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CHAPTER 7

PHASE DIAGRAMS
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Chapter 7

Topic Outcomes

After studying this topic, the student should be able to; ;


Schematically sketch simple isomorphous and eutectic phase diagram p g On these diagram, label the various phase regions Label liquidus, solidus lines

Chapter 7

Topic Outcomes

Given a binary phase diagram, the composition of an alloy, its temperature, p y, p , and assuming that the alloy is at equilibrium, determine q ,
What phase(s) is (are) present The composition(s) of the phase(s) The mass fraction(s) of the phase(s)

Chapter 7

Topic Outcomes

Given the composition of an iron-carbon alloy containing between 0 022 wt% C and 2 14 0.022 2.14 wt% C, be able to
Specify whether the alloy is hypoeutectoid or p y y yp hypereutectoid Name the proeutectoid phase Compute the mass fractions of proeutectoid phase and pearlite Make a schematic diagram of the microstructure at a temperature just below the eutectoid t t t j tb l th t t id

Chapter 7

Chapter 7

INTRODUCTION

Phase diagram provides valuable g p information about melting, y crystallization, etc. Why study phase diagram? Important to engineers, related to design and control of heat treating heat-treating procedures since there is a strong correlation between microstructure and mechanical properties

Chapter 7

DEFINITIONS

Components: The elements or compounds which are present in the mixture (e g Al and Cu) (e.g., Phases: The physically and chemically distinct material regions, e.g., and in Aluminum-Copper alloy. Aluminum Copper Aluminum-Copper Alloy
(Darker phase)

(ligher phase)

Chapter 7

Phase Equilibria: Solubility Limit

Solubility Limit:
Max concentration for which only a single phase solution occurs.

Question: What is the


solubility limit at 20C?
100 Te emperature (C) 80 60 40 20

Sucrose/Water Phase Diagram


Solubility Limit

Answer: 65 wt% sugar.


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

L
(liquid)

L
(liquid solution i.e., syrup)

+ S
(solid sugar) )

The solubility limit of sugar in water y g Depends on the of water e.g., if T = 100C, solubility limit = 80wt% sugar.

0
Pure Water

Pure Sugar r
8

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

Chapter 7

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)
water- sugar system

100
Temperature (C) e

1 phase

2 phases

80 60 40 20 0
0

L
(liquid)

L
(liquid solution
i.e., syrup)

+ S

(solid sugar) g ) A (20C,70) 2 phases

Adapted from Fig. 9.1, Callister 7e.

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

Chapter 7

Phase Diagrams

Provides information about the microstructure, predicting phase transformation and the resulting microstructures Equilibrium p q phase diagram represents g p relationship between temperature (T), p phases ( ) and at constant (Co) composition of p pressure (P) (1 atm). Binary alloy- consist 2 components alloy Ternary alloy- consist of 3 components
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Chapter 7

Binary System

Alloy that contain 2 components (1) Isomorphous complete liquid and y p , g solid solubility of the 2 components, e.g. Cu-Ni L <=> (Cu-Ni solid solution) < > (Cu Ni (2) Eutectic limited solubility, upon cooling liquid phase is transformed into 2 solid phases. e.g. Cu-Ag, Pb-Sn L < > + <=>
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Chapter 7

Binary Isomorphous Phase Diagrams

-binary systems: just 2 components.


- independent variables: T and Co (P = 1 atm is almost always used).

Phase
Diagram for Cu-Ni Cu Ni system

T(C)
1600 1500 1400 1300 1200 1100 1000 0 20

2 phases:

L (liquid)

L (liquid) ( q ) (FCC solid solution)


3 phase fields: L L+
Noted: Solidus line q & Liquidus line
100

(FCC solid solution)


40 60 80

wt% Ni

12

Chapter 7

Binary Isomorphous

At temperature below 1080 C, 1080C Cu & Ni are soluble in each other (complete solubility) due to; Same crystal structure ( (FCC) ) Nearly identical atomic radii Nearly identical electronegetivity Similar valences

13

Chapter 7

Interpretation of Phase Diagrams


3 kind of information are available:
Type of phase that are present ( phase or L phase or + L phase?) p p p ) The composition of these phases The percentage or weight fractions of the phases

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Chapter 7

i. Type of Phase that are present

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


--the # and types of p yp phases p present.

