Material Science and Metallurgy

Phases in Solids

CHAPTER-3
Phases in solids: Phases-Single phase and multiphase, Gibb’s phase rule,
solid solutions and types, intermediate phases, equilibrium diagrams(only
binary) –construction and explanation of isomorphous and eutectic systems,
equilibrium and non-equilibrium cooling, invariant reactions (euctectic,
peritectic and eutectoid), lever rule and its application on isomorphous and
eutectic systems, equilibrium and non-equilibrium cooling of an alloy and
congruent melting alloy phase. [10]

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Phases in Solids [PART-II Invariant Systems]

Classification of phase diagrams:

Based on number of components in the system:
(a) Unary phase diagram (one component – pure metal system)
(b) Binary phase diagram (two components system)
(c) Ternary phase diagram (three components system)
(d) Quarternary phase diagram (four components system)

Based on the relationship between components in the liquid and solid states.
All phase diagrams can be classified according to the appearance of the following
reactions or transformations in them:
(a) Solid solution (Isomorphous system)
(b) Eutectic System
(c) Pertectic System
(d) Monotectic System
(e) Eutectoid transformation
(f) Peritectoid transformation
To understand the concept of constructing and study of phase diagrams, we may first make
a study of the binary phase diagrams where temperature is plotted along Y axis and
percentage composition by weight on the X axis.

Soluble in liquid and insoluble in solid State

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The phase diagram can be developed from a series of cooling curves in a manner
similar to that isomorphous system. The cooling curves for the pure metals A and B show a
single horizontal line at their freezing points.
Roult’s law states that the freezing point of pure substance will be lowered by the
addition of a second substance provided the later is soluble in the pure substance in liquid
phase and insoluble in the solid phase. As A is added to B or B is added to A, the
temperature of beginning of solidification for those alloys is also lowered. Therefore, since
each metal lowers the freezing point of the other, the line connecting the points showing
the beginning of solidification (liquidus line) must show a minimum. This is illustrated by the
line TAETB. The point E at composition XB is the eutectic point and that alloy is the lowest
melting point alloy in the system. The isotherm at temperature T, is the solidus line for the
alloy.
Let us consider the alloy (1), its cooling curve is as shown in figure. During the cooling
it remains the liquid phase until the point E is reached. Since the liquidus and solidus meet
at E, the solidification process takes place at constant temperature to give a finely divided
mechanical mixture of A & B. It can be seen from E & G [Composition of Solid A +
Composition of Solid B] i.e at the point E, the chemical composition of the liquid phase is
sufficient to undergo a eutectic reaction. Let us assume that a small amount of pure metal A
is solidified. Then the liquid becomes richer in B. To restore the liquid composition to its
equilibrium value [E], B will solidify. So, to maintain the equilibrium [To maintain L in
eutectic composition], the liquid solidifies alternatively into pure A & pure B at constant
temperature. This is known as eutectic mixture.
Now let us consider the alloy (2) cooled from liquid phase. In this alloy, the
concentration of A is more than it is required for eutectic transformation. So during
solidification (i.e. below T) high melting point richer concentration A solidifies first (pro
eutectic A). When the temperature drops to T, A concentration in the liquid is sufficiently
decreased to undergo a eutectic reaction and the reaming liquid transforms into finely
divided eutectic mixture.
Alloy (3) behaves similar to alloy (2), but here, it got pro eutectic B, because the
concentration of B is more than it is required for reaction. Final microstructure consists of
pro eutectic B & eutectic mixture.

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Mutual liquid solubility & Partial solid solubility

The system shows limited solubility i.e. at higher temperature (in liquid phase) B is
mutually soluble in A and A is mutually soluble in B to form single liquid phase. During
cooling, in the solid phase, at certain alloy composition, there will be two phase solid
solutions. Α is the solid solution formed with limited solubility of B in A. Similarly β is the
solid solution of limited solubility of A in B. The maximum solubility of B in A to get α solid
solution is X %. The maximum solubility of A in B to get β solid solution is (100-Y) %. With
decreasing temperature, the maximum amount of solute that can be dissolved decreases, it
can be seen by solvus lines.

