Introduction to Material Science and Engineering

Lecture 11-16 | Phase Diagrams

Need for phase diagrams
ALLOY PHASE DIAGRAMS are useful to metallurgists, materials engineers, and materials scientists.

 development of new alloys and understanding the evolution of microstructures for specific applications

 fabrication of these alloys into useful configurations

 design and control of heat treatment procedures for specific alloys that will produce the required

mechanical, physical and chemical properties

 solving problems that arise with specific alloys in their performance in commercial applications, thus

improving product predictability.

In summary, phase diagrams allow research, development, and production to be done more efficiently and
cost effectively.
Definitions and basic concepts in Phase Diagrams

Phase Diagram

 Phase diagrams are also called as Equilibrium Phase Diagrams as they represent the phases

developed under equilibrium conditions. They are also called constitutional diagrams.

 Phase diagrams are essentially stability maps as they represent the stable phases indicated in

the diagram.

Phase Equilibrium

 A system is at equilibrium if its free energy is at a minimum under some specified combination

of temperature, pressure and composition.

 In a macroscopic sense, equilibrium implies that the characteristics of the system do not

change with time but persist indefinitely, i.e., the system is stable. 3
There are three types of equilibria
 Stable equilibrium exists when the object is in its lowest energy condition
 Metastable equilibrium exists when additional energy must be introduced before the object
can reach true stability
 Unstable equilibrium exists when no additional energy is needed before reaching metastability
or stability

Mechanical equilibria (a) Stable (b) Metastable (c) Unstable

Components are pure metals and/or

compounds of which an alloy is composed.

System relates to the series of possible alloys

consisting of the same components, but

without regard to alloy composition.

Solid solution consists of atoms of at least two

different types.
 the solute atoms occupy either substitutional or
interstitial positions in the solvent lattice
 the crystal structure of the solvent is maintained
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Solubility limit
 The maximum concentration of solute atoms that can be dissolved in the solvent under specific
conditions to form a solid solution, is called as solubility limit.
 The addition of solute in excess of solubility limit results in the formation of another solid solution or
compound that has a distinctly different composition.

The solubility limit of sugar (solute) in water

(solvent) depends on temperature of
water.
Solvus line
At 20ºC, if C < 65 wt% sugar: syrup
At 20ºC, if C > 65 wt% sugar: syrup + sugar

Solubility Limit is maximum concentration for

which only a single phase solution exists.

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Phase
A phase is a homogeneous portion of a system that has uniform physical and chemical
characteristics.

For single component system, the solid, liquid, and gaseous state is considered to be a phase.

For two component system, when two phases are present, it is not necessary that there be a
difference in both physical and chemical properties; a disparity in one or the other set of
properties is sufficient.
Examples:
 Water and ice (chemically similar but physically dissimilar)
 BCC Iron and FCC Iron (chemically similar but physically dissimilar, crystal structure)

Systems composed of two or more phases are termed “heterogeneous systems” or “mixtures”.

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Types of Phase Diagrams: Based on number of components
Based on number of components, phase diagrams can be classified as -

 Unary phase diagram – It is a single component phase diagram.

 Binary phase diagram – It is a two component phase diagram.
 Ternary phase diagram – It is a three component phase diagram.
 In reality, most materials of commercial importance are multi-component.

One component Two Component Three Component

(Unary) (Binary) (Ternary)

• Water • Water-Sugar • Al-Si-Mg

• Carbon dioxide • Al-Si • Fe-C-Cr
• Carbon • Pb-Sn • Ti-Ni-Zr
• Silica • Al-Cu • Mg-Al-Zn
• Ti-Ni
• Fe-C
• Al2O3-SiO2

Composition is fixed Pressure is fixed, 1 atmosphere 8

Unary phase diagram of H2O

ao: sublimation curve

bo: melting curve
co: vapourisation curve
c: critical point
(here the physical distinction between
the liquid and gas phase disappears)
o: Triple point or invariant point
(three phases are in equilibrium)

Explain the transition from ice to steam at 1 atmospheric pressure.

Why does food cook faster in a pressure cooker?

Why does food take longer time to cook in higher altitude?

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Unary phase diagram of CO2

CO2 at RT is gas.

At what temperature does dry ice

(solid CO2) convert to gas?

Which is the stable phase of CO2

under normal conditions?

