Chapter 9: Phase Diagrams

ISSUES TO ADDRESS...
When we combine two elements...
what equilibrium state do we get?

In particular, if we specify...
--a composition (e.g., wt% Cu - wt% Ni), and --a temperature (T )

then...
How many phases do we get? What is the composition of each phase? How much of each phase do we get?

Phase A
Nickel atom Copper atom

Phase B

Chapter 9 - 1

Phase Equilibria: Solubility Limit

Introduction Solutions solid solutions, single phase Mixtures more than one phase Adapted from Fig. 9.1,
Callister 7e.

Solubility Limit:
Temperature (C)

Sucrose/Water Phase Diagram

100 80 60 40 20 Solubility Limit

Max concentration for which only a single phase solution occurs.

L
(liquid)

Question: What is the

solubility limit at 20C?

L
(liquid solution i.e., syrup)

+ S
(solid sugar)

Answer: 65 wt% sugar.

Pure Water

Chapter 9 - 2

Pure Sugar

If Co < 65 wt% sugar: syrup 0 20 40 6065 80 100 If Co > 65 wt% sugar: syrup + sugar. Co =Composition (wt% sugar)

Components and Phases

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., and ).
AluminumCopper Alloy

(lighter phase) (darker phase)

Adapted from chapter-opening photograph, Chapter 9, Callister 3e. Chapter 9 - 3

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 (100C,70) D (100C,90) 100
Temperature (C)
1 phase 2 phases

80 60 40 20 0
0

L
(liquid)

watersugar system

L
(liquid solution
i.e., syrup)

+ S
(solid sugar)

A (20C,70)
2 phases

Adapted from Fig. 9.1, Callister 7e.

20 40 60 70 80 100 Co =Composition (wt% sugar)

Chapter 9 - 4

Phase Equilibria
Simple solution system (e.g., Ni-Cu solution) Crystal Structure Ni Cu FCC FCC
electroneg

r (nm) 0.1246 0.1278

1.9 1.8

Both have the same crystal structure (FCC) and have similar electronegativities and atomic radii (W. Hume Rothery rules) suggesting high mutual solubility. Ni and Cu are totally miscible in all proportions.
Chapter 9 - 5

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
Diagram for Cu-Ni system
1600 1500 1400 1300 1200 1100 1000 0 20
liq us uid

2 phases:

L (liquid)
+ s

L (liquid) (FCC solid solution)

3 phase fields: L L+
Adapted from Fig. 9.3(a), Callister 7e. (Fig. 9.3(a) is adapted from Phase Diagrams of Binary Nickel Alloys, P. Nash (Ed.), ASM International, Materials Park, OH (1991).

(FCC solid solution)

40 60 80

u lid so

100

wt% Ni

Chapter 9 - 6

 Note:The Ni-Cu alloy system shown in the previous slide is a binary isomorphous system; Note: Isomorphous : Having the same structure. In the phase diagram sense, isomorphicity means having the same crystal structure or complete solid solubility for all compositions.

Chapter 9 - 7

Phase Diagrams:
# and types of phases
Rule 1: If we know T and Co, then we know:
--the # and types of phases present.

Examples:
A(1100C, 60): 1 phase: B(1250C, 35): 2 phases: L +

T(C)
1600

L (liquid)
B (1250C,35) 1500 1400 1300 1200
u liq s idu us lid so

L +(FCC solid
solution)

Cu-Ni phase diagram

Adapted from Fig. 9.3(a), Callister 7e. (Fig. 9.3(a) is adapted from Phase Diagrams of Binary Nickel Alloys, P. Nash (Ed.), ASM International, Materials Park, OH, 1991).

