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?

1
Materials are not always perfect.
• sometimes atoms are in the wrong place

• there are missing atoms

• foreign atoms are present

Influence of Imperfections:

•Accounts for the behavior of semiconductors.

• Accounts for the ductility of metals

• Color of sapphire

• The rule within polymers and glasses.

• Permits the movement of atoms during heat treatment so that

new structures and enhanced properties are realized.
 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 Adapted from Fig. 4.14(b), Callister & Rethwisch 8e.

• Crystals grow until they meet each other

4
 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.
5
 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
Adapted from Fig. 5.17, T) near wall
Callister & Rethwisch 3e.

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

6
 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.

7
 Types of Imperfections
• Vacancy atoms
• Interstitial atoms Point defects
• Substitutional atoms

• Dislocations Line defects

• Grain Boundaries Area defects

8
 Point Defects in Metals
• Vacancies:
-vacant atomic sites in a structure.

Vacancy
distortion
of planes

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

self-
interstitial
distortion
of planes

9
 Point Defects in Metals
• Vacancies:
-vacant atomic sites in a structure.

Vacancy
distortion
of planes

• Simplest point defect

• Involves a missing atom within a crystal.
• can be a result of imperfect packing during the original
crystallization
• or may arise from thermal vibrations of atoms at
elevated temperatures.

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

Vacancy
distortion
of planes

• because as thermal energy increased, there is an

increased probability that individual atoms will jump
out of their positions of lowest energy.
• All crystalline solids contain vacancies and it is not
possible to create such a material that is free of
these defects.
• Presence of vacancies increases the entropy
(randomness) of the crystal. 11
 Point Defects in Metals
• Self-Interstitials:
-"extra" atoms positioned between atomic sites.

self-
interstitial
distortion
of planes

• an interstitial site is a small void space that under

ordinary circumstances is not occupied.
• The formation of this defect is not highly probable.
• It exists in very small concentrations which are
significantly lower than for vacancies.

12
 Point Defects in Metals
• Self-Interstitials:
-"extra" atoms positioned between atomic sites.

self-
interstitial
distortion
of planes

• Exhibit mostly if the atomic packing factor is low.

• Also called interstitialcy
• In metals, self-interstitial introduces relatively large
distortions in the surrounding lattice because the
atom is substantially larger than the interstitial
position in which it is situated.
13
 Equilibrium Concentration:
Point Defects
• Equilibrium concentration varies with temperature!

No. of defects Activation energy

Nv Q v 
No. of potential = exp  
defect sites N  k T 
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
14
 Measuring Activation Energy
• We can get Qv from Nv Q v 
= exp 
 
an experiment. N  k T 
• Measure this... • Replot it...

Nv Nv slope
ln
N N
-Qv /k
exponential
dependence!

T
1/ T
defect concentration
15
 Estimating Vacancy Concentration

Problem 1:

Calculate the equilibrium number of vacancies per cubic

meter for copper at 1000 oC. The energy for vacancy
formation is 0.90 eV/atom, the at.wt. and density (at
1000 oC) for copper are 63.5 g/mol and 8.40 g/cm3
respectively.
 Estimating Vacancy Concentration
• Find the equil. # of vacancies in 1 m3 of Cu at 1000C.
• Given:
r = 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
Q 
exp 
Nv =
 v = 2.7 x 10-4
N  k T 
1273 K
8.62 x 10-5 eV/atom-K
For 1 m3 , solve for N

17
N = NA r
ACu

= (6.023x1023 atoms/mol) x (8.40 g/cm3)(100 cm/m)3

63.5 g/mol
N = 8.0x1028 atoms/m3

0.9 eV/atom
Q 
exp 
Nv =
 v = 2.7 x 10-4
N  k T 
1273 K
8.62 x 10-5 eV/atom-K

• Answer:
Nv = (2.7 x 10-4)(8.0 x 1028) sites = 2.2 x 1025 vacancies
Problem 2:
Determine the number of vacancies needed for a BCC iron lattice to
have a density of 7.87 g/cm3. The lattice parameter of the iron is
2.866x10-8 cm.
Given:
BCC Iron, r = 7.87 g/cm3, a = 2.866x10-8 cm

Reqd: Number of vacancies

Soln:

BCC has 2 atoms in each unit cell

The expected density is:
r = nA = (2 atoms/cell)(55.847 g/mol)
VcNA (2.866x10-8cm)3 (6.02x1023 atom/mol)

r = 7.8814 g/cm3
We are required to produce a density of 7.87 g/cm3 (lower than
7.8814 g/cm3)
This is accomplished by introducing vacancies into the lattice.
Solve N  number of atoms/cell from the required density.

