Chapter 6 1 Ceramic

Topic 6.
Ceramic materials (I)
Universidad
Carlos III de Madrid
MATERIALS SCIENCE AND ENGINEERING
www.uc3m.es
TOPIC 6. CERAMIC MATERIALS
•  Introduction
•  Structure of Ceramic Materials
•  Glasses
•  Mechanical Properties of Ceramic Materials
•  Processing of Ceramic Materials
•  Examples of applications
Dpt. Materials Sci. and Eng. and Chem. Eng. UC3M Sophia A. Tsipas / Mª Eugenia Rabanal / Alejandro Várez 1
Topic 6. Ceramic materials (I)
INTRODUCTION
Inorganic Materials made from Metals and Non Metals united by ionic
and/or covalent bonds
Can be: crystalline, amorphous or mixture of both
Dpt. Materials Sci. and Eng. and Chem. Eng. UC3M Sophia A. Tsipas / Francisco Velasco / Belén Levenfeld 2
GENERAL PROPERTIES
• High Young’s Modulus and high melting points

⇒  Strong bonds (covalent and /or ionic)
• Limited electrical and thermal conductivity
⇒  Absence of electronic cloud (directional bond)
• Low thermal shock resistance
⇒  Coefficients of thermal expansion and thermal conductivity are low
• Refractory
⇒  Stability at high temperature (NO CREEP)
• Resistance to oxidation/corrosion
⇒  Chemical stability
CLASSIFICATION
Based on SiO2 + additives for ↓ Tf
Clay: Al2O3· SiO2·H2O

  Porous ceramics (bricks, pottery, china)
Silica: SiO2
  Compact ceramics (porcelain, earthware)
Feldspar: K2O· Al2O3 6SiO2
  Refractory ceramics
  Refractory ceramics (SiC, Al2O3, ZrO2, BeO, MgO).

  Piezoelectrics and Ferroelectrics: BaTiO3, SrTiO3
  Electro-optics: LiNbO3
  Abrasive ceramics: nitrides and carbides Si3N4 , SiC
  Molecular membranes
  Superconductive ceramics (YBa2Cu3O7)
  Biomaterials : Hydroxyapatite
STRUCTURE
Percentage of ionic and covalent character of the bond for some ceramic
materials  determines the CRYSTALLINE STRUCTURE
Ceramic Atoms % Ionic % Covalent

XA - XB
Material in bond Character Character
MgO Mg—O 2,3 73 27

Al2O3 Al—O 2,0 63 37
SiO2 Si—O 1,7 51 49
Si3N4 Si—N 1,2 30 70
SiC Si-C 0,7 11 89
STRUCTURE
  Ions packing
  Electroneutrality of ionic ceramics
  Crystalline type structures
ELECTRONEUTRALITY IN IONIC CERAMICS
Ionic structure : packing of anions with cations in interstitials
Sizes C+ A- (rcation< ranion)
The ions tend to Electroneutrality

pack densely in
order to reduce Etotal Coordination Index (By increasing C.I 
increase stability)
Sharing of polyhedral (sharing vertices

instead of edges or faces (increases the
distance between cations)
PACKING OF IONS
Cation/anion
Arrangement of A- around C+ Radius ratio
central and C.I.
rC/rA
C.I. 8
0.732-1.0
Corners of a cube
C.I 6
0.414-0.732
Corners of an octahedron
C.I 4
0.225-0.414
Corners of a tetrahedron
C.I. 3
0.155-0.225
Corners of a triangle
SIMPLE CUBIC STRUCTURE: CsCl
 Cl- : cubic
 Cs+: centre of the cube
Cl-
 C.I.: 8
Cs+
Ceramics that have this type of structure: CsBr, TlCl, TlBr.
FCC STRUCTURE: NaCl
Cl-
Na+
 Cl-: FCC packing

 Na: all octahedral interstitials.
 4 Na+ and 4 Cl- per unit cell C.I.=6
Ceramics that have this type of structure: MgO, CaO, FeO, NiO
FCC STRUCTURE: Zn Blende-ZnS
 S2-: FCC packing

 Zn2+: ½ tetrahedral interstitials
 4 Zn2+ and 4 S2- per unit cell
S2- Zn2+
According to Pauling bond Zn-S ~87% covalent

Ceramics that have this type of structure: Typical semiconductors : CdS,
HgTe, NiAs, SiC, GaAs
HCP STRUCTURE: CORUNDUM (ALUMINA)
 O2-: HCP packing → 6 ions

 Al3+: 2/3 octahedral interstitials → 4 ions
 I.C.(Al3+): 6 ; I.C.(O2-): 6
Top view
Al3+
O2-
Unit cell
Closed-packed layer of O2- with 2/3
of octahedral sites filled with Al3+
Ceramics that have this type of structure: Cr2O3, Fe2O3, Al2O3 …
CRYSTALLINE STRUCTURE OF PEROVSKITE ABO3
TYPE B
A and B cations with different size
(rA>>>rB)
  O2- and Ca2+: fcc packing

