Engineering Materials

Phase Diagram

Djarot Widagdo
Faculty of Mechanical and
Aerospace Engineering
ITB

Introduction

1
Introduction
Metal Alloys

Ferrous Nonferrous

Steels
Steels Cast Irons
Cast Irons Cu Al Mg Ti
<1.4 wt% C
<1.4wt%C 3-4.5 wt%C
3-4.5 wt% C

T(°C) microstructure:
1600 ferrite, graphite
δ
cementite
1400 L
γ+L
1200 γ 1148°C L+Fe3C
austenite Eutectic:
1000 4.30

γ+Fe3C
α800 727°C Fe3C
ferrite Eutectoid: cementite
600 0.76 α+Fe3C
400
0 1 2 3 4 5 6 6.7
(Fe)
Co , wt%
C

Introduction

2
Introduction

Introduction

3
 Phase Equilibria: Solubility Limit
Introduction
– Solutions – solid solutions, single phase
– Mixtures – more than one phase

Sucrose/Water Phase Diagram

• Solubility Limit:
Max concentration for 10 0
Solubility
which only a single phase L

erature (°C)
80 Limit
solution occurs.
(liquid)
60 L +
Question: What is the (liquid solution S

Tempe
40
solubility limit at 20°C? i.e., syrup) (solid
20 sugar)
Answer: 65 wt% sugar.
If Co < 65 wt% sugar: syrup
If Co > 65 wt% sugar: syrup + sugar. 0 20 40 60 65 80 100

Sugar
Water

Co =Composition (wt% sugar)

Pure

Components and Phases Pure

• Components:
The elements or compounds which are present in the mixture
(e.g., Al and Cu)
• Phases:
The physically and chemically distinct material regions
that result (e.g., α and β).

β (lighter
phase)

α (darker
phase)

8
Aluminum – Copper alloy

4
Effect of T & Composition (Co)
• Changing T can change # of phases: path A to B.
• Changing Co can change # of phases: path B to D.
B (100°C,70) D (100°C,90)
1 phase 2 phases
100

80 L
Temperature (°C)
(liquid)
water- 60 +
L
sugar S
system ( liquid solution
40 (solid
i e syrup)
i.e., sugar))
20 A (20°C,70)
2 phases
0
0 20 40 60 70 80 100
Co = Composition (wt% sugar)
9

Phase Diagrams
• Indicate phases as function of T, Co, and P.
• For this course:
- binary systems : just 2 components.
- independent variables : T and Co (P = 1 atm is almost always used).

T(°C)
• Phase 1600 • 2 phases:
Diagram L (liquid)
1500 L (liquid)
for Cu-Ni α (FCC solid solution)
system
1400 • 3 phase fields:
L
1300 L+ α
1200 α α
(FCC solid
1100
solution)
1000
0 20 40 60 80 100 wt% Ni 10

5
Phase Diagrams: amount and types of phases

• Rule 1: If we know T and Co, then we know:

--the # and types of phases present.
T(°C)
( )
• Examples:
1600
A(1100°C, 60): L (liquid)
1 phase: α

B (1250°C,35)
1500
Cu-Ni
phase
B(1250°C, 35): 1400
diagram
2 phases: L + α
1300 α
(
(FCC solid
1200 solution)

1100 A(1100°C,60)

1000
0 20 40 60 80 100 wt% Ni
11

Phase Diagrams: composition of phases

• Rule 2: If we know T and Co, then we know:
- the composition of each phase.

p
• Examples:
Cu-Ni
system
T(°C)
TA A
tie line
1300 L (liquid)
B
TB
α
1200 (solid)
D
TD
20 3032 35 4043 50
CLCo Cα wt% Ni
12

6
Phase Diagrams: weight fractions of phases
• Rule 3: If we know T and Co, then we know:
- the amount of each phase (given in wt%).

Cu-Ni
system
T(°C)
TA A
tie line
1300 L (liquid)

B
TB
R S
α
1200 D (solid)
TD

20 3032 35 404 3 50
C LC o C α wt% Ni

Cored vs Equilibrium Phases

7
Cored vs Equilibrium Phases
• Cα changes as we solidify.
• Cu-Ni case: First α to solidify has Cα = 46 wt% Ni.
Last α to solidify has Cα = 35 wt% Ni.
• Fast rate of cooling: • Slow rate of cooling:
Cored structure Equilibrium structure

Uniform Cα :
First α to solidify:
46 wt% Ni 35 wt% Ni
Last α to solidify:
< 35 wt% Ni

15

Mechanical Properties: Cu-Ni System

• Effect of solid solution strengthening on:

60
nsile 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 20
Ten

0 20 40 60 80 100 0 20 40 60 80 100
Cu Ni Cu Ni
Composition, wt% Ni Composition, wt% Ni

