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Lecture 09
Defects in Ceramics 1
Ref: Barsoum, Fundamentals of Ceramics, Ch6, McGraw-Hill, 2000
Topics to discuss....
Electronic defects
Free electron and hole: electrons excited into higher energy levels, leaving
vacant positions in the normally-filled electronic energy-level bands
Atomic defects
Occur as isolated points, lines and surfaces in the structure
during the arrangement of atoms in the space lattice.
1. Point defects: Vacancy, interstitials
2. Line defects: Grain and twin boundaries
3. Planer defects: Edge and screw dislocations
4. Volume defects: Pores, cracks, and inclusions
Point defects – why bother?
Interstitial
Ca Zr
Only cations shown
Cation M O M O M O M O Anion
vacancy vacancy
O M O M O M O M
Substitutional
impurity
M L M O M O M O
I Interstitial
O M O M O M O M impurity
M
Cation M O M O M O M O
interstitial
Misplaced
O O O M M M O M
atoms
M O M O M O M O
Various defects found in binary ceramics.
Misplaced atoms can only occur in covalent ceramics due to charge considerations.
Kroger-Vink Defects Notations
Main Symbol, A
C
AB
The entity occupying the defect site.
It is either the species involved (i.e., the chemical symbol
of the element), or the letter V for vacancy.
Examples are M, X, V, or substitution elements.
Superscript, C
For the excess (or, effective electric) charge
associated with the site.
It is the difference between the real charge of the
defect species and that of the species that would
have occupied the site in a perfect crystal.
The superscript is a prime (’) for each negative
charge, a dot (.) for every positive charge, or an x
for zero effective charge.
C
AB Subscript, B
For the type of site occupied.
It is either the crystallographic position occupies
by species involved, or the letter i for interstitial.
Examples include M, X, or i
Example: Lattice defects in MX binary compound ( M+2, X–2)
’’’
(1) Vacancy on Al+3 sub-lattice: VAl
(2) Vacancy on O-2 sub-lattice: V
O
’
(1) Vacancy on Na+ sub-lattice: VNa
(2) Vacancy on Cl- sub-lattice: V
Cl
Approach:
Find an expression for G of perfect crystal and one for defective crystal;
the one with the lower (more negative G) wins…
Free Energy of a Perfect Crystal
N n n = vacant site
Sconfig = – k N ln + n ln N = atom site
N+n N+n
k = Boltzmann’s constant
kT
ST = 3 N k ln +1 h = Plank’s constant
hn n = vibration frequency of bond
For perfect crystal, Sconfig = 0
since there is only one way of arranging N atoms on N lattice sites.
kT
Sperf = ST = 3 N k ln + 1
hn
Hdef = Hperf + n hd
Sdef = Sconfig + ST
N n
Sconfig = – k N ln + n ln
N+n N+n
kT
ST = 3 N k ln +1 (For perfect crystal)
hn
kT
3 (N - ζn) ln +1
hn
kT
– kT + 3ζn ln +1
hn’
N n
– N ln + n ln
N+n N+n
kT
Gperf = Hperf – 3 N k T ln + 1
hn
DG = Gdef - Gperf
n’
= n hd + 3kTζn ln
n
N n
+ kT N ln + n ln
N+n N+n
Lecture 10
Defects in Ceramics 2