4/12/2024

IE0242/IE 223: Materials

Science & Engineering

Dr. Rula Allaf

Associate Professor of Industrial Engineering

Chapter 4:
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?

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Imperfections in Solids

Crystalline defects
Others
Volume defects

Point Line / Linear Planar Surface pores,

defects

Vacancies external surfaces,

cracks,
Atomic
Edge vibrations
Dislocation grain boundaries,
Interstitial foreign
Atom Screw inclusions
dislocation
twin boundaries,
Self
Interstitial Mixed
dislocation

Interstitial stacking faults,

impurity atom

Substitutional phase boundaries.

Atom

Types of Crystalline
Imperfections

There is no such thing as a perfect crystal.

– What are these imperfections (defects)?
– Why are they important?

A crystalline defect is a lattice irregularity having one or

more of its dimensions on the order of an atomic
diameter.
Many of the important properties of materials are due to the
presence of imperfections.

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Types of Crystalline Imperfections

Classification of crystalline imperfections is frequently made

according to geometry or dimensionality of the defect

• Vacancy
Point defects 0D • Interstitial atoms
1 or 2 atomic positions • Substitutional atoms

Line defects 1D • Dislocations

Area defects 2D • Boundaries/interfacial

(grain, twin, phase,..)

[1] Point Defects in Metals

(1) Vacancies:
vacant atomic site in a structure: one normally occupied from which
an atom is missing. Number of vacancies depends on and increases
with temperature.

Vacancy
distortion
of planes

(2) Self-Interstitials:
"extra" atom positioned between atomic sites (in an interstitial site: a
small void space that under ordinary circumstances is not occupied).

self-
distortion interstitial
of planes

- In metals, Vacancies are more common than self-interstitials

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Equilibrium number of
vacancies
4.5E+26
4E+26
3.5E+26

Nv (vacancy/m3)
3E+26
2.5E+26
2E+26
Nv =F(T)
1.5E+26
1E+26
5E+25
0
-5E+25 0 500 1000 1500 2000
Temperature (C)

➢ For most metals, the fraction of vacancies, Nv/N, just below the melting
temperature is on the order of 10-4; that is, one lattice site out of 10,000
will be empty.

EXAMPLE PROBLEM 4.1

Nv =F(T)
4.5E+26

4E+26

3.5E+26

3E+26
Nv (vacancy/m3)

2.5E+26

2E+26

1.5E+26

1E+26

5E+25

0
0 500 1000 1500 2000
-5E+25
Temperature (C)

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[1] Point defects in metals

(3) Impurities as interstitial & substitutional atoms:
▪ A pure metal, consisting of only one type of atom, isn’t possible;
impurity or foreign atoms will always be present, and some exist as
crystalline point defects.

▪ Impurity atoms can be intentionally added to the material to impart

specific characteristics - most metals are alloyed.

▪ The addition of impurity atoms (B) to a metal (A) will result in the
formation of a solid solution and/or a second phase, depending on
the kinds of impurity, their concentrations, and the temperature of
the alloy.
Second phase particle
Solid -- different composition
solution -- often different structure.

Solid solution of B in A plus particles of a new phase (usually for a larger amount of B)
❖Alloy: a metallic substance, a mixture, composed of two or more elements.
❖Phase: a homogeneous portion of material that has uniform physical and chemical characteristics

[1] Point defects in metals

Impurities (interstitial & substitutional atoms):
The present discussion is concerned with solid solutions:

Solid solution is a uniform mixture of two crystalline solids

that share a common crystal lattice, where the minor
concentration component (solute, added impurity element,
B) is uniformly distributed within a major concentration
component (solvent, host, A) (i.e., random distribution of
point defects in the solvent lattice)

➢ The crystal structure of the host is maintained, and no

new structures are formed.
➢ A solid solution is also compositionally homogeneous
(single phase); the impurity atoms are randomly and
uniformly dispersed within the solid.