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

T(C)
1600 1500 1400 1300 1200 1100 1000 0 20 40 B (12 250C,35)

L (liquid) ( qu d) Cu-Ni phase diagram

(FCC solid ) solution)

A(1100C,60) 60 80 100

wt% Ni t%
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Chapter 7

Composition of phases
Rule 2: If we know T and Co, then we know: kno the composition of each phase phase.

There are 2 cases: Th a. Single phase region b. Two phases region

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Chapter 7

a. Single phase region

The phase compositions are easy to be determined e.g.: Point A (60 wt% Ni-40 wt% Cu at 1100oC) At this Co and T Only O l phase is present h i t Composition = 60 wt% Ni-40 wt% Cu
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Chapter 7

b. Two phase region


Cu-Ni system t A L (liquid) B D
30 35 32 tie line

The phase composition can be determined by tie line. Examples:


Co = 35 wt% Ni At T A = 1320C: 1320 C: Only Liquid (L) CL = Co ( = 35 wt% Ni) At T D = 1190 C: 1190C: Only Solid ( ) C = Co ( = 35 wt% Ni) T(C) TA
1300

TB
1200

(solid)
4043 43 50

TD
20

At T B = 1250C: Both and L CL = C liquidus ( = 32 wt% Ni here) C = C solidus ( = 43 wt% Ni here)

CLCo

C wt% Ni

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Chapter 7

iii. Weight fraction of phase

Rule 3: If we know T and Co, then we know:


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

There are 2 cases: a) Single phase region b) Two phase region

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Chapter 7

a) Single phase region

Example: Point A (60 wt% Ni-40 wt% Cu at 1100oC) At this Co and T; Only phase is present The alloy is composed entirely of this phase, so the phase fraction; W = 1.0 (o 100%) 0 (or 00%)

20

Chapter 7

b) Two phase region


Tie line and Lever Rule (inverse lever Rule) must be utilized
CL
R

Co

C
S

WL

W
= C - Co = S WL + C - CL R S C o - CL = R W = C - CL R + S

total weight fraction: WL + W = 1

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Chapter 7

b) Two phase region (continue)


Cu-Ni system A L (liquid) B R S D
30 35 32 tie line

Examples:
T(C) 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% 0, t% At T B : Both and L TA
1300

TB
1200

(solid)
50

TD

C WL = C -

20 Co 43 35 = = 73 wt % CL 43 32 C - CL = 27 wt% W = C - CL

CLCo

40 43 43

C wt% Ni

22

Chapter 7

The Lever Rule

Tie line connects the phases in equilibrium with each other


T(C)
tie line 1300

L (liquid) B (solid) ( lid)


R S
50

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


ML M

TB
1200 20

30C C 40 C L o

wt% Ni

M S = M L R

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

C0 CL R W = = R + S C CL
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Chapter 7

Development of Microstructure

a. Equilibrium cooling extremely slow cooling Readjustment cooling. in the L and phases composition in accordance with th phase diagram d ith the h di b. Nonequilibrium cooling cooling rate too rapid to allow these g p compositional readjustment, thus nonequilibrium microstructure develop
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Chapter 7

a. Equilibrium cooling

i. Point a (1300C) Alloy is in liquid form ii. Point ii P i t b (1260C) phase begin to form at liquidus line, based on tie line, the composition is; L = 35wt% Ni-65wt% Cu = 46wt% Ni-54wt% Cu iii. Point c (1250C) solid & liquid composition L = 32wt% Ni-68wt% Cu = 43wt% Ni-57wt% Cu iv. Point d (1220C) Solidification is virtually completed v. v Point e (1180 C) (1180C) Solidification complete, Final productpolycrystalline phase solid solution = 35 wt % Ni- 65 wt% Cu

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Chapter 7

b. Nonequilibrium cooling

Nonequilibrium cooling :
Point c (1250C) grain boundary Point d (1220C) Solidification should be completed, however there is still liquid remaining Point e (1180C) Solidification reaches completion

26

Chapter Nonequilibrium vs. Equilibrium Cooling 7 In nonequilibrium system Cu-Ni system: First to solidify has C = 46wt%Ni.
Last to solidify has C = 35wt%Ni.
First to solidify: 46wt%Ni Last to solidify: < 35wt%Ni Uniform C: 35wt%Ni 35 t%Ni

