LECTURE #08

P i t Defects
Point
D f t in
i Crystals
C
t l
Chapter 5
Learning objectives:
1. What are the different types of defects in materials?
2 What do these defects do to the structure and
2.
properties of materials?

R l
Relevant
tR
Reading
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
Substitutional atoms

Point defects

[0-D]

Dislocations

Line defects

[1-D]

Grain Boundaries

Planar defects

[2-D]

Cracks, voids

Volume defects [3-D]

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 with
ith
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
0 128 nm
C = 0.128
rNi = 0.125 nm

Ni = solute, Cu = solvent
Ni and Cu are so close in size, they can form a solid solution
in all proportions
5

MECHANICAL PROPERTIES: Cu
Cu--Ni System
Effect of solid solution strengthening on:

400
TS for
pure Ni

300
TS for pure Cu

200
0 20 40 60 80 100
Cu
Ni

Composition, wt%Ni

Adapted from Fig. 9.5(a), Callister 6e.

--Peak as a function of Co

rCu = 0.128nm
rNi = 0.125nm

--Ductility
y (%EL,%AR)
(
,
)
Elon
ngation (%
%EL)

Tensile S
T
Strength
h (MPa)

--Tensile strength
g (TS)
( )

60

%EL for pure Cu

%EL for
pure Ni

50
40
30

20
0 20 40 60 80 100
Cu
Ni

Composition, wt%Ni

Adapted from Fig. 9.5(b), Callister 6e.

--Min. as a function of Co

Small atomic size difference causes the bonds to stretch

which makes the alloy stronger!

Hume-Rothery Rules
Humefor Forming a Solid Solution
1. < 15% difference in atomic radii
2. The same crystal structure
3. Similar electronegativity (i.e., ability of an
atom to attract an electron)
4. Same valence
If one or more of these rules are violated,
only partial solubility is possible.

Ordering of the solid solutionsolution- Intermetallics

in the AuCu3 alloy system.

( ) > ~390C, random

(a)
distribution of Au and Cu
atoms among FCC sites.

( ) < ~390C, Au atoms

(b)
preferentially occupy corners, while
Cu atoms occupy faces (the Au
forms a simple cubic Bravais lattice)
lattice).

When atoms occupy specific site the bond strength can be directional and
can make the material stronger (but more brittle)

Zero Dimensional Defects

An interstitial defect: the p
placement of an atom in a
interstitial (in between regular lattice sites).

Interstitial Solid Solutions

Some atoms are too small to substitute for primary atoms
atoms.
They may occupy interstitial sites.
HUME-ROTHERY RULES DO NOT APPLY TO INTERSTITIALS.

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.]
10

Zero Dimensional Defects

A vacancy :a vacant lattice site

11

Are vacancies an equilibrium defect?

Yes, vacancies contribute to entropy to the
system and can help to reduce the
crystals energy, up to a point.
Energy to breaking bonds

n
nV w

Enerrgy

GV

Total energy
number of vacancies, nV

n1
ne

TS

Energy gained by entropy (disorder)

12

Do you think vacancy

concentration
t ti goes up with
ith
temperature?

 In ionic crystals (such as NaCl), single vacancies

can not occur. Why?
y

Because of the constraints of charge neutrality, either a

Frenkel defect OR a Schottky defect forms.
forms
Frenkel defect: vacancy-interstitial combination.
Schottky defect: pair of oppositely charged ion vacancies.
Shottky
Defect:

Frenkel
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.)

13

Random, substitutional solid solution of NiO in MgO.

The O2 arrangement is unaffected.
The substitution occurs only among Ni2+ and Mg2+ ions.

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

99 mol O sites (from MgO)

+ 3 mol O sites (from Al2O3)
102 mol O sites in solid solution

99 mol cation sites (from MgO)

+ 2 mol cation sites (from Al2O3)
101 mol cation sites in solid solution

102 mol 101 mol = I mol Mg2+ vacancies or 6.02 x1023 vacancies

16

Stoichiometric vs. NonNon-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

Fig. 4.7 Iron oxide, Fe1xO (x 0.05), is an example of a nonstoichiometric

compound.
d Si
Similar
il tto Fi
Fig 4
4.6,
6 b
both
th F
Fe2+ and
dF
Fe3+ ions
i
occupy th
the cation
ti sites.
it
2+
3+
One Fe vacancy occurs for every two Fe ions.
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)

19

If different valence ions exist in

the lattice as impurities,
p
, the
concentration of vacancies
adjusts.
Example: Adding a Ca2+ to NaCl.
Extra Na+ vacancies are needed to
maintain charge neutrality
neutrality.
Nonstoichiometric composition
can cause color differences
Consequence is the number of anion sites
vacant (electrons associated with the anion
sites to keep charge neutrality)
Electrons
El t
near the
th vacancy, vibrate
ib t
differently yielding a color change (NaCl
becomes yellowish-brown)

Structure controls properties (optical properties in this case!)

20

NaCl

(Na(1
(1--x)Cax)Cl

http://1.bp.blogspot.com/_EBqHz1Oipb4/TCtpx7Sk6jI/AAAAAAAAABQ/_2OsinoQ5Q/s1600/sodium-chloride.jpg

http://www.fromnaturewithlove.com/images/SaltBolivianCoarse.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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