently, such additives are called
network modifiers
•For example, the accompanied schematic
represents the general structure of a sodium
silica glass, where the sodium ions become
incorporated within the silica network.
Network modifiers are added to silica glasses in order to impart
specific properties, such as a reduced softening or vitrification
temperature, a different viscosity, or a particular color or tint.
Chapter 12 -
 Polymorphic Forms of Carbon
Diamond
– tetrahedral bonding of
carbon
• hardest material known
• very high thermal
conductivity
– large single crystals –
gem stones
– small crystals – used to
grind/cut other materials
– diamond thin films
• hard surface coatings –
used for cutting tools,
medical devices, etc.

Chapter 12 - 61
Polymorphic Forms of Carbon (cont)
Graphite
– layered structure – parallel hexagonal arrays of carbon atoms

– weak van der Waal’s forces between layers

– planes slide easily over one another -- good lubricant

Chapter 12 - 62
 Point Defects in Ceramics (i)
• Vacancies
-- vacancies exist in ceramics for both cations and anions

Cation
Interstitial
Cation
Vacancy

Anion
Vacancy

Chapter 12 - 63
 Point Defects in Ceramics (i)
• Vacancies
-- vacancies exist in ceramics for both cations and anions
• Interstitials
-- interstitials exist for cations
-- interstitials are not normally observed for anions because anions
are large relative to the interstitial sites

Cation
Interstitial
Cation
Vacancy

Anion
Vacancy

Chapter 12 - 64
 Point Defects in Ceramics (i)
• Vacancies
-- vacancies exist in ceramics for both cations and anions
• Interstitials
-- interstitials exist for cations
-- interstitials are not normally observed for anions because anions
are large relative to the interstitial sites

Cation
Interstitial
Cation
Vacancy

Anion
Vacancy

In an ionic ceramic, a cation vacancy must be accompanied by a

corresponding anion vacancy in order to maintain charge neutrality.
Chapter 12 - 65
 Point Defects in Ceramics (ii)
• Frenkel Defect
-- a cation vacancy-cation interstitial pair.

Shottky
Defect:

Frenkel
Defect

Chapter 12 - 66
 Point Defects in Ceramics (ii)
• Frenkel Defect
-- a cation vacancy-cation interstitial pair.
• Schottky Defect
-- a paired set of cation and anion vacancies.

Schottky
Defect:

Frenkel
Defect

-QD / kT
• Equilibrium concentration of defects µe

Chapter 12 - 67
 Imperfections in Ceramics
Electroneutrality (charge balance) must be maintained when impurities are present
• Ex: NaCl
Na + Cl -
cation
Substitutional cation impurity, Ca2+
vacancy
2+
Ca Since the substitution of a
Na+ by a Ca2+ increases the
Na + charge by +1, it imposes the
creation of a Na+ vacancy to
Na + keep electroneutrality
Ca2+
without impurity Ca 2+ impurity with impurity

Substitutional anion impurity, O2-

2-
anion vacancy
O
Since the substitution of a
Cl- by a O2- decreases the
charge by -1, it imposes the
creation of a Cl- vacancy to
Cl - Cl - keep electroneutrality

without impurity O 2- impurity with impurity

Chapter 12 - 68
 Imperfections in Ceramics
Electroneutrality (charge balance) must be maintained when impurities are present
• Ex: NaCl
Na + Cl -
cation
Substitutional cation impurity, Ca2+
vacancy
2+
Ca Since the substitution of a
Na+ by a Ca2+ increases the
Na + charge by +1, it imposes the
creation of a Na+ vacancy to
Na + keep electroneutrality
Ca2+
without impurity Ca 2+ impurity with impurity

