Introduction to

Materials Science & Engineering

Chapter 9.
9 Phase Diagrams

1
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 Contents

1 Introduction

2 Solubility Limit

3 Phase Diagrams
g

4 Microstructural
M crostructura Evolution
E o ut on during
ur ng Cooling
oo ng

5 Eutectic Systems

6 Fe C Alloy
Fe-C
2
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 Issues to address
¾ When
Wh we combine
bi two
t elements...
l t
Æ What equilibrium state do we get?
¾ In particular,
l if
f we specify...
f
√ Composition (e.g., atomic % Ge – atomic % Sn), and
Temperature (T )
Then...
√ How many phases do we get?
√ What is the composition of each phase?
√ How much of each phase do we get?

Ph
Phase A Phase B

Nickel atom
3 Copper atom
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 ¾ Phase: chemically and structurally homogeneous region of material.
¾ Components: chemically distinct and essentially indivisible
substance.
¾ Solubility limit - maximum concentration of solute that may
dissolve in a solvent at a g
given temperature
p to form a solid solution.
¾ Precipitate - a solid phase that forms from the original matrix
phase when the solubility
p y limit is exceeded.
¾ Phase diagram - graphical representation of the phases present
and the
an th ranges
rang in
n composition,
c mp t n, temperature,
t mp ratur , and
an pressure
pr ur overr
which the phases are stable.
¾ Gibbs phase rule: F =C + 2 – P
√ C : # components
√ P : # phases in equilibrium
4 √ F : degree of freedom (temperature, pressure, composition.)
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 ¾ Binary phase diagram - A phase diagram for a system with two
components.
t
¾ Ternary phase diagram - A phase diagram for a system with three
components.
components
¾ Isomorphous phase diagram - A phase diagram in which components
display unlimited solid solubility.
¾ Liquidus temperature - The temperature at which the first solid
begins to form during solidification.
¾ Solidus temperature - The temperature below which all liquid has
completely solidified.
¾ Intermetallic compound - A compound formed of two or more
metals that has its own unique composition, structure, and
p p
properties.
¾ Eutectic - A three-phase invariant reaction in which one liquid
phase solidifies to produce two solid phases.
¾ Peritectic - A three-phase reaction in which a solid and a liquid
5 combine to produce a second solid on cooling.
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 Contents

1 Introduction

2 Solubility Limit

3 Phase Diagrams
g

4 Microstructural
M crostructura Evolution
E o ut on during
ur ng Cooling
oo ng

5 Eutectic Systems

6 Fe C Alloy
Fe-C
6
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 Phases & Solubility

(a) The three forms of water –

gas, li
liquid
id & solid
lid – are
each a phase.

(b) Water and alcohol have

unlimited solubility.

(c) Salt and water have limited

solubility.

(d) Oil and water have virtually

no solubility.
7
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 Solubility Limit
-Liquid copper-nickel are
completely soluble.

- Solid copper-nickel are

p y soluble, with
completely
copper and nickel atoms
occupying random lattice
sites.

- In copper-zinc alloys containing more than 30 at. % Zn,

8 a second phase forms because of the limited solubility of zinc in copper.
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 Solubility Limit
¾ Solubility limit - maximum concentration of solute that may dissolve in a
solvent at a given temperature to form a solid solution.
¾ Precipitate - a new solid phase that forms when the solubility limit is
exceeded.

(Fig. 9-1)

청동

9
C12H22O11 – H2O
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 Solubility Limit

¾ Phase Diagram of 100

Solubility

C)
Water - Sugar System L

ature (ºC
80 Limit
(liquid)
60 +
L

Tempera
40 (liquid solution S
i.e., syrup) (solid
Question: What is the 20 g )
sugar)

T
solubility limit at 20ºC? 0 20 40 6065 80 100

ar
er
Answer: 65 wt
wt. % sugar Co=Composition (wt% sugar)