7.87 g/cm3 = (N)(55.847 g/mol)

(2.866x10-8cm)3 x (6.023x1023atom/mol)

N; # of atoms/cell = 1.9981
Vacancy/cell = 2 – 1.9981
= 1.90x10-3

# of vacancy = 1.90x10-3 vacancies/cell

cm3 (2.866x10-8 cm)3/cell

# of vacancy = 8.071x1019
cm3
 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.

21
 Imperfections in Metals (i)
• Solid solution of B in A (i.e., random dist. of point defects)

• Introduced when one atom

(host) is replaced by a
different type of atom (solute-
impurity).
• The substitutional atom
Substitutional solid soln. remains at the original
(e.g., Cu in Ni)
position.
• Substitutional atoms may either be larger than the normal
atoms in the lattice (in w/c case the surrounding atoms
are compressed) or smaller (causing the surrounding
atoms to be in tension).
22
Small Substitutional Large Substitutional
Atom Atom
 Imperfections in Metals (i)
• Solid solution of B in A (i.e., random dist. of point defects)

• Formed when an extra atom is

inserted into the lattice structure at a
normally unoccupied position.

Interstitial solid soln.

• Interstitial atoms/impurity atoms fill
(e.g., C in Fe) the voids or interstices among the
host atoms.

• In metallic materials w/ relatively

high APF, interstitial positions are
relatively small.
24
 Imperfections in Metals (i)
• Solid solution of B in A (i.e., random dist. of point defects)

• Normally, the maximum allowable

concentration of interstitial impurity
atoms is low (<10%).

• Interstitial atoms are larger than the

Interstitial solid soln.
(e.g., C in Fe)
interstitial sites they occupy,
compressing & distorting the
surrounding lattice.

• They introduce some lattice strains

on adjacent host atoms.
25
 Imperfections in Metals (i)
• Solid solution of B in A (i.e., random dist. of point defects)

• Carbon atoms are intentionally

added to iron to produce steel.

• Carbon forms an interstitial solid

solution when added to iron;
Interstitial solid soln.
(e.g., C in Fe)
• The maximum concentration of
carbon is about 2%.

26
 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

27
 Imperfections in Metals (ii)
1. r (atomic radius) < 15%

The difference in atomic radii between the two atoms

must be less than 15%, otherwise the solute atoms
will create substantial lattice distortions & a new phase
will form.

Example:
RCu = 0.128 nm and RNi = 0.125 nm are soluble in all
proportion

28
 Imperfections in Metals (ii)
Proximity in periodic table
• i.e., similar electronegativities

The more electropositive one element and the more

electronegative the other, the greater is the likelihood of that
they will form an intermetallic compound instead of a
substitutional solid solution.

29
 Imperfections in Metals (ii)
Same crystal structure for pure metals

• The crystal structures for metals of both atoms must be

the same for appreciable solids solubility.

Example:
Cu (FCC) & Ni (FCC) are soluble in all proportion

30
 Imperfections in Metals (ii)
Valency

• A metal will have more of a tendency to dissolve another

metal of higher valency than one of a lower valency if the
other factors are the same/equal.

Fe3+ replacing Fe2+ in FeO = Fe2+ vacancy

31
 Imperfections in Metals (iii)
Application of Hume–Rothery rules – Solid Solutions
Element Atomic Crystal Electro- Valence
Radius Structure nega-
Would you predict (nm) tivity
more Al or Ag Cu 0.1278 FCC 1.9 +2
C 0.071
to dissolve in Zn? H 0.046
O 0.060
Ag 0.1445 FCC 1.9 +1
Al 0.1431 FCC 1.5 +3
Co 0.1253 HCP 1.8 +2
Cr 0.1249 BCC 1.6 +3
Fe 0.1241 BCC 1.8 +2
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.

32
 Impurities in Solids
• 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

33
 C1’A1
C1 = ------------------------X 100
C1’ A1 + C2’A2

C2’A2
C2 = ------------------------X 100
C1’ A1 + C2’A2

C1 + C2 = 100
C1’ + C2’ = 100

C1 and C2 = weight percent

C1 ’ and C2 ’ = atom percent
A1 and A2 = atomic weights
34
 C1A2
C1’ = ------------------------X 100
C1A2 + C2A1

C2A1
C2 ’ = ------------------------X 100
C1A2 + C2A1

C1 + C2 = 100
C1’ + C2’ = 100

C1 and C2 = weight percent

C1 ’ and C2 ’ = atom percent
A1 and A2 = atomic weights
35
Finding the number of atoms per cm3 of a substitutional element in
a solid solution:

N1 = NAC1
(C1A1/r1) + (A1/r2)(100 – C1)

C1 = 100
1 + NAr2 - r2 .
N1A1 r1
Where:
N1 = number of atoms/cm3
C1 = % weight
A1, A2 = atomic weights of the two elements
r1, r2 = densities of the two elements
NA = Avogadro’s number
Problems:
1. What is the composition in weight percent of an alloy that consist
of 6 At % Pb and 94 At% Sn? APb = 207.2, ASn = 118.69

CPb’APb CSn’ASn
CPb = ------------------------X 100 CSn = ------------------------X 100
CPb’ APb + CSn’ASn CPb’ APb + CSn’ASn

6(207.2) 94(118.69
CPb = ---------------------------------X 100 CSn = ---------------------------------X 100
6(207.2)+ 94(118.69) 6(207.2)+ 94(118.69)

