2014-03-22

Chapter 12: Structures & Properties of Ceramics

Chapter Outline:
Introduction to ceramics ! Crystal structures of ceramic materials Point defects and impurities in ceramics ! Ceramic phase diagrams ! Mechanical properties of ceramics
Chapter 12 - 1

Comparison of Metal and Ceramic Properties

Metals Metallic atoms Metallic bonds Crystalline Unit cells (BCC, FCC and HCP) CN = 8 and 12 Solid solutions Slip planes Ceramics Metallic plus non-metallic atoms Ionic and covalent bonds Crystalline and amorphous Unit cells of metallic and nonmetallic atoms CN = 2, 3, 4, 6, 8 and 12 Solid solutions Cleavage planes

Use of phase diagrams to determine Same equilibrium structures

Chapter 12 - 2

Ceramic Properties
In general, ceramics are:
! Hard and brittle ! Low toughness and ductility ! Good electrical and thermal insulators ! Relatively high melting temperatures ! High chemical stability in many hostile environments

Classification of Ceramics
Traditional ceramics are made from three basic components
! Clay (hydrated alumina silicates) ! Flint (silica) ! Feldspar (alkali alumina silicates)

Examples:
! Chinaware ! Bricks and tiles ! Dental and electrical porcelain (e.g. fillings and spark plugs)
Chapter 12 - 4

Because of these properties, ceramic materials are indispensible for many engineering applications.
Chapter 12 - 3

2014-03-22

Classification of Ceramics
Engineering ceramics are made from pure or nearly pure compounds, such as;
! Aluminum oxide (Al2O3) ! Silicon carbide (SiC) ! Silicon nitride (Si3N4)

Simple Ceramic Properties

Some simple ceramic compounds with their melting temperatures
Ceramic Compound Hafnium carbide, HfC Titanium carbide, TiC Tungsten carbide, WC Magnesium oxide, MgO Silicon carbide, SiC Boron carbide, B4C Aluminum oxide, Al2O3 Silicon dioxide, SiO2 (Cristobalite) Silicon nitride, Si3N4 Titanium dioxide, TiO2 Melting Temperature (oC) 4150 3120 2850 2798 2500 2450 2050 1715 1900 1605
Adapted from, Smith, Foundations of Materials Science and Engineering

Examples:
! High temperature areas of turbine engines ! Integrated circuit chips ! Advanced cutting tools
Chapter 12 - 5

Chapter 12 - 6

Simple Ceramic Properties

Percent Ionic and Covalent Bonding Character for Some Ceramics
Ceramic Compound Magnesium oxide, MgO Aluminum oxide, Al2O3 Silicon dioxide, SiO2 (Cristobalite) Silicon nitride, Si3N4 Silicon carbide, SiC Bonding atoms Mg - O Al - O Si - O Electronegativity difference 2.3 2.0 1.7 % Ionic character 73 63 51 % Covalent character 27 37 49

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

Si - N Si - C

1.2 0.7

30 11

70 89
Adapted from Fig. 2.7, Callister & Rethwisch 8e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the Chemical Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Chapter 12 - 8 Cornell University.)

Adapted from, Smith, Foundations of Materials Science and Engineering

Chapter 12 - 7

2014-03-22

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

Crystallography of Ceramics

Chapter 12 - 9

Chapter 12 - 10

Factors that Determine Crystal Structure

1. Relative sizes of ions Formation of stable structures:
--maximize the # of oppositely charged ion neighbors.

Adapted from Fig. 12.1, Callister & Rethwisch 8e.

To form a stable structure, how many anions can surround around a cation?
r cation r anion < 0.155 Coord # linear 2 3 triangular ZnS (zinc blende)
Adapted from Fig. 12.4, Callister & Rethwisch 8e.

r cation Coordination # increases with r anion

Coordination # and Ionic Radii

unstable 2. Maintenance of Charge Neutrality :

--Net charge in ceramic should be zero. --Reflected in chemical formula:

stable

stable Ca 2+ + cation Fanions F-

0.155 - 0.225 0.225 - 0.414 0.414 - 0.732 0.732 - 1.0

CaF 2 :

4 tetrahedral 6 octahedral 8 cubic

Adapted from Fig. 12.2, Callister & Rethwisch 8e.

NaCl (sodium chloride) CsCl (cesium chloride)

A m Xp
m, p values to achieve charge neutrality
Chapter 12 - 11

Adapted from Table 12.2, Callister & Rethwisch 8e.

