CHAPTER 9: Phase diagrams The Solubility limit

ISSUES TO ADDRESS... • Solubility Limit: 100

Max concentration for Solubility
• When we combine two elements... 80 Limit L
what equilibrium state do we get? which only a solution (liquid)
occurs. 60 +
• In particular, if we specify... L
--a composition (e.g., wt%Al - wt%Cu), and • Ex: Phase Diagram: 40 (liquid solution S
--a temperature (T) i.e., syrup) (solid
Water-Sugar System 20 sugar)
then...
How many phases do we get? Question: What is the
solubility limit at 20C? 0 20 40 6065 80 100
What is the composition of each phase?
Answer: 65wt% sugar. Co =Composition (wt% sugar)
How much of each phase do we get?
If Co < 65wt% sugar: sugar
Phase A Phase B If Co > 65wt% sugar: syrup + sugar. Adapted from Fig. 9.1,
Callister 6e.

• Solubility limit increases with T:

e.g., if T = 100C, solubility limit = 80wt% sugar.
Aluminum atom
Copper atom
Chapter 9- 1 Chapter 9- 2

Components and phases Effect of t & composition (Co)

• Components: • Changing T can change # of phases: path A to B.
The elements or compounds which are mixed initially • Changing Co can change # of phases: path B to D.
(e.g., Al and Cu) B (100,70) D(100,90)
• Phases: 1 phase 2 phases
The physically and chemically distinct material regions 10 0
that result (e.g., α and β). L
• water- 80
(liquid)
Aluminum- β (lighter sugar +
Copper system 60 L
phase) S
Alloy (liquid solution
40 (solid
i.e., syrup)
α (darker sugar)

phase) 20 A (70, 20)

2 phases
Adapted from Adapted from 0
Fig. 9.0, Fig. 9.1, 0 20 40 60 70 80 100
Callister 3e. Callister 6e.
Co =Composition (wt% sugar)
Chapter 9- 3 Chapter 9- 4
 Phase diagrams Phase diagrams: # and types of phases
• Tell us about phases as function of T, Co, P. • Rule 1: If we know T and Co, then we know:
• For this course: --the # and types of phases present.
--binary systems: just 2 components.
--independent variables: T and Co (P = 1atm is always used). T(°C)
• Examples: 160 0
T(°C) A(1100, 60):
160 0 • 2 phases: L (liquid)
• Phase 1 phase: α 150 0
Cu-Ni
Diagram L (liquid)
150 0 L (liquid) phase
for Cu-Ni α (FCC solid solution) B(1250, 35): 140 0
2 phases: L + α diagram
system • 3 phase fields:
140 0 130 0 α
L (FCC solid
130 0 L+α 120 0 solution)
α
120 0 α Adapted from Fig. 9.2(a), Callister 6e.
Adapted from Fig. 9.2(a), Callister 6e.
(Fig. 9.2(a) is adapted from Phase 110 0 A(1100,60)
(Fig. 9.2(a) is adapted from Phase Diagrams of Binary Nickel Alloys, P. Nash
110 0 (FCC solid Diagrams of Binary Nickel Alloys, P. Nash (Ed.), ASM International, Materials Park,
(Ed.), ASM International, Materials Park, 100 0
solution) OH (1991).
OH, 1991).
0 20 40 60 80 100 wt% Ni
100 0
0 20 40 60 80 100 wt% Ni Chapter 9- 5 Chapter 9- 6

