Solidification

in Metals

Dr Rosmamuhamadani Ramli

4-1
 At the end of topic, students will able to;

1.State and differentiate between different states of matter

in terms of structure and properties
2.Describe the structural and energy changes in phase
transformation from one to another
 What is a solid?
• A solid object is in the states of matter characterized by resistance
to deformation and changes of volume.
• In other words, it has high values both of Young's modulus and of shear
modulus; this contrasts e.g. with a liquid, which has a low shear
modulus.

At the microscopic scale, a solid has these properties :

• The atoms or molecules that compose the solid are packed closely
together.
• These constituent elements have fixed positions in space relative to
each other. This accounts for the solid's rigidity.
 Solids – Crystalline / Amorphous ?
• a crystal structure is a unique arrangement of atoms in a crystal.
• A crystal structure is composed of a unit cell, a set of atoms arranged in
a particular way; which is periodically repeated in three dimensions on
a lattice.
• The spacing between unit cells in various directions is called its lattice
parameters

Crystalline Silica

• An amorphous solid is a solid in which there is no long-range order of

the positions of the atoms. 

Amorphous Silica
 What is a liquid ?
• Liquid is one of the principal states of matter.
• A liquid is a fluid that has the particles loose and can freely form a
distinct surface at the boundaries of its bulk material.
 Principles of Solidification

• Of all the processing techniques used in the manufacturing

of materials, solidification is probably the most important.
• Like water freezes to ice, molten materials solidify as they
cool below their freezing temperature.
• During the solidification of materials that crystallize, the
atomic arrangement changes from a short-range order
(SRO) to a long-range order (LRO).
 Solidification of Metals

• Metals are melted to produce finished and semi-

finished parts.
• Two steps of solidification
 Nucleation : Formation of stable nuclei.
 Growth of nuclei : Formation of grain structure.

• Thermal gradients define the shape of each grain.

Grains
Nuclei

Crystals that will Grain Boundaries

Liquid Figure 4.2
Form grains
4-2
• The solidification of crystalline materials requires 2 steps.
• In the first step, ultra-fine crystallites, known as the
nuclei of a solid phase, form from the liquid.

• In the second step, which can overlap with the first, the
ultra-fine solid crystallites begin to grow as atoms from
the liquid are attached to the nuclei until no liquid
remains.
QUESTION: Describe and illustrate the solidification process of a pure
metal in terms of the nucleation and growth of crystals (5 marks).

ANSWER:
In general, the solidification of a pure metal involves:
-the formation of stable nuclei in the liquid melt;
-the growth of these nuclei into stable nuclei in the liquid melt;
-the formation of a solidified structure containing grains formed from the
crystals. These three stages are illustrated below.
 Homogenous nucleation
This chapter deals with the simplest nucleation
event, namely the homogeneous nucleation of solid
crystals during the freezing of a pure metal. On
completion, the student should be able to:
•Explain the term homogeneous, as applied to nucleation
events
•Understand the concept of a critical size or radius, r* and a
critical free energy to nucleation, ΔG*,
•Differentiate between unstable clusters (or embryos) and
stable nuclei,
•Derive expressions for r* and ΔG* in terms of volume free
energy, ΔGv and undercooling, ΔT
• This chapter starts by explaining that a driving force for
solification, ΔGv exits below the equilibrium melting
temperature, Tm and that is approximately propertional to
degree of undercooling, ΔT.

• Solidification and melting can be defined as

transformation between crystallographic and non-
crystallographic states of a metal and alloy”. These
transformations are of course basic to such technological
applications:
-Ingot casting
-Foundy casting
• A foundry is a factory that produces metal castings.
Metals are cast into shapes by melting them into a liquid,
pouring the metal into a mold, and removing the mold
material after the metal has solidified as it cools. The most
common metals processed are aluminium and cast iron.

• Ingots usually require a second procedure of shaping,

such as cold/hot working, cutting, or milling to produce a
useful final product.
• Importance parameter used in solidification
-Temperature
-Cooling rate and alloying
 Formation of Stable Nuclei

• Two main mechanisms: Homogenous and

heterogeneous.

• Homogenous Nucleation :
 First and simplest case.
 Metal itself will provide atoms to form nuclei.
 Metal, when significantly undercooled, has several slow
moving atoms which bond each other to form nuclei.
 Cluster of atoms below critical size is called embryo.
 If the cluster of atoms reach critical size, they grow into
crystals.
 Cluster of atoms that are grater than critical size are
called nucleus.

4-3
 Energies involved in homogenous nucleation.