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[1] Point defects in metals

➢ 2 types of solid solutions 2 types of impurity point defects

in solid solutions:

Substitutional OR Interstitial
atom atom

Substitutional solid soln. Interstitial solid soln.

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

solute or impurity atoms impurity atoms fill the voids

replace or substitute the or interstices among the
host atoms in the lattice host atoms

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[1] Point defects in metals

Conditions for substitutional solid solution
(features of the solute and solvent atoms that determine the degree to
which the former dissolves in the latter-conditions for appreciable solid
solubility-Hume – Rothery rule)
1. Difference in atomic radii < 15%; otherwise the solute
atoms will create substantial lattice distortions and a
new phase will form.
2. Same crystal structure for both pure metals
3. Proximity in periodic table (similar electronegativities;
otherwise they will form an intermetallic compound)
4. Valences (similar valences)
– All else being equal, a metal will have a greater tendency to dissolve a metal
of higher valency than one of lower valency

–Example: Cu-Ni alloy: completely soluble in one

another at all proportions
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[1] Point defects in metals

Conditions for interstitial solid solution
▪ The diameter of an interstitial atom must be substantially
smaller than that of the host atoms, specially for hosts with
high APF (interstitial positions are relatively small); impurity
atoms fill the voids or interstices among the host atoms.
▪ Normally, the maximum allowable concentration of interstitial
impurity atoms is low (<10%)
– Example: Fe-C interstitial solid solution (2.14 wt.%C)
For both FCC and BCC crystal
structures, there are two types of
interstitial sites—tetrahedral (4
atoms) and octahedral (6 atoms)

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[2] Line/linear (1D) crystalline Defects

Dislocations
– one-dimensional defects around which atoms are misaligned
– 3 types: edge, screw, and mixed dislocations.

1. Edge dislocation ⊥
⊥
:
– extra portion/half of a plane of atoms inserted in a crystal structure, the
edge of which terminates within the crystal
– a linear defect that centers on the line (dislocation line) that is defined
along the end of the extra half-plane of atoms. Within the region around
the dislocation line there is some localized lattice distortion (the atoms
above the dislocation line are squeezed together, and those below are
pulled apart).

r0

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[2] Line/linear Defects

1. Edge dislocation ⊥
⊥
:

b y
x
– the Burgers vector, b: is what closes a loop
that travels an equal number of atom
spacings in each direction
– Burgers vector, b: measure of magnitude
and direction of lattice distortion; b is
perpendicular to dislocation line.

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[2] Line/linear Defects

2. Screw dislocation :
– the upper front region of the crystal is shifted one atomic distance to the
right relative to the bottom portion.
– spiral planar path resulting from shear deformation (spiral or helical path
is traced around the dislocation line by the atomic planes of atoms)
– the atomic distortion associated with a screw dislocation is also linear
and along a dislocation line, line AB.
– b parallel () to dislocation line
Screw Dislocation

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

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Screw Dislocation

Front View Top View

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Edge, Screw, and Mixed Dislocations

Most dislocations found in crystalline materials are
probably neither pure edge nor pure screw, but
exhibit components of both types: mixed dislocation
Mixed

Edge

Screw
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[3] Planar (Area) 2D Crystalline Defects

• Interfacial defects are boundaries that have two
dimensions and normally separate regions of the
materials that have different crystal structures,
phases and/or crystallographic orientations.
• These imperfections include:
1) external surfaces,
2) grain boundaries,
3) twin boundaries,
4) stacking faults, and
5) phase boundaries.

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Interfacial Defects
(1) External surfaces: along which the crystal
structure terminates.
– Surface atoms are not bonded to the maximum
number of nearest neighbors and are therefore in a
higher energy state than the atoms at interior positions.
– The bonds of these surface atoms that are not satisfied
give rise to a surface energy, expressed in units of
energy per unit area (J/m2).
– To reduce this energy, materials tend to minimize, if
possible, the total surface area.
• For example, liquids assume a shape having a
minimum area—the droplets become spherical.

