Unit- 3 Solidification

UNIT- 3
SOLIDIFICATION
Solidification or crystallization or freezing is the process of phase transformation of metals form liquid
to solid state.
Mechanism of Solidification in Pure metal and Alloys:
Solidification of all liquid metal consists of two stages:
1) Nucleation
2) Growth

The metals and alloys in molten conditions posses high energy; as it cools, it lose energy from crystals.
During the process of solidification, the molten metal first forms nuclei and then crystallises. The nuclei
formed will tend to grow in the second stage of solidification.

During solidification the growth occurs in the dendritic form. During

crystal growth, the atoms arrange themselves in 3-D pattern. This
arrangement of atoms in 3-D pattern will form repeatedly to produce
number of unit cells. These unit cells will arrange themselves in straight
lines and at right angles to each others as shown in Fig.3.1, producing the
dendritic structure. The dendritic growth continues until it comes in
contact with another dendritic growth where it forms a grain boundary.
The steps in the growth pattern of a crystal form nuclei to grain is as in
Fig. 3.2.
Fig. 3.1Structure of dendrite

a) Nucleation b) Growth of the crystallites

c) Upon completion of d) The grain structure as it would

solidification, grains having appear under the microscope; dark
irregular shapes have formed. lines are the grain boundaries

Figure 3.2 Schematic diagrams showing various stages in the solidification of a polycrystalline
material; the square grids depict unit cells.

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Undercooling or Supercooing in Pure Metals:

The pure metals will melt and solidify at the single point known as melting point or freezing point.
Above the melting point in the Time-Temperature curve, the metal is in liquid phase and below that
curve, it is in solid phase.

A cooling curve shows how the temperature of a material (in this case, a pure metal) decreases with
time [Figure 3.3 (a) and (b)]. The liquid is poured into a mould at the pouring temperature, point A. The
difference between the pouring temperature and the freezing temperature is the superheat. The specific
heat is extracted by the mould until the liquid reaches the freezing temperature (point B). If the liquid
metal does not consist of any impurities, it must be undercooled or supercooled (point B to C). As
nucleation begins (point C), latent heat of fusion is given off, and the temperature rises. This increase in
temperature of the undercooled liquid as a result of nucleation is known as recalescence (point C to D).
Solidification proceeds isothermally at the melting temperature (point D to E) as the latent heat given
off from continued solidification is balanced by the heat lost by cooling. This region between points D
and E, where the temperature is constant, is known as the thermal arrest. A thermal arrest, or plateau, is
produced because the evolution of the latent heat of fusion balances the heat being lost because of
cooling. At point E, solidification is complete, and the solid casting cools from point E to room
temperature.

If the liquid metal is well-inoculated, the extent of undercooling and recalescence is usually very small
and can be observed in cooling curves only by very careful measurements. If effective heterogeneous
nuclei are present in the liquid, solidification begins at the freezing temperature [Figure 3.3 (b)]. The
latent heat keeps the remaining liquid at the freezing temperature until all of the liquid has solidified and
no more heat can be evolved.

Figure.3.3 a): Under cooling or supercooling Figure 3.3 b): Cooling curve of a pure
metal

Nucleation:
Nucleation is the formation of the first tiny particles formed in the molten metal at the beginning of the
solidification. These tiny particles are known as nuclei. It is the beginning of the phase transformation
from liquid to solid phase.

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There are two types of nucleation

(i) Homogenous nucleation
(ii) Heterogeneous nucleation

Homogenous Nucleation:
When nucleation takes place in a liquid metal in a metal without the help of any impurities, then it is
known as homogeneous nucleation. Homogeneous nucleation occurs in perfectly homogeneous
materials such as pure liquid metals. It is the occurrence of ordered group of 2-3 atoms forming small
clusters called nuclei. For each nucleus so formed to be stable and to grow into crystal, it must reach a
certain size, called the ‘critical size’ or ‘critical radius’.

When solidification takes place, latent heat is released by the solidification released by the solidifying
atoms
This is given by
∆f v = −(4π r 3 / 3)∆Fv (1)

Where r= radius of the nucleus formed, ∆Fv = latent heat energy released per unit volume (-ve sign
because heat is released)

∆f s = 4π r 2 γ s = Surface free energy change

∆f = total freeenergy change

4
∆f v = − π r 3 ∆Fv = Volume free-energy
3
change

Figure 3.4 a) an interface is created Figure 3.4 b) Variation of Latent heat energy (volume
when a solid forms from the liquid free-energy), surface free-energy and total free-energy
with radius of particle (nucleus)

Whenever a new surface is formed, an energy known as the surface free-energy is associated with it. in
the melt, the surface energy associated with the newly formed nucleus is given by the relation,
2
∆f = −4π r γ
s s (2)
Where r is the radius of the nucleus, γs is the surface energy per unit area (+ve because heat is absorbed)
Thus the net energy change for a particle of radius r is given by

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∆f = ∆f v + ∆f s
∆f = −(4π r 3 / 3)∆Fv + 4π r 2γ s
(3)

Fig. 3.4(b), the top curve shows the parabolic variation of the total surface free-energy ( ∆ f s = 4π r 2 γ s ).
4
The bottom most curve shows the total volume free energy change term ∆fv = − π r 3 ∆Fv . The curve in
3
middle shows the variation of ∆f . It represents the sum of the other two curves as given by eq. (3). It is
also clear from the Figure. 3.4(b) that as the particle radius increases, the net free energy (∆f) also
increases till the nucleus reaches a critical radius ‘rc’ but with further increase in particle radius the free
energy decreases and even becomes negative. In order for the grain growth to take place around a
particular nucleus, it should have reached the critical radius.

The size of the critical, radius can be estimated by differentiating equation (3) with respect to ‘r’ and
equating to zero.

d ( ∆f ) d  −(4π r / 3)∆Fv + 4π r γ s 
3 2

= =0
dr dr

= −(4π r 2 )∆Fv + 8π rγ s = 0
2γ s
r = rc =
∆Fv
The net energy change for radius r* is given by substituting values of r* in eq. (3)

16 πγ s3
∆F =
3 (∆f v ) 2
Heterogeneous Nucleation:
When nucleation takes place in a liquid metal with the help of impurities, then it is known as
heterogeneous nucleation. Impurities could be insoluble matter like sand particles, alloy additions to
the solidifying metal, even mould walls or any other foreign agent deliberately added to bring about
nucleation and then begin the process of solidification.

Nuclei in heterogeneous nucleation are formed on the surfaces of the above possible surfaces often
called the substrate. But for nucleation to actually take place, if the possible surface should satisfy the
following requirements
i) The substrate surface must be actually wetted by the liquid metal. Imagine surface like
plastic which do not get wetted by water particles which fall on them, and hence do not hold
them.
ii) The contact angle θ of the cap-shaped nucleus should be less than 90° theoretically. In
general, all liquid particles resulting on flat or circular surfaces and wetting them will yield
angles less than 90°.

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In this type of nucleation, the first nuclei formed is considered as a spherical cap on a solid flat substrate.
The volume of this nuclei cap depends on the contact angle θ at the nuclei-liquid-substrate junction
which is as shown in Figure 3.5.

Figure 3.5 Heterogeneous Nucleation

The value of the surface energy will be considerably reduced in this case, so that the net force energy
required for nucleation is considerably lower. The change in free energy in this case is given by
∆F = V ∆Fv + ASLγ SL + π r 2γ SI − π r 2γ IL
where V is volume of spherical cap or nuclei, ASL is the interfacial surface area between liquid and cap,
R is the radius of cap, γ SL , γ SI , γ IL is the interfacial surface energies between cap-liquid, substrate-cap,
substrate –liquid. (Required for continuation of the solidification).

