COLLEGE OF Engineering

GENG211:
Material Science

Lecture 4:

chapter 4: Imperfections in Solids

• Dr. Hamdan Hamdan

• hamdan.hamdan@pu.edu.lb
 • Solidification- result of casting of molten material
• 2 steps
1. Nuclei form
2. Nuclei grow to form crystals – grain structure
Imperfections in • Start with a molten material – all liquid
Solids • Crystals grow until they meet each other
 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
• high diffusivity
• high chemical reactivity
 Crystals in 2D!!!

https://www.youtube.com/watch?v=xuL2yT-B2TM
 • Real crystals are never perfect: there are always
defects
• The main desire is to control these defects
• There is no such thing as a perfect crystal.
• Many of the important properties of materials are

REAL due to the presence of imperfections.

• Questions to address:
1. What types of defects arise in solids?
CRYSTALS 2. Can the number and type of defects be
varied and controlled ?
3. How do defects affect material properties?
4. Are all defects undesirable?
 • Point defects
➢ Vacancy atoms
➢ Self-Interstitial atoms
➢ Impurities: Substitutional and
Imperfections Interstitial atoms
in Solids: • Line defects
➢ Dislocations
Types of
• Area defects
Imperfections ➢ Grain Boundaries
Point Defects
Vacancies: vacant atomic sites in a structure.
 Point Defects

• Substitutional impurity
• impurity atom in lattice

• Interstitial impurity
• impurity atom not in
regular lattice site

• In principle, all of these

defects can be eliminated
except vacancies
• because vacancies arise
from a built – in
principle of
thermodynamics:
entropy
Equilibrium Concentrations:
Vacancies
Equilibrium Concentrations: Vacancies
 Equilibrium Vacancy
Concentration

• Low energy electron microscope view

of a (110) surface of NiAl.

• Increasing the temperature, causes

surface island of atoms to grow.

• The equilibrium vacancy

concentration increases via atom
motion from the crystal to the Island grows/shrinks to maintain
surface, where they join the island. equil. vancancy conc. in the bulk.
 Imperfections in Metals (i)
Two outcomes if impurity (B) added to host (A):
• Solid solution of B in A (i.e., random dist. of point defects)

OR

Substitutional solid soln. Interstitial solid soln.

(e.g., Cu in Ni) (e.g., C in Fe)
• Solid solution of B in A plus particles of a new
phase (usually for a larger amount of B)
Second phase particle
-- different composition
-- often different structure.
 Imperfections in Metals (ii)

Conditions for substitutional solid solution (S.S.)

• 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
• All else being equal, a metal will have a greater tendency
to dissolve a metal of higher valency than one of lower
valency
 Imperfections in Metals (iii)
Application of Hume–Rothery rules – Solid
Solutions Element Atomic Crystal Electro- Valence
Radius Structure nega-
(nm) tivity
1. Would you predict Cu 0.1278 FCC 1.9 +2
C 0.071
more Al or Ag H 0.046
O 0.060
to dissolve in Zn? Ag 0.1445 FCC 1.9 +1
Al 0.1431 FCC 1.5 +3
Co 0.1253 HCP 1.8 +2
Cr 0.1249 BCC 1.6 +3
2. More Zn or Al Fe 0.1241 BCC 1.8 +2
Ni 0.1246 FCC 1.8 +2
in Cu? Pd 0.1376 FCC 2.2 +2
Zn 0.1332 HCP 1.6 +2
 Impurities in Solids
• Specification of composition
m1
– weight percent C1 = x 100
m1 + m2
m1 = mass of component 1

n m1
– atom percent C =
'
x 100
n m1 + n m 2
1

nm1 = number of moles of component 1

 Methods of Producing
Point Defects
❑ Growth and synthesis
➢ Impurities may be added to the material during synthesis

❑ Thermal & thermochemical treatments and other stimuli

➢ Heating to high temperature and quench
➢ Heating in reactive atmosphere
➢ Heating in vacuum. e.g. in oxides it may lead to loss of oxygen

❑ Plastic Deformation
➢ Example: Beinding

❑ Ion implantation and irradiation

➢ Electron irradiation (typically >1MeV)
• → Direct momentum transfer or during relaxation of electronic
excitations)
➢ Ion beam implantation (As, B etc.)
➢ Neutron irradiation
 Alloys

1. An alloy is a combination, either in solution or

compound, of two or more elements, at least one of
which is a metal.
2. An alloy with two components is called a binary alloy;
one with
1. three components is a ternary alloy;
2. one with four components is a quaternary alloy.

