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 - 1
 Chapter 4 - Learning Objectives
After studying this chapter you should be able to do the following:
1. Describe both vacancy and self-interstitial crystalline defects.
2. Calculate the equilibrium number of vacancies in a material at
some specified temperature, given the relevant constants.
3. Name the two types of solid solutions, and provide a brief written
definition and/or schematic sketch of each.
4. Given the masses and atomic weights of two or more elements
in a metal alloy, calculate the weight percent and atom percent
for each element.
5. For each of edge, screw, and mixed dislocations:
(a) describe and make a drawing of the dislocation.
(b) note the location of the dislocation line, and
(c) indicate the direction along which the dislocation line extends.
6. Describe the atomic structure within the vicinity of
(a) a grain boundary, and
(b) a twin boundary. Chapter 4 - 2
 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

Chapter 4 - 3
 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

Chapter 4 - 4
 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.

Chapter 4 - 5
 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 - 6
Imperfections in Solids - Examples
• The mechanical properties of pure metals
experience significant alterations when alloyed
(i.e., when impurity atoms are added)—for
example, brass (70% copper–30% zinc) is
much harder and stronger than pure copper
• Integrated circuit microelectronic devices
found in our computers, calculators, and home
appliances function because of highly
controlled concentrations of specific impurities
that are incorporated into small, localized
regions of semiconducting materials
Chapter 4 - 7
 Types of 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.

• Vacancy atoms
• Interstitial atoms Point defects
• Substitutional atoms

• Dislocations Line defects

• Grain Boundaries Area defects

Chapter 4 - 8
 Point Defects
• Vacancies:
vacant atomic sites in a structure.

Vacancy
distortion
of planes

• Self-Interstitials:
"extra" atoms positioned between atomic sites. A scanning probe micrograph
(generated using a scanning-
tunneling microscope) that shows
self-interstitial a (111)-type surface plane for
silicon. The arrow points to the
location of a silicon atom that was
removed using a tungsten nanotip
distortion probe. This site from which an
atom is missing is the surface
of planes analogue of a vacancy defect—
that is, a vacant lattice site within
the bulk material. Approximately
20,000,000x.
Chapter 4 - 9
 Equilibrium Concentration:
Point Defects
• Equilibrium concentration varies with temperature!

No. of defects Activation energy

Nv  −Q 
No. of potential = exp  v 
N  kT 
defect sites.
Temperature
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
Chapter 4 - 10
 Measuring Activation Energy
• We can get Qv from Nv  −Q 
= exp  v 
an experiment.
N  kT 
• Measure this... • Replot it...

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

T 1/T
defect concentration
Chapter 4 - 11
 Estimating Vacancy Concentration
• Find the equil. # of vacancies in 1 m3 of Cu at 1000°C.
• Given:
ρ = 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
Nv =  −Q 
exp  v  = 2.7 x 10-4
N  kT 
1273K
8.62 x 10-5 eV/atom-K
NA
For 1 m3 , N= ρ x x 1 m3 = 8.0 x 1028 sites
A Cu
• Answer:
Nv = (2.7 x 10-4)(8.0 x 1028) sites = 2.2 x 1025 vacancies
Chapter 4 - 12
Observing Equilibrium Vacancy Conc.
• 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 Island grows/shrinks to maintain
motion from the crystal equil. vancancy conc. in the bulk.
to the surface, where
they join the island.

Chapter 4 - 13
 Point Defects in Alloys
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 - 14
 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

Chapter 4 - 15
 Imperfections in Solids
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
to dissolve in Zn? O
Ag
0.060
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
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

Chapter 4 - 16
 Imperfections in Solids
¾ It is often necessary to express the composition (or
concentration) of an alloy in terms of its constituent elements.
¾ The two most common ways to specify composition are weight (or
mass) percent and atom percent.
• Specification of composition
m1
– weight percent C1 = x 100
m1 + m2
m1 = mass of component 1

n m1
– atom percent C =
'
1 x 100
n m1 + n m 2

nm1 = number of moles of component 1

Chapter 4 - 17
 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 - 18
 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 ⊥ to dislocation line
• Screw dislocation:
– spiral planar ramp resulting from shear deformation
– b || to dislocation line
Burger’s vector, b: measure of lattice distortion

Chapter 4 - 19
 Imperfections in Solids
Edge Dislocation

Chapter 4 - 20
 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.