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Binary phase diagram: Isomorphous system
At.% B 
Axes
Temperature and Composition (represents Pure A, Pure B
or alloys) Liquid (L)

Temperature
Points TB
TA and TB represents melting point of Pure A and Pure B
Lines
Liquidus Line - the line above which only liquid exists α+L
Solidus Line - the line below which only solid exists

Temperatures
Liquidus temperature (TL) TA
Solidus temperature (TS) Solid solution
Freezing range = TL – TS
Semisolid region/mushy zone contains α + L (α)
Need to know the solute content in α +L A B
Need to quantify the change in amount of α and L as
the alloy is solidifying, i.e. with decrease in temperature
Composition, Wt.% B 
Binary phase diagram of Cu and Ni
 Axes: Bottom (in wt.%), Top (in at.%)
R
 Melting point: Cu and Ni

 Single phase regions: Liquid and α

Q
 Two phase region: α + L

 Liquidus Line: PQR (Line separating liquid phase S

and a + Liquid phase) OR the line above which
only liquid exists
 Solidus Line: PSR (Line separating solid phase and
a + solid phase) OR the line below which only P
solid exists

The Cu-Ni system is termed isomorphous because

of complete liquid and solid solubility of the two
components. Cu-Ni phase diagram 12
Hume-Rothery rules for substitutional solid solution

1. Atomic size factor - The difference in atomic radii between the two atom types should be
< ±15%, else the solute atoms will create substantial lattice distortions and a new phase will form.
2. Crystal structure - The crystal structures for
metals of both atom types must be the same.
3. Electronegativity - The difference in electronegativity should be minimum to form substitutional
solid solution, else intermetallic compound may form.
4. Valences - Other factors being equal, a metal will have more of a tendency to dissolve
another metal of higher valency than one of a lower valency.
Copper-Nickel system satisfies all the four
Hume-Rothery rules for a substitutional solid
R
solution, and hence are completely soluble in
one another at all proportions.
Q
 The atomic radii for copper and nickel are

0.128 and 0.125 nm, respectively

S
 Both have FCC crystal structure

 Electronegativities are 1.9 and 1.8

 The most common valences are 1 for P

copper (sometimes 2) and 2 for nickel.

Development of Cu-Ni phase diagram using cooling curves
Tie Line Rule
At.% B 
 Tie line Rule is used to determine the composition
of the phases, i.e., the amount of solutes in the L

Temperature
phases. TB
 Tie lines are isothermal lines (horizontal lines) α+L
drawn in two phase regions.

 The solute content (wt.% B) in the phases (α and

TA
L) change as solidification progresses.

A 40 B
Composition, Wt.% B 
Lever Rule At.% B 
Lever Rule is used to determine the amount of the
L
phases (in wt. %).

Temperature
TB
Consider an alloy of Composition Co at Temperature T
α+L
Two assumptions based on Laws of conservation of mass
 The sum of weight fraction of phases is equal to unity.
Wα + WL = 1
 The weight of one of the components that is present in
TA

both phases (here, α and L) must be equal to the weight of

that component in the total alloy. α
Wα Cα + WL CL = Co
A C0 B
Composition, Wt.% B 
 At.% B 

Temperature
TB

A solidification process can α+L

be explained using a
combination of Tie line rule
TA
and Lever rule.
α

A C0 B
Composition, Wt.% B 
Estimation of volume fraction of phases

Area fraction of a phase is equivalent to its Microstructure of two phase material

volume fraction, i.e., Af,α~ Vf,α - α and β

Knowing the density of phases, the weight fraction of α

phases can be calculated as -
β

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Equilibrium solidification: Slow cooling
Extreme slow cooling in a furnace can be assumed to
be equilibrium solidification.

At a, the alloy is in 100% liquid state

At b, the alloy starts to solidify by nucleating α grains

which contain 46%Ni and almost 100% liquid that
contains 35%Ni (Tie line rule)

At c, α grains continue to grow and contain 43%Ni

and liquid contains 32%Ni (Tie line rule)

At d, solidification is almost complete with α grains

containing 35%Ni and negligible amount of liquid
containing 24%Ni (Tie line rule)

Each grain at every stage of solidification has uniform

composition governed by the phase diagram. 20
Non-equilibrium solidification: Fast cooling
Almost all the solidification process are fast cooling
processes and result in “Coring or dendritic
segregation”.

Assumptions
 diffusion rates in liquid phase is rapid such that
equilibrium is maintained in the liquid
 diffusion rates in solid phase is low.

Each grain has a concentration gradient of solute(s)

as solidification progresses which is called coring.

Coring is not predicted by equilibrium phase

diagram.

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Summary
o solidus line on the phase diagram has been
shifted to higher Ni contents

o degree of displacement of the non-

equilibrium solidus curve w.r.t. equilibrium
solidus curve will depend on rate of cooling

How to minimize coring?

Coring is minimized by holding the alloy at a
temperature below the solidus temperature
for long times. This is called homogenization
heat treatment.

