CH 09

2014-03-22
Chapter 9: Phase Diagrams

Chapter Outline:
! ! ! ! Types of Phases Solubility and Phase Equilibria Binary Phase Diagrams Lever Rule: Quantification of Phase Amounts / Mass Fractions Developments of Microstructure in Isomorphous Alloys ! Creating a Phase Diagram ! Equilibrium Cooling ! Nonequilibrium Cooling ! Mechanical Properties of Isomorphous Alloys ! Binary Eutectic Systems
Chapter 9 - 1
What is a Phase?
! Phase - Any portion of a system, which is chemically and
physically homogeneous within it and bounded by a surface so that it is mechanically separable from any other portions.
Liquid Ni-Cu Alloy
Solid Solution of Ni-Cu
Solid Solution + Secondary Phase
2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.
2 !
Chapter 9 - 2
Types of Phases
Solubility and Solid Solutions Definitions

!! Solubility - The amount of one material that will completely dissolve in a second material without creating a second phase. !! Unlimited solubility - When the amount of one material that will dissolve in a second material without creating a second phase is unlimited. !! Limited solubility - When only a maximum amount of a solute material can be dissolved in a solvent material. !! Mixture More than one phase.
Illustration of phases and solubility: (a) The three forms of water gas, liquid, and solid 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. Chapter 9 - 3
Chapter 9 -
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Phase Equilibria: Solubility Limit

Question: What is the
solubility limit for sugar in water at 20C? Sugar/Water Phase Diagram
10! 0!
Temperature (C)!
Components and Phases

Components:
The elements or compounds which are present in the alloy
(e.g., Al and Cu)
8! 0! 6! 0!
Solubility ! Limit!
(liquid) !
L!
Phases:
The physically and chemically distinct material regions that form (e.g., ! and ").
AluminumCopper Alloy
Sugar!
4! 0! (liquid solution ! i.e., syrup)! 20!

Water!
L!!
(solid ! sugar)!
+! S!
" (lighter phase)
Answer: 65 wt% sugar.

At 20C, if C < 65 wt% sugar:
syrup
0!
20! 40! 6065 ! ! 80! 100! C!= Composition (wt% sugar)!

Adapted from Fig. 9.1, Callister & Rethwisch 8e.
! (darker phase)
Adapted from chapteropening photograph, Chapter 9, Callister, Materials Science & Engineering: An Introduction, 3e. Chapter 9 - 6
At 20C, if C > 65 wt% sugar:

syrup + sugar
Chapter 9 - 5
Effect of Temperature & Composition

Altering T can change # of phases: path A to B. ! Altering C can change # of phases: path B to D. B (100C,C = 70) D (100C,C = 90) 100
Temperature (C)
1 phase 2 phases
Criteria for Solid Solubility

Simple system (e.g., Ni-Cu solution) Crystal Structure Ni Cu FCC FCC
electroneg
r (nm) 0.1246 0.1278
80 60 40 20 0
0
(l!iquid solution
i.e., syrup)
L
(liquid)
1.9 1.8
watersugar system
L!
+ S
(solid sugar)
A (20C,C = 70)
2 phases
! 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 soluble in one another for all proportions.
Chapter 9 - 8
20 40 60 70 80 100 C = Composition (wt% sugar)

Chapter 9 - 7
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Phase Diagrams
Indicate phases as a function of T, C, and P. For this course:
- binary systems: just 2 components. - independent variables: T and C (P = 1 atm is almost always used).
Phase Diagram for Cu-Ni system
Phase Diagrams Definitions

!! Binary phase diagram - A phase diagram for a system with two components. !! Ternary phase diagram - A phase diagram for a system with three components. !! Isomorphous phase diagram - A phase diagram in which components display unlimited solid solubility. !! Liquidus temperature - The temperature at which the first solid begins to form during solidification. !! Solidus temperature - The temperature below which all liquid has completely solidified.
Chapter 9 -
T(C)! 1600!
1500! 1400! 1300! 1200! 1100! 1000! 0! 20!
liq uid
2 phases:! !
L (liquid)!
us
L( !liquid)! !!( !FCC solid solution)!

