CHPT 5: Imperfections in Solids: Issues To Address..

MatSE 280: Introduction to Engineering Materials D.D.
Johnson 2004,2006-08
1
Chpt 5: Imperfections in Solids
ISSUES TO ADDRESS...
What types of defects arise in solids? Describe them.
Can the number and type of defects be varied
and controlled?
How do defects affect material properties?
Are defects undesirable?
Given masses or atomic weights of two or more elements in an alloy,
calculate weight or atomic percentages.
MatSE 280: Introduction to Engineering Materials D.D. Johnson 2004,2006-08
2
Lattice Defects
The concept of a perfect lattice is adequate for explaining structure-
insensitive properties (esp. for metals).

But, to understand structure-sensitive properties, it is necessary to
consider numerous lattice defects.

Practically all mechanical properties are structure-sensitive properties.
(almost) structure-insensitive structure-sensitive
elastic constants Electrical conductivity
Melting points Semiconducting properties
density Yield stress
Specific heat Fracture strength
coefficient of thermal expansion Creep strength
3
Vacancy atoms
Interstitial atoms
Substitutional atoms
Dislocations
Edges, Screws, Mixed
Grain Boundaries
Stacking Faults
Anti-Phase and Twin Boundaries
Point defects

Line defects

Area/Planar defects
Types of Imperfections
We need to describe them and understand their effects.
4
Length Scale of Imperfections
Vacancies,
impurities
dislocations
Grain and twin
boundaries
Voids
Inclusions
precipitates
point, line, planar, and volumetric defects
5
Point Defects
Vacancies:
vacant atomic sites in a structure.
Vacancy
distortion
of planes
Self-Interstitials: "extra" atoms in between atomic sites.
self-
interstitial
distortion
of planes
6
Point Defects
Vacancy: a vacant lattice site
Self-interstitial: atom crowded in holes
It is not possible to create a crystal free of vacancies.
About 1 out of 10,000 sites are vacant near melting.

Self-interstitials are much less likely in metals, e.g.,,
as it is hard to get big atom into small hole - there is
large distortions in lattice required that costs energy.
Thermodynamics (temperature and counting) provides an expression for

Vacancy Concentration:
(see handout)
N
v
N
= exp
Q
v
k
B
T
|
\
|
.
|
Q
v
=vacancy formation energy
k
B
= 1.38 x 10
23
J/atom-K = 8.62 x 10
5
eV/atom-K
k
B
/mole = R = 1.987 cal/mol-K
Defects ALWAYS cost energy!
atom
Vac
7
Point Defects in Ceramics
Cation Interstitial
Anion Vacancy
Cation Vacancy
Why is it rather improbable that anion interstitials exist?
8
Frenkel and Schottky Defects:
paired anions and cations
Electronic neutrality must be maintained in crystal.
Defects must come in pairs to maintain AQ=0.

Cation-vacancy + Cation-interstitial = Frenkel Defect (AQ=0)

In AX-type crystals,
Cation-vacancy + Anion-vacancy = Schottky Defect (AQ=0)
Schottky
Frenkel
Color centers: Balancing missing cation by bound extra electron is also possible.
9
Ionic Crystals and Impurities:
Interstitial, anion-substitutional, cation-substitutional
Interstitial impurity
Substitutional impurities
Consider NaCl. (use charge neutrality)
What point defects are possible when a Ca
2+
substitutes for Na
+
?
How many of these defects exits for every Ca
2+
ion?
10
Replacement of Na
+
by a Ca
2+
introduces 1 excess positive (+1).

AQ=0 only if
a single positive charge is eliminated. (Make a Na
+
vacancy. 1)
a single negative charge is added. (Make a Cl
-
interstitial, 1)
Consider NaCl. (use charge neutrality)

What point defects are possible when a Ca
2+
substitutes for Na
+
?
How many of these defects exits for every Ca
2+
ion?
Na
Cl
Ca
2+
Vac
Cl
11
With multiple valances, it is possible not to have correct cation/anion ratio.
e.g., NaCl or FeO are 1-to-1 ratio.