Suga
Wate
Pure
e

Pure
e
If Co < 65 wt. % sugar: syrup
If Co > 65 wt.
t % sugar: syrup + sugar

¾ Solub
Solubility
l ty llimit
m t increases w th T :
ncreases with
10
e.g., if T = 100ºC, solubility limit = 80 wt. % sugar
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 Components and Phases
¾ Components:
The elements or compounds which are mixed initially
(e.g., Al and Cu).
¾ Phases:
The physically and chemically distinct material regions
that result.
1 component (H2O)
Aluminum-Copper Alloy
β (lighter
phase)

α (darker
(d k
phase)

11
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 Contents

1 Introduction

2 Solubility Limit

3 Phase Diagrams
g

4 Microstructural
M crostructura Evolution
E o ut on during
ur ng Cooling
oo ng

5 Eutectic Systems

6 Fe C Alloy
Fe-C
12
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 Fundamental Concepts
¾ Phase diagram: graphical representation of the phases
present
pr s nt and
an the
th ranges
rang s in
n compos
composition,
t on, ttemperature,
mp ratur ,
and pressure over which the phases are stable.
¾ Gibbs
G bb phase
h l F=C+2–P
rule: (Eq. 9-16)
C: # components,
p P: # p
phases in equilibrium
q
F: degree of freedom (temperature, pressure, composition.)
O C = 1,
ex)) H2O, 1 F=C+2–P=3-P
1 phase F = 2
2 phase F = 1
3 phase F = 0 (invariant)

* pressure constant Æ F = C + 1 – P
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 One-Component Phase Diagram

(Fig 9-2)
(Fig.

Pressure-temperature diagram for H2O. Notice the solid-liquid

line sloping to the left.
left At normal pressure (1 atm or 760 torr),
torr)
the melting temperature is 273 K.

14
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 Isomorphous Phase Diagram
Complete liquid and solid solutions

(Fig. 9-3)
Constant p
pressure:
- 2009-10-28
15 F = C + 1 – P, C = 2, F = 3 - P http://bp.snu.ac.kr
 Phase Diagrams
¾ Tell us about the phases as a function of T, Co, and P
¾ For this course:
- Binary systems: just 2 components
p
- Independent variables: T and Co (at P = 1 atm)

1600

1500 L (liquid)
T(ºC)
1400
L (liquid)
Cu-Ni 1300
α (FCC solid solution)
Phase diagram 1200 α
1100
(FCC solid
solution)
l ti )
1000
16 0 20 40 60 80 100 wt% Ni http://bp.snu.ac.kr
 Phase Diagrams: Number and Types of Phases
Rule 1: If we know T and Co, then we know:
- the number and types
yp of phases
p present.
p

Examples: T(ºC)
1600

A(1100, 60):
A(1100 1500 L (liquid)
1 phase: α

250,35)
1400 Cu-Ni
B(1250, 35):
B(1250 phase diagram

B(12
2 phases: L + α 1300 α
(FCC solid
1200 solution)
1100 A(1100,60)

1000
17
0 20 40 60 80 100 wt% Ni
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 Phase Diagrams: Composition of Phases
Rule 2: If we know T and Co, then we know:
- the composition of each phase.

Examples: T(ºC) Cu-Ni system (Fig. 9-3)

Co = 35wt%Ni A
TA tie line
At TA:
Only Liquid (L) 130 0 L (liquid)
CL = Co ( = 35wt% Ni)
At TD: B
TB
Only Solid (α)
Cα = Co ( = 35wt% Ni) α

At TB: 120 0 (solid)