3 different phase fields: ! L! L +!!! !!
Adapted from Fig. 9.3(a), Callister & Rethwisch 8e. (Fig. 9.3(a) is adapted from Phase Diagrams of Binary Nickel Alloys, P. Nash (Ed.), ASM International, Materials Park, OH (1991).
us L! + lid so !! ! (FCC solid ! solution)!
!!!!
40!
60!
80! 100!
wt% Ni!
Chapter 9 - 9
Isomorphous Binary Phase Diagram

Phase diagram:
Cu-Ni system.
Phase Diagrams:
Determination of phase(s) present
Rule 1: If we know T and Co, then we know:
-- which phase(s) is (are) present.
T(C)! 1600!
1500! 1400! 1300! 1200! 1100! 1000! 0! 20!
liq uid
System is:
-- binary
i.e., 2 components: Cu and Ni.
L (liquid)!
us
-- isomorphous
i.e., complete solubility of one component in another; ! phase field extends from 0 to 100 wt% Ni.
us L! + lid so !! ! (FCC solid ! solution)!
!!!!
B!(1250C,35)!
Cu-Ni phase diagram
Examples:
T(C)! 1600!
A(1100C, 60 wt% Ni): ! 1500! 1 phase: !! B! (1250C, 35 wt% Ni): ! 1400! 2 phases: L + ! !
1300! 1200!
L (liquid)!
liq uid us
!
s!
L! +
!!!
li so
du
Cu-Ni phase diagram
40!
60!
80! 100!
wt% Ni!
Adapted from Fig. 9.3(a), Callister & Rethwisch 8e. (Fig. 9.3(a) is adapted from Phase Diagrams of Binary Nickel Alloys, P. Nash (Ed.), ASM International, Materials Park, OH (1991). Chapter 9 - 11
Adapted from Fig. 9.3(a), Callister & Rethwisch 8e. (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) !

A(1100C,60)!
!!
1100! 1000! 0! 20! 40!
60!
80! 100!
wt% Ni!
Chapter 9 - 12
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Phase Diagrams: Determination of phase compositions

Rule 2: If we know T and C0, then we can determine:
-- the composition of each phase.
Phase Diagrams: Determination of phase weight fractions

Rule 3: If we know T and C0, then can determine:
-- the weight fraction of each phase.
Examples:
Consider C0 = 35 wt% Ni At TA! = 1320C: ! Only Liquid (L) present ! CL = C0!! ( = 35 wt% Ni)! At TD! = 1190C: Only Solid (!) present! C ! = C 0! ( ! = 35 wt% Ni)!
T(C)! TA!
1300
Cu-Ni system
tie line s! idu liqu
A! B!
! L (liquid)!
! !! L!+
Examples: Consider C0 = 35 wt% Ni

At TA : Only Liquid (L) present ! ! ! WL ! = 1.00, W! = 0 ! At TD :! !Only Solid (!!)# present ! ! ! WL = 0, W! !# = 1.00! At TB :! !Both !!# and L present!
T(C)! TA
1300
Cu-Ni system A!
tie line s! idu liqu
TB
1200 TD
! !! L!+ !
d soli us
! L (liquid)!
!! +!
! !
D!
!! (solid)!
4043
TB
1200 TD
B! R! S! D!
L!+
soli
! !!
dus
! !
L!
!! (solid)!
50
At TB! = 1250C: Both !!# and L present! C ! L = C!liquidus! ( ! = 32 wt% Ni) ! C ! !# = C!solidus! ( ! = 43 wt% Ni)!
20
30 32 35
CL C0
! ! !
!!!
50
C!# wt% Ni!
S WL =! R +S
43 ! 35 = 0.73 43 ! 32
20
30 32 35
! ! ! ! 4! 0! 4! 3!
CL C0
R = 0.27 W! =! R +S
C!# wt% Ni!
!!
The Lever Rule