Consider Fe
2+
O
2-
and add Al
3+
(via Al
2
O
3
) to replace Fe
2+
.

Add Al
3+
in place Fe
2+
(not neutral), so excess charge of +1 must be offset.

What happens? With two Al
3+
defects, need one Fe
2+
vacancy for neutrality,
i.e., 2(+1) - (+2) = 0.
Al
3+
Fe
2+
O
2
12
Boltzmann's constant
(1.38 x 10
-23
J/atom K)
(8.62 x 10
-5
eV/at om K)
|
N
D
N
=
exp

Q
D
kT
|
\

|
.
|
No. of defects
No. of potential
defect sites.
Activation energy
Temperature
Each lattice site
is a potential
vacancy site
Equilibrium concentration varies with temperature!
Equilibrium Concentration of Point Defects
C
V
=
13
Measuring Activation Energy
We can get Q from
an experiment.
Measure this... Replot it...
1/ T
N
N
D
ln
1
-Q
D
/k
slope
14
Estimating Vacancy Concentration
Find the equil. # of vacancies in 1m of Cu at 1000C.
Given:
3
8.62 x 10
-5
eV/atom-K
0.9eV/atom
1273K
|
N
D
N
=
exp

Q
D
kT
|
\

|
.
|
For 1m
3
, N =
N
A
A
Cu
x x 1m
3
= 8.0 x 10
28
sites
= 2.7 10
-4
Solve:
10
6
cm
3
= 1 m
3

* What happens when temperature is slowly
reduced to 500 C, or is rapidly quenched to 500 C?
C
V
=
15
Low-energy electron
microscope view of
(110) surface of NiAl.
Larger T causes surface
island of atoms to grow.
Why? Equilibrium vacancy
conc. increases via atom motion
from the crystal to the surface,
where they join the island.
Reprinted with permission from Nature
(K.F. McCarty, J.A. Nobel, and N.C. Bartelt, "Vacancies in
Solids and the Stability of Surface Morphology",
Nature, 412, 622-625 (2001). Image is 5.75 m by 5.75 m.)
Copyright (2001) Macmillan Publishers, Ltd.
Observing Equil. Vacancy Concentration
QuickTime and a
Cinepak decompressor
are needed to see this picture.
16
Radiation damage creates numerous defects
In nuclear reactor, this effects causes expected lifetime and failures.
In space, charged particles bombard objects always.
17
Volumetric Defects from Radiation Damage
In nuclear reactor, this effects causes expected lifetime and failures.
In space, charged particles bombard objects always.
Cracks, voids, inclusions, pores, other phases usually caused by processing.
18
Alloying: atoms mixed on a lattice
Solid Solutions and Ordered Compounds
Two Possibilities for Solid Solutions: B atoms in A atoms

Substitutional Interstitials
new element replaces host atoms new element goes in holes
Can we roughly estimate what atoms will form solid solutions?
e.g. semiconductor devices:
doped-Si C in Fe
e.g. Ni in Cu, steels
19
Ordered Substitutional and Interstititials Compounds

Substitutional Interstitial
element replaces host atoms element goes into holes
in an orderly arrangement in an orderly arrangement
e.g., Ni
3
Al (hi-T yield strength),
Al
3
(Li,Zr) (strengthening)
e.g., small impurities, clays
ionic crystals, ceramics.
Alloying: atoms mixed on a lattice
Solid Solutions and Ordered Compounds
20
8
Solid solution of B in A plus particles of a new
phase (usually for a larger amount of B)
Second phase particle
--different composition
--often different structure.
Particles of New Phase in Solid-Solution Alloys
Solid Solution phase B atoms in A
21
Hume-Rothery Rules for Alloys
(atoms mixing on a lattice)

Will mixing 2 (or more) different types of atoms lead to a solid-solution phase?

