Solidifications, Phase Relations and

Strengthening Mechanism
 Solidification
 Process of a material of transforming from liquid
to solid state when its temp is lowered below its
freezing point is called solidification
 Why study solidification
◦ It affects properties of a material
◦ Most metal are made through casting
(In pure metal ,the grain size and shape may be control by
solidification)
◦ For process and quality control during casting
◦ Welding processes involve solidification phenomena
◦ Alloy powders are often atomized, and rapidly
solidified
 Step/ mechanism in Solidification
◦ Liquid state
◦ Nucleation
◦ Crystallization and solid liquid interface
◦ Grain growth

 Nucleation occurs when a small piece of solid

forms from the liquid.
 Growth of solid occurs as atoms from the liquid are
attached to the tiny solid until no liquid remains
Dendrite formation:
The crystal which form in the process of
solidification of a metal may have many different
structure depending on the rate of cooling and
type and amount of admixtures or impurities in
the melt.
 In major case, branched or tree like crystals are
obtained which are called dendrites
Cooling Curve for the solidification of a pure metal

 Under equilibrium conditions, all metal exhibit a

definite melting or freezing point.
 If a cooling curve is plotted for a pure metal, it
will show a horizontal line at the melting or
freezing temperature
 Cooling curve
 A cooling curve is a line graph that represents the change of phase of matter,
typically from a gas to a solid or a liquid to a solid. The independent variable
(X-axis) is time and the dependent variable (Y-axis) is temperature. Below is
an example of a cooling curve used in castings.
 The initial point of the graph is the starting temperature of the matter, here
noted as the "pouring temperature".
 The slope of the cooling curve before solidification begins is the cooling rate.
 When the phase change occurs there is a "thermal arrest", that is the
temperature stays constant. This is because the matter has more internal
energy as a liquid or gas than in the solid .The amount of energy required for
a phase change is known as latent heat.
 The total solidification time of the casting is the time required to remove
both the specific heat of the superheated liquid and the latent heat of fusion.

 In the part of the curve where the temperature decreases, the kinetic energy
also decreases while the potential energy stays the same. However, at the
phase transition, where the curve is flat, the kinetic energy stays the same
while the potential energy decreases.
Cooling Curve
 Solid Solution

 Solid solution may be defined as a solution state

which consists of two kinds of atoms combined
in one type of space lattice
 Examples: Cu- Zn alloys(brass)
 Fe –C alloys ( steel)
 Fe- Cr- Ni alloys ( Stainless Steel)
 Type of solid solution
 As atoms of the parent metal ( or solvent)
are replaced or substituted by atoms of the
alloying metal( solute metal)
 In this case , the atoms of the two metal in
the alloy are of almost same size
 Interstitial solid solution
 When the atoms of the solute occupy the interstitial
space in the lattice of the solvent, it is known as
interstitial solid solution.
 If the size of the solute is less than 40 % that of solvent
,interstitial solid solution is formed/
 Common elements are hydrogen, carbon, nitrogen,
boron
 Eg.interstitial solution of carbon in iron consititutes the
basic of steel
 Hume-Rothery Rules
In other for an alloy system to have unlimited solid
solubility, certain condition must be satisfied .
These conditions are known as the Hume – Rothery
rules and are as follows :
 The atom of the metals must be of similar size
with no more than a 15 % difference in atomic
radius in order to miniize the lattice strain
 The metal must have the same crystal structure
 The atoms of the metal have the same valence and
similar electro-negativities, otherwise the
formation of compound is encouraged
 Solid solution Strengthening
 By producing solid solution alloys, we cause solid
solution strengthening
 Addition of one or more metals can increase the strength
of metals
 For this strengthening mechanism, solute atoms of one
elements are added to another, resulting in either
subtitutional or interstial point defects in the crystal.
 the solute atoms cause lattice distortion that impede
dislocation motion , increase the yield strength of the
material
 Examples : 70 % Cu & 30 % Zn has tensile strength 500
Mpa whereas unalloyed Cu has 330
 Larger atoms generally produce less strengthing than the
small atoms

Effect of solid solution on the properties of
the material
 The yield strength, tensile strength and hardness
of the alloy are greater than of pure metal
 The ductility of the alloy is less than that of the
pure metal
 Electrical conductivity is lower than metal
 Resistance to creep is improved by solid
solution strengthening
 Cast metal Structure
four of the typical in casting processes described
below.
The process are divided into several groups – sand moulds,
ceramics moulds and metal moulds.
The process using metal moulds tend to give the highest
strength castings due to rapid solidification.
Ceramics molds, because they are good insulators, give the
slowest cooling and lowest strength changes.
a)Green and sand molding in which
clay-bonded sand in packed around a pattern.
Sand cores can produce internal cavities
in the casting.
b)The permanent mold process
in which metal is poured into an iron
or steel mold.
c)Die casting in which metal is injected at high pressures
into a steel die

d)Investment casting, in which a wax pattern is

surrounded by a ceramic; after the wax is melted and
drained, metal is poured into the mold.
Solidification Defects
Although a large number of potential defects can be
introduced during solidification, two deserve special
mention.