  Ti4+: 1/4 octahedral sites
  C.I.(Ti2+): 6 ; C.I.(Ca2+): 12
Ceramics that adopt this type

structure:
BaTiO3, CaTiO3, SrTiO3,
PbZrO3,, KNbO3, LiNbO3,…
Ferroelectric Materials,
Magnetic Superconductor properties
(YBa2Cu3O7)
TYPE A
Summary of Some Common Ceramic Crystal Structures
Structure name Structu Anion Coordination numbers Examples

re type packing
cation anion
Rock salt (sodium AX FCC 6 6 NCl, MgO, FeO

chloride)
Cesium chloride AX Simple cubic 8 8 CsCl
Zinc Blende AX FCC 4 4 ZnS, SiC

(sphalerite)
Fluorite AX2 Simple cubic 8 4 CaF2, UO2 ThO2
Perovskite AΒX3 FCC 12 (A) 6 BaTiO3, SrZrO3,

6(B) SrSnO3
Spinel AΒ2X4 FCC 4(A) 4 MgAl2O4,
6(B) FeAl2O4
Dpt. Materials Sci. and Eng. and Chem. Eng. UC3M Sophia A. Tsipas / Francisco Velasco / Belén Levenfeld
COVALENT CERAMICS
C→ sp3 → c.i. 4 → Tetrahedral CC4. Bond 100% covalent.
 ↑ wear resistance ↑ hardness

 ↑ tensile strength Insulator
 Applications: Good abrasive properties. 89% covalent bond

 High hardness, chemically inert.
COVALENT CERAMICS
Si → sp3 → c.i. 4 → SiN4 Tetrahedra

N → sp2 → c.i. 3 → N coordinated to 3 Si β-SiN4
Open structure.
70% covalent bond
It is a solid solution between nitrides and oxides. Derived from Si3N4, by substituting z
atoms of Si for Al atoms. In order to compensate the valence difference, the same
number of N atoms are substituted by O. Cutting tools, antifriction rollers, motors
components.
STRUCTURE OF SILICATES
Composition (wt%)
Ceramic SiO2 Al2O3 K2O Mg CaO Othe
O r
Silica refractory 96 4
Fireclay refractory 50-70 45-25 5
Mullite refractory 28 72 -
Electrical porcelain 61 32 6 1
Steatite porcelain 64 5 30 1
Portland cement 25 9 64 2
Composition of some silicate ceramics
Type
• Orthoslilicates or olivines
(island tetrahedra SiO44-)
Example: Forsterite (Mg2SiO4)
• pyroslilicate
(island tetrahedra Si2O76-)
Example: (Ca2MgSi2O7)
• metasilicates (SiO3)n2n- (ring and chain structures) Mg2SiO4 (olivine)
Ring structures
Examples: Wollastonite (CaSiO3), beryl Be3Al2(SiO3)6
chain structures
Example: Enstatite (MgSiO3)
• sheet or layered silicates
(Si2O5) 2-
Example: Kaolinite clay Al2 (Si2O5)(OH)4
are talc [Mg3 (Si2O5) 2(OH) 2]
micas [e.g., muscovite, KAl3Si3O10(OH) 2
• 3D (SiO2)
Quartz , tridymite,
cristobalite (SiO2) pyroslilicates
Metasilicates (Ring and Chain Structure)
2 of the 4 O- atoms in the tetrahedral SiO44- are united to

another tetrahedral in order to form chains of silicate
Formula: (SiO3)n2n-
Chain Structure
http://commons.wikimedia.org/wiki/
File:Cyclosilicates_3.svg
Ring Structure Wollastonite (CaSiO3)
http://commons.wikimedia.org/wiki/File:Wollastonite_a_%2B_c.png
Sheet or layered structure
3 of the 4 O- atoms of in the tetrahedral SiO44- are united to another
tetrahedral in order to form layers of silicates
  Kaolinite Al2(OH)42+ There is one O- without bond in each tetrahedral

  Talc: Mg3(OH)42+ ⇒ charge (-)  Joining laminas (+)
negative Electrically neutral
KAOLINITE
positive
Silica Feldspars
  They share all the corners in the
tetrahedra   Similar structure to Silica (Al3+
replaces Si4+) ⇒ lattice with (-)
  Unit formula : SiO2 charge ⇒ compensates the charge
  Presents Allotropy with voluminous cations (Na+, K+,
Ca2+, Ba2+) in interstitial positions .
  Important component in many
traditional ceramics and many types of   Principal component of traditional
glasses ceramics
β-quartz
β-cristobalite
α-quartz
NON CRYSTALLINE CERAMICS : GLASSES
Behaviour of glass during solidification
Crystalline Solid GLASS Contraction

s due to
As ↓T crystallizes As ↓T: ↑viscosity Glas freezing
e s.
in Tm Plastic stage ⇔ Rigid tallin
Crys
stage
CONSTITUENTS OF GLASSES
CONSTITUENTS OF GLASSES
COLOURS THAT METALLIC IONS GIVE TO