Chapter 4 - 21
 Imperfections in Solids
Screw Dislocation
Screw Dislocation

b
Dislocation
line
Burgers vector b (b)
(a)

Chapter 4 - 22
Edge, Screw, and Mixed Dislocations
Mixed

Edge

Screw

Chapter 4 - 23
 Imperfections in Solids
Dislocations are visible in ¾ Virtually all crystalline materials
electron micrographs contain some dislocations that
were introduced during
solidification, during plastic
deformation, and as a
consequence of thermal stresses
that result from rapid cooling.
¾ Dislocations are involved in the
plastic deformation of crystalline
materials, both metals and
ceramics.

Chapter 4 - 24
 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 - 25
 Planar Defects in Solids
• Grain Boundaries
• 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
Chapter 4 - 26
 Structure

200
.00
≈ 10-1 m
x

0x
Bulk ceramics
0
25

x
= 2x10-9 m

20
TEM
Atomic ordering

= 5x10-7 m ≈ 10-10 m
SEM micrograph showing grains Crystal Structure Chapter 4 - 27
 Microscopic Examination
• Crystallites (grains) and grain Example microstructure
boundaries.
• Their size may vary considerably.
Can be quite large (to be visible by
naked eye)
– ex: Large single crystal of quartz or
diamond or Si
– ex: Aluminum light post or highway
guard rails-
Can be quite small (mm or less) – High-purity polycrystalline lead
ingot in which the individual
(necessary to observe with a grains may be discerned.

microscope.)

Chapter 4 - 28
Microscopic Examination

Chapter 4 - 29
Microscopy Techniques

Chapter 4 - 30
 Optical Microscopy
¾ Useful up to 2000X magnification.
¾ Polishing removes surface features (e.g., scratches)
¾ Etching changes reflectance, depending on crystal orientation.

0.75mm

Micrograph of brass (a Cu-Zn alloy)

Chapter 4 - 31
crystallographic planes
 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.
ASTM grain
size number

N = 2n-1
Fe-Cr alloy
number of grains/in2
at 100x (b)
magnification Chapter 4 - 32
 Electron Microscopy
Optical resolution ca. 10-7 m = 0.1 µm = 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 - 33
 Transmission Electron Microscopy (TEM)
¾ The image seen with a TEM is
formed by an electron beam that
passes through the specimen.
¾ Contrasts in the image are
produced by differences in beam
scattering or diffraction produced
between various elements of the
microstructure or defect.
¾ Since solid materials are highly
absorptive to electron beams, a
specimen to be examined must be
prepared in the form of a very thin
High-resolution TEM micrograph that shows
foil. single crystals of (Ce0.5Zr0.5)O2.
This material is used in catalytic converters
¾ Magnifications approaching for automobiles.

1,000,000X are possible Chapter 4 - 34

 Scanning Electron Microscopy (SEM)
¾The surface of a specimen to be examined is scanned with
an electron beam, and the reflected (or back-scattered) beam
of electrons is collected, then displayed on a cathode ray tube.
¾ The image represents the surface features of the specimen.
¾ Magnifications ranging from 10 to in excess of 50,000 times
are possible, as are also very great depths of field.

SEM micrograph of Pb(Zr0.5Ti0.5)O3 ceramics. SEM micrograph of nanofiber mats of Pb(Zr0.5Ti0.5)O3.

This material is used in piezoelectric
transducers. Chapter 4 - 35
 Scanning Probe Microscopy (SPM)
¾ SPM differs from the optical and electron microscopes in that
neither light nor electrons is used to form an image.
¾ Rather, the microscope generates a topographical map, on an
atomic scale, that is a representation of surface features and
characteristics of the specimen being examined.
¾ Examination on the nanometer scale is possible inasmuch as
magnifications as high as 109x are possible. Higher resolutions
are attainable than with other microscopic techniques.
¾ Atoms can be arranged and imaged!
Surface
topography of Carbon monoxide
PbZrO3 thin films molecules
showing nanosize arranged on a
grains platinum (111)
surface.

Iron atoms arranged on a copper (111)

surface. These Kanji characters Chapter 4 - 36
represent the word “atom”.
 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 - 37