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
 Solidification
• Solidification- phase transformation
• From liquid to solid by cooling

Freezing point/
Melting point

L S+L S

Chapter 4 -
 Solidification of metals
• Solidification- result of casting of molten material
• Start with a molten material – all liquid
2 steps process
– Nucleation: Stable nuclei formation
– Growth: Nuclei growth into crystals – grain structure

nuclei crystals growing grain structure

liquid

• Crystals grow until they meet each other

Chapter 4 -
 Solidification
• How to commencement solidification in pure metals?

• Nuclei formation?

Undercooling: Process of
lowering the temperature of
liquid below its freezing point.

Chapter 4 -
 Nucleation

Homogeneous Heterogeneous
Nucleation Nucleation

Formed nuclei are uniform Nuclei form at

throughout the parent structural
phase. inhomogeneity/
impurity
Metal itself provides atoms
to form nuclei. Chapter 4 -
 Homogeneous Nucleation
• Pure metal is cooled below equilibrium freezing
temperature (melting temp).

• Considerably large undercooling.

Embryo Critical Size Nucleus

• Embryos are unstable.

• Nucleus are stable

• Thermal gradient (temperature change is important)

Chapter 4 -
 Homogeneous Nucleation
• Thermodynamics- Energies involved;
1. Volume free energy
(energy released by liquid to solid transformation)

2. Surface energy (to form new phase surface)

Retarding energy

Driving energy
Total energy? Chapter 4 -
 Homogeneous Nucleation
• Sum of volume free energy and surface free energy

• Critical radius (r*)

• Activation free energy (ΔG*)-

energy req. to form stable nucleus

For r < r* For r > r*

solid particles begin to growth continues with

form and re-dissolve. decrease in energy.
Chapter 4 -
 Homogeneous Nucleation
Calculation of critical radius (r*) and activation free energy (ΔG*)

Differentiate w.r.t. r

Chapter 4 -
 Homogeneous Nucleation

• Force for the solidification transformation

• At solidification equilibrium, ΔG*=0

• Temperature dependent

Chapter 4 -
 Homogeneous Nucleation

Both critical radius (r*) and activation free energy (ΔG*)

decrease with temperature.

Rapid nucleation occurs

for lower temp. (T2)

Chapter 4 -
Example: Calculate the critical radius of homogeneous
nucleus forms from pure liquid Cu, with

Also, calculate the number of atoms in critical sized

nucleus at the undercooling?

Chapter 4 -
Chapter 4 - 13
 Heterogeneous Nucleation
 Assisted by pre-existing surface.
 Favorable along interfaces and at surfaces.
 Lower the surface energy.
 Small amount of undercooling.

Chapter 4 -
Heterogeneous Nucleation

Contact angle

Chapter 4 - 15
Comparison of Homo- and Heterogeneous
Nucleation

For heterogeneous nucleation;

 Smaller free energy change.
 Smaller critical size for the nucleus.
Heterogeneous nucleation is more practical and occur at
smaller under cooling. Chapter 4 -
 Growth
• Growth begins after embryo reaches r* (stable nucleus)

• Growth rate (G)~ function of rate of diffusion and temp.

Few and relatively large

grains (coarse grains)

Q= activation energy

Transformation at high temp

(near Tm), Many small particles
Low nucleation and high Fine grains
growth rates
Transformation at low temp,
High nucleation rate and growth rates are slow Chapter 4 -
 Single crystalline materials
• Some engineering applications require single crystals:
--diamond single --turbine blades
crystals for abrasives

Chapter 4 -
 Polycrystals
• Most engineering materials are polycrystals. Anisotropic

1 mm

Isotropic
• Each "grain" is a single crystal.

• The most engineering materials are polycrystalline materials,

as grains are randomly oriented.
Chapter 4 -
 Solidification
Grains can be - Equiaxed (roughly same size in all directions)
- Columnar (elongated grains)
~ 8 cm

Shell of
Columnar in equiaxed grains
area with less due to rapid
undercooling cooling (greater
T) near wall

Heat flow
Chapter 4 -
 Imperfections in Solids

“There is no such thing as a perfect crystal.”