In heterogeneous nucleation, as the interfacial surface energy is much smaller, the size of nuclei formed
will also be very small. This type of nucleation does not require any super cooling. The critical particle
radius in this type of nucleation will be given by
2γ SL
r=−
∆F v
In this type of nucleation, the nucleation begins at comparatively higher temperatures itself.

CRYSTAL GROWTH:
After nucleation, growth will takes place. In general, growth is defined as the increase in size of the
nuclei or continuation of solidification. The process of growth determines the final grain size in the
solid.
The growth process depends upon the thermal conditions during the solidification and the constituted
alloys present in the material. During growth, each nuclei is the molten metal grows by the addition of
atoms to form crystals. This growth in the materials with takes place by diffusion of atoms from liquid
to solid phase. The rate of transformation or rate of solidification will obeys the Arrhenius equation, i.e.,
rate of transformation constant
−Q
RT
e where Q is activation energy, R is a constant, T it the absolute temperature.

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Cast metal structures:

In manufacturing components by casting, molten metals are often poured into moulds and permitted to
solidify. The mould produces a finished shape, known as a casting. In other cases, the mould produces a
simple shape called an ingot. An ingot usually requires extensive plastic deformation before a finished
product is created. A macrostructure sometimes referred to as the ingot structure, consists of as many as
three regions (Figure 3.6).

Figure 3.6 Development of the ingot structure of a casting during solidification: (a) nucleation
begins, (b) the chill zone forms, (c) preferred growth produces the columnar zone, and (d)
additional nucleation creates the equiaxed zone.

The rate of crystal growth during solidification is influenced by the degree of under cooling. Nucleation
is predominant in the early stages of freezing. As a result of this, the first layer of solid metal at the
metal-mould interface consists of fine grained equi-axed crystals. As solidification proceeds; the nuclei
grow with the release of latent heat of fusion from the liquid metal. The crystals are arranged in a
regular pattern, but each crystal will have its own orientation. Once the crystal grows fully, at the
expense of liquid metal, they come in contact at their surfaces. But due to mismatch in their orientations,
they will never unite, and form a weaker area called the grain boundary. Smaller the size of the grains,
larger is the area of mismatch and larger is the grain boundaries. The factors which control the type of
cast metal structure are:
1. temperature of the melt and pouring temperature
2. melt composition, presence of impurities and alloying elements
3. The type of mould, like metal, sand, etc.

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4. Solidification conditions.
Basically there are three types of cast metal structures are obtained. They include,
a. columnar grains
b. Equi-axed grains
c. combined equi-axed and columnar grains
Columnar Grains: Columnar grains are long and coarse in sizes that grow perpendicular to the mould
walls. Such grains are grown generally in metal moulds, and where the thermal gradients are very high.
When a molten metal is poured into a metal, mould, equi-axed fine grains are formed immediately by
spontaneous nucleation and quick crystal growth due to chilling action of the mould wall leading to
large under cooling. The molten metal adjacent to the solidified skin with few nuclei will start
solidifying and growing perpendicular to the mould wall as the heat is transferred from the metal to the
mould wall in that direction. The columnar crystals, under these conditions, continue to grow and meet
at the mould centre. A typical cast metal structure with columnar crystals is shown in Figure 3.7b. Such
a grain structure is common in pure metals.

Equi-axed Grained Structure: When a molten metal undergoes a large amount of supercooling, like in
pure metals, the cast metal structure will have equi-axed grains. This requires uniform rate of nucleation
throughout the metal, and a uniform crystal growth condition. In the case of alloys undergoing
heterogeneous nucleation, the presence of impurity/foreign atoms helps in the formation of stable nuclei
uniformly throughout the melt and under controlled solidification conditions; equi-axed grains are
formed. A cast metal structure will equi-axed grains is schematically shown in Figure 3.7c.

a) Columnar Grains b) Combined equi-axed and c) Equi- axed

columnar
Fig. 3.7 Cast metal structures:

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Combined equi-axed and columnar crystals: Exhibit fine-grained crystals at the outer skins adjacent
to the mould walls. In an alloy (Figure3.7 c) the solidification initially occurs at the metal mould surface
by chilling action, with fine-grained structure. However, the presence of other metal (solid solution) at
the centre also causes nucleation (heterogeneous) leading to the grain formation and growth. The liquid
metal in between the outer skin and the central metal (both equi-axed) start receiving the latent heat of
fusion and slow down the nucleation and growth process. This leads to the formation of columnar
crystals. The grains in the mould centre have slightly bigger sizes because of slow rate of heat
dissipation as, compared to the skin at the mould walls.
.
SOLID SOLUTIONS:
A solid solution is a solution in solid state. It is the mixture of two or more materials in the solid state.
All alloys are solid solutions. In a solid solution, the metal in the major proportion is called the solvent
and the metal in the minor portion is called the solute. Example: Cu-Ni, Au-Ag etc.

Classification of solid solution

1. Substitutional solid solutions
2. Interstitial solid solutions

Substitutional solid solutions

During the formation of solid solutions, if the solid solution is formed by the substitution of atoms of
one metal by the atoms of other metal is known as substitutional solid solution.(the solute atoms
substitute the atoms of the solvent in the crystal structure of the solvent). For example in Au-Ag solid
solution, the silver atoms substitute for the gold atoms in the FCC structure of gold.

Figure 3.8
Depending upon the arrangement of atoms during the formation of solid solutions, it has been classified
into
a) Ordered substitutional solid solutions
b) Disordered substitutional solid solutions

Ordered substitutional solid solutions

In this type, the solute atoms substitute the solvent atoms in an orderly manner, taking up fixed
positions of symmetry in the lattice. Therefore this type of solid solutions has an uniform distribution of
solute and solvent atoms.

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Figure 3.9(a): Schematic diagram showing Ordered Substitutional Solid Solution

Disordered substitutional solid solutions:

The solute atoms here do not occupy any fixed positions but are distributed at random in the lattice
structure of the solvent. In this typed solid solution, the concentration of solute atoms may vary
considerably throughout the lattice structure.

Figure 3.9 (b): Schematic diagram showing Disordered Substitutional Solid Solution

HUME-ROTHARY RULES:
These rules govern the formation of substitutional solid solurtions. In other words, only words, Only
these rules are satisfied, a substitutional solid solution can form.

Crystal structure factor:

b) of both solvent and solute material should be same
For complete solid solubility, the crystal structure
structure. For example Au-Ag solid solution, both have FCC structure.

Relative size factor:

The atoms of the solute and the solvent materials must be approximately of same size. If the size varies
more than 15%, the substitutional solid solution will not form.

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Chemical –affinity factor:

For a substutional solid solution to form, the two metals should have very less chemical affinity. Greater
the chemical affinity between the two metals, lesser are the chances of forming a solid solution.

Relative valence factor:

The solid solubility is greatly affected by the relative valency of the metals. Only when there is some
relative valency between the two metals, the substitutional solid solution can form. The metal with the
lower valency tends to dissolve more of a metal of higher valency than vice-versa.

For example in the Al-Ni alloy system, both the metals are Face Centred Cubic and their elative size
difference is less than 15%. However Nickel which has a valency or two dissolves 5% Aluminium,
while on the other hand Aluminium (which has a valency of three) dissolves only 0.04% Ni.

Interstitial solid solution:

While forming a solid solution, if atoms of one metal (solute) is very very much less than the atoms of
other metal (solvent), then solute atoms occupy interstitial positions in between the solvent atoms; the
solid solution formed in this way is known as interstitial solid solution as in Figure3.10.
For example: Ferrous materials where Carbon atoms occupy the interstitial position between Fe atoms.

