CHAPTER 4:

IMPERFECTIONS IN SOLIDS
ISSUES TO ADDRESS...
• What are the solidification mechanisms?

• What types of defects arise in solids?

• How do defects affect material properties?

• Are defects undesirable?

Chapter 4 - 1
 Solidifcation

• 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

nuclei crystals growing grain structure

liquid Adapted from Fig.4.14 (b), Callister 7e.

• Crystals grow until they meet each other

Chapter 4 - 2
 Grain Structure
Grains can be - equiaxed (roughly same size in all directions)
- columnar (elongated grains)
~ 8 cm

heat
flow

Shell of
Columnar in equiaxed grains
area with less due to rapid
undercooling cooling (greater
T) near wall
High Purity, polycrystalline Lead ingot
Adapted from Fig. 4.12, Callister 7e.

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

Chapter 4 - 3
 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.

Chapter 4 - 4
An ideal crystal can be described in terms
a three-dimensionally periodic
arrangement of points called lattice and an
atom or group of atoms associated with
each lattice point called unit cell:

Crystal = Lattice + Unit Cell

However, there can be deviations from this

ideality.

These deviations are known as crystal defects.

Chapter 4 - 5
 Types of Imperfections

• Vacancy atoms
• Interstitial atoms Point defects
• Substitutional atoms

• Dislocations Line defects

• Grain Boundaries Area defects

Chapter 4 - 6
Vacancy: A point defect

Chapter 4 - 7
Vacancy

scanning probe micrograph

(generated using a scanning-tunneling
microscope) that shows a (111)-type
surface plane* for silicon. The arrow
points to the location of a silicon
atom that was removed using a tungsten
nanotip probe. This site from
which an atom is missing is the surface
analogue of a vacancy defect—
that is, a vacant lattice site within
the bulk material. Approximately
20,000,000. (Micrograph courtesy
of D. Huang, Stanford University.)

Chapter 4 - 8
 Crystalline Imperfections

• “Crystalline defect” is a lattice

irregularity having one or more of its
dimensions on the order of an atomic
diameter.
• Classification of crystalline
imperfections is frequently made
according to geometry or dimensionality
of the defect.

Chapter 4 - 9
Defects Dimensionality Examples

Point 0 Vacancy

Line 1 Dislocation

Surface 2 Free surface,

Grain boundary

Chapter 4 - 10
 Point Defects
• Vacancies:
-vacant atomic sites in a structure.

Vacancy
distortion
of planes

• Self-Interstitials:
-"extra" atoms positioned between atomic sites.

self-
interstitial
distortion
of planes

Chapter 4 - 11
Defects in Ionic Solids

Frenkel
defect
Cation vacancy
+
cation interstitial

Schottky
defect
Cation vacancy
+
anion vacancy
Chapter 4 - 12
 Impurities in Solids
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.

Chapter 4 - 13
 Substitutional Solid Solutions
Conditions for substitutional solid solution (S.S.)
• W. Hume – Rothery rules
– 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

Chapter 4 - 14
 Hume-Rothery Rules
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
C 0.071
more Al or Ag H 0.046
O 0.060
to dissolve in Zn? Ag 0.1445 FCC 1.9 +1
Al 0.1431 FCC 1.5 +3
More Al ! Co 0.1253 HCP 1.8 +2
Cr 0.1249 BCC 1.6 +3
2. More Zn or Al Fe 0.1241 BCC 1.8 +2
Ni 0.1246 FCC 1.8 +2
in Cu? Pd 0.1376 FCC 2.2 +2
Zn 0.1332 HCP 1.6 +2
More Al !
Table on p. 106, Callister 7e.

Chapter 4 - 15
 Specification of
Impurities/Solutes
• Specification of composition
m1
– weight percent C1 = x 100
m1 + m2
m1 = mass of component 1

nm1
– atom percent C =
'
x 100
nm1 + nm 2
1

nm1 = number of moles of component 1

Chapter 4 - 16
Line Defects
Dislocations
Chapter 4 - 17
Missing half plane→ A Defect

Chapter 4 - 18
An extra half plane…

…or a missing half

Chapter plane
4 - 19
 What kind of
defect is this?