Substitutional anion impurity, O2-

2-
anion vacancy
O
Since the substitution of a
Cl- by a O2- decreases the
charge by -1, it imposes the
creation of a Cl- vacancy to
Cl - Cl - keep electroneutrality

without impurity O 2- impurity with impurity

Chapter 12 - 69
 Imperfections in Ceramics
Electroneutrality (charge balance) must be maintained when impurities are present
• Ex: NaCl
Na + Cl -
cation
Substitutional cation impurity, Ca2+
vacancy
2+
Ca Since the substitution of a
Na+ by a Ca2+ increases the
Na + charge by +1, it imposes the
creation of a Na+ vacancy to
Na + keep electroneutrality
Ca2+
without impurity Ca 2+ impurity with impurity

Substitutional anion impurity, O2-

2-
anion vacancy
O
Since the substitution of a
Cl- by a O2- decreases the
charge by -1, it imposes the
creation of a Cl- vacancy to
Cl - Cl - keep electroneutrality

without impurity O 2- impurity with impurity

Chapter 12 - 70
 Imperfections in Ceramics
Electroneutrality (charge balance) must be maintained when impurities are present
• Ex: NaCl
Na + Cl -
cation
Substitutional cation impurity, Ca2+
vacancy
2+
Ca Since the substitution of a
Na+ by a Ca2+ increases the
Na + charge by +1, it imposes the
creation of a Na+ vacancy to
Na + keep electroneutrality
Ca2+
without impurity Ca 2+ impurity with impurity

Substitutional anion impurity, O2-

2-
anion vacancy
O
Since the substitution of a
Cl- by a O2- decreases the
charge by -1, it imposes the
creation of a Cl- vacancy to
Cl - Cl - keep electroneutrality

without impurity O 2- impurity with impurity

Chapter 12 - 71
 Ceramic Phase Diagrams

Phase diagrams for ceramic materials obey the same rules as for metal
systems. An important difference is that the components are usually
themselves binary compounds, rather than pure elements.

Chapter 12 -
 Ceramic Phase Diagrams

Phase diagrams for ceramic materials obey the same rules as for metal
systems. An important difference is that the components are usually
themselves binary compounds, rather than pure elements.

Cr2O3 -Al2O3
➢One of the simplest ceramic binary
phase diagrams.
• Complete solubility:
✓ Al, Cr atoms possess similar
size and chemical valence
✓Both oxides have the same
crystal structure
✓ Al3+ substitutes for the Cr3+
ion in Cr2O3 (and vice versa)

Chapter 12 -
 Ceramic Phase Diagrams

Phase diagrams for ceramic materials obey the same rules as for metal
systems. An important difference is that the components are usually
themselves binary compounds, rather than pure elements.

Cr2O3 -Al2O3
➢One of the simplest ceramic binary
phase diagrams.
• Complete solubility:
✓ Al, Cr atoms possess similar
size and chemical valence
✓Both oxides have the same
crystal structure
✓ Al3+ substitutes for the Cr3+
ion in Cr2O3 (and vice versa)

Chapter 12 -
 Ceramic Phase Diagrams

Note: This system

contains two eutectics,
one on either side of
the spinel (AB2X4) spinel
phase.

Chapter 12 -
 Mechanical Properties

Metals/ Graphite/
Ceramics/
Alloys
Semicond
5000
3000

Tensile strength, TS (MPa)

2000 Steel (4140) qt

1000 W (pure) Diamond

Ti (5Al-2.5Sn)aa
Steel (4140)
Cu (71500) cw Si nitride
Cu (71500) hr Al oxide
Steel (1020)
300 Al (6061) ag
Ti (pure) a
200 Ta (pure)
Al (6061) a Si crystal
100 <100>
Glass-soda
40 Concrete
30

20 Graphite

10

1
Chapter 12 -
 Mechanical Properties
Ceramic materials are more brittle than metals. Why is this so?
Metals/ Graphite/
Ceramics/
Alloys
Semicond
5000
3000

Tensile strength, TS (MPa)

2000 Steel (4140) qt

1000 W (pure) Diamond

Ti (5Al-2.5Sn)aa
Steel (4140)
Cu (71500) cw Si nitride
Cu (71500) hr Al oxide
Steel (1020)
300 Al (6061) ag
Ti (pure) a
200 Ta (pure)
Al (6061) a Si crystal
100 <100>
Glass-soda
40 Concrete
30

20 Graphite

10

1
Chapter 12 -
 Mechanical Properties
Ceramic materials are more brittle than metals. Why is this so?

Dislocation Characteristics Ceramics

(slide picked up from Chapter 7 Dislocations & Strengthening Mechanisms)

Chapter 12 -
 Mechanical Properties
Ceramic materials are more brittle than metals. Why is this so?