Phase diagrams: composition of phases Phase diagrams: weight fractions of phases

• Rule 2: If we know T and Co, then we know: • Rule 3: If we know T and Co, then we know:
--the amount of each phase (given in wt%) -
--the composition of each phase.
Cu-Ni Cu-Ni
system • Examples: system
• Examples: T(°C) T(°C)
C o = 35wt%Ni
TA A TA A
C o = 35wt%Ni tie line
At T A : Only Liquid (L) tie line
At T A : 130 0 L (liquid) 1300 L (liquid)
WL = 100wt%, W α = 0
Only Liquid (L) B At T D: Only Solid ( α) B
CL = Co ( = 35wt% Ni) TB TB R S
α WL = 0, Wα = 100wt%
At T D : α
120 0 D (solid) At T B : Both α and L 1200 D
Only Solid ( α) TD TD (solid)
Cα = Co ( = 35wt% Ni ) S 43 − 35
20 3032 35 40 43 50 WL = + = = 73wt % 20 3032 35 40 43 50
At T B : CLCo Cα wt% Ni R S 43 − 32 C LC o Cα
Both α and L Adapted from Fig. 9.2(b), Callister 6e. wt% Ni
R
Wα =
(Fig. 9.2(b) is adapted from Phase Diagrams of
C L = Cliquidus ( = 32wt% Ni here) Binary Nickel Alloys, P. Nash (Ed.), ASM = 27wt%
C α = Csolidus ( = 43wt% Ni here)
International, Materials Park, OH, 1991.) R+S
Chapter 9- 7 Chapter 9- 8
 The lever rule: a proof Ex: Cooling in a Cu-Ni binary
• Sum of weight fractions: WL + Wα = 1 • Phase diagram: T(°C) L (liquid) L: 35wt%Ni

Co = WL CL + Wα Cα Cu-Ni system. Cu-Ni

• Conservation of mass (Ni):
• System is: 130 0 system
A
• Combine above equations: --binary L: 35wt%Ni
α: 46wt%Ni B
C − Co = S C − CL = R i.e., 2 components: 35 46
WL = α Wα = o Cu and Ni. 32 C 43
Cα − CL R + S Cα − CL R + S --isomorphous D36 L: 32wt%Ni
24
i.e., complete α: 43wt%Ni
• A geometric interpretation: solubility of one 120 0 E
L: 24wt%Ni
moment equilibrium: component in
CL Co Cα α: 36wt%Ni
WLR = WαS another; α phase α
R S field extends from (solid)
0 to 100wt% Ni.
WL Wα 1 − Wα • Consider 110 0
Co = 35wt%Ni. 20 30 35 40 50
solving gives Lever Rule wt% Ni
Adapted from Fig. 9.3, Co
Callister 6e.
Chapter 9- 9 Chapter 9- 10

Cored vs equilibrium phases Mechanical properties: Cu-Ni System

• Cα changes as we solidify. • Effect of solid solution strengthening on:
• Cu-Ni case: First α to solidify has Cα = 46wt%Ni. --Tensile strength (TS) --Ductility (%EL,%AR)
Last α to solidify has Cα = 35wt%Ni.
• Fast rate of cooling: • Slow rate of cooling: 60
%EL for pure Cu
Cored structure Equilibrium structure 400 50 %EL for
TS for pure Ni
Uniform C α:
First α to solidfy: pure Ni 40
46wt%Ni 35wt%Ni 300
Last α to solidfy: TS for pure Cu 30
< 35wt%Ni
200 20
0 20 40 60 80 100 0 20 40 60 80 100
Cu Ni Cu Ni
Composition, wt%Ni Composition, wt%Ni
Adapted from Fig. 9.5(a), Callister 6e. Adapted from Fig. 9.5(b), Callister 6e.

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

Chapter 9- 11 Chapter 9- 12
 Binary-eutectic systems Ex: Pb-Sn eutectic system (1)
has a special composition • For a 40wt%Sn-60wt%Pb alloy at 150C, find...
2 components with a min. melting T. --the phases present: Pb-Sn
Cu-Ag
T(°C) α+β T(°C) system
system
Ex.: Cu-Ag system 120 0 --the compositions of
• 3 single phase regions L (liquid) the phases: 300
(L, α, β) 1000 L (liquid)
• Limited solubility: α L +α L+β β α L +α
T 800 779°C 200 183 °C L+β β
α: mostly Cu E 8.0 71.9 91.2 18.3 61.9 97.8
β: mostly Ni 600
150
• TE: No liquid below T E α+β 100 α+β
• CE: Min. melting T 400