Let us consider the alloy (1) upon cooling at temperature T, the solidification starts
isothermally by eutectic reaction to give a very fine mixture of two solids α+β. The eutectic
mixture composition, α of composition F and β of composition G. The eutectic reaction is L⇌
𝛼+𝛽

Consider the alloy (2) during cooling the solidification starts at temperature T1 into α
solid solution. Due to the solidification of α (rich in A) known as pro eutectic α, the A
concentration in the liquid gradually decreases. (Shown by the line T1E) When the
concentration of the liquid decreases composition E, then the eutectic reaction leads the
liquid into eutectic mixture (2 solid mixture). So the final microstructure shows eutectic
mixture and pro eutectic α crystal.

Consider the alloy (3) here the composition of alloy shows the higher concentration
of B than it is required for eutectic reaction. So during solidification, β crystals (higher
concentration B) known as pro eutectic β are formed till it reaches temperature T. When

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temperature falls to T, then the concentration of the liquid falls to E, (indicated by T BE line)
and the reaction under goes to yield eutectic mixture. The micro structure at room
temperature consists of pro eutectic β and eutectic mixture.

Consider the alloy (4) in which no eutectic reaction is observed. But there will be
allotropic change of α to β during cooling i.e. the alloy is in single phase as soon as it is
solidified. This phase exists up to temperature T5. At M, α is unsaturated solid solution,
since it can contain little higher composition of B, as indicated by M’. As the temperature
decreases, the solubility of B in α decreases as indicated by the slopping curve FM’T 5. At T5,
α is saturated with B. As the temperature decreases further, it will become super saturated
and the solid solution rejects extra B atoms, which combine with small amount of α to give β
solid solution. So at room temperature it has α solid solution surrounded by the continuous
networks of β particles along the grain boundaries. The property of this alloy depends up on
the particles of β solid solution. If β is a hard phase, the entire alloy shows brittleness even
though larger constituent soft α phase. The reason is, β phase is network of hard phase. For
such alloys (< X%), the age hardening ( precipitation hardening) heat treatment van be
given.

Peritectic Reaction

It is the reversible isothermal reaction in which the liquid reacts with the solid phase to give
another solid upon cooling.
𝐿 + 𝑠1 ⇌ 𝑠2 𝑜𝑟 𝐿+𝛼 ⇌𝛽

The solid formed may be solid solution or an intermetallic compound.

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Let us consider the alloy (1) during solidification, at temperature T 1, the crystals of α
(A rich) solid is formed. Due to the solidification of α, A concentration in the liquid decreases
(as denoted by the line T1N). When temperature falls to Tp, the concentration of the liquid
reaches N concentration. Now the precipitation α reacts with L to give β solid solution i.e.
𝐿 + 𝛼 ⇌ 𝛽 ( as shown by cooling curve1). The microstructure is shown in the diagram.

Consider the alloy (2), during solidification more amount of α crystals are formed
and at the same time the concentration of A in the liquid decreases as the temperature
decreases. When the temperature decreases to Tp, the concentration of L falls to N. Now
this liquid reacts with limited amount of α to give β. So, there will be some unused α in the
structure. Below T3 an allotropic change converts α to β crystals i.e. at room temperature,
there will be only β crystals.

Consider the alloy (3), during solidification small amount of α is precipitated because
A concentration in the alloy is less compared to alloy (1) and (2). When the temperature
decreases to Tp, the formed α reacts with proportionate amount of L to give β. There will be
some unused liquid exists, which can be seen between Tp and Ts. During this temperature
range, the unused liquid solidifies into crystals of β. So below T 5°C, the structure consists of
single phase β.

