Chapter 6

Imperfections in Solids

Chapter 3 - 94
 Are crystalline materials always
perfectly ordered (THROUGHOUT) on
an atomic scale??
• This is what we’ve been assuming thus
far..
• Such an IDEALIZED solid does NOT
exist
• All contain large numbers/volume
fractions of different type defects
• Also known as “Imperfections”

Chapter 3 - 95
 Is this bad??

• Not always…
• Many properties are profoundly
sensitive to deviation from crystalline
perfection
• Often, specific characteristics are
DELIBERATELY fashioned by
introducing particular amounts/numbers
of particular defects

Chapter 3 - 96
 Example: Alloying

• By adding impurity atoms to a matrix of

homogenous substrate in terms of
identity (e.g. pure metal)…
• We alter mechanical properties
significantly
• e.g. Brass (70% Cu / 30% Zn)+ is much
HARDER and STRONGER than PURE
Cu

Chapter 3 - 97
 What is a “Crystalline Defect”??

It refers to a lattice IRREGULARITY

having one or more of it’s dimensions on
the order of an atomic diameter.

Chapter 3 - 98
 Classification
Based on “geometry” & “dimensionality” of
defects CRYSTALLINE defects are either:
– Point defects: those associated with 1 or 2
atomic positions [e.g. vacancies & interstitials*]
– Linear (1D) [e.g. dislocations]
– Interfacial/ Planar (2D) [e.g. grain boundaries,
dislocation loops & materials edges]
– Volumetric (3D) [e.g. voids & 2nd phase
inclusions+)

Chapter 3 - 99
 Point Defects in Metals
• The simplest,
inevitable, consistently
present &
thermodynamically
favored type is a
vacancy
• Which is a vacant
lattice site, one
normally occupied but
from which an atom is
missing Chapter 3 - 100
 Vacancies (Cn’d)
• Present in crystalline
solids
• Not possible to create a
material free of vacancies
• Why is that so??

Chapter 3 - 101
 Why are vacancies necessarily
existent??
• 2nd law of thermodynamics
• Natural processes spontaneously
proceed towards increased disorder
(randomness) of their states or
decreasing the quality of their energy
• (low entropy) s ➔ (high entropy) S
• (high quality) Q ➔ (low quality) q
The less ordered state arrived at is
lesser energy state ➔ more
thermodynamically stable* Chapter 3 - 102
 Temperature Dependency

• The equilibrium No. of vacancies (Nv)

for a given quantity of material (usually
per m3) increases with temperature
• Hence, we borrow the Arrhenius
concept to adopt here

𝑄
− 𝑣
𝑁𝑣 = 𝑁𝑒 𝑘𝑇

Chapter 3 - 103
Where,
– N is the tot. No. of atomic sites (usually per
m3)
– Qv is energy for vacancy formation (J/gmol
or eV/atom)
– T is absolute temperature (K)
– k can either be the Boltzmann constant
(1.38 x 10-23 J/atom.K, 8.62 x 10-5
eV/atom.K) or the gas const. (8.314
J/gmol.K) –depending on Qv UNITS-

Chapter 3 - 104
• Nv increases exponentially with increase
in T
• Since, macro-scopic physical properties
are intimately governed by micro-scopic
defect structure
• Physical properties too vary
exponentially with T
• Nv/N (just bellow Tmelt) is ~ 10-4 (for
most metals)
• i.e. 1 lattice site out of 10,000 will be
empty Chapter 3 - 105
 Interstitials
• Is an atom from the crystal (self-
interstitial*) or a foreign atom that is
crowded into an interstitial site
• The latter is a term used to refer to a
small void space (often interatomic) that
under ordinary circumstances is not
occupied+.

Chapter 3 - 106
 Energy state ➔ Thermodynamic
Tendency
In metals, a self-interstitial introduces ➔
relatively large distortions in the
surrounding lattice ➔ causing contours
of concentric strain fields with the
interstitial as the locus➔ since, the newly
arriving interstitial atoms is
SUBSTANTIALLY larger than the
interstitial position in which it is situated
➔ large size MISFIT
Chapter 3 - 107
• Hence, the formation of such a defect is
NOT highly probable ➔ as it
represents a high energy state ➔ i.e.
Not thermodynamically favored &
unstable
• It exist in very small concentrations that
are SIGNIFICANTLY lower than for
vacancies.

