Imperfections

in Crystals
What types of defects arise in solids?
Can the number and type of defects
be varied?
How do defects affect material
properties?

1
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

nuclei crystals growing grain structure

liquid
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

3
Solidification
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

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

4
Crystal imperfections

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.

5
Types of imperfections
Vacancy atoms
Interstitial atoms Point defects
Substitutional atoms

Dislocations Line defects

Grain Boundaries Area defects

Voids Volume defects

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Definitions
Point defects - Imperfections, such as vacancies, that are
located typically at one (in some cases a few) sites in the
crystal.
Extended defects - Defects that involve several atoms/ions
and thus occur over a finite volume of the crystalline
material (e.g., dislocations, stacking faults, etc.).
Vacancy - An atom or an ion missing from its regular
crystallographic site.
Interstitial defect - A point defect produced when an atom is
placed into the crystal at a site that is normally not a lattice
point.
Substitutional defect - A point defect produced when an atom
is removed from a regular lattice point and replaced with a
different atom, usually of a different size.
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Definitions
Interstitialcy - A point defect caused when a normal
atom occupies an interstitial site in the crystal.
Frenkel defect - A pair of point defects produced when
an ion moves to create an interstitial site, leaving behind
a vacancy.
Schottky defect - A point defect in ionically bonded
materials. In order to maintain a neutral charge, a
stoichiometric number of cation and anion vacancies
must form.
Krger-Vink notation - A system used to indicate point
defects in materials. The main body of the notation
indicates the type of defect or the element involved.

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 (c) 2003 Brooks/Cole Publishing / Thomson Learning
Figure 4.1 Point defects: (a) vacancy, (b) interstitial atom, (c) small
substitutional atom, (d) large substitutional atom, (e) Frenkel defect,
(f) Schottky defect. All of these defects disrupt the perfect
arrangement of the surrounding atoms.
9
Learning
(c) 2003 Brooks/Cole Publishing / Thomson

Figure 4.3 When a divalent cation replaces a monovalent

cation, a second monovalent cation must also be removed,
creating a vacancy.

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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

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Point Defects: Equilibrium
concentration
Equilibrium concentration varies with temperature!

No. of defects Activation energy

ND = Q
exp D
N kT
No. of potential Temperature
defect sites. Boltzmann's constant
(1.38 x 10-23 J/atom K)
(8.62 x 10-5 eV/atom K)
Each lattice site
is a potential
vacancy site 12
Measuring Activation Energy

We can get Q from ND = Q

exp D
an experiment. N kT
Measure this... Replot it...

ND ND slope
1
ln
N N
-QD/k
exponential
dependence!

T
1/T
defect concentration
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Estimating Vacancy Concentration
Find the equil. # of vacancies in 1m 3of Cu at 1000C.
Given:
= 8.4 g/cm3 ACu = 63.5g/mol
QV = 0.9eV/atom NA = 6.02 x 1023 atoms/mole
0.9eV/atom
ND Q
= exp D
= 2.7 10-4
N kT
1273K
8.62 x 10-5 eV/atom-K
NA
For 1m3, N = x x 1m3 = 8.0 x 1028 sites
ACu
Answer:
ND = 2.7 10-4 8.0 x 1028 sites = 2.2x 1025 vacancies
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Observing Equilibrium Vacancy
Concentration
Low energy electron
microscope view of
a (110) surface of NiAl.
Increasing T 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, J.A. Nobel, and N.C. Bartelt, "Vacancies in
they join the island. Solids and the Stability of Surface Morphology",
Nature, Vol. 412, pp. 622-625 (2001). Image is
Island grows/shrinks to maintain 5.75 m by 5.75 m.) Copyright (2001) Macmillan
equil. vancancy conc. in the bulk. Publishers, Ltd.

15
Point Defects in Alloys
Two outcomes if impurity (B) added to host (A):

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.