Nonequilibrium cooling Rapid cooling rate. Segregation or concentration gradients are established

Equilibrium cooling Slow rate, composition in accordance with the phase diagram 27

Chapter 7

Mechanical Properties
--Ductility (%EL) Ductility
Elon ngation (% %EL)
60 50 40 30 20 0 20 40 60 80 100 Cu Ni %EL for pure Cu %EL for pure Ni

Effect of composition on mechanical properties (Tensile strength and elongation) of Copper-nickel system:
T Tensile Strength (MPa) S h

--Tensile Strength (TS)


400

300 TS for pure Cu

TS for pure Ni

200 0 20 40 60 80 100 Cu Ni

Composition, wt%Ni

Composition, wt%Ni

--At some intermediate composition, the curve passes through the maximum

--The ductility decreases with the addition of second component, where the curve 28 exhibit the minimum

Chapter 7

Binary Eutectic System


Liquid -The solubility of solid phases ( and ) is limited, e.g. solubility limit phase is at CBA b boundary li d line. -Example coppersilver phase diagram - 3 singlephase region exist i) phase (rich in copper) ii) phase- (rich in silver) iii) liquid
29

L+

L+

779C, E = 71.9

+
Composition, wt% Ag

Eutectic transition

L(CE)

(CE) + (CE)

Chapter 7

EX: Pb-Sn Eutectic System (1)


Pb-Sn system

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


--the phases present: + T( C) T(C) --compositions of phases:
CO = 40 wt% Sn C = 11 wt% Sn C = 99 wt% Sn
300

L (liquid)

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

--the relative amount of each phase:

200 150 100

L+
18.3

183C

L+
61.9 97.8

S
+

59 99 - 40 = = 67 wt% 99 - 11 88
0 11 20 C 40 Co

CO - C R W = = C - C R+S 40 - 11 29 = = 33 wt% = 99 - 11 88

Adapted from Fig 9 8 Fig. 9.8, Callister 7e.

C, wt% Sn

60

80

99100 C

30

Chapter 7

EX: Pb-Sn Eutectic System (2)

For a 40 wt% Sn-60 wt% Pb alloy at 200C, find...


--the phases present: + L T( C) 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:


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

L+
R

L (liquid)
S
183C

L+

100

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

C, wt% Sn

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

31

Chapter Microstructures in Eutectic Systems: I 7

Co < 2 wt% Sn Result:


--at extreme ends --polycrystal of grains f i.e., only one solid phase.

T(C) ( )
400

L: Co wt% Sn L

300

L
: Co wt% Sn

L+ (Pb-Sn System)

200

TE
100

0 Co

10

20

2 (room T solubility limit)

Co, wt% Sn
32

30

Chapter Microstructures 7 in Eutectic Systems: II

2 wt% Sn < Co < 18 3 wt% Sn 400 18.3 Result:


Initially liquid + then th alone l finally two phases polycrystal fine -phase inclusions
300

T(C) ( ) L L+

L: Co wt% Sn

L : Co wt% Sn

200

TE

100

+
0 10 20 30

Pb-Sn Pb Sn system Sn
33

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

Chapter 7

Microstructures in Eutectic Systems: III

Co = CE Result: Eutectic microstructure (lamellar structure) ( )


--alternating layers (lamellae) of and crystals.

T(C)
L: Co wt% Sn

Pb-Sn system

300

200
TE

L+

L
183C

Micrograph of Pb-Sn eutectic microstructure

L+
160 m

100

: 97.8 + : 18.3 wt%Sn wt% Sn

Adapted from Fig. 9.14, Callister 7e.

18.3

20

40

60 CE 61.9

80

C, wt% Sn

100 97.8

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Chapter 7

Eutectic reaction; L <=> + (Refer to coppersilver phase diagram at 71.9 wt% Ag) 71 9

Eutectoid reaction 1 solid phase 2 other solid phases (upon cooling) <=> + Peritectic reaction 1 solid phase + 1 liquid phase 1 l l d h liquid phase (upon d h ( cooling) + L <=>
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Chapter 7

Copper-Zinc Phase Diagram +L + +L


Peritectic

Eutectoid

36

Chapter THE IRON IRON CARBON (Fe Fe3C ) 7

In practice, all steel and cast iron have carbon content less than 6.7 wt % C, thus we consider only this phase diagram- iron-iron carbide system Carbon is an interstitial impurity in iron. p y