Chapter 3 - 108
 Point Defects in Ceramics*
• As they contain ions of at least 2 kinds
(e.g. Na+ Cl- in table salt)
• Point defects of both (Na+ & Cl-) might
be present
• i.e. for Na+
– Vacancies
– Interstitials
• & for Cl-
– Vacancies
– Interstitials (less likely) ….. WHY?? Chapter 3 - 109
 Anion Interstitials
• Highly improbable in appreciable
concentrations
• An ANION is relatively large* to fit into a
small INTERSTITIAL position
• Substantial strains+ on surrounding ions
must be introduced

Chapter 3 - 110
Point Defects in Ceramics*

Chapter 3 - 111
 Defect Structure
• The NEED for such a term has risen due
to the charge-biased nature of ions in
ceramics
• Hence, to maintain “Electroneutrality”,
that is to maintain equal numbers of
(+ve) & (-ve) charges of ions,
• The expression “Defect Structure” is
utilized to justify the presence/absence
of electroneutrality by point defect type
combinations and their concentrations
present Chapter 3 - 112
As Ceramic Electroneutrality is often
Maintained
• Point defects in ceramics do NOT occur
ALONE but in PAIRS
• Examples on such PAIRS:
– Frenkel defect (cation-vacancy + cation
interstitial)
– Schottky defect (cation-vacancy + anion-
vacancy)

Chapter 3 - 113
 Frenkel Pairs/Defects

• Due to, for instance, a cation leaving an

equilibrium lattice position and residing
in an interstitial site*
• No net charge is generated (or no
overall charge change) is incurred as
the cation MAINTAINS the same (+ve)
charge whilst assuming an
INTERSTITIAL position

Chapter 3 - 114
 Schottky Defects*
• Might be taken as being created by
removing 1 cation and 1 anion from a
crystal interior and placing them both on
an external surface
• As MAGNITUDE of (-ve) charge on cation
= MAGNITUDE of (+ve) charge on anion
• And, since for every CATION VACANCY
their exists an ANION VACANCY
• THEN, charge NEUTRALITY of crystal is
maintained Chapter 3 - 115
 Related Issues…
• RATIO of cations/anions altered by
neither FRENKEL nor SCHOTTKY defects
• If this is the case (provided that other
defects are absent) the materials is said to
be “Stoichiometric”
• The latter is “a state for IONIC
COMPOUNDS wherein there is the
EXACT RATIO of cations/anions as
predicted by the CHEMICAL FORMULA”
Chapter 3 - 116
 For example…
NaCl is STOICHIOMETRIC if…

The ratio of Na+ ions to Cl- ions…

Is EXACTLY ➔ 1 : 1

A ceramic compound is
NONSTOICHIOMETRIC given any
deviation from such an EXACT ratio
Chapter 3 - 117
Frenkel & Schottky Pairs

Chapter 3 - 118
 Common Phenomenon: Non-
Stoichiometry with Electroneutrality
• When 2 valence (or ionic) states exist
for a single particular ion type in the
a ceramic compound* ➔ such a
ceramic is dubbed “Non-
Stoichiometric”
• e.g. in (wüstite, FeO) ➔ Iron might be
present in both states:
– Fe2+
– Fe3+
Chapter 3 - 119
 Common Phenomenon: Non-
Stoichiometry with Electroneutrality

• The No. of each type-ion* depends on:

– Temperature
– Ambient Oxygen Pressure (i.e.
abundancy of O2 to react with Fe)

Chapter 3 - 120
Given the divalent (-ve) charge-bias on
the anion (O2-)…
• The presence of other than an
EQUIVALENTLY divalent (+ve) charge-
bias on the Cation (Fe2+) is
PROBLEMATIC with respect to
“Electroneutrality”…
• i.e. existence of (Fe3+)* disrupts the
LATTER+ by introducing an excess of
(+1) charge
• This must be OFFSET by some type of
defect Chapter 3 - 121
Remedies to lack of Electroneutrality….

• The formation of ONE (Fe2+)

VACANCY* for every TWO (Fe3+) ions
that are FORMED.
• Despite the fact that the crystal is
RENDERED “Non-Stoichiometric”…
“As an O2- ion is left behind uncoupled with
an Fe2+ ion that was omitted”
• It is NONTHELESS “Electroneutral”.
Chapter 3 - 122
Remedies to lack of Electroneutrality….

