Imperfections in Solids

ISSUES TO ADDRESS...

• 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?

• Are defects undesirable?
How does an oxygen sensor work?
Fuel + O2 CO2 + H2O

O2 + 4e- 2O-2

https://www.carid.com/articles/oxygen-sensor-why-does-my-car-have-four.html
https://www.yokogawa.com/eu/library/resources/yokogawa-technical-reports/ox400-low-
concentration-zirconia-oxygen-analyzer-2/
• Are defects undesirable?

For the processing of silicon as a semiconducting

material, it is important to specify impurity
concentration in appropriate units.
• Development of the desirable mechanical
properties
for steel alloys relies on the presence of specific
impurities, some of which form solid solutions.
Thus, an understanding of the concept of a solid
solution is important.
• The mechanisms of hardening and
strengthening for steel alloys involve a crystalline
defect called a dislocation. In this chapter we
discuss the dislocation concept and the different
types
 Imperfection

Such an idealized solid generally does not exist

All solids contain large number of various

defects or imperfections

Perfectly ordered
crystalline structure

q Defects may exist:

1) In impure metals or alloys (Substitutional or interstitial foreign
atoms)
2) During solidification (e.g. Grain boundaries, dislocations,
vacancies)
3) During deformation (e.g. Dislocations)
 Defects can be introduced/removed during processing

Processing allows one to achieve the required properties without changes in

composition of the material, but just by manipulating the crystal defects.
 Defects in Crystals
A 2D representation of a perfect single crystal
with regular arrangement of atoms.

Real crystals are never perfect,

there are always defects !!!

A crystalline defect refers to a lattice

irregularity having one or more of its
dimensions on the order of an atomic
diameter.
 Types of Imperfections/Defects

• Vacancy atoms
• Interstitial atoms Point defects
• Substitutional atoms

• Dislocations Line defects

• Grain Boundaries Interfacial/Surface/Area

defects
• Porosity
• Inclusions Bulk/Volume defects
• Cracks
 Types of Defects
Defects may be classified into four categories depending on their dimension:

0D, Point Defects: atoms missing or in irregular places in the lattice.

(lattice vacancies, substitutional and interstitial impurities, self-interstitials)

1D, Linear Defects: groups of atoms in irregular positions.

(e.g. screw and edge dislocations)

2D, Planar Defects: the interfaces between homogeneous regions

of the material.
(e.g. grain boundaries, stacking faults, external surfaces)

3D, Volume Defects: extended defects.

(pores, cracks)
 Point Defects in Metals
• Vacancy & Interstitial

2D representations of a vacancy and a self-interstitial

 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
In metals, a self-interstitial introduces
distortion relatively large distortions in the
surrounding lattice because the atom is
of planes substantially larger than the interstitial
position in which it is situated.
 Equilibrium Vacancy Concentration
• Equilibrium vacancy concentration varies with temperature!

Each lattice site is

a potential
vacancy site !

Equilibrium No. of vacancies Energy Required to form vacancy

NV -Q v
Total No. of = exp
N kBT
atomic sites
NA × ρ Temperature
N= Boltzmann's constant
A (1.38 x 10-23 J / atomŸK)
(8.62 x 10-5 eV / atomŸK)
 Estimating Vacancy Concentration
Example: Calculate the equilibrium number of vacancies (NV)
per cubic meter (1 m3) for copper at 1000 oC (1273 K).
Given: ρ = 8.4 g/cm3 ACu = 63.5 g/mol
QV = 0.9 eV/atom NA = 6.022 x 1023 atoms/mol

N A × ρ (6.022 ×10 23 atoms / mol)(8.4g / cm 3 )(10 6 cm 3 / m 3 )

For 1 m3 è N= = = 8 ×10 28 atoms / m 3
ACu (63.5g / mol)

-Q v ⎡ −(0.9eV / atom) ⎤
NV = N exp 28 3
= (8 ×10 atoms / m )exp ⎢ ⎥
⎣ (8.62 ×10 −5 eV / K )(1273K ) ⎦
kBT
= 2.2 ×10 25 vacancies / m 3
 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)
For metallic materials
that have relatively high
atomic packing factors,
OR these interstitial
positions are relatively
small. Consequently, the
atomic diameter of an
interstitial impurity
Substitutional alloy Interstitial alloy must be substantially
(e.g., Cu in Ni) (e.g., C in Fe) smaller than that of the
host atoms.
• Solid solution of B in A plus particles of a new Concentration of
phase (usually for a larger amount of B) inter- stitial
impurity atoms is
Second phase particle low!!!
--different composition
--often different structure.
Conditions for substitutional solid solution:

Ø W. Hume – Rothery Rules

1. Δr (atomic radius) < 15%

2. Similar electronegativities

3. Same crystal structure

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.
WHY?
 Some important features for
substitutional solid solution
1) Atomic size difference should be less than 15%. Otherwise the solute
atoms will create substantial lattice distortions and a new phase will
form.

