Lecture 6.

Imperfections in solids (1)

Learning Objectives

After this lecture, you should be able to do the following:

1. Describe what types of defects exist in solids.

2. Know how the number and type of defects can be varied and
controlled.
3. Understand the solidification mechanisms.
4. Understand how defects affect material properties?
5. Are defects undesirable?

Reading
Chapter 4: Imperfections in Solids (4.14.3, 4.5)

Multimedia
Virtual Materials Science & Engineering (VMSE):
http://www.wiley.com/college/callister/CL_EWSTU01031_S/vmse/
MSE 3300 / 5300 UTA SPRING 2015

Lecture 6 - 1

Imperfections in Solids
There is no such thing as a perfect crystal.
What are these imperfections?
Why are they important?
Most real materials have one or more errors in
perfection with dimensions on the order of an
atomic diameter to many lattice sites.

Many of the important properties of materials are

due to the presence of imperfections.

MSE 3300 / 5300 UTA SPRING 2015

Lecture 6 - 2

Types of Imperfections
Vacancy atoms
Interstitial atoms
Substitutional atoms

Point defects

Dislocations

Line defects

Grain Boundaries

Area defects

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Lecture 6 - 3

Point Defects in Metals

Vacancies:

-vacant atomic sites in a structure.

Vacancy
distortion
of planes

Self-Interstitials:

-"extra" atoms positioned between atomic sites.

distortion
of planes

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selfinterstitial

Lecture 6 - 4

Copyright 2014 John Wiley & Sons, Inc. All rights reserved

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Lecture 6 - 5

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Lecture 6 - 6

Equilibrium Concentration:
Point Defects
Equilibrium concentration of vacancies varies and increases
with temperature!
No. of defects
No. of potential
defect sites

Activation energy

Q v
Nv
= exp
N
kT

Temperature

Boltzmann's constant
-23
(1.38 x 10 J/atom-K)
-5
(8.62 x 10 eV/atom-K)
Each lattice site
is a potential
vacancy site
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Lecture 6 - 7

Measuring Activation Energy

We can get Qv from
an experiment.

Nv
- Qv
= exp
N
kT

Measure this...

Replot it...

Nv

ln

N
exponential
dependence!

defect concentration
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Nv
N

slope
-Qv /k

1/ T

Lecture 6 - 8

Estimating Vacancy Concentration

Find the equil. # of vacancies in 1 m3 of Cu at 1000C.
Given:
= 8.4 g /cm 3
A Cu = 63.5 g/mol
Qv = 0.9 eV/atom NA = 6.02 x 1023 atoms/mol
0.9 eV/atom
- Qv
Nv =
-4
exp

For 1

kT

m3 ,

NA
N= x
A Cu

Answer:

= 2.7 x 10

1273 K
8.62 x 10-5 eV/atom-K
x 1 m3 = 8.0 x 1028 sites

Nv = (2.7 x 10-4)(8.0 x 1028) sites = 2.2 x 1025 vacancies

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Lecture 6 - 9

Example Problem 5.1

Calculate the equilibrium number of vacancies per cubic meter for copper at
1000C. The energy for vacancy formation is 0.9 eV/atom; the atomic weight
and density (at 1000 C) for copper are 63.5 g/mol and 8.4 g/cm3,
respectively.
Solution.
Use equation 5.1. Find the value of N, number of atomic sites per cubic meter
for copper, from its atomic weight Acu, its density, and Avogadros number NA.

N A (6.023x10 23 atoms / mol )(8.4 g / cm3 )(106 cm3 / m 3 )

N=
=
63.5 g / mol
ACu
= 8.0x10 28 atoms / m 3
Thus, the number of vacancies at 1000 C (1273K ) ie equal to

2.2 x 1025 vacancies

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Lecture 6 - 10

Observing Equilibrium Vacancy Conc.

Low energy electron
microscope view of
a (110) surface of NiAl.
Increasing temperature
causes surface island of
atoms to grow.
Why? The equil. vacancy
conc. increases via atom
motion from the crystal
to the surface, where
they join the island.
I sland grows/shrinks to maintain
equil. vancancy conc. in the bulk.

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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, Vol. 412, pp. 622-625 (2001). Image is
5.75 mm by 5.75 mm.) Copyright (2001) Macmillan
Publishers, Ltd.

Lecture 6 - 11

Imperfections in Solids
Solidification- result of casting of molten material
2 steps

Start with a molten material all liquid

nuclei

liquid

crystals growing

grain structure

[Photomicrograph courtesy of L. C.
Smith and C. Brady, the National
Bureau of Standards, Washington, DC
(now the National Institute of Standards
and Technology, Gaithersburg, MD.)]

Nuclei form
Nuclei grow to form crystals grain structure

Adapted from Fig. 4.15 (b), Callister & Rethwisch 9e.

Crystals grow until they meet each other

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Lecture 6 - 12

Nichrome is an alloy of 70% nickel and 30% chromium, which is a face centered
cubic (FCC) solid solution.
http://www.georgesbasement.com/Microstructures/CastIronsHighAlloySteelsSuperalloys/Lesson-3/Specimen03.htm

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Lecture 6 - 13

Polycrystalline Materials
These are interfacial defect separating two small grains or crystals
having different crystallographic orientations.

Grain Boundaries
regions between crystals
transition from lattice of
one region to that of the
other
slightly disordered
low density in grain
boundaries
high mobility
high diffusivity
high chemical reactivity
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Adapted from Fig. 4.8,

Callister & Rethwisch 9e.
Lecture 6 - 14

Planar Defects in Solids

One case is a twin boundary (plane)

Essentially a reflection of atom positions across the twin

plane.

Adapted from Fig. 5.14,

Callister & Rethwisch 9e.

Stacking faults

For FCC metals an error in ABCABC packing sequence

Ex: ABCABABC

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Lecture 6 - 15

Imperfections in Metals (i)

Two outcomes if impurity (B) added to host (A):

Solid solution of B in A (i.e., random dist. of point defects)

OR
Substitutional solid soln.
(e.g., Cu in Ni)

Interstitial solid soln.

(e.g., C in Fe)

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.
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Lecture 6 - 16

Imperfections in Metals (ii)

Conditions for substitutional solid solution (S.S.)
W. Hume Rothery rule
1. r (atomic radius) < 15%
2. Proximity in periodic table
i.e., similar electronegativities

3. Same crystal structure for pure metals

4. Valency
All else being equal, a metal will have a greater tendency
to dissolve a metal of higher valency than one of lower
valency

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Lecture 6 - 17

Imperfections in Metals (iii)

Application of HumeRothery rules Solid
Solutions
Element
Atomic Crystal
Electro1. Would you predict
more Al or Ag
to dissolve in Zn?
2. More Zn or Al
in Cu?

Radius Structure
(nm)

Cu
C
H
O
Ag
Al
Co
Cr
Fe
Ni
Pd
Zn

0.1278
0.071
0.046
0.060
0.1445
0.1431
0.1253
0.1249
0.1241
0.1246
0.1376
0.1332

negativity

Valence

FCC

1.9

+2

FCC
FCC
HCP
BCC
BCC
FCC
FCC
HCP

1.9
1.5
1.8
1.6
1.8
1.8
2.2
1.6

+1
+3
+2
+3
+2
+2
+2
+2

Table on p. 166, Callister & Rethwisch 9e.

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Lecture 6 - 18

Summary
Point, Line and Area defects exist in solids.
The number and type of defects can be varied
and controlled (e.g., temperature controls vacancy
concentration).
Defects affect material properties (e.g., grain
boundaries control crystal slip).
Defects in solids and metals.

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Lecture 6 - 19