ASSIGNMENT-1

Question 1:
Below is Pb-Ag Phase Diagram. Describe the diagram in terms of points marked, Phase
transformations, different regions and lines .
Apply the Gibbs phase rule on regions ,curves and where ever possible. Mention the
changeable parameters in terms of degree of freedom.

Solid lead+ Eutectic

ASSIGNMENT-1
Question 2:
Given here are the solidus and liquidus temperatures for copper-gold system. Construct the
phase diagram for this system and label each region.

Composition wt% Au

Solidus Temp(oC)

Liquidus Temp (oC)

1085

1085

20

1019

1042

40

972

996

60

934

946

80

911

911

90

928

942

95

974

984

100

1064

1064

ASSIGNMENT-1
Question 1:
Below is Pb-Ag Phase Diagram. Describe the diagram in terms of points marked, Phase
transformations, different regions and lines .
Apply the Gibbs phase rule on regions ,curves and where ever possible. Mention the
changeable parameters in terms of degree of freedom.

Solid lead+ Eutectic

ASSIGNMENT-SOLUTION
A and C are the freezing points of pure lead and silver respectively. Curve AB indicates the
temperatures at which lead begins to separate from various compositions of melt while BC
indicates initial separation of silver.
D is the eutectic temperature of the
system and the eutectic composition is
given by B.
Curve ABC is the liquidus curve as it gives
the composition of the liquid phase that is in

equilibrium with the solid phase. ADBEC is

the solidus curve; AD represents solid lead,
DBE mixture of lead and Ag in equilibrium

with liquid phase of composition B and EC

solid silver.
Solid lead+
Eutectic

ASSIGNMENT-SOLUTION
A

Freezing point of lead

C=1, P=2, F=0

Fixed T

Freezing point of silver

C=1, P=2, F=0

Fixed T

Eutectic point

C=2, P=3, F=0

Fixed T and
composition

AB

Crystallization of lead
begins

C=2, P=2, F=1

T or
composition

BC

Crystallization of silver
begins

C=2, P=2, F=1

T or
composition

Area above ABC

Liquid phase

C=2, P=1, F=2

T and
composition

Area below DBE

Solid mixture

C=2, P=2, F=1

T or
composition

Area ADBA

Solid lead in equilibrium

with liquid having
composition given by the
curve AB

C=2, P=2, F=1

T or
composition

Solid lead+
Eutectic

Area CEBC

Solid silver in equilibrium

with liquid having
composition given by the
curve BC

C=2, P=2, F=1

T or
composition

DBE

Both lead and silver

separate from liquid of
composition B

C=2, P=3, F=0

Fixed T

Phase Diagram of Zn-Mg

The melting points of pure Zn and pure Mg are represented by points A and E respectively.
AB is the freezing point curve of Zn. In the area ABFA, solid zinc is in equilibrium with

liquid containing zinc and magnesium, the composition of which is given by the curve AB.

Similarly, ED is the freezing point curve

of magnesium. Solid magnesium is in
equilibrium with liquid containing
magnesium and zinc, composition of
the liquid phase lying on the curve DE.

Phase Diagram of Zn-Mg

If a liquid having the composition c' is cooled, the liquid merely cools till it reaches the point
C.
At the point C, a solid compound, having the same composition as the liquid starts separating.

This temperature, the congruent melting

point of the compound, remains constant
till the entire liquid phase freezes. On
further cooling, the temperature of the
solid decreases. Thus, the cooling pattern
of the liquid of composition c' is similar to
that of a pure component. The formula of
the compound formed is Mg (Zn)2 which
corresponds to the composition c'.
c

Phase Diagram of Zn-Mg

CB and CD give the freezing point curves of Mg (Zn)2. Addition of zinc depresses the freezing
point of Mg(Zn)2 and the temperatures at which the solid compound Mg (Zn)2 will begin to
freeze (separate) from various liquids, composition lying between B and G, fall on the curve
CB.
Similarly CD gives the temperatures at which
the solid compound Mg(Zn)2 starts freezing

from liquids having their composition lying

between H and D. The curve CD gives the
depression in the freezing point of Mg (Zn)2

due to the addition of Mg. B is an eutectic

point at which solid zinc and solid Mg (Zn)2
are in equilibrium with liquid of composition

B. Similarly at D, another eutectic point,

solid magnesium and solid Mg(Zn)2 are in
equilibrium with liquid of composition D.

