ENGG 103

Materials in Design

Phase Diagrams I
Callister Chapter 9.1 to 9.7
18 April 2016
Why do we want to study Phase Diagrams

Phase diagrams tell us what phases are present in an alloy

system at any given temperature

It is largely the phases present that determine the

properties of alloys

Knowledge of the phases present allows us to manipulate

the properties of alloys

e.g. how it is possible too change the yield strength of the very same
steel (4340) from 400 MPa to 1600 MPa
 Issues to Address
• When we combine two elements...
what is the resulting equilibrium state?

• In particular, if we specify...
-- the composition (e.g., wt% Cu - wt% Ni), and
-- the temperature (T )
then...
How many phases form?
What is the composition of each phase?
What is the amount of each phase?

Phase A Phase B

Nickel atom Copper atom 3

Why do metals solidify? Look at G simply as the
energy of the system

ΔG is the change in energy

Liquid All systems wish to be in

the lowest state of energy

Solid At low temperature solid is

ΔG more stable

At high temperature liquid is

more stable
Melting Point

T
4
Critical Size
of a Nucleus
ΔG is simply the change in
energy of the system

All systems wish to be in

the lowest state of energy

5
 Solidification

Atoms attach to each other randomly

‒ until the critical size to form a
stable nucleus is reached.

These stable nuclei then grow

‒ until they impinge to form grain
boundaries

6
Example of the solidification on industrial scale

The Continuous Casting of Steel

More than one billion tonnes of steel

are cast annually by means of this technique 7
 What is a phase diagram?
A phase diagram is simply a diagram that tells us which phase or phases are
present under a certain set of conditions

Phases of pure H2O

as a function of pressure and temperature

8
Pressure-Temperature Phase Diagram for
H2 O
Page_297
11
Pressure-Temperature Phase Diagram for
H2 O

At one atmosphere

Solid (ice) is in
equilibrium with liquid
(water) at 0°C

Liquid (water) is in
equilibrium with vapour
(steam) at 100°C

What happens when an

ice-skater skates on
ice?

12
 Before we attack multi-component metallic systems let us turn our
attention to something more familiar

Water and alcohol form a liquid solution

This discussion on the water-alcohol equilibria is for background

information only

If we want to increase the alcohol content of a water-alcohol mixture

produced by natural fermentation, we can do it by fractional distillation
as many moonshiners do

Consider the binary phase diagram water - ethanol

13
 Fractional distillation

At temperature T, Liquid with composition C1 is in equilibrium with

vapour of composition C2

14
 Primitive still in
East Timor

Kettle
Zambian still
and cooler Cooling
(condensing) the
vapour

Condensate

15
 The Water-Ethanol Phase Diagram

The following four slides were taken from the

following link

http://www.chemguide.co.uk/physical/phaseeqia/no
nideal.html
The Water-Ethanol Phase Diagram
T
If we now take the liquid (condensate) of composition C2 and heat it up to temperature
T2, this liquid will be in equilibrium with vapour of composition C3
If we cool this vapour to room temperature, liquid of composition C3 will form
Hence,
The water alcohol mixture that initially contained C1% ethanol, now contains C3%
ethanol

T2

C3

19
Cooling curves in a binary system

Vapour (V)

V+L

Liquid (L)

Time

20
Water –Sugar Phase Diagram
 Solubility Limit
Solution – solid, liquid, or gas solutions, single phase
Mixture – more than one phase

Solubility Limit:
Maximum concentration for
which only a single phase Sugar/Water Phase Diagram
solution exists.
10 0

Temperature (°C)
Solubility
Question 80 Limit L
What is the (liquid)
solubility limit for sugar in 60
L +
water at 20C?
40 (liquid solution S
i.e., syrup) (solid
Answer 20 sugar)
65 wt% sugar.
At 20C, if C < 65 wt% sugar:
syrup 0 20 40 60 80 100

Sugar
Water

At 20°C, if C > 65 wt% C = Composition (wt% sugar)

syrup + sugar
22
 Effect of Temperature & Composition
• Altering T can change # of phases: path A to B.
• Altering C can change # of phases: path B to D.

100
B (100°C,C = 70) D (100°C,C = 90)
1 phase L
Temperature (°C)

2 phases
80
(liquid)
Water-Sugar +
System 60 L S
(liquid solution (solid
40 i.e., syrup) sugar)
20 A (20°C,C = 70)
2 phases
0
0 20 40 60 70 80 100
C = Composition (wt% sugar)
23
The Water- NaCl System
Note

The melting point of ice is

lowered by the addition of salt

With the addition of 10%

NaCl, the melting point of ice
is lowered to -7C

This diagram is an
example of an eutectic
system
 Components and Phases
Components
The elements or compounds which are present in the alloy
(e.g., Al and Cu)

Phases
The physically and chemically distinct material regions that form
(e.g., α and β).

