Chapter 6 - Phase Diagram

11/9/2022
MATERIALS SCIENCE
Chapter 6
Phase diagrams
Giang V. H. Phan
9 November 2022 Giang VH Phan_Materials Science – Chapter 6 1
6.1. Introduction
• The phase diagram for pure H2O (external pressure versus
temperature)
• Field: 1 phase
• Line: 2 phases
coexistence
• Triple point: 3 phases
coexistence
Triple point: solid, liquid,

and gaseous water can
coexist in a stable
equilibrium
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6.1. Introduction
0.01 oC, 0.00603 atm
• The water phase diagram has a triple point at which solid, liquid, and
gaseous water can coexist in a stable equilibrium
6.1. Introduction
• The phase diagram for Nickel-Copper alloy system (temperature
versus composition)
 Phases presence  Composition of phases

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6.1. Introduction
• Phase diagram is a type of graph used to show all the equilibrium
phases as a function of temperature, pressure, and composition
• The understanding of phase diagrams for alloy systems is extremely
important because there is a strong correlation between microstructure
and mechanical properties
• Phase diagrams provide valuable information about melting, casting,
crystallization, and other phenomena
6.1. Introduction
Supercritical fluid
Gas
Liquid
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6.1. Introduction
• Terminology
• Component (C) is normally elements or stable compounds from which
the phase is formed
• For example, in a copper–zinc brass, the components are Cu and Zn.
Water – ethanol system, the components are ethanol and water
• Cấu tử: là những nguyên tố hoặc hợp chất độc lập, có thành phần
không thay đổi tạo nên các pha của hệ
• A phase (P) is a chemically and structurally homogenous region of a
material. Region of uniform physical and chemical characteristics. Phase
boundaries separate two distinct phases.
• Pha là tập hợp những phần đồng thể của hệ, có cùng thành phần hoá
học và tính chất lý hoá ở mọi điểm
• A single phase system is called homogeneous. A system with two or
more phases is called heterogeneous
6.1. Introduction
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6.1. Introduction
• A system is at equilibrium if at particular temperature, pressure and
composition the system is stable, not changing with time
• In thermodynamics the equilibrium is described as a state of a system
that corresponds to the minimum of thermodynamic function called the
free energy
• Number of degree of freedom (F) is the number of variables (T, p, and
composition) that can be changed independently without changing the
phases of the system in equilibrium
• Số bậc tự do là số yếu tố bên trong

(thành phần của hệ) và yếu tố bên
ngoài (nhiệt độ, áp suất) có thể thay
đổi được trong một phạm vi nào đó
mà không làm thay đổi số pha và
tính chất pha của hệ
6.1. Introduction
• Number of degree of freedom (F)
• F= 0, zero degrees of freedom. Neither P or T or Composition can be
change
• F = 1 one degree of freedom. One variable (P or T or Composition) can
be changed independently
• F = 2 two degrees of freedom. Two variables (P or T or Composition)
can be changed independently
• In a solution: solvent - host or major component, solute – minor
component
• Solubility limit - maximum concentration of solute that may dissolve in
a solvent at a given temperature to form a solid solution (single phase)
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6.1. Introduction
• Microstructure: arrangement of phases in structure at the microscopic
level
• 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
6.2. Gibbs phase rule

• Gibbs phase rule: F =2 + C – P
• C : number of components in the system
• P : number of phases in equilibrium
• F : degree of freedom (T, P, composition)
Josiah Willard Gibbs (Feb 11, 1839 -

Apr 28, 1903), an American scientist
Point C P F
1
2
3
4
5
6
7
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6.2. Gibbs phase rule

• In materials science, pressure is often considered to be constant (for
example at one atmosphere)
• Gibbs phase rule for pressure constant F = 1 + C – P
Cu-Ni phase diagram

