Phase Diagrams

Concepts discussed in this chapter provide a foundation that is necessary in order to

understand phase transformations that occur in steel alloys, as well as
the consequences of these transformations
 Definitions: Components and Phases

• Component - chemically recognizable species (e.g. Fe and C in carbon

steel). A binary alloy contains two components, a ternary alloy –
three, etc.

• Phase – a portion of a system that has uniform physical and chemical

characteristics. Two distinct phases in a system have distinct physical
and/or chemical characteristics (e.g. water and oil) and are separated
from each other by definite phase boundaries. A phase may contain
one or more components. A single-phase system is called
homogeneous; systems with two or more phases are mixtures or
heterogeneous systems.
Microstructure
The properties of an alloy depend not only on proportions of the phases but
also on how they are arranged structurally at the microscopic level. Thus, the
microstructure is specified by the number of phases, their proportions, and
their arrangement in space.

Microstructure of cast Iron Phase diagrams will help to

understand and predict
microstructures like the one shown
in this page
Phase Diagram
• Phase diagram = equilibrium diagram
• A phase diagram is a graphical representation of the phases that are
present in a material at various temperatures and pressures and
compositions.
• It usually describes the equilibrium conditions
• Helpful in predicting phase transformations and the resulting
microstructures
• Solvent - host or major component in solution, solute - minor
component.
Solubility Limit
• Solubility limit 
Maximum concentration
of solute that will
dissolve in a solvent to
form a solution

 Example:
Water-Sugar
• Add sugar (solute) to
water (solvent)

The solubility limit at some temperature is – Initially all the sugar dissolves
the composition that corresponds to the – After a certain amount, solid sugar
intersection of the given temperature starts to deposit on the bottom of
coordinate and the solubility limit line. the vessel
Solid Solubility Limit (cont.) 10 0 Solubility Limit
L
• Example 80
(liquid)
• What is the maximum solubility

Temperature (°C)
60 +
of sugar (wt% sugar) in water at L
20 and 80℃ ? (liquid solution S
40
i.e., syrup) (solid
20 sugar)
For 20 °C
C0 = 63 wt%
0 20 40 60 63 75 80 100

Sugar
Pure
Co =Composition (wt% sugar)

Water
Pure
For 80 °C
C0 = 75 wt% Increased Temp increases
Solid Solubility Limit
Isomorphous Binary Phase Diagram
• Indicate phases as a function of T, C, and P.

T(°C) •2 phases:
1600 L (liquid) Maps that represent
α (FCC solid solution) the relationships
1500 L (liquid) between temperature
1400 • 3 different phase fields: and the compositions
L and quantities of
1300 L+a phases at equilibrium,
a which influence the
1200 α microstructure of an
(FCC solid alloy.
1100
solution)
1000
0 20 40 60 80 100 wt% Ni
Tie line ( aka isotherm)
Interpretation of phase diagram
Three things that can be obtained from phase diagram
1. Phases present
2. The composition of the phases
3. The percentages or fractions of the phases
Finding the composition in a two phase region:
i. Locate composition and temperature in diagram
ii. In two phase region draw the tie line or isotherm
iii. Note intersection with phase boundaries. Read compositions at
the intersections.
iv. The liquid and solid phases have these compositions.
Phase compositions and phase weight fraction at given T and C

• Examples: TA A
tie line
Consider C0 = 35 wt% Ni L (liquid)
At TA = 1320°C: 1300
Only liquid (L) present
CL = C0 ( = 35 wt% Ni)
TB B
At TD = 1190°C: R S

Only Solid (α) present

Cα = C0 ( = 35 wt% Ni) a (solid)
1200
At TB = 1250°C: TD D
Both α and L present
CL = C liquidus ( = 32 wt% Ni) 20 3 032 35 4 0 43 5 0

Cα = C solidus ( = 43 wt% Ni) CL C0 Ca wt% Ni

Cu-Ni Binary Phase System
T(°C) L (liquid) L: 35wt%Ni

1300
A
L: 35wt%Ni
a: 46wt%Ni B
35 46
32 C
43
D L: ? wt%Ni
24 36
a: ? wt%Ni
1200 E
L: ? wt%Ni
a a: ? wt%Ni
(solid)

1100
20 30 35 40 50
C0 wt% Ni
Cu-Ni Binary Phase System
T(°C) L (liquid) L: 35wt%Ni

1300
A
L: 35wt%Ni
a: 46wt%Ni B
35 46
32 C
43
D L: 32wt%Ni
24 36
a: 43wt%Ni
1200 E
L: 24wt%Ni
a a: 36wt%Ni
(solid)

1100
20 30 35 40 50
C0 wt% Ni
A copper-nickel alloy of composition 70 wt% Ni-30 wt%
Cu is slowly heated from a temperature of 1300°C
(2370°F).