1.Shrinkage defects
 Almost all materials are more dense in the solid than
in the liquid state. During solidification , shrinkage
can reduce the 5 – 10 % volume of cast.
 Shrinkage defects occur when feed metal is not
available to compensate for shrinkage as the metal
solidifies.
 unidirectional

 The mould can be made oversized by the appropriate

amount to compensate for the Unidirectional
shrinkage
 A common technique for controlling cavity and pipe
shrinkage is to place a rise or an extra reservoir of
metal adjacent and connected to the casting .As the
casting solidifies and shrinks, liquid metal flow from
the riser into the casting to fill the shrinkage void.
2.Gas porosity
 Many metal dissolve large quantity of gas when they are liquid.
 Gas porosity is the formation of bubbles within the casting after it has
cooled. Gas porosity may present itself on the surface of the casting as
porosity or the pore may be trapped inside the metal which reduces
strength in that vicinity.
 Nitrogen, oxygen and hydrogen are the most encountered gases in cases
of gas porosity.
 In aluminum castings, hydrogen is the only gas that dissolves in
significant quantity, which can result in hydrogen gas porosity
To prevent gas porosity:
 the superheat temperatures can be kept low
 Adding materials to the liquid to combined with the gas.Ex. For
instance, oxygen can be removed from copper by adding phosphorus;
aluminum or silicon can be added to steel to remove oxygen.
 the material may be melted in a vacuum, in an environment of low-
solubility gases, such as argon or carbon dioxide, or under a flux that
prevents contact with the air.
 Turbulence from pouring the liquid metal into the mold can introduce
gases, so the molds are often streamlined to minimize such turbulence. .
 Phase Equilibrium
 The mechanical properties of materials can be controlled by addition of
point defects such as subtitutional and intersitial atoms . Particularly in
metals, the point defects disturb the atomic arrangement in the lattice and
interfere with the movement of dislocations or slip. The point defects
therefore cause the material to be solid solution strengthened.
 In addition, the introduction of point defects changes the composition of
the material and influences solidification behavior. We examine this effect
by introducing the equilibrium phase diagram.

 Phase: A phase has the following characteristics

a) A phase has the same structure or atomic arrangement throughout
b) A phase has roughly the same composition & properties throughout
c) There is a definite interface between the phase and any surrounding or
adjoining phases. E.g.. solid state, liquid state, gaseous state
 Solution: mixture of two or more liquid material
i.e. (solute + solvent)
 Phase Diagram
 Phase Diagram: The diagram that shows the
state or phase of the solution at various
conditions of temp., pressure and composition.
 A phase diagram shows the phases and their
compositions at any combination of temp. and
alloy composition.
 Phase diagrams are usually plotted with temperature as the ordinate,
and the alloy composition as the abscissa as shown in Figure 1. The
data for the construction of equilibrium diagrams are determined
experimentally by a variety of methods, the most common methods
are:
 Metallographic Methods
 X-ray Diffraction Technique
 Thermal Analysis

Fig .Sample Phase Diagram

 ℃

 T liquidus = 1280 ºC T solidus = 12040 º

 Freezing range = 1280 -1240 =40 º C
 At 1300 º C : Only liquid L is present
 At 1250 º C : both liquid L and α solid are present
 At 1200 º C : Only solid α is present
 Cooling Curve of pure metal
Under equilibrium conditions, all metals exhibit a definite melting or
freezing point. If a cooling curve is plotted for a pure metal. It will show a
horizontal line at the melting or freezing temperature.

Liquid phase

Solid phase
 Cooling Curve of a Solid Solution
 A solid solution is a solution in the solid state and consists of two kinds of
atoms combined in one type of space lattice. A solution is composed of
two parts: a solute and a solvent. The solute is the minor part of the
solution or the material which is dissolved, while the solvent constitutes
the major portion of the solution. When solidification of the solution starts,
the temperature may be higher or lower than the freezing point of the pure
solvent. Most solid solutions solidify over a range in temperature.
 Figure below shows the cooling curve for the solidification of a solid
solution.

Cooling curve for a solid solution.

Fig:Series of cooling curves for different alloys in a completely soluble
system.The dotted lines indicate the form of the phase diagram.
Phase Diagram of alloy A+B
 Inverse lever rule
 Inverse lever rule is used to determine the percentage of each phase that is
present at various temperatures.
 The length of line XY represents the sum of the two phases as 100 percent.
 The inverse lever rule states that liquid phase can be calculated by taking
the length of the line XZ and dividing this by XY. (Liquid Phase = XZ /XY
)
 The solid phase can be calculated by taking the length of the line ZY and
dividing it by XY. ( Solid Phase = ZY /XY )
 To get the percentages, the values are multiplied by 100.
Sample Calculation :
Alloy with 40 % A and 60 %B at room temperature is heated to a
temperature T1 . Calculate the liquid and solid phase and indicate the
composition of each phase.
Liquid Phase =( XZ / XY) x 100 = [(40-10) / (70-10)] x100 = 50%
Solid Phase = ( ZY / XY) x 100 = [(70-40) / (70-10)] x100 = 50%

At temperature T1, the solid composition is found by the intersection

(point X) of isothermal line T1 and the solidus curve.
Solid composition: 10 % A and 90 % B
The liquid composition at temperature T1 is found by the intersection
(point Y) of isothermal line T1 and the liquidus curve.
Liquid composition: 70% A and 30 % B
 Eutectic System
Eutectic system is a phase transformation that takes place
when a single-phase liquid transforms directly to a two-
phase solid.
Eutectic meaning easy to melt
L ---> S1 + S2
Liquid ---> Solid 1 + Solid 2
(This is a reversible phase transformation)
 Eutectoid System
The eutectoid phase transformation occurs when a single-phase solid
transforms directly to two-phase solid.
S1 --->S2 + S3
Solid 1 ---> Solid 2 + Solid 3
(This is a reversible phase transformation)
 Peritectic System

The peritectic phase transformation

occurs when a liquid and solid phase
of fixed proportions react at fixed
temperature to yield a single solid phase.
S1 + L =S2 i.e., solid 1 + liquid = solid 2
This transformation exists in the Iron-Iron Carbide System.

• Monotectic System
The Monotectic phase transformation occurs when a liquid
transforms directly to a second liquid and a solid.
Liquid 1 = Liquid 2 + solid
This transformation is reversible phase transformation and
occurs during cooling.
Phase reaction types
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