A line defect?

Or a planar
defect? Chapter 4 - 20
Extra half plane No extra plane!

Chapter 4 - 21
Missing plane No missing plane!!!
Chapter 4 - 22
An extra half plane…

Edge
Dislocation

…or a missing half

Chapter plane
4 - 23
This is a line defect called an
EDGE DISLOCATION
Chapter 4 - 24
Callister FIGURE 4.3

The atom positions around an edge

dislocation; extra half-plane of atoms
shown in perspective. (Adapted from
A. G. Guy, Essentials of Materials
Science, McGraw-Hill Book Company,
New York, 1976, p. 153.)

Chapter 4 - 25
 Slip
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

Adapted from Fig. 7.8, Callister 7e.

Chapter 4 - 26
 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.

(Courtesy P.M. Anderson)

Chapter 4 - 27
 Glide of 
an Edge
Dislocation


Chapter 4 - 28
 Glide of
an Edge
Dislocation

Chapter 4 - 29
 Glide of
an Edge
Dislocation

Chapter 4 - 30
 Glide of
an Edge
Dislocation

Chapter 4 - 31
 Glide of
an Edge
Dislocation

Chapter 4 - 32
 Glide of
an Edge
Dislocation

A surface
step of b
is created
if a Surface
dislocation
step, not a
sweeps
over the dislocation
entire slip
plane

Chapter 4 - 33
Dislocation Motion

Chapter 4 - 34
Figure 4.6 A transmission electron
micrograph of a titanium alloy in which the
dark lines are dislocations.
(Courtesy of M. R. Plichta, Michigan
Chapter 4 - 35
Technological University.)
 Burgers Vector

Johannes Martinus
BURGERS

Burger’s vector Burgers vector

Chapter 4 - 36
The magnitude and direction of the lattice distortion
associated with a dislocation is expressed in terms of a
Burgers vector, denoted by a b.

For metallic materials, the Burgers vector for a dislocation

will point in a close-packed crystallographic direction and
will be of magnitude equal to the interatomic spacing.

Chapter 4 - 37
In general, there can be any angle
between the Burgers vector b (magnitude
and the direction of slip) and the line
vector t (unit vector tangent to the
dislocation line)
b ⊥ t  Edge dislocation

b  t  Screw dislocation

b ⊥ t , b  t  Mixed dislocation

Chapter 4 - 38
Edge & Screw Dislocations

Chapter 4 -
 t

b || t

3
2 Chapter 4 - 40
1
 S 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
F 1
9
2
8
3
7 A closed
4
6 Burgers
5 Circuit in an 5

4 ideal crystal 6
7
3
8
2
1 9

16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1

Chapter 4 - 41
F b
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

9 S 1
2
8
3
7
Map the ⊥ same 4
6
5
Burgers circuit on a 5

4 real crystal 6
7
3
8
2
1 9

16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1

Chapter 4 - 42
 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
F
9 S 1
2
8
3
7 ⊥ 4
6
5
5
6
4
7
3
8
2
1 9

16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1

Chapter 4 - 43
 If b || t

Then parallel planes ⊥ to the dislocation line

lose their distinct identity and become one
continuous spiral ramp

Hence the name SCREW DISLOCATION

Chapter 4 - 44
Screw Dislocation

Chapter 4 - 45
 Edge, Screw, and Mixed Dislocations
Mixed

Edge

Adapted from Fig. 4.5, Callister 7e.

Screw

Chapter 4 - 46
Energy of a dislocation line
is proportional to b2.

Thus dislocations with

b is a lattice translation
short b are preferred.

b is the shortest lattice

translation
Chapter 4 - 47
 A dislocation line cannot end
abruptly inside a crystal

It can end on

Free surfaces

Grain boundaries

On other dislocations at a point called a node

On itself forming a loop

Chapter 4 - 48
 Dislocations & Plastic Deformation
Dislocations & plastic deformation
• Cubic & hexagonal metals - plastic deformation by
plastic shear or slip where one plane of atoms slides
over adjacent plane by defect motion (dislocations).