16
Imperfections in Solids
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

17
Alloying a surface
Low energy electron
microscope view of
a (111) surface of Cu.
Sn islands move along
the surface and "alloy"
the Cu with Sn atoms,
to make "bronze".
The islands continually
move into "unalloyed"
regions and leave tiny
Reprinted with permission from: A.K. Schmid,
bronze particles in N.C. Bartelt, and R.Q. Hwang, "Alloying at
Surfaces by the Migration of Reactive Two-
their wake. Dimensional Islands", Science, Vol. 290, No.
5496, pp. 1561-64 (2000). Field of view is 1.5
Eventually, the islands m and the temperature is 290K.

disappear. 18
Composition
Definition: Amount of impurity (B) and host (A)
in the system.
Two descriptions:
Weight % Atom %
mass of Bx 100 # atoms of Bx 100
CB = C'B =
total mass total # atoms
Conversion between wt % and at% in an A-B alloy:
C'BAB CB/AB
CB = x 100 C'B =
C'AAA + C'BAB CA/AA + CB/AB
Basis for conversion: atomic weight of B
mass of B = moles of B x AB atomic weight of A
mass of A = moles of A x AA
19
Line Defects
Dislocations:
are line defects,
cause slip between crystal plane when they move,
produce permanent (plastic) deformation.

Schematic of a Zinc (HCP):

before deformation after tensile elongation

slip steps

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Definitions
Dislocation - A line imperfection in a crystalline
material.
Screw dislocation - A dislocation produced by
skewing a crystal so that one atomic plane
produces a spiral ramp about the dislocation.
Edge dislocation - A dislocation introduced into
the crystal by adding an extra half plane of
atoms.
Mixed dislocation - A dislocation that contains
partly edge components and partly screw
components.
Slip - Deformation of a metallic material by the
movement of dislocations through the crystal.
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Edge Dislocation

Figure 4.5 The perfect crystal in (a) is cut and an extra

plane of atoms is inserted (b). The bottom edge of the
extra plane is an edge dislocation (c). A Burgers
vector b is required to close a loop of equal atom
spacings around the edge dislocation. (Adapted from
J.D. Verhoeven, Fundamentals of Physical Metallurgy,
Wiley, 1975.)
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Slip plane

Figure 4.7 Schematic of slip line, slip plane, and slip

(Burgers) vector for (a) an edge dislocation and (b) for a
screw dislocation. (Adapted from J.D. Verhoeven,
Fundamentals of Physical Metallurgy, Wiley, 1975.)

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 Screw Dislocation
(c) 2003 Brooks/Cole Publishing / Thomson Learning

Figure 4.4 the perfect crystal (a) is cut and sheared one atom
spacing, (b) and (c). The line along which shearing occurs is a
screw dislocation. A Burgers vector b is required to close a loop
of equal atom spacings around the screw dislocation.
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 Peierls-Nabarro stress
kd
= c exp
b

Figure 4.8 (a) When a shear stress is applied to the dislocation in (a),
the atoms are displaced, causing the dislocation to move one Burgers
vector in the slip direction (b). Continued movement of the dislocation
eventually creates a step (c), and the crystal is deformed. (Adapted
from A.G. Guy, Essentials of Materials Science, McGraw-Hill, 1976.)
(b) Motion of caterpillar is analogous to the motion of a dislocation.
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Common Slip planes and Directions

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Incremental Slip
Dislocations slip planes incrementally...
The dislocation line (the moving red dot)...
...separates slipped material on the left
from unslipped material on the right.

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

Elastic Strain Energy

E b /2 2

Splits into smaller burgers

vector if energy is lowered27
Dislocation motion
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)

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Figure 4.12 Optical image of etch pits in silicon
carbide (SiC). The etch pits correspond to
intersection points of pure edge dislocations with
Burgers vector a/3 1 1 20 and the dislocation line
direction along [0001] (perpendicular to the
etched surface). Lines of etch pits represent low
angle grain boundaries (Courtesy of Dr. Marek
Skowronski, Carnegie Mellon University.)
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Edge, screw, mixed dislocation
Positive and negative edge dislocation
Positive and negative screw dislocation

T b
t T
b t t b
t

edge dislocation climb

screw dislocation cross slip
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Learning
(c) 2003 Brooks/Cole Publishing / Thomson

Learning
(c) 2003 Brooks/Cole Publishing / Thomson
(c)2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.

