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 Phase B

Nickel atom
Copper atom
Chapter 9 -
 Phase Equilibria: Solubility Limit
Introduction
– Solutions – solid solutions, single phase
– Mixtures – more than one phase Adapted from Fig. 9.1,
Callister 7e.

Sucrose/Water Phase Diagram

• Solubility Limit: 100
Max concentration for Solubility

Temperature (°C)
which only a single phase 80 Limit L
solution occurs. (liquid)
60 +
L
Question: What is the 40 (liquid solution S
i.e., syrup) (solid
solubility limit at 20°C?
20 sugar)
Answer: 65 wt% sugar.
0 20 40 6065 80 100
If Co < 65 wt% sugar: syrup

Sugar
Water

Co =Composition (wt% sugar)

Pure

Pure
If Co > 65 wt% sugar: syrup + sugar.
Chapter 9 - 2
 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., a and b).

b (lighter
phase)
Aluminum-
Copper a (darker
Alloy
phase)

Chapter 9 -
 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 (100°C,70) D (100°C,90)
1 phase 2 phases
100

80 L
Temperature (°C)

(liquid)
water- 60 +
sugar L S
system (liquid solution (solid
40 i.e., syrup) sugar)
20 A (20°C,70)
2 phases
Adapted from 0
Fig. 9.1, 0 20 40 60 70 80 100
Callister 7e.
Co =Composition (wt% sugar)
Chapter 9 -
 Types of solid solutions

e.g. Bi-Cd SS e.g. Al-Cu SS

e.g. Ni-Cu SS

Chapter 9 - 5
 Phase Equilibria

Simple solution system (e.g., Ni-Cu solution)

Crystal electroneg r (nm)

Structure
Ni FCC 1.9 0.1246
Cu FCC 1.8 0.1278

• 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
69-
 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)
1600 • 2 phases:
L (liquid)
1500 L (liquid) a (FCC solid solution)
Phase 1400 • 3 phase fields:
Diagram us L
uid a
for Cu-Ni 1300 liq + s
L lidu L+a
system
so a
1200 a
1100
(FCC solid
solution)
1000
0 20 40 60 80 100 wt% Ni Chapter 9 -
Isomorphous Binary Phase Diagrams

Chapter 9 - 8
Construction of Phase Diagrams
- Complete solubility -

Chapter 9 -
Construction of Phase Diagrams
- Complete solubility -

Chapter 9 -
Interpretation of Phase Diagrams
- Complete solubility -

Chapter 9 -
 Phase Diagrams:
# and types of phases
• Rule 1: If we know T and Co, then we know:
--the # and types of phases present.
T(°C)
• Examples: 1600
A(1100°C, 60 wt% Ni): L (liquid)
1 phase: a 1500

B (1250°C,35)
dus Cu-Ni
u i
B(1250°C, 35 wt% Ni): 1400 liq us
phase
lid
2 phases: L + a so diagram
1300 + a a
L (FCC solid
1200 solution)
1100 A(1100°C,60)

1000
0 20 40 60 80 100 wt% Ni
Chapter 9 -
 Phase Diagrams:
composition of phases
• Rule 2: If we know T and Co, then we know:
--the composition of each phase.
• Examples:
Co = 35 wt% Ni
At T A = 1320°C:
Only Liquid (L)
CL = Co ( = 35 wt% Ni)
At T D = 1190°C:
Only Solid ( a)
Ca = Co ( = 35 wt% Ni)
At T B = 1250°C:
Both a and L
CL = C liquidus ( = 32 wt% Ni here)
Ca = C solidus ( = 43 wt% Ni here)
Chapter 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%).
• Examples:
Co = 35 wt% Ni
At T A: Only Liquid (L)
W L = 100 wt%, W a = 0
At T D: Only Solid ( a)
W L = 0, Wa = 100 wt%
At T B : Both a and L

= S  43  35 73 wt %
WL
R + S 43  32
R
Wa = = 27 wt%
R +S
Chapter
149 -
 The Lever Rule
• Tie line – connects the phases in equilibrium with
each other - essentially an isotherm

How much of each phase at point B?