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Interfacial Defects
(2) Grain boundaries
Solidification- result of casting/cooling of molten material
– Start with a molten material – all liquid
– Nuclei form
– Nuclei grow to form crystals – grain structure
– Crystals grow until they meet each other

nuclei crystals growing grain structure

liquid
Grains can be:
- equiaxed (roughly same size in all directions) due to rapid
cooling (greater T) near mold wall
- columnar (elongated grains) in area with less undercooling

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Interfacial Defects
Grain Boundaries
• Regions between crystals/
grains having different
crystallographic orientations in
polycrystalline materials
• Atomic mismatch (disordered)
in a transition from lattice
(crystalline orientation) of one
region to that of the other
• Low density in grain boundaries
• Various degrees of
– high mobility crystallographic
– high diffusivity misalignment: small to high
– high chemical reactivity
Diffusivity: the ability of a substance to permit or undergo diffusion: the phenomenon of
material transport by atomic motion

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Interfacial Defects
Grain Boundaries
• Atoms are bonded less regularly along a grain boundary;
there is an interfacial or grain boundary energy (function
of degree of misorientation/misalignment)
– Grain boundaries are more chemically reactive than the
grains themselves.
– Impurity atoms often preferentially segregate along these
boundaries because of their higher energy state.
– The total interfacial energy is lower in large or coarse-
grained materials than in fine-grained ones, since there is
less total boundary area in the former.
– Grains grow at elevated temperatures to reduce the total
boundary energy

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Interfacial defects
(3)Twin boundaries:
▪ special type of grain boundary across which there is a
specific mirror lattice symmetry. The region of material
between these boundaries is appropriately termed a twin.
Twins result from atomic displacements that are produced
from applied mechanical shear forces (mechanical twins)
and also during annealing heat treatments following
deformation (annealing twins)

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Interfacial Defects
(4) Phase Boundaries
• Exist in multiphase materials; a different
phase exists on each side of the boundary.
• Each phase has its own distinctive physical
and/or chemical characteristics.
Pearlite &
proeutectoid
(5) Stacking faults
• For FCC metals an error in ABCABC…. packing
sequence of the close-packed planes
• Ex: ABCABABC

ABABAB… stacking
sequence in HCP

ABCABCABC… stacking sequence in FCC

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Surface Defects
Several types of surface
defects, represented
schematically in the figure,
include ledges, kinks, terraces,
vacancies, and individual
adatoms (i.e., atoms adsorbed
on the surface).

Single crystals of
(Ce0.5Zr0.5)O2
used in an automotive
catalytic converter
Fig. 4.11, Callister & Rethwisch 8e.

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Volume Defects & Atomic Vibrations

• Bulk/volume defects: much larger defects
– They include pores, cracks, foreign inclusions,
– Normally introduced during processing and
fabrication steps

• Atomic vibrations may be thought of as

imperfections or defects
– Every atom in a solid material is vibrating very
rapidly about its lattice position within the crystal.
– At any instant of time not all atoms vibrate at the
same frequency and amplitude, nor with the same
energy.

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SPECIFICATION OF COMPOSITION
• Specification of composition (concentration) of an alloy
in terms of its constituent elements (i.e., the relative
content of a specific element or constituent in an alloy)
• The two most common ways to specify composition are
weight (or mass) percent and atom percent.
– weight percent (wt%): the weight of a particular
element relative to the total alloy weight.
– atom percent (at%): the number of moles of an
element in relation to the total moles of the elements
in the alloy.
❖ other ways include: volume percent (vol%) and weight per
volume.

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SPECIFICATION OF COMPOSITION
• Binary alloy
– weight percent (wt%)
m1
C1 = x 100 C1 + C2 = 100
m1 + m2
mi = mass of component i

– atom percent (at%)

nm1
C1' = x 100 C′1 + C′2 = 100
nm1 + nm 2
nmi = number of moles of component i
= m′i/Ai,
m′i: the mass of component i (g)
Ai : atomic weight (g/mole)

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Example

Calculate the composition, in weight percent, of

an alloy that contains 218.0 kg titanium, 15 kg of
aluminum, and 10 kg of vanadium.