• If dislocations don't move, Adapted from Fig. 7.1,

Callister 7e.
deformation doesn't occur! Chapter 4 - 49
 Dislocations & Crystal Structures
• Structure: close-packed view onto two
planes & directions close-packed
planes.
are preferred.
close-packed directions
close-packed plane (bottom) close-packed plane (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 - 50
 Deformation Mechanisms
Slip System
– Slip plane - plane allowing easiest slippage
• Wide interplanar spacings - highest planar densities
– Slip direction - direction of movement - Highest linear
densities
Adapted from Fig.
7.6, Callister 7e.

– FCC Slip occurs on {111} planes (close-packed) in <110>

directions (close-packed)
=> total of 12 slip systems in FCC
– in BCC & HCP other slip systems occur Chapter 4 - 51
 Dislocation Motion
• Dislocation moves along slip plane in slip direction
perpendicular to dislocation line
• Slip direction same direction as Burgers vector
Edge dislocation

Adapted from Fig. 7.2,

Callister 7e.

Screw dislocation

Chapter 4 - 52
 Dislocations & Materials Classes
• Metals: Disl. mvt easier.
+ + + + + + + +
-non-directional bonding + + + + + + + +
-close-packed directions + + + + + + + +
for slip. electron cloud ion cores

• Covalent Ceramics
(Si, diamond): Movement
difficult.
-directional (angular) bonding
• Ionic Ceramics (NaCl):
+ - + - + - +
Movement difficult.
- + - + - + -
-need to avoid ++ and - -
neighbors. + - + - + - +

Chapter 4 - 53
 Positive Negative

Extra half Extra half

Edge plane above plane below
Dislocation the slip plane the slip plane

Left-handed Right-handed
spiral ramp spiral ramp
Screw
Dislocation b parallel to t b parallel to t

Chapter 4 - 54
Chapter 4 - 55
Surface
Defects
Chapter 4 - 56
 Surface Defects

External Internal

Free surface Grain boundary

Twin boundary Same
Stacking fault phase

Domain Wall

Interphase Different
phases
boundary
Chapter 4 - 57
 Surface energy is anisotropic

Surface energy depends on the

orientation, i.e., the Miller indices of
the free surface

nA, nB are different for different

surfaces

Chapter 4 - 58
 Is a lattice finite or infinite?
Is a crystal finite or infinite?

Free surface:
a 2D defect

Chapter 4 - 59
Surface Defects

High-resolution transmission electron

micrograph that shows single crystals of
(Ce0.5Zr0.5)O2;
this material is used in catalytic converters for
automobiles. Surface defects represented
schematically
in Figure 4.10 are noted on the crystals.

Chapter 4 - 60
 Internal surface: grain boundary
Grain
Boundary

Grain 2
Grain 1
A grain boundary is a boundary between two
regions of identical crystal structure but
different orientation Chapter 4 - 61
 Grain Boundaries and Dislocations

The atoms are bonded less regularly along

a grain boundary (e.g., bond angles
are longer), and consequently, there is an
interfacial or grain boundary energy similar
to the surface energy.

The magnitude of this energy is a function

of the degree of misorientation, being
larger for high-angle boundaries.

Impurity atoms often preferentially

segregate along these boundaries because
of their higher energy state.

The total interfacial energy is lower in large

or coarse-grained materials than in fine-
grained ones, since there is less total
boundary area in the former.
Chapter 4 - 62
 Grain Size Number
Grain boundaries...
• are imperfections,
• are more susceptible
to etching,
• may be revealed as polished surface
dark lines,
• change in crystal surface groove
orientation across grain boundary
(a)
boundary. Adapted from Fig. 4.14(a)
and (b), Callister 7e.
ASTM grain (Fig. 4.14(b) is courtesy
of L.C. Smith and C. Brady,
size number the National Bureau of
Standards, Washington, DC

N = 2n-1 [now the National Institute of

Standards and Technology,
Gaithersburg, MD].)

number of grains/in2 Fe-Cr alloy

at 100x (b)
magnification Chapter 4 - 63
 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 7e.