Think of it as a lever (teeter-totter)
ML M

R S

M  S M L R

ML S C  C0 R C  CL
WL     W   0
M L  M  R  S C   CL R  S C   CL
Chapter 9 - 15
 Ex: Cooling in a Cu-Ni Binary

• Phase diagram: T(°C) L (liquid) L: 35wt%Ni

Cu-Ni system. Cu-Ni
• System is: system
130 0 A a
--binary L: 35 wt% Ni L+
i.e., 2 components:
a: 46 wt% Ni
35 B
46
32 C
Cu and Ni. 43
--isomorphous 24 D L: 32 wt% Ni
36
i.e., complete a a: 43 wt% Ni
L+
120 0 E
solubility of one
L: 24 wt% Ni
component in
another; a phase a: 36 wt% Ni
a
field extends from (solid)
0 to 100 wt% Ni.
• Consider 110 0
Co = 35 wt%Ni.
20 30 35 40 50
Co wt% Ni
Chapter 9 -
Microsegregation

Chapter 9 -
 Microsegragation
• If a copper-nickel alloy is solidified, a subsequent material test
often reveals that the nickel content within a grain can differ
greatly from region to region
• While the grain center is characterized by a relatively high
nickel content, the edge areas of the grain, for example, are
rather low in nickel
• Such concentration differences within a grain are called crystal
segregations or microsegregation
• However, since the alloy concentration has a decisive influence
on the material properties, the grain centre thus shows a
different property (e.g. harder) than the edge area (e.g. softer)
• Such different properties within a grain are generally not
desired, as this can lead to unpredictable material failure
• In order to explain the formation of crystal segregations, a
CuNi55 alloy with 55 % nickel is considered

Chapter 9 - 18
Microsegragation

Chapter 9 - 19
 Microsegragation
• The phase diagram shows that during solidification, the nickel
concentration within the resulting solid solution decreases over
time
• The first solid solution formed, has a nickel content of around
66% immediately upon the onset of solidification at the time t0
• As the cooling progresses, additional atoms from the melt
accumulate around the crystals that have already formed
• At a later point in time t1, a new layer has finally accumulated,
which according to the phase diagram leads to an average nickel
content in the entire grain of only 63.5%
• Since this is an average value within the entire solid solution, the
deposited layer must obviously have a lower nickel content than
the previously solidified layer
• Finally, as solidification progresses, the mean nickel content in
the solid solution decreases further (t1→ t2→ t3)
• If the solidification process is completed at the time t4, the nickel
content has finally dropped to 55% and is now completely in the
solidified microstructure Chapter 9 - 20
 Microsegragation
• In reality, the atomic layers are not deposited gradually but
continuously around the solidified crystals
• Consequently, a continuous decrease of nickel concentration is
obtained starting from the grain centre (start of solidification) up
to the corresponding edge areas (end of solidification)
• Note that crystal segregation is not a phenomenon of copper-
nickel alloys, but a fundamental phenomenon of all solid
solutions!
• In principle, crystal segregation could be avoided by a
sufficiently slow cooling, as the resulting differences in
concentration can always be compensated by diffusion processes
• In reality, however, cooling processes cannot take place
infinitely slowly, which inevitably results in differences in
concentration in the microstructure
• In such cases, the resulting differences in concentration can be
partially compensated by subsequent heat treatment at
sufficiently high temperatures (called annealing)
Chapter 9 - 21
 Mechanical Properties: Cu-Ni System

• Effect of solid solution strengthening on:

Tensile strength (TS) Ductility (%EL,%AR)

60
Tensile Strength (MPa)

%EL for pure Cu

Elongation (%EL)
400 50 %EL for
TS for pure Ni
pure Ni 40
300
TS for pure Cu 30

200 20
0 20 40 60 80 100 0 20 40 60 80 100
Cu Ni Cu Ni
Composition, wt% Ni Composition, wt% Ni
--Peak as a function of Co --Min. as a function of Co