Figure 4.13 Electron photomicrographs of dislocations in

Ti3Al: (a) Dislocation pileups (x26,500). (b) Micrograph at
x 100 showing slip lines and grain boundaries in AI. (c)
Schematic of slip bands development.
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Dislocations and crystal structure
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

Results of tensile Mg (HCP)

testing.
tensile direction
Al (FCC)
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Area Defects: Grain Boundaries
Grain boundaries:
are boundaries between crystals.
are produced by the solidification process, for example.
have a change in crystal orientation across them.
impede dislocation motion. Metal Ingot
Schematic ~ 8cm

grain
boundaries

Adapted from Fig. 4.7, Callister 6e.
heat
flow Adapted from Fig. 4.10, Callister 6e.
(Fig. 4.10 is from Metals Handbook, Vol. 9, 9th edition,
Metallography and Microstructures, Am. Society for 33
Metals, Metals Park, OH, 1985.) 15
Definitions
Surface defects - Imperfections, such as grain
boundaries, that form a two-dimensional plane within
the crystal.
Hall-Petch equation - The relationship between yield
strength and grain size in a metallic materialthat is,
y= 0 + Kd 1/ 2
ASTM grain size number (n) - A measure of the size of
the grains in a crystalline material obtained by counting
the number of grains per square inch a magnification
100.
Small angle grain boundary - An array of dislocations
causing a small misorientation of the crystal across the
surface of the imperfection.
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Area Defect: Grain Boundary

Figure 4.16 (a) The atoms near the boundaries of the

three grains do not have an equilibrium spacing or
arrangement. (b) Grains and grain boundaries in a
stainless steel sample high angle boundary, > 10-15o

Grain boundary between BCC crystals : 0.89 Jm-2

Grain boundary between FCC crystals : 0.85 Jm-2
Grain boundary between BCC & FCC crystals : 0.63 Jm-2
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 (c) 2003 Brooks/Cole Publishing / Thomson Learning
1

Y = 0 + kd 2

Figure 4.17 The effect of grain size on the yield

strength of steel at room temperature.
1 2
Hall Petch relation: Y = 0 + kd
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Area Defects: Twin Boundaries
One case is a twin boundary (plane)
Essentially a reflection of atom positions across the twin
plane occur in pairs.
Region between pair boundary in twinned region.
Annealing twins form during recrystallization
Deformation twins form during deformation

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 Twin Boundary
(c) 2003 Brooks/Cole Publishing / Thomson Learning

Figure 4.20 Application of a stress to the perfect crystal (a) may

cause a displacement of the atoms, (b) causing the formation of a
twin. Note that the crystal has deformed as a result of twinning.
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Area Defects: Stacking fault
Stacking faults
For FCC metals an error in ABCABC packing sequence
Ex: ABCABABC (intermediate HCP stacking)
Number of nearest neighbours is the same (12)
The second nearest neighbour bonds are faulted
Low energy: 0.01 to 0.05 Jm-2

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(c) 2003 Brooks/Cole Publishing / Thomson Learning

A micrograph of twins within brass grains (x250).

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Tilt Boundary

Figure 4.19 The small angle

grain boundary is produced by
an array of dislocations,
causing an angular mismatch
between lattices on either side

(c) 2003 Brooks/Cole Publishing / Thomson Learning

of the boundary.

b
tan =
D

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42
Optical Microscopy
Useful up to 2000X magnification.
Polishing removes surface features (e.g., scratches)
Etching changes reflectance, depending on crystal
orientation.
microscope

close-packed planes
Adapted from Fig. 4.11(b) and (c),
Callister 6e. (Fig. 4.11(c) is courtesy
of J.E. Burke, General Electric Co.

micrograph of
Brass (Cu and Zn)

0.75mm 43
Optical Microscopy
Grain boundaries... microscope
are imperfections,
are more susceptible
to etching, polished surface
may be revealed as surface groove
dark lines, grain boundary
change direction in a
polycrystal.
ASTM grain
size number
Adapted from Fig. 4.12(a)
N = 2n-1 and (b), Callister 6e.
(Fig. 4.12(b) is courtesy
of L.C. Smith and C. Brady,
no. grains/in2 the National Bureau of

at 100x Fe-Cr alloy Standards, Washington

magnification
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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.)

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