JASHORE UNIVERSITY OF SCIENCE AND TECHNOLOGY (JUST)

IPE- 2203: Engineering Materials II (3 credit hours)

Dr. Md Mahfuzur Rahman

Assistant Professor, Dept. of IPE
2nd Jan, 2021
Intended Learning Outcomes (ILOs)

Review of previous class

Phase Diagram
Phase Diagram
Phase Diagram
 Much of the information about the control of the phase structure of a particular system is conveniently
and concisely displayed in what is called a phase diagram, also often termed an equilibrium diagram.

 There are three externally controllable parameters that will affect phase structure: temperature,
pressure, and composition—and phase diagrams are constructed when various combinations of these
parameters are plotted against one another.

A great deal of information concerning the phase changes in many alloy systems has been accumulated,
and the best method of recording the data is in the form of phase diagrams, also known as equilibrium
diagrams or constitutional diagrams.

Three independent variables which are externally controllable, temperature, pressure, and composition,
are specified .

With pressure assumed to be constant at atmospheric value, the equilibrium diagram indicates the
structural changes due to variation of temperature and composition. The diagram is essentially a
graphical representation of an alloy system.
Phase Diagram I
Three phases for the H2O system:

 ice (the iceberg),

 water (the ocean or sea), and
 vapor (the clouds).
Graph is the phase diagram for pure H2O
Parameters plotted are external pressure versus temperature
Map of regions for the three familiar phases—solid (ice),
liquid (water), and vapor (steam).
Three red curves represent phase boundaries that define the
regions.
 Definitions: Components and Phases
Component - chemically recognizable species (Fe and C in
carbon steel, H2O and Sucrose in sugar solution in water).
A binary alloy contains two components,
a ternary alloy – three, etc.
Phase – a portion of a system that has uniform physical and
chemical characteristics.
Two distinct phases in a system have distinct physical and/or
chemical characteristics (e.g. water and ice, water and oil) and
are separated from each other by definite phase boundaries.
A single-phase system is called homogeneous, systems with
two or more phases are mixtures or heterogeneous systems.
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 Definitions: Solubility Limit
Solvent - host or major component in solution,
Solute - minor component.
Solubility Limit of a
component in a phase is the
maximum amount of the
component.
The same concepts apply to
solid phases:
 Cu and Ni are mutually
soluble in any amount
(unlimited solid solubility),
 while C has a limited
solubility in Fe.

8
 Microstructure
Properties of an alloy depend not only on proportions of the phases
but also on how they are arranged structurally at microscopic level.
Thus, the microstructure is specified by:
 the number of phases,
 their proportions, and
 their arrangement in space.

The long gray regions are

flakes of graphite.
The matrix is a fine
mixture of BCC Fe and
Fe3C compound.

Phase diagrams will help us to understand and predict microstructures

9
 Equilibrium States
Free energy:
 is a function of internal energy of a system and
 randomness or disorder of the atoms or molecules
A system is at equilibrium if its free energy is at a minimum
under some specified combination of temperature, pressure, and
composition

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 Equilibrium and Metastable States
• A system is at equilibrium if at constant temperature,
pressure and composition, the system is stable ( i.e., not
changing with time).
• Equilibrium is the state achieved in a sufficient time.
• But the time to achieve equilibrium may be very long (the
kinetics can be slow) that a state along the path to the
equilibrium may appear to be stable. This is called a
metastable state.
• In thermodynamics equilibrium is
described as a state of a system that
corresponds to the minimum of
thermodynamic function called the
free energy.
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 Questions for Discussions

• Cite three variables that determine the

microstructure of an alloy.

• What is the difference between the states

of phase equilibrium and metastability?

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 Phase diagram
Phase diagram is a graphical representation of all the
equilibrium phases as a function of temperature, pressure, and
composition.
For one component systems, the equilibrium state of the system
is defined by two independent parameters :
 (P and T),
 (T and V), or
 (P and V).