Eutectoid Reaction

It is the reversible isothermal reaction in which a single solid phase converts into two solids
up on cooling. It can be expressed as 𝛾 ⇌ 𝛼 + 𝛽 (Eutectoid mixture)

The above phase diagram consists of isomorphous system and eutectoid system. At
higher temperature, the alloy system behaves like isomorphous system to give γ solid phase.
Upon cooling at temperature TJ, the eutectoid reaction takes place to give fine eutectoid

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mixture of α+β. The alloy present left side and right side of the J are known as
hypoeutectoid and hyper eutectoid alloys respectively, at lower temperature, the solid
shows limited solubility and solubility still decreases as the temperature decreases i.e. it
resembles the eutectic system provided, and the initial phase is a solid phase.

Consider the alloy (1), when it is cooled from γ phase, there is no change in the
system till the temperature TJ is reached. At TJ, isothermally this alloy converts into two
intimately mixed solids α and β. Where α is the solid solution of A in B and β is the solid
solution of B in A i.e. α and β shows limited solubility.

Consider the alloy (2), the composition of this alloys shows that there will be more
concentration of A than it is required for eutectoid transformation. So, during cooling, at
temperature T2 there will be precipitation of pro eutectoid α solid solution to decrease A
concentration in the γ phase. During cooling to TJ temperature, the γ phase concentration
decreases by the precipitation of α phase. It is shown by the line XJ. At TJ temperature the
concentration of the γ phase falls to J concentration. So the alloy undergoes eutectoid
transformation to give the eutectoid mixture (α+β). The pro eutectoid α particles
precipitates along the grain boundary.

Consider the alloy (3), the same phenomenon is observed as that of alloy (2). Here
pro eutectoid β particles precipitate along the grain boundary.

Numerical on Type 1- Eutectic system.

Melting temperatures of pure metals ‘A’ & ‘B’ are 1000oC and 800oC respectively. The
metals ‘A’ and ‘B’ are mutually soluble in the liquid state and completely insoluble in the
solid state. A liquid phase alloy containing 40% A completely transforms into a mixture of
two pure metals at 600oC. Assuming the curves to be linear, draw phase diagram to scale
and label the regions. For 40% B alloy determine the following:
a) Composition of the nucleus.
b) Composition of the last drop of the liquid precipitating
c) Weight percentage of eutectic formed at 400oC.
d) Weight ratio of the solid phases in the eutectic mixture
e) Temperature at which there is 80 weight % of liquid phase present.
f) Temperature at which there is 80 weight % of solid phase present.
g) Composition of the liquid phase undergoing eutectic reaction.

Solution:
(1) Plot the phase diagram by taking temperature on Y axis and composition (% weight) of
A or B on X axis. Locate the points TA = 1000oC on the ordinate through ‘A’ and TB =
800oC on the ordinate through ‘B’. Draw a horizontal line (isotherm) FG at 600 oC. Mark

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the Eutectic point ‘E’ on the FG at 60%B. Draw the Liquidus as a straight lines
connecting TA-E-TB. Draw solidus as straight lines connecting TA-F-E-G-TB. Mark the two-
phase regions ‘L + A’ and ‘L + B’ between the liquidus and solidus. Also denote the A
+ (A + B), B + (A + B) and (A + B) regions as shown in the fig.
(2) The alloy of 60%A-40%B under consideration is represented by drawing an ordinate at
40%B.
(3) (a) Composition of the nucleus is nothing but the composition of the first particle of
solid formed. Here, the first solid formed is pro-eutectic phase ‘A’. To determine the
composition of the first nucleus we draw an isotherm at the point of intersection of the
alloy with the liquidus. The intersection of this isotherm with the solidus will give us the
composition of the solid phase. From fig. 4.12 it is 100%A.
(b) Composition of the last drop of the liquid precipitating is obtained where the alloy
intersects the solidus, i.e., at ‘H’. At H we draw an isotherm to intersect the liquidus at E
which gives us the required composition of the last drop of liquid precipitating, i.e.,
60%B. It may be noted that this is the Eutectic temperature.