! Tie line connects the phases in equilibrium with each other also sometimes called an isotherm T(C)! What fraction of each phase? tie line! us! id Think of the tie line as a lever liqu 1300! L (liquid)! !! (teeter-totter) !+ ! L ! B! dus T! M! ML soli B! !! !! +! ! L (solid)! 1200!
R! S!
20
Ex: Cooling of a Cu-Ni Alloy

Phase diagram:
Cu-Ni system.
T(C) L (liquid)
130 0 L: 35 wt% Ni !: 46 wt% Ni 32 24 120 0 L: 35wt%Ni
Consider microstuctural changes that accompany the cooling of a
A
35
B C D
36
L+
46 43
!#
Cu-Ni system
L: 32 wt% Ni !: 43 wt% Ni L: 24 wt% Ni !: 36 wt% Ni
C0 = 35 wt% Ni alloy
L+
!#
3 0CL
!!
0!C ! C 0! 4! !
50
!!
wt% Ni!
Adapted from Fig. 9.3(b), Callister & Rethwisch 8e.
M" x S = ML x R
W" = C ! CL R = 0 R + S C " ! CL
Chapter 9 - 15
!# (solid)
110 0 20 30
C ! C0 ML S WL = = = " M L + M " R + S C " ! CL !
35 C0
40
50
wt% Ni
Chapter 9 - 16
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Creating a Phase Diagram

! Equilibrium diagrams may be interpreted as well as
Temperature (oC)
1500
Pure Cu

20% Ni 60% Ni Pure Ni
40% Ni
1455 oC
1455 oC L Liquidus Solidus
determined, in terms of the cooling curves for different compositions. ! The actual slopes are not of great significance but the inflection points are significant. ! These indicate the start or completion of a phase transformation or phase change.
1400 1300 1200 1100 1000

1085 oC
! 1085 oC
Time
20
40
60
80
100
(Cu)
wt% Nickel
(Ni)
Chapter 9 - 17
Chapter 9 - 18
Nonequilibrium Solidification and Segregation

!! Coring - Chemical segregation in cast products, also known as microsegregation or interdendritic segregation. !! Homogenization heat treatment - The heat treatment used to reduce the microsegregation caused during nonequilibrium solidification. !! Macrosegregation - The presence of composition differences in a material over large distances caused by nonequilibrium solidification.
Chapter 9 - 19
Chapter 9 -
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Cored vs Equilibrium Structures

C! changes as we solidify. Cu-Ni case: First ! to solidify has C! = 46 wt% Ni.
Last ! to solidify has C! = 35 wt% Ni.
Slow rate of cooling:

Equilibrium structure
Uniform C!: 35 wt% Ni
Fast rate of cooling:

Cored structure
First ! to solidify: 46 wt% Ni Last ! to solidify: < 35 wt% Ni
The change in structure of a Cu-40% Ni alloy during nonequilibrium solidification. Insufficient time for diffusion in the solid produces a segregated structure.
Chapter 9 - 21
Chapter 9 -
Ex: Nonequilibrium Solidification of Cu-Ni Alloys

Calculate the composition and amount of each phase in a Cu-40% Ni alloy that is present under the nonequilibrium conditions shown in the previous Figure at 1300oC, 1280oC, 1260oC, 1240oC, 1200oC, and 1150oC. Compare with the equilibrium compositions and amounts of each phase.
SOLUTION
We use the tie line up to the equilibrium solidus temperature to calculate composition and percentages of phases as per the lever rule. Similarly, the nonequilibrium solidus temperature curve is used to calculate percentages and concentrations of different phases formed under nonequilibrium conditions.
Chapter 9 -
24 !
Chapter 9 -
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SOLUTION (Continued)
Mechanical Properties: Cu-Ni System

Effect of solid solution strengthening on:
-- Tensile strength (TS)
Tensile Strength (MPa)
-- Ductility (%EL)
Elongation (%EL)
60 50 40 30 20 0 20 Cu 40 60 80 100 Ni %EL for pure Cu %EL for pure Ni
400 300 TS for pure Cu 200 0 20 40 60 80 100 Cu Ni