GLASSES
M+ as a MODIFIER
ION C. I. COLOUR
Cr 3+ 6 Blue
Cr6+ 6 Green
Cu 2+ 8 Blue –green
Cu+ 6-8 Transparent
Co 2+ 6-8 Rose
Ni2+ 8 Yellow –green
Mn 2+ 6 Light orange
Mn3+ 6-8
Fe 2+ 6 Blue-green
Fe3+ 6-10 Light yellow
U 6+ 6 Light yellow
V3+ 6 Green
V4+ Blue
PROPERTIES OF GLASSES
Mechanical Properties
Brittle Materials (↑↑ elastic modulus ) = f (composition, macroscopic

(surface) imperfections, volume of material and T)
Low modulus of Weibull
Mechanical strength ↓ (presence of water/air + humidity )
Electrical Properties
Generally insulators (σ ≈ 10-10 -10-20 Ωcm-1)

σ↑↑ with Temperature
σ↑↑ with modifier (=f(size and amount of modifier))
Material Thermal Expansion Thermal Shock
coeff. (oC-1) failure (oC)
Thermal Shock Soda-lime glass 10-5 80
Sodium borosilicate 10-4 270

( Pyrex TM type)
↑↑α = ↓Rthermal shock Fused silica 10-6 1600
Lithia-alumina-silicate 10-6 670

glass ceramic
(Pyroceram TM type)
Transparent lithia- 10-6 1330

alumina-silicate glass
ceramic (Visions TM
type)
Thermal shock resistance of common glasses and glass ceramics


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Topic 6.

Ceramic materials (I)

TOPIC 6. CERAMIC MATERIALS

Can be: crystalline, amorphous or mixture of both

• High Young’s Modulus and high melting points

Based on SiO2 + additives for ↓ Tf

Clay: Al2O3· SiO2·H2O

 Refractory ceramics (SiC, Al2O3, ZrO2, BeO, MgO).

Ceramic Atoms % Ionic % Covalent

MgO Mg—O 2,3 73 27

ELECTRONEUTRALITY IN IONIC CERAMICS

Ionic structure : packing of anions with cations in interstitials

Sizes C+ A- (rcation< ranion)

The ions tend to Electroneutrality

Sharing of polyhedral (sharing vertices

SIMPLE CUBIC STRUCTURE: CsCl

Ceramics that have this type of structure: CsBr, TlCl, TlBr.

FCC STRUCTURE: NaCl

 Cl-: FCC packing

FCC STRUCTURE: Zn Blende-ZnS

 S2-: FCC packing

According to Pauling bond Zn-S ~87% covalent

HCP STRUCTURE: CORUNDUM (ALUMINA)

 O2-: HCP packing → 6 ions

Ceramics that have this type of structure: Cr2O3, Fe2O3, Al2O3 …

CRYSTALLINE STRUCTURE OF PEROVSKITE ABO3

 O2- and Ca2+: fcc packing

Ceramics that adopt this type

Summary of Some Common Ceramic Crystal Structures

Structure name Structu Anion Coordination numbers Examples

Rock salt (sodium AX FCC 6 6 NCl, MgO, FeO

Zinc Blende AX FCC 4 4 ZnS, SiC

Perovskite AΒX3 FCC 12 (A) 6 BaTiO3, SrZrO3,

C→ sp3 → c.i. 4 → Tetrahedral CC4. Bond 100% covalent.

 ↑ wear resistance ↑ hardness

 Applications: Good abrasive properties. 89% covalent bond

Si → sp3 → c.i. 4 → SiN4 Tetrahedra

Composition of some silicate ceramics

2 of the 4 O- atoms in the tetrahedral SiO44- are united to

 Kaolinite Al2(OH)42+ There is one O- without bond in each tetrahedral

negative Electrically neutral

NON CRYSTALLINE CERAMICS : GLASSES

Behaviour of glass during solidification

Crystalline Solid GLASS Contraction

As ↓T crystallizes As ↓T: ↑viscosity Glas freezing

COLOURS THAT METALLIC IONS GIVE TO

Brittle Materials (↑↑ elastic modulus ) = f (composition, macroscopic

Generally insulators (σ ≈ 10-10 -10-20 Ωcm-1)

Sodium borosilicate 10-4 270

Lithia-alumina-silicate 10-6 670

Transparent lithia- 10-6 1330

Thermal shock resistance of common glasses and glass ceramics

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• High Young’s Modulus and high melting points

  Refractory ceramics (SiC, Al2O3, ZrO2, BeO, MgO).

 Cl-: FCC packing

 S2-: FCC packing

 O2-: HCP packing → 6 ions

  O2- and Ca2+: fcc packing

 ↑ wear resistance ↑ hardness

 Applications: Good abrasive properties. 89% covalent bond

  Kaolinite Al2(OH)42+ There is one O- without bond in each tetrahedral