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Types of Phase Diagrams: Based on phase transformation

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Binary phase diagram: Eutectic system
TA
Liquidus Line - the lines in RED TB
Solidus Line - the lines in BLUE L
Solvus lines - the lines in GREEN
α+L
Label single phase regions

Label two phase regions TE β+L

α is the A rich solid solution of A and B
α P Q
β
β is the B rich solid solution of A and B
α+β
Eutectic point corresponds to TE and CE

P is the maximum solid solubility of B in A B

A CE
Q is the maximum solid solubility of A in B
Composition, Wt.% B 
Eutectic reaction
TA
The alloy with composition CE wt.% B is TB

called eutectic alloy, i.e., the alloy with L

lowest melting point.
α+L
In eutectic alloy, the liquid upon reaching
eutectic temperature transforms to two TE β+L
solid solutions, α + β, on cooling. This is
α P Q
β
called eutectic reaction.
α+β
The eutectic reaction

cooling
A CE B
Liquid α+β
heating Composition, Wt.% B 

There is no freezing range for the eutectic alloy.

Characteristics of Binary Eutectic phase diagrams
o There exists an alloy composition that freezes at a
lowest melting point amongst all other alloy
compositions.
o Three phases exist at equilibrium at the eutectic point.
o The microstructure consists of mixture of two different
phases, called eutectic or lamellar microstructure.

eutectic colonies or
eutectic grains

• The alloys towards the left of eutectic composition are called hypoeutectic alloys.
• The alloys towards the right of eutectic composition are called hypereutectic alloys.
• The alloy composition close to eutectic composition are called near-eutectic alloys. 26
Lamellar Eutectic Structure

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Binary Eutectic phase diagram of Pb-Sn

 Axes: Bottom (in wt.%), Top (in at.%)

 Melting point: Pb and Sn

 Single phase regions: Liquid, α and β

 Two phase regions: α + L, β + L, α + β

 Liquidus line

 Solidus line

 Solvus lines
 Eutectic point: Temperature and
composition

 Eutectic reaction: L α+β

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Binary eutectic phase diagram
Case 1
Both elements completely soluble in liquid state and completely insoluble in solid state

There is no solid solubility of

Bi and Cd in each other.

The eutectic reaction

cooling
Liquid Bi + Cd
heating
Binary eutectic phase diagram
Case 2
Completely soluble in liquid state and partly soluble in solid state

There is partial solid solubility of

Cu and Ag in each other.

The maximum solid solubility of

 Ag in Cu is 8% and
 Cu in Ag is 8.8%

The eutectic reaction

cooling
Liquid α+β
heating
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Binary eutectic phase diagram
Case 3
Both components completely soluble in liquid state and one of them partly soluble in solid state

Lead free solder

There is partial solid solubility of Bi in Sn

and no solid solubility of Sn in Bi.

The eutectic reaction

cooling
Liquid β + Bi
heating

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Development of microstructure in a binary eutectic phase diagram

The development of
microstructure during
solidification of five alloys
will be discussed.

Alloys 1 2 3 4 5 32
4
As the liquid reaches the eutectic
temperature, it will solidify via eutectic
reaction forming α and β.
This α is called eutectic α and
β is called eutectic β.

Eutectic mixture or Eutectic

The eutectic alloy contains, 100% eutectic. What is the amount of α and β

The eutectic alloy contains entirely (100%) lamellar microstructure. in the eutectic alloy?
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1 2

34
3
At liquidus temperature, the first phase to
solidify is α and this α is called primary α or
pro-eutectic α (as is solidifies before
eutectic temperature)

At eutectic temperature, the remaining

liquid will solidify via eutectic reaction
forming α and β. This α is called eutectic α
as it solidifies at eutectic temperature.

Final microstructure will consist of primary α, eutectic α and eutectic β

Primary α is coarser than eutectic α.
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5
o Solidification of Alloy 5 is similar to
Alloy 3
o The primary solidifying phase is β
o Final microstructure:

Primary β + Eutectic mixture

The phase diagrams suggest that all the

five alloys contain α + β, but does not
predict the nature and distribution of
phases.

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Pb-Sn Identify the type of alloy and its composition from
the microstructure.

Primary α + Eutectic

Black - Pb rich phase

White - Sn rich β phase

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Question 1
Calculate the fraction of primary Si and eutectic Si in Al-18wt.%Si alloy.

Question 2
Draw the equilibrium phase diagram with the given information in the grid. Element A and
Element B are completely soluble in both liquid and solid states. The melting point of A and B are
1769 and 1065 oC respectively. An alloy containing 40% B starts to solidify at 1600 oC by separating
grains of 15% B. An alloy containing 70% B starts to solidify at 1400 oC by separating grains of 40%B.