Adapted from Fig. 9.6(a), Callister & Rethwisch 8e.
TS for pure Ni
Composition, wt% Ni
Composition, wt% Ni
Adapted from Fig. 9.6(b), Callister & Rethwisch 8e.
25 !
Chapter 9 -
Chapter 9 - 26
!! Solid-solution strengthening - Increasing the strength of a metallic material via the formation of a solid solution. !! Dispersion strengthening - Strengthening, typically used in metallic materials, by the formation of ultra-fine dispersions of a second phase.
Chapter 9 -
Solid-Solution Strengthening Definitions
The effects of several alloying elements on the yield strength of copper. Nickel and zinc atoms are about the same size as copper atoms, but beryllium and tin atoms are much different from copper atoms. Increasing both atomic size difference and amount of alloying element increases solidsolution strengthening.
Chapter 9 -
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Ex: Design of a Melting Procedure for a Casting

You need to produce a Cu-Ni alloy having minimum yield strength of 20,000 psi, a minimum tensile strength of 60,000 psi, and a minimum % elongation of 20%. You have in your inventory a Cu-20% Ni alloy and pure nickel. Design a method for producing castings having the required properties.
SOLUTION From the previous Figure, we determine the required composition of the alloy. To satisfy all of these conditions, we could use: Cu-90% Ni or Cu-40% to 60% Ni We prefer to select a low nickel content, since nickel is more expensive than copper. In addition, the lower nickel alloys have a lower liquidus, permitting castings to be made with less energy being expended. Therefore, a reasonable alloy might be Cu-40% Ni.
The mechanical properties of coppernickel alloys. Copper is strengthened by up to 60% Ni and nickel is strengthened by up to 40% Cu.
Chapter 9 -
Chapter 9 -
SOLUTION (Continued) To produce this composition from the available melting stock, we must blend some of the pure nickel with the Cu-20% Ni ingot. Assume we wish to produce 10 kg of the alloy. Let x be the mass of Cu-20% Ni alloy we will need. The mass of pure Ni needed will be 10 - x. Since the final alloy consists of 40% Ni, the total mass of Ni needed will be: (10 kg)( 40% Ni / 100%) = 4.0 kg Ni Now lets write a mass balance for nickel. Nickel from the Cu-20% alloy + pure nickel added = total nickel in the 40% alloy being produced. 0.2x + 10 - x = 4.0 6.0 = 0.8x x = 7.5 kg Therefore, we need 2.5 kg of pure nickel.
Chapter 9 -
Binary-Eutectic Systems
2 components has a special composition with a min. melting T.
1200
Ex.: Cu-Ag system !
T(C) !
Cu-Ag system
3 single phase regions ! L (liquid) ! 1000 (L, !, ") ! !! L + !! 779C Limited solubility: ! !! L +"!" ! Te 800 ! 8.0 !: mostly Cu ! 71.9 91.2 ": mostly Ag ! 600 Te : No liquid below Te ! !+ ! " !! ! 400 Ce : Composition at temperature Te ! 200 Eutectic reaction
0 20 40 60 Ce 80
100
L (C e ) ! .9 wt% Ag) L(71

cooling heating
!(C!e) + "(C"e)
C , wt% Ag
32
"(8.0 wt% Ag) + !(91.2 wt% Ag) Chapter 9 -
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The Eutectic Phase Diagram Definitions

!! Solvus - A solubility curve that separates a single-solid phase region from a two-solid phase region in the phase diagram. !! Isopleth - A line on a phase diagram that shows constant chemical composition. !! Hypoeutectic alloy - An alloy composition between that of the left-hand-side end of the tie line defining the eutectic reaction and the eutectic composition. !! Hypereutectic alloys - An alloy composition between that of the right-hand-side end of the tie line defining the eutectic reaction and the eutectic composition.
Chapter 9 -
Cooling Curve for Eutectic Solidification

Eutectic Composition Cooling curve indicates type of solidification. Depends on composition Hypoeutectic Composition
!+L
Solvus
(c)2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.
Chapter 9 - 34
Pb-Sn Equilibrium Phase Diagram
Ex 1: Pb-Sn Eutectic System