37

Chapter 7

38

Chapter 7

, austenite

+ Fe3C

ferrite

+ Fe3C

Cementite
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Chapter 7

Iron-Carbon (Fe-C) Phase Diagram


T(C)
1600

2 important points -Eutectic (A):


L + Fe3C + Fe3C

1400 1200 1000 800 600

L Fe3C (c cementite e)
6.7
40

-Eutectoid (B): Eutectoid

+L (austenite)

1148C

A
S +Fe3C

L+Fe3C

B
R
2

727 C 727C = Teutectoid

S
3

+Fe3C
4 5 6

Result: Pearlite = alternating layers of and Fe3C phases


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

C eutec ctoid

120 m

400 0 1 0.76 (Fe)

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

Adapted from Fig. 9.24,Callister 7e.

Co less than Eutectoid; 0.002 0.76 wt% C

Chapter 7

Hypoeutectoid Steel
1600

T(C) L Fe3C (cemen ntite)


1148C

1400

+L 1200 (austenite)
1000 800

L+Fe3C

(Fe-C System)

+ Fe3C
r s
727C

pearlite

C0

w pearlite = w w =S/(R+S) w F 3 =(1-w ) (1 w Fe


C

0.76 6

w =s/(r +s) 600 w =(1- w ) 400 0 (Fe)

RS
1

+ Fe3C
2 3 4 5 6

Co , wt% C
100 m Hypoeutectoid steel

6.7

pearlite
Adapted from Fig. 9.30,Callister 7e.

proeutectoid ferrite
41

Chapter 7

Hypereutectoid Steel
1600

T(C) L
1148C

0.76 2.14wt% C 1400

Fe3C

1000 800

+Fe3C r s S
1 Co 2 3

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

R 600
0.76

+Fe3C
4 5 6

400 0 (Fe) pearlite lit

w pearlite = w

Co , wt%C
60 mHypereutectoid steel

6.7

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

pearlite
Adapted from Fig. 9.33,Callister 7e.

proeutectoid Fe3C
42

Fe3C (cemen ntite)

+L 1200 (austenite)

(Fe C (Fe-C System) L+Fe3C

Chapter 7

Fraction of Pearlite & Proeutectoid

Fraction of P F ti f Pearlite, lit Wp = T T+U Fraction f F cti n of Proeutectoid , W = U T+U

Ferrite that is present in the pearlite is called eutectoid ferrite In terms of % C, terms like hypo and hyper-eutectoid alloys are used In term of T, Ferrite that formed before eutectoid T is called as proeutectoid 43 ferrite

Chapter 7

Example: Phase Equilibria

For a 99.6 wt% Fe-0.40 wt% C at a temperature j t below the eutectoid, t t just b l th t t id 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 ()
44

Chapter 7 a)

Solution:

composition of Fe3C and ferrite ()


1600

+ Fe3C
S + Fe3C

800 600 400 0

727C

Co , wt% C

CFe

6.7 67
3C

45

Fe3C (cement tite)

1400 CO = 0 40 wt% C 0.40 T(C) C = 0.022 wt% C 1200 +L 3 (austenite) CFe C = 6 70 wt% C 1000 6.70

L
1148C

L+Fe3C

Chapter 7

Solution:

b)

the amount of carbide (cementite) in grams that forms per 100 g of steel
Co C Fe 3 C = x 100 C Fe 3 C C Fe 3 C + = 0 . 4 0 . 022 x 100 = 5 . 7 g 6 . 7 0 . 022

Fe 3 C = 5.7 g = 94 . 3 g
46

Chapter 7

Solution:

c) the amount of pearlite and proeutectoid ferrite () note: amount of pearlite = amount of g just above TE
1600

1200 1000 800 600

(austenite)

1148C

L+Fe3C

+ Fe3C
727C

C C = o x 100= 51.2 g + C C

RS
1 2 3

+ Fe3C
4 5 6

pearlite = 51.2 g proeutectoid = 48.8 g

400 0

C CO C

6.7

Co , wt% C

47

F Fe3C (cem mentite)

Co = 0.40 wt% C % C = 0.022 wt% C Cpearlite = C = 0.76 wt% C

T( C) T(C)

1400

+L