Empirical observations have identified 4 major contributors through :
+1
+2
Atomic Size Factor , Crystal Structure, Electronegativity, Valences
22
Hume-Rothery Rules for Mixing
Empirical rules for substitutional solid-solution formation were identified
from experiment that are not exact, but give an expectation of formation.
Briefly,

1) Atomic Size Factor The 15% Rule
If "size difference" of elements are greater than 15%, the lattice distortions
(i.e. local lattice strain) are too big and solid-solution will not be favored.

DR%= < 15% will not disallow formation.

2) Crystal Structure Like elemental crystal structures are better
For appreciable solubility, the crystal structure for metals must be the same.

3) Electronegativity DE ~ 0 favors solid-solution.
The more electropositive one element and the more electronegative the other, then
"intermetallic compounds" (order alloys) are more likely.

4) Valences Higher in lower alright. Lower in higher, its a fight.
A metal will dissolve another metal of higher valency more than one of lower valency.
r
solute
r
solvent
r
solvent
x100%
23
Example Applications Si-Ge semiconductor, Cu-Ni and Cu-Ag metal alloys.
Is solid-solution favorable, or not?

- Si-Ge Alloys
Rule 1: r
Si
= 0.117 nm and r
Ge
= 0.122 nm.

DR%= = 4% favorable

Rule 2: Si and Ge have the diamond crystal structure. favorable

Rule 3: E
Si
= 1.90 and E
Ge
= 2.01. Thus, DE%= 5.8% favorable

Rule 4: Valency of Si and Ge are both 4. favorable

Expect Si and Ge to form S.S. over wide composition range.

In fact, S.S. forms over entire composition at high temperature.
Hume-Rothery Empirical Rules In Action
r
solute
r
solvent
r
solvent
x100%
24


- Cu-Ni Alloys
Rule 1: r
Cu
= 0.128 nm and r
Ni
= 0.125 nm.

DR%= = 2.3% favorable

Rule 2: Ni and Cu have the FCC crystal structure. favorable

Rule 3: E
Cu
= 1.90 and E
Ni
= 1.80. Thus, DE%= -5.2% favorable

Rule 4: Valency of Ni and Cu are both +2. favorable

Expect Ni and Cu forms S.S. over wide composition range.

At high T, it does (helpful processing info), but actually phase
separates at low T due to energetics (quantum mechanics).
r
solute
r
solvent
r
solvent
x100%
25

- Cu-Ag Alloys
Rule 1: r
Cu
= 0.128 nm and r
Ag
= 0.144 nm.

DR%= = 9.4% favorable

Rule 2: Ag and Cu have the FCC crystal structure. favorable

Rule 3: E
Cu
= 1.90 and E
Ni
= 1.80. Thus, DE%= -5.2% favorable

Rule 4: Valency of Cu is +2 and Ag is +1. NOT favorable

Expect Ag and Cu have limited solubility.

In fact, the Cu-Ag phase diagram (T vs. c) shows that a solubility of
only 18% Ag can be achieved at high T in the Cu-rich alloys.
r
solute
r
solvent
r
solvent
x100%
26
Low-energy electron microscope
view of a (111) surface of Cu.

Sn islands move on surface and
alloy Cu with Sn making "bronze".

Islands continually move into
"unalloyed regions and leave tiny
bronze particles in their wake.

Eventually, the islands disappear.
Reprinted with permission from: A.K. Schmid, N.C.
Bartelt, and R.Q. Hwang, "Alloying at Surfaces by
the Migration of Reactive Two-Dimensional Islands",
Science, Vol. 290, No. 5496, pp. 1561-64 (2000).
Field of view is 1.5 m and the temperature is
290K.
Alloying A Surface: Sn on Cu
QuickTime and a
Cinepak decompressor
are needed to see this picture.
Bronze
27
Amount of impurity (B) and host (A) in the system.
Weight %
Two descriptions:
Atom %
Conversion between wt % and at% in an A-B alloy:
C
B
=
C'
B
A
B

C'
A
A
A
+ C'
B
A
B
x 100
Defining Composition of Alloy

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