D
TD
Both α and L
CL = Cliquidus ( = 32wt% Ni here)
20 3 03235 4 0 43 50
Cα = Csolidus ( = 43
43wt%
t% Ni h
here))
C LC o C α wt% Ni
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 Phase Diagrams: Fractions of Phases
Rule 3: If we know T and Co, then we know:
- the amount of each phase (given in wt. or at. %).
• Examples:
T(ºC) Cu-Ni system
Co = 35wt%Ni
TA A
At TA: Only Liquid (L) ti li
tie line
1300 L (liquid)
WL = 100wt%, Wα = 0 B
At TD: Only Solid (α)
TB
WL = 0, Wα = 100wt% R S
At TB: Both α and L α
1200 D
TD (solid)
What would be WL and Wα?
20 303235 4044 50
S 44 − 35 C LC o Cα
WL = + = = 75wtt % wt% Ni
R S 44 − 32
R 35 − 32
Wα = + = = 25wt %
19
R S 44 − 32
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 The Lever Rule (Proof)
¾ Sum of weight fractions: WL + Wα = 1 (Example 9-1)
¾ Conservation of mass (Ni): Co = WL CL + Wα Cα

¾ Combine above equations:

= Cα − Co = S Co − CL = R
WL Wα =
Cα − CL R + S Cα − CL R + S

¾ A geometric interpretation
interpretation: moment equilibrium:
CL Co Cα WLR = WαS
R S

WL Wα 1− Wα
solving gives Lever Rule
20
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 Contents

1 Introduction

2 Solubility Limit

3 Phase Diagrams
g

4 Microstructural
M crostructura Evolution
E o ut on during
ur ng Cooling
oo ng

5 Eutectic Systems

6 Fe C Alloy
Fe-C
21
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 Cooling in a Cu-Ni Binary (equilibrium)
¾Phase diagram: Cu-Ni system. (Fig. 9-4 incorrect)
¾ System is:
- binary
2 components: Cu and Ni
- isomorphous .
complete
p solubility
y
A phase field extends .
From 0 to 100 wt. % Ni

¾ Consider
Co = 35 wt. % Ni
What would be the
microstructures?
22
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Cooling
g in Cu-Ni
(nonequilibrium) .

(skip)
( i 9-5)
(Fig. 9 )

¾Consider
Co = 35 wt. % Ni. X

23
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 Contents

1 Introduction

2 Solubility Limit

3 Phase Diagrams
g

4 Microstructural
M crostructura Evolution
E o ut on during
ur ng Cooling
oo ng

5 Eutectic Systems

6 Fe C Alloy
Fe-C
24
http://bp.snu.ac.kr
 Binary Eutectic Systems
Greek - Easily melting
A special composition (Fig. 9-7)
with an easy gT
y melting
m

2 components
Eutectic
E i reaction
i
L Æ α+β

____
α+β

25
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 Binary Eutectic Systems
It h
has a special
i l composition
iti
2 components with a minimum melting T.

T(ºC) (Fig. 9-7)

Ex.: Cu-Ag system 120 0
3 single phase regions L (liquid)
(L,α, β) 10 00
Limited solubility: α L+α L+ β β
779ºC
779 C
α: mostly Cu TE 800 8.0 71 .9 91.2
β: mostly Ag 600
TE : No liquid below TE α+β
400
C E : Min. melting T
composition 200
0 20 40 60 C E 80 10 0
Cu Composition (wt. %) Ag
- 2009-11-02
26
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 Example: Pb-Sn Eutectic System

For a 40 wt. % Sn – 60 wt. % Pb alloy at 150ºC, find...

- the phases present: α + β
(Fig. 9-8)
- the compositions of the phases:
(Fig. 9-9)
Cα = 11 wt. % S
Sn T(ºC)
(º )
Cβ = 99 wt. % Sn
300
- the relative amounts L (liquid)
(li id)
of each phase: α L+α
200
00 183ºC
183 C L+ β β
L
18.3 61.9 97.8
150
59 R S
Wα = = 67 wt % 1 00
88 α+β
29
Wβ = = 33 wt % 0 11 20 40 60 80 9910 0
88
27
Pb Composition (wt. %) Sn
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 Microstructures in Eutectic Systems - I
T(ºC) L: Co wt. % Sn (Fig. 9-11)
¾ Co < 2 wt. % Sn 4 00