TA = 1000 1000

900 900
L
800 TB = 800

700 L+A z 700

x y L+B
Temperature, oC

H E
600 F G 600

500 500

400 J M K 400

300 300
(A + B)

200 A + (A + B) B + (A + B) 200

100 100

A 20%B 40%B 60%B 80%B B

Composition by weight of B, %
Hypo Eutectic Alloys Hyper Eutectic Alloys
TA: M. P. of ‘A’ Eutectic Point: E
TB: M. P. of ‘B’ Eutectic Composition: 40%A-60%B
Liquidus: TA-E-TB Eutectic Temperature: 600oC
Solidus: TA-F-E-G-TB Eutectic Mixture: (A + B)
Fig. 4.12 Numerical on Type 1 Eutectic system

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(c) Weight percentage of eutectic formed at 400oC is obtained by applying lever rule to the
tie line JK through M.
JM 40%
wt.% of Eutectic ( A  B)  100  100  66.67%
JK 60%
(d) Weight ratio of the solid phases in the eutectic mixture
We need to find the ratio A/B or B/A in the Eutectic mixture.
wt. % of A in (A+B) = Total wt. % of A after Eutectic reaction – wt. % of Pro-eutectic A
HG 60%
Total wt.% of A after Eutectic reaction  100  100  60%
FG 100%
HE 20%
wt.% of Pr o  Eutectic A  100  100  33.33%
FE 60%
wt. % of A in (A + B) = 60% - 33.33% = 26.67%
FH 40%
wt.% of B  100  100  40%
FG 100%
wt.% of A 26.67
 wt.ratio of A to B    0.667
wt.% of B 40
Note: The weight ratio of the two phases in the Eutectic mixture is found to be constant
for any alloy undergoing Eutectic reaction.
(e) Temperature at which there is 80 weight % of liquid phase present.
This can be done by a trial and error procedure. A tie line is drawn in the L + A region in
such a way that the lever arm touching the solidus is 80% of the total tie-line length. At
approximately 670oC when such a tie line (xz) is drawn (refer fig. 4.12), the total tie line
length is xz = 50%B, the lever arm length touching solidus is xy = 40%B and 40/50 = 80%.
 Temperature where there is 80 weight % of liquid phase present is 670 oC
(f) Temperature at which there is 80 weight % of solid phase present.
This means that we need to determine the temperature at which 80% of the
solidification is complete. From the Fig., up till H pro-Eutectic phase A is formed whose
amount is:
HE 20%
wt.% of Pr o  Eutectic A  100  100  33.33%
FE 60%
i.e., 33.33% of solidification is complete and remaining 66.66% of solidification will take
place during Eutectic reaction. From this we understand that when 80% of solid is
formed (80% solidification is completed), Eutectic reaction will still be in progress, i.e.,
the corresponding temperature is Eutectic temperature = 600oC.
(g) Composition of the liquid phase undergoing eutectic reaction
During slow cooling, the liquid of the alloy under consideration, will reach Eutectic
Composition and Eutectic Temperature at H. So, the tie line FE at H will be useful to find
the liquid composition. The tie line FE intersects the liquidus at E. An ordinate through E
dropped on the composition axis will give the composition of the liquid phase
undergoing Eutectic reaction.
 Composition of ‘L’ to undergo eutectic reaction is 40%A+60%B.

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Numerical on Type 2 Eutectic system