• Stacking faults
– For FCC metals an error in ABCABC packing sequence
– Ex: ABCABABC
Chapter 4 - 64
 Strategies for Strengthening:
Reduce Grain Size

• Grain boundaries are

barriers to slip.
• Barrier "strength"
increases with
Increasing angle of
misorientation. Adapted from Fig. 7.14, Callister 7e.
(Fig. 7.14 is from A Textbook of Materials
• Smaller grain size: Technology, by Van Vlack, Pearson Education,
Inc., Upper Saddle River, NJ.)
more barriers to slip.

Chapter 4 - 65
 Strategies for Strengthening:
Solid Solutions

• Impurity atoms distort the lattice & generate stress.

• Stress can produce a barrier to dislocation motion.
• Smaller substitutional • Larger substitutional
impurity impurity

A C

B D

Impurity generates local stress at A Impurity generates local stress at C

and B that opposes dislocation and D that opposes dislocation
motion to the right. motion to the right.

Chapter 4 - 66
 Strengthening by Alloying
• small impurities tend to concentrate at dislocations
• reduce mobility of dislocation  increase strength

Adapted from Fig.

7.17, Callister 7e.

Chapter 4 - 67
 Strengthening by alloying
• large impurities concentrate at dislocations on low
density side

Adapted from Fig.

7.18, Callister 7e.

Chapter 4 - 68
 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 - see the individual grains
• Crystallites (grains) can be quite small (mm
or less) – necessary to observe with a
microscope.

Photograph of xyz positioning microstage, Quartz Single Crystal Chapter 4 - 69

realized in single crystal silicon.
 Optical Microscopy
• Useful up to 2000X magnification.
• Polishing removes surface features (e.g., scratches)
• Etching changes reflectance, depending on crystallographic
orientation.

crystallographic planes
Adapted from Fig. 4.13(b) and (c), Callister
7e. (Fig. 4.13(c) is courtesy
of J.E. Burke, General Electric Co.

Micrograph of
brass (a Cu-Zn alloy)

0.75mm
Chapter 4 - 70
 Polarized Light

– metallographic scopes often use polarized

light to increase contrast
– Also used for transparent samples such as
polymers

Chapter 4 - 71
 Concept Check

• Does the grain size number (n of Equation

4.16) increase or decrease with decreasing
grain size? Why?
• Answer: Taking logarithms of Equation 4.16
and then rearranging such that the grain size
number n is the dependent variable leads to
the expression!
n = 1 + log N / log 2
• In other words, the value of n increases with
decreasing grain size.

Chapter 4 -
 Electron 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 (10-12m ~0.003 nm)
– (Magnification - 1,000,000X)
• Atomic resolution possible
• Electron beam focused by magnetic lenses.

Chapter 4 - 73
 Scanning Probe Microscopy

• Neither light nor electrons are used to form an image!

• The microscope generates a topographical map, on an atomic
scale, that is a representation of the surface features and
characteristics of the specimen.
• Examination on the nanometer scale is possible, magnifications
as high as109x are possible;
• Three-dimensional magnified images are generated that provide
topographical information about features of interest.
• Some SPMs may be operated in a variety of environments (e.g.,
vacuum, air,liquid); thus, a particular specimen may be
examined in its most suitable environment.

Chapter 4 - 74
Scanning Tunneling Microscopy
(STM)

Chapter 4 - 75
 Scanning Electron Microscopy

Pollen Seed Space Shuttle Tile

Lead-Tin Solder
Ceramic with pores
Fracture Surface
Chapter 4 - 76
 Scanning Electron Microscopy

Dislocations in Ti Zirconia/Alumina Interface

Ant’s Head Alloy at 51,450X

Chapter 4 - 77
 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 - 78
 Scanning Tunneling Microscopy
(STM)

(110) Surface of Ni 2 point defects on (111)

plane of Cu lattice

Chapter 4 - 79
Chapter 4 - 80
 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.)
• Strength can be increased by making dislocation
motion difficult.
• Heating (annealing) can reduce dislocation density
and increase grain size. This decreases the strength.
Chapter 4 - 81