Fig:
Pressure-temperature
phase diagram for H2O

13
A pure substance is heated at constant pressure

14
Pressure-temperature phase diagram for carbon

15
Phase Diagrams II

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 Phase diagrams for binary systems
A phase diagrams show what phases exist at equilibrium
and what phase transformations we can expect when we
change one of the parameters of the system.

Real materials are almost always mixtures of different

elements rather than pure substances: in addition to T and P,
composition is also a variable.
For phase diagrams of multicomponent systems (binary
alloys) assume pressure to be constant at one atmosphere.
Phase diagrams for materials with more than two
components are complex and difficult to represent.
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 Binary Isomorphous Systems (I)
Isomorphous system - complete solid solubility of the two
components (both in the liquid and solid phases).
Three phase region can be
identified on the phase
diagram:
Liquid (L) ,
solid + liquid (α +L),
solid (α )

Liquidus line separates

liquid from liquid + solid

Solidus line separates

solid from liquid + solid
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 Binary Isomorphous Systems (II)
Example of isomorphous system: Cu-Ni
(complete solubility occurs because both Cu and Ni have the same
FCC crystal structure, similar radii and electronegativity).

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 Binary Isomorphous Systems (III)
In one-component system
 melting occurs at a well-defined melting temperature
In multi-component systems
 melting occurs over the range of temperatures, between
the solidus and liquidus lines.
 Solid and liquid phases
are at equilibrium with
each other in this
temperature range.

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Interpretation of a binary phase diagrams
For a given temperature and composition we can use phase
diagram to determine:
1) The phases that are present
2) Compositions of the phases
3) The relative fractions of the phases.
Finding composition in two phase region:
1. Locate composition and temperature in
diagram
2. In two phase region draw the tie line
or isotherm
3. Note intersection with phase
boundaries. Read compositions at
intersections.
The liquid and solid phases have these
compositions. 21
 The lever rule
Finding the amounts of phases in a two phase region:
1. Locate composition and temperature in diagram
2. In two phase region draw the tie line or isotherm
3. Fraction of a phase is determined by taking the length of the tie
line to the phase boundary for the other phase, and dividing by
the total length of tie line

The lever rule is a mechanical

analogy to the mass balance
calculation.
The tie line in the two-phase
region is analogous to a lever
balanced on a fulcrum.

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 Derivation of the lever rule
 All material must be in one
phase or the other:
Wα + WL = 1
 Mass of a component that is
present in both phases equal
to the mass of the
component in one phase +
mass of the component in
the second phase:
WαCα + WLCL = Co

 Solution of these equations

gives us the lever rule.
WL= (Cα -Co) / (Cα-CL)
Wα= (Co -CL) / (Cα-CL)
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The Cooling Curve

24
 The Cooling Curve
• Series of cooling curves for different alloys

• The dotted lines indicate the form of the phase diagram

25
 Questions for Discussions
A copper–nickel alloy of composition 70 wt% Ni–
30 wt% Cu is slowly heated from a temperature of
1300C.

(a) At what temperature does the first

liquid phase form?
(b) What is the composition of this liquid
phase?
(c) At what temperature does complete
melting of the alloy occur?
(d) What is the composition of the last solid
remaining prior to complete melting?
26
Cu-Ni phase diagram

27
 Solution
(a) Upon heating from 1300°C, the first liquid phase forms at the temperature
at which this vertical line intersects the α-(α + L) phase boundary--i.e.,
about 1345°C.

(b) The composition of this liquid phase corresponds to the intersection with
the (α + L)-L phase boundary, of a tie line constructed across the α + L
phase region at 1345°C--i.e., 59 wt% Ni;
(c) Complete melting of the alloy occurs at the intersection of this same
vertical line at 70 wt% Ni with the (α + L)-L phase boundary--i.e., about
1380°C.

(d) The composition of the last solid remaining prior to complete melting
corresponds to the intersection with α -(α + L) phase boundary, of the tie
line constructed across the α + L phase region at 1380°C--i.e., about 79
wt% Ni.
28
 Questions for Discussions
Is it possible to have a copper–nickel alloy that,
at equilibrium, consists of an α phase of
composition 37 wt% Ni–63 wt% Cu, and also a
liquid phase of composition 20 wt% Ni–80 wt%
Cu?