(a) At what temperature does the first liquid phase form?

(b) What is the composition of this liquid phase?

(c) At what temperature does complete melting of the

alloy occur?

(d) What is the composition of the last solid remaining

prior to complete melting?
 The Lever Rule
The Lever Rule is used to calculate the mass fraction of the phase in any two-phase region of the
Phase diagram

1.Locate composition and temperature in diagram

2.In two phase region draw the tie line or isotherm
3.Fraction of a phase is determined by taking the length of the tie line to the phase boundary for
the other phase, and dividing by the total length of tie line

Phase percent = opposite arm of lever x 100

total length of the tie line
The Lever Rule
What fraction of each phase (mass fractions of liquid and α phases)?

The mass fractions can be represented by WL and Wa for the liquid and solid
phases, respectively T(°C)
tie line
1300 L (liquid)

B
TB
α
1200 (solid)
R S

20 3 0C 4 0 5 0
L C0 Cα
wt% Ni
Phase compositions and amounts. An example.

Co = 35 wt. %, CL = 31.5 wt. %, Ca = 42.5 wt. %

Mass fractions:
WL = S / (R+S) = (Ca - Co) / (Ca - CL) = 0.68

Wa = R / (R+S) = (Co - CL) / (Ca - CL) = 0.32

Attention!

Compositions of phases are expressed in terms of weight percents of the

components (e.g., wt% Cu, wt% Ni).

For fractional phase amounts (e.g.,mass fraction of the a or liquid phase),

when a single phase exists, the alloy is completely that phase. For a two-
phase alloy, on the other hand, the lever rule is utilized, in which a ratio of
tie line segment lengths is taken.
Eutectic Systems
Eutectic = easily melted

Three single-phase
regions are found on the
diagram:

a, b (solid solutions) and

liquid.
The a phase is a solid
solution rich in copper
while the b phase is a
solid solution rich in
silver.
Eutectic Systems
1200
Ex.: Cu-Ag system T(°C) L (liquid)
• 3 single phase regions (L, α, β) 1000
• Limited solubility: α L+ α
α: mostly Cu
779°C L+ β β
TE 800
8.0 71.9 91.2
β: mostly Ag
600
• TE : No liquid below TE
α + β
• CE : Composition at 400
temperature TE
200
• Eutectic reaction 0 20 40 60 CE 80 100
L(CE) α(CαE) + β(CβE) C, wt% Ag

cooling
heating
The horizontal solidus line at TE is called eutectic isotherm
Q1: Pb-Sn Eutectic System
• For a 40 wt% Sn-60 wt% Pb alloy at 150°C,
determine: Pb-Sn
T(°C) system
-- the phases present
-- the phase compositions 300 L (liquid)
-- the relative amount α L+ α
200 183°C L+β β
of each phase 18.3 61.9 97.8
150
R S
100
α+β

0 11 20 40 60 80 99100
Cα C0 Cβ
C, wt% Sn
EX Ans: Pb-Sn Eutectic System
• For a 40 wt% Sn-60 wt% Pb alloy at 150°C, determine:
-- the phases present Pb-Sn
Answer: α + β T(°C) system
-- the phase compositions
300
L (liquid)
-- the relative amount of α L+ α
200 183°C L+β β
each phase 18.3 61.9 97.8
150
R S
100
α+β

0 11 20 40 60 80 99100
Cα C0 Cβ
C, wt% Sn

22
EX Ans: Pb-Sn Eutectic System
• For a 40 wt% Sn-60 wt% Pb alloy at 150°C, determine:
-- the phases present Pb-Sn
Answer: α + β T(°C) system
-- the phase compositions
300
Answer: Cα = 11 wt% Sn L (liquid)
Cβ = 99 wt% Sn
-- the relative amount of α L+ α
200 183°C L+β β
each phase 18.3 61.9 97.8
Answer: 150
R S
100
α+β

0 11 20 40 60 80 99100
Cα C0 Cβ
C, wt% Sn

23
EX Ans: Pb-Sn Eutectic System
• For a 40 wt% Sn-60 wt% Pb alloy at 150°C, determine:
-- the phases present Pb-Sn
Answer: α + β T(°C) system
-- the phase compositions
300
Answer: Cα = 11 wt% Sn L (liquid)
Cβ = 99 wt% Sn
-- the relative amount of α L+ α
200 183°C L+β β
each phase 18.3 61.9 97.8
Answer: 150
S Cβ - C0 R S
Wα = = 100
R+S Cβ - Cα α+β
99 - 40 59
= = = 0.67
99 - 11 88 0 11 20 40 60 80 99100
C0 - Cα Cα C0 Cβ
Wβ = R = C, wt% Sn
R+S Cβ - Cα
40 - 11 29
= = = 0.33 24
99 - 11 88
At 500°C, what is the
maximum solubility
(a) of Cu in Ag?
(b) Of Ag in Cu?
At 500°C, what is the
maximum solubility
(a) of Cu in Ag?