Figure 3.10: Schematic diagram showing Interstitial Solid Solution

Difference between Substitutional & Interstitial Solid Solutions:

The important difference between substitutional and interstitial solid solustions are follows.

1. Atomic position: in substitutional solid solutions, the solvent atom in the lattice are replaced by the
solute atoms, while in interstitial solid solutions the solute atoms occupy the interstices (gaps
between the atoms i.e., inter-atomic space) in the lattice structure.

2. Size of Atoms: In substitutional solid solutions, the atoms of solvent and sloulte need to be same
size for the solid solubility to take place. The relative size factor of 7 to 15% is a favourable factor
of good solid solubility. In interstitial types, the solute atoms must be very small (less than 1 A), so
that they can conveniently occupy the spaces between solvent atoms. FCC structures have more

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spacious interstices as compared to BCC structures and hence solvent atoms with FCC structure
have good solubility.

Intermediate Phases:
An intermediate phase is nothing but a compound and is made up of two or more elements of which
at least one of them is a metal. A compound as we generally know, is atoms of different elements
are combined in define proportions and are expressed by chemical formulae Eg. H2O, NaCl. The
atoms here have combined to form the molecule, which is the smallest unit of the compound. The
atoms are held together by ionic or covalent bonds which are quite strong. And this explanation of a
compound holds good for an intermediate phase too expect that one of the elements here is a metal.
When a compound or an intermediate phase is formed, the elements lose their individual identity
and properties to a great extent and the compound will have its own characteristic physical,
mechanical and chemical properties. Na and Cl provide a good contrast from their individual
properties to their properties as a combination.

Most intermediate phases are crystalline in nature, exhibit definite melting points and have the same
cooling curves as pure metals. With reference to phase diagrams, intermediate phase whose
chemical composition are intermediate between the two pure metals and generally have a crystal
structure different from those of the pure metal.

Intermetallic compounds of valency compounds:

These are formed usually between chemically dissimilar metals based on chemical valence laws
and hence the name valency compounds. There compounds have strong bonding (ionic or covalent),
and show non-metallic properties. They have poor ductility, poor electrical conductivity, with
complex crystal structures. Fe3C is an example of such an intermetallic compound. This forms a
chemically complex orthorhombic lattice with Fe and C atoms in the ratio of 3:1. Also, these
compounds have a higher melting point than their parent metals.

Interstitial compounds: These are similar to interstitial solid solutions expect that they have more
or less a fixed composition. Eg. Fe3C, TiC. The interstitial compounds are metallic in nature, have
high melting points and are extremely hard.

Electron Compounds:
These compounds are of variable composition and do not obey the valency law, but have a definite
electron to atom ratio. For example in the compound Cu9Al4, each atom of copper has one valence
electron and each atom of aluminium has three valence electrons. So that 13 atoms which make up
the compound have 21valence electron to atom ratio being 21:13.
Many electron compounds have properties these of solid solutions, they exist in wide range of
composition, have high ductility and low hardness.

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PHASE DIAGRAM
Phase (P): A phase can be defined as a physically distinct and chemically homogeneous portion of a
system that has a particular chemical composition and structure.
Water in liquid or vapor state is single phase. Ice floating on water is an example two phase system.
Similarly other examples are:

Gases Gaseous state always a single phase mixed at atomic or molecular level Liquids

Liquid solution is a single phase e.g. NaCl in H2O

Liquid mixture consists of two or more phases e.g. Oil in water (no mixing at the atomic/molecular
level)

Component (C) : It is the smallest number of independent variable constituents taking part in the state
of equilibrium. For example Steel, which is an alloy of Iron and Carbon, has two chemical substances;
hence it is a two components in a system, and binary system. If there are three components in a system,
it is called a ternary system.
E.g.

Au-Cu system : ComponentsAu, Cu (elements)

Ice-water system : ComponentH2O (compound)

Al2O3 –Cr2O3 system : ComponentsAl2O3, Cr2O3

Gibbs Phase rule

The number of degrees of freedom, F (no. of independently variable factors), number of components, C,
and number of phases in equilibrium, P, are related by Gibbs phase rule as
F=C–P+2
Number of external factors = 2 (pressure and temperature).
For metallurgical system pressure has no appreciable effect on phase equilibrium and hence,
F=C–P+1
Degrees of Freedom: The number of degrees of freedom of a system is the number of variables that
may be changed independently without causing the disappearance of the a phase. In other words the
equilibrium of a system is not disturbed by altering the variable. These variable may be external
(temperature, pressure) and internal (components).

The number of degrees of freedom is essentially the number of independent variables, both internal
(composition and phases) and external ones (temperature, pressure, concentration etc.), which can be
changed without changing the number of phases in equilibrium. The number of degree of freedom
cannot be less than 0
C+1-P ≥ 0
P ≤ C+1
It means that the number of phases in a system cannot exceed the number of components plus one.

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COOLING CURVES
A cooling curve is a line graph that
represents the change of phase of matter,
typically from liquid to a solid.
The independent variable (X-axis) is time
and the dependent variable (Y-axis) is
temperature. Figure 3.11 shows three types
of cooling curve, these cooling curves are
very useful to study the different
transformations which occur during
solidification and other changes which
takes place during solidification.

Figure 3.11 Cooling Curve

They are 3 types of cooling curves.
a) Cooling curve for pure metal
b) Cooling curve for binary alloy
c) Cooling curve of binary eutectic alloy

a) Cooling curve for pure metal :

(i) Curve shown in Figure 3.11 (a) represents the solidification of pure metal. Curve AB indicates
the cooling of molten metal. The solidification will begin at point B.
(ii) Curve BC, the solidification begins at Band completes at C. During this, the metal liberates the
latent heat of fusion. In between B & C, the metal will be in the intermediate solid + liquid
phase.
(iii) Curve CD indicated the solid metal cools to room temperature. The slope of lines AB and CD
indicate specific heat of liquid and solid metals, respectively.

b) Cooling curve of binary alloy

When two or more metals are mixed in liquid state to form an alloy and allowed to cool, the
solidification occurs over a range of temperature. Figure 3.11(b) shows a cooling curve for an alloy of
metals A and B.
i) Curve AB indicates cooling of molten metal
ii) Curve BC- The solidification begins at B and it completely solidifies at C. In this the temperature
do not remain constant, but drops along BC as the alloy cannot solidify at a particular temperature

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but solidifies along a complete freezing range. It is due to the change in the composition of
material resulting in the varying freezing points. In this freezing range varies with variation of
composition of alloys.
iii) Curve CD indicates the solid metal cools to room temperature.
c) Cooling curve for binary eutectic alloy.
Figure 3.11(c) is the freezing curve for another binary system whose two components are completely
soluble in liquid state but not at all soluble in solid state. They are liquid along AB up to point B of the
cooling curve. At point B the component whose Melting point is higher starts to solidify. And the
temperature drops along BC, maintaining a freezing range during solidification. At point C, a particular
composition of material is reached [known as eutectic composition] where in, at this composition, the
material solidifies as pure metal. At this temperature both the components solidifies simultaneously at
constant temperature. At D the only phase that is present is solid and cools along DE as usual. Point D
on the curve is called as eutectic point.

Phase Diagram:
The study of phase relationships plays an important and vital role in the better understanding of the
properties of materials. Much of the information about the control of microstructure or phase structure
of a particular alloy system is properly displayed in what is called a phase diagram, also called as an
equilibrium or constitutional diagram.

Phase diagrams are clear maps that give the relationships between phases in a thermodynamic
equilibrium system as a function of temperature, pressure and composition. The phase diagram is drawn
as temperature on Y-axis and composition on x-axis. The phase diagram not only shows the relationship
between the composition, temperature and the phases, but it also gives information about phase
composition and phase stability.