--Peak as a function of Co --Min. as a function of Co

16

8
Binary-Eutectic Systems
has a special composition
2 components with a min. melting T.
Cu-Ag
T(°C) system
Ex.: Cu-Ag g system
y 1200
• 3 single phase regions L (liquid)
(L, α, β ) 1000
• Limited solubility: α L+ α
800 779°C L+β β
α: mostly Cu T E 8.0 71.9 91.2
β : mostly Ag 600
• TE : No liquid below TE α + β
• CE : Min.
Mi melting
lti TE 400

composition 200
0 20 40 60 CE 80 100
• Eutectic transition Co , wt% Ag
L(CE) α(CαE) + β(CβE)
17

EX: Pb-Sn Eutectic System (1)

• For a 40 wt% Sn-60 wt% Pb alloy at 150°C, find...
- the phases present: α + β
Pb-Sn
- compositions of phases: T(°C) system
CO = 40 wt% Sn
Cα = 11 wt% Sn 300 L (liquid)
Cβ = 99 wt% Sn
α L+ α
- the relative amount L+ β β
200 183°C
of each phase: 18.3 61.9 97.8
150 R S
100
α + β

0 11 20 40 60 80 99100
Cα Co C, wt% Sn Cβ

18

9
EX: Pb-Sn Eutectic System (2)
• For a 40 wt% Sn-60 wt% Pb alloy at 200°C, find...
- the phases present: α + L
Pb-Sn
- compositions of phases: T(°C)
system
CO = 40 wt% Sn
Cα = 17 wt% Sn 300 L (liquid)
CL = 46 wt% Sn L+ α
- the relative amount 220 α
200 R S L+ β β
of each phase:
183°C

100
α + β

0 17 20 40 46 60 80 100
Cα Co CL C, wt% Sn

19

Microstructures in Eutectic Systems: I

• Co < 2 wt% Sn T(°C) L: Co wt% Sn

• Result: 400
- at extreme ends L
α
- polycrystal of α grains 300 L
i.e., only one solid phase.
L+ α
α
200 (Pb-Sn
TE α: Co wt% Sn System)

100 α+β

0 10 20 30
Co Co , wt% Sn
2
(room T solubility limit)
20

10
Microstructures in Eutectic Systems: II

T(°C) L: Co wt% Sn
• 2 wt% Sn < Co < 18.3 wt% Sn
• Result: 400
ƒ Initially liquid + α L
L
ƒ then α alone 300 α
ƒ finally two phases L+ α
α: Co wt% Sn
¾ α polycrystal α
¾ fine β-phase inclusions 200
TE
α
β
100 α+ β Pb-Sn
system

0 10 20 30
2 Co Co , wt% Sn
(sol. limit at Troom) 18.3
(sol. limit at TE) 21

Microstructures in Eutectic Systems: III

• Co = CE
• Result: Eutectic microstructure (lamellar structure)
- alternating layers (lamellae) of α and β crystals.

T(°C) Micrograph of Pb-Sn

eutectic
L: Co wt% Sn microstructure
300 L
Pb-Sn
L+ α
system
α
200 183°C L+β β
TE

100
α+β 160 μm
β: 97.8 wt% Sn
α: 18.3 wt%Sn

0 20 40 60 80 100
18.3 CE 97.8
61.9 C, wt% Sn 22

11
 Lamellar Eutectic Structure

23

Microstructures in Eutectic Systems: IV

• 18.3 wt% Sn < Co < 61.9 wt% Sn

• Result: α crystals and a eutectic microstructure

T(°C) L: Co wt% Sn L
α
L

300 L α

Pb-Sn
system L+ α
α
200 R S L+ β β
TE
R S
• Just below TE :
100 α + β Cα = 18.3 wt% Sn
primary α Cβ = 97.8 wt% Sn
eutectic α
eutectic β Wα= S = 73 wt%
0 20 40 60 80 100 R+S
18.3 61.9 97.8 Wβ = 27 wt%
Co, wt% Sn 24

12
Hypoeutectic & Hypereutectic
300 L
T(°C)
α L+ α
200 L+β β (Pb-Sn
TE System)
α+β
100

Co, wt% Sn
0 20 40 60 80 100
eutectic
hypoeutectic: Co = 50 wt% Sn 61.9 hypereutectic: (illustration only)

α eutectic: Co = 61.9 wt% Sn

β
α β
α α β β
α β
α β

175 μm 160 μm
eutectic micro-constituent
25

Intermetallic Compounds

Mg2Pb

Note: intermetallic compound forms a line - not an area - because

stoichiometry (i.e. composition) is exact. 26

13
Eutectoid & Peritectic
z Eutectic - liquid in equilibrium with two solids
L cool α + β
heat

• Eutectoid - solid phase in equation with two solid

phases
intermetallic
S2 S1+S3 compound -
cementite
γ cool
α + Fe3C (727ºC)
heat

• Peritectic - liquid + solid 1 Æ solid 2

S1 + L S2
cool
δ + L heat γ (1493ºC)