For a 40 wt% Sn-60 wt% Pb alloy at 150C, determine:
-- the phases present Answer: ! + "# -- the phase compositions
Answer: C! = 11 wt% Sn C" = 99 wt% Sn
T(C)
300
Pb-Sn system
L (liquid)
18.3
183C
-- the relative amount of each phase
!! L+!!! 200 !
150 100
Answer: C - C0 S = " W!!= R+S C" - C! 99 - 40 99 - 11 W"# = R = R+S 40 - 11 = 99 - 11 = = 59 = 0.67 88 C0 - C!! C" - C ! 29 = 0.33 88
61.9
L +"! "!
97.8
S
!!+!"!
40 C0 60 80 99100 C"
0 11 20 C!
C, wt% Sn
(c)2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.
Chapter 9 -
Chapter 9 - 36
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Ex 2: Pb-Sn Eutectic System

For a 40 wt% Sn-60 wt% Pb alloy at 220C, determine:
-- the phases present: Answer: ! + L# -- the phase compositions
Answer: C! = 17 wt% Sn CL = 46 wt% Sn
Microstructural Developments in Eutectic Systems I

For alloys for which C0 < 2 wt% Sn Result: at room temperature
-- polycrystalline with grains of ! phase having composition C0
T(C)
400 L ! 300 L: C0 wt% Sn
T(C)
300 220 200
Pb-Sn system
! L+ ! !! ! !! !
0 17 20 C!
L (liquid)
S
183C
!
L
-- the relative amount of each phase

CL - C 0 46 - 40 = CL - C ! 46 - 17 6 = = 0.21 29
L +"! "!
200
!!!
!: C0 wt% Sn
L + !! (Pb-Sn System)
Answer:
100
Te
100
W!!=
!!+!"!
40 46 60 C0 CL 80 100
+ "! !!
C0 - C!! 23 = WL = = 0.79 CL - C ! 29
C, wt% Sn
Chapter 9 - 37
0 10 20 30 C0 C , wt% Sn 2 (room T solubility limit)
Chapter 9 - 38
Microstructural Developments in Eutectic Systems II

T(C) For alloys for which 400 2 wt% Sn < C0 < 18.3 wt% Sn L Result: 300 at temperatures in ! + " range -- polycrystalline with ! grains and small "-phase particles 200
Te
L: C0 wt% Sn
Microstructural Developments in Eutectic Systems III

For alloy of composition C0 = Ce Result: Eutectic microstructure (lamellar structure)
-- alternating layers (lamellae) of ! and " phases.
L+! !! !!
L !
!
Pb-Sn system
T(C)
L: C0 wt% Sn
!: C0 wt% Sn
300
! L+ ! !! ! !! !
0 20 18.3
L !
L + " "!
Micrograph of Pb-Sn eutectic microstructure
! " 100
! !
Pb-Sn system
200
Te
183C
+!"! !!
100
! + "!
40
0 10 20 30 C0 C , wt% 2 (sol. limit at T room ) 18.3 (sol. limit at Te)
": 97.8 wt% Sn !: 18.3 wt%Sn
160 m
Sn
Chapter 9 - 39
60 Ce 61.9
80
C, wt% Sn
100 97.8
Chapter 9 - 40
10
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Lamellar Eutectic Structure
Microstructural Developments in Eutectic Systems IV

For alloys for which 18.3 wt% Sn < C0 < 61.9 wt% Sn Result: ! phase particles and a eutectic microconstituent T(C)
Pb-Sn system
Te
L: C0 wt% Sn L
!# L
Just above Te :
C! = ! 18.3 wt% Sn! CL = 61.9 wt% Sn S W! = = 0.50 R! +S WL = (1- W!! ) = 0.50
300
!
L +!!#
L
R S
!!
L+"!
200
! !! !
0
"!
Just below Te :
primary ! eutectic ! eutectic "
100
!#+!"#
20 18.3 40 60 61.9 80
Adapted from Figs. 9.14 & 9.15, Callister & Rethwisch 8e.
Chapter 9 - 41
100 97.8
C, wt% Sn
C!# = 18.3 wt% Sn C! ! 97.8 wt% Sn "# = W!#= S = 0.73 R+ ! S W"# ! = 0.27
Chapter 9 - 42
Hypoeutectic & Hypereutectic