There are 3 types of phase diagrams:

a) Unary phase diagram
b) Binary phase diagram
c) Ternary phase diagram

a) Unary phase diagram: It is a single component phase diagram wherein usually the pressure will
be taken on y-axis and temperature on x –axis. The simplest phase diagram is the water which is a one
component system. It is also known as pressure-temperature or P-T diagram. Two phases exist along
each of the three phase boundaries. At low pressure (0.006 atm) and temperature (0.01 °C) all the
three phases coexist at a point called triple point.

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Figure: Water phase diagram

b) Binary phase diagram: It is a two component system. In this the temperature will be taken on y-
axis and composition on x-axis. Binary phase diagrams are most commonly used in alloy designing.
The simplest binary system is the Cu-Ni which exhibits complete solubility in liquid and solid state.

Cu-Ni equilibrium phase diagram

The line above which the alloy is liquid is called the liquidus line. At temperature just below this line crystals
of α solid solution start forming.

The line below which solidification completes is called solidus line. Hence, only α solid solution exists at
any temperature below the solidus line.

The intermediate region between liquidus and solidus lines is the two-phase region where liquid and solid
coexist.

It can be noted that the two metals are soluble in each other in the entire range of compositions in both liquid
and solid state. This kind of system is known as ‘Isomorphous’ system.

The Tie line

The composition of phases in the two-phase region is not same. To find the composition of the
individual phases in the two phase region, a horizontal line (XY), called tie line, is drawn and its
intercepts on the liquidus and solidus lines, Cl and Cs, are taken as the composition of the liquid and
solid respectively.

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Lever rule
The relative fractions of the phases at a given temperature for an alloy composition Co is obtained by
the lever rule. This rule gives the fraction of a phase by the ratio of the lengths of the tie line between
Co and composition of the other phase to the total length of the tie line. For example, fraction solid, fs
is given by similarly fraction liquid, fl
MX CO − Cl
fs = =
XY Cs − Cl
Similarly frction liquid fl
MY Cl − Co
fl = =
XY Cs − Cl

Ternary phase diagram: It is a three component phase diagram. In this, the phase diagram will be
visualised as a 3-sided prism.
Construction of a phase diagram:

Fig. 3.12Phase diagram construction from cooling curves

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A phase diagram can be obtained by plotting the cooling curves at different compositions of an alloy.
For example consider a binary solid solution; let it has been mixed at different temperatures and
compositions in the liquid state and cooled to room temperature.

Consider for example, a binary alloy system comprising two metals Cu(X) and Ni(Y). For simplicity,
let us take six compositions - pure metal X, 80X-20Y, 60X-40Y, 40X-60Y, 20X-80Y, and pure metal Y.
The cooling curves for all these compositions and plot them on the same graph as shown in Fig.3.8
Consider briefly how these diagrams are constructed. Pure metals X(Cu) and Y(Ni) have solidified Tmx
(curve AB) and Tmy (curve A4B4) respectively, while the rest or the alloy compositions have solidified
over a range of temperature, like A1B1, A2B2 etc. the upper points A1, A2, A3, and A4, indicates the
melting points while the lower points B1,B2,B3, and B4 indicates the freezing points of the respective
compositions. Now, knowing the melting/freezing points for different compositions, we can construct
the phase diagram (temperature versus alloy composition) as shown in fig b. first, mark the alloy
composition 100X-Y, 80X-20Y, 60X-40Y, 40X-60Y, 20X-80Y, and 0X-100Y on the x-axis. Transfer
the melting and freezing points A(B), A1, A2, A3, A4, B1 B2, B3, and A4(B4) on to their respective
compositions. If all the points A(B), A1, A2, A3, and A4(B4) joined result is a line known as the liquidus,
which indicates the temperature at which any given alloy will begin to solidify. The resulting curve we
get the upper curve called liquidus. Likewise, by joining the points A(B), B1,B2,B3, and A4(B4) the
solidus line, which is the temperature at which any given alloy will become completely solid, is
obtained. In other words, at all temperatures above the liquidus, the alloy will be a liquid, and at all
temperatures below the solidus, the alloy will be a solid. The resulting diagram called the phase diagram
for the given alloy. The region within the liquius and solidus represents the two phase region (mushy
layer), in which the solid crystals of homogeneous solid solutions are in equilibrium with the liquid of
suitable composition (i.e. α +L). Above the liquids line the system will have only a single liquid phase
(L) and below the solidus line it will have a single solid phase ( α )

Interpretation of phase diagram:

A binary phase diagram can be used to determine three important types of information:
• The phases that are present
• The composition of the phases
• The percentages or fractions of the phases

The phase that are present (Prediction of Phases): The phases that are present can be determined by
locating the temperature-composition point on the diagram and noting the phase(s) present in the
corresponding phase field. For example, an alloy of composition 30wt%Ni-70wt%Cu at 1316 °C would
be located at point A. Because this point lies totally within the liquid field, the alloy would be a liquid.
For the same alloy at 1093 °C, point C is within the solid-solution α field; only the single α phase
would be present. On the other hand, a 30wt%Ni-70wt%Cu alloy at point B (1188 °C) would consist of
a two-phase mixture of solid α and liquid L.

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Fig 3.13 Copper-Nickel Phase diagram

Prediction of Chemical Compositions of Phases (The composition of the phases): To determine the
composition of the phases present, locate the point on the phase diagram. If only one phase is present,
the composition of the phase is the overall composition of the alloy. For example, for an alloy of
30wt%Ni-70wt%Cu at 1093 °C (2000 °F), designated as point C, only the α phase is present, and the
composition is 30wt%Ni-70wt%Cu. For an alloy having a composition and temperature located in a
two-phase region, draw a horizontal tie line between the two phase boundaries at the temperature of
interest. Drop perpendicular lines from the intersections of each boundary down to the composition axis
and read the compositions. For example, again consider the 30wt%Ni-70wt%Cu alloy at 1188 °C
located at point B and lying within the two-phase α + L field. The perpendicular line from the liquidus
boundary to the composition axis is 20wt%Ni-80wt%Cu, which is the composition CL of the liquid
phase. In a similar manner, the composition of the solid-solution phase C α is read from the
perpendicular line from the solidus line down to the composition axis, in this case 35wt%Ni-65wt%Cu.

Prediction of Amounts of Phases. The percentages or fractions of the phases present at equilibrium
can also be determined with phase diagrams. In a single-phase region, because only one phase is present,
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the alloy is comprised entirely of that phase; that is, the phase fraction is 1.0 and the percentage is 100%.
From the previous example for the 30wt%Ni-70wt%Cu alloy at point C at 1093 °C (2000 °F), only the
α phase is present, and the alloy is 100% α. If the composition and temperature position is located
within a two-phase field, a horizontal tie line must be used in conjunction with the lever rule. First, a tie
line is drawn across the two-phase region at the composition and temperature of the alloy. The fraction
of one phase is determined by taking the length of tie line from the overall alloy composition to the
phase boundary for the other phase and dividing by the total tie line length. The fraction of the other
phase is then determined in the same manner. If phase percentages are desired, each phase fraction is
multiplied by 100. When the composition axis is scaled in weight percent, the phase fractions computed
using the lever rule are mass fractions—the mass (or weight) of a specific phase divided by the total
alloy mass (or weight). The mass of each phase is computed from the product of each phase fraction
and the total alloy mass.