• What are these imperfections?

• Why are they important?

• Are impurities adverse always?

Chapter 4 - 21
 Types of Imperfections/defects
Point defects
0D (Vacancy, Interstitial,
Substitutional atoms)

1D Defects 3D

Line defects Bulk defects

(dislocation) (Pores, Cracks)
2D
Area defects
(Grain boundaries, voids) Chapter 4 - 22
 Point Defects
• Vacancies:
-vacant atomic sites in a structure.

Vacancy
distortion (missing atom)
of planes

• Main causes:
Local distortion during crystal growth/Atomic rearrangements
in crystals
Other: Plastic deformation, Rapid cooling, energetic particles
bombardment
• Exchange positions with neighbors at high temp. (diffusion of
atoms)
Chapter 4 - 23
 Equilibrium Concentration:
Point Defects
• Equilibrium concentration of vacancies varies with temperature!

No. of defects/m3 Activation energy

-Q 
= exp  
Nv
 v
Total no. of
N  kT 
atomic 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 Activation energy: Energy required for
vacancy site formation of vacancy Chapter 4 - 24
 Measuring Activation Energy

• We can get Qv from -Q 

Nv
= exp 
 v 
an experiment. N  kT 
• Replot it...

Nv Nv slope
ln
N N
-Qv
exponential
dependence!

T
1/kT
defect concentration
Chapter 4 - 25
 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   = 2.7 x 10-4
Nv =
 v
N  kT 
1273K
8.62 x 10-5 eV/atom-K
NA
For 1m3 , N= r 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 - 26
 Solid Solution
• Extrinsic point defects

• Solid solution: Two or more elements atomically dispersed in

a single phase structure.

• Solute atoms are added to host atoms

Solute
(Impurity)
Solvent/host atoms
Chapter 4 - 27
 Solid Solution
• Two outcomes for Metallic Solid solution of B in A
(i.e., random distribution of point defects)

OR

1. Substitutional solid solution. 2. Interstitial solid solution.

(e.g., Cu in Ni) (e.g., C in Fe)

• Crystal structure is unchanged, but the lattice may

endure distortion
• Does size of solute atom affect distortion? Chapter 4 - 28
 Substitutional Solid Solution
Conditions for substitutional solid solution (S.S.)
• W. Hume – Rothery rules
1. r (atomic radius) < 15%
2. Similar Crystal structure
3. Proximity in periodic table
• i.e., similar electro-negativity values
(if there is large electro-negativity difference, the
metals will form intermetallic compounds rather
than substitutional S.S.
4. Valency
• Same valency elements are favorable for extensive
S.S.
Chapter 4 - 29
 Substitutional Solid Solution
Application of Hume–Rothery rules – Solid Solutions

Element Atomic Crystal Electro- Valence

Radius Structure nega-
(nm) tivity
Cu 0.1278 FCC 1.9 +2
Q: Would you predict, C 0.071
H 0.046
which elements form O 0.060
substitutional solution Ag 0.1445 FCC 1.9 +1
Al 0.1431 FCC 1.5 +3
with Copper? 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

• Ni, Pd form substitutional solution with Copper.

Chapter 4 - 30
 Interstitial Solid Solution
• Interstitial sites are very small due to high packing density
of metals

• Solute and Solvent have large size difference.

Interstitial solid solution.

(e.g., C in Fe)
• Interstitial defects are less frequent than vacancy defects.
Chapter 4 - 31
 Composition of Solid Solution
• 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 - 32
 Line Defects
Dislocations: Lattice distortion centered around a line.
• produce permanent (plastic) deformation.

Cause: Atomic mismatch in solid solution.

• slip between crystal planes result when dislocations move.

• before deformation • after tensile elongation

slip steps

Chapter 4 - 33
 Line Defects
Two main dislocations
1. Edge dislocation:
– extra half-plane of atoms inserted in a crystal structure.

