CEB4022

Materials Science
for Chemical Engineering

Lecture 2 : 
Phase Diagram

1
 Outline

1 Definitions and Basic Concept

2 Unary Phase Diagram

Chapter
2
Binary Phase
3 Diagram

Miscrostructure and
4 Mechanical Properties in
isomorphous alloys 

2
 Lecture Outcomes
At the end of this lecture, students should be able to:

1. schematically sketch simple isomorphous and

phase diagrams.
2. in phase diagrams, label the various phase
regions.
3. given a binary phase diagram, determine:
(a) what phase(s) is (are) present;
(b) the composition(s) of the phase(s); and
(c) the mass fraction(s) of the phase(s).

3
 RECAPS

WHY STUDY
phase
diagram?
HOW IT RELATES
with materials?
WHAT IS
phase diagram?

WHEN TO USE
phase diagram?

4
 Introduction

 The understanding of phase diagrams for all

materials is extremely important especially in
alloy systems
 Strong correlation between microstructure and
mechanical properties
 Development of microstructure of a material is
related to the characteristics of its phase diagram
 Phase diagrams provide valuable information
about melting, casting, crystallization, and other
phenomena.

5
 System and Phase
System
• Definition – may refer to a specific body of material under
consideration or, relates to the series of possible materials consisting
of the same components, but without regard to its composition
• Example - Iron–carbon system. oil–water–surfactant system

Phase
• Definition - may be defined as a homogeneous portion of a system
that has uniform physical and chemical characteristics.
• every solid, liquid, and gaseous for pure materials
• Example- sugar–water syrup solution is

6
 Example: System and Phase
A single phase/Homogenous system: Ni-Cu solution
• Both have the same crystal structure (FCC) and have similar
electronegativities and atomic radii (W. Hume – Rothery rules)
suggesting high mutual solubility.

Crystal electronegativity r (nm)

Structure
Ni FCC 1.9 0.1246
Cu FCC 1.8 0.1278

Mixture/ Heterogenous system: Composites

• System consists of ≥ 2 phases

7
 Equilibrium Phase Diagram
 Phase diagrams are helpful in predicting phase
transformations and the resulting microstructures
 Microstructure is subject to direct microscopic
observation, using optical or electron microscopes;
 In metal alloys, microstructure is characterized by
• number of phases present
• their proportions
• manner in which they are distributed or arranged
 Equilibrium phase diagrams represent the relationships
between temperature and the compositions and the
quantities of phases at equilibrium.
 External pressure is also a parameter that influences the
phase structure.
8
 Components and Phases
• Components:
The elements or compounds which are present in the materials
Example: Al and Cu are present in alloy
• Phases:
The physically and chemically distinct material regions
that form (e.g., α and β).

Aluminum- Copper Alloy

β (lighter
phase)

α (darker
phase)

Adapted from chapter-opening

photograph, Chapter 9, Callister,
Materials Science & Engineering: An
Introduction, 3e.

9
 Solubility Limit
•  Solution – solid, liquid, or gas solutions, single phase
•  Mixture – more than one phase

10
 Solubility Limit

Solid Solution :
• Solid consists at least of two different types of atoms.
• For alloys, solute and solvent are terms commonly used. ‘‘Solvent’’ :
element present in the greatest amount (also called host atoms)
• ‘‘Solute’’ : element present in a minor concentration (impurity)

11
 Solubility Limit
•  Solution – solid, liquid, or gas solutions, single phase
•  Mixture – more than one phase
• Solubility Limit: Adapted from Fig. 9.1,
Callister & Rethwisch 8e.
Maximum concentration for
Sugar/Water Phase Diagram
which only a single phase
solution exists. 10 0
Solubility
L

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

Sugar
At 20ºC, if C > 65 wt% sugar: C = Composition (wt% sugar)
syrup + sugar
12
 Effect of Temperature & Composition
• Altering T can change number of phases:
• Altering C can change number of phases:

B (100ºC,C = 70) D (100ºC,C = 90)

Water-Sugar system 1 phase 2 phases
100
path B to D.
80 L
path A to B.
Temperature (ºC)

(liquid)
60 +
L S
( liquid solution (solid
40 i.e., syrup) sugar)
20 A (20ºC,C = 70)
2 phases
0
0 20 40 60 70 80 100
Adapted from Fig. 9.1,
Callister & Rethwisch 8e.
C = Composition (wt% sugar)
13
 Class activity: Question 1
• How much sugar
will dissolve in 1 kg
of water at 80˚ C?
• If that saturated
liquid solution is
cooled down to 20˚
C, is there any phase
changes? What will
be the composition
of the liquid
solution?
• How much of solid
sugar will come out
of solution upon
cooling to 20˚ C?

14
 One Component (or Unary) Phase Diagrams

 Information about the control of phase structure of a particular

system is graphically displayed called Phase diagram
 One component system – Simplest (P-T Diagram)

15
 Example
Consider a specimen of ice that is at −10°C and 101.3 kPa pressure.
Using the pressure–temperature phase diagram for H2O below,
determine the pressure to which the specimen must be raised or
lowered to cause it (a) to melt, and (b) to sublime.