3. The result of alloying is a metallic substance with

properties different from those of its components.

• Steel is a metallic alloy whose major constituent is iron.

• One classical definition is that steels are iron-carbon
alloys with up to 2.1% carbon.
• With the increased carbon, steel is harder and has a
much higher tensile strength than iron, but is also
more brittle.
 Solid Solutions

• The extent to which the components of an alloy are

miscible depends on the interaction between the atoms:

1. If strong mutual attraction occurs, a single crystal of

a different phase can form, such as in intermetallic
compounds

2. If there is little difference between like and unlike

bonds, then a solid solution can occur, over a wide
range of elemental compositions

3. If the species do not tend to bond to each other, then

separate phases will form with limited or zero
miscibility (pseudo-alloys).
Types of Solid Solutions
Types of Solid Solutions

• For the substitutional type, solute or impurity atoms replace or

substitute for the host atoms. The four Hume – Rothery rules of the
solute and solvent atoms determine the degree to which the former
dissolves in the latter:

1. Atomic size factor: Appreciable quantities of a solute may be

accommodated in this type of solid solution only when the
difference in atomic radii between the two atom types is less
than about 15%. Otherwise, the solute atoms create substantial
lattice distortions and a new phase forms.

2. Crystal structure: For appreciable solid solubility, the crystal

structures for metals of both atom types must be the same.

3. Electronegativity factor: The more electropositive one

element and the more electronegative the other, the greater
the likelihood that they will form an intermetallic compound
instead of a substitutional solid solution.

4. Valences: Other factors being equal, a metal has more of a

tendency to dissolve another metal of higher valency than to
dissolve one of a lower valency.
Types of Solid
Solutions

• An example of a substitutional solid solution is found for copper and nickel, which are completely
soluble in one another at all proportions.
1. The atomic radii for copper and nickel are 0.128 nm and 0.125 nm, respectively
2. Both have the FCC crystal structure
3. Their electronegativities are 1.9 and 1.8
4. The most common valences are 1 for copper (although it sometimes can be 2) and 2 for nickel.

• Uses: Copper – nickel alloys (known as cupronickel) are widely used for marine applications due to:
1. Excellent resistance to seawater corrosion
2. Low macro – fouling rates (macro fouling is the process of unwanted materials
accumulating on the surface of another substance)
3. Good fabricability
Types of Solid Solutions

• For interstitial solid solutions, impurity

atoms fill the voids or interstices among the
host atoms.
• For both FCC and BCC crystal structures,
there are two types of interstitial sites
distinguished by the coordination number:
number of nearest neighbor host atoms.

• 1. Tetrahedral: this type has a

coordination number of 4 – the interstitial
atom is in the center of a tetrahedron forms by
four lattice atoms.
• 2. Octahedral: this type has a
coordination number of 6 – the interstitial
atom is in the space in the interstices between
6 regular atoms that form an octahedron.
 Types of Solid
Solutions

• Metallic materials have relatively high atomic packing factors,

which means that these interstitial positions are relatively
small.

• Consequently, the atomic diameter of an interstitial impurity

must be substantially smaller than that of the host atoms:
1. Normally, the maximum allowable concentration of
interstitial impurity atoms is low (less than10%).
2. Even very small impurity atoms are ordinarily larger than
the interstitial sites, and as a consequence, they introduce
some lattice strains on the adjacent host atoms.

