CHAPTER 4

NMK 12003
ENGINEERING MATERIALS

CHAPTER 4
SOLIDIFICATION AND CRYSTAL IMPERFECTION

Fakulti Kejuruteraan & Teknologi Elektronik

(FKTEN), Universiti Malaysia Perlis (UniMAP)
 MATERIALS SCIENCE & ENGINEERING

LEARNING OBJECTIVES:
1. Describe the process of solidification of metals and
distinguish between homogenous and heterogeneous
nucleation.
2. Describe the two energies involves in the solidification
together with the equation applied for the total free energy.
3. Distinguish between equiaxed and columnar grains.
4. Describe various forms of metallic solid solutions.
5. Classify various types of crystalline imperfections and
explain the role of each defects.
 SOLIDIFICATION OF METALS
❑ Transformation of a molten liquid to a solid is probably the
most important phase transformation in applications of materials
science and engineering → Process in which atoms are
converted into an ordered solid state from a liquid
disordered state.

❑ Solidification plays a critical role in the processing of metals,

alloys, thermoplastics & inorganic glasses → Also important in
techniques used for the joining of metallic materials.

❑ The ability to use heat to produce, melt & cast metals such as
copper, bronze, and steel is regarded as an important hallmark
in the development process. E.g. The use of fire for reducing
naturally occurring ores into metals and alloys led to the
production of useful tools and other products.
 SOLIDIFICATION OF METALS

❑ Metals are melted and cast to produce finished and semi-

finished parts.
❑ Two steps of solidification :
❑ Nucleation : Formation of stable nuclei in the melt (a)
❑ Growth of nuclei into crystals (b) & Formation of a grain
structure (c)
 FORMATION OF STABLE NUCLEI

❑ Two main mechanisms: Homogenous & Heterogeneous.

Homogenous Nucleation

❖ First and simplest case.

❖ Occurs when the metal itself provide atoms to form nuclei.
❖ Metal, when significantly undercooled (i.e. cooled below
its equilibrium), many homogenous nuclei are created by
slow moving atoms bonding together.
❖ For a nucleus to be stable so that it can grow into a
crystal, it must reach a critical size
❖ Cluster of atoms below critical size: Embryo.
❖ If the cluster of atoms reach critical size, they grow into
crystals. Else it gets dissolved.
❖ Cluster of atoms that are greater than critical size:
Nucleus.
 ENERGIES INVOLVED IN HOMOGENOUS NUCLEATION

(a) Volume free energy Gv (b) Surface energy Gs

❖ Released by liquid to solid ❖ Required to form new solid surface.
transformation. ❖ ΔGs : Energy needed to create a
❖ ΔGv : Difference /Change in surface.
free energy per unit volume ❖ γ : Specific surface free energy.
between liquid and solid.
❖ Free energy change for a ❖ ΔGs = 4𝜋𝑟 2 γ
spherical nucleus of radius r
is given by
4 3
3
𝜋𝑟 ΔGv
4 3
𝜋𝑟 :Volume of sphere
3
ENERGIES INVOLVED IN HOMOGENOUS NUCLEATION

Nucleus

Above critical Below critical

radius r* radius r*

Energy Energy
lowered by Lowered by
growing into redissolving
crystals
 CRITICAL RADIUS VS UNDERCOOLING

❑ Greater the degree of undercooling, greater the change in

volume free energy ΔGv
❑ ΔGs does not change significantly.
❑ As the amount of undercooling ΔT increases, critical nucleus
size decreases.
❑ Critical radius is related to the amount of undercooling by the
relation :
r* = critical radius of nucleus
γ = Surface free energy
ΔHf = Latent heat of fusion
Δ T = Amount of undercooling.
Tm=Freezing Temperature in Kelvin
 CRITICAL RADIUS VERSUS UNDERCOOLING

(a) Calculate the critical radius (in cm) of a homogeneous nucleus that
forms when pure liquid copper solidifies. Assume ΔT=0.2Tm Use data from
Table below.
(b) Calculate the number of atoms in the critical sized nucleus at this
undercooling. (Given copper has FCC crystal structure and length a =
0.361nm)
CRITICAL RADIUS VERSUS UNDERCOOLING
 HETEROGENOUS NUCLEATION
❑ Nucleation that occurs in a liquid on the surfaces of structural material.
Eg:- Insoluble impurities.
❑ These structures, called nucleating agents (impurities solids), lower the
free energy required to form the stable nucleus.
❑ Since the surface energy is lower, the total free-energy change for the
formation of a stable nucleus will be lower, and the critical size of the
nucleus will be smaller.
❑ Thus, a much smaller amount of undercooling is required to form a stable
nucleus produced by heterogeneous nucleation.
❑ Used excessively in industries.
 GROWTH OF CRYSTAL FORMATION OF GRAIN STRUCTURE

❑ After stable nuclei is form, nucleus grow into crystals in different

orientations. Solidified metal containing many crystals is said to be
polycrystalline.
❑ Crystal boundaries are formed when crystals join together at
complete solidification.
❑ Crystals in solidified metals are called grains- separated by grain
boundaries.
❑ The more the number of nucleation sites available, the more number
of grains formed.
❑ The number of nucleation sites will affect the structure of the
solid metal produced.
❑ If relative few nucleation sites are available, a coarse / large-grain
structure will be produced.
❑ If many nucleation sites are available, a fine-grain structure will be
produced.
 TYPES OF GRAINS

❑ Equiaxed Grains:
❑ Crystals, smaller in size, grow equally in all directions.
❑ Commonly found adjacent with to a cold mold walls.
❑ Large amount of undercooling near the wall create high
concentration of the nuclei.

