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09 - Defects in Ceramics 1
09 - Defects in Ceramics 1
Lecture 09
Defects in Ceramics 1
Ref: Barsoum, Fundamentals of Ceramics, Ch6, McGraw-Hill, 2000
Topics to discuss....
Defects and their classifications
Point defects and their notations
Thermodynamics of point defects
Introduction
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 Interstitia
O M O M O M O M l impurity
M
Cation M O M O M O M O
interstitia
l
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 The entity occupying the defect site.
’’’
(1) Vacancy on Al+3 sub-lattice:VAl
(2) Vacancy on O-2 sub-lattice: V
O
’
(1) Vacancy on Na+ sub-lattice: V Na
(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