Adapted from Fig. 12.3, Callister & Rethwisch 8e. Chapter 12 - 12

2014-03-22

Computation of Minimum Cation-Anion Radius Ratio

! Determine minimum rcation/ranion for an octahedral site (C.N. = 6) 2ranion + 2rcation = 2a

Bond Hybridization
Bond Hybridization is possible when there is significant covalent bonding ! hybrid electron orbitals form ! For example for SiC
! XSi = 1.8 and XC = 2.5

a = 2ranion
2ranion + 2rcation = 2 2ranion ranion + rcation = 2ranion ! ! rcation = ( 2 " 1) ranion

% ionic character = 100 {1- exp[-0.25(X Si " X C )2 ]} = 11.5%

! ~ 89% covalent bonding ! Both Si and C prefer sp3 hybridization ! Therefore, for SiC, Si atoms occupy tetrahedral sites

rcation = 2 ! 1 = 0.414 ranion !

Chapter 12 - 13 Chapter 12 - 14

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 O2Cl F Answer:

AX Crystal Structures
! Structures containing equal number of cations (A) and anions (X). ! Each structure is named after a common material that assumes that crystal structure.

rcation 0.077 = ranion 0.140 = 0.550

based on this ratio, -- coord # = 6 because 0.414 < 0.550 < 0.732 -- crystal structure is Rock Salt

! AX structures include:
! Rock Salt Structure ! Cesium Chloride Structure ! Zinc Blende Structure
Chapter 12 - 16

0.140 0.181 0.133

Data from Table 12.3, Callister & Rethwisch 8e. Chapter 12 - 15

2014-03-22

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

MgO and FeO

MgO and FeO also have the NaCl structure
O2Mg2+ rO = 0.140 nm rMg = 0.072 nm

rNa/rCl = 0.564 !! Cations (Na+) prefer Octahedral sites

Adapted from Fig. 12.2, Callister & Rethwisch 8e.

rMg/rO = 0.514 !! cations prefer octahedral sites

Adapted from Fig. 12.2, Callister & Rethwisch 8e.

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

Chapter 12 - 17 Chapter 12 - 18

Anion Packing: FCC

Cesium Chloride Structures

Cesium Chloride structure:

Zinc Blende (Sphalerite) Structure

rCs + rCl!

0.170 = 0.939 0.181

rZn + rS!

0.074 = 0.402 0.184

! Since 0.732 ! 0.939 ! 1.0, Cube centre sites preferred

Adapted from Fig. 12.3, Callister & Rethwisch 8e.

! Since 0.225 ! 0.402 ! 0.414, Tetrahedral sites preferred Zn+ has 4 neighbor SAnion packing: FCC

Cs+ has 8 neighbor Cl-

Anion Packing: Simple Cubic

Chapter 12 - 19 Adapted from Fig. 12.4, Callister & Rethwisch 8e.

Ceramics with this Structure: ZnS, ZnTe, SiC

Chapter 12 - 20

2014-03-22

AX2 Crystal Structures

Fluorite structure
! Calcium Fluorite (CaF2)
rCa 2+ rF! 0.100 = = 0.752 0.133

ABX3 Crystal Structures

! Perovskite structure Ex: complex oxide BaTiO3

! Since 0.732 ! 0.752 ! 1.0, Co-ordination Number: 8 ! Similar to CsCl structure, only half the number of cations. Ceramics with this Structure: UO2, ThO2, ZrO2, CeO2
Adapted from Fig. 12.5, Callister & Rethwisch 8e.

Adapted from Fig. 12.6, Callister & Rethwisch 8e.

Anion packing: Simple Cubic

! Antifluorite structure: Positions of cations and Chapter 12 - 21 anions reversed

Anion packing: FCC

Chapter 12 - 22

Packing in Ceramic Materials

! Anions pack in close-packed structures similar to metals (red and blue spheres)
Tetrahedral

! Cations may reside in interstitial positions ! Interstitial positions reside in either tetrahedrons (CN=4) or octahedrons (CN=6)

Octahedral

Chapter 12 - 23

Chapter 12 - 24

2014-03-22

Packing in Ceramic Materials

Rock Salt ! Green anions (Cl) form a FCC unit cell, plane shown is (111) ! The red cations (Na) sit as interstitials in octahedral positions Zinc Blende ! Cations sit as interstitials in tetrahedral positions Spinel structure (e.g. MgAl2O4) ! Mg2+ ions fill tetrahedral sites and Al3+ fill octahedral sites.
Ref: W.D. Callister and D.G.Rethwisch , Materials Science and Engineering An Introduction, 8th Edition, John Wiley & Sons (2009).
Chapter 12 - 25

Density Computations for Ceramics

Number of formula units/unit cell

#=

n"(!AC + !AA ) VC N A

Avogadros number

Volume of unit cell

NaCl (Rock Salt Structure)

"AC = sum of atomic weights of all cations in formula unit "AA = sum of atomic weights of all anions in formula unit !