Chapter 3 - 123
Aforementioned Phenomenon is Fairly
Common in Iron Oxide

In fact, its chemical formula is often

written as
𝐹𝑒1−𝑥 𝑂
“Where x is some small & variable fraction
that is substantially << UNITY”
This indicates a condition of “Non-
Stoichiometry” with a deficiency in IRON*

Chapter 3 - 124
As is the approach to Nv for METALS…

The equilibrium No. of Frenkel &

Schottky PAIRS formed within a
CERAMIC increase with & depend on
TEMPERATURE

Chapter 3 - 125
 For Frenkel PAIRS
• No. of equilibrium cation-vacancy/cation-
interstitial defect PAIRS (𝑁𝒇𝒓 ) formed = f (T) is
given by:
𝑄𝒇𝒓
−
𝑁𝒇𝒓 = 𝑁𝑒 𝟐𝑘𝑇
• Where,
– 𝑸𝒇𝒓 : is the energy of formation for each Frenkel
defect PAIR
– N : is the total No. of lattice sites
– The factor 2 is incorporated to account for an
effective couple of defects (a missing cation & an
interstitial cation) that constitute the Frenkel
ChapterPAIR.
3 - 126
 For Schottky PAIRS
• No. of equilibrium cation-vacancy/anion-
vacancy defect PAIRS (𝑁𝒔 ) formed = f (T) is
given by:
𝑄𝒔
−
𝑁𝒔 = 𝑁𝑒 𝟐𝑘𝑇
• Where,
– 𝑸𝒔 : is the energy of formation for each Schottky
defect PAIR
– N : is the total No. of lattice sites
– The factor 2 is incorporated to account for an
effective couple of defects (a missing cation & a
missing anion) that constitute the Schottky PAIR.
Chapter 3 - 127
 Impurities in Solids
1st: From Metals Perspective
• NO such thing as PURE metals (i.e.
comprised of only ONE TYPE atoms)
• Impurity/foreign atoms always co-present
• Latter often present as “Crystalline Point
Defects”
• In fact, EVEN with relatively sophisticated
techniques ➔ difficult to refine metals to >
99.9999 % purity (i.e. in order of 1022 to 1023
foreign atoms residing in 1 m3 materials)
Chapter 3 - 128
 Impurities in Solids
1st: From Metals Perspective

• Most familiar metals are rather

ALLOYS.
• In fact, impurities are intentionally
added to improve desired
characteristics, e.g.:
– Mechanical Strength
– Corrosion Resistance

Chapter 3 - 129
 Impurities in Solids
1st: From Metals Perspective
• For instance, (Sterling Silver)
(92.5% Ag / 7.5% Cu)
• At normal Ambient Environments
– Pure Ag
• Highly Corrosion Resistant
• But rather SOFT
• Alloying with Cu
– significantly enhances “mechanical strength”
– Without depreciating “corrosion resistance”
too much
Chapter 3 - 130
The addition of an IMPURITY atom to a
metals:

• Forms a “Solid Solution”*

• And/ or generates new “Intermetallic 2nd
Phases”+, this depends on:
– Kinds of impurities$
– Their concentrations
– Temperature of alloy

Chapter 3 - 131
 Getting terminology out of the way:
• Solvent: is an element or compound present
in the greatest amount (solvent atoms also
known as “host atoms”)
• Solute: is an element or compound present
in minor concentration(solute atoms also
known as “foreign atoms”)
• Solid Solution: forms when adding SOLUTE
atoms to HOST material does NOT result in
the formation of a NEW STRUCTURE (i.e.
the overall continuity of the crystal structure
for the matrix is maintained throughout)*
Chapter 3 - 132
• A solid solution is also
COMPOSITIONALLY “homogeneous”
➔ impurity atoms uniformly dispersed
throughout the solid

Chapter 3 - 133
 Impurity Point Defects in SOLID
SOLUTIONS

• Substitutional: where SOLUTE atoms

replace or substitute for HOST atoms

• Interstitials: where SOLUTE atoms fill

voids/interstices amongst HOST atoms

Chapter 3 - 134
 Substitutional or Interstitial??
Solid Solution (Single Phase) or
Multi-phase*??
Several features of the SOLUTE and
SOLVENT atoms determine the degree to
which the FORMER dissolves in the
LATTER+, i.e
– Whether substitutional OR interstitial
solid solutions are favored
– Whether solid solution (single phase)
OR multi-phases* are maintained

Chapter 3 - 135
Underpinning the aforementioned are:
The Hume-Rothery rules

• Atomic Size Factor

• Crystal Structure

• Electronegativity Factor

• Valences

Chapter 3 - 136
 Solvent “host”
atoms

Otherwise, they would

form a COMPOUND
Solute “foreign” rather than remain in
atoms SOLUTION, which is what
is know as an
“INTERMETALLIC”

Forms with the “host” atoms a

Forms with the “host” atoms a SINGLE
SINGLE PHASE, as long as:
PHASE, as long as:
1. Radii differences is
1. Radii differences is less than ± 15%*
significantly large
2. Crystal structure common (i.e. both
2. Conc. ≤ 10%
bcc, or both fcc, etc.)
3. Close in electronegitivity+