¾ Result
R s lt Æ L
α
polycrystal of α grains 3 00 L

L + α
α
2 00 (Pb S
(Pb-Sn
TE α : C o wt%Sn
System)

1 00
α + β

0 10 20 30
Co C o , wt% Sn
2
28
(room T solubility limit) http://bp.snu.ac.kr
 Microstructures in Eutectic Systems - II

¾ 2 wt. % Sn < Co < 18.3 wt. % Sn (Fig. 9-12)

T(ºC)
( ) L: C o wt.% Sn
¾ Result Æ α polycrystal 400
with fine β crystals. L
L
300 α
L+α
α: C o wt%Sn
α
200
TE
α
β

α + βX
1 00
X
Pb-Sn
system 0 10 20 30
2.0
2 0 C o C o , wt. % Sn
(solubility limit at Troom ) 18.3
(solubility limit at TE )
29
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 Microstructures in Eutectic Systems - III
¾ Co = CE
¾ Result Æ Eutectic microstructure --- alternating
layers of α and β crystals.
crystals
(Fig. 9-13) (Fig. 9-14)
Pb-Sn system
T(ºC)
L: C o wt%Sn
300 L

L+α
200
TE α 183ºC
183 C L+ββ

1 00 α+β
β: 97.8wt%Sn
α: 18.3wt%Sn 160μm
0
0 20 40 60 80 100
18.3 CE 97.8
30 61.9 C o , wt% Sn
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 Formation of Eutectic Lamellar Structure

(Fig. 9-15)

31
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 Microstructures in Eutectic Systems
¾ 18.3 wt. % Sn < Co < 61.9 wt. % Sn
¾ Result: α crystals
y and an eutectic microstructure

(Fig. 9-16)
Just above TE :
T(ºC) L: C o wt%Sn α L
C α = 18.3 wt. % Sn
L
300 L α C L = 61.9 wt. % Sn
X
Pb-Sn
Pb Sn
L+α Wα = S =50 wt. %
system R+S
200 α R S L+β β WL = (1-Wa ) =50 wt. %
TE
R S X
Just below TE :
1 00
α+β C α = 18.3 wt. % Sn
primary
p im α
eutectic α
C β = 97.8
9 wt. % Sn
0
0 20 40 60 80 100
eutectic β
Wα = S =73 wt. %
18.3 Co 61.9 97.8 R+S
C o , wt.
t % Sn
S Wβ = 27 wt. %
(Fig. 9-17)
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 Invariant Reactions

___

____

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 Other Examples

((Fig.
g 9-20))

34
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 Other Examples

(Fig 9-21)
(Fig. 9 21)

35
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 Other Examples
(Fig. 9-22)

36
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 Contents

1 Introduction

2 Solubility Limit

3 Phase Diagrams
g

Microstructural Evolution during

4
C li
Cooling

5 Eutectic Systems

6 Fe C Alloy
Fe-C
37
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 Fe-C phase diagram

γ iron (Fig. 9-24)

Austenite
(FCC)
A

B
α iron Cementite ((Fe3C))
F
Ferrite
i hard & brittle
(BCC)
soft & ductile

A; eutectic
C concentration
t ti 0.008w%
0 008 % 2.14w%
2 14 % 67 %
6.7w%
B; eutectoid
iron steel cast iron
38
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 Summary
¾ Phase diagrams are useful tools to determine:

√ The number and types of phases.

√ The at. % or wt. % of each phase.

√ The fraction of each phase.

phase

For the given T and composition of the system.

¾ Binary alloys allow various ranges of microstructures.

¾ Problems from Chap. 9 http://bp.snu.ac.kr

Prob 9
Prob. 9-3
3 Prob 9
Prob. 9-4
4 Prob 9
Prob. 9-5
5 Prob.
Prob 99-8
8
Prob. 9-9 Prob. 9-11 Prob. 9-12 Prob. 9-17
P b 9-27
Prob. 9 27 P
Prob.
b 99-28
28 Prob.
P b 9 9-36
36 Prob.
P b 9 9-45
45
39
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