If so, what will be the approximate temperature

of the alloy? If this is not possible, explain why.

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Number and types of phases

30
Composition of each phase

31
Relative amount of each phase

32
To summarise

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 Problem
One kilogram of an alloy of 70% Pb and 30% Sn is slowly
cooled from 300ºC. Calculate the following:

1. Chemical composition
of the liquid and
a phases at 225ºC.

2. Weight % of liquid
and a at 225ºC.

34
Solution

35
Development of Microstructures During Equilibrium Cooling

36
Development of microstructure in isomorphous alloys

37
 The slow cooling of a 70A-30B alloy

• Microstructure
at various
points during
solidification

Schematic picture
of the alloy at
temperature T2

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Development of microstructure in isomorphous
alloys Equilibrium (very slow) cooling
 Solidification in the solid + liquid phase occurs gradually
upon cooling from the liquidus line.

 The composition of the solid and the liquid change

gradually during cooling (as can be determined by the tie-
line method)

 Nuclei of the solid phase form and they grow to consume

all the liquid at the solidus line.

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Development of Microstructures
During Non-equilibrium Cooling

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41
Development of microstructure in isomorphous alloys
Fast (non-equilibrium) cooling
• Compositional changes require diffusion in solid and
liquid phases.

• Diffusion in the solid state is very slow.

⇒New layers that solidify on top of the existing grains

have the equilibrium composition at that temperature but
once they are solid their composition does not change.

⇒ Formation of layered (cored) grains and the invalidity

of the tie-line method to determine the composition of the
solid phase.

42
Development of microstructure in isomorphous alloys
Fast (non-equilibrium) cooling

• The tie-line method still works for the liquid phase,

where diffusion is fast.

• Average Ni content of solid grains is higher.

⇒Application of the lever rule gives us a greater proportion
of liquid phase as compared to the one for equilibrium
cooling at the same T.

⇒ Solidus line is shifted to the right (higher Ni contents),

solidification is complete at lower T, the outer part of the
grains are richer in the low-melting component (Cu).

43
Development of microstructure in isomorphous alloys
Fast (non-equilibrium) cooling
Cooling rates too
rapid to allow
composition
readjustment/diff
usion
 Microstructure
other than
equilibrium
phase
Assuming,
diffusion in liquid
phase is rapid
 equilibrium
maintained
44
Development of microstructure in isomorphous alloys
Fast (non-equilibrium) cooling
No changes @ a՛

1260ºC, α-phase@ b՛

1240ºC, solidus line

shifts @ c՛

1220ºC,
solidification
incomplete @ d՛
1205ºC,
solidification
complete @ e՛

Totally solid @ f՛

45
46
 Metals completely soluble in liquid and solid state
• Alloy has a melting point between the melting points of
A and B

liquidus and solidus lines go through a minimum (Fig-a)

or a maximum (Fig-b) 47
 Two metals completely soluble in liquid state
insoluble in solid state
Cooling curves for pure metals
A and B show a single
horizontal line at their freezing
points.

As B is added to A,
temperature for beginning of
solidification is lowered.

As A is added to B, temperature
for beginning of solidification
for those alloys is also lowered.

Since each metal lowers freezing point of the other, the line connecting the
points showing the beginning of solidification, the liquidus line, must show a
minimum, at E (eutectic point), for a composition of 40A-60B)
 Two metals completely soluble in liquid state
insoluble in solid state

Since each metal lowers

freezing point of the other, the
line connecting the points
showing the beginning of
solidification, the liquidus line,
must show a minimum, at E

(eutectic point), for a

composition of 40A-60B)

over a wide range of compositions, a portion of cooling curve that shows end
of solidification occurs at a fixed temperature.