Otherwise, Impurity/Host Size Misfit ➔ Lattice Strain ➔ Crystal Structure Distortion ➔

Chapter 3 - 137
Structure Homogeneity Interrupted ➔ New Phase Appears ➔ Two/Several Phase Mixture
Example on SUBSTITUTIONAL Solid
Solution
• Cu/Ni Alloys
• Constituting elements are
COMPLETELY soluble in one another
at all proportions
• e.g. common Cu/Ni alloys are:
– 70% Cu-30% Ni
– 90% Cu-10% Ni

Chapter 3 - 138
 Validating Degree of Solubility
according to Hume-Rothery rules

Microconstituent
Cu Ni
Atomic Radius
0.128 0.125
(nm)
Crystal Structure FCC FCC
Factor
Electronegativity 1.9 1.8
+1 (most
Valence +2
common)*
Chapter 3 - 139
 INTERSTITIAL Solid Solutions

Possible interstitial sites to fill:

Are “tetrahedral” & “octahedral” for both

FCC and BCC*
Chapter 3 - 140
 INTERSTITIAL Sites for FCC

2 possible positions for

“octahedral sites” with
representative POINT
coordinates of*:

𝟏 𝟏𝟏𝟏
𝟎 𝟏 𝒉𝒂𝒍𝒇 𝒘𝒂𝒚 𝒂𝒍𝒐𝒏𝒈 𝒆𝒅𝒈𝒆 & 𝑩𝒐𝒅𝒚 𝒄𝒆𝒏𝒕𝒓𝒆
𝟐 𝟐𝟐𝟐
A single possible “tetrahedral site” type resides
at a representative POINT coordinate of:

𝟏𝟑𝟏
(𝒄𝒐𝒏𝒇𝒊𝒏𝒆𝒅 𝒃𝒚 𝒂 𝒄𝒐𝒓𝒏𝒆𝒓 & 𝟑 𝒇𝒂𝒄𝒆 𝒂𝒕𝒐𝒎𝒔)
Chapter 3 - 141
𝟒𝟒𝟒
 INTERSTITIAL Sites for BCC
One possible position
for each of
“octahedrals” and
“tetrahedrals” are found
for BCC with
representative POINT
coordinates of:

𝟏 ∗
𝟏𝟎 𝐡𝐚𝐥𝐟 𝐰𝐚𝐲 𝐚𝐥𝐨𝐧𝐠 𝐚𝐝𝐠𝐞
𝟐
𝟏 𝟏 𝒓𝒅
𝟏 (𝟑 𝒄𝒐𝒓𝒏𝒆𝒓 𝒐𝒇 𝒃𝒂𝒔𝒆 𝒕𝒓𝒊𝒂𝒏𝒈𝒍𝒆
𝟐𝟒
𝒊𝒔 𝒂 𝒃𝒐𝒅𝒚 𝒄𝒆𝒏𝒕𝒆𝒓 𝒇𝒓𝒐𝒎 𝒂 𝒏𝒆𝒊𝒈𝒉𝒃𝒐𝒓𝒊𝒏𝒈 𝒄𝒆𝒍𝒍)
Chapter 3 - 142
 Related Issues…
• Due to the nature of “metallic bonding”
• Metallic materials exhibit relatively high
“atomic packing factors (APF)”
• i.e. their interstitial positions are
relatively SMALL
• Hence, atomic Diam. of interstitial
SOLUTE must be SUBSTANTIALLY
SMALLER than that of HOST.
• Max. allowable concentration of
interstitial impurity atoms < 10%.
Chapter 3 - 143
 Related Issues…
• Even very SMALL impurity atoms are
ORDINARILY LARGER than interstitial
SITES ➔ hence, they introduce some
lattice strain on adjacent HOST atoms.
• e.g. on “INTERSTITIAL solid solution”
Fe-C (2 wt% C, max.)
Atomic radius of Fe (0.124 nm)
significantly larger than that of C (0.071
nm)
Chapter 3 - 144
 Composition/Concentration*
• It is customary to express the
composition of an alloy in terms of
constituent elements.
• Most common ways to do this are:
– Weight/Mass percent (wt%)
Weight of particular element relative to total
weight of alloy
– Atom percent (at%)
No. of moles of a particular element relative
to total No. of moles of elements constituting
alloy+. Chapter 3 - 145
 Formula for weight/mass%

• For a binary-system alloy, comprising

two hypothetical elements denoted by 1
& 2:
• C1: the concentration of element 1 in
(wt%) is given by:
𝒎𝟏
𝑪𝟏 = × 𝟏𝟎𝟎
𝒎𝟏 + 𝒎 𝟐
Where, m1 & m2 represent the weight/mass of
elements 1 & 2, respectively.
Chapter 3 - 146
 Formula for weight/mass%

For “n” element constituting an alloy,

𝒎𝟏
𝑪𝟏 = × 𝟏𝟎𝟎
𝒎𝟏 + 𝒎𝟐 + 𝒎𝟑 + ⋯ + 𝒎𝒏
Where, mn represents the weight/mass of the
nth alloy constituent.