1100 1000 0 20 40

A(1100C,60) 60 80 100

wt% Ni

Chapter 9 - 8

Phase Diagrams:
composition of phases
Rule 2: If we know T and Co, then we know:
--the composition of each phase. T(C) Cu-Ni system

Examples:

A TA Co = 35 wt% Ni tie line dus i l i qu 1300 L (liquid) At T A = 1320C: L+ s Only Liquid (L) B idu TB s ol CL = Co ( = 35 wt% Ni) At T D = 1190C: L+ (solid) 1200 D Only Solid ( ) TD C = Co ( = 35 wt% Ni) 20 30 35 4043 50 32 At T B = 1250C: CLCo C wt% Ni Both and L Adapted from Fig. 9.3(b), Callister 7e. Phase Diagrams CL = C liquidus ( = 32 wt% Ni here) (Fig. 9.3(b) is adapted fromNash (Ed.), ASM of Binary Nickel Alloys, P. C = C solidus ( = 43 wt% Ni here) International, Materials Park, OH, 1991.)
Chapter 9 - 9

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 A L (liquid)
tie line dus i l i qu

Examples:
Co = 35 wt% Ni At T A : Only Liquid (L) W L = 100 wt%, W = 0 At T D: Only Solid ( ) W L = 0, W = 100 wt% At T B : Both and L

T(C) TA
1300

TB
1200

B R S D CLCo

L+
s

(solid)
50

us olid

TD
20

WL = W =

43 35 S = = 73 wt % R + S 43 32

30 35 32

40 43

C wt% Ni

R = 27 wt% R +S

Adapted from Fig. 9.3(b), Callister 7e. (Fig. 9.3(b) is adapted from Phase Diagrams of Binary Nickel Alloys, P. Nash (Ed.), ASM International, Materials Park, OH, 1991.) Chapter 9 - 10

The Lever Rule

Tie line connects the phases in equilibrium with each other - essentially an isotherm
T(C)
1300

L (liquid) B
L+
R

tie line dus i l i qu

How much of each phase? Think of it as a lever (teeter-totter)

ML M

L+

TB
1200

(solid)
S
50

idu s ol

20

30C C 40 C L o

M S = M L R
R C CL = 0 R + S C CL
Chapter 9 - 11

wt% Ni

Adapted from Fig. 9.3(b), Callister 7e.

WL =

ML S C C0 = = M L + M R + S C CL

W =

Ex: Cooling in a Cu-Ni Binary

Phase diagram:
Cu-Ni system.
T(C) L (liquid)
130 0 L: 35 wt% Ni : 46 wt% Ni 32 24 1200 L: 35wt%Ni

System is:
--binary
i.e., 2 components: Cu and Ni.

A
35

B C D
36

L+
46 43

Cu-Ni system

--isomorphous
i.e., complete solubility of one component in another; phase field extends from 0 to 100 wt% Ni.

L: 32 wt% Ni : 43 wt% Ni L: 24 wt% Ni : 36 wt% Ni

(solid)
1100 20 30

Consider
Co = 35 wt%Ni.

Adapted from Fig. 9.4, Callister 7e.

35 Co

40

50

wt% Ni
Chapter 9 - 12

Cored vs Equilibrium Phases

C changes as we solidify. Cu-Ni case: First to solidify has C = 46 wt% Ni. Fast rate of cooling:
Cored structure
First to solidify: 46 wt% Ni Last to solidify: < 35 wt% Ni

Last to solidify has C = 35 wt% Ni.

Slow rate of cooling:

Equilibrium structure
Uniform C : 35 wt% Ni

Chapter 9 - 13

Mechanical Properties: Cu-Ni System

Effect of solid solution strengthening on:
--Tensile strength (TS)
Tensile Strength (MPa)

--Ductility (%EL,%AR)
Elongation (%EL)
60 50 40 30 20 0 20 Cu 40 60 80 100 Ni %EL for pure Cu %EL for pure Ni

400 TS for pure Ni TS for pure Cu 200 0 20 40 60 80 100 Cu Ni

Adapted from Fig. 9.6(a), Callister 7e.

300

Composition, wt% Ni

Composition, wt% Ni

Adapted from Fig. 9.6(b), Callister 7e.

