CHAPTER 10: 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

THE SOLU ILITY LIMIT

Solubility Limit:
Temperature (C) 100
80

Max concentration for which only a solution occurs.

Solubility Limit

L
(li ui )

60
40

L
(li ui solution i.e., syrup)

Ex: hase Diagram: Water-Sugar System

Question: What is the
solubility limit at 20C?

+ S
(soli sugar)

20 0

ure Water

Answer: 65wt% sugar.

A apte from Fig. 9.1, Callister 6e.

Solubility limit increases with T:

e.g., if T = 100C, solubility limit = 80wt% sugar.
2

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

ure Sugar

20 40 6065 80 100 Co=Composition (wt% sugar)

COM ONENTS AND HASES

Components:
The elements or compounds which are mixed initially
(e.g., Al and Cu)

hases:
The physically and chemically distinct material regions that result (e.g., E and F).
AluminumCopper Alloy

F (lighter phase) E(dar er phase)

Adapted from Fig. 9.0, Callister 3e. 3

EFFECT OF T & COM O ITION (Co)

Changing T can change # of phases: path A to . Changing Co can change # of phases: path to D. ( 00,70) D(100, 0)
phase 2 phases

100
Temperature (C)
watersugar system

80 60 40 20 0
0
(li ui solution
i.e., syrup)

L
(li ui )

(soli sugar)

A(70,20)
2 phases

A apte from Fig. .1, Callister 6e.

0 40 7 Co Composition (wt

sugar)
4

HASE DIAGRAMS
Tell us about phases as function of T, Co, . For this course:
--binary systems: just 2 components. --independent variables: T and Co ( = 1atm is always used).

T(C)
hase Diagram for Cu-Ni system
1600 1500 1400 1300 1200
1100 1000 0

L (li uid)
i du u s

li

20

40

60

80

100

wt

Ni

E (FCC solid solution)

s du i ol s

2 phases: L (li uid) E (FCC solid solution) 3 phase fields: L L E E

Adapted from Fig. 9.2(a), Callister 6e. (Fig. 9.2(a) is adapted from hase Diagrams of inary Nic el Alloys, . Nash (Ed.), ASM International, Materials ar , OH (1991).

 Rule 1: If we now T and Co, then we now:

--the # and types of phases present.

H SE DI GR MS: # and types of phases

T(C)
1600
(12 0,3 )

Examples:
(1100, 60): 1 phase: E
(12 0, 3 ): 2 phases: L
E

1 00 1400 1300 1200

L (li uid)

L ( CC solid
solution)
(1100,60)

E E

s idu u s li du i ol s

Cu- i phase diagram

dapted from ig. 9.2(a), Callister 6e. ( ig. 9.2(a) is adapted from hase Diagrams of inary ic el lloys, . ash (Ed.), SM International, Materials ar , OH, 1991).

 

1100 1000 0

20

40

60

80

100

wt
6

E I GR M : composition of
phases

Rule 2: If we now T and Co, then we now:

--the composition of each phase.

Examples:
Co wt i tT : nly i uid ( ) C Co ( wt tT : nly olid ( E ) wt CE Co ( t TB: Both E and C Cli uidus ( CE Csolidus (

T(C) T (li uid)

Cu- i system
tie line dus i li u

E
B
us o li d s

i)

TB

E
2

E (solid)
2 C Co

i)

C E wt
        

  

2wt wt

i here) i here)

dapted from Fig. 9.2(b), Callister 6e. (Fig. 9.2(b) is adapted from hase iagrams of Binary ic el lloys, . ash (Ed.), M International, Materials ar , H, 99 .)

HASE DIAGRAMS: weight fractions

Rule 3: If we Examples:
Co 35wt%Ni nly Li uid (L) L 100wt%, E 0 nly olid (E ) L 0, E 100wt% oth E and L At TA: At T : tT :

of phases now T and Co, then we

T( )
TA
1300

now:
Cu-Ni system
A
ti li

--the amount of each phase (given in wt%).

L (li

i )
B R S

li

TB
1200

i sol

L!