CPb=10.03% CSn =89.97%

2. Determine the composition in an atom percent of an alloy that
consists of 97 wt% aluminun and 3 wt% copper.

CAlACu CCuAAl
CAl’ = ------------------------X 100 CCu’ = ------------------------X 100
CAlACu + CCuAAl CCuAAl+CAlACu

97(63.55) 3(26.98)
CAl = ---------------------------------X 100 CCu = -------------------------------X 100
97(63.55)+ 3(26.98) 3(26.98) + 97(63.55)

CAl = 98.7% CCu = 1.30%

 3. Gold forms a substitutional solid solution with Ag. Compute
the number of gold atoms per cm3 for a silver-gold alloy that
contains 10% wt Au and 90% wt Ag. The density of pure gold
and silver are 9.32 and 10.49 g/cm3 respectively. AAu = 196.97,
AAg = 107.87

Given: substitutional solid soln

10% wt Au ; rAu = 19.32 g/cm3;
AAu = 196.97
90% wt Ag; rAg = 10.49 g/cm3;
AAg = 107.87
Reqd: # of Au atoms/cm3
Soln:
NAu = NA CAu .

(CAuAAu/rAu) + (AAu/rAg)(100 – CAu)

NAu = 3.361 x 1021 atoms/cm3
Given: substitutional solid soln
10% wt Au ; rAu = 19.32 g/cm3;
AAu =
196.97
90% wt Ag; rAg = 10.49 g/cm3;
AAg = 107.87
Reqd: # of Au atoms/cm3
Soln:
NAu = NA CAu .

(CAuAAu/rAu) + (AAu/rAg)(100 – CAu)

NAu = 3.361 x 1021 atoms/cm3
4. Molybdenum forms a substitutional solid solution w/ tungsten.
Compute the weight percent of Mo that must be added to
tungsten to yield an alloy that contains 1.0x1022 Mo atoms/cm3.
rMo = 10.22 g/cm3, rW = 19.30 g/cm3. AMo = 95.94

CMo = 100 .
1 + NA rW - rW
NMoAMo rMo

CMo = 100
1 + (6.023x1023atom/mol)(19.30 g/cm3) - 19.30 g/cm3
(1.0x1022 atoms/cm3 )(95.94 g/mol) 10.22 g/cm3

. CMo = 8.91%
 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

42
 Imperfections in Solids
Edge Dislocation

Fig. 4.3, Callister & Rethwisch 8e.

43
 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)
44
 Imperfections in Solids
Screw Dislocation
Screw Dislocation

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

46
 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 47
 Edge, Screw, and Mixed Dislocations
Mixed

Edge

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

Screw

48
 Imperfections in Solids
Dislocations are visible in electron micrographs

Fig. 4.6, Callister & Rethwisch 8e.

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)
50
 Planar Defects in Solids
• One case is a twin boundary (plane)
– Essentially a reflection of atom positions across the twin plane.

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

Adapted from Fig. 4.9,

Callister & Rethwisch 8e.

51
 Area or Surface Defects
Grain boundaries
Any dislocation moves until it encounter a
grain boundary.

Control of grain boundary

High Strength – goal is to stop dislocation,

-small grain size , increase
in grain and grain
boundaries ; fine grained
structure

High ductility– goal is to encourage gliding of atoms or dislocation,

-coarse grain size

52
 Catalysts and Surface Defects
• A catalyst increases the rate of a
chemical reaction without being
consumed
• Active sites on catalysts are normally
surface defects Fig. 4.10, Callister & Rethwisch 8e.

• Free surface has a high energy and

therefore high reactivity.
• High energy is because of low number
of neighbors in the surface.

Single crystals of
(Ce0.5Zr0.5)O2
used in an automotive
catalytic converter
Fig. 4.11, Callister & Rethwisch 8e.
53
 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.

54
 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
55
 Optical Microscopy
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 &
ASTM grain Rethwisch 8e.
(Fig. 4.14(b) is courtesy
size number of L.C. Smith and C. Brady,
the National Bureau of

N = 2n-1 Standards, Washington, DC

[now the National Institute of
Standards and Technology,
Gaithersburg, MD].)
number of grains/in2 Fe-Cr alloy
at 100x (b)
magnification 56
 Optical Microscopy
• Polarized light
– metallographic scopes often use polarized light
to increase contrast
– Also used for transparent samples such as
polymers

57
 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.

58
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”.

59
 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.)

60
 Glasses

An introduction

61
 Amorphous - Glass
Solid which is dimensionally stable i.e has a volume of its own

Classification of solids by atomic arrangement

ordered disordered
Atomic arrangement regular random
Order long range short range
Name crystalline amorphous

Glass- solid lacking long range order

62
 Disordered solids

Inorganic compounds – silicates

Organic compounds – polymer
Elements – sulfur
Alloys – metallic glasses – 80% metal – 20% metalloids
example Fe80B20
Crystalline – quartz
Both SiO2
amorphous - glass

63
Conditions promoting glass formation

- Amorphous
- crystal

- Mobility of atoms

64
Silicates - based on SiO2 – silica oxide
Si- silicon element
SiO4 -Silicate – fully oxidize

Sp3 hybridized

O O
I I
Si Si

O O O O O

65