Point C P F
1
2
3
4
5
6.3. One-component phase diagram

• One-component phase diagram (giản đồ pha hệ 1 cấu tử)
• at any point on one of these curves (phase boundaries), the two phases on
either side of the curve are in equilibrium (or coexist) with one another.
• At O (273.16 K and a pressure of 6.04 × 10-3 atm), all of the solid, liquid,
and vapor phases are simultaneously in equilibrium with one another. Any
deviation from this point by a change of temperature and/or pressure will
cause at least one of the phases to disappear.
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6.4. Binary phase diagrams

• Binary phase diagram
• Giản đồ pha hệ 2 cấu tử (nhiệt độ - thành phần % wt. or % mol)
• Binary isomorphous systems (Hệ 2 cấu tử hoà tan vô hạn vào nhau)
• Binary eutectic systems (limited solid solubility, Hệ 2 cấu tử hoà tan
có hạn vào nhau)
• Binary systems with intermediate phases/compounds (the iron-carbon
system/ steel and cast iron)

• Binary isomorphous systems (Hệ 2 cấu tử hoà tan vô hạn vào nhau)
• Isomorphous system - complete solubility of the two components (both
in the liquid and solid states)
Miscible liquid
Melting point of A
Solid solution
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• Three phase region can be identified on the phase diagram: Liquid (L),
solid + liquid (α +L), solid (α)
• Liquidus line (đường lỏng) separates liquid from liquid + solid
• Solidus line (đường rắn) separates solid from liquid + solid
• Example of isomorphous system: Cu-Ni, MgO-NiO, Al2O3-Cr2O3
• For a given temperature and composition of system, we can use
phase diagram to determine:
1. The phases that are present
2. Composition of the phases
3. The fraction of the phases
• Tại một điều kiện cụ thể của hệ trên giản đồ pha (có nhiệt độ và thành
phần xác định), các đặc trưng của hệ bao gồm loại pha tồn tại, thành
phần hoá học của từng pha và tỷ lệ giữa các pha được xác định

Complete
solubility in
liquid state
Crystalline
solid in matrix
of liquid
Complete
solubility in
solid state
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• Rule 1: If we know T and Co, then we know the number and types
of phases present (biết nhiệt độ và thành phần của hệ  biết loại
pha tồn tại)
Point Phase
A 1 phase: S (α)
B 2 phases: L+ S (α)

• Rule 2: If we know T and Co, then we know the chemical
composition of each phase (biết nhiệt độ và thành phần của hệ 
xác định được thành phần hoá học từng pha)
Point Phase Phases composition

A L 100% L, 35% Ni
B L + S (α) L: 32% Ni
S (α) : 43% Ni
D S (α) 100% S, 35% Ni
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• Rule 3: If we know T and Co, then we know the fraction of each phase
(in % wt. or % mol) (biết nhiệt độ và thành phần của hệ  xác định
được tỷ lệ % từng pha)
• The lever rule for finding the amounts of phases in a two phase region:
draw the tie line or isotherm, 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
Moment equilibrium

• An alloy of composition 35 wt% Ni–65 wt% Cu
Phases composition
Point Phase
and fraction
A L 100% L, 35% Ni
L: 32% Ni
α: 44% Ni
S
%L  x100%
B L+α RS
44  35
 x100%  75%
44  32
R
%S  x100%
RS
35  32
 x100%  25%
44  32
D S 100% S, 35% Ni
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• Determine mass fractions of phases (L, α) at point O

• An alloy of composition
35 wt% Ni–65 wt% Cu
• Microstructure of this
isomorphous alloys
during solidification
(cooling occurs very
slowly for phase
equilibrium)
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• Binary eutectic systems (limited solid solubility)
• Hệ 2 cấu tử hoà tan có hạn vào nhau
• Eutectic (Greek 'eutektos') - Easily melting
• Two components system has a special composition with a minimum
melting, for example the copper-silver system, lead-tin system
• Consider the lead-tin system
• The α phase is a solid solution rich in Pb; it has Sn as the solute
• The β phase is solid solution, but Pb is the solute
• The solubility in each of these solid phases is limited, a limited
concentration of Sn dissolves in Pb (for the α phase), and similarly for Pb
in Sn (for the β phase)
Solubility limit Solubility limit

of Sn in α of Pb in β
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• Consider copper-silver system
Eutectic point 71.9 wt%