Chapter 9 -
Construction of Phase Diagrams
- Complete insolubility -

Chapter 9 - 23
Construction of Phase Diagrams
- Complete insolubility -

Chapter 9 - 24
All possible Microstructures
- Complete insolubility -

Chapter 9 - 25
Phase Diagrams
- Limited solubility -

Chapter 9 - 26
Chapter 9 - 27
 Binary-Eutectic Systems
has a special composition
2 components with a min. melting T.
Cu-Ag
T(°C) system
Ex.: Cu-Ag system 1200
• 3 single phase regions L (liquid)
(L, a, b) 1000
• Limited solubility: a L+a L+b b
779°C
a: mostly Cu TE 800 8.0 71.9 91.2
b: mostly Ag 600
• TE : No liquid below TE a+ b
400
• CE : Min. melting TE
composition 200
0 20 40 60 CE 80 100
Co , wt% Ag

Chapter 9 -
 EX: Pb-Sn Eutectic System (1)
• For a 40 wt% Sn-60 wt% Pb alloy at 150°C, find...
--the phases present: a + b
Pb-Sn
--compositions of phases: T(°C) system
CO = 40 wt% Sn
Ca = 11 wt% Sn 300
Cb = 99 wt% Sn L (liquid)
--the relative amount a L+ a
of each phase: 200 183°C L+b b
18.3 61.9 97.8
S C - CO 150
Wa = =  R S
R+S C - C
100
99 - 40 59 a+b
= = = 67 wt%
99 - 11 88
C - C 99100
W = R = O
0 11 20 40 60 80
R+S C - C  C Co C
C, wt% Sn
40 - 11 29
= = = 33 wt%
99 - 11 88 Chapter 9 -
 EX: Pb-Sn Eutectic System (2)
• For a 40 wt% Sn-60 wt% Pb alloy at 200°C, find...
--the phases present: a + L
Pb-Sn
--compositions of phases: T(°C) system
CO = 40 wt% Sn
Ca = 17 wt% Sn 300
CL = 46 wt% Sn
L (liquid)
L+ a
--the relative amount 220 a
200 R S L+b b
of each phase:
183°C
CL - C O 46 - 40
Wa = =
CL - C  46 - 17 100
a+b
6
= = 21 wt%
29
0 17 20 40 46 60 80 100
CO - C  23 C Co CL
WL = = = 79 wt% C, wt% Sn
CL - C  29

30
Chapter 9-
 Microstructures
in Eutectic Systems: I
• Co < 2 wt% Sn T(°C) L: Co wt% Sn
• Result: 400
L
--at extreme ends a
--polycrystal of a grains 300 L
i.e., only one solid phase
L+ a
(at room temperature). 200
a
a: Co wt% Sn
(Pb-Sn
TE
System)

100
a+ b

0 10 20 30
Co Co , wt% Sn
2
(room T solubility limit)

Chapter 9 -
 Microstructures
in Eutectic Systems: II
L: Co wt% Sn
• 2 wt% Sn < Co < 18.3 wt% Sn T(°C)
400
• Result:
L
 Initially liquid +  L
 then  alone 300 a
L+a
 finally two phases a: Co wt% Sn
 a
a polycrystal 200
 fine -phase inclusions TE
a
b
100
a+ b Pb-Sn
system
0 10 20 30
2 Co Co , wt% Sn
(sol. limit at T room ) 18.3
(sol. limit at TE)
Chapter 9 -
 Microstructures
in Eutectic Systems: III
• Co = CE
• Result: Eutectic microstructure (lamellar structure)
--alternating layers (lamellae) of a and b crystals.

T(°C) Micrograph of Pb-Sn

L: Co wt% Sn eutecticmicrostructure
300 L
Pb-Sn
system
L+ a
200
a 183°C L   b
TE

100
a : 97.8 wt% Sn
: 18.3 wt%Sn 160 m

0 20 40 60 80 100
18.3 CE 97.8
61.9 C, wt% Sn Chapter 9 - 33
 Microstructures
in Eutectic Systems: III