Again, consider the 30wt%Ni-70wt%Cu alloy at 1188 °C (2170 °F) located at point B containing both
the solid α and the liquid L phases. The same tie line that was used for determination of the phase
compositions can again be used for the lever rule calculation. The overall alloy composition located
along the tie line is C α - CL or 35 - 20 wt%. The weight percentage of liquid present is then:

Likewise, the amount of solid present is:

APPLICATION OF GIBB’S PHASE RULE

If we consider a binary solid solution, where the number of component, C=2, from the phase rule, the
number of phases existing simultaneously in a binary system cannot be more than three (P ≤ C+1
=2+1=3). These three phases can only exist at a definite phase composition and a definite temperature.
If the number of phases in a binary system turns out to be more than three, this means that either the
alloy is not in the equilibrium state or the number of phases and constituents has been determined
incorrectly.

The phase diagram shown in Figure 3.14 has 3 regions. Applying the Gibb’s phase to each of these
regions we get:

This is a binary system (C = 2). The two components are Cu and Ni. We will assume constant pressure.
Therefore, Equation (1 + C = F + P) can be used as follows.

Region(1) For example, At 1300°C, P = 1, since only one phase (liquid) is present; C = 2, since both
copper and nickel atoms are present. Thus,
1 + C = F + P ‹ 1 + 2 = F + 1 or F = 2 (the degree of freedom are two)

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This means that temperature and composition can be varied independently up to a certain extent without
disturbing the equilibrium of the system i.e., causing the disappearance of the liquid phase.

Region(2): For example, At 1250°C, P = 2, since both liquid and solid are present; C = 2, since copper
and nickel atoms are present. Now,
1 + C = F + P ‹ 1 + 2 = F + 2 or F = 1 (the degree of freedom is one)

This means that only one variable can be varied keeping the other constant without disturbing the
equilibrium of the system. Here at a constant temperature, say T°C as shown in Figure 3.14, the
composition can be varied between the points O and P without disturbing the nature of the two phases
solid and liquid. At a constant composition, if temperature is varied, the relative compositions of the
solid and liquid phase are disturbed. Hence there is only one degree of freedom i.e., composition.

Region(3): For example, At 1200°C, P = 1, since only one phase (solid) is present; C = 2, since both
copper and nickel atoms are present. Again,
1 + C = F + P ‹ 1 + 2 = F + 1 or F = 2 (the degree of freedom are two)
And similar to region 1,we must fix both temperature and composition to completely describe the state
of the solid.

At solidification temperature, a pure metal is a one-component system consisting of two phases of

identical composition
F=1+2–2=0

Clearly, the number of phases and number of degrees of freedom equals zero, i.e. F = 0. This is known
as non-variant or invariant equilibrium. This means that if the temperature is changed the two phase
mixture will become all solid or all liquid while there is no question of changing the composition
because it is a single component system.

When the number of phases is less than the maximum possible number by one, the number of degrees
of freedom will also increase by one (F = 1). Such type of system is called as monovariant.
When F = 2, the system is said to be a divariant. Obviously, a system may be in equilibrium at different
temperatures and concentrations.

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1500

Region (1) Ni

1400
Region (2)

1300

T °C O P
------------------------------
Temperature °C

1200

Region (3)
1100
Cu

1000
Cu 20 40 60 80 Ni
Weight percent Nickel

Figure 3.14: The equilibrium phase diagrams for the Cu-Ni

EQUILIBRIUM DIAGRAMS:
The equilibrium diagram is the diagram which shows the different phases of an alloy as a function of its
composition and temperature under equilibrium conditions. Depending on the relation between the
components in liquid and solid phase, this is classified as,
I. Components completely soluble in the liquid states
a) and completely soluble in the solid state
b) but partially soluble in the solid state (eutectic reaction).
c) But insoluble in the solid state (eutectic reaction).
d) The Peritectic reaction
II. Components partially soluble in the liquid state
a) but completely soluble in the solid state
b) and partially soluble in the solid state
III. Components completely insoluble in the liquid state and completely insoluble in the solid state
A study of these diagrams will illustrate basic principle which may be applied to understand more
complex alloy systems.

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The equilibrium diagram for two metals completely soluble in liquid and solid states
(Isomorphism system):
In this type, since both the metals are completely soluble in the solid state, only substitutional type of
solid solution will be formed in the solid phase. These alloys generally will have metals of same type of
crystal structure and one of the metals will have atomic radius less than 8% of the other element. The
examples of this type alloys are Cu-Ni, Ag-Au, Cr-Mo, W-Mo, etc.

1453°C

y
y x

l
T1°C----------------------
T2°C ----------------------m
T3°C---------------------- n
T4°C ---------------------- o

Fig. 3.15 The change in structure of Cu-40% Ni alloy during equilubrium solidification.
(The Nickel and copper atoms must diffuse during cooling in order to satisfy the phase diagram and produce a uniform
equilibrium structure)

The phase diagram of Cu-Ni systems is illustrated in Fig. 3.10. Pure copper and poor nickel solidify at
1083°C and 1453°C respectively. Cu-Ni alloys of various combinations solidify over a range of
temperatures as shown in the figure. The phase diagram of this type of alloy is the most simple of all
other systems. It consists of two lines only, the upper i.e., liquidus and the lower i.e., solidus. Any given
point on the liquidus line represents the temperature and composition of an alloy, which is completely in
liquid phase. Any point on the solidus gives the temperature and composition of the alloy in a solid
phase. The phase between these two lines represents the region in which both liquid and solid phases
co-exist. By applying Gibbs phase rule (P+F=C+1) to the single phase above the liquidus and below the
solidus, we get-
P+F=C+1
i.e., 1+F=2+1
or F=2
Hence, the system is bi-variant and thus both temperature and composition can be varied independently
within limits without affecting the structure. In between the liquidus and solidus, where both liquid and
solid phases co-exist (i.e., number of phases=2).
P+F=C+1
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2+F=2+1
Or F=1
Hence, the system of univariant, thus temperature and composition cannot be altered independently
without a loss of equilibrium. Any change in temperature is accompanied by a corresponding change in
composition, and vice versa, otherwise the balance between the proportions of the phases will get upset.

The solidification of an alloy containing 60% Ni and 40% Cu can be explained with the help of the
vertical line xy (Figure. 3.15)
At T1°C - Solidification begins at point l.
T2°C -Solidification is in progress. At point m the solid portion contains 24% Cu and 76% Ni while
the liquid phase is made up of 55% Cu and 45% Ni (approx)
T3°C - Solidification is nearing completion. Liquid phase at n contains 66% Cu and 34% Ni and solid
phase contains 37% Cu and 63% Ni.
T4°C - Solidification is complete with solid solution containing 40% Cu and 60% Ni.

EUTECTIC REACTION:
In the solidification of a binary alloy, the liquid solution of a fixed composition will solidifies at a
constant temperature forming a solid solution with two solids phases. These types of reaction are known
as Eutectic reaction. This process reverses on heating.

This eutectic reaction takes place in an alloy at a particular fixed composition known as Eutectic
composition and this will solidifies at a very low temperature than all other compositions. This
temperature is called Eutectic temperature.

At this eutectic temperature, the two solid phases will be formed from a single liquid phase. The
eutectic temperature and eutectic composition marks a particular point on the phase diagram known as
eutectic point.

The system in which the two metal completely soluble in liquid phase; completely insoluble in solid
phase or partly soluble in solid phase come under this category of eutectic reaction.

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The Equilibrium diagram for the two metals completely soluble in liquid state and totally insoluble
solid state:

Fig. 3.16 Phase diagram of Bi-Cd System

The phase diagram of a Bi-Cd alloy is shown in Fig.3.16.

