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P i t Defects
Point D f t ini Crystals
C t l
Chapter 5
Learning objectives:
1. What are the different types of defects in materials?
R l
Relevant
tRReading
di ffor thi
this L
Lecture...
t
Pages 135-142.
1
Types of Imperfections:
There is no such thing as a perfect crystal
Vacancy atoms
Interstitial atoms Point defects [0-D]
Substitutional atoms
2
Zero Dimensional Defects
A substitutional defect:
another type of atom substitutes on a particular
lattice site.
In chemistry, you are likely are familiar with mixing two liquids
t make
to k a liquid
li id solution.you
l ti can do
d th
the same withith
solids! But in this case the different atoms in the solid occupy
the equivalent crystal (lattice) sites making a solid solution
4
Solid Solution
Solid solution of nickel in copper
pp shown along g a ((100)) p
plane. This is a
substitutional solid solution with nickel atoms substituting for copper
atoms on FCC atom lattice sites.
rCu
C = 0.128
0 128 nm
rNi = 0.125 nm
Ni = solute, Cu = solvent
Ni and Cu are so close in size, they can form a solid solution
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in all proportions
MECHANICAL PROPERTIES: Cu
Cu--Ni System
Effect of solid solution strengthening on:
--Tensile strength
g (TS)
( ) --Ductility
y (%EL,%AR)
( , )
h (MPa)
60
%EL)
50 %EL for
Strength
TS for pure Ni
pure Ni 40
300
Tensile S
30
Elon
TS for pure Cu
200 20
0 20 40 60 80 100 0 20 40 60 80 100
Cu Ni Cu Ni
T
Figure 4.4 Interstitial solid solution of carbon in -iron. The carbon atom is small
enough to fit with some strain in the interstice (or opening) among adjacent Fe atoms in
this structure of importance
p to the steel industry.
y [[This unit-cell structure can be
compared with that shown in Figure 3.4b.]
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Zero Dimensional Defects
11
GV Total energy
Enerrgy
n1 number of vacancies, nV
ne
Do you think vacancy
TS
concentration
t ti goes up with
ith
temperature?
Energy gained by entropy (disorder)
12
In ionic crystals (such as NaCl), single vacancies
can not occur. Why? y
Shottky
Defect: Adapted from Fig.12.21, Callister
& Rethwisch 8e. (Fig. 12.21 is
from W.G. Moffatt, G.W. Pearsall,
and JJ. Wulff
Wulff, The Structure and
Properties of Materials, Vol. 1,
Structure, John Wiley and Sons,
Inc., p. 78.)
Frenkel
Defect
13
Ri = 0.069 nm
Ri = 0.072 nm
14
What happens if the charges do not balance?
Substitutional solid solution of Al2O3 in MgO is not as simple as
NiO in MgO. The overall compound must be charge neutral, this permits only two
Al3+ ions to fill every three Mg2+ vacant sites, leaving one Mg2+ vacancy.
Ri = 0.053 nm
Ri = 0.072 nm
15
In class example:
Calculate the number of Mg2+ vacancies produced by the solubility of 1 mol of
Al2O3 in 99 mol of MgO
Approach:
Calculate amount of O
Calculate
C l l t amountt off cations
ti
Difference btw. O & cations = amt. vacancies
102 mol 101 mol = I mol Mg2+ vacancies or 6.02 x1023 vacancies
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Stoichiometric vs. Non-
Non-Stoichiometric Compounds
Stoichiometric
The amounts (moles) of each element are given by the
formula, Fe2O3, NiO2, Fe304, CuSO4, etc.
The ratio does not vary!
Non-Stoichiometric
The amounts (moles) of each element does vary, this
can be reflected by using variables in the formula, FexOy
or Fe1-xO (x 0.05)
The ratio does vary!
17
18
Example: Ferrous oxide, FeO (Fe2+ + O2-)
If an Fe
F 3+ (the
(th ferric
f i state)
t t ) is
i substituted
b tit t d for
f an Fe
F 2+, cation
ti vacancies
i
are needed to offset charge
Extra oxygen associated with the ferric iron is accommodated in the
normall oxygen sublattice
bl tti (leaves
(l some cation
ti iion sites
it unoccupied)
i d)
Thus the composition is Fe1-xO, where x is small and <1 (~ 0.05)
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inoQ5Q/s1600/sodium-chloride.jpg
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Summary
Three types
yp of 0-D defects ((Point Defects):
)
Vacancies
Interstitial atoms
Substitutional
Substitutional atoms
Vacancies help control charge neutrality in ionic crystals; variations in charge
state change vac. Concentration and properties (like color)
What
What is a solid solution?
A solid solution forms when, as the solute atoms are added to the host
material, the crystal structure is maintained and no new crystal structures are
formed.
Hume-Rothery Rules:
1. < 15% difference in atomic radii
2 The same crystal structure
2.
3. Similar electronegativity (i.e. ability of an atom to attract an electron)
4. Same valence
WHY ARE HR RULES IMPORTANT:
If one or more rules are violated, only partial solubility is possible.
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