MME 467: Ceramics for Advanced Applications

Lecture 10
Defects in Ceramics 2
Ref: Barsoum, Fundamentals of Ceramics, Ch6, McGraw-Hill, 2000
Topics to discuss....

Defects reactions
 Rules for defect reactions
 Stoichiometric defect reactions
 Defect reactions for compound crystals
 Non-stoichiometric defect reactions
 Extrinsic defect reactions
 Defect Reactions

 Each defect can be treated as chemical entities

and treat them in a manner referred to as defect
chemistry.

 Formation of various defects and interactions of

various defects may be conceptualised in terms of
mass action equilibria by means of defect equations.
Rules for defect reactions

1. Mass Balance
 Mass cannot be created or destroyed. Vacancies have zero mass.

2. Electroneutrality, or charge balance

 Charge cannot be created or destroyed.

3. Preservation of regular site ratio

 Ratio between the numbers of regular cation and anion sites must
remain constant and equal to the ratio of the parent lattice.
 Thus if a normal lattice site of one component is created or destroyed,
the corresponding number of normal sites of the other constituent must
be simultaneously created or destroyed so as to preserve the site ratio
of the compound.
 To generalise, for an MaXb compound, the
following relation has to be maintained at all
times:
a( X X +VX ) = b( M M +VM )
M M +VM a
=
X X +VX b

 For example, in Al2O3 :

M Al +VAl 2 Note that, this does not mean that

= the number of atoms or ions has

XO +VO 3 to maintain that ratio, but only the

number of sites.
Stoichiometric Defect Reactions

Crystal chemistry (cations/

anions ratio) does not change.
No mass is transferred across the
crystal boundary.
Schottky Defect
Vacancy – vacancy pair

Important defects in this

category include:
1. Schottky defects
2. Frenkel defects
Frenkel Defect
Vacancy – interstitial pair
 Schottky defects

 In schottky defects, electric-charge-equivalent numbers

of vacancies are formed on each sub-lattice.

 For any compound MX (M+2, X–2), the Schottky defect

reaction is:
null = VM'' + V X ; DgS
or, perfect DgS = the free energy change for
crystal the formation of Schottky defect

 Schottky defect reaction for Al2O3: null = 2V Al''' + 3VO

 In general, for an MaOb oxide: null = aVMb – + bVOa +

 Thermodynamics of Schottky defects

 Assume that the number of ways of distributing cation

vacancies Vcat on (Ncat + Vcat) sites be W 1, and
number of ways of distributing anion vacancies Van on
(Nan + Van) sites be W 2.

 The configuration entropy

where

and ( Ncat + ncat ) ( Nan + nan) = 1

 Finding minimum in free energy will yield

Product of cation and anion vacancy concentrations

is a constant that depends only on temperature
Frenkel Defects

 A cation removed from its normal site to an

interstitial site to form an interstitial – vacancy pair

 For any trivalent cation (M+3), the Frenkel defect

reaction is:

MM x
=VM''' + Mi

 For anti-Frenkel defect, an anion is removed form

an interstitial – vacancy pair
 For oxygen ion (O–2), the Anti-Frenkel defect reaction is:

x
OO =VO +Oi
''
Thermodynamics of Frenkel defects

 number of ways of distributing ni interstitials on N*

interstitial sites be W 1, and

number of ways of distributing cation vacancies Vcat

on NT total sites be W 2.

N T!
W2 =
( NT - Vcat ) !Vcat!
 The configurational entropy is the same

 At equilibrium,

DgF = the free energy change for

the formation of Frenkel defect
 Note that N* depends on crystal structure.

 For example, for 1 mol NaCl, if the ions migrate to tetrahedral sites,
N* ≈ 2NAV.
Worked Example 6.1
Estimate the number of Frenkel defects in AgBr (rocksalt structure) at
500 ºC. The enthalpy of formation of the defect is 110 kJ/mol, and the
entropy of formation is 6.6R. The density and molecular weight are 6.5
g/cm3 and 187.8 g/mol, respectively. State all necessary assumptions.

Let us assume that

[1] the Frenkel disorder occurs on the cation sub-lattice
[2] silver ions go into the tetrahedral sites. Then
number of interstitial sites = 2 x number of lattice sites ≈ 2N AV

Vceatqnieq T DSF æ Dh ö
= exp exp ç - F
÷
NT N *
kT è kT ø
eq eq
Vcat ni 6.6R æ 110x1000 ö
= exp expç - ÷
2(6.02x10 ) 23 2
R è 8.314(500+ 273) ø

ni = 1.957x1043 defects/ mol 2

eq eq
Vcat
Worked Example 6.1
Estimate the number of Frenkel defects in AgBr (rocksalt structure) at
500 ºC. The enthalpy of formation of the defect is 110 kJ/mol, and the
entropy of formation is 6.6R. The density and molecular weight are 6.5
g/cm3 and 187.8 g/mol, respectively. State all necessary assumptions.