--Peak as a function of Co

--Min. as a function of Co
Chapter 9 - 14

Binary-Eutectic Systems
2 components has a special composition with a min. melting T.

Ex.: Cu-Ag system

T(C)
1200

Cu-Ag system

3 single phase regions L (liquid) 1000 (L, , ) L + 779C Limited solubility: L+ 800 TE : mostly Cu 8.0 71.9 91.2 : mostly Ag 600 TE : No liquid below TE + 400 CE : Min. melting TE composition 200 Eutectic transition
0 20 40 60 CE 80

100

L(CE)

(CE) + (CE)

Co , wt% Ag
Adapted from Fig. 9.7, Callister 7e. Chapter 9 - 15

EX: Pb-Sn Eutectic System (1)

For a 40 wt% Sn-60 wt% Pb alloy at 150C, find...
--the phases present: + T(C) --compositions of phases:
CO = 40 wt% Sn C = 11 wt% Sn C = 99 wt% Sn
300

Pb-Sn system

L (liquid) L+
18.3
183C

--the relative amount of each phase:

C - CO S = W = R+S C - C =

200 150 100

L+
61.9 97.8

S
+

99 - 40 59 = = 67 wt% 99 - 11 88 C - C W = R = O C - C R+S 40 - 11 29 = = 33 wt% = 99 - 11 88

0 11 20 C

40 Co

60

80

C, wt% Sn

99100 C

Adapted from Fig. 9.8, Callister 7e. Chapter 9 - 16

EX: Pb-Sn Eutectic System (2)

For a 40 wt% Sn-60 wt% Pb alloy at 200C, find...
--the phases present: + L T(C) --compositions of phases:
CO = 40 wt% Sn C = 17 wt% Sn CL = 46 wt% Sn
300 220 200

Pb-Sn system

--the relative amount of each phase:

W = CL - CO 46 - 40 = CL - C 46 - 17 6 = = 21 wt% 29

L+
R

L (liquid)
S
183C

L+

100

+
0 17 20 C 40 46 60 Co CL 80 100

23 CO - C = WL = = 79 wt% 29 CL - C

C, wt% Sn
Chapter 9 - 17

Adapted from Fig. 9.8, Callister 7e.

Microstructures in Eutectic Systems: I

Co < 2 wt% Sn Result:
--at extreme ends --polycrystal of grains i.e., only one solid phase.
T(C)
400 L 300 L: Co wt% Sn

L
: Co wt% Sn

L+ (Pb-Sn System)

200

TE
100

Adapted from Fig. 9.11, Callister 7e.

0 Co

10

20

30

o 2 (room T solubility limit)

C , wt% Sn

Chapter 9 - 18

Microstructures in Eutectic Systems: II

T(C) 2 wt% Sn < Co < 18.3 wt% Sn 400 Result: L
L: Co wt% Sn

Initially liquid + then alone finally two phases polycrystal fine -phase inclusions

300

L+
200

L : Co wt% Sn

TE

100

Pb-Sn system Sn

Adapted from Fig. 9.12, Callister 7e. (sol.

10 20 30 Co Co , wt% 2 limit at T room ) 18.3 (sol. limit at TE)

Chapter 9 - 19

Microstructures in Eutectic Systems: III

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

T(C)
L: Co wt% Sn

Micrograph of Pb-Sn eutectic microstructure

300

Pb-Sn system
200
TE

L L+
183C

L+
160 m
Adapted from Fig. 9.14, Callister 7e.

100

+
0 20 18.3 40

: 97.8 wt% Sn : 18.3 wt%Sn

Adapted from Fig. 9.13, Callister 7e.

60 CE 61.9

80

C, wt% Sn

100 97.8

Chapter 9 - 20

10

Lamellar Eutectic Structure

Adapted from Figs. 9.14 & 9.15, Callister 7e.