Pure Bismuth solidifies at 271°C and pure Cadmium solidifies at 321°C.
At 144°C, the 60%Bi-40%Cd alloy solidifies like a pure metal, and is called as an eutectic alloy, the
temperature at which it solidifies is called the eutectic temperature144°C, and the composition as the
eutectic composition.
The alloys to the left of eutectic composition are called hypoeutectic alloys and to the right as
hypereutectic alloys. The phase diagram consists of two sloping liquidus lines AE and BE both
meeting at the eutectic point ‘E’. The solidus line is always a continuous line connecting the melting
points of the pure metals and the eutectic alloy that is the line ACEDB.
The phase diagram consists of four areas. The area above the liquiaus is a single homogeneous liquid
solution, since the two metals are completely miscible in the liquid state. The remaining three areas are
two-phase areas as shown in the Fig.3.16.

Solidification of Hypoeutectic Alloy1 ( 25%Bi and 75% Cd):

Consider the solidification of a 25%Bi and 75% Cd alloy, indicated by XX line in figure. The
crystallisation is schematically represented on the right side of the phase diagram. This alloy starts to
solidify at T°C where the line meets the liquids line AEB. At the beginning of solidification the
material which is in excess will begins to solidify first, so at this temperature dendrites of pure
cadmium begin to form and the rest of the liquid becomes correspondingly richer in Bismuth. As the
composition moves down along BE, say X1, with further fall in temperature to T1, more pure cadmium
will crystallise. This crystallisation continues till the temperature reaches 144°C, at which the
remaining liquid contains 60% Bi and 40% Cd, the eutectic composition.

Solidification of a hypereutectic alloy2 (80%Bi and 20%Cd):

Consider the solidification of an alloy of 80%Bi and 20%Cd shown by YY line in figure. Initially the
process starts with the formation of primary dendrites of bismuth below the point. Since, Bismuth has
been rejected from solution the alloy becomes correspondingly richer in cadmium so that the
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composition moves down along the liquidus line AE, and towards eutectic E. Finally, liquid contains
60% Bi and 40% Cd, the eutectic temperature 144°C and solidify as a eutectic alloy.

Hence in these systems, any solution of composition on either side of eutectic point will first deposit
the metal which ever in excess of the eutectic composition in the form of primary crystals until the
liquid reaches the eutectic composition at 144°C. Also, in the eutectic portion of these alloy the
alternate layer of pure metals can be readily seen by even a low power microscope, thus indicating the
complete insolubility in the solid state.
At the eutectic point three phases i.e., liquid, solid cadmium and solid bismuth co-exist in equilibrium.
Hence, there are two components and three phases. By applying Gibbs phase rule,
P+F=C+1
i.e., 3+F=2+1
or F=0.
Since the degree of freedom is zero, the system is invariant, which
means, if either the composition or temperature are altered, at least
one of phases will disappear.

The Equilibrium diagram for the two metals completely soluble in liquid state but partially
insoluble in solid state:

Fig. 3.17 Cu-Ag Eutectic System

The equilibrium diagram of this system is as shown in the figure example Cu and Ag alloy.

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As in this system, the components have some solubility in each other in the solid state also; two solid
solution will be formed. They are
a) solid solution of B in A is α ( where A is solvent and B is solute)
b) Solid solution of A in B is β ( where B is solvent and A is solute)

Solidification of alloy 1 (28% Cu and 72% Ag)

TE = the homogenous liquid mixture of A and B begins and completes solidification at this constant
temperature with layers of α and β forming a lamellar eutectic structure.
At any temperature below eutectic point C all the grains are of pure eutectic (α+ β). The eutectic
point here is also an invariant point.

Solidification of alloy 2 (70%Cu and 30% Ag):

T1°C -solidification begins with solid solution α precipitating out of the liquid.
T2°C -solidification continues with the formation of α. At point M the composition of the solid
solution portion is obtained by extending the line up to solidus and brining it down to x-axis
and the composition of the remaining liquid is obtained by extending the line up to liquidus
and bringing it down. It is also to be noted here that as solidification progresses, the
composition of α continuously changes and moves along the line AB while the composition
of remaining liquid moves along the slope AC.
TE - as the temperature comes down and approaches eutectic temperature, the composition of the
remaining liquid approaches the eutectic composition of 28% Cu and 72%Ag. Since the
tendency of liquid metal reaching eutectic composition would be to freeze as a lamellar eutectic
structure, the final structure would be contain α grains which are already solidified and eutectic
grains (α+ β).

Solidification of alloy 3(95%Cu and 5%Ag):

1083°C - Melting temperature of pure copper.
T3°C- Solidification begins with solid solution α precipitating out of liquid.
T4°C- Solidification is complete with all the grains being α between o and P.
TE°C- At this temperature a maximum of 80% Ag can dissolve in Cu to form solid solution α.
T5°C - At this temperature the amount of Ag that can dissolve in Cu decreases. Hence the excess Ag
comes out along with some Cu and forms the eutectic (α+ β) below point P.

Solidification of alloy 4 (15% Cu and 85% Ag)

961°C - Melting temperature of pure sliver.
T6°C - Solidification begins with solid solution β precipitating out of the liquid.
TE°C - Since the remaining liquid approaches eutectic composition, the final structure at any
temperature below TE°C would contain β grains and eutectic (α+ β) grains.

Solidification of alloy 5 (5% Cu and 95% Ag):

T7°C - Solidification begins with the formation of β.
T8°C - Solidification is complete with all grain being β.
TE°C -At this temperature a maximum of 9% Cu can dissolve in Ag to form β.

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T9°C -At this temperature the amount of Cu that can dissolve in Ag decreases. Hence the excess Cu
comes out of β along with some Ag and forms the eutectic (α+ β) below the solvus line DG.
(A solvus line is the one which separates single phase and two phase solid regions)

Peritectic Phase diagram

During the solidification of an alloy, if a solid phase formed first due to cooling reacts with the
remaining liquid phase and forms a new solid phase of different structure, then this type of reaction or
process is known as peritectic reaction and it reverses on heating.
Solid1 + Liquid New solid2
This peritectic reaction takes place at peritectic temperature and at peritectic composition; where there
two lines meet, denotes by point ‘P’ known as peritectic point.

Alloy 2
Peritectic systems Pt-Ag, Ni-Re, Fe-Ge,Sn-Sb (babbit)

Alloy 1

Alloy 1

Figure 3.18

The peritectic reaction will occur during slow rate of cooling. Eg., platinum alloys (Ag-Pt alloys). The
equirlibrium diagram which shows the pertectic reaction is as shown in Figure 3.18. The peritectic
reaction will takes place at peritectic tempereature Tp and peritectic composition.

This equilibrium diagarams can be interpreted by considering solidification composition alloys.

These alloys are also partly soluble in the solid state. So, the solid solution of of B

Solidification of alloy1:
This alloy starts to solidify at T1°C. As the proportion of metal ‘A’ is more, the first solid solution
formed will be the α . The formation of α will continues until it reaches the peritectic temperature
Tp.At Tp the peritectic reaction will takes place wherein the remaining liquid will react with the solid

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solution forming already α forming a new solid δ . As the proportion of the α is more, compared to
the liquid remaining at the peritectic temperature Tp, the final solid solution formed will be the solid
solution α + δ .

Solidification of alloy 2:
The solidification of this alloy will takes place below the peritectic temperature Tp. as the proportion of
metal ‘B’ is more, the solid first formed will be solid solution β . As the temperature is less than the Tp,
the simultaneous peritectic reaction will takes place where in the β formed will immediately react with
the liquid present, forming the solid solution δ . So, the final solid solution formed will be only the solid
solution δ

Eutectoid Transformation
It is the solid to solid transformation reaction. It is an isothermal reversible reaction in which a solid
solution at higher temperature is converted into two solids on cooling. The number of solids phases
formed after cooling will depends upon the number of components in the system.