Chapter 3 - 147
 Calculating (at%)
The No. of MOLES comprising some
specified MASS of a hypothetical element
1, denoted by “nm1”
𝒎′𝟏
𝒏𝒎𝟏 =
𝑨𝟏
Here,
– 𝒎′𝟏 : denote the mass in (gm) for element 1
– A: denote the atomic weight of element 1

Chapter 3 - 148
 Calculating (at%)

Concentration in (at%) of element 1 in an

alloy containing element 1 & 2 atoms “𝑪′𝟏 ”:

𝒏𝒎𝟏
𝑪′𝟏 = × 𝟏𝟎𝟎
𝒏𝒎𝟏 + 𝒏𝒎𝟐

For “n” element constituting an alloy,

′ 𝒏𝒎𝟏
𝑪𝟏 = × 𝟏𝟎𝟎
𝒏𝒎𝟏 + 𝒏𝒎𝟐 + 𝒏𝒎𝟑 + ⋯ + 𝒏𝒎𝒏
Chapter 3 - 149
 Conversion between Different
Composition Schemes
• at% vs. wt%, for hypthetical elements 1
& 2:
′ 𝑪𝟏 𝑨𝟐
𝑪𝟏 = × 𝟏𝟎𝟎
𝑪𝟏 𝑨𝟐 + 𝑪𝟐 𝑨𝟏

′ 𝑪𝟐 𝑨𝟏
𝑪𝟐 = × 𝟏𝟎𝟎
𝑪𝟏 𝑨𝟐 + 𝑪𝟐 𝑨𝟏

Chapter 3 - 150
Conversion between Different
Composition Schemes

𝑪′𝟏 𝑨𝟏
𝑪𝟏 = ′ ′ × 𝟏𝟎𝟎
𝑪𝟏 𝑨𝟏 + 𝑪𝟐 𝑨𝟐

𝑪′𝟐 𝑨𝟐
𝑪𝟐 = ′ ′ × 𝟏𝟎𝟎
𝑪𝟏 𝑨𝟏 + 𝑪𝟐 𝑨𝟐

Chapter 3 - 151
Conversion from wt% (𝑪) into mass/vol
′′
(𝑪 )
• Applicable to Diffusion calculations to
convert from (wt% into kg/m3)
′′ 𝑪𝟏
𝑪𝟏 = × 𝟏𝟎𝟎𝟎
𝑪𝟏 𝑪𝟐
+
ρ𝟏 ρ𝟐
′′ 𝑪𝟐
𝑪𝟐 = × 𝟏𝟎𝟎𝟎
𝑪𝟏 𝑪𝟐
+
ρ𝟏 ρ𝟐
For ρ (g/cm3) these expressions yield 𝑪′′ (kg/m3)
Chapter 3 - 152
Alloy density as f (wt% or at%)

𝟏𝟎𝟎
ρ𝒂𝒗𝒈 =
𝑪𝟏 𝑪𝟐
+
ρ𝟏 ρ𝟐

𝑪′𝟏 𝑨𝟏 + 𝑪′𝟐 𝑨𝟐
ρ𝒂𝒗𝒈 =
𝑪′𝟏 𝑨𝟏 𝑪′𝟐 𝑨𝟐
+
ρ𝟏 ρ𝟐

Chapter 3 - 153
Alloy Atomic Weight as f (wt% or at%)

𝟏𝟎𝟎
𝑨𝒂𝒗𝒈 =
𝑪𝟏 𝑪𝟐
+
𝑨𝟏 𝑨𝟐

𝑪′𝟏 𝑨𝟏 + 𝑪′𝟐 𝑨𝟐
𝑨𝒂𝒗𝒈 =
𝟏𝟎𝟎

Chapter 3 - 154
Linear (1D) Defects

Dislocations

Chapter 3 - 155
 Dislocations

• Are linear (1D) defects ➔ immediately

around which atomic misalignment* is
maximum ➔ gradually fades with
distance
• Dislocations might be classified into:
– Edge dislocations
– Screw dislocations

Chapter 3 - 156
 Edge Dislocations
• Results from the wedging of an extra
half-plane of atoms within an ordered
lattice
• The edge of which terminates within
the crystal*
• This dislocation in the edge-type
centers on the line connecting the
atoms at the base of the extra half-
plane, formally known as the
“dislocation line” Chapter 3 - 157
 Edge Dislocations (Cnt’d)

For an EDGE dislocation the “dislocation

line” is perpendicular to plane of page.

