Chapter 4:

Imperfections in Solids
ISSUES TO ADDRESS...
• What are the solidification mechanisms?

• What types of defects arise in solids?

• Can the number and type of defects be varied

and controlled?

• How do defects affect material properties?

• Are defects undesirable?

Chapter 4 - 0
 Imperfections in Solids

• Solidification- result of casting of molten material

– 2 steps
• Nuclei form
• Nuclei grow to form crystals – grain structure
• Start with a molten material – all liquid

nucle crystals grain structure

i liquid growing Adapted from Fig. 4.14(b), Callister & Rethwisch 8e.

• Crystals grow until they meet each other

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 Polycrystalline Materials

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
Adapted from Fig. 4.7,
Callister & Rethwisch 8e.
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 Solidification
Grains can be - equiaxed (roughly same size in all directions)
- columnar (elongated grains)
~ 8 cm

heat
flo
w
Shell of
Columnar in equiaxed grains
area with less due to rapid
undercooling cooling (greater
Adapted from Fig. 5.17, T) near wall
Callister & Rethwisch 3e.

Grain Refiner - added to make smaller, more uniform, equiaxed grains.

Chapter 4 - 0
 Imperfections in Solids
There is no such thing as a perfect crystal.

• What are these imperfections?

• Why are they important?

Many of the important properties of

materials are due to the presence of
imperfections.

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 Types of Imperfections

• Vacancy atoms
• Interstitial atoms Point
• Substitutional defects
atoms
• Line defects
Dislocations
• Grain Area
Boundaries defects

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• Vacancies:
Point Defects in Metals
-vacant atomic sites in a
structure.
Vacancy
distortion
of
planes
• Self-Interstitials:
-"extra" atoms positioned between atomic sites.

self
-interstitia
distortion l
of
planes
Chapter 4 - 0
 Equilibrium Concentration:
Point Defects
• Equilibrium concentration varies with temperature!

No. of defects Activation energy

Nv = æ Qv ö
No. of potential ex ç
defect sites N p è kT ø
Temperature
Boltzmann's constant
(1.38 x 10 -2 J/atom-K)
3
(8.62 x 10 - eV/atom-K)
5
Each lattice site
is a potential
vacancy site
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 Measuring Activation Energy
• We can get Qv from Nv æ- Q v ö
an experiment. = ex ç
ç
N p è kT ø
• Measure this... • Replot it...

Nv Nv slope
ln
N N
- Q v /k
exponential
dependence
!
T atom
1/ T
Im
defect
concentration Chapter 4 - 0
 Estimating Vacancy Concentration
• Find the equil. # of vacancies in 1 m3 of Cu at 1000 C.
• Given:
r = 8.4 g / cm 3 A = 63.5 g/mol
C
Q v = 0.9 eV/atom N u = 6.02 x 1023 atoms/mol
A
0.9 eV/atom
Nv = æ- Q v ö
ex ç
ø= 2.7 x 10-
ç
N p è kT 4 K
1273
8.62 x 10-5 eV/atom-K
NA
For 1 m3 ,N= r x x 1 m3 = 8.0 x 1028 sites
AC
u
• Answer:

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

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 Observing Equilibrium Vacancy Conc.
• Low energy electron
microscope view of Click once on image to start animation
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 Reprinted with permission from Nature (K.F. McCarty,
they join the island. 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
Island grows/shrinks to maintain
5.75 mm by 5.75 mm.) Copyright (2001) Macmillan
equil. vancancy conc. in the Publishers, Ltd.
bulk.

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 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. Interstitial solid soln.

(e.g., Cu in Ni) (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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 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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 Imperfections in Metals (iii)
Application of Hume–Rothery rules – Solid
Solutions
Element Atomic Crystal Electro- Valence
Radius Structure nega-
(nm) tivity
1. Would you predict Cu 0.1278 FCC 1.9 +2
more Al or Ag C
H
0.071
0.046
to dissolve in Zn? O 0.060
Ag 0.1445 FCC 1.9 +1
Al 0.1431 FCC 1.5 +3
Co 0.1253 HCP 1.8 +2
2. More Zn or Al Cr 0.1249 BCC 1.6 +3
Fe 0.1241 BCC 1.8 +2
in Cu? Ni 0.1246 FCC 1.8 +2
Pd 0.1376 FCC 2.2 +2
Zn 0.1332 HCP 1.6 +2
Table on p. 118, Callister & Rethwisch 8e.

Chapter 4 - 0
 Impurities in Solids
• Specification of composition
– weight percent

m1 = mass of component
1

– atom percent

nm1 = number of moles of component

1

Chapter 4 - 0
 Line Defects
Dislocations:
• are line defects,
• slip between crystal planes result when dislocations move,
• produce permanent (plastic) deformation.

Schematic of Zinc (HCP):

• before deformation • after tensile
elongation
slip steps

Chapter 4 - 0
 Imperfections in Solids
Linear Defects (Dislocations)
– Are one-dimensional defects around which atoms are
misaligned
• Edge dislocation:
– extra half-plane of atoms inserted in a crystal structure
– b perpendicular ( ) to dislocation line
• Screw dislocation:
– spiral planar ramp resulting from shear deformation
– b parallel ( ) to dislocation line

Burger’s vector, b: measure of lattice distortion

Chapter 4 - 0
 Imperfections in Solids
Edge Dislocation

Fig. 4.3, Callister & Rethwisch 8e.