16
 CLASS ACTIVITY: Question 2

 The yolk needs

around 65°C to get
hard and the egg
white needs around
85°C  to get
completely hard.
 Determine whether
an egg will harden
in a boiling water at
top of Mount
Everest. If no,
suggest how to solve
the problem?

17
 CLASS ACTIVITY: Question 3
Using the water-salt
phase diagram:
1. Briefly explain how
spreading salt on ice
that is at a
temperature below
0⁰C can cause the ice
to melt.
2. At what temperature
is salt no longer
useful in causing ice
to melt?
3. Give 2 examples of
application

18
How does salt melt ice

19
 Phase Diagrams of Binary Systems
• 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 is almost always used).

T(ºC) Phase Diagram for Cu-Ni system

1600
• 2 phases:
1500 L (liquid)
L (liquid)
α (FCC solid solution)
1400
• 3 different phase fields:
id us
1300 liq
u α L
L l+idus L+ α
so
1200 a α
1100
(FCC solid
solution)
1000
0 20 40 60 80 100 wt% Ni
Adapted from Fig. 9.3(a), Callister & Rethwisch 8e. (Fig. 9.3(a) is adapted from Phase Diagrams of Binary Nickel Alloys, P. Nash (Ed.), ASM
International, Materials Park, OH (1991).
20
 Isomorphous Binary Phase Diagram
• Phase diagram: T(ºC)
Cu-Ni system. 1600

• System is: 1500 L (liquid) Cu-Ni

-- binary phase
i.e., 2 components: 1400 diagram
Cu and Ni. d us
u i α
1300 liq
-- isomorphous L l+idus
i.e., complete so
1200 α
solubility of one
component in 1100 (FCC solid
another; a phase solution)
field extends from 1000
0 20 40 60 80 100 wt% Ni
0 to 100 wt% Ni.
Adapted from Fig. 9.3(a), Callister &
Rethwisch 8e. (Fig. 9.3(a) is adapted from
Phase Diagrams of Binary Nickel Alloys, P.
Nash (Ed.), ASM International, Materials Park,
OH (1991).

21
 Phase Diagrams:
Determination of phase(s) present
• Rule 1: If we know T and Co, then we know:
-- which phase(s) is (are) present.

• Examples: T(ºC)
1600
A(1100ºC, 60 wt% Ni): L (liquid)
1 phase: a 1500

B (1250ºC,35)
u s
uid Cu-Ni
B (1250ºC, 35 wt% Ni): 1400 liq phase
i dus
2 phases: L + a s ol diagram
1300
a
L+ a
(FCC solid
Adapted from Fig. 9.3(a), Callister & 1200
Rethwisch 8e. (Fig. 9.3(a) is adapted
from Phase Diagrams of Binary Nickel
solution)
Alloys, P. Nash (Ed.), ASM 1100 A(1100ºC,60)
International, Materials Park, OH
(1991).
1000
0 20 40 60 80 100 wt% Ni

22
 Phase Diagrams:
Determination of phase compositions
• Rule 2: If we know T and C0, then we can determine:
-- the composition of each phase.
Cu-Ni system
T(ºC)
• Examples:
A
Consider C0 = 35 wt% Ni TA tie line
s
id u
L (liquid) liqu
1300
At TA = 1320ºC: a
B L +
Only Liquid (L) present TB dus
soli
CL = C0 ( = 35 wt% Ni) a
a
At TD = 1190ºC: 1200 L + (solid)
D
TD
Only Solid (a) present
C = C0 ( = 35 wt% Ni) 20 30 32 35 40 43 50
CL C0 C
At TB = 1250ºC: wt% Ni

Both and L present Adapted from Fig. 9.3(a), Callister &

 Rethwisch 8e. (Fig. 9.3(a) is adapted from
CL = C liquidus ( = 32 wt% Ni) Phase Diagrams of Binary Nickel Alloys,
P. Nash (Ed.), ASM International,
C = C solidus ( = 43 wt% Ni) Materials Park, OH (1991).

23
 Phase Diagrams:
Determination of phase weight fractions

• Rule 3: If we know T and C0, then can determine:

-- the weight fraction of each phase.
Cu-Ni system
• Examples: T(ºC)
A
Consider C0 = 35 wt% Ni TA tie line s
idu
L (liquid) liqu
At TA : Only Liquid (L) present 1300
a
B L +
WL = 1.00, Wa = 0 dus
TB soli
At TD : Only Solid ( ) present

R S
a
a
WL = 0, W = 1.00 L + (solid)
a 1200 D
At TB : Both

and L present TD

WL = S  ¿ 43 −35 =0.73 20 30 32 35
CL C0
40 43
C wt% Ni
50

R +S 43 −32
Adapted from Fig. 9.3(a), Callister & Rethwisch 8e. (Fig.
9.3(a) is adapted from Phase Diagrams of Binary Nickel
R Alloys, P. Nash (Ed.), ASM International, Materials Park,
Wa = = 0.27 OH (1991).