2wt% Cu

(b) Of Ag in Cu?

1.5 wt% Ag
For a 40 wt% Sn–60 wt% Pb alloy at
150C,
(a) what phase(s) is (are)
present?
(b) What is (are) the
composition(s) of the phase(s)?
Cite the phases that are present and the
phase compositions for the following:

1. 75 wt% Sn-25 wt% Pb at 175°C (345 F)

2. 4.5 mol Sn and 0.45 mol Pb at 200°C
(390°F)
3. Determine the relative amounts (in
terms of mass fractions) of the phases
in the above conditions

4. Determine the relative amounts (in

terms of volume fractions) of the phase
in part 1.
A hypothetical A–B alloy of composition 55 wt% B–45 wt% A at some
temperature is found to consist of mass fractions of 0.5 for both α and β
phases. If the composition of the β phase is 90 wt% B–10 wt% A, what
is the composition of the α phase?
Microstructural Developments in Eutectic Systems I

• For alloys for which

C0 < 2 wt% Sn
• Result: at room temperature
-- polycrystalline with grains of
a phase having
composition C0
 Microstructural Developments
in Eutectic Systems II
L: C0 wt% Sn
T(ºC)
400
• For alloys for which L
2 wt% Sn < C0 < 18.3 wt% Sn L
300 a
• Result: L+a
at temperatures in a + b range a: C0 wt% Sn
a
-- polycrystalline with a grains 200
TE
and small b-phase particles a
b
100
a+ b Pb-Sn
system
0 10 20 30
2 C0 C, wt% Sn
(sol. limit at T room ) 18.3
(sol. limit at TE)
 Microstructural Developments in Eutectic Systems III
• For alloy of composition C0 = CE
• Result: Eutectic microstructure (lamellar structure)
-- alternating layers (lamellae) of a and b phases.
T(ºC) Micrograph of Pb-Sn
L: C0 wt% Sn eutectic
300 microstructure
L
Pb-Sn
system
L+ a
200
a 183ºC L+b b
TE

100 160 m
a+b b: 97.8 wt% Sn
a: 18.3 wt%Sn

0 20 40 60 80 100
18.3 CE 97.8
61.9 C, wt% Sn
Lamellar Eutectic Structure
Microstructural Developments in Eutectic Systems IV
• For alloys for which 18.3 wt% Sn < C0 < 61.9 wt% Sn
• Result: a phase particles and an eutectic microconstituent
• Just above TE :
T(ºC) L: C0 wt% Sn L
a Ca = 18.3 wt% Sn
L
300 L CL = 61.9 wt% Sn
Pb-Sn a S
L+ a Wa = = 0.50
system R+S
a
b b
200 R S L+ WL = (1- Wa) = 0.50
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 = 0.73
0 20 40 60 80 100 R+S
18.3 61.9 97.8 Wb = 0.27
C, wt% Sn
HYPO/HYPER-eutectic
T(°C) Pb-Sn
300 L
 HYPOeutectic → Phase
Below eutectic L+ a
200 a L+ b Diagram
TE b
composition
a+ b
• Yields island-like 100
a-regions with lamellar C0 C0
eutectic structure hypoeutectic hypereutectic
0
0 20 40 60 80 100 C o , wt% Sn
 HYPEReutectic → 18.3 eutectic 97.8

Above eutectic hypoeutectic = 61.9wt%Sn hypereutectic

composition
eutectic
• Yields a b
island-like a b
a a b b
b-regions with a b
lamellar
a b
eutectic structure
175 µm 160 µm
eutectic micro-constituent
Eutectic, Eutectoid, & Peritectic
• Eutectic - liquid transforms to two solid phases
L cool a + b (For Pb-Sn, 183ºC, 61.9 wt% Sn)
heat

• Eutectoid (eutectic-like) – one solid phase transforms

to two other solid phases
intermetallic compound
S2 S1+S3 - cementite

 cool a + Fe3C (For Fe-C, 727ºC, 0.76 wt% C)

heat

• Peritectic - one solid phase transforms into a liquid

phase and a second solid phase
S1 + L S2
cool
 +L heat
 (For Fe-C, 1493ºC, 0.16 wt% C)
Eutectoid & Peritectic
Peritectic transformation  + L 

Cu-Zn Phase diagram

Eutectoid transformation  +

Iron-Carbon (Fe-C) Phase Diagram
• 2 important T(ºC)
1600
points 
- Eutectic (A): 1400 L
L   + Fe3C   +L
1200 1148ºC
A L+Fe3C
- Eutectoid (B): (austenite)