• Slip/Burger’s vector, b: measure of lattice distortion.

b is perpendicular to dislocation line. Chapter 4 - 34
 Line Defects
1. Edge dislocation

Compressive
Strain

Tensile Strain

• Non-equilibrium defects.
• Energy is stored in distorted regions.
• Bonds across the slipping planes are broken and remade in
succession. Chapter 4 - 35
 Line Defects
2. Screw dislocation:
– Distortion in the form of spiral ramp of distorted atoms.
– Resulting from shear deformation
– b parallel to dislocation line
Screw Dislocation

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

• Energy is stored in the form of shear strain Chapter 4 -

Edge, Screw, and Mixed Dislocations
Mixed

Edge

Screw

Chapter 4 - 37
 Imperfections in Solids
Dislocations are visible in electron micrographs

Chapter 4 - 38
 Planar Defects in Solids
External Surfaces: where crystal structure terminates.
Surface atoms tends to have higher energy than inner atoms.

Grain Boundaries: Where crystallographic direction changes

abruptly. Chapter 4 - 39
 Planar Defects in Solids
Twists: reflection of atom positions across the twin plane/
mirror image of structure exists across the plane.

Stacking faults
For FCC metals an error in ABCABC packing sequence
Ex: ABCABABC
Chapter 4 - 40
 Microscopic Examination

• Size of crystallites (grains) and defects vary

considerably.

• Can be quite large

• Can be quite small (mm or less) – necessary

to observe with a microscope.

Chapter 4 - 41
 Optical Microscopy
• Useful up to 2000X magnification.
• Polishing removes surface features (e.g., scratches)
• Etching changes reflectance, depending on crystal
orientation.

crystallographic planes

Micrograph of
brass (a Cu-Zn alloy)

0.75mm
Chapter 4 - 42
 Optical Microscopy
• Visible light is used.
• Useful up to 2000x magnification.

Sample Preparation:
• Need polishing
(removes scratches)

• Etching (attack the

boundaries region).

• Etching changes
reflectance, depending
on crystal orientation.
Chapter 4 - 43
 Optical Microscopy

• Wavelength of visible light (400 ~ 700 nm).

• Wavelength of electron (1nm)
Chapter 4 - 44
 Transmission 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 (0.003 nm)
– (Magnification - 1,000,000X)
• Atomic resolution possible
• Electron beam focused by magnetic lenses.

Chapter 4 - 45
 Scanning Electron Microscopy
• Instead of optical light, a beam of electrons is targeted to
surface.
• Resolution: 5nm (about 15 to 100,000x)

Chapter 4 - 46
 Scanning Electron Microscopy

SEM image of Silicon.

• No need of sample etching/polishing

• Heavy metal coting for better resolution.
Chapter 4 - 47
 Transmission Electron Microscopy
(100 ~ 300 kV)
Resolution in nm
scale.

Thickness of
specimen (sample)
must be in several
hundred nm range.

Focused ion beam

is used for thinning.

Sample preparation
is very complex.

Chapter 4 - 48
 Transmission Electron Microscopy
High resolution transmission electron microscopy
Resolution ~ 0.1 nm
Thinner sample 10 ~ 15 nm
TEM images of Metal-hBN-Metal devices
(a) Top electrode (b
(b)
)

hBN (c)

Chapter 4 -
Bottom electrode
 Scanning Probe Microscopy (SPM)
• A probe/tip is used.

• Magnify the feature of surface to sub-nm scale.

• Surface morphology, roughness and topography

1. Scanning Tunneling Microscopy

• A sharp tip is used.

Tip material:
Tungsten, Nickle,
platinum-iridium or gold
Chapter 4 - 50
 Scanning Probe Microscopy (SPM)

1. Scanning Tunneling Microscopy

Crystal array by STM

• Tunneling current is sensitive to “gap”
• Limitation: Only surface analysis, Conductive materials
Chapter 4 - 51
 Atomic Force Microscopy (AFM)
• Tip is attached to a cantilever beam
• Surface forces deflect the cantilever.

• Also applicable for non-conducting materials Chapter 4 - 52

Atomic Force Microscopy (AFM)

40

Height (nm)
20
t ~ 42nm

0 1 2 3
x (m)

Chapter 4 -
 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 - 54