S R S

43  35 ! 73wt % 43  32

TD
20

E (soli )
50

30 35 4043 32

CLCo

$ ! #! !

$ #

" "

R WE !  R S

CE wt% i

= 27wt%

Adapt d from Fig. 9.2(b), Callist r 6 . (Fig. 9.2(b) is adapt d from hase Diagrams of Bi ary ic el Alloys, . ash (Ed.), ASM I ter ational, Materials ar , OH, 1991.)

"

THE LEVER RULE: A ROOF

Sum of weight fractions: WL  WE ! 1 Conservation of mass (Ni): Co ! WL CL  WE CE Combine above equations: S ! CE  Co L CE  CL R  S A geometric interpretation: Co CL CE

Co  CL ! R CE  CL R  S
i i ri m:

moment e

LR ! 1
E

ES

solving gives Lever Rule

9

X: COOLING IN A Cu-Ni BINARY

hase diagram:
Cu-Ni system.
T(C) L (li uid) A
35 L: 35wt%Ni

System is:
Cu and Ni.

1300 L: 35wt%Ni --binary i.e., 2 components: E: 46wt%Ni

E L
46 43

Cu-Ni system

32
24 1200

B C

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

D 36
E

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

E (solid)
1100 20 30

E: 36wt%Ni

Consider
Co = 35wt%Ni.

Adapted from Fig. 9.3, Callister 6e.

35 Co

40

50

wt% Ni
10

CORED VS EQ ILI RI M HASES

CE changes as we solidify. Cu-Ni case: First E to solidify has CE = 46wt%Ni.
Last E to solidify has CE = 35wt%Ni.

Fast rate of cooling:

Cored structure
First E to solidfy: 46wt%Ni

Slow rate of cooling:

Equilibrium structure
niform CE: 35wt%Ni

Last E to solidfy: 35wt%Ni

11

MECHANICAL RO ERTIES: Cu-Ni

System
Effect of solid solution strengthening on:
--Tensile strength (TS)
Tensile Strength (M a) Elongation (%EL)
6 5

--Ductility (%EL,%AR)
%EL for pure Cu %EL for pure Ni

TS for pure Ni TS for pure Cu

2

2 Cu

Composition,

1 Ni

2 Cu

t%Ni

Composition,

1 Ni

t%Ni

Adapted from Fig. 9.5(a), Callister 6e.

Adapted from Fig. 9.5(b), Callister 6e.

-- ea as a function of Co

--Min. as a function of Co
12

RY

UT
T

TI SYST

S
g s stem

2 components

has a special composition with a min. melting T.

. g s stem 1200 3 single phase egions

EF
1000 800 600

li E
8.0

i
71.9 91.2

imite sol ilit T E mostl i F mostl T o li i elow T in. melting T composition

+ E

779

+FF

400 200 0 20
(

EF
40 60 80 100

apte f om Fig. 9.6 alliste 6e. Fig. 9.6 a apte f om ina hase Diag ams 2n e . Vol. 1 T. . assals i ito in hief S Inte national ate ials a OH 1990.

o wt% g
( 1 (
13

( (5' 3 ' 4 ' 4 % ( 8 )7 7' &60 5 4 (& & ( 8 ' 3 2' 1 ' & & 0 ' ) ' & &%

EX:

b-Sn EUTECTIC SYSTEM (1)

T( C)
300

For a 40wt%Sn-60wt% b alloy at 150C, find...

--the phases present: E+F --the compositions of the phases:
b-Sn system

(li E + E
1 .3 1 3C 61.9

id)
+F F
97.

200 150 100

E F
20 40 Co 60 0 100

Adapted from Fig. 9.7, Callister 6e. (Fig. 9.7 adapted from inary hase Diagrams, 2nd ed., Vol. 3, T. . Massals i (Editor-in-Chief), ASM International, Materials ar , OH, 1990.) 14

Co, wt% Sn
9

A @

EX:

b-Sn EUTECTIC SYSTEM (2)

For a 40wt%Sn-60wt% b alloy at 150C, find...