composition 200
0 20 40 60 CE 80 100 0 20 40 60 80 100
Co
Adapted from Fig. 9.6, Co, wt% Ag Adapted from Fig. 9.7, C o, wt% Sn
Callister 6e. (Fig. 9.6 adapted
Callister 6e. (Fig. 9.7 adapted
from Binary Phase Diagrams, 2nd ed., Vol. 1, T.B. from Binary Phase Diagrams, 2nd ed., Vol. 3, T.B.
Massalski (Editor-in-Chief), ASM International, Materials
Massalski (Editor-in-Chief), ASM International, Materials
Park, OH, 1990.)
Park, OH, 1990.)
Chapter 9- 13 Chapter 9- 14

Microstructures
Ex: Pb-Sn eutectic system (2)
in eutectic systems-I
• For a 40wt%Sn-60wt%Pb alloy at 150C, find...
--the phases present: α + β Pb-Sn
--the compositions of T(°C) • Co < 2wt%Sn T(°C) L: C o wt%Sn
system 400
the phases: • Result: L
Cα = 11wt%Sn 300
L (liquid) --polycrystal of α grains. α

Cβ = 99wt%Sn 300 L
L +α
--the relative amounts 200 α 183 °C L+β β L +α
of each phase: 18.3 61.9 97.8 α
200
TE (Pb-Sn
150 α: Co wt%Sn
59 R S System)
Wα = = 67 wt % 100
88 α+β 100
α+β
29
Wβ = = 33 wt %
88 0 11 20 40 60 80 99100
Co 0 10 20 30
Adapted from Fig. 9.7, Co, wt% Sn Co Co, wt% Sn
Adapted from Fig. 9.9,
Callister 6e. (Fig. 9.7 adapted 2
Callister 6e.
from Binary Phase Diagrams, 2nd ed., Vol. 3, T.B. (room T solubility limit)
Massalski (Editor-in-Chief), ASM International, Materials
Park, OH, 1990.)
Chapter 9- 15 Chapter 9- 16
 Microstructures Microstructures
in eutectic systems-II in eutectic systems-III
L: C o wt%Sn
• Co = C E
• 2wt%Sn < Co < 18.3wt%Sn T(°C)
400 • Result: Eutectic microstructure
• Result: L --alternating layers of α and β crystals.
--α polycrystal with fine L
Micrograph of Pb-Sn
T(°C) eutectic
β crystals. 300 α
L: C o wt%Sn microstructure
L +α 300
α: C o wt%Sn L
α Pb-Sn
200 system
TE L +α
α 200
TE α 183°C L +β β
β
100
α+β Pb-Sn 100 α+β 160 μm
system β: 97.8wt%Sn Adapted from Fig. 9.12, Callister 6e.
α: 18.3wt%Sn (Fig. 9.12 from Metals Handbook, Vol. 9,
0 10 20 30 9th ed., Metallography and
Adapted from Fig. 9.10, 2 Co Co , wt% Sn 0 Microstructures, American Society for
0 20 40 60 80 100 Metals, Materials Park, OH, 1985.)
Callister 6e. (sol. limit at T room ) 18.3
(sol. limit at T E) 18.3 CE 97.8
Adapted from Fig. 9.11,
Chapter 9- 17 Callister 6e. 61.9 C o, wt% Sn Chapter 9- 18

Microstructures
Hypoeutectic & Hypereutectic
in eutectic systems-IV T(°C)
300 L
• 18.3wt%Sn < Co < 61.9wt%Sn Adapted from Fig. 9.7,
L +α
• Result: α crystals and a eutectic microstructure Callister 6e. (Fig. 9.7 200
adapted from Binary Phase TE α L +β
β (Pb-Sn
• Just above T E: Diagrams, 2nd ed., Vol. 3,
α+β System)
α L
L: C owt%Sn T.B. Massalski (Editor-in-
T(°C) Chief), ASM International, 100
C α = 18.3wt%Sn Materials Park, OH, 1990.)
L Co
hypoeutectic hypereutectic
Co
300 L α C L = 61.9wt%Sn 0
0 20 40 60 80 100 Co , wt% Sn
Pb-Sn
L +α Wα = S =50wt% 18.3 eutectic
61.9
97.8

system R+S hypoeutectic: C o =50wt%Sn hypereutectic: (illustration only)