❑ Columnar Grains:
❑ Long thin and coarse.
❑ Grow predominantly in one direction.
❑ Formed at the sites of slow cooling
❑ and steep temperature gradient.
❑ Example:- Grains that are away from the mold wall.
TYPES OF GRAINS
 CASTING IN INDUSTRIES
In industries, molten metal is cast into either semi finished or finished
parts.

Continuous casting
of steel ingots

Casting unit for aluminum in a

Direct-Chill semi continuous unit
 GRAIN STRUCTURE IN INDUSTRIAL CASTINGS

❑ To produce cast ingots with fine grain size, grain refiners

are added(i.e. materials added to a molten metals to attain
finer grains.
❑ Example:- For aluminum alloy, small amount of Titanium,
Boron or Zirconium is added.

Grain structure
of Aluminum
cast with (b)
and without (a)
grain refiners.

(a) (b)
 SOLIDIFICATION OF SINGLE CRYSTAL
❑ Almost all engineering crystalline materials are composed of many
crystals and are therefore polycrystalline. However, there are a few
that consist of only one crystal and are therefore single crystals.
❑ e.g. Gas turbine blades-high temperature environment, single
crystals are needed.
❑ Single crystals have high temperature creep resistance.
❑ Latent head of solidification (i.e. thermal energy released when a
metal solidifies)must be conducted through solidifying solid
crystal to grow single crystal.
❑ Growth rate is kept slow so that temperature at solid-liquid
interface is slightly below melting point.
SOLIDIFICATION OF SINGLE CRYSTAL
 CZOCHRALSKI PROCESS
❑ This method is used to produce single crystal of silicon for electronic
wafers.
1. High-purity polycrystalline silicon is first melted in a nonreactive
crucible and held at a temperature just above the melting point.
2. A high-quality seed crystal of silicon of the desired orientation is
lowered into the melt while it is rotated.
3. Part of the surface of the seed crystal is melted in the liquid to
remove the outer strained region and to produce a surface for the
liquid to solidify on.
4. The seed crystal is withdrawn slowly while silicon adheres to seed
crystal and grows as a single crystal.
 METALLIC SOLID SOLUTIONS
❑ Although very few metals are used in the pure or nearly pure
state, a few are used in the nearly pure form. E.g. High purity
copper in electronic wire and high-purity aluminum used for
bright metallic surface.
❑ Alloys are used in most engineering applications.
❑ Alloy is an mixture of two or more metals and nonmetals.
❑ Example:
• Cartridge brass is binary alloy of 70% Cu and 30% Zinc.
• Iconel is a nickel based superalloy with about 10
elements.
❑ Solid solution is a simple type of alloy in which elements are
dispersed in a single phase.
❑ There are two types of solid solutions: substitutional and
interstitial.
 SUBSTITUTIONAL SOLID SOLUTIONS
❑ Solute atoms substitute for parent solvent atom (main) in a crystal lattice.
❑ The structure remains unchanged. The atomic size of soluble atoms
and parent solvent atom are nearly similar.
❑ Lattice might get slightly distorted due to change in diameter of the
atoms.
❑ Forms only if the solute atoms are large enough to replace the solvent
atoms in the lattice.
❑ The fraction of atoms of one element that can dissolve in another can
vary from a fraction of an atomic percent to 100%.

Solvent atoms (main)

Solute atoms
 SUBSTITUTIONAL SOLID SOLUTIONS
❑ According to the Hume-Rothery rules, the solubility of solids is
greater if
❑ The diameter of atoms not differ by more than 15%.
❑ Crystal structures are similar.
❑ No much difference in electronegativity (else compounds
will be formed).
❑ Have some valence.
Atomic Electron- Solid
System radius egativity Solibility
Difference difference
Cu-Zn 3.9% 0.1 38.3%

Cu-Pb 36.7% 0.2 0.17%

Cu-Ni 2.3% 0 100%

 INTERSTITIAL SOLID SOLUTION
❑ Solute atoms fit in (enter) between the voids (interstices) of
solvent atoms.
❑ Solvent atoms (main) in this case should be much larger
than the radius of the solute atoms (i.e. Forms only if the
solute atoms are small enough to replace the solvent atoms
in the lattice. The atomic size of solute atoms should be at
least 40% about the size of solvent atoms.