Melting temperatures of pure metals ‘A’ & ‘B’ are 1000oC and 800oC respectively. The
metals ‘A’ and ‘B’ are mutually soluble in the liquid state and partly soluble in the solid state.
A liquid phase alloy containing 40% A completely transforms into a mixture of two solid
solutions at 600oC. Maximum solubility of ‘A’ in ‘B’ and ‘B’ in ‘A’ are 10% and 20%
respectively at 600oC, 5% and 10% respectively at 0oC. Assuming the curves to be linear,
draw phase diagram to scale and label the regions. For 40% B alloy determine the following:
h) Composition of the nucleus.
i) Composition of the last drop of the liquid precipitating
j) Weight percentage of eutectic formed at 400oC.
k) Weight ratio of the solid phases in the eutectic mixture
l) Temperature where there is 80 weight % of liquid phase present.
m) Composition of the liquid phase undergoing eutectic reaction.
Solution:
(1) Plot the phase diagram by taking temperature on Y axis and composition (% weight)
of A or B on X axis. Locate the points TA = 1000oC on the ordinate through ‘A’ and TB
= 800oC on the ordinate through ‘B’. Draw a horizontal line (isotherm) at 600oC. On
this isotherm mark ‘F’ to represent maximum solubility of ‘B’ in ‘A’. Mark ‘G’ to
represent the maximum solubility of ‘A’ in ‘B’. Similarly, mark ‘M’ & ‘N’ on the 0 oC
line to represent the minimum solubilities of ‘B’ in ‘A’ and ‘B’ in ‘A’ respectively.
Mark the Eutectic point ‘E’ on the 600oC line. Draw the Liquidus as a straight lines
connecting TA-E-TB. Draw solidus as straight lines connecting TA-F-E-G-TB. Draw the
solvus lines as straight lines connecting F to M and G to N. Mark the terminal solid
solution regions of ‘’ and ‘β’ to the left of F and to the right of G respectively. Mark
the two-phase regions ‘L + ’ and ‘L + β’ between the liquidus and solidus. Also
denote the  + ( + β), β + ( + β) and ( + β) regions as shown in the fig.
(2) The alloy of 60%A-40%B under consideration is represented by drawing an ordinate
at 40%B.
(a) Composition of the nucleus is nothing but the composition of the first particle of solid
formed. Here, the first solid formed is pro-eutectic phase . To determine the composition
of the first nucleus we draw an isotherm at the point of intersection of the alloy with the
liquidus. The intersection of this isotherm with the solidus will give us the composition of
the solid phase. From fig. it is approximately 13%B.

(b) Composition of the last drop of the liquid precipitating is obtained where the alloy
intersects the solidus, i.e., at ‘H’. At ‘H’ we draw an isotherm to intersect the liquidus at ‘E’
which gives us the required composition of the last drop of liquid precipitating, i.e., 60%B.

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TA = 1000 1000

900 900
L
800 TB = 800
x z
700 L+ y 700
L+
Temperature, oC

E
600 G 600
F H

500 500
β
400 P Q R 400

( + )
300  + ( + )  + ( + ) 300

200 200

100 100

M
A 20%B 40%B 60%B 80%B N B
Composition by weight of B, %

Hypo Eutectic Alloys Hyper Eutectic Alloys

TA: M. P. of ‘A’ Eutectic Point: E

TB: M. P. of ‘B’ Eutectic Composition: 40%A-60%B
Liquidus: TA-E-TB Eutectic Temperature: 600oC
Solidus: TA-F-E-G-TB Eutectic Mixture: ( + )
Solvus: FM & GN Terminal Solid Solutions:  & 
: ‘A’ rich solid solution : ‘B’ rich solid solution

Fig. Numerical on Type 2 Eutectic system

(c) Weight percentage of eutectic formed at 400oC is obtained by applying lever rule to the
tie line PQ through R.
PQ 40% B  17% B
wt.% of Eutectic (   )  100  100  53.49%
PR 60% B  17% B

(d) Weight ratio of the solid phases in the eutectic mixture

We need to find the ratio / β or β/ in the Eutectic mixture.
wt. % of  in ( + β) = Total wt. % of  after Eutectic reaction – wt. % of Pro-eutectic 
HG 90% B  40% B
Total wt.% of  after Eutectic reaction  100  100  71.43%
FG 90% B  20% B

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HE 60%B  40%B
wt.% of Pr o  Eutectic   100  100  50%
FE 60%B  20%B
wt. % of  in ( + β) = 71.43% - 50% = 21.43%
FH 40%B  20%B
wt. % of   100  100  28.57%
FG 90%B  20%B
wt.% of  21.43
 wt. ratio of  to     0.75
wt.% of  28.57
Note: The weight ratio of the two phases in the Eutectic mixture is found to be constant for
any alloy undergoing Eutectic reaction.