Chapter 9 - 21

Microstructures in Eutectic Systems: IV

18.3 wt% Sn < Co < 61.9 wt% Sn Result: crystals and a eutectic microstructure T(C)
300

L: Co wt% Sn

Just above TE :
C = 18.3 wt% Sn CL = 61.9 wt% Sn S W = = 50 wt% R+S WL = (1- W) = 50 wt%

Pb-Sn system
200
TE

L
L+
R S

L+
S

Just below TE :
primary eutectic eutectic

100

20 18.3

40

60 61.9

80

100 97.8

Adapted from Fig. 9.16, Callister 7e.

C = 18.3 wt% Sn C = 97.8 wt% Sn W= S = 73 wt% R+S W = 27 wt%

Chapter 9 - 22

Co, wt% Sn

11

Hypoeutectic & Hypereutectic

300

T(C) Adapted from Fig. 9.8, Callister 7e. (Fig. 9.8 200 adapted from Binary Phase TE Diagrams, 2nd ed., Vol. 3, T.B. Massalski (Editor-inChief), ASM International, 100 Materials Park, OH, 1990.)
0
(Figs. 9.14 and 9.17 from Metals Handbook, 9th ed., Vol. 9, Metallography and Microstructures, American Society for Metals, Materials Park, OH, 1985.)

L L+ + L+

(Pb-Sn System)

20

40

60
eutectic 61.9

80

100

Co, wt% Sn

hypoeutectic: Co = 50 wt% Sn

hypereutectic: (illustration only)

175 m

eutectic: Co = 61.9 wt% Sn

160 m eutectic micro-constituent
Adapted from Fig. 9.14, Callister 7e.

Adapted from Fig. 9.17, Callister 7e.

Adapted from Fig. 9.17, Callister 7e. (Illustration only) Chapter 9 - 23

Intermetallic Compounds
Adapted from Fig. 9.20, Callister 7e.

Mg2Pb
Note: intermetallic compound forms a line - not an area because stoichiometry (i.e. composition) is exact. Chapter 9 - 24

12

Eutectoid & Peritectic

Eutectic() - liquid in equilibrium with two solids L cool +
heat

Eutectoid() - solid phase in equation with two solid phases intermetallic compound S2 S1+S3 - cementite cool + Fe3C (727C)
heat

Peritectic() - liquid + solid 1 S1 + L S2 cool + L heat

solid 2 (Fig 9.21) (1493C)

Chapter 9 - 25

Eutectoid & Peritectic

Cu-Zn Phase diagram
Peritectic transition + L

Eutectoid transition

Adapted from Fig. 9.21, Callister 7e.

Chapter 9 - 26

13

Iron-Carbon (Fe-C) Phase Diagram

2 important points -Eutectic (A):
L + Fe3C T(C)
1600

1400 1200 1000 800 600

L Fe3C (cementite) +L (austenite)

1148C

A
+Fe3C

-Eutectoid (B):
+Fe3C

L+Fe3C

Result: Pearlite = alternating layers of and Fe3C phases

(Adapted from Fig. 9.27, Callister 7e.)

C eutectoid

120 m

400 0 (Fe)

Hypoeutectoid Steel
T(C)
1600

B
S

727C = T eutectoid

+Fe3C
4 5 6

0.76

4.30 Co, wt% C Fe3C (cementite-hard) (ferrite-soft)

Chapter 9 - 27

6.7

Adapted from Fig. 9.24,Callister 7e.

1400

L Fe3C (cementite) +L (austenite)

1148C

1200 1000 800

L+Fe3C

(Fe-C System)
Adapted from Figs. 9.24 and 9.29,Callister 7e. (Fig. 9.24 adapted from Binary Alloy Phase Diagrams, 2nd ed., Vol. 1, T.B. Massalski (Ed.-inChief), ASM International, Materials Park, OH, 1990.)