Ag and 779°C
• Solid α and solid β: ?
E • An important reaction
occurs for an alloy of
composition CE as it
changes temperature
in passing through TE ,
this reaction may be
written as follows

• The point E on the diagram is called the eutectic point, CE and TE
represent the eutectic composition and temperature
• A eutectic reaction is defined as the one which generates two solids
from the liquid at a given temperature and composition, L  α + β
• The horizontal solidus line pass through TE is sometimes called the
eutectic isotherm
• CαE an CβE are the respective compositions of the phases α and β
phases at TE
• For a eutectic system, three phases (α, β and L) may be in equilibrium,
but only at points along the eutectic isotherm
• Left of E is called hypoeutectic whereas right of E is called
hypereutectic.
.
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• Practical problem
• Determination of phases present,
composition of the phases and
computation of phase
compositions for a 40 wt% Sn –
60 wt% Pb alloy at 220°C α L+α A L+β β
Phases composition
Point Phase
and fraction
L: 46% Sn
α: 17% Sn
46  40
A L + α %  46  17 x100%
 20.70%
40  17
%L  x100%
46  17
 79.30%

• Practical problem
• Determination of phases
present, composition of the
phases and computation of
phase fraction for a 40 wt% Sn
– 60 wt% Pb alloy at 150°C
B
Phases composition
Point Phase
and fraction
B
Eutectic reaction?
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• Microstructures in Eutectic system
• Co= 40 wt. % Sn

• Consider Al-Si system
L E(12.6% wt Si)  α  Si
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Review
• Using Gibbs phase rule, determine Degree of Freedom (DOF) at the
points A, B, C, X of phase diagram for magnesium
Point C P F
A
B
C
X
Review
• Using Gibbs phase rule, determine Degree of Freedom at points A, B,
C, X of phase diagram for carbon dioxide
P (atm)
73.0
A
Solid Liquid
C
B
5.11
X Gas
T (oC)
-56.4 31.1
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Review
• Using Gibbs phase rule, determine Degree of Freedom at points A, B, C,
D of phase diagram for water
Point C P F
A
B
C
D
Review
• Phase diagram of Cu-Ni, an alloy contains 45 wt. % of Ni
• What type of phase diagram
• At each point A, B, C, determine DOF, phase presence, composition of
phases and phase fraction
Phases composition
Point Phase
and fraction
A
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Review
• Phase diagram of Al2O3-Cr2O3 as shown below, the system contains
45 wt.% Cr2O3
• Determine DOF, phase presence, composition of phases and phase
fraction at points of A, B, C
Phases composition
Point Phase
and fraction
A
Review
• Phase rule at points A, B, C, D, E of binary phase diagram for Cu-Ni
Point C P F
C
E A
B
C
D
E
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Review
• Phase rule at points A, B, C of binary phase diagram for NiO-MgO
• At point B, determine phase presence, composition of phases and phase
fraction
Point C P F
A
B
C
Phases composition
Point Phase
and fraction
Review
• Phase rule at points A, B, C, D, E of binary phase diagram for Pb-Sn
• What kind of phase diagram
• Write the eutectic reaction, What is α phase and β phase
Point C P F
A
B
C
D
E
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Review
• Phase rule at points A, B, C, D, M of binary phase diagram for Al-Si
• Write the eutectic reaction
Point C P F
A
B
C
D
M
Review
• The phase diagram for nickel oxide and magnesium oxide (NiO-MgO)
• At 2600, 2300, 2100 oC, composition of 40 wt.% MgO, determine DOF,
phase presence, composition of phases and phase fraction
Phases composition
Point Phase
and fraction
2600oC
2300oC
2100oC
MgO crystallizes in a cubic cell with a rock-salt structure (FCC), ionic radii about 0.02 Å
difference
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Review
• The phase diagram for Lead and Tin (Pb-Sn)
• What is α phase and β phase in the diagram
• At 300, 225, 150 oC, composition of 40 wt.% Sn, determine DOF, phase
presence, composition of phases and phase fraction
Phases composition
Point Phase
and fraction
300oC
225oC
150oC
Review
• The phase diagram for Al-Si
• What is the α phase, write the eutectic reaction
• At points A, B, C the system contains 65 wt.% Si, determine phases
presence, composition of phases and phase fraction
• At point B, the system has mass of 500 g, find mass of each component
22