Phase Diagram of Zn-Mg

Theoretically, the curves BC and DC should meet to give a sharp point at C. But normally a
rounded maximum is observed as shown in the phase diagram.

This is because the compound formed is

usually not very stable and dissociates
partly. The dissociation products in the

liquid phase depress the actual melting of

the compound resulting in a rounded
melting point.

Application of Gibbs Phase Rule on Zn-Mg System

A

Freezing point of Zn

C=1, P=2, F=0

Fixed T

Freezing point of Mg

C=1, P=2, F=0

Fixed T

Freezing point of Mg(Zn)2

C=2, P=2,F=0

Fixed T and composition

C=2, P=3, F=0

Fixed T and composition

C=2, P=3, F=0

Fixed T and composition

Eutectic point (Zn,Mg(Zn)2, liq. Of

composition B)
Eutectic point (Mg,Mg(Zn)2, liq of

composition D)
Freezing point curve of Zn,

AB

crystallization of Zn begins

C=2, P=2, F=1

T or composition

BC and CD

Crystallization of Mg(Zn)2 begins

C=2, P=2, F=1

T or composition

ED

Crystallization of Mg begins

C=2, P=2, F=1

T or composition

Area ABFA

Zn +liquid (composition given by AB)

C=2, P=2, F=1

T or composition

C=2, P=2, F=1

T or composition

C=2, P=2, F=1

T or composition

C=2, P=2, F=1

T or composition

C=2, P=2, F=1

T or composition

C=2, P=2, F=1

T or composition

Mg(Zn)2 + liquid (composition given

Area CBGC

by CB)
Mg(Zn)2 + liquid

Area CHDC

(composition given by CD)

Mg + liquid

Area EDIE

(composition given by ED)

Solid mixtures of Zn and

Area below FBG

Mg (Zn)2
Solid mixtures of Mg and

Area below HDI

Mg (Zn)2
Liquid containing Zn and

Development of Microstructures in Binary Alloys

Development of Microstructures in Isomorphous Alloys

Development of Microstructures in Isomorphous Alloys

Equilibrium Cooling
An alloy of composition 35 wt% Ni65 wt% Cu
as it is cooled from 1300oC

a
b

Cooling of an alloy of the above composition

corresponds to moving down the vertical
dashed line.

c
d
e

Development of Microstructures in Isomorphous Alloys

At 1300oC point a, the alloy is completely

liquid (of composition 35 wt% Ni65 wt%
Cu) and has the microstructure.

a
b

As cooling begins, no microstructural or

compositional changes .
until the liquidus line (point b, ~1260 )

At this point, the first solid begins to form,

which has a composition dictated by the tie
line drawn at this temperature [i.e., 46 wt%
Ni54 wt% Cu, noted as (46 Ni)];the
composition of liquid is still approximately 35
wt% Ni65 wt% Cu [L(35 Ni)]

Development of Microstructures in Isomorphous Alloys

Note that the overall alloy composition (35
wt% Ni65 wt% Cu) remains unchanged
during cooling even though there is a
redistribution of copper and nickel between
the phases.

At (1250oC)point c , the compositions of the

liquid and phases are 32 wt% Ni68 wt% Cu
[L(32 Ni)] and 43 wt% Ni57 wt% Cu [ (43
Ni)],respectively.
The solidification process is virtually complete
at (1220oC) about point d; the composition of
the solid is approximately 35 wt% Ni65 wt%
Cu (the overall alloy composition) while that of
the last remaining liquid is 24 wt% Ni76 wt%
Cu.

a
b
c
d

Development of Microstructures in Isomorphous Alloys

Upon crossing the solidus line, this remaining

b

liquid solidifies; the final product then is a

polycrystalline-phase solid solution that has a

uniform 35 wt% Ni65 wt% Cu composition
(point e). Subsequent cooling will produce no

microstructural or compositional alterations.

c
d

Development of Microstructures in Isomorphous Alloys

Non-Equilibrium Cooling
Let us begin cooling from a temperature of
about 1300oC; a point liquid region. This liquid
has a composition of 35 wt% Ni65 wt% Cu
,L(35 Ni) , and no changes occur while cooling
through the liquid phase region At point
b(approximately ) 1260oC, -phase particles
begin to form, which, from the tie line
constructed, have a composition of 46 wt% Ni
54 wt% Cu [(46 Ni)].