• For example, carbon forms an interstitial solid solution when

added to iron:
1. The maximum concentration of carbon is about 2%
2. The atomic radius of the carbon atom is much smaller than
that of iron: 0.071 nm versus 0.124 nm.
 Interstitial Solid Solutions:
Example:
Steel is an interstitial iron carbon alloy
Cu-Ni Binary System
Cu-Ag Binary System
 Alloying a Surface

1. Low energy electron microscope view of a surface of Cu.

2. Sn islands move along the surface and "alloy“ the Cu with Sn
atoms, to make "bronze".
3. The islands continually move into "unalloyed" regions and leave
tiny bronze particles in their wake.
4. Eventually, the islands disappear.
 Line Defects

• Based on the bond strength most materials should be

much stronger than they are. The strength for an ionic
bond should be about 1 Gpa, but the more typical
strength observed is 200 Mpa and physical phenomenon
are observed.
• Deformation of ductile materials occurs when a
line defect (dislocation) moves (slip) through the
material.

• Dislocations are:
I. Line defects that cause atoms to misalign
II. Slip between crystal planes result when
dislocations move
III. Produce permanent (plastic) deformation

• Types of Dislocations:
I. Edge dislocation
II. Screw dislocation
III. Mixed dislocation
 Edge Dislocation

• An edge dislocation is defined as the

formation/introduction of an extra portion
of a plane of atoms, or half-plane, the
edge of which terminates within the
crystal. 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; there is a slight curvature for the
vertical planes of atoms as they bend around
this extra half-plane.

• The magnitude of this distortion decreases

with distance away from the dislocation line.
Screw
Dislocation
• 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 below: the upper front region of the
crystal is shifted one atomic distance to the
right relative to the bottom portion.

• The atomic distortion associated with a

screw dislocation is also linear and along a
dislocation line (line AB in the figure).
Mixed Dislocation

The figure to the left is a representation of a

dislocation that has edge, screw, and
mixed character.
At point A, the dislocation is pure screw, while
at point B, it is pure edge. For regions in
between where there is curvature in the
dislocation line, the character is mixed edge
and screw.
A transmission electron
micrograph of a titanium
alloy in which the dark
lines are dislocations.
Virtually all crystalline
materials contain some
dislocations that were
introduced
during solidification,
plastic deformation, and
thermal stresses that
result from rapid cooling.
Interfacial Defects

• When a shear force is applied to a material, the dislocations move,

which makes the strength of the material a function of the force
required to make the dislocation move, not the bonding energy.

• There are four different types of interfacial defects:

1. External Surface Defects:
2. Grain Boundaries
3. Phase Boundaries
4. Twin Boundaries
Interfacial Defects

• When a shear force is applied to a material, the dislocations move, which makes the
strength of the material a function of the force required to make the dislocation move,
not the bonding energy.

• There are four different types of interfacial defects:

1. External Surface Defects:
• 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 at all possible, the total surface area. For example, liquids assume a
shape having a minimum area—the droplets become spherical. Of course, this is not
possible with solids, which are mechanically rigid.
Catalysts and Surface Defects
• A catalyst increases the rate
of a chemical reaction
without being consumed
• Active sites on catalysts are Fig. 4.10, Callister & Rethwisch 8e.

normally surface defects

Single crystals of
(Ce0.5Zr0.5)O2
used in an automotive
catalytic converter
Interfacial Defects
 2.Grain Boundaries:

Interfacial The atoms are bonded less regularly along a grain

Defects boundary, and consequently there is an interfacial or

grain boundary energy similar to the surface energy. The
magnitude of this energy is a result of having higher –
angle at the boundaries.

Grain boundaries are more chemically reactive than the

grains themselves as a consequence of this boundary
energy. Furthermore, 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 because
there is less total boundary area in the former.
Interfacial Defects
 Dislocations and
Mechanical Properties

• The strength of a material with no dislocations is 20-

100 times greater than
• the strength of a material with a high dislocation
density.
• So, materials with no dislocations may be very strong,
but they cannot be
• deformed.
• The dislocations weaken a material, but
make plastic deformation possible.
• During plastic deformation, the number of
dislocations increase
• dramatically to densities of 1010/mm.
• Grain boundaries, internal defects and
surface irregularities serve as
formation sites for
dislocations during deformation.
Questions