The temperature at which this reaction takes place is known as eutectoid temperature and the
composition in known as eutectoid composition; and where these two lines meet, the point is called
eutectoid point E.
Alloy 2

Figure 3.19
The equilibrium diagram which shows eutectoid reaction is shown in Figure 3.19. The eutectoid
reaction will takes place in the solid phase of the material as it is the solid to solid transformation
reaction.

Transformation of alloy 1
This alloy will completely solidified at solidus line forming the solid solution γ with further
decrease in temperature when it crosses the solvus line, the solid to solid transformation begins at
Y3. As the percentage of metal ‘A’ is more, the first transformation product formed will be solid
solution α . The transformation of solid solution γ into α will continues until it reaches the

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eutectiod temperature TE , the eutectoid reaction will takes place, there by, at this temperature, the
remaining solid solution γ will transformed into eutectoid mixture α + β . The final solid solution
formed will consists of solid solution α and the eutectoid mixture α + β .

Transformation of alloy 2
This alloy will be completely solidified at solidus line forming the solid solution γ . With further
decrease in temperature, when it crosses the solvus line, the solid to solid transformation begins at
X1.
As the percentage of metal ‘B’ is more, the first transformation product formed will be solid
solution β . The transformation of solid solution δ into β will takes place or continues until it
reaches the eutectoid temperature TEu°C. At TEu°C, the eutectoid reaction will takes place, there by,
at this eutectoid reaction will takes place, there by, at this temperature, the remaining solid solution
δ will transformed into eutectoid mixture α + β . The final solid solution formed will consists of
solid β and the eutectoid mixture α + β .

Peritectoid Transformation
The peritectoid reaction is similar to that of peritetic reaction. In this the reaction takes place in the
solid state of material.
In this reaction, the solid phase reacts with another solid phase forming a new solid phase. It can be
reversed. It is represented as

Figure 3.20

The equilibrium diagram which shows the peritectoid reaction is as shown in Figure 3.20. This
equilibrium diagram shows the liquidus and the solidus lines and also the solvus lines. This diagram
lines and also the solvus lines. The diagram also shows peritectoid temperature peritectoid composition
and peritectoid point.

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IRON CARBON SYSTEM

Introduction:
Steels and Cast irons are among the most extensively used range of engineering materials in the world
today. They are essentially iron-carbon alloys and hence of all binary alloys systems, the one that is
most important is the Iron-Carbon. Iron and carbon upto a percent of 2%C and remaining Fe, is known
as Steel. The carbon percentage above 2% upto 6.67% is known as Cast iron.

Iron in the pure form, usually known as ingot-iron, basically consists of:
Carbon 0.012%, Manganese 0.017%, Phosphorous 0.005%, Sulphur 0.025% and Silicon traces.
Typical mechanical properties of Ingot-Iron:

Tensile strength - 40000 psi (275 MPa), Elongation in 2 inches 40% Rockwell B hardness 30

Iron is allotropic metal, which means that it can exist in more than one type of lattice structure
depending upon temperature. A study of cooling curve of pure iron shows that it can exist in more than
one allotropic form.

The Figure 3.21 shows the different changes that takes place during
solidification of pure iron. Iron is an allotropic metal, which means that it Mild steel 0.1-0.25
can exist in more than one type or crystal structure depending upon Medium carbon steel 0.25-0.45
temperature. Pure iron exists as BCC structure at room temperature and is High carbon steel 0.45-1.50
called as Ferrite of α-iron. At 912°C BCC iron undergoes allotropic Rarely used 1.50-2.5
changes and becomes FCC structure which is retained till 1394°C. FCC- Cast Iron 2.5-4.0
iron is also known as Austenite or γ-iron. At 1394°C it changes back once again to BCC structure
called δ-ferrite and this is retained till its melting point at 1538°C.

Equilibrium phases of Iron and carbon:

α – Ferrite: α-Ferrite is nothing but an interstitial solid solution of
small amounts of carbon dissolved in BCC-iron, the maximum solid
solubility of carbon in iron is 0.025% at 727°C and 0.008% at room
temperature. It is the softest among all phases of iron and carbon.

Microstructure of Ferrite
Austenite: Austenite is again an interstitial solid solution of carbon
but in FCC-iron. The maximum solid solubility is 2.1% at 1148°C.
Austenite is not stable below 727°C and will not be normally present
in the microstructure at room temperature. Austenite has an FCC
structure and is not magnetic.
Microstructure of Austenite

δ –ferrite: It is also and interstitial solid solution of carbon in BCC-iron because austenite changes its
structure at 1394°C from FCC to BCC maximum solid solubility of carbon in δ-iron is 0.1%C at 1495°C.

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Cementite: This is also known as iron carbide and has a chemical

formula Fe3C. It is considered a chemical compound because it
contains fixed carbon percentage but is crystalline in nature.
Cemetite always contains 6.67% carbon by weight and has an
orthorhombic crystal structure. Cementite is a very hard and
brittle compound of low tensile strength but high compressive
strength. It is the hardest structure that appears on Fe-C diagram.
The presence of cementite greatly enhances the properties of
steel.
Pearlite: when austenite exactly 0.83% C is cooled very slowly to
below 727°C, it transforms into pearlite. Pearlite is nothing but a
lamellar structure of a α-ferrite and cememtite. It is a fairly soft
structure and its hardness lies between that of a α-ferrite and
cementite. Pearlite can also be coarse, medium or fine depending
on the thickness of the layer of a α-ferrite and cementite. It has a
finegerprint like appearance.
Ledeburite: It is the eutectic lamellar mixture of austenite (light
phase) and cementite (dark phase). The eutectic reaction occurs at
4.33%C at 1148°C . Austenite in the eutectic mixture of
ledeburite is unstable below 727°C and hence transforms into α-
ferrite and cementitie.

Liquid
1538
δ Fe (BCC)

1394

γ Fe (FCC)
Temperature,

Non-Magnetic

912
C

α Fe (BCC)
o

Non-Magnetic
770

α Fe (BCC)
Magnetic

The Iron-Carbon Equilibrium Diagram: Time

Fig 3.21 Cooling curve for pure

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This diagram is known as Fe-C equilibrium diagram, but practically C will not present as a single
element separately, but it present in the form of Fe3C [Iron Carbide or Cementite] or in the form of
graphite flakes. So, this diagram is also known as Iron-Cementite equilibrium diagram.

This diagram represents the effect of compositions at different temperature by showing the different
phases present with the variation in composition and temperature. It also provides the information about
different microstructure which can be obtained, depending on which the properties of the material
changes.

The left vertical axis represents 100% iron and shows all the allotropic changes of pure iron with
temperature. The temperature at which allotropic changes occur in iron changes when it is alloyed with
different amounts of carbon.

The right vertical axis does not represent 100% carbon but instead represents only 6.67% C by weight.
This is because only a maximum of 6.67% C can be added to molten iron at which it becomes saturated.
Any further addition of carbon will not dissolve in iron but rather floats or gets blown away owing to its
very low density. Iron when contains exactly 6.67% C by weight forms an intermediate phase called
Cementite or Iron Carbide (Fe3C). Hence, the Iron-Carbon equilibrium diagram is actually called as
the Iron – Iron Carbide Equilibrium Diagram with pure iron and pure Fe3C (Iron Carbide) forming the
extremities.

Actually, the phase Fe3C (Iron Carbide) is called meta stable state because it decomposes with passage
of time. Here, the equilibrium phase diagram for iron and carbon assumes that Fe3C is stable with
respect to time. Hence, it is not a true equilibrium diagram.

The diagram shows 3 horizontal lines (isotherms) which represent 3 invariant reactions.

