Chapter 4:

Imperfections in Solids

Chapter 4 - 1
 Imperfections in Solids
• Is there a perfect crystal?
• What dictates presence or lack of
presence of imperfections?
• What are these imperfections?
• Why are they important?
– Many of the important properties of
materials are due to the presence of
imperfections.

Chapter 4 - 2
Chapter 4 - 3
 Types of Imperfections

• Stoichiometric:
•Vacancy atoms
•Interstitial atoms Non-Ionic
Point defects
•Frenkel
Ionic
•Schottky
•Substitutional atoms

• Dislocations Line defects

• Grain Boundaries
• Twin Boundaries Interfacial/Area defects
• Stacking Faults Chapter 4 - 4
 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

Chapter 4 - 5
 Point Defects in Ceramics (i)
• Vacancies
-- vacancies exist in ceramics for both cations and anions
• Interstitials
-- interstitials exist for cations
-- interstitials are not normally observed for anions because anions
are large relative to the interstitial sites

Cation
Interstitial
Cation
Vacancy

Anion
Chapter 4 - 6
Vacancy
 Point Defects in Ceramics (ii)
• Frenkel Defect
-- a cation vacancy-cation interstitial pair.
• Shottky Defect
-- a paired set of cation and anion vacancies.

Shottky
Defect:

Frenkel
Defect

Chapter 4 - 7
 Equilibrium Concentration:
Point Defects
• Equilibrium concentration varies with temperature!

No. of defects Activation energy

Nv Q v 
No. of potential  exp  
defect sites N  kT 
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
Chapter 4 - 8
 Measuring Activation Energy

• We can get Qv from Nv Q v 

an experiment.
= exp 
 
N  kT 
• Measure this... • Replot it...

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

T
1/T
defect concentration
Chapter 4 - 9
 Imperfections in metal systems
When two ore more metals are mixed with each other then
two phenomenon may occur.

1. (i) Solid solution (no chemical reaction) – two metals

distributed randomly within one crystal structure.
(ii) Phase separation (no chemical reaction) – two metals
may separate like oil and water.

2. Intermetallic compounds (chemically & crys. struc. different

from both of the base metal)

Chapter 4 - 11
 Metal solid solution: Alloy
• Solid solution of B in A
(i.e., random dist. of point defects)

• Crystal structure is unchanged…

OR

Substitutional solid soln. Interstitial solid soln.

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

Chapter 4 - 12
 Metal Solubility
Conditions for solubility of metals

• 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  equal valency

These should be viewed as general guidelines rather than rigid rules. The best way to
determine solid solubility is from the phase diagram for a particular pair of elements. This
will be introduced in the coming chapters.

Chapter 4 - 13
Chapter 4 - 15
A- Stoichiometric intermetallic
compounds

Chapter 4 - 16
B- Nonstoichiometric intermetallic
compounds

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
 LINE DEFECTS
Dislocations
Dislocations are line imperfections in an otherwise perfect crystal. They typically
are introduced into a crystal during solidification of the material or when the
material is deformed permanently.
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

A dislocation can be described by two vectors:

The first is the line vector t, the vector pointing in the

direction of the dislocation line.

The second vector is the Burger’s vector, b: direction

and distance that dislocation moves each step
Chapter 4 - 19
 Imperfections in Solids
Edge Dislocation

Chapter 4 - 20
Edge, Screw, and Mixed Dislocations
Mixed

Edge

Screw

Chapter 4 - 21
 Dislocation Motion
• A plane that contains both the dislocation line and the Burgers
vector is known as a slip plane
• The dislocation can move through a process known as slip
• Note that slip plane and a slip direction comprises a «slip
system»

Chapter 4 - 22
 Dislocation Motion
• During slip, a dislocation moves from one set of surroundings to an
identical set of surroundings. The Peierls-Nabarro stress (below) is
required to move the dislocation from one equilibrium location to
another,

• Ταυ is the shear stress required to move the

dislocation,
• d is the interplanar spacing between adjacent slip
planes,
• b is the magnitude of the Burgers vector,
• c and k are constants for the material.

The dislocation moves in a slip system that requires

the least expenditure of energy. Several important
factors determine the most likely slip systems that
will be active: Chapter 4 - 23
 Dislocation Motion

&

d should be high
&
b should be low
Chapter 4 - 24
Chapter 4 - 25
Chapter 4 - 26
Chapter 4 - 27
 Lastly
Dislocations can be observed in electron micrographs

Chapter 4 - 28
Interfacial/Planar Defects in Solids
• Solidification- result of casting of molten material
– 2 steps
• Nuclei form (nucleation)
• Nuclei grow to form crystals – grain structure (growth)
• Start with a molten material – all liquid

nuclei crystals growing grain structure

liquid
Crystals grow until they meet each other
Chapter 4 - 29
Interfacial/Planar Defects in Solids

Chapter 4 - 30
 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 «low angle
means
– high diffusivity < 15
– high chemical reactivity degrees

Chapter 4 - 31
Interfacial/Planar Defects in Solids

Chapter 4 - 32
Chapter 4 - 33
Interfacial/Planar Defects in Solids

Chapter 4 - 34
Chapter 4 - 35
 Characterization of Defects
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.

Chapter 4 - 36
 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 - 37
 Optical Microscopy
Grain boundaries...
polished surface
• are imperfections,
surface groove
• are more susceptible grain boundary
to etching, (a)

• may be revealed as
dark lines,

• change in crystal
orientation across
Fe-Cr alloy
boundary.
(b)

Chapter 4 - 38
Chapter 4 - 39
 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 - 40