--the phases present: E + F b-Sn T(C) --the compositions of system the phases: 300 CE = 11wt%Sn (li uid) CF = 99wt%Sn + E E --the relative amounts 200 +F F 183C of each phase: 18.3 61.9 97.8

59 !67wt % ! WE 88 29 !33wt % WF ! 88

150 100

S
EF
40 Co 60 80 99100

0 11 20

Adapted from Fig. 9.7, Callister 6e. (Fig. 9.7 adapted from inary hase Diagrams, 2nd ed., Vol. 3, T. . Massals i (Editor-in-Chief), ASM International, Materials ar , OH, 1990.) 15

Co, wt% Sn
B

D C

MI RO IN EU E
< wt% R lt:
--p l c tal f E g ai .

RU URE I Y EM -I
WV IH RQ UTS FF
E E

E
fe ba` Y dc FFE u

l bilit limit)
16

Adapt d f m Fig. 9.9 alli t r 6 .

GP

FE

s Ir pIIih q E IH G

GG

GGP

g v v xw v

E Pbt m)

MICROS RUC UR S IN U C IC SYS MS-II

2wt%Sn < Co < 18.3wt%Sn Result:
--E polycrystal with fine F crystals.
3

: C owt%Sn

E
2

E

E: C owt%Sn

E F 1

b-Sn syste
3

2 Co C o 18.3 sol. li it at

Adapted fro Callister 6e.

Fig. 9.1

2 sol. li it at roo

wt% Sn
17

MI RO RU UR IN U I Y M
= R l
l

III

l y

dF

l .

P y

E E
1 18

FF
1 Q

F 97.8

E 18
8
Ad all d F . 9.11,

18

1 8

k j e i i e h h g f e d
F . 9.1 , all . Adap d F . 9.1 al Ha d , V l. 9, 9 d., M all ap y a d Mc c ,A ca c y M al , Ma al Pa k, OH, 1985. 18

MICROSTRUCTUR S IN UT CTIC SYST MS-IV

18 3wt Sn < Co < 61 wt Sn Result: E r st ls nd eute ti
T C)
300

i rostru ture

L: Cowt Sn L L E
S
S

E L

Just bo e T :
CE CL 18 3wt Sn 61 wt Sn S 0wt E R S L 1- E ) 0wt
18 3wt Sn 7 8wt Sn S 73wt R S 27wt
1

b-Sn s ste
200 T

L
E
l

E
R R

Just below T :
E
20 18 3
Fig

100

F
40 Co 60 61 80
100 78

CE
u u
ri r E eute ti E eute ti

CF
F

0 0
Ad ted fro C llister 6e

14

Co wt

Sn

t t s rq p

E
F

n o

on

{ z z v

z y

xw

HY O UT CTIC & HY R UT CTIC T(C)

300

L
L E
Co

F
Co

0 0

20

40

60

80

E
E

eute ti : Co=61.

E E
E
175Q 160Q

Ad ted fro C llister 6e.

Fig. .12,

Ad ted fro eute Fig. .15, C llister 6e.

ti

i ro- onstituent

(Figs. .12 nd .15 fro Met ls H nd ook, t ed., Vol. , Met llogr nd Mi rostru tures, A eri n So iet for Met ls, M teri ls r , OH, 1 85.)

t Sn

Ad ted fro Fig. .15, C llister 6e. (Illustr tion onl )

oeute ti : Co=50 t Sn

ereute ti : (illustr tion onl )

20

61.

18.3

eute ti

oeute ti

ereute ti

100

7.8

}
Co, t

E

Ad ted fro Fig. .7, C llister 6e. (Fig. .7 200 T d ted fro in r se Di gr s, 2nd ed., Vol. 3, T. . M ss lski 100 ( ditor-in-C ief), ASM Intern tion l, M teri ls r , OH, 1 0.)

( -Sn S ste )

Sn

 2 important points -Eutectic (A):

L K  Fe3C

IRON-CAR ON (Fe-C) HASE DIAGRAM

T(C)
1600

H
1400 1200 1000 800

L Fe3C (cementite)

21

-Eutectoid ( ):
K E  Fe3C

K L K austenite)
K K K K

1148C

R
K+Fe3C S E+Fe3C

L+Fe3C S

600

Result: earlite = alternating layers of E and Fe3C phases.