Chapter 3 - 158
• Also can be depicted from the last
schematic, is the plane of easy slide/slip
for the dislocation (indicated in dark
blue).
• The “slip direction” denoted by “Burger’s
vector”
• The latter two are both perpendicular to
the “dislocation line”
• The type stress required to move
dislocations across (SHEAR stress)
Chapter 3 - 159
• Notice: the EDGE/STEP immerging eventually
at the external surface reflecting the underlying
reason behind the term “EDGE dislocation”
• In the region in immediate vicinity to dislocation
line exists evident localized lattice distortion
– Above dislocation line*: atoms are squeezed
together (crowded by extra half-plane)
– Below dislocation line: atoms are (ON the
VERGE of being) pulled apart
• Hence, the slight curvature for the vertical
planes of atoms as they bend around extra
half-plane wedge.
Chapter 3 - 160
Stress Concentration at Dislocations

Adapted from Fig. 7.4,

Callister 7e.

Chapter 3 - 161
• Magnitude of distortion DECREASES
with distance AWAY from “dislocation
line”
• At positions FAR REMOVED, the
crystal lattice is virtually perfect.
• An EDGE dislocation is conventionally
designated by “┴”
• However, if the extra half-plane of atom
is WEDGED from the bottom portion of
a crystal, it is represented by “┬”.
Chapter 3 - 162
 Screw Dislocations
• Formed due to a shear stress applied
to distort the material in an overall
helical/spiral path/ramp*.
• Notice: the upper front region of the
crystal is shifted “one atomic distance”
to the right relative to the bottom
portion.
• The overall deformation EVENTUALLY
appears on the external surface as a
step (with magnitude equal to “one
inter-atomic distance”) Chapter 3 - 163
Screw Dislocations (Cnt’d)

Chapter 3 - 164
Screw Dislocations (Cnt’d)

Chapter 3 - 165
 Screw Dislocations (Cnt’d)
• This type is also LINEAR and along a
“dislocation line” AB ➔ however, this
time it is parallel to slip direction.
• Often designated by “ ”

Chapter 3 - 166
 Mixed Dislocations
• In crystalline materials dislocations are
often neither PURE edge nor PURE
screw
• In fact, they exhibit components with
variable degrees of both depending on
distance from either*

Chapter 3 - 167
Mixed Dislocations

Chapter 3 - 168
Mixed Dislocations

Notice this particular

vertical plane is
wedged in (as it
disrupts the overall
order of the crystal)

Notice the curvature INWARDS of

the vertical planes on either side
of the extra half plane as they
continue towards the bottom half
below the slip plane with
crowding closer as they clear
the ½ plane (solid circles)
Chapter 3 - 169
 Stress fields
• Unlike “edge” dislocations their screw counter
parts are “PURE SHEAR” dislocations.
• Hence, NO “compression or tension” fields
might be found in near vicinity to the latter's
dislocation lines.
• This might be evident from the
shearing/tearing that renders the unit cells in
the distorted proximity with sides at angles
deviating from 90°
• The extent of shear would reduce radially
with distance away from the dislocation line*
Chapter 3 - 170
Eventually same Final Outcome*

Edge dislocation

Adapted from Fig. 7.2, Callister

7e.

Screw dislocation

Chapter 3 - 171
What defects can you find here?

Chapter 3 - 172
 Burgers Vector “b”

• Is an expression of the “magnitude” &

“direction” of lattice distortion

associated with a dislocation

• Now if you were to draw a CIRCUIT in a

“perfect” crystal lattice…

Chapter 3 - 173
 Circuit is
complete for
a “perfect
crystal”

Chapter 3 - 174
Attempting to do the same thing

around a “dislocation”

Chapter 3 - 175
 Approach
1. Locate the extra half-plane of atoms
(the edge dislocation/wedge)
2. Identify a sense vector$ (to facilitate the
definition of the sign of “b”)
3. The latter might be achieved by using
a “Right Hand Start to Finish
Convention” or RH/SF+ (Thumb
pointing into plane of page)
4. Choose a start point
5. Draw lines 5 atoms a side* that are 90°
to each other looping to form a circuit.
Chapter 3 - 176
1 unit cell length Sense
vector
denoted by “𝒃”
S
F

Start point,
arbitrarily chosen Chapter 3 - 177
 Screw Dislocation
• Instead of introducing an extra half-
plane of atoms, here the lattice is
sheared ➔ i.e. part of the lattice is
offset by a bit from the remaining part
• It gets the name “screw” due to the fact
that if we were to start from a point and
proceed looping around the dislocation
we would end up with a circuit that
terminates at a point exactly below the
preceding point each time tracing a
helical path of a screw Chapter 3 - 178
Chapter 3 - 179
 RH/SF
Convention

Sense vector

Draw circuit around

S
dislocation that is 5
atoms aside
Chapter 3 - 180
 Edge ?? Screw ?? Or Mixed ??