a
b'

Development of Microstructures in Isomorphous Alloys

At point c (1240oC), the liquid composition is

29 wt% Ni71 wt% Cu; at this temperature the
composition phase that solidified is 40 wt%
Ni60 wt% Cu, (40 Ni). Diffusion in the solid
phase is relatively slow, the phase that
formed

at

point

has

not

b'
c'
d'

changed

composition appreciablythat is, it is still

about 46 wt% Niand the composition of the
grains has continuously changed with radial
position, from 46 wt% Ni at grain centers to 40
wt% Ni at the outer grain perimeters.

e'

Development of Microstructures in Isomorphous Alloys

At point (d,1220oC ) and for equilibrium
cooling
rates, solidification should be
completed. However, for this non-equilibrium
situation, there is still an appreciable
proportion of liquid remaining, and the
phase that is forming has a composition of 35
wt% Ni [ (35 Ni)]; also the average -phase
composition at this point
is 38 wt% Ni [ (38 Ni)].
Non-equilibrium solidification finally reaches
completion at point ( e,1205oC). The
composition of the last phase to solidify at this
point is about 31 wt% Ni; the average
composition of the phase at complete
solidification is 35 wt% Ni. The inset at point
(f) shows the microstructure of the totally
solid material.

Development of Microstructures in Isomorphous Alloys

Coring
the distribution of the two elements within the
grains is non uniform, a phenomenon termed
segregation;
that is, concentration gradients are established
across the grains.
The center of each grain, which is the first part
to freeze, is rich in the high-melting element
(e.g., nickel for this CuNi system), whereas
the concentration of the low-melting element
increases with position from this region to the
grain boundary. This is termed a cored
structure, which gives rise to less than the
optimal properties.
Coring may be eliminated by a homogenization
heat treatment carried out at a temperature
below the solidus point for the particular alloy
composition. During this process, atomic
diffusion
occurs,
which
produces
compositionally homogeneous grains.

Mechanical Properties in Isomorphous Alloys

For all temperatures and compositions

below the melting temperature of the
lowest-melting component, only a single
solid phase will exist. Therefore, each
component will experience solid-solution
strengthening or an increase in strength
and hardness by additions of the other
component.

Mechanical Properties in Isomorphous Alloys

Ductility(%EL)composition behavior,
which is just the opposite of tensile

strength; that is, ductility decreases

with

additions

of

the

second

component, and the curve exhibits

a minimum.

Development of Microstructures in Eutectic Alloys

First case

For

compositions

ranging between a pure

component

and

the

maximum solid solubility

for that component at
room

temperature

( 20oC).

For the leadtin system, this includes lead-rich alloys containing between 0 and about 2
wt% Sn (for the phase solid solution), and also between approximately 99 wt% Sn and
pure tin (for the phase).

Development of Microstructures in Eutectic Alloys

For leadtin system, this includes lead-rich

alloys containing between 0 and about 2 wt%

Sn (for the phase solid solution), and also
between approximately 99 wt% Sn and pure

tin (for the phase).

Alloy of composition C1 , slowly cooled from
a temperature within the liquid- phase
region, this corresponds to moving down the
dashed vertical line.
At 330oC, will begin to form
No subsequent changes will occur upon
cooling to room temperature.

Development of Microstructures in Eutectic Alloys

Second case
Compositions that range between the room
temperature solubility limit and the maximum

solid solubility at the eutectic temperature.

Composition ,cooled along the vertical line xx

Compositions extend from about 2 wt% Sn to

18.3 wt% Sn (for lead-rich alloys) and from

97.8 wt% Sn to approx 99 wt% Sn (for tin-rich

alloys).

Development of Microstructures in Eutectic Alloys

Upon crossing the solvus line, the solid

solubility is exceeded, results in the formation
of small -phase particles.

With continued cooling, these particles will

grow in size because the mass fraction of the
phase increases slightly with
temperature.

decreasing

Development of Microstructures in Eutectic Alloys

Third case
Involves solidification of the eutectic
composition, 61.9 wt% Sn(C3) .
Alloy having this composition is cooled
from a temperature within the liquidphase region (e.g., 250C) down the
vertical line yy

No changes occur until

reach the

(183oC) eutectic temperature.

Upon crossing the eutectic isotherm, the liquid transforms to the two and phases.