Dislocation Characteristics Ceramics

(slide picked up from Chapter 7 Dislocations & Strengthening Mechanisms)

• Ceramics—Covalently Bonded
- Examples: silicon, diamond
- Dislocation motion— relatively
difficult because of Covalent
bonding—directional

Chapter 12 -
 Mechanical Properties
Ceramic materials are more brittle than metals. Why is this so?

Dislocation Characteristics Ceramics

(slide picked up from Chapter 7 Dislocations & Strengthening Mechanisms)

• Ceramics—Covalently Bonded
- Examples: silicon, diamond
- Dislocation motion— relatively
difficult because of Covalent
bonding—directional

• Ceramics—Ionically Bonded + - + - + - +
- Examples: MgO, Al2O3
- + - + - + -
- Dislocation motion—relatively
difficult because of: + - + - + - +
- motion of nearby ions of like charge (+ or -)
restricted by electrostatic repulsive forces

Chapter 12 -
 Mechanical Properties
Ceramic materials are more brittle than metals. Why is this so?

Dislocation Characteristics Ceramics

(slide picked up from Chapter 7 Dislocations & Strengthening Mechanisms)

• Ceramics—Covalently Bonded
- Examples: silicon, diamond
- Dislocation motion— relatively
difficult because of Covalent
bonding—directional

• Ceramics—Ionically Bonded + - + - + - +
- Examples: MgO, Al2O3
- + - + - + -
- Dislocation motion—relatively
difficult because of: + - + - + - +
- motion of nearby ions of like charge (+ or -)
restricted by electrostatic repulsive forces
- Few slip systems

Chapter 12 -
 difficult to prepare and shape specimens with the required geometry

Ceramics are typically too brittle to be difficult to grip brittle materials without fracturing them
Submitted to conventional tensile tests
ceramics fail after only about 0.1% strain, specimens should
be perfectly aligned to avoid bending stresses

Chapter 12 - 82
 difficult to prepare and shape specimens with the required geometry

Ceramics are typically too brittle to be difficult to grip brittle materials without fracturing them
Submitted to conventional tensile tests
ceramics fail after only about 0.1% strain, specimens should
be perfectly aligned to avoid bending stresses

Flexural Tests – Measurement of Elastic Modulus

• Room T behavior is usually elastic, with brittle failure.
• 3-Point Bend Testing often used.
cross section F
L/2 L/2
d R
b δ = midpoint
rect. circ.
deflection

Chapter 12 - 83
 difficult to prepare and shape specimens with the required geometry

Ceramics are typically too brittle to be difficult to grip brittle materials without fracturing them
Submitted to conventional tensile tests
ceramics fail after only about 0.1% strain, specimens should
be perfectly aligned to avoid bending stresses

Flexural Tests – Measurement of Elastic Modulus

• Room T behavior is usually elastic, with brittle failure.
• 3-Point Bend Testing often used.
cross section F
L/2 L/2
d R
b δ = midpoint
rect. circ.
deflection
• Determine elastic modulus according to:
F L3
E= (rect. cross section)
F
d 4bd 3
slope =
δ
F L3
E= (circ. cross section)
linear-elastic behavior
d 12p R 4
Chapter 12 - 84
 Flexural Tests – Measurement of Flexural Strength (Eq. Tensile strength)

3-point bend test (till fracture) to measure room-T flexural strength.

cross section F
L/2 L/2
d R
b δ = midpoint
rect. circ.
deflection
location of max tension

Chapter 12 - 85
 Flexural Tests – Measurement of Flexural Strength (Eq. Tensile strength)

3-point bend test (till fracture) to measure room-T flexural strength.