• The nature of a given dislocation is

determined by the “relative orientation”
between dislocation line and Burger’s
vector*
• Although, dislocation changes
direction+ & nature within a crystal (i.e.
screw ➔ mixed ➔ edge) the Burger’s
vector remains the same at all points
along its line
Chapter 3 - 181
Taking the schematic presented last as
a general theme…

• MORE SPECIFICALLY, for metallic

materials, the Burger’s vector for a
dislocation (or direction of slip) adopts
the easy path for slip that is the closely
packed crystallographic direction (on a
closely packed plane)*.
• Burger’s vectors also exhibit
magnitudes in interatomic spacing.
Chapter 3 - 182
 From Perspective of Mechanics
• Permanent (Plastic) deformation of
most crystalline materials (metals and
ceramics) and to some extent
amorphous polymers occurs through
flow of dislocations.
• “𝒃” is an element of theory developed
namely to explain such a type of
deformation.

Chapter 3 - 183
 Occurrence

Virtually all crystalline materials contain

some dislocations that were introduced in
association with:
– Solidification

– Plastic Deformation

– Thermal stresses resulting from rapid

cooling
Chapter 3 - 184
High
magnification
TEM image
showing
tangled
dislocations
lines (dark
lines)

Chapter 3 - 185
 Interfacial/Planar (2D) Defects

• Boundaries that have 2 dimensions

• Constitute areas/regions/interfaces of
mismatch
• Separate regions of materials that
exhibit different:
– Crystal Structures
and/or
– Crystallographic Orientation

Chapter 3 - 186
 Interfacial (2D) Defects
Such imperfections include:
– External Surfaces:
mismatch/discontinuity/interruption of periodic
structure
– Grain Boundaries: atomic mismatch or lack of
coincidence due contrast in grain orientation
– Phase boundaries: discontinuity/ interruption of
structure between matrix/ foreign intermetallic
inclusion* (very likely misorientation implicit)
– Twin boundaries: contrast in orientation, though
mirror couples are formed
– Stacking Faults: interruption in order/structural
continuity Chapter 3 - 187
 Underpinning Thermodynamics
• What is common between all the
aforementioned types is that they exist
at high energy states (i.e. they are
thermodynamically unstable)*.
• They seek thermodynamic stability by
acting as sinks for other types of defects
(i.e. point defects such as vacancies &
interstitials and line defects such as
other line/loop dislocations migrate
towards such sinks and terminates
there) Chapter 3 - 188
 External Surfaces
• Along such surfaces “Crystal Structure”
terminates (essentially, “Interrupted”)
• Despite “Metallic Bonding” nature
• Surface atoms are NOT bonded to
MAXIMUM number of immediate
neighbors
• i.e. Surface atoms are at “High Energy”
state relative to counterparts at
“INTERIOR positions”
Chapter 3 - 189
 External Surfaces
• Unsatisfied bonds amongst those of
“Surface atoms”+ ➔ give rise to
“Surface Energy” ➔ Energy / Unit Area
(J/m2 or erg/cm2*)
• To reduce this energy ➔ materials tend
to MINIMIZE (if at all possible) ➔ total
SURFACE AREA (which contain the
NET UNI-directed cohesive forces on
atoms = i.e. high energy state atoms)

Chapter 3 - 190
Analogy with water “Surface Tension”

Chapter 3 - 191
Analogy with water “Surface Tension”

Chapter 3 - 192
Analogy with water “Surface Tension”

Chapter 3 - 193
 Back to METALS
• However, this high energy state at
METAL surface CANNOT be relieved
➔ by assuming a geometry with
minimized surface area ➔ due to
mechanical REGIDITY
• As such, “External Surfaces” in
METALS remain HIGH ENERGY &
thermodynamically unstable positions*

Chapter 3 - 194
 Grain Boundaries

Boundaries separating two single

crystals/grains having different
crystallographic orientations in a
polycrystalline material.

Examining the next schematic from an

atomic perspective
Chapter 3 - 195
Chapter 3 - 196
 Within the boundary region….