Chapter 6 - Phase Diagram

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11/9/2022

9 November 2022 Giang VH Phan_Materials Science – Chapter 6 1

Triple point: solid, liquid,

9 November 2022 Giang VH Phan_Materials Science – Chapter 6 2

0.01 oC, 0.00603 atm

9 November 2022 Giang VH Phan_Materials Science – Chapter 6 3

 Phases presence  Composition of phases

9 November 2022 Giang VH Phan_Materials Science – Chapter 6 5

9 November 2022 Giang VH Phan_Materials Science – Chapter 6 6

9 November 2022 Giang VH Phan_Materials Science – Chapter 6 7

9 November 2022 Giang VH Phan_Materials Science – Chapter 6 8

• Số bậc tự do là số yếu tố bên trong

9 November 2022 Giang VH Phan_Materials Science – Chapter 6 9

9 November 2022 Giang VH Phan_Materials Science – Chapter 6 10

6.2. Gibbs phase rule

Josiah Willard Gibbs (Feb 11, 1839 -

9 November 2022 Giang VH Phan_Materials Science – Chapter 6 12

6.2. Gibbs phase rule

Cu-Ni phase diagram

9 November 2022 Giang VH Phan_Materials Science – Chapter 6 13

6.3. One-component phase diagram

6.4. Binary phase diagrams

9 November 2022 Giang VH Phan_Materials Science – Chapter 6 15

6.4. Binary phase diagrams

9 November 2022 Giang VH Phan_Materials Science – Chapter 6 16

6.4. Binary phase diagrams

9 November 2022 Giang VH Phan_Materials Science – Chapter 6 17

6.4. Binary phase diagrams

9 November 2022 Giang VH Phan_Materials Science – Chapter 6 18

6.4. Binary phase diagrams

9 November 2022 Giang VH Phan_Materials Science – Chapter 6 19

6.4. Binary phase diagrams

Point Phase Phases composition

9 November 2022 Giang VH Phan_Materials Science – Chapter 6 20

6.4. Binary phase diagrams

9 November 2022 Giang VH Phan_Materials Science – Chapter 6 21

6.4. Binary phase diagrams

6.4. Binary phase diagrams

• Determine mass fractions of phases (L, α) at point O

9 November 2022 Giang VH Phan_Materials Science – Chapter 6 23

6.4. Binary phase diagrams

9 November 2022 Giang VH Phan_Materials Science – Chapter 6 24

6.4. Binary phase diagrams

9 November 2022 Giang VH Phan_Materials Science – Chapter 6 25

6.4. Binary phase diagrams

Solubility limit Solubility limit

9 November 2022 Giang VH Phan_Materials Science – Chapter 6 26

6.4. Binary phase diagrams

Eutectic point 71.9 wt%

9 November 2022 Giang VH Phan_Materials Science – Chapter 6 27

6.4. Binary phase diagrams

9 November 2022 Giang VH Phan_Materials Science – Chapter 6 28

6.4. Binary phase diagrams

6.4. Binary phase diagrams

9 November 2022 Giang VH Phan_Materials Science – Chapter 6 30

6.4. Binary phase diagrams

9 November 2022 Giang VH Phan_Materials Science – Chapter 6 31

6.4. Binary phase diagrams

9 November 2022 Giang VH Phan_Materials Science – Chapter 6 33

9 November 2022 Giang VH Phan_Materials Science – Chapter 6 34

9 November 2022 Giang VH Phan_Materials Science – Chapter 6 35

9 November 2022 Giang VH Phan_Materials Science – Chapter 6 36