27

Eutectoid & Peritectic

28

14
Eutectoid & Peritectic
Peritectic transition γ + L δ
Cu-Zn Phase diagram

Eutectoid transition δ γ+ε

Iron-Carbon (Fe-C) Phase Diagram

• 2 important T(°C)
points 1600
δ
-Eutectic (A): 1400 L
L ⇒ γ + Fe3C γ γ +L A
1200 1148°C L+Fe3C
Fe3C (cementite)

-Eutectoid (B): (austenite)

R S
γ ⇒ α +Fe3C 1000 γ γ
γ γ γ +Fe3C

α
800 B 727°C = Teutectoid

R S
600
α+Fe3C
400
0 1 2 3 4 5 6 6.7
(Fe) 0.76 4.30 Co, wt% C
120 μm
C eutectoid

Result: Pearlite = Fe3C (cementite-hard)

alternating layers of α (ferrite-soft)
α and Fe3C phases
30

15
 Hypoeutectoid Steel
T(°C)
1600
δ
1400 L
γ γ (Fe-C
γ γ +L
γ γ 1200 S t )
System)

Fe3C (cementite)
1148°C L+Fe3C
(austenite)
γ γ 1000
γ γ γ + Fe3C
α
αγ γ 800 r s 727°C
γ αγ α RS
w α =s/(r+s) 600
w γ =(1- wα )
α + Fe3C
400
α 0 1 2 3 4 5 6 6.7
(Fe) Co , wt% C
0.76

C0
pearlite
w pearlite = w γ
Hypoeutectoid
w α =S/(R+S) 100 μm
steel
w Fe3 =(1-wα )
C
pearlite proeutectoid
ferrite

Hypereutectoid Steel
T(°C)
1600
δ
1400 L (Fe-C
γ γ +L System)
γ γ
γ 1200
Fe3C (cementite)

γ (austenite)
1148°C L+Fe3C
γ γ 1000
γ γ γ +Fe3C
Fe3C
γ γ 800 r s
γ γ α
R S
w Fe3C =r/(r+s) 600 α +Fe3C
w γ =(1-w Fe3C )
400
0 1 Co 2 3 4 5 6 6.7
0.76

(Fe)
pearlite Co , wt%C
w pearlite = w γ
w α =S/(R+S)
w Fe3C =(1-w α ) 60 μmHypereutectoid
steel
pearlite proeutectoid Fe3C
32
Adapted from Fig. 9.33,Callister 7e.

16
Example

33

Example

34

17
Example

35

Example

36

18
Example

37

Example

38

19
 Example: Phase Equilibria
For a 99.6 wt% Fe-0.40 wt% C at a temperature just below the
eutectoid, determine the following
a. composition of Fe3C and ferrite (α)
b. the amount of cementite in grams that forms per 100 g of steel
c. the amount of pearlite and proeutectoid phase (α)

39

Chapter 9 – Phase Equilibria

Solution: a) composition of Fe3C and ferrite (α)

b) the amount of carbide (cementite) in CO = 0.40 wt% C

grams that forms per 100 g of steel Cα = 0.022 wt% C
CFe C = 6.70 wt% C
3

1600
δ

Fe3C Co − Cα 1400
L
= x100 T(°C)
γ +L
Fe3C + α CFe3C − Cα 1200
γ
L+Fe3C
1148°C
(austenite)
0.4 − 0.022
ementite)

= x 100 = 5.7g 1000

γ + Fe3C
6.7 − 0.022
Fe3C (ce

800 727°C
R S
Fe3C = 5.7 g 600 α + Fe3C

α = 94.3 g 400
0 1 2 3 4 5 6 6.7
Cα CO Co , wt% C CFe C
3
40

20
Chapter 9 – Phase Equilibria
c. the amount of pearlite and proeutectoid ferrite (α)
note: amount of pearlite = amount of γ just above TE

Co = 0.40 wt% C
Cα = 0.022 wt% C
Cpearlite = Cγ = 0.76 wt% C 1600
δ
1400 L
T(°C)
γ C − Cα γ γ +L

ementite)
= o x 100 = 51.2 g 1200 1148°C L+Fe3C
γ + α Cγ − Cα (austenite)
1000
γ + Fe3C

Fe3C (ce
800 727°C
RS
pearlite = 51.2 g 600 α + Fe3C
proeutectoid α = 48.8 g 400
0 1 2 3 4 5 6 6.7
Cα CO Cγ Co , wt% C
41

Alloying Steel with More Elements

• Teutectoid changes: • Ceutectoid changes:
C eutectoid (wtt%C)

Ti
T Eutectoid (°C))

Si
Mo W Ni
Cr
Cr Si
Mn
Mn W
Ti Mo
Ni

wt % of alloying elements
wt. wt. % of alloying
y g elements

42

21