cross section F
L/2 L/2
d R
b δ = midpoint
rect. circ.
deflection
location of max tension
Flexural strength:

Ff = load on fracture

3Ff L
s fs =
2bd 2
(rect. cross section)

Ff L
s fs =
p R3
(circ. cross section)
Chapter 12 - 86
 Flexural Tests – Measurement of Flexural Strength (Eq. Tensile strength)

3-point bend test (till fracture) to measure room-T flexural strength.

cross section F
L/2 L/2
d R
b δ = midpoint
rect. circ.
deflection
location of max tension
Flexural strength: Typical values:

Ff = load on fracture Material σ fs (MPa) E(GPa)

Si nitride 250-1000 304
Si carbide 100-820 345
3Ff L Al oxide 275-700 393
s fs =
2bd 2 glass (soda-lime) 69 69
(rect. cross section)

Ff L
s fs =
p R3
(circ. cross section)
Chapter 12 - 87
 Classification of Ceramics

Ceramic Materials

Glasses Clay Refractories Abrasives Cements Ceramic Carbon Advanced

products biomaterials ceramics

-optical -whiteware -bricks for -sandpaper -composites -implants -composites -engine

-composite -structural high T - cutting - structural - abrasives rotors
reinforce (furnaces) - polishing valves
-containers/ bearings
household -sensors

Chapter 12 - 88
 Ceramics Application: Die Blanks

• Die blanks: die Ad

-- Need wear resistant properties Ao tensile
force
die
• Die surface:
-- 4 μm polycrystalline diamond
particles that are sintered onto a
cemented tungsten carbide
substrate.
-- polycrystalline diamond gives uniform
hardness in all directions to reduce
wear.

Chapter 12 - 89
 Ceramics Application:
Cutting Tools
• Tools:
-- for grinding glass, tungsten
carbide, ceramics
-- for cutting Si wafers
-- for oil drilling

• Materials: oil drill bits blades

-- manufactured single crystal
or polycrystalline diamonds Single crystal
diamonds
in a metal or resin matrix.
-- polycrystalline diamonds
polycrystalline
resharpen by microfracturing diamonds in a resin
along cleavage planes. matrix.

Chapter 12 - 90
 Refractories
• Materials to be used at high temperatures (e.g., in
high temperature furnaces).
• Consider the Silica (SiO2) - Alumina (Al2O3) system.
• Supports high temperatures, unreactive, thermal
insulation…
2200 3Al2O3-2SiO2
T(ºC)
mullite
2000 Liquid
(L) alumina + L

1800
crystobalite mullite alumina
+L +L +
1600 mullite
mullite
+ crystobalite
1400
0 20 40 60 80 100
Composition (wt% alumina)
Chapter 12 - 91
 Advanced Ceramics: Materials for Automobile (aircrafts, rockets, …)
(brake discs, fuel injectors,…)

• Advantages:
– Operate at high • Disadvantages:
temperatures – high – Ceramic materials are
efficiencies brittle
– Low frictional losses – Difficult to remove internal
– Operate without a cooling voids (that weaken
system structures)
– Lower weights than – Ceramic parts are difficult
current materials to form and machine

• Potential candidate materials: Si3N4, SiC, & ZrO2

• Possible engine parts: engine block & piston coatings
Chapter 12 - 92
 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
change in oxygen concentration
• Approach: A substituting Ca2+ ion
removes a Zr 4+ ion and
Add Ca impurity to ZrO2: an O2- ion.
-- increases O2- vacancies
-- increases O2- diffusion rate
• Operation: sensor
-- voltage difference produced when gas with an reference
O2- ions diffuse from the external unknown, higher gas at fixed
oxygen content O2-
surface through the sensor to the oxygen content
diffusion
reference gas surface.
-- magnitude of voltage difference
 partial pressure of oxygen at the + -
voltage difference produced!
external surface
Chapter 12 - 93
 Advanced Ceramics:
Materials for Ceramic Armor

Components:
-- Outer facing plates
-- Backing sheet

Properties/Materials:
-- Facing plates -- hard and brittle
—
—
-- Backing sheets -- soft and ductile
—
—