(e) Temperature where there is 80 weight % of liquid phase present.

This can be done by a trial and error procedure. A tie line is drawn in the L +  region in such
a way that the lever arm touching the solidus is 80% of the total tie-line length. At
approximately 690oC when such a tie line (xz) is drawn (refer fig. 4.18), the total tie line
length is xz = 31%, the lever arm length touching solidus is xy = 25% and 25/31 = 80.65%
 Temperature where there is 80 weight % of liquid phase present is 690 oC

(f) Composition of the liquid phase undergoing eutectic reaction

During slow cooling, the liquid of the alloy under consideration, will reach Eutectic
Composition and Eutectic Temperature at H. So, the tie line FE at H will be useful to find the
liquid composition. The tie line FE intersects the liquidus at E. An ordinate through E
dropped on the composition axis will give the composition of the liquid phase undergoing
Eutectic reaction.
 Composition of ‘L’ to undergo eutectic reaction is 40%A+60%B

Exercise Problems:-
[1]. Two metals A and B have their melting points at 900°C and 800°C respectively. The alloy
pair forms a eutectic at 600°C of composition 60% B and 40%A. A and B have unlimited
mutual liquid solubilities. Their solid solubilities are as follows:
10% B in A at 600°C and 5% B in A at 0°C
8% A in B at 600°C and 4% A in B at O°C
Assume the liquidus, solidus and solvus lines to be straight. No solid state reactions or any
intermediate phase changes occur in the series.
i) Draw the phase diagram for the series and label all salient temperatures,
compositions and regions.
ii) Find the room temperature structure of an alloy of composition 60% A and 40% B,
with respect to the number, type, extent and composition of the phases.

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[2]. Two metals A and B used to form an alloy containing 75% A and 25% B. A melts at 650°C
and B at 450°C. When alloyed together, A and B do not form any compound or
intermediate phase. The solid solubility of metal A in B and B in A are negligible. The
metal pair forms an eutectic at 40% A and 60% B which solidifies at 300°C. Assume the
liquidus and solidus lines to be straight. Draw the phase for the alloy series and find:
I. The temperature at which the alloy starts and completes solidification.
II. The percentage of eutectic in the alloy at room temperature.
III. The amount of liquid present and its composition, at a temperature of 390°C.

[3]. Melting temperatures of pure metals ‘A’ & ‘B’ are 1200oC and 900oC respectively. The
metals ‘A’ and ‘B’ are mutually soluble in the liquid state and partly soluble in the solid
state. A liquid phase alloy containing 40% A completely transforms into a mixture of two
solid solutions at 700oC. Maximum solubility of ‘A’ in ‘B’ and ‘B’ in ‘A’ are 15% and 25%
respectively at 700oC, 5% and 10% respectively at 100oC. Assuming the curves to be
linear, draw phase diagram to scale and label the regions. For 70% B alloy determine the
following:
I. Weight percentage of eutectic formed.
II. Temperature where there is equal proportions of liquid and solid phases present

[4]. Melting temperatures of metal A and metal B are 800oC and 1200oC respectively. Metal
A and B are mutually soluble in the liquid state and partly soluble in the solid state. A
liquid phase alloy containing approximately 30% B completely transforms into a mixture
of two solid solutions at 600oC. Maximum solubility of A in B and B in A are
approximately 15% and 10% respectively at 600oC, 10% and 5% respectively at 300oC.
Assuming the solubility curves to be linear, draw phase diagram to scale and label the
regions. For 60% B alloy determine the following:
I. Weight percentage of the Eutectic mixture formed.
II. Composition of the liquid phase for the reaction.

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