Chapter 4 - 0
 Motion of Edge Dislocation
• Dislocation motion requires the successive bumping
of a half plane of atoms (from left to right here).
• Bonds across the slipping planes are broken and
remade in succession.

Atomic view of edge

dislocation motion
from
left to right as a crystal
is sheared.

Click once on image to start animation

(Courtesy P.M. Anderson)
Chapter 4 - 0
 Imperfections in Solids
Screw Dislocation
Screw Dislocation

b
Dislocation
line
Burgers vector b (b)
(a)
Adapted from Fig. 4.4, Callister & Rethwisch 8e.

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 VMSE: Screw Dislocation
• In VMSE:
– a region of crystal containing a dislocation can be rotated in 3D
– dislocation motion may be animated

Front View Top View

VMSE Screen Shots Chapter 4 - 0
 Edge, Screw, and Mixed Dislocations
Mixed

Edge

Screw
Adapted from Fig. 4.5, Callister & Rethwisch 8e.

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 Imperfections in Solids
Dislocations are visible in electron micrographs

Fig. 4.6, Callister & Rethwisch 8e.

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 Dislocations & Crystal Structures
• Structure: close-packed view onto
planes & directions two
are preferred. close-packed
planes.
close-packed directions
close-packed plane close-packed plane
(bottom) (top)
• Comparison among crystal structures:
FCC: many close-packed planes/directions;
HCP: only one plane, 3 directions;
BCC: none

• Specimens that Mg (HCP)

were tensile
tested.
tensile
direction Al (FCC)
Chapter 4 - 0
 Planar Defects in Solids
• One case is a twin boundary (plane)
– Essentially a reflection of atom positions across the twin
plane.

Adapted from Fig. 4.9,

Callister & Rethwisch 8e.

• Stacking faults
– For FCC metals an error in ABCABC packing sequence
– Ex: ABCABABC

Chapter 4 - 0
 Catalysts and Surface Defects
• A catalyst increases the
rate of a chemical
reaction without being
consumed Fig. 4.10, Callister & Rethwisch 8e.

• Active sites on catalysts

are normally surface
defects

Single crystals of
(Ce0.5Zr0.5)O2
used in an automotive
catalytic converter
Fig. 4.11, Callister & Rethwisch 8e.
Chapter 4 - 0
 Microscopic Examination
• Crystallites (grains) and grain boundaries.
Vary considerably in size. Can be quite large.
– ex: Large single crystal of quartz or diamond or Si
– ex: Aluminum light post or garbage can - see the
individual grains
• Crystallites (grains) can be quite small (mm or
less) – necessary to observe with a
microscope.

Chapter 4 - 0
 Optical Microscopy
• Useful up to 2000X magnification.
• Polishing removes surface features (e.g., scratches)
• Etching changes reflectance, depending on crystal
orientation.

crystallographic planes
Adapted from Fig. 4.13(b) and (c), Callister
& Rethwisch 8e. (Fig. 4.13(c) is courtesy
of J.E. Burke, General Electric Co.)

Micrograph of
brass (a Cu-Zn alloy)

0.75mm
Chapter 4 - 0
 Optical Microscopy
Grain boundaries...

• are imperfections,
• are more
susceptible
to etching,
polished surface
• may be revealed as
dark lines, surface
• change in crystal groove
grain
(a)
orientation across boundary
Adapted from Fig. 4.14(a)
boundary. and (b), Callister &
ASTM grain Rethwisch 8e.
(Fig. 4.14(b) is courtesy
size of L.C. Smith and C. Brady,
number the National Bureau of
N = 2 n -1 Standards, Washington, DC
[now the National Institute of
Standards and Technology,
Fe-Cr alloy Gaithersburg, MD].)
number of
at 100x
grains/in2 (b)
magnificatio Chapter 4 - 0
n
 Optical Microscopy

• Polarized light
– metallographic scopes often use polarized
light to increase contrast
– Also used for transparent samples such as
polymers

Chapter 4 - 0
 Microscopy
Optical resolution ca. 10-7 m = 0.1 m = 100 nm
For higher resolution need higher frequency
– X-Rays? Difficult to focus.
– Electrons
• wavelengths ca. 3 pm (0.003 nm)
– (Magnification - 1,000,000X)
• Atomic resolution possible
• Electron beam focused by magnetic lenses.

Chapter 4 - 0
 Scanning Tunneling Microscopy
(STM)
• Atoms can be arranged and imaged!
Photos produced from
the work of C.P. Lutz,
Zeppenfeld, and D.M.
Eigler. Reprinted with
permission from
International Business
Machines Corporation,
copyright 1995.

Carbon monoxide Iron atoms arranged

molecules arranged on a copper (111)
on a platinum (111) surface. These Kanji
surface. characters represent
the word “atom”.

Chapter 4 - 0
 Summary
• Point, Line, and Area defects exist in solids.

• The number and type of defects can be varied

and controlled (e.g., T controls vacancy conc.)

• Defects affect material properties (e.g., grain

boundaries control crystal slip).

• Defects may be desirable or undesirable

(e.g., dislocations may be good or bad, depending
on whether plastic deformation is desirable or not.)

Chapter 4 - 0
 ANNOUNCEMENTS
Reading
:

Core
Problems:

Self-help
Problems:

Chapter 4 - 0