β (lighter phase)

It is convention
to give Greek
symbols to solid α (darker phase)
phases

Aluminum-Copper
Alloy

25
 Binary Phase Diagrams
A phase diagram Indicate phases as a function of T, C, and P.
For this course:
- binary systems: just 2 components.
- independent variables: T and C (P = 1 atm)

2 phases
T(°C) L (liquid)
1600 α (FCC solid solution)
Phase
Diagram 1500 L (liquid)
for the 3 different phase fields
1400
Cu-Ni L
system 1300
(L +α)
1200 α
α
1100 (FCC solid
solution)
1000 26
0 20 40 60 80 100 wt% Ni
 Isomorphous Binary Phase Diagram

The system is T(°C)

1600
-- binary 1500
i.e., 2 components - Cu and Ni. L (liquid)
1400
-- isomorphous
i.e., complete solubility of one 1300
component in another;
1200 α
α phase field extends from
0 to 100 wt% Ni. 1100
(FCC solid
solution)
1000
0 20 40 60 80 100 wt% Ni
Phase diagram
Cu-Ni system
27
 Criteria for Solid Solubility
Simple system (e.g., Ni-Cu solution)

Crystal Electro r (nm)

Structure negativity

Ni FCC 1.9 0.1246

Cu FCC 1.8 0.1278

Both have the same crystal structure (FCC)

and have similar electro-negativities
and atomic radii
(W. Hume – Rothery rules)
suggesting high mutual solubility

Ni and Cu are totally soluble in one another for all proportions28

Construction of Phase Diagrams

By the use of Cooling Curves

29
 Cooling Curves

If a one-component system, such as a pure metal (or water for

that matter water), is allowed to cool at constant pressure and
the temperature is recorded as a function of time, the following
graph is obtained.

There are 5 regions

1. Vapour
2. Vapour plus Liquid (phase change)
3. Liquid
4. Liquid plus Solid (phase change)
5. Solid

30
 The heating curve of water,
which is the reverse of the cooling curve

31
Experimental Determination of Cooling Curves

32
 The heating curve of water,
which is the reverse of the cooling curve

33
 Interpretation of Binary Cooling Curves
Most systems consisting of two or more components exhibit a
temperature range over which the solid and liquid phases are in
equilibrium.

 Instead of a single melting temperature, the system

now has two different temperatures, the liquidus T
temperature and the solidus temperature which are
needed to describe the change from liquid to solid
L
 The liquidus temperature is the temperature above
which the system is entirely liquid L+S
 The solidus is the temperature below which the S
system is completely solid

 Between these two points the liquid and solid

phases are in equilibrium
t
34
 Interpretation of Binary Cooling Curves Cont.

 When the liquidus temperature is

reached, solidification begins and there T
is a reduction in cooling rate caused by
latent heat evolution and a consequent
reduction in the gradient of the cooling L
curve. L+S
 Upon the completion of solidification the
cooling rate alters again allowing the S
temperature of the solidus to be
determined.

t
35
Phase Diagrams of Binary alloys

36
 Phase Diagrams in Metallic and Ceramic
systems

In metallic or ceramic systems a phase diagram is usually a graphic

representation of the equilibrium temperature and composition limits of
phase fields

The stability of phases in condensed materials such as metals and

ceramics is essential independent of pressure
( in normal life situations)

Hence it is customary to construct a two-dimensional diagram of the

stability of the relevant phases at constant pressure
(usually atmospheric pressure)
on a diagram with Temperature and Chemical composition as axes

37
Construction of a phase diagram from cooling
curves

38
Important Information that can be Extracted
from a Phase Diagram

1. The phase(s) present at a given temperature and composition

2. The chemical composition of each phase present

3. The mass fraction (%) of each phase present

These three rules are of the utmost importance.

You need to make sure that you fully understand the rules
the implications thereof and
the application off these three rules

39
The Phase(s) Present at a Given Temperature
and Composition
The intersection of the isotherm with the composition line define the
phase(s) present

Phases present at
Isotherm 1300C

Liquid and Solid

Composition line

40
 The Tie-Line
We call the line that intersects an isotherm at the phase boundaries a Tie-Line

For composition X, the line A-B is called a tie-line

(The isotherm intersects the liquidus in A and the solidus in B)

A B

X
 The Chemical Composition of Each
Phase Present
For a given composition, the intersections of the tie-line with the phase
boundaries define the chemical composition of the respective phases

For composition X
at temperature 1275C

The tie-line intersect the phase

boundaries:

 The liquidus in A
 The solidus in B

A gives the composition of the liquid (35% in this case)

B gives the chemical composition of the solid (53% in this case)

The Mass Fraction (%) of Each Phase Present

By the lever rule

Mass fraction solid = XA/BA

Mass fraction Liquid = BX/BA

The Lever Rule
Fraction of α = b/(a+b)

Fraction of β = a/(a+b)

Hint

Do not use mass % α

or mass % β

Although mass% α is equivalent to

fraction α, the use of mass% to
indicate the amount of α present in
the microstructure at a given
temperature leads to confusion

It is therefore much clearer to use

fractions

44
 The Lever Rule
Tie line
– connects the phases in equilibrium with each other – also sometimes
called an isotherm
What fraction of each phase?
T(C) Think of the tie line as a lever
tie line
1300 L (liquid) ML Mα
B
TB
α
1200 (solid) R S
R S

20 3 0CL
C0 4 0 Cα 50

wt% Ni
Substitute ML in next equation

45
 Home Assignment
Do this assignment before the next lecture

Bring pen and paper to the next lecture since we shall do some
practical examples in class

 What phases are present in a Cu-40%Ni alloy at 1250C?

 What are the chemical compositions of the respective phases?

 At what temperature will the first solid appear on slow cooling a Cu-70%Ni alloy?
 What is the chemical composition of this solid?
 At what temperature will the alloy be completely solid on slow cooling?
 What is the composition of the last remaining liquid?
 Sketch the cooling curve of a Cu-30%Ni alloy
 Sketch the cooling curve of a Cu-60%Ni alloy