Chapter 9 -
 Lamellar Eutectic Structure

Sidewise nucleation and

Edgewise growth
Chapter 9 - 35
 Microstructures
in Eutectic Systems: IV
• 18.3 wt% Sn < Co < 61.9 wt% Sn
• Result: a crystals and a eutectic microstructure
• Just above TE :
T(°C) L: Co wt% Sn a L
Ca = 18.3 wt% Sn
L
300 a CL = 61.9 wt% Sn
L
Pb-Sn
L+a Wa = S = 50 wt%
system R+S
200
a R S L+ b b WL = (1- Wa) = 50 wt%
TE S
R
• Just below TE :
100 a+b Ca = 18.3 wt% Sn
primary a Cb = 97.8 wt% Sn
eutectic a
eutectic b Wa = S = 73 wt%
0 20 40 60 80 100 R+S
18.3 61.9 97.8 Wb = 27 wt%
Co, wt% Sn Chapter 9 -
 Hypoeutectic & Hypereutectic
(Pb-Sn System)
300
L
T(°C)
a L+ a
200 L+b b
TE
Beta precipitates
in alpha matrix a+b
100 Alpha precipitates
in beta matrix

0 20 40 60 80 100 Co, wt% Sn

eutectic
hypoeutectic 61.9 hypereutectic

eutectic: Co = 61.9 wt% Sn

b a
b a
b b a a
b a
b a
160 mm 175 mm
eutectic micro-constituent

Chapter 9 - 37
Hypoeutectic Microstructures
- With Precipitations -

Chapter 9 - 38
Hypoeutectic Microstructures
- Without Precipitations -

Chapter 9 - 39
Hypereutectic Microstructures
- With Precipitations -

Chapter 9 - 40
All possible Microstructures
- Partial solubility -

Chapter 9 - 41
 Intermetallic Compounds

Mg2Pb

Note: intermetallic compound forms a line - not an area -

because stoichiometry (i.e. composition) is exact. Chapter 9 -
 Eutectoid & Peritectic

• Eutectic - liquid in equilibrium with two solids

coolL +
heat

• Eutectoid - solid phase in equation with two solid

phases
intermetallic compound
S2 S1+S3 - cementite
cool
  + Fe3C
heat
(727ºC)
• Peritectic - liquid + solid 1  solid 2
S1 + L S2
cool
heat
+L 
(1493ºC)

Chapter 9 - 43
 Eutectoid & Peritectic
Peritectic transition  + L 
Cu-Zn Phase diagram

Eutectoid transition  +

Chapter 9 - 44
 Iron-Carbon (Fe-C) Phase Diagram

• 2 important T(°C)
points 1600
d
-Eutectic (A): L
1400
L Þ g + Fe3C
g g +L
-Eutectoid (B): 1200 1148°C
A L+Fe3C
(austenite)

Fe3C (cementite)
g Þ a + Fe3C R S
1000 g g g+Fe3C
a+ g g
800
a B 727°C = Teutectoid
g

R S
600
a+Fe3C
400
0 1 2 3 4 5 6 6.7
120 mm (Fe) 0.76 4.30 Co, wt% C
Result: Pearlite =
C eutectoid

alternating layers of Fe3C (cementite-hard)

a and Fe3C phases a (ferrite-soft)
Chapter 9 -
 Phases in Fe-C Phase Diagram
Austenite
• Within a certain temperature range, iron undergoes a polymorphic
transformation from the bcc to an fcc structure, becoming gamma
iron or (more commonly) austenite.
Ferrite
• Alpha ferrite, or simply ferrite, is a solid solution of body-centered
cubic iron; it has a maximum solid solubility of 0.022% C at a
temperature of 727°C.
• Ferrite is relatively soft and ductile; it is magnetic from room
temperature to 768°C—the Curie temperature.
Cementite
• The right boundary of Fe-C Phase diagram represents cementite,
which is 100% iron carbide having a carbon content of 6.67%.