200 α R S L +β β WL = (1-Wα) =50wt% (Figs. 9.12 and 9.15
TE
R S from Metals
eutectic: C o =61.9wt%Sn
• Just below T E:
Handbook, 9th ed.,
Vol. 9,
α β
100 Metallography and α β
α+β C α = 18.3wt%Sn Microstructures, α α β β
primary α
C β = 97.8wt%Sn
American Society for α β
eutectic α Metals, Materials
α β
Wα = S =73wt%
0 eutectic β Park, OH, 1985.)
0 20 40 60 80 100
18.3 Co 61.9 97.8 R+S 175 μm 160 μm
Adapted from Fig. 9.14, Co, wt% Sn Wβ = 27wt% Adapted from eutectic micro-constituent Adapted from Fig. 9.15,
Callister 6e. Fig. 9.15, Callister 6e. Adapted from Fig. 9.12, Callister 6e. (Illustration
Callister 6e. only)
Chapter 9- 19 Chapter 9- 20
 Iron-carbon (Fe-C) phase diagram Eutectoid decomposition
• 2 important T(°C)
1600
points δ
-Eutectic (A): 1400 L Eutectoid reaction – All solid phases
L ⇒ γ + Fe3 C γ+L
γ A
1200 L+Fe 3 C
γ (0.76 %C) α (0.022 %C) + Fe3C (6.7 %C)
1148°C
-Eutectoid (B): (austenite) R S
γ ⇒ α + Fe 3 C 1000 γ γ
γ γ γ+Fe 3C
800 Austenite, FCC Ferrite, bcc Cementite, iron carbide
α B 727°C = T eutectoid
(Metastable, bct)
R S
600
α+Fe 3C
400
0 1 2 3 4 5 6 6.7 Pearlite (mixture of phases)
(Fe) 0.77 4.30 Co , wt% C
120 μm
Result: Pearlite = Fe 3C (cementite-hard)
alternating layers of
α and Fe 3 C phases. α (ferrite-soft)
(Adapted from Fig. 9.24, Callister 6e. (Fig. Adapted from Fig. 9.21,Callister 6e. (Fig. 9.21 adapted
9.24 from Metals Handbook, 9th ed., Vol. 9, from Binary Alloy Phase Diagrams, 2nd ed.,
Metallography and Microstructures, American Vol. 1, T.B. Massalski (Ed.-in-Chief), ASM International,
Society for Metals, Materials Park, OH, Materials Park, OH, 1990.)
1985.)
Chapter 9- 21 Chapter 9-