+ Fe3C
r s
727C

w =s/(r +s) 600 w =(1- w )

RS
1
C0

+ Fe3C
2 3 4 5 6
0.76

400 0 (Fe)
pearlite

6.7

Co , wt% C
100 m Hypoeutectoid steel

w pearlite = w w =S/(R+S) w Fe3C =(1-w )

pearlite
Adapted from Fig. 9.30,Callister 7e.

proeutectoid ferrite
Chapter 9 - 28

14

Hypereutectoid Steel
T(C)
1600

1400

L +L (austenite)
1148C

1000 800

+Fe3C r s S
1 Co 2 3

Fe3C (cementite)

Fe3C

(Fe-C System) L+Fe3C

1200

w Fe3C =r/(r +s) 600 w =(1-w Fe3C )

R
0.76

+Fe3C
4 5 6

400 0 (Fe) pearlite

Adapted from Figs. 9.24 and 9.32,Callister 7e. (Fig. 9.24 adapted from Binary Alloy Phase Diagrams, 2nd ed., Vol. 1, T.B. Massalski (Ed.-inChief), ASM International, Materials Park, OH, 1990.)

6.7

w pearlite = w

Co , wt%C
60 mHypereutectoid steel

w =S/(R+S) w Fe3C =(1-w )

pearlite
Adapted from Fig. 9.33,Callister 7e.

proeutectoid Fe3C
Chapter 9 - 29

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 () b) the amount of carbide (cementite) in grams that forms per 100 g of steel c) the amount of pearlite and proeutectoid ferrite ()

Chapter 9 - 30

15

Chapter 9 Phase Equilibria

Solution: a) composition of Fe3C and ferrite ()
b) the amount of carbide (cementite) in grams that forms per 100 g of steel
Co C Fe3C 1400 = x100 T(C) Fe3C + CFe3C C
1600

CO = 0.40 wt% C C = 0.022 wt% C CFe C = 6.70 wt% C

3

L
L+Fe3C

0.4 0.022 x 100 = 5.7g = 6.7 0.022 Fe3C = 5.7 g = 94.3 g

1000 800
727C

+ Fe3C
R S

600 400 0 1 2 3

+ Fe3C
4 5 6

C CO

Co , wt% C
Chapter 9 - 31

CFe

6.7
3C

Chapter 9 Phase Equilibria

c. the amount of pearlite and proeutectoid ferrite () note: amount of pearlite = amount of just above TE Co = 0.40 wt% C C = 0.022 wt% C Cpearlite = C = 0.76 wt% C
C C = o x 100 = 51.2 g + C C

1600

T(C)

1400

L
L+Fe3C

1200 1000 800

+ Fe3C
727C

RS

pearlite = 51.2 g proeutectoid = 48.8 g

600 400 0 1 2 3

+ Fe3C
4 5 6

C C C O

6.7

Co , wt% C
Chapter 9 - 32

Fe3C (cementite)

+L 1148C (austenite)

Fe3C (cementite)

+L 1200 1148C (austenite)

16

Alloying Steel with More Elements

Teutectoid changes:
T Eutectoid (C)
Ti Mo Si W Cr Mn Ni

Ceutectoid changes:
C eutectoid (wt%C)

Ni Cr Si Ti Mo W Mn

wt. % of alloying elements

Adapted from Fig. 9.34,Callister 7e. (Fig. 9.34 from Edgar C. Bain, Functions of the Alloying Elements in Steel, American Society for Metals, 1939, p. 127.)

wt. % of alloying elements

Adapted from Fig. 9.35,Callister 7e. (Fig. 9.35 from Edgar C. Bain, Functions of the Alloying Elements in Steel, American Society for Metals, 1939, p. 127.)

Chapter 9 - 33

Summary
Phase diagrams are useful tools to determine:
--the number and types of phases, --the wt% of each phase, --and the composition of each phase

for a given T and composition of the system. Alloying to produce a solid solution usually
--increases the tensile strength (TS) --decreases the ductility.

Binary eutectics and binary eutectoids allow for a range of microstructures.

Chapter 9 - 34

17

ANNOUNCEMENTS
Reading:

Core Problems:

Self-help Problems:

Chapter 9 - 35

18