Volume free energy Gv Surface energy Gs

• Released by liquid to solid • Required to form new solid

transformation. surface
• ΔGv is change in free energy • ΔGs is energy needed to
per unit volume between create a surface.
γ
liquid and solid. • γ is specific surface free
• free energy change for a energy.
spherical nucleus of radius r Then  G s  4 r 2

is given by

4 3
Gv (r )  r Gv
3

4-4
 Total Free Energy
4
• Total free energy is given by GT  r 3Gv  4r 2
3
2
Since when r=r*, d(ΔGT)/dr = 0 r*  
r*is critical radius of nucleus
GV
ΔGs
+
Nucleus

ΔGT
Above critical Below critical
ΔG radius r* radius r*
r
r*r*

Energy Energy
lowered by Lowered by
- Figure 4.4 ΔGv growing into Redissolving
(pemelarutan semula)
crystals
4-4
 Critical Radius Versus 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 undercooling by relation

r* = critical radius of nucleus

2Tm γ = Surface free energy
r*  ΔHf = Latent heat of fusion
H f T Δ T = Amount of undercooling.

4-6
• The undercooling (ΔT) is the difference between the
equilibrium freezing temperature and the actual
temperature of the liquid.
• As the extent of undercooling increases, the
thermodynamic driving force for the formation of a solid
phase from the liquid overtakes the resistance to create a
solid-liquid interface.
Question 1
 Question 2

• Calculate the size of the critical radius and

the number of atoms in the critical nucleus
when solid copper forms by homogenous
nucleation. The freezing temperature for
copper is 1085 C, the heat of fusion is
1628/cm3, the solid-liquid interfacial
energy is -177 x 10 -7 J/cm2, and the
typical undercooling for homogenous
nucleation is 236 C. Copper is FCC a lattice
parameter of 0.3615 nm
QUESTION: Solidification temperature plays major role on
thermodynamics of nucleation. Consider two temperatures T1 and T2 for
solidification of liquid metals (T2 > T1).
– Draw Volume, surface and total free energy curves for nucleation
at two different temperatures (5 marks)
– Explain the changes in critical size of the nucleolus with two
solidification temperatures (5 marks)
Answer:
-Lower solidification temperatures means higher undercooling.
-At higher undercooling, volume free energy, Gv of solid formation is
higher; where as surface free energy, Gs doesn’t change with
undercooling.
-Increase in Gv; lower the total free energy of transformations, which in
turn lowers critical nucleolus size as show in figure above.
 Heterogenous Nucleation

• Water will not solidify into ice via homogenous nucleation

until we reach a temperature of -40 C (undercooling of 40
C)
• Except in controlled laboratory experiments, homogenous
nucleation never occurs in liquids.
• Instead, impurities in contact with the liquid, either
suspended in the liquid or on the walls of the container that
holds the liquid, provide a surface on which the solid can
form.
• Now a radius of curvature greater than the critical radius is
achieved with very little total surface between the solid
and liquid.
• Much less undercooling is required to achieve the critical
size, so nucleation occurs more readily.
• Nucleation on pre existing surfaces is known as
heterogeneous nucleation.
 Hetrogenous Nucleation

• Nucleation occurs in a liquid on the surfaces of

structural material. Eg:- Insoluble impurities.
• These structures, called nucleating agents, lower the
free energy required to form stable nucleus.
Liquid

Solid
θ
Nucleating
Agent
• Nucleating agents also lower the critical size. (Impurities)
• Smaller amount of undercooling (control temperature)
is required to solidify.

4-7
 Growth of Crystals and Formation of Grain Structure

• Nucleus grow into crystals in different orientations.

• Crystal boundaries are formed when crystals join
together at complete solidification.
• Crystals in solidified metals are called grains.
• Grains are separated by grain boundaries.
• More the number of
nucleation sites
available, more
the number of
grains formed.

Nuclei growing into grains

Forming grain boundaries
4-8
 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
 Solidification
Grains can be - equiaxed (roughly same size in all directions)
- columnar (elongated grains)
~ 8 cm

heat
flow

Shell of
Columnar in equiaxed grains
area with less due to rapid
undercooling cooling (greater
T) near wall

Grain Refiner - added to make smaller, more uniform, equiaxed grains.

 Types of Grains

• Equiaxed Grains:
 Crystals, smaller in size, grow equally in all directions.
 Formed at the sites of high concentration of the nuclie.
 Example:- Cold mold wall Mold

• 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.
Columnar Grains

Equiaxed Grains Figure 4.7a

4-9
 Grain Structure in Industrial castings

• To produce cast ingots with fine grain size, grain

refiners are added.
• Example:- For aluminum alloy, small amount of
Titanium, Boron or Zirconium is added.

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

(a) (b)
Figure 4.10
4-11 After “Metals Handbook” vol. 8, 8th ed., American Society of Metals, 1973, p.164)
 Grain Refinement

• Grain refinement is an important factor to improve the

microstructure uniformity and mechanical properties.