R +S
24
1.
The Lever Rule
The tie line is constructed across the two-phase region at the temperature of the
alloy.

2. The overall alloy composition is located on the tie line.

3. The fraction of one phase is computed by taking the length of tie line from the
overall alloy composition to the phase boundary for the other phase and dividing
by the total tie line length.

4. The fraction of the other phase is determined in the same manner. 

5. If phase percentages are desired, each phase fraction is multiplied by 100. 

6. When the composition axis is scaled in weight percent, the phase fractions
computed using the lever rule are mass fractions—the mass (or weight) of a
specific phase divided by the total alloy mass (or weight).

7. The mass of each phase is computed from the product of each phase fraction
and the total alloy mass.

25
 The Lever Rule
 Tie line – connects the phases in equilibrium with each other –
also sometimes called an isotherm
T(ºC)
tie line dus
What fraction of each phase?
i
1300 L (liquid) liqu Think of the tie line as a lever
+ a (teeter-totter)
B L
d us
TB soli ML M
a a
1200 L+ (solid)
R S

20 30 40 50 R S
CL C0 C
wt% Ni Adapted from Fig. 9.3(b),
Callister & Rethwisch 8e.

26
 Volume Fraction
 For multiphase alloys, it is often more convenient to specify relative phase
amount in terms of volume fraction rather than mass fraction.
 Phase volume fractions are preferred because they (rather than mass
fractions) may be determined from examination of the microstructure;
 furthermore, the properties of a multiphase alloy may be estimated on the
basis of volume fractions.
 For an alloy consisting of α and β phases, the volume fraction of the α
phase, Vα , is defined as:

where vα and vβ are volume of the respective phase in the alloy.

27
 Cooling of a Cu-Ni Alloy
• Phase diagram: Cu-Ni system.
T(ºC) L (liquid) L: 35wt%Ni
Cu-Ni
130 0 a system
A
L: 35 wt% Ni L+
a: 46 wt% Ni B
35 46
• Consider 32 C 43
microstructural 24 D L: 32 wt% Ni
36
changes that a a: 43 wt% Ni
accompany the 120 0
L+ E
L: 24 wt% Ni
cooling of a a: 36 wt% Ni
C0 = 35 wt% Ni a
(solid)
alloy
110 0
20 30 35 40 50
Adapted from Fig. 9.4, C0 wt% Ni
Callister & Rethwisch 8e.
28
 Cored vs Equilibrium Structures
• Ca changes as we solidify.
• Cu-Ni case: First a to solidify has Ca = 46 wt% Ni.
Last a to solidify has Ca = 35 wt% Ni.

• Slow rate of cooling: • Fast rate of cooling:

Equilibrium structure Cored structure First a to solidify:
Uniform Ca: 46 wt% Ni
35 wt% Ni

Last a to solidify:

< 35 wt% Ni

29
 Mechanical Properties: Cu-Ni System
• Effect of solid solution strengthening on:
-- Tensile strength (TS) -- Ductility (%EL)

60
Tensile Strength (MPa)

%EL for pure Cu

Elongation (%EL)
400
50 %EL for
TS for pure Ni
pure Ni 40
300
TS for pure Cu 30
200
0 20 40 60 80 100 20
Cu Ni 0 20 40 60 80 100
Cu Ni
Composition, wt% Ni Composition, wt% Ni
Adapted from Fig. 9.6(a), Callister Adapted from Fig. 9.6(b), Callister
& Rethwisch 8e. & Rethwisch 8e.

30
 CLASS ACTIVITY: Question 4
A copper–nickel alloy of composition
70 wt% Ni–30 wt% Cu is slowly
heated from a temperature of 1300ᴼC
(1573 F). 
(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? 

31
 CLASS ACTIVITY: Question 5
• It is desirable to produce a copper-nickel alloy that has a minimum non
cold-worked tensile strength of 350 MPa and a ductility of at least 48%
elongation. Is such an alloy possible? If so, what must be its
composition? If this is not possible, then explain why.

32
 Summary
 Equilibrium phase diagrams = representing the most stable
relationships between phases in alloy systems.
 In Unary phase diagram: only one component present. Diagram 
Pressure plotted vs T : solid, liquid, vapor region
 In Binary phase diagram: two component present. Diagram T vs %wt
, P held constant
 For an alloy of specified composition and at a known temperature,
the phases present, their compositions, and relative amounts under
equilibrium conditions may be determined. 
 Within two-phase regions, tie lines and the lever rule must be used
for phase composition and mass fraction computations, respectively.
 Isomorphous diagrams are those for which there is complete
solubility in the solid phase; the copper–nickel system displays this
behavior. 
 Microstructure for both cases of equilibrium and non-equilibrium
cooling
 Mechanical characteristics depends on composition.

33
Thank You

34