In case of Frenkel disorder,

number of cation vacant site = number of interstitial sites occupied

ni = 1.957x1043 defects/ mol 2

eq eq
Vcat
eq
Vcat = nieq = 4.43x1021 defects/ mol

And the corresponding number of defects/cm3 is

æ 6.5 ö
V eq
cat = n = 4.43x10 ç
eq
i
21
÷ = 1.5 x10 20
defects/cm 3

è 187.7 ø
Defects in Compound Crystals

Possible defects:
1. vacant sites on each sub-lattice
2. ions/atoms on interstitial sites
3. impurity ions/atoms on each sub-lattice
4. unassociated electrons and holes
5. combination of these defects
Example:

 Consider a crystal with a formula MaXb.

 If valence of M is z, then the valence of X

will be -(a/b)z.

 Reaction with its surroundings when M is added

to its normal cation site:

MaXb æ bö (a/ b)z

M(g) ¾ ¾¾® M M
x
+ ç ÷VX + ze¢
è aø
Example: Incorporating Si into SiO2

SiO2
® SiSix + 2VO + 4e¢
Si(g) ¾ ¾¾

Example: Incorporating Al into Al2O3

Al(g) ¾Al
¾¾2O3
® AlAl
x
+ 3 VO + 3e¢
2
Al2O3
or, 2Al(g) ¾ ¾¾® 2AlAl x
+ 3VO + 6e¢
Non-stoichiometric Defect Reactions

 Composition of crystal changes due to this defect

because mass is transferred across the boundary
of the crystal.

 For a general MaOb oxide compound, two non-

stoichiometric defects can occur:
1. Metal excess, or oxygen deficient
2. Oxygen excess, or metal deficient

 In both of these cases, a/b ratio is changed.

Metal excess, or oxygen deficient
(low oxygen partial pressure)

 has the general formula Ma+dOb , or MaOb-d.

 places cation into interstitial site, or creating vacancy

in oxygen site.

 using anion, typical defect reaction is:

OOx = 1 O2(g)+VO + 2e¢ electrons are usually weakly

2 bonded; can be excited into
the conduction band
Redox reaction
VOx when species O2 escape as
natural, it leaves two electron
behind
 1
O Þ O2 ( g) + VOx
x
O
2
1
x
O

V Þ V + e¢
O O Þ O 2 ( g) + VO + 2e¢
x
O
2
VO Þ VO + e¢
Example: TiO2-y

OOx TiO2
¾ ¾¾ ® 1 O2(g)+VO + 2e¢
2
2Ti +4 + 2e¢ = 2Ti +3

2TiTix +OOx = 2TiTi' + 1 O2(g)+VO

2
Oxygen excess, or metal deficient
(high oxygen partial pressure)

 has the general formula MaOb+d , or Ma-dOb.

 places oxygen into interstitial site, or creating vacancy

in cation site.

 using anion, typical defect reaction is:

1 O2(g) = Oi'' + 2h This ionization creates

2 holes in valence band
This hole moves through
Oix lattice and contribute to
electrical conductivity
Example: Fe1-xO

1 O2(g) ¾Fe O
¾¾ ®OOx +VFe
''
+ 2h
2
2Fe+2 + 2h = 2Fe+3

x
2FeFe + 1 O2(g) = 2FeFe +OOx +VFe
''
2
 Extrinsic Defect Reactions
 Defects created by impurities.

 Usually substitute host ions of the same or nearest

electronegativity, even if the sizes of the ions differ.
So cations substitute for cations and anions for anions. For example, in
NaCl, Ca and O would be expected to occupy Na and Cl sites, respectively.
Example 1: Incorporating CaCl2 into NaCl

CaCl2 ¾ ¾¾®CaNa +VNa

2NaCl'
+ 2ClClx
NaCl
®CaNa +Cli ' +ClClx
CaCl2 ¾ ¾¾
Between these two reactions, which one is more probable?

Example 2: Doping MgO with Al2O3


Al 2 O3 ¾¾¾® 2 Al
3 MgO
Mg +V ''
Mg + 3Ox
O

Example 3: Doping Al2O3 with

MgO 
2MgO ¾¾¾® 2Mg Al + 2OO + V
Al2O3 ' x
O