MME 467: Ceramics for Advanced Applications

Lecture 18
Defects in Ceramics 2
Ref: Barsoum, Fundamentals of Ceramics, Ch6, McGraw-Hill, 2000

Prof. A. K. M. B. Rashid
Department of MME, BUET, Dhaka

Topics to discuss....

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

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 Defect Reactions

q Each defect can be treated as chemical entities

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

q 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
v Mass cannot be created or destroyed. Vacancies have zero mass.

2. Electroneutrality, or charge balance

v Charge cannot be created or destroyed.

3. Preservation of regular site ratio

v Ratio between the numbers of regular cation and anion sites must
remain constant and equal to the ratio of the parent lattice.
v 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.

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q To generalise, for an MaXb compound, the following
relation has to be maintained at all times:

a ( X X +VX ) = b ( M M +V M )
M M +V M a
=
X X +VX b

q For example, in Al2O3 :

Note that, this does not mean that
M Al +V Al 2 the number of atoms or ions has
= to maintain that ratio, but only the
X O +VO 3 number of sites.

Stoichiometric Defect Reactions

Crystal chemistry (cations/

anions ratio) does not change.
No mass is transferred across the crystal
boundary.
Scho%ky Defect
Vacancy vacancy pair

Important defects in this

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

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 Schottky defects

q In schottky defects, electric-charge-equivalent numbers

of vacancies are formed on each sub-lattice.

q For any compound MX (M+2, X2), the Schottky defect

reaction is:
null =V M'' +VX ; gS
or, perfect
gS = the free energy change for
crystal
the formation of Schottky defect

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

q In general, for an MaOb oxide: null = aV Mb + bVOa+

Thermodynamics of Schottky defects

q Assume that the number of ways of distributing cation

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

q The configuration entropy

S = k ln = k ln12

where =
( N cat + Vcat )! ( N an + Van)!
( N cat )!( Vcat )! ( N an)!( Van )!
and ( N cat + ncat ) ( N an + nan) = 1

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 q Finding minimum in free energy will yield

Vaneq Vcat
eq
Vaneq Vcat
eq
% h T sS (
= exp' S *
(N an )(
+ Vaneq Vcat
eq
+ N cat ) N an N cat & kT )
Product of cation and anion vacancy concentrations
is a constant that depends only on temperature

q When Schottky defects dominate, then

sS $ h '
[Va ] = [Vc ] = exp exp& S )
2k % 2kT (
Vcat Van
where [Vc ] = and [Va ] =
Vcat + N cat Van + N an
Square brackets denote mole fractions of defects!
They are dimensionless!

Frenkel Defects

q A cation removed from its normal site to an

interstitial site to form an interstitial vacancy pair

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

reaction is:

M Mx =V M''' + M i

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

an interstitial vacancy pair
q For oxygen ion (O2), the Anti-Frenkel defect reaction is:

OOx =VO +Oi''

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 Thermodynamics of Frenkel defects

q number of ways of distributing ni interstitials on N*

interstitial sites be 1, and

number of ways of distributing cation vacancies Vcat

on NT total sites be 2.

N *!
1 =
( N * ni )!n i!
N T!
2 =
( NT Vcat )!Vcat!

q The configurational entropy is the same

S = k ln12

q At equilibrium,

eq eq
% ( % (
n i* exp' gF * exp TSF exp' hF *
Vcat
NT N & kT ) kT & kT )
gF = the free energy change for
the formation of Frenkel defect
v Note that N* depends on crystal structure.

v For example, for 1 mol NaCl, if the ions migrate to tetrahedral sites,
N* 2NAV.

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Worked Example 6.1
Estimate the number of Frenkel defects in AgBr (rocksalt structure) at
500 C. 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 2NAV

Vcateq nieq T S F # h &

*
= exp exp % F (
NT N kT $ kT '
eq eq # &
Vcat ni 6.6R 110 x1000
23 2
= exp exp % (
2(6.02 x10 ) R $ 8.314(500 + 273) '

Vcateq nieq = 1.957 x10 43 defects/mol 2

Worked Example 6.1

Estimate the number of Frenkel defects in AgBr (rocksalt structure) at
500 C. 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

Vcateq nieq = 1.957 x10 43 defects/mol 2

Vcateq = nieq = 4.43x1021 defects/mol

And the corresponding number of defects/cm3 is

! 6.5 $
Vcateq = nieq = 4.43x1021 # & = 1.5x1020 defects/cm 2
" 187.7 %

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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:

q Consider a crystal with a formula MaXb.

q If valence of M is z, then the valence of X
will be -(a/b)z.

q Reaction with its surroundings when M is added

to its normal cation site:

#b&
M ( g) !M!!
a Xb
M Mx + % (VX(a/b) z + ze )
$a'

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 Example: Incorporating Si into SiO2

Si( g) !SiO
!! 2
SiSix + 2VO + 4 e #

Example: Incorporating Al into Al2O3

Al ( g) !Al
!!2O3 x
Al Al + 3 VO + 3e #
2
or, 2Al ( g) !Al!!2O3 x
2Al Al + 3VO + 6e #

Non-stoichiometric Defect Reactions

q Composition of crystal changes due to this defect

because mass is transferred across the boundary
of the crystal.

q For a general MaOb oxide compound, two non-

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

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

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

q has the general formula Ma+Ob , or MaOb-.

q places cation into interstitial site, or creating vacancy
in oxygen site.

q 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 reac5on
VOx when species O2 escape as
natural, it leaves two electron
behind

1
OxO O2 ( g) + VOx
2
1
VOx VO + e # OxO O2 ( g) + VO + 2e #
2
VO VO + e #

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Example: TiO2-y

OOx !TiO
!!2
1 O2 ( g) +VO + 2e #
2
2Ti + 2e # = 2Ti +3
+4

2TiTix +OOx = 2TiTi' + 1 O2 ( g) +VO

2

Oxygen excess, or metal deficient

(high oxygen partial pressure)

q has the general formula MaOb+ , or Ma-Ob.

q places oxygen into interstitial site, or creating vacancy
in cation site.

q 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

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Example: Fe1-xO

1 O2 ( g) !FeO
!!OOx +V Fe'' + 2h
2
2Fe +2 + 2h = 2Fe +3

x
2Fe Fe + 1 O2 ( g) = 2Fe Fe +OOx +V Fe''
2

Extrinsic Defect Reactions

q Defects created by impurities.

q 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

NaCl
CaCl 2 !2!! CaNa +VNa
'
+ 2ClClx
CaCl 2 !NaCl
!! CaNa +Cl i ' +ClClx
Between these two reactions, which one is more probable?

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Example 2: Doping MgO with Al2O3

Al 2O3 !3MgO
!! 2Al Mg ''
+V Mg + 3OOx

Example 3: Doping Al2O3 with MgO

2MgO !Al
!! 2O3 '
2Mg Al + 2OOx +VO

Next Class

Lecture 19
Electrical and Ionic
Conduction in Ceramics

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