• It plays important role in improving characteristics and

properties of cast and wrought metal and alloys.

• The important reason to control the grain size especially in

cast alloy, to reduce the mechanical properties like yield
strength, reduce ability and tensile to fracture.

• When the grain sizes are not uniform achieved, the coarse
grain structure will result in a variety of surface defect in
alloy
 Grain Refinement
• Al-Si alloys is one of the most Metal Matrix Composites
(MMCs) have important high-strength Al alloys. They have
been employed extensively in the aircraft and military
industries, in which materials are frequently subjected to
elevated temperature. The Al casting alloys, based on the Al-Si
system are widely used in light-weight constructions and
transport applications requiring a combination of high strength
and ductility (Wang et. al., 2010).

1) Al and its alloys will have coarse grain size in as cast

condition. Mechanical properties of Al are strongly connected to
their microstructure obtained after heat treatment. This coarse
grain size of as cast alloys results in low Al mechanical
properties. 
• 2) The low mechanical properties make it unreliable for further
advance application. To overcome this, Al with smaller grain size
must be produced. A finer grain sizes promotes improved casting
soundness by minimizing shrinkage, hot cracking and hydrogen
porosity. This fine equiaxed grain structure is normally desired in
Al final product. 
•
3) In cast house applications, the control of grain size is absolutely
essential in maintaining product consistency and quality, in
reducing costs and maintaining high levels of productivity. The
type of size and grain formed are determined by the composition of
alloy, solidification rate, and the addition of master alloys (grain
refiners). 
• 4) The grain refinement is the main thing in improving
characteristics and properties of cast and wrought alloy.
There are some reasons about importantly to control the grain
size in semi continuously cast alloy. The first reason is to
reduce mechanical properties like a yield strength, reduce
fabric ability and tensile to fracture. When the grain sizes are
not uniform achieved, the coarse grain structure will result in
a variety of surface defect in alloy. 

5) The uses of Al alloys in automotive applications have been

limited due to their inferior strength, rigidity and wear
resistance. As a result, this study is conducted to investigate
the microstructures as well as the property on Al-Si with
Titanium-Boron (Ti-B) grain refiners.
 Metallic Solid Solutions

• 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.

4-14
 Substitutional Solid Solution

• Solute atoms substitute for parent solvent atom in a

crystal lattice.
• The structure remains unchanged.
• Lattice might get slightly distorted due to change in
diameter of the atoms.
• Solute percentage in solvent
can vary from fraction of a
percentage to 100%

Solvent atoms
Figure 4.14
Solute atoms

4-15
 Substitutional Solid Solution (Cont..)

• 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.

• Examples:- 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 between the voids (interstices) of

solvent atoms.
• Solvent atoms in this case should be much larger than
solute atoms.
• Example:- between 912 and 13940C, interstitial solid
solution of carbon in γ iron (FCC) is formed.
• A maximum of 2.0%
of carbon can dissolve
interstitially in iron.

Iron atoms r=00.129nm

Carbon atoms r=0.075nm Figure 4.15a

 Observing Grain Boundaries - Metallography
• To observe grain boundaries, the metal sample must
be first mounted for easy handling
• Then the sample should be ground and polished with
different grades of abrasive
paper and abrasive solution.
• The surface is then etched
chemically.
• Tiny groves are produced
at grain boundaries.
• Groves do not intensely
reflect light. Hence
Figure 4.27
observed by optical
microscope.

4-28 After M. Eisenstadt, “Introduction to Mechanical Properties of Materials,” Macmillan, 1971, p.126
 Grain Size

• Affects the mechanical properties of the

material
• The smaller the grain size, more are the
grain boundaries.
• More grain boundaries means higher
resistance to slip (plastic deformation occurs
due to slip).
• More grains means more uniform the
mechanical properties are.

4-30
 Measuring Grain Size

• ASTM grain size number ‘n’ is a measure of grain

size.
N = 2 n-1 N = Number of grains per
N < 3 – Coarse grained square inch of a polished
4 < n < 6 – Medium grained
and etched specimen at 100 x.
7 < n < 9 – Fine grained
N > 10 – ultrafine grained n = ASTM grain size
number.

200 X 200 X

1018 cold rolled steel, n=10 1045 cold rolled steel, n=8
4-31
 Average Grain Diameter

• Average grain diameter more directly

represents grain size.
• Random line of known length is drawn on
photomicrograph.
• Number of grains intersected is counted.
• Ratio of number of grains intersected to length
of line, nL is determined.

d = C/nLM
C=1.5, and M is 3 inches 5 grains.
magnification
 Effect of Etching

Figure 4.28

Unetched Etched
Unetched Etched
Brass Brass
Steel Steel
200 X 200 X
200 X 200 X

4-32