300
Intermetallic Compounds
! ! !! !
0 20
T(C) Adapted from Fig. 9.8, Callister & Rethwisch 8e. 200 (Fig. 10.8 adapted from Te Binary Phase Diagrams, 2nd ed., Vol. 3, T.B. Massalski (Editor-in-Chief), 100 ASM International, Materials Park, OH, 1990.)
L L+!!! !!+!"! ! L+"! "!
(Pb-Sn System)
40
60
eutectic 61.9
80
100
C, wt% Sn
hypoeutectic: C0 = 50 wt% Sn
(Figs. 9.14 and 9.17 from Metals Handbook, 9th ed., Vol. 9, Metallography and Microstructures, American Society for Metals, Materials Park, OH, 1985.)
hypereutectic: (illustration only)
!! !!
!! !! !! !!
175 m
eutectic: C0 = 61.9 wt% Sn
"! "!
160 m eutectic micro-constituent
"! "! "! "!
Mg2Pb
Note: intermetallic compound exists as a line on the diagram - not an area - because of stoichiometry (i.e. composition of a compound Chapter 9 - 44 is a fixed value).
Adapted from Fig. 9.17, Callister & Rethwisch 8e. (Illustration only) Chapter 9 - 43
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Eutectic, Eutectoid, & Peritectic

! Eutectic - liquid transforms to two solid phases L cool ! + " (For Pb-Sn, 183C, 61.9 wt% Sn)
heat
Eutectoid & Peritectic

Cu-Zn Phase diagram
Peritectic transformation $ + L %
! Eutectoid one solid phase transforms to two other solid phases intermetallic compound - cementite S2 S1+S3 cool $ ! + Fe3C (For Fe-C, 727C, 0.76 wt% C)
heat
! Peritectic - liquid and one solid phase transform to a second solid phase S1 + L S2 % +L
cool heat
(For Fe-C, 1493C, 0.16 wt% C)

Eutectoid transformation %
Chapter 9 - 45
$+&
Chapter 9 - 46
Iron-Carbon (Fe-C) Phase Diagram

2 important points - Eutectic (A):
L ' $ + Fe3C T(C)
1600 1600
T(C)
Hypoeutectoid Steel
L
Fe3C (cementite)
1148C
%
1400 1200 1000 800 600 400 0 (Fe) 1 2 3
% L
Fe3C (cementite)
1400
- Eutectoid (B):
$ ' ! + Fe3C
$ +L $ (austenite) $ $ $ $
1148C
A
$ +Fe3C
$ $ $ $ L+Fe3C $ $ $ $
!$
$ +L $ 1200 (austenite)
1000 800 600
727C
L+Fe3C
(Fe-C System)
Adapted from Figs. 9.24 and 9.29,Callister & Rethwisch 8e. (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
727C = T eutectoid
$ $ !$
Result: Pearlite = alternating layers of ! and Fe3C phases

(Adapted from Fig. 9.27, Callister & Rethwisch 8e.)
120 m
0.76
4.30
C, wt% C
6.7
pearlite
0.76
$ !+
!
1 2 3
! + Fe3C
4 5 6
!+Fe3C
!'
400 0 (Fe)C0
C, wt% C
100 m
6.7
Fe3C (cementite-hard) ! (ferrite-soft)

Adapted from Fig. 9.24, Callister & Rethwisch 8e. Chapter 9 - 47
Hypoeutectoid steel
pearlite
proeutectoid ferrite
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1600
T(C)
Hypoeutectoid Steel
L
Fe3C (cementite)
1600
T(C)
Hypereutectoid Steel
L
(Fe-C System)
%
1400 !$ ! 1200 1000
727C
%
L+Fe3C (Fe-C System)
Adapted from Figs. 9.24 and 9.29,Callister & Rethwisch 8e. (Fig. 9.24 adapted from Binary Alloy Phase Diagrams, 2nd ed., Vol. 1, T.B. Massalski (Ed.-inChief), ASM International, Materials Park, OH, 1990.)
1400
W! = s/(r + s) 800 r s W$ =(1 - W!)