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SPECIFICATION OF COMPOSITION
• Composition (concentration) conversion

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Example
What is the composition, in weight percent, of an alloy that
consists of 6 at% Pb and 94 at% Sn?

CSn = 100 – 10.0 = 90 wt%

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SPECIFICATION OF COMPOSITION
𝑚1
– weight per unit volume (kg/m3) 𝐶1 =
𝑚1 + 𝑚2
× 100
❖ often used in diffusion computations
𝐶1 (𝑚1 + 𝑚2 )/100 = 𝑚1
𝑚1
𝜌1 =
m1 𝑉1
C1" =
V1 + V2 𝑉1 =
𝑚1
𝜌1

m2
C2" = 103 for unit
V1 + V2 conversion

 = density in units of g/cm3

it is assumed that total alloy volume is exactly equal to the sum

of the volumes of the individual elements

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SPECIFICATION OF COMPOSITION
Density (ave) and atomic weight (Aave) of a binary alloy
given the composition in terms of either weight percent or atom percent

it is assumed that total alloy

volume is exactly equal to the
sum of the volumes of the
individual elements.

This normally is not the case

for most alloys; however, it is a
reasonably valid assumption
and does not lead to significant
errors for dilute solutions and
over composition ranges where
solid solutions exist.

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Remember
• Theoretical density of a metallic solid given its
crystal structure; same applies to solid solutions

n A 𝑛 × 𝐴𝑎𝑣𝑔
= 𝜌𝑎𝑣𝑔 =
VC  N A 𝑉𝐶 × 𝑁𝐴

• Number of atomic sites per unit volume, N

(atoms/cm3), same applies to alloys

𝑁𝐴 × 𝜌 𝑁𝐴 × 𝜌𝑎𝑣𝑔
𝑁= 𝑁=
𝐴 𝐴𝑎𝑣𝑔

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Suggested Problems
➢ Explain the following:
a) External surfaces of a crystal having a surface energy
b) Grain boundaries are more chemically reactive than the grains
themselves.
c) The total interfacial energy is lower in large or coarse-grained
materials than in fine-grained ones,
d) Grains grow at elevated temperatures.
e) Atomic vibrations may be thought of as imperfections or defects
➢ What is the composition, in atom percent, of an alloy that
consists of 30 wt% Zn and 70 wt% Cu?
➢ What is the composition, in atom percent, of an alloy that
contains 100 g tin and 68 g of lead?
➢ Calculate the number of atoms per cubic meter in
aluminum.

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Suggested Problems
➢ Calculate the fraction of atom sites that are vacant for copper
(Cu) at its melting temperature of 1084 °C (1357 K). Assume
an energy for vacancy formation of 0.90 eV/atom.
➢ Compute the radius r of an impurity atom that just fits into a
BCC (and FCC) octahedral site in terms of the atomic radius
R of the host atom (without introducing lattice strains).
➢ For an FCC single crystal, would you expect the surface
energy for a (100) plane to be greater or less than that for a
(111) plane? Why?
• Calculate the unit cell edge length for an 80 wt% Ag-20 wt%
Pd alloy. All of the palladium is in solid solution, the crystal
structure for this alloy is FCC, and the room-temperature
density of Pd is 12.02 g/cm3.

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Suggested Problems
➢ Aluminum–lithium alloys have been developed by the
aircraft industry to reduce the weight and improve the
performance of its aircraft. A commercial aircraft skin
material having a density of 2.50 g/cm3 is desired.
Compute the concentration of Li (in wt%) that is
required.

➢ Iron and vanadium both have the BCC crystal

structure and V forms a substitutional solid solution in
Fe for concentrations up to approximately 20 wt% V
at room temperature. Determine the concentration in
weight percent of V that must be added to iron to
yield a unit cell edge length of 0.290 nm.

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Summary
• Point, Line, and Area defects exist in solids.

• The number and type of defects can be varied

and controlled (e.g., Temperature 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.)

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