• Which is probably merely several atom

distances wide
• There exists varying degrees of atomic
MISMATCH or lack of coincidence*
• That is, in the transition from “crystalline
orientation” of a given grain to that of an
adjacent counterpart

Chapter 3 - 197
 Various Degrees of Crystallographic
Misalignment between Adjacent Grains
are Possible
Boundaries might be dubbed “small- (or
low-) angle” or “High-angle” depending on
whether slight or severe orientation
degrees of mismatch is encountered.
However, such boundaries might also be
described in terms of

“Dislocation Arrays*”
Chapter 3 - 198
Tilt Boundary
• One Simple Low-Angle
grain boundary is formed
when EDGE dislocations
are aligned as on right ➔
• Here, a “Tilt Boundary” is
described by an array of
“Edge Dislocations”
• The angle of
misorientation is “θ”
Chapter 3 - 199
 Twist Boundaries
• When the angle of
misorientation is
parallel* to the boundary
• A “Twist Boundary”
results
• This might be described
by an array of “Screw
Dislocations”

Chapter 3 - 200
Difference between Tilt & Twist

Chapter 3 - 201
To Approach Thermodynamic Stability
• We need to minimize the “Total Grain
Boundary Area”
• This might be realized through
“Recrystallization/Ageing/Solution
Annealing”
• In which “Grain Growth” is induced by
thermal means
• This lowers the “Total Interfacial
Energy” as fine-grained materials
evolve into coarser-grained versions of
themselves. Chapter 3 - 202
• In spite:
– This disordered arrangement of atoms
– Lack of regular bonding (that generates
unsatisfied misaligned atoms) along grain
boundaries
• A polycrystalline material is STILL very
strong
• Cohesive forces within and across the
boundary are present.
• (ρ) of a polycrystalline specimen is
virtually identical to that of single crystal
of the same material. Chapter 3 - 203
Modeling the High Energy Grain
Boundary Interfaces

Chapter 3 - 204
 Phase Boundaries
• These exist in multi-phase materials
where, essentially, the Hume-Rothery
conditions are not satisfied
• A different phase exists on each side of the
boundary
• This also implies a contrast in crystalline
systems/structures/orientation on either
side of the boundary
• Physical and/or chemical* characteristics
might be unique on either side
Chapter 3 - 205
• Needless to say, the boundary itself (let
alone the surrounded phases) is
thermodynamically prone to
dissociation*.
• This is due to its high energy (unstable
state) associated with the highly
strained crystalline misfit/misorientation

Chapter 3 - 206
Preferential and graduation LOCALIZED
dissociation at phase boundaries

Chapter 3 - 207
• Given the fact that the misfit of 2nd
phase structures generates surrounding
strain fields
• It aids in manipulating mechanical
strength/hardness by obstructing flow of
dislocations

Chapter 3 - 208
Contour Strain Fields

Chapter 3 - 209
Precipitation Strengthening

Chapter 3 - 210
 Twin Boundaries

• A special type of grain boundary

• Across which exists a mirror lattice
SYMMETRY
• i.e. atoms on one side of the boundary
are located in mirror image positions to
those on the other side
• The material between these boundaries
is termed a “Twin”

Chapter 3 - 211
 Classification of Twins
• Mechanical Twins: Formed through
atomic displacements induced by
applied mechanical shear forces (e.g.
BCC, HCP)
• Annealing+ Twins: Generated during
annealing heat treatments following
deformation (e.g. FCC)
• As is the case with slip (dislocation
flow), “Twinning” favors:
– A definite crystallographic plane
– A specific crystallographic direction* Chapter 3 - 212
Chapter 3 - 213
Chapter 3 - 214
 On a Photomicrograph…

The twins correspond to those regions

having relatively straight and parallel
sides and a different visual contrast than
the untwinned regions of the grains within
which they reside.

Chapter 3 - 215
Annelaing Twins

Chapter 3 - 216
 Stacking Faults
• Commonly found in FCC
• That is , when the stacking sequence
“ABCABCABC…” closed packed planes is
interrupted

Chapter 3 - 217
 Domain Walls
For ferromagnetic and ferrimagnetic materials
the boundary that separates regions having
different directions of magnetization is termed a
“Domain Wall”

Chapter 3 - 218
Domain Walls

Chapter 3 - 219
Domain Walls

Chapter 3 - 220
 Summary

• Associated with each type of 2D defects

is an “Interfacial Energy”
• The magnitude of which depends on
“Boundary Type”
• This varies from one material to another
• Normally, the extent of such energy is:
– Greatest for external surfaces*
– Least for domain walls
Chapter 3 - 221