Development of Microstructures in Eutectic Alloys

L (61.9 wt% Sn)

(18.3 wt% Sn) + (97.8 wt% Sn)

During this transformation, there

must necessarily be a redistribution

of the lead and tin components,
inasmuch as the and phases have

different

compositions neither of

which is the same as that of the

liquid.
This redistribution is accomplished
by atomic diffusion.

Development of Microstructures in Isomorphous Alloys

The microstructure of the solid that results from this

transformation consists of alternating layers (sometimes
called lamellae) of the and phases that form
simultaneously during the transformation.
This is called Eutectic Structure

This microstructure consists of

alternating layers of a lead rich
-phase

solid

solution

(dark

layers), and a tin-rich -phase

solid solution (light layers).

Photomicrograph
showing
the
microstructure of a
leadtin
alloy
of
eutectic composition.

Development of Microstructures in Eutectic Alloys

Eutectic Microstructures in different Alloys

Sn-50%In. Globules of tin rich

intermetallic phase (light) in a matrix of
dark indium rich intermetallic phase

Al-13% Si. Acicular structure consisting of

short ,angular particles of Si(dark) in a
matrix of Aluminum.

Eutectic Microstructures in different Alloys

Al-33%Cu.
Lamellar
structure
consisting of dark platelets of CuAl2
and light platelets of aluminum solid
solution

Mg-37%Sn.
Lamellar
structure
consisting
of
Mg2Sn
Chinese
script(dark) in am matrix of Mg Solid
Solution.

Development of Microstructures in Eutectic Alloys

Fourth case:

system includes all compositions other

than the eutectic that, when cooled,
cross the eutectic isotherm.
Composition, which lies to the left of
the eutectic; as the temperature is
lowered, we move down the zz line
beginning at point j.

Photomicrograph showing the microstructure of a

leadtin alloy of composition 50 wt% Sn50 wt% Pb.

Development of Microstructures in Eutectic Alloys

Hypereutectic Alloy

HYPOEUTECTIC & HYPEREUTECTIC

HYPOEUTECTIC & HYPEREUTECTIC

Physical/Mechanical Properties in Eutectic Alloys

Properties of Alloys depends on
individual characteristics of phases
and upon the mode of distribution
of
these
phases
in
the
microstructure.
If phase behave as solid solution
whose properties very within the
composition range covered in
same manner as those in
isomorphous solid solutions.
Properties changes with first
addition of the solute to the
solvent component.

Hardness and Tensile strength

increases with alloying .
Elongation
and
Electrical
conductivity decreases.

Physical/Mechanical Properties in Eutectic Alloys

When two phases occur together in a structure, the resulting properties of the mixture
resembles most nearly those of physically continuous phase.

The phase which forms matrix ,in which particles of the other phase are embedded. As the
quantity of embedded phase increases with composition, its properties are gradually
changes.
These changes are linear in most system, but in some cases these deviates widely.

These deviations are due to

1-Inhomogenity of individual phase

2-Peculiarties of particle shape that cause one of the phase to remain physically continue over
a disproportionately large range of composition.
3-Variation of particle size across the two phase zone.

Eutectoid Reaction

Eutectoid Reaction in Binary Phase Diagrams

copperzinc system

at 560oC

and 74

wt% Zn26 wt% Cu.

Upon cooling, a solid

phase transforms

into two other solid

phases

according

and
to

)
the

reaction

Eutectoid Reaction in Binary Phase Diagrams

The reverse reaction
occurs upon heating. It
is called a eutectoid (or
eutectic-like) reaction,
and the invariant point
,E and the horizontal
tie line at 560oC are
termed the eutectoid
and

eutectoid

isotherm, respectively.

Eutectoid Reaction in Binary Phase Diagrams

Difference of eutectoid
from eutectic is that
one solid phase instead
of a liquid transforms into
two other solid phases at
a single temperature. A
eutectoid

reaction

is

found in the ironcarbon

system

that is very

important in the heat

treating of steels.

Microstructures of Eutectoid Reaction

(A) Hypoeutectoid steel ,0.3%C,Light areas are proeutectoid ferrite(alpha)and dark areas
are pearlite.500X
(B) Eutectoid steel,0.8 % carbon, typically pearlite.500X
(C) Hypereutectoid steel ,1.2% carbon. Thin bands of proeutectoid Cementite, light gray
,outline the grains of pearlite. 500X