!
pearlite
$ + Fe3C
1000 800 600
Fe3C
$ +Fe3C
Fe3C (cementite)
$ $ !$
$ +L $ (austenite)
1148C
$! $! $! $! $! $! $! $! $! $! $! $!
1200
$ +L $ (austenite)
1148C
L+Fe3C
600
!RS
1
0.76
! + Fe3C
2 3 4 5 6
!
0.76
! +Fe3C
1 C0 2 3 4 5
Wpearlite = W$#
400 0 (Fe)C0
C, wt% C
100 m
6.7
400 0 (Fe) pearlite
Adapted from Figs. 9.24 and 9.32,Callister & Rethwisch 8e. (Fig. 9.24 adapted from Binary Alloy Phase Diagrams, 2nd ed., Vol. 1, T.B. Massalski (Ed.-in-Chief), ASM International, Materials Park, OH, 1990.)
C, wt%C
6.7
W! = S/(R + S) WFe3C =(1 W!) pearlite
Hypoeutectoid steel
60 mHypereutectoid steel
proeutectoid ferrite
pearlite
proeutectoid Fe3C
Chapter 9 - 50
1600
T(C)
Hypereutectoid Steel
L
(Fe-C System)
Example Problem
For a 99.6 wt% Fe-0.40 wt% C steel at a temperature just below the eutectoid, determine the following: a)! The compositions of Fe3C and ferrite (!). b)! The amount of cementite (in grams) that forms in 100 g of steel. c)! The amounts of pearlite and proeutectoid ferrite (!) in the 100 g.
%
1400 Fe3C
1000 800
W$ =x/(v + x) WFe3C =(1-W$)
$ +Fe3C v x X
1 C0 2 3
Fe3C (cementite)
$! $! $! $!
1200
$ +L $ (austenite)
1148C
L+Fe3C
0.76
Wpearlite = W$# WFe
600 pearlite 400 0 (Fe)
! V
! +Fe3C
4 5
Adapted from Figs. 9.24 and 9.32,Callister & Rethwisch 8e. (Fig. 9.24 adapted from Binary Alloy Phase Diagrams, 2nd ed., Vol. 1, T.B. Massalski (Ed.-in-Chief), ASM International, Materials Park, OH, 1990.)
C, wt%C
6.7
W! = X/(V + X)
3C
=(1 - W!)
60 mHypereutectoid steel
pearlite
proeutectoid Fe3C
Chapter 9 - 51 Chapter 9 - 52
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Solution to Example Problem

a) Using the RS tie line just below the eutectoid
C! = 0.022 wt% C CFe3C = 6.70 wt% C
Solution to Example Problem (cont.)

c) Using the VX tie line just above the eutectoid and realizing that
C0 = 0.40 wt% C C! = 0.022 wt% C Cpearlite = C$ = 0.76 wt% C
b)! Using the lever rule with the tie line shown
WFe 3C = R C " C# = = 0 R + S CFe 3C " C# 0.40 " 0.022 = 0.057 6.70 " 0.022
1600
1600
Fe3C (cementite)
1200 1000 800
(austenite)
1148C
L+Fe3C
1200 1000 800
(austenite)
1148C
L+Fe3C
$ + Fe3C
727C
0.40 " 0.022 = 0.512 0.76 " 0.022
$ + Fe3C VX
727C
Amount of Fe3C in 100 g

!
R
600 400 0 1 2 3
! + Fe3C
4 5 6
Amount of pearlite in 100 g = (100 g)Wpearlite
600 400 0
! + Fe3C
1 2 3 4 5 6
= (100 g)WFe3C = (100 g)(0.057) = 5.7 g
C! C0
C , wt% C
Chapter 9 - 53
CFe
6.7
3C
= (100 g)(0.512) = 51.2 g
C! C0 C$
6.7
C, wt% C
Chapter 9 - 54
Alloying with Other Elements