Question 3
A crucible made of pure nickel contains 500 grams of liquid copper at 1200 oC. Describe what
happens to the system as it is held at this temperature for several hours. Also calculate the
amount of crucible dissolved at 1200 oC.
Solution to Question 1

Total weight % of Si in the alloy = 18 wt.%

Weight % of primary Si + eutectic Si = 18 wt.%

Amount of eutectic in the alloy = (100 – 18)/(100 – 12.6)

= 0.938 = 93.8%

100 % eutectic contains 12.6% eutectic Si

93.8% eutectic contains 11.8% eutectic Si

So, primary Si = 18 – 11.8 = 6.2 %

Primary Si = 18 -12.6/100 – 12.6 = 6.2 %

So, eutectic Si = 18 – 6.2 = 11.8 %

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Solution to Question 2
Solution to Question 3

If the system is held at 1200 oC for several hours,

it tries to attain equilibrium by dissolving Ni
crucible.

The first solid is formed at ~ 20 wt% Ni.

If x gram of Ni is dissolved in 500 gram of liquid
Cu, then at 20 wt.% Ni we can write,
0.2 = x/(x + 500) or x = 125 grams

The maximum amount of Ni dissolved is ~30

wt.% at 1200 oC
If y gram of Ni is dissolved in 500 gram of liquid
Cu, then at 30 wt.% Ni we can write,
0.3 = y/(y + 500) or y = 214.3 grams

Thereafter, complete equilibrium is attained

and there is no further dissolution of Ni crucible.
Phase Diagrams with
intermediate phases or intermetallic compounds
 For many systems, discrete intermediate compounds with distinct chemical formulas are found
on the phase diagram.
 For metal–metal systems, they are called intermetallic compounds.
Metal – non metal system

Metal - metal system

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Phase diagrams with
intermetallic compounds

Mg2Pb forms at 81 wt.% Pb

or 33 at.% Pb

43
Phase diagrams with
intermetallic compounds

ZrAl forms at 24 wt.% Al or

50 at.% Al

Intermetallic compounds
are also called line
compound (as they appear
as lines in the phase
diagram) and have high

melting points.

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Cu-Zn
Terminal solid solution
They exist over composition ranges near
the extremities of the phase diagram.
Ex. Cu-Zn system has 2 terminal solid
solution

Intermediate solid solution

They exist at other than the two
composition extremes.
Ex. Cu-Zn system has 4 intermediate solid
solution

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Binary Eutectoid and Peritectic Phase Diagrams

At E, Eutectoid Reaction

At P, Peritectic Reaction

46
Ternary phase diagram

Al-Cr-Mn isothermal
Al-Cr-Mn isothermal
Section at
Section at 600
550 °C
°C

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Iron - Carbon Phase Diagram
Application range

Steel Cast Iron

9/11/2019
Important reactions in Fe-C system

Peritectic reaction
δ +L γ
Development of microstructure in steels
Hypo-eutectoid steel Eutectoid steel Hyper-eutectoid steel

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Microstructure of Ferrite Austenite Pearlite
phases in steels Colonies of Pearlite

Rapid Cooling T < 727oC

(Quenching) 18-24 hours

Martensite (BCT) Spheroidite

Gibbs Phase Rule
A criterion for the number of phases to co-exist within a system at equilibrium.
P+F=C+N
P : Number of phases present
F: Number of degrees of freedom
C: Number of components
N: Number of non-compositional variables i.e. pressure and/or temperature

For binary temperature-composition phase diagrams, pressure is constant, hence N =1

Degrees of Freedom, F
 Number of externally controlled variables (e.g., temperature, pressure, composition) which must be
specified to completely define the state of a system
 F is the number of these externally controlled variables that can be changed independently without
altering the number of phases that coexist at equilibrium.

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Example: Application of Gibbs Phase Rule

Here C = 2 and N =1 A B

At point A, P = 1 T(ºC)
So, F = C + N – P = 2 1200
L (liquid)
To completely describe the characteristics of an alloy in 1000
the single-phase region, two parameters need to be a L + a
specified, composition and temperature 800 779ºC L +b b
8.0 71.9 91.2
X
At point B, P = 2 600
So, F =1 a + b
To completely describe the characteristics of an 400
alloy in the two-phase region, one parameters need
to be specified, composition or temperature 200
0 20 40 60 CE 80 100

At point X, P = 3
So, F = 0
Composition of all three phases and temperature are fixed.

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Phase Diagrams for Ceramic systems

54
Phase Diagrams for Ceramic systems

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