This lower horizontal line at TE (shown dotted in Fig), is known as the

eutectic temperature.
Two metals completely soluble in liquid state
insoluble in solid state

50
Two metals completely soluble in liquid state
insoluble in solid state
Actual phase diagram
is constructed
 by transferring the
breaks on the
cooling curves to a
plot of temperature
vs. composition
For alloy 80A-20B,
 beginning of
solidification T1,
 end of
solidification TE
51
Eutectic point

52
The Eutectic Reaction

Eutectic mixture

53
Phase Diagrams III

54
Binary Eutectic Systems (I: Metals Partially Soluble
in solid state)

55
 Binary Eutectic Systems (I: Metals
Partially Soluble in solid state)
• Three single phase regions
(α- solid solution of Ag in Cu matrix, β=
solid solution of Cu in Ag matrix, L - liquid)
• Three two-phase regions
(α+ L, ß+L, α+ß)
• Solvus line separates one solid solution
from a mixture of solid solutions.
• Solvus line shows limit of solubility
56
Binary Eutectic Systems

57
Eutectic point

58
 The Eutectic Reaction

Eutectic mixture

Eutectic temperature for Pb-Sn phase diagram 183°C,

Eutectic composition 61.9% Sn.

59
 Binary Eutectic Systems

Compositions and relative amounts of phases are determined

from the same tie lines and lever rule, as for isomorphous alloys
60
Development of microstructure(alloys with no eutectic and
forming unsaturated solid solution)
Equilibrium microstructures
of
lead-tin alloy

Cooled from 350ºC within

the liquid-phase region

In this case of lead-rich alloy

(0-2 wt. % of Sn) solidification
proceeds in the same manner
as for isomorphous alloys (e.g.
Cu-Ni).

L → α+L→ α

61
Development of microstructure (Alloys with no eutectic and
forming supersaturated solid solutions)
At compositions between the
room temperature solubility
limit and the maximum solid
solubility at the eutectic
temperature, β phase nucleates
as the α solid solubility is
exceeded upon crossing the
solvus line.

Alloy compositions extends from:

• 2% ~ 18.3% Sn ( Pb rich alloy)
• 97.8% ~ 99% Sn ( Sn rich alloy)

L α+L α α +β

62
Development of microstructure in eutectic alloy

Cooled from
250ºC
within the
liquid-phase
region

63
Development of microstructure in eutectic alloy

eutectic microstructure consists of

eutectic structure alternating layers of a lead-rich α-
(α-β layered) phase solid solution (dark layers),
lead–tin system and a tin-rich β-phase solid solution
(light layers)
64
Development of microstructure in hypoeutectic alloys

Primary α phase
is formed in the
α+ L region, and
the
eutectic structure
that includes
layers of α and β
phases (called
eutectic α and
eutectic β
phases) is
formed upon
crossing the
eutectic
isotherm. 65
Development of microstructure in hypoeutectic alloys

Microstructure of a
lead–tin alloy of
composition 50 %
Sn–50 % Pb.

Composed of a primary lead-rich α phase (large dark

regions) within a lamellar eutectic structure
 consisting of a tin-rich β phase (light layers) and a
lead-rich α phase (dark layers)
66
Problems related to binary eutectic diagram

67
68
69
70
Cooling curves

71
72
73
74
 Problems related to binary eutectic diagram
Problem
Two metals A (melting point 900 C) and B (melting point 600
C) form a eutectic at 400 C with a composition 40 wt.% A.
The metal A is soluble to B to the extent of 5 wt.% A at room
temperature which increases to 20 wt.% A at the eutectic
temperature. Metal B is not soluble to A in the solid state.
1. Construct the phase diagram for metals A and B and label all
points, lines and areas.
2. For an alloy containing 70 wt.% B,
(a) Indicate the start and end of solidification temperatures.
(b) Determine the compositions and relative amounts of the
phases present at 300 C.
(c) Draw and label the microstructure of the alloy at the room
temperature.
(d) Draw the cooling curve.
75
Problems related to binary eutectic diagram

Melting point of A – a
Melting point of B – g
Eutectic point – E
Liquidus line – a E g
Solidus line – a b E f g
Solvus line – f h

76
Problems related to binary eutectic diagram
2. (a): The start and end
of solidification
temperatures are 450
and 400 C respectively.