Iron atoms r= 00.129nm

Carbon atoms r=0.075nm

 CRYSTALLINE IMPERFECTION

❑ No crystal is perfect.

❑ Imperfections affect mechanical properties, chemical

properties and electrical properties.

❑ Imperfections can be classified as

1. Zero dimension /point defects.
2. One dimension / line defects (dislocations).
3. Two-dimension defects/Planar defects
4. Three-dimension defects (cracks).
 POINT DEFECTS (VACANCY)

❑ Vacancy is formed due to a missing atom from the atom site.

❑ May be produced during solidification as a result of (i) Local disturbances
during the growth of crystals (ii) May be created by atomic rearrangements-
due atomic mobility.
❑ Energy of formation : 1 eV.
❑ Mobility of vacancy results in cluster of vacancies.
❑ Also caused due to plastic deformation, rapid cooling from higher
temperature to lower temperature or particle bombardment.
 POINT DEFECTS (INTERSTITIALLY)

❑ Atom in a crystal, sometimes, occupies interstitial site - Self-interstitial/

interstitialcy.
❑ These defects do not generally occur naturally because of the structural
distortion they cause, but they can be introduced into a structure by
irradiation.
❑ This defects caused structural distortion.
 POINT DEFECTS (IN IONIC CRYSTAL)
❑ More complex as electric neutrality has to be maintained.
❑ If two oppositely charged particles are missing, cation-anion
divacancy is created. This is Schottky imperfection.
❑ Frenkel imperfection is created when cation moves to interstitial site.
❑ Impurity atoms are also considered as point defects.
 LINE DEFECTS (DISLOCATIONS)

❑ Cause lattice distortions centered around a line.

❑ Formed during:
❑ Solidification of crystalline solids
❑ Permanent/Plastic deformation of crystalline solids
❑ Vacancy condensation
❑ Atomic mismatch in solid solutions
❑ Different types of line defects are
❑ Edge dislocation
❑ Screw dislocation
❑ Mixed dislocation
 EDGE DISLOCATIONS
❑ Created by insertion of extra half planes of atoms.
❑ The displacement distance of the atoms around the dislocation is called
slip/ Burgers vector b and is perpendicular to the edge-dislocation line.

Positive edge dislocation

Negative edge dislocation

 SCREW DISLOCATIONS
❑ Created by applying upward and downward shear stresses to regions of a
perfect crystal that have been separated by a cutting plane.
❑ These shear stresses introduce a region of distorted crystal lattice in the
form of a spiral ramp of distorted atoms/screw dislocation
❑ Burgers vector b is parallel to dislocation line.
 MIXED DISLOCATIONS
❑ Most crystal have components of both edge and screw dislocation.
❑ Dislocation, when have irregular atomic arrangement will appear as
dark lines when observed in electron microscope.
 PLANAR DEFECTS

❑ Grain boundaries, twins, low/high angle boundaries, twists

and stacking faults.
❑ Free/external surface is also a defect - Because the atoms
on the surface are bonded to other atoms only on one side
❑ the surface atoms have a lower number of neighbors.
❑ As a result, these atoms have a higher state of energy when
compared to the atoms positioned inside the crystal with an
optimal number of neighbors. The higher energy associated
with the atoms on the surface of a material makes the
surface susceptible to erosion and reaction with elements in
the environment - illustrates the importance of defects in the
behavior of materials.
 GRAIN BOUDARIES
❑ Grain boundaries separate grains - Surface imperfections that separate grains
(crystals) of different orientation.
❑ Formed due to simultaneously growing crystals meeting each other where the
width = 2-5 atomic diameters (narrow regions between the two grains).
❑ Some atoms in grain boundaries have higher energy (open structure).
❑ At normal temperatures, it restrict plastic flow and prevent dislocation
movement.

Grain Boundaries
In 1018 steel

(After A.G. Guy, “ Essentials of materials Science,” McGraw-Hill, 1976.)

 TWIN BOUNDARIES
❑ Twin: A region in which mirror image of structure exists
across a boundary
❑ Formed during Permanent/plastic deformation (Deformation
twins) and recrystallization i.e. atoms reposition themselves in
a deformed crystals (Annealing twins)
❑ Strengthens the metal (similar to dislocations).
 TWIN BOUNDARIES

❑ When an array of edge dislocations are oriented in a crystal in a manner

that seems to misorient or tilt two regions of a crystal (a) Small-angle tilt
boundary.
❑ A similar phenomenon can occur when a network of screw dislocations
create a (b) Small-angle twist boundary
❑ The misorientation angle θ for a small-angle boundary is generally < 10

❑ Stacking of atomic structure (e.g. FCC and HCP crystal structures – Leads
to (i) Collapse of a vacancy cluster or (ii) Interaction of dislocations (iii) One
or more of the stacking planes may be missing - Giving rise to another 2D
defect – Stacking faults/ pilling up faults- Also tend to strengthen the
materials
THANK YOU