Hypoeutectoid steel Hypereutectoid steel

T(°C)
T(°C) 1600
1600
δ δ
L 1400 L
1400
(Fe-C (Fe-C
γ γ γ γ+L System) γ γ γ γ+L System)
γ γ 1200 L+Fe 3 C γ γ 1200 1148°C L+Fe 3C
(austenite) 1148°C (austenite)
γ γ 1000 Adapted from Figs. 9.21 γ γ 1000
γ γ γ+Fe 3C and 9.26,Callister 6e. γ γ γ+Fe 3C Adapted from Figs. 9.21
and 9.29,Callister 6e.
(Fig. 9.21 adapted from Fe 3 C
α (Fig. 9.21 adapted from
αγ γ 800 r s 727°C Binary Alloy Phase γ γ 800 r s Binary Alloy Phase
γ γ α αR S Diagrams, 2nd ed., Vol.
1, T.B. Massalski (Ed.-in- γ γ α R
Diagrams, 2nd ed., Vol.
w α =s/(r +s) 600
S 1, T.B. Massalski (Ed.-in-
α+Fe 3 C Chief), ASM
International, Materials
w Fe3C =r/(r +s)600 α+Fe 3 C Chief), ASM
w γ =(1-w α) w γ =(1-w Fe3C ) International, Materials
Park, OH, 1990.)
400 Park, OH, 1990.)
0 1 2 3 4 5 6 6.7 400
α Co
0 1 Co 2 3 4 5 6 6.7
α pearlite C o , wt% C
α w pearlite = w γ pearlite Co, wt% C
w pearlite = w γ
w α =S/(R+S) 100 μm Hypo eutectoid
steel w α =S/(R+S) 60μm Hypereutectoid
w Fe3C =(1-w α )
w Fe3C =(1-w α) steel
Adapted from
Adapted from Fig. 9.30,Callister
Fig. 9.27,Callister 6e. (Fig. 9.30
6e. (Fig. 9.27 courtesy Republic Steel Corporation.) Chapter 9- 22 copyright 1971 by United States Steel Corporation.) Chapter 9- 23
 Amounts of pearlite & pearlite
Alloying steel with more elements
constituents
T(°C) γ
1600 γ • Teutectoid changes: • Ceutectoid changes:
δ γ
1400 L γγ γ 0.8
Amount of austenite left
γ+L Amount of γ 1200 Ti Si
above eutectoid γ Mo
1200 austenite
1148°C left L+Fe 3 C W 0.6 Ni
temperature, Wγ (austenite) above eutectoid Cr
transforms into pearlite 1000
1000 temperature, Wγ Cr 0.4
γ+Feinto
transforms 3C 800
Si
pearlite Mn
800 r s Mn 0.2 W
727°C Ti Mo
αR S 600 Ni
0
600
α+Fe 3 C 0 4 8 12 0 4 8 12
wt. % of alloying elements wt. % of alloying elements
400
0 Co 1 2 3 4 5 6 6.7
Adapted from Fig. 9.31,Callister 6e. (Fig. 9.31 Adapted from Fig. 9.32,Callister 6e. (Fig. 9.32
C o , wt% C from Edgar C. Bain, Functions of the Alloying from Edgar C. Bain, Functions of the Alloying
Elements in Steel, American Society for Metals, Elements in Steel, American Society for Metals,
w α =S/(R+S) 1939, p. 127.) 1939, p. 127.)
w Fe3C =(1-w α) Amounts of pearlite constituents

Amount of pearlite = Amount of austenite left

above eutectoid temperature, Wγ
Chapter 9- Chapter 9- 24

Nomenclature for AISI and SAE steels Summary

10xx Plain carbon steels*
11xx Plain-carbon (resulfurized for machinability)
15xx Manganese (1.0-2.0%)
40xx Molybdenum (0.2-0.3%) • Phase diagrams are useful tools to determine:
41xx Chromium (0.40-1.2%), molybdenum (0.08-0.25%) -- the number and types of phases present,
43xx Nickel (1.65-2.00%), chromium (0.40-0.90%),
-- the composition of each phase
molybdenum (0.5%)
44xx Molybdenum (0.5%) -- and the fractional amount wt% of each phase,
46xx Nickel (1.40-2.00%), molybdenum (0.15-0.30%) -- and the microstructure of the alloy
48xx Nickel (3.25-3.75%), molybdenum (0.20-0.30%) for a given T and composition of the system.
51xx Chromium (0.70-1.20%)
61xx Chromium (0.70-1.10%), vanadium (0.10%) • Alloying to produce a solid solution usually
81xx Nickel (0.20-0.40%), chromium (0.30-0.55%), --increases the tensile strength (TS)
molybdenum (0.08-0.15%)
86xx Nickel (0.30-0.70%), chromium (0.40-0.85%),
--decreases the ductility.
molybdenum (0.08-0.25%) • Binary eutectics and binary eutectoids allow for
87xx Nickel (0.40-0.70%), chromium (0.40-0.60%), a range of microstructures.
molybdenum (0.20-0.30%)
92xx Silicon (1.80-2.20%)
xx - carbon content, 0.xx All plain carbon steel contain 0.50% Mn Chapter 9- Chapter 9- 25