!
Chapter 12 - 26

Density Computations for Ceramics

"=

!nC AC + !nA AA VU .C. N Avogadro

Silicates

"AC = sum of atomic weights of all cations in formula unit "AA = sum of atomic weights of all anions in formula unit !

!
Chapter 12 - 27 Chapter 12 - 28

2014-03-22

Silicate Ceramics
Most common elements on earth are Si & O

Silicates
Bonding of adjacent SiO44- accomplished by the sharing of common corners, edges, or faces

Si4+ O2Adapted from Figs. 12.9-10, Callister & Rethwisch 8e

crystobalite Mg2SiO4 Ca2MgSi2O7

! SiO2 (silica) polymorphic forms are quartz, crystobalite, & tridymite ! The strong Si-O bonds lead to a high melting temperature (1710C) for this material
Chapter 12 - 29

Adapted from Fig. 12.12, Callister & Rethwisch 8e.

Presence of cations such as Ca2+, Mg2+, & Al3+ 1. maintain charge neutrality, and 2. ionically bond SiO44- to one another
Chapter 12 - 30

Glass Structure
Basic Unit:
4Si0 4 tetrahedron
Si 4+ O2 -

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

Glass is noncrystalline (amorphous) Fused silica is SiO2 to which no impurities have been added Other common glasses contain impurity ions such as Na+, Ca2+, Al3+, and B3+
Na + Si 4+ O2 -

Quartz is crystalline SiO2:

! A net negative charge is associated with each (Si2O5)2- unit ! Negative charge balanced by adjacent plane rich in positively charged cations
Adapted from Fig. 12.13, Callister & Rethwisch 8e. Chapter 12 - 32

(soda glass)
Adapted from Fig. 12.11, Callister & Rethwisch 8e. Chapter 12 - 31

2014-03-22

Layered Silicates (cont.)

! Kaolinite clay alternates (Si2O5)2- layer with Al2(OH)42+ layer

Silicates

Adapted from Fig. 12.14, Callister & Rethwisch 8e.

Note: Adjacent sheets of this type are loosely bound to one another by van der Waals forces. !

Chapter 12 - 33

Chapter 12 - 34

Polymorphic Forms of Carbon

Diamond
! tetrahedral bonding of carbon
! hardest material known ! very high thermal conductivity

Polymorphic Forms of Carbon

! 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.
Adapted from Fig. 12.15, Callister & Rethwisch 8e.

Chapter 12 - 35

Chapter 12 - 36

2014-03-22

Polymorphic Forms of Carbon (cont)

Graphite
! layered structure parallel hexagonal arrays of carbon atoms

Polymorphic Forms of Carbon (cont) Fullerenes and Nanotubes

! Fullerenes spherical cluster of 60 carbon atoms, C60 ! Like a soccer ball (Called Buckyball) ! Carbon nanotubes sheet of graphite rolled into a tube ! Ends capped with fullerene hemispheres

Adapted from Fig. 12.17, Callister & Rethwisch 8e.

! weak van der Waals forces between layers ! planes slide easily over one another -- good lubricant
Chapter 12 - 37

Adapted from Figs. 12.18 & 12.19, Callister & Rethwisch 8e.

Chapter 12 - 38

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

Defects in Ceramics
Cation Interstitial Cation Vacancy
Adapted from Fig. 12.20, Callister & Rethwisch 8e. (Fig. 12.20 is from W.G. Moffatt, G.W. Pearsall, and J. Wulff, The Structure and Properties of Materials, Vol. 1, Structure, John Wiley and Sons, Inc., p. 78.) Chapter 12 - 40

Chapter 12 - 39

Anion Vacancy

10

2014-03-22

Point Defects in Ceramics (ii)

Frenkel Defect -- a cation vacancy-cation interstitial pair. Shottky Defect -- a paired set of cation and anion vacancies.
Shottky Defect:
Adapted from Fig.12.21, Callister & Rethwisch 8e. (Fig. 12.21 is from W.G. Moffatt, G.W. Pearsall, and J. Wulff, The Structure and Properties of Materials, Vol. 1, Structure, John Wiley and Sons, Inc., p. 78.)