(Adapted from Fig. 9.24, Callister 6e. (Fig. 9.24 from Metals Handboo , 9th ed., Vol. 9, Metallography and Microstructures, American Society for Metals, Materials ar , OH, 1985.)

Ceutectoid

120Qm

400 0 (Fe)

K E+
R 0.77
1

727C = Teutectoid

4.30 Co, t C Fe3C (cementite-hard) E(ferrite-soft)

6.7

Adapted from Fig. 9.21,Callister 6e. (Fig. 9.21 adapted from inary Alloy hase Diagrams, 2 d ed., Vol. 1, T. . Massals i (Ed.-in-Chief), ASM International, Materials ar , OH, 1990.)

HY OEUTECTOID STEEL
T( )
1600

H
1 00
11

1000 00

Fe C (cementite)

K K K K K K K K K EK E K EK

1200

E Fe C
0.77

E E E

pearlite

K
100Qm Hypoeutectoid steel

E S/(R S) Fe C (1- E)

Adapted from Fig. 9.27,Callister 6e. (Fig. 9.27 courtesy Republic Steel Corporation.)

6.7

Co,

00 0 Co pearlite

E s/(r s) 600 K (1- E)

ERS

727

K L K austenite)

L Fe C

(Fe-C System)
Adapted from Figs. 9.21 and 9.26,Callister 6e. (Fig. 9.21 adapted from inary Alloy hase Diagrams, 2nd ed., Vol. 1, T. . Massals i (Ed.-inChief), ASM International, Materials ar , OH, 1990.)

K Fe C r s

22

Y E EU E
( )

OID

EE
(F t
tit )

H K K K K
F

K K t it )

K F

E
) )
.77

p arlit

t t

rp r ti

.)

( ) ( - E)

p arlit

K
Q
A pt fr Fig. 9. , lli t r . (Fig. 9. c p right 97 b U it

K ( -

.7

t
p r

r (r

E F

(c

fr Fig . 9. 9, lli t r . (Fig. 9. pt fr i r All ha Di gr , ., V l. , . . M l i (E .-i hi f ), A M I t r ti l, M t ri l r , O , 99 .) A 9.

t ct i t l

pt

K K K K K K K K

ALLOYING STEEL WITH MORE ELEMENTS

Teutectoid changes:
T Eutectoid (C)
1200
1000 Ti Mo

Ceutectoid changes:
Ceutectoid (wt%C)
0.8 0.6 0.4 0.2
0 0

Si
W

Ni Cr Si Ti Mo
4

Cr
800 Mn

W
8

Mn

600 0

Ni 4 8 12

12

wt. % of alloying elements

Adapted from Fig. 9.31,Callister 6e. (Fig. 9.31 from Edgar C. ain, Functions of the Alloying Elements in Steel, American Society for Metals, 1939, p. 127.)

wt. % of alloying elements

Adapted from Fig. 9.32,Callister 6e. (Fig. 9.32 from Edgar C. ain, Functions of the Alloying Elements in Steel, American Society for Metals, 1939, p. 127.)

24

LICATION: REFRACTORIES

Need a material to use in high temperature furnaces. Consider Silica (SiO2) - Alumina (Al2O3) system. hase diagram shows:
mullite, alumina, and crystobalite (made up of SiO2) tetrahedra as candidate refractories.
2200 T(C) 2000 1800 crystobalite +L 1600 1400 0
3Al2O3-2SiO2 Li uid (L)
mullite

alumina + L
mullite +L
Adapted from Fig. 12.27, Callister 6e. (Fig. 12.27 is adapted from F. . Klug and R.H. Doremus, "Alumina Silica hase Diagram in the Mullite Region", . American Ceramic Society 70(10), p. 758, 1987.)

mullite + crystobalite

20

40 60 80 100 Composition (wt alumina)

25

alumina + mullite

Phase Diagrams with Other Invariant Reactions

Monotectic Phase Diagram

Peritectic and Eutectoid Reactions

Ceramic Phases And Cements

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.

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

26