2. (b): The phases present

at 300 C are E and β. Their
compositions are:
CE = 60 wt.% B
Cβ = 86 wt.% B
The relative amounts of
the phases:
WE = 100 QR/PR
= 100 (86-70)/(86-60)
= 61.5 %
Wβ = 100 – 61.5
= 38.5 % 77
 Problems related to binary eutectic diagram
2. (d): The cooling curve
of the alloy:

2. (c): The room

temperature microstructure
of the alloy contains
Proeutectic β and Eutectic.
78
 Homework 1

Problem for Homework 1:

(a) In a plain graph paper draw a phase diagram of a system,
containing two metals: A and B, which are completely
insoluble in the solid state, and having a eutectic point at
60B. Also, for an alloy of composition 40B, schematically
show the changes in microstructure occurred during slow
cooling from liquid state to room temperature.
(b) For the alloy mentioned in (a), calculate the phase fractions
at
(i) just above liquidus line,
(ii) just below liquidus line,
(iii) just above eutectic temperature and
(iv) at room temperature.
You can assume the melting points of A & B
79
 Homework 2

Problem for Homework 2:

Cu melts at 1083°C and A 2g melts at 961°C. They form a
eutectic containing 71.9 wt% Ag at 779°C. The maximum solid
solubility of Ag in Cu at this temperature is 8 wt% and that of
Cu in Ag is 8.8 wt%. Assume the solubility of each at room
temperature is 0.5 wt%.
(a) Draw the equilibrium diagram to scale on a piece of graph
paper labeling all points, lines and areas.
(b) For a 30 wt% Ag 70 wt% Cu at 600°C:
(i) What phases are present? (ii) What are the compositions of
phases? (iii) Calculate the relative amount of each phase
present in terms of mass fraction and volume fraction. At
600°C take the densities of Cu and Ag to be 8.72 and 10.12
g/cm3 respectively.
80
 Homework 3

Problem for Homework 3:

For the equilibrium diagram shown (next page) answer the

following questions.
(i) Which alloy composition has the lowest melting point?
(ii) At 600°C what composition range(s) will give only a
single phase?
(iii) In α and β what is the solvent and what is the solute?
(iv) What is the maximum solubility of Ag in Cu and Cu in Ag
and at what temperature?
(v) The eutectic mixture contains alternate lamellae of α and β.
When the eutectic mixture first forms (at 7800 C) , what is
the relative amount of each phase inside the mixture and
what is their composition?
81
Homework 3

82
 Assignment
on
binary eutectic diagram

Submission due
by
27 January 2021

83
 Assignment for Even Roll No
Problem for Even Roll No: due 27 January 2021
Lead melts at 327°C. and tin melts at 232°C. They form a
eutectic containing 62 percent tin at 182°C. The maximum solid
solubility of tin in lead at this temperature is 19 percent; and that
of lead in tin, 3 percent. Assume that the solubility of each at
room temperature is 1percent.
(i) Draw the equilibrium diagram to scale on a piece of graph
paper labeling all points, lines and areas
(ii)For a slowly cooled alloy containing 40 percent tin,
(A) Give the temperature of initial solidification,
(B) Give the Temperature affinal 'solidification,
(C) Give the chemical composition and relative amounts
of phases present at temperature of 200°C.
(D) Sketch the microstructure at room temperature.
(E) Draw the cooling curve 84
 Assignment for Odd Roll No
Problem for Odd Roll No: due 27 January 2021

Metals A and B of melting points 750°C and 920°C,

respectively, are completely soluble in the liquid state but
partially soluble in the solid state.
At 400°C a eutectic composition is formed with 60% A and 40%
B. At eutectic temperature the solubility of B in A is 20%
and that of A in B is 15%, while at O°C the solubility of B in A
is 8% and that of A in B is 5%.
(a) Draw the A-B phase diagram in a graph paper, assuming all
the liquidus and solidus lines to be straight and label all the
phase fields.
(b) Draw the cooling curves and sketch the microstructures of
three alloys at O°C containing 30%, 60% and 75% A and rest B
85
Homework
References:
1. Callister. Materials Science and Engineering: An Introduction
2. Askeland. The Science and Engineering of Materials