Teutectoid changes:
T eutectoid (C)
Ti Mo Si Cr Mn Ni
Summary
Phase diagrams are useful tools to determine:
-- the number and types of phases present, -- the composition of each phase, -- and the weight fraction of each phase
Ceutectoid changes:
Ceutectoid (wt% C)
Ni Cr Si Ti Mo W Mn
given the temperature and composition of the system. The microstructure of an alloy depends on
-- its composition, and -- whether or not cooling rate allows for maintenance of equilibrium.
wt % of alloying elements
Adapted from Fig. 9.34,Callister & Rethwisch 8e. (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 & Rethwisch 8e. (Fig. 9.35 from Edgar C. Bain, Functions of the Alloying Elements in Steel, American Society for Metals, 1939, p. 127.)
Important phase diagram phase transformations include eutectic, eutectoid, and peritectic.
Chapter 9 - 55
Chapter 9 - 56
Fe3C (cementite)
T(C)
1400
$ +L
Wpearlite
V C " C# = = 0 V + X C$ " C#
T(C)
1400
$ +L
14
2014-03-22
Reading:
End Core Problems:
of Chapter 9
Self-help Problems:
Questions?
Suggested Problems:
Chapter 9 - 57
Chapter 9 - 58
15

CH 09

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2014-03-22

Chapter 9: Phase Diagrams

Liquid Ni-Cu Alloy

Solid Solution of Ni-Cu

Solid Solution + Secondary Phase

Solubility and Solid Solutions Definitions

Phase Equilibria: Solubility Limit

Components and Phases

4! 0! (liquid solution ! i.e., syrup)! 20!

" (lighter phase)

Answer: 65 wt% sugar.

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

At 20C, if C > 65 wt% sugar:

Effect of Temperature & Composition

Criteria for Solid Solubility

r (nm) 0.1246 0.1278

Adapted from Fig. 9.1, Callister & Rethwisch 8e.

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

Phase Diagrams Definitions

L( !liquid)! !!( !FCC solid solution)!

us L! + lid so !! ! (FCC solid ! solution)!

Isomorphous Binary Phase Diagram

us L! + lid so !! ! (FCC solid ! solution)!

Cu-Ni phase diagram

Cu-Ni phase diagram

(FCC solid ! solution) !

1100! 1000! 0! 20! 40!

Phase Diagrams: Determination of phase compositions

Phase Diagrams: Determination of phase weight fractions

Examples: Consider C0 = 35 wt% Ni

C!# wt% Ni!

C!# wt% Ni!

The Lever Rule

Ex: Cooling of a Cu-Ni Alloy

Consider microstuctural changes that accompany the cooling of a

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

Adapted from Fig. 9.3(b), Callister & Rethwisch 8e.

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

Adapted from Fig. 9.4, Callister & Rethwisch 8e.

Creating a Phase Diagram

Creating a Phase Diagram

1455 oC L Liquidus Solidus

1400 1300 1200 1100 1000

Creating a Phase Diagram

Nonequilibrium Solidification and Segregation

Cored vs Equilibrium Structures

Slow rate of cooling:

Fast rate of cooling:

Ex: Nonequilibrium Solidification of Cu-Ni Alloys

Mechanical Properties: Cu-Ni System

400 300 TS for pure Cu 200 0 20 40 60 80 100 Cu Ni

Adapted from Fig. 9.6(b), Callister & Rethwisch 8e.

Solid-Solution Strengthening Definitions

Ex: Design of a Melting Procedure for a Casting

Ex.: Cu-Ag system !

L (C e ) ! .9 wt% Ag) L(71

Adapted from Fig. 9.7, Callister & Rethwisch 8e.

"(8.0 wt% Ag) + !(91.2 wt% Ag) Chapter 9 -

The Eutectic Phase Diagram Definitions

Cooling Curve for Eutectic Solidification

Pb-Sn Equilibrium Phase Diagram

Ex 1: Pb-Sn Eutectic System

-- the relative amount of each phase