Chapter 12 - 94
 Advanced Ceramics:
Materials for Ceramic Armor

Components:
-- Outer facing plates
-- Backing sheet

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

Chapter 12 - 95
 Nanocarbons
• Fullerenes – spherical cluster of 60 carbon atoms, C60
– Like a soccer ball
• Carbon nanotubes – sheet of graphite rolled into a tube
– Ends capped with fullerene hemispheres

Chapter 12 - 96
 Nanocarbons (cont.)
• Graphene – single-atomic-layer of graphite
– composed of hexagonally sp2 bonded carbon atoms

Chapter 12 - 97
 Ceramic Fabrication Methods (i)

GLASS PARTICULATE CEMENTATION

FORMING FORMING
• Blowing of Glass Bottles: • Pressing: plates, cheap glasses
Pressing -- glass formed by application of
Gob
operation
pressure
Parison
-- mold is steel with graphite
mold lining
• Fiber drawing:
Compressed
air

Suspended
parison

Finishing wind up
mold

Chapter 12 - 98
 Sheet Glass Forming

• Sheet forming – continuous casting

– sheets are formed by floating the molten glass on a pool of
molten tin

Chapter 12 - 99
 Ceramic Fabrication Methods (iia)

GLASS PARTICULATE CEMENTATION

FORMING FORMING
Hydroplastic forming:
• Mill (grind) and screen constituents: desired particle size
• Extrude this mass (e.g., into a brick)

Ao
container die holder
force
ram billet extrusion Ad
container die

• Dry and fire the formed piece

Chapter 12 - 10
 Ceramic Fabrication Methods (iia)

GLASS PARTICULATE CEMENTATION

FORMING FORMING
Slip casting:
• Mill (grind) and screen constituents: desired particle size
• Mix with water and other constituents to form slip
• Slip casting operation
pour slip absorb water pour slip drain “green
into mold into mold into mold mold ceramic”
“green
ceramic”

solid component hollow component

• Dry and fire the cast piece

Chapter 12 - 10
 Typical Porcelain Composition

(50%) 1. Clay
(25%) 2. Filler – e.g. quartz (finely ground)
(25%) 3. Fluxing agent (Feldspar)
-- aluminosilicates plus K+, Na+, Ca+
-- upon firing - forms low-melting-temp. glass

Chapter 12 - 10
 Drying and Firing
• Drying: as water is removed - interparticle spacings decrease
– shrinkage .

wet body partially dry completely dry

Drying too fast causes sample to warp or crack due to non-uniform shrinkage

micrograph of porcelain
Si02 particle
• Firing: (quartz)
-- heat treatment between glass formed
900-1400°C around
-- vitrification: liquid glass forms the particle

from clay and flux – flows

between SiO2 particles. (Flux 70μm
lowers melting temperature).

Chapter 12 - 10
 Ceramic Fabrication Methods (iib)

GLASS PARTICULATE CEMENTATION

FORMING FORMING

Powder Pressing: used for both clay and non-clay compositions.

• Powder (plus binder) compacted by pressure in a mold

-- Uniaxial compression - compacted in single direction
-- Isostatic (hydrostatic) compression - pressure applied by
fluid - powder in rubber envelope
-- Hot pressing - pressure + heat

Chapter 12 - 10
 Sintering
Sintering occurs during firing of a piece that has
been powder pressed
-- powder particles coalesce and reduction of pore size

Aluminum oxide powder:

-- sintered at 1700°C
for 6 minutes.

15 μm
Chapter 12 - 10
 Ceramic Fabrication Methods (iii)

GLASS PARTICULATE CEMENTATION

FORMING FORMING
• Hardening of a paste – paste formed by mixing cement
material with water
• Formation of rigid structures having varied and complex
shapes
• Hardening process – hydration (complex chemical
reactions involving water and cement particles)
• Portland cement – production of:
-- mix clay and lime-bearing minerals
-- calcine (heat to 1400°C)
-- grind into fine powder

Chapter 12 - 10