2) Crystal structure should be the same.

3) Electronegativities should be similar to prevent the ionic bonding.

4) Valances:Other factors being equal, a metal has a higher tendency to

dissolve another metal of higher valency…

EXAMPLE: Cu-Ni solid solution. The type is substitutional. WHY?

Because:
a) Radii for Cu and Ni are 0.128 and 0.125 nm respectively.
b) They both have FCC structure.
c) Their electronegativities are nearly (1.9 and 1.8 for Cu and Ni, respectively.
d) The most common valence is +1 for Cu and +2 for Ni.
Summary of point defects
 Solid Solution Strengthening
Ø The presence of solute atoms produces lattice strain, either
tensile or compressive, depending on the relative size of the
solute atom.
Ø Solute atom generates local shear that opposes dislocation
motion.

Smaller substitutional atom Bigger substitutional atom

creates tensile lattice strain creates compressive lattice
to the host atom. strain to the host atom.

Callister, Materials Science and Engineering: An Introduction, 7th ed., John Wiley&Sons, Inc, 2007.
 Line Defects: Dislocations

• produce permanent (plastic) deformation.

• cause slip between crystal plane when they move,

Schematic of a Zinc (HCP):

• after tensile elongation
• before deformation

slip steps
 Dislocations
Ø Dislocations (Linear defects around which atoms are
“dislocated” from their equilibrium lattice positions).

Edge dislocation

An extra portion of a plane of atoms, or half-

plane, the edge of which terminates within the
crystal. This is termed an edge dislocation; it is
a linear defect that centers on the line that is
defined along the end of the extra half-plane of
atoms.
An analogy
 Dislocations
Ø Dislocations (Linear defects around which atoms are
“dislocated” from their equilibrium lattice positions).

Another type of dislocation, called a screw

dislocation, may be thought of as being formed
by a shear stress that is applied to produce the
distortion shown in the figure top: the upper
front region of the crystal is shifted one atomic
distance to the right relative to the bottom
portion.

Dislocation line ?
 Dislocations & Crystal Structure
Extra planes of dislocations do not form and move randomly
rather
they prefer to move
on …………… planes & in ……………. directions
https://www.youtube.com/watch?v=RyxBK_GBC3w
https://www.youtube.com/watch?v=RyxBK_GBC3w
Slip Systems for FCC, BCC and HCP
FCC and BCC have at least 12 active slip systems

Extensive plastic deformation

Ductile
 Slip Systems for FCC, BCC and HCP
FCC and BCC have at least 12 active slip systems

Extensive plastic deformation

Ductile

Guan, Y. Et al. Crystal plasticity modelling and HR-DIC measurement of slip activation and strain localization in single and oligo-crystal Ni
alloys under fatigue Int. J. Plasticity, 2017.
2-Dimensional (area) defects
Interfacial (area) defects are boundaries that have two dimensions and separate regions of
different crystal structures or crystallographic orientations.

External Area Defects Internal Area Defects

q External Surface q Grain Boundaries
q Twin Boundaries
q Stacking Fault
q Phase boundaries

1)External surface: is the boundary of material at which the

structure terminates.
e.g. Solid-gas, solid-liquid
q Surface atoms are not bonded (surface have higher energy state than the atoms at
the inner parts of the structure). This energy is called surface energy (J/m2 or
erg/cm2). To minimize this energy, materials minimizes the surface area.
 Area Defects: Grain Boundaries
Grain boundaries:
• are boundaries between crystals.
• are produced during phase transformations.
• have a change in crystal orientation across them.
• impede dislocation motion.
~ 8cm

Metal Ingot
 Energies of Boundaries
q Energy is related to number of unbonded atoms through the interface

External Surface
Increasing energy
High Angle Grain Boundary

Low Angle grain Boundary

q Chemical reactivity increases as the energy of the boundary increases

q Grain boundaries are more chemically reactive than the grains themselves
q Impurity atoms prefernentially segregate along grain boundaries

LOWER
More grain boundary means more Larger grains INTERFACIAL
interfacial energy have
ENERGY
than smaller grains
 Optical Microscopy
Grain boundaries,
• are imperfections,
• are more susceptible to etching,
• may be revealed as dark lines,
• change direction in a polycrystal.
 Grain Boundary Strengthening

Smaller grain size: Hall-Petch Equation:

more barriers to slip, k
higher strength. σ y =σi +
D
 Planar Defects:
Twin Boundaries, Stacking Faults
 Volume Defects

Voids Inclusions

Precipitates Dispersed particles

 Interaction of Dislocations with Precipitates

Callister, Materials Science and Engineering: An Introduction, 7th ed., John Wiley&Sons, Inc, 2007.
https://www.youtube.com/watch?v=n7LXYyohmgg
 Summary

• Point, Line, Area and Volume defects arise 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.)