Chapter 9 - 46
Phases in Fe-C Phase Diagram

Chapter 9 - 47
 Eutectoid reaction in Fe-C Phase
Diagram
Eutectoid reaction means that at a certain
temperature, a single, solid phase (austenite) is
transformed into two other solid phases (ferrite
and cementite)
Figure shows the schematic illustration of the
microstructures for an iron-carbon alloy of
eutectoid composition (0.76% carbon) above
and below the eutectoid temperature of 727°C
The structure of eutectoid steel is called pearlite
In this lamellar structure shown, the lighter
regions are ferrite, and the darker regions are
carbide
The ferrite in the pearlite is called eutectoid
ferrite, and the ferrite phase is called
proeutectoid ferrite
The cementite in the pearlite is called eutectoid
cementite, and the cementite phase is called
proeutectoid cementite Chapter 9 - 48
 Hypoeutectoid Steel
T(°C)
1600
d
1400 L
g g (Fe-C
g g+L
g g 1200 1148°C L+Fe3C System)

Fe3C (cementite)
(austenite)
g g 1000
g g g + Fe3C
a
a g
g 800 r s 727°C
g ag aRS
w a =s/(r +s) 600
wg =(1- wa )
a + Fe3C
400
a 0 1 2 3 4 5 6 6.7
(Fe) Co , wt% C
0.76

C0
pearlite
w pearlite = wg
w a =S/(R+S) 100 mm Hypoeutectoid
steel
w Fe3C =(1-w a )
pearlite proeutectoid ferrite
Chapter 9 - 49
 Hypereutectoid Steel
T(°C)
1600
d
1400 L (Fe-C
g g g+L System)
1200
g
g g 1148°C L+Fe3C

Fe3C (cementite)
(austenite)
g g 1000
g g g +Fe3C
Fe3C
g g 800 r s
gg a R S
600
w Fe3C =r/(r +s) a +Fe3C
wg =(1-w Fe3C )
400
0 1 Co 2 3 4 5 6 6.7
0.76

(Fe)
pearlite Co , wt%C
w pearlite = wg
w a =S/(R+S)
w Fe3C =(1-w a ) 60 mmHypereutectoid
steel
pearlite proeutectoid Fe3C
Chapter 9 - 50
 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 - 51
 Phase Equilibria
Solution: a) composition of Fe3C and ferrite ()
b) the amount of carbide CO = 0.40 wt% C
(cementite) in grams that Ca = 0.022 wt% C
forms per 100 g of steel CFe C = 6.70 wt% C
3
1600
d
1400 L
Fe3C C  C T(°C) g+L
 o x100 g

Fe C (cementite)
1200 1148°C L+Fe3C
Fe3C   CFe 3C  C (austenite)
1000
0.4  0.022 g + Fe3C
 x 100 5.7g
6.7  0.022 800 727°C
R S
600 a + Fe3C
Fe3C 5.7 g
400
 94.3 g 0 1 2 3 4 5 6 6.7
CFe
C CO Co , wt% C 3C

Chapter
529 -
 Phase Equilibria
c. the amount of pearlite and proeutectoid ferrite ()
note: amount of pearlite = amount of g just above TE
as whole of g will transform to pearlite
1600
Co = 0.40 wt% C d
1400 L
Ca = 0.022 wt% C T(°C)
g g+L

Fe3C (cementite)
Cpearlite = C = 0.76 wt% C 1200
(austenite)
1148°C L+Fe3C

 Co  C 1000
 x 100 51.2 g g + Fe3C
  C  C
800 727°C
RS
600 a + Fe3C
pearlite = 51.2 g 400
0 1 2 3 4 5 6 6.7
proeutectoid  = 48.8 g C CO C Co , wt% C

Chapter 9 - 53
 Age Hardening
• Three step heat treatment
– Solution treat
– Quench
– Age
• Natural
• Artificial composition

• Forms coherent precipitates

• Used most frequently for
non-ferrous metals
Age Hardening
vs. Slow
Cooling
Overaging
 Growth of Precipitates
• Guinier Preston Zones
– GP-I
– GP-II
• Coherent precipitate, q’
• Non-coherent
precipitate, q
Growth of Precipitates

GP-Zones q’ Precipitate

q Precipitate
Effect of Aging Temperature and
Time
 Requirements for Age
Hardening
• Display decreasing solid solubility
with decreasing temperature
• Matrix should be soft/ductile
• Precipitate should be hard/brittle
• Alloy must be quenchable
• Coherent precipitate must form