Imperfections in Ceramics
Electroneutrality (charge balance) must be maintained Ex: NaCl

when impurities are present Na + Cl Substitutional cation impurity

Ca 2+ Na + Na + without impurity Ca 2+ impurity O2-

cation vacancy

Ca 2+ with impurity
an ion vacancy

Frenkel Defect

Substitutional anion impurity

Equilibrium concentration of defects: ! Q / 2 kT (Frenkel) N = Ne fr

N s = Ne ! Qs / 2 kT

fr

Cl Chapter 12 - 41

Cl with impurity
Chapter 12 - 42

(Shottky)

without impurity

O2- impurity

Diffusion in Ceramics
! Diffusion of atomic materials typically by vacancy mechanism. ! To maintain charge neutrality, diffusing ions move in pairs with ion of equal and opposite charge. ! Applied electric field causes ions to move.
! Electrical conductivity in ceramics is directly related to diffusion coefficient of ions.
Chapter 12 - 43

Ceramic Phase Diagrams

Cr2O3 - Al2O3 diagram:
Why Isomorphous?
1.!Al3+ and Cr3+ have Same Charge. 2.! Similar ionic radius (Al3+:
0.053nm, Cr3+: 0.062nm)

3.! Same crystal structure

(Al2O3 and Cr2O3)

Chapter 12 - 44

11

2014-03-22

Ceramic Phase Diagrams

MgO - Al2O3 diagram: MgO-Al2O3 diagram: Limited Solubility
1.!Mg2+ and Al3+ have Different Charge. 2.! Different ionic radius
(Al3+: 0.053nm, Mg2+: 0.072nm)

Mechanical Behaviour of Crystalline Ceramics

Ceramic materials are more brittle than metals. Why is this so?
! Consider mechanism of plastic deformation
! In crystalline, by dislocation motion ! In highly ionic ceramics, dislocation motion is difficult ! few slip systems ! resistance to motion of ions of like charge (e.g., anions) past one another (electrostatic repulsion) ! Covalent ceramics also brittle due to strong bonds, limited slip systems and complex dislocation structures.

! Limited slip during stress application results in crack formation and propagation (i.e. cleavage)
Chapter 12 - 45 Chapter 12 - 46

Mechanical Behaviour of Non-crystalline (Amorphous) Ceramics

! Plastic deformation occurs by viscous flow (same as for liquids).
! Atoms slide past one another by breaking and reforming bonds. ! Similar to slip, but no predescribed direction. ! Characteristic property: Viscosity ["] (non-crystalline materials resistance to deformation).

Room T behavior is usually elastic, with brittle failure.

Flexural Tests Measurement of Elastic Modulus

3-Point Bend Testing often used.

-- tensile tests are difficult for brittle materials. F cross section
L/2 L/2 d
rect.
Adapted from Fig. 12.32, Callister & Rethwisch 8e.

R
circ.

! = midpoint deflection

Determine elastic modulus according to:

x!
slope =

F "!

E=
E=

F L3 ! 4bd 3

(rect. cross section)

"=

dv

dy

linear-elastic behavior
Chapter 12 - 47

"!

F L3 (circ. cross section) " 12 !R 4

Chapter 12 - 48

12

2014-03-22

3-point bend test to measure room-T flexural strength.

cross section

Flexural Tests Measurement of Flexural Strength

L/2

SUMMARY
Interatomic bonding in ceramics is ionic and/or covalent. Ceramic crystal structures are based on:
-- maintaining charge neutrality -- cation-anion radii ratios. Imperfections -- Atomic point: vacancy, interstitial (cation), Frenkel, Schottky -- Impurities: substitutional, interstitial -- Maintenance of charge neutrality Room-temperature mechanical behavior flexural tests -- linear-elastic; measurement of elastic modulus -- brittle fracture; measurement of flexural modulus

L/2

d
rect.

R
circ.
location of max tension

Adapted from Fig. 12.32, Callister & Rethwisch 8e.

! = midpoint deflection

Flexural strength:

Typical values:
Material #fs ! (MPa) E(GPa) Si nitride 250-1000 304 Si carbide 100-820 345 Al oxide 275-700 393 glass (soda-lime) 69 69

!fs = "fs =

3Ff L 2bd Ff L

(rect. cross section)

!R 3

(circ. cross section)

Data from Table 12.5, Callister & Rethwisch 8e.

Chapter 12 - 49

Chapter 12 - 50

TERNARY PHASE DIAGRAM

Reading: Core Problems:

End of Chapter 12

Suggested Problems: Self-help Problems: 12.2, 12.3, 12.20, 12.22, 12.30

Chapter 12 - 51

Chapter 12 - 52

13