(a) The first isotherm at 1493oC indicates the peritectic reaction. This region where the peritectic
reaction takes place is called the Delta region.

(b) The second isotherm at 1148oC indicates the eutectic reaction. This region where the eutectic
reaction takes place is called the Eutectic region.

(c) The third isotherm at 727oC indicates the eutectoid reaction. This region where the eutectoid
reaction takes place is called the Eutectoid region.

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1600 δ+L
1538 A
1500 B 1495oC
L
δ
1400
1394 N

1300 δ+γ γ+L

Fe3C + L
1200
1148oC E
C D
2% 4.33%
1100 γ
Temperature, oC

1000

912 γ + Fe3C
900

800
α+γ J
727oC
0.8% K
700 H

600

500 α + Fe3C

400

300
1 2 3 4 5 6 6.67
Carbon % (by

STEEL CAST IRONS

Hypo Eutectic Hyper Eutectic

Cast Irons Cast Irons

Hypo Hyper Eutectoid

Eutectoid Steels
Fig 3.22 Iron – Iron Carbide Equilibrium
Diagram

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 Unit- 3 Solidification

Invariant reaction in Iron-Carbon System:

(a) Peritectic reaction(The Delta Region):
The first horizontal line MB at 1495oC indicates the Peritectic reaction. This region is called as the delta
region because of the solid solutionδ. The point P is known as the peritectic point at 1495oC & 0.18%C.
The peritectic reaction may be written as:
cooling
1538oC A
Liquid + δ-Iron (Feδ) γ (Austenite) 0.5% C
heating L+δ
M P
The maximum solubility of carbon in bcc δ iron is 1495oC δ
B
0.1% (point M) while in fcc γ iron , the solubility is
much greater.
0.18% C
L+γ
o
The presence of carbon influences the δ ⇔ γ 1395 C N 0.1% C
allotropic change. As carbon is added to iron, the γ
allotropic change increases from 1394oC to 1495oC Fig. 3 .23 The Delta
at 0.1%C. region

On cooling, the portion NM represents the beginning of the crystal structure change from bcc δ iron to
fcc γ-iron for alloys containing less than 0.1%C. The portion MP represents the beginning of this
crystal structure change by means of a peritectic reaction for alloys between 0.1 and 0.18% C. For
alloys containing less than 0.18% C, on cooling, the end of the crystal structure change is given by the
line NP.

The portion PB represents the beginning and ending of the crystal structure change by means of
peritectic reaction. That is, for alloys between 0.18%C and 0.5% C, the allotropic change begins and
ends at constant temperature.
For alloys containing more than 0.5%C, the liquid will solidify to austenite (γ) directly, i.e., there is no
allotropic change.
The Eutectic Region:
The Eutectic reaction takes place at
L 1148oC. The Eutectic point ‘E’ is at
1148oC and at 4.33% C. whenever an
alloy crosses the line line CED, and
L+γ
L+ Eutectic reaction takes place, giving rise
o
1148 C E
γ 2% D to a fine mixture of Austenite +
C 4.33% Cementite (γ + Fe3C). This eutectic
mixture is commonly called a
Ledeburite. This reaction can be
γ+
expressed as:
Fig.3.24 The Eutectic

Liquid (L) cooling Austenite (γ) + Cementite (Fe3C)

heating
Eutectic mixture (Ledeburite)
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 Unit- 3 Solidification

Since austenite (γ) is not stable at room temperature, its microstructure cannot be seen for slow cooling.
However, it has to undergo another reaction (Eutectoid reaction).

The Eutectoid Reaction: C

A small solid solution region to the left of the line
GH, which represents α-Fe (Ferrite), is a solid 912oC
γ
solution with small amounts of carbon dissolved in γ+Fe3C
BCC Fe. At 912oC, the FCC γ-Fe changes to BCC γ+ α
J 727oC
α-Fe. Line HJK represents the Eutectoid reaction K
H
taking place at 727oC. The Eutectoid point is ‘J’ α
which has 0.8%C & 727oC. 0.8% C

Whenever an alloy crosses the line HJK, the α+Fe3C

Eutectoid reaction takes place giving rise to the fine
Fig. 3.25 The Eutectoid
Eutectoid mixture of Ferrite + Cementite (α + Fe3C)
commonly known as Pearlite.
This reaction can be expressed as:
cooling
Austenite (γ) Ferrite (α) + Cementite (Fe3C)
heating
Eutectoid mixture (Pearlite)

Solidification of a few Composition of steel and Cast Irons

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 Unit- 3 Solidification

Solidification of steel containing 0.15% C

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 Unit- 3 Solidification

Point 1: Solidification begins with δ -iron precipitating out of the liquid.

Point 2: At this point, a portion of the solidified δ -iron re-mixes with all remaining liquid and forms
γ (Austenite), a totally new solid. Hence between point 2 and 3 we have γ –iron as well as
the remaining δ -iron.
Point 3: The remaining δ -iron diffuses into γ –iron and forms Austenite.
Point 4: At this point, excess carbon comes out to form α-iron, and occurs along with γ –iron which
is rich in carbon.
Point 5: Below this point γ –iron is not stable. Hence γ –iron (along with some α-iron) reduces to the
eutectoid mixture of ( α -iron + Fe3C) and occurs along with α -iron crystals. Therefore at
room temperature the solid contains pearlite of α -iron+ Fe3C) grains as well as α-iron
grains.
Solidification of steel containing 0.4% C
Point 1: Solidification begins with δ -iron precipitating out of the liquid.
Point 2: A portion of the liquid re-mixes with all the precipitated δ -iron and forms γ –iron.
Point 3: Solidification is complete with the remaining liquid solidifying as γ –iron.
Point 4: At this point, excess carbon comes out of the α -iron, and occurs along with γ –iron which is
rich in carbon.
Point 5: Below this point γ –iron is not stable. Hence γ –iron (along with some α -iron) reduces to
the eutectoid mixture of ( α -iron + Fe3C) and occurs along with α -iron crystals. Therefore at
room temperature the solid contains pearlite of ( α -iron+ Fe3C) grains as well as α-iron
grains.
Solidification of steel containing 1.2% C
Point 1 Solidification begins, with γ –iron precipitating out.
Point 2 Solidification is complete and we have all austenite ( γ )
Point 3 Austenites cannot hold all the carbon at this temperature. Hance excess carbon comes out and
forms Fe3C.
Point 4 γ is not stable below this point and transform into pearlite. Hence we have below this point
grains of pearlite and Fe3C.
Solidification of steel containing 3% C
Point 1: Solidification begins with γ –iron precipitating out.
Point 2: Solidification is complete. A portion of γ –iron remixes with all the remaining liquid to be
solidified to form ledeburite a eutectic mixture of ( γ –iron+ Fe3C). Between point 2 and 3
we have γ –iron grains and Ledeburite grains.
Point 3: Austenite ( γ –iron) within eutectic and outside eutectic is not stable below this temperature.
Hence it transforms into a mixture of α-iron and Fe3C grains.

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 Unit- 3 Solidification

1 What are different stages of the phase transformations?

2 What are homogeneous and heterogeneous nucleations? Derive the expression for critical 10
radius of the nucleation.
What is nucleation? Distinguish between the homogenous and heterogeneous nucleation. 8
What is solid solution? With suitable example, explain the different types of solid solutions. 8
State the Gibbs phase rule and explain with suitable example 6
Brief about the phase rule, lever rule and Tie-line 6
Construct phase diagram where two elements are completely soluble in liquid state and 8
partially soluble in the solid state.
Discuss the factors that are worked out by Hume Rothery that governs the formation of ideal 6
solid solution. Or explain the factors governing the formation of substitutional solid solution

Engineering Materials and Metallurgy Page 70