Fe3C (cementite)
  a + Fe3C 1000  
   +Fe3C

a
800 727ºC = T eutectoid
B
600
a+Fe3C
400
0 1 2 3 4 5 6 6.7
(Fe) 0.76 4.30 C, wt% C
120 m
Result: Pearlite = Fe3C (cementite-hard)
alternating layers of
a and Fe3C phases a (ferrite-soft)
 Fe-C Phase Diagram
T(°C)
 Cool from solid 1600

Austenite L
1400
@1460C
    +L
1. @ 1000C →   1200
1148°C L+Fe3 C
(austenite)
Grains of -only
 

Fe 3 C (cementite)
1000
2. @ ~800C →    +Fe 3 C
Tiny islands of a
  800 r s
a (ferrite) form a 727°C
 a a
along -grain R S
w a = s /( r + s ) 6 00
boundaries a +Fe3 C
w  = (1- w a)
3. @727C → 4 00
0 Co 1 2 3 4 5 6 6.7
 + Ferrite in a

0.77
a pearlite C o , wt% C
a
proportions as wpearlite = w 
given by wa = S /( R + S )
Lever Rule wFe3C = (1- w a )
 Fe-C Phase Diagram
T(°C)
 Cool From Solid 1600
Austenite @1000C 
1400 L
1. @1000C →
grains of -only     +L
  1200 1148°C L+Fe 3 C
2. @~860C → Tiny (austenite)

Fe 3C (cementite)
islands of   1000
cementite    +Fe 3 C
Fe 3 C
form along   800 r s
-grain   a
R S
boundaries wFe3C = r/( r+s )600 a +Fe 3 C
w  =(1- wFe3C )
3. @727C →  +
400
Cementite in 0 1 Co 2 3 4 5 6 6.7

0.77
proportions as pearlite C o , wt% C
wpearlite = w 
given by wa =S /( R +S )
Lever Rule wFe3C = (1- wa )
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 cementite(Fe3C) and ferrite (α).
b) The amount of cementite (in grams) that forms in 100 g of
steel.
c) The amounts of pearlite(ϒ) and proeutectoid ferrite (α) in the
100 g of steel.

47
 T(°C)
Fe-C Phase Diagram
1600


1400 L

  +L
1200 1148°C L+Fe3C
(austenite)

1000

(cementite)
 +Fe3C

800
a
R S
6 00
a +Fe3C

Fe3C
0.40
4 00
0 1 2 3 4 5 6 6.7
0.76 4.30
0.022 C o , wt% C
a 
Fe3C (cementite)
a (ferrite)  (pearlite)
Solution to Example Problem
a) The compositions of Fe3C and ferrite (α).

Using the RS tie line just below the eutectoid

Cα = 0.022 wt% C
CFe3C = 6.70 wt% C 1600
δ
1400 L
T(°C) γ +L
γ

Fe3C (cementite)
1200 L+Fe3C
b) The amount of cementite (in (austenite)
1148°C

grams) that forms in 100 g of 1000

γ + Fe3C
steel. ?
800 727°C
α R S
600 α + Fe3C
400
0 1 2 3 4 5 6 6.7
Cα C0 C, wt% C CFe
3C
0.022 0.40 6.70
wt%C wt%C wt%C
Solution to Example Problem
a) Using the RS tie line just below the eutectoid
Cα = 0.022 wt% C
CFe3C = 6.70 wt% C

b) Using the lever rule with 1600

the tie line shown δ
1400 L
T(°C) γ +L
γ

Fe3C (cementite)
1200 1148°C L+Fe3C
(austenite)
1000
γ + Fe3C
800 727°C
α R S
Amount of Fe3C in 100 g 600 α + Fe3C
400
= (100 g)WFe3C 0 1 2 3 4 5 6 6.7
Cα C0 C, wt% C CFe
3C
= (100 g)(0.057) = 5.7 g 0.022 0.40 6.70
wt%C wt%C wt%C
Solution to Example Problem (cont.)
c) The amounts of pearlite and proeutectoid ferrite (α) in
the 100 g.

Using the VX tie line the eutectoid

1600
δ
C0 = 0.40 wt% C L
1400
Cα = 0.022 wt% C T(°C)
γ γ +L
Cpearlite = Cγ = 0.76 wt% C

Fe3C (cementite)
1200 1148°C L+Fe3C
(austenite)
1000
γ + Fe3C
800 727°°C
VX
600 α + Fe3C
400
0 1 2 3 4 5 6 6.7
Cα C0 Cγ C, wt% C

51
Solution to Example Problem (cont.)
c) Using the VX tie line just above the eutectoid and
realizing that
C0 = 0.40 wt% C
Cα = 0.022 wt% C
Cpearlite = Cγ = 0.76 wt% C
1600
δ
1400 L
T(°C) γ +L
γ

Fe3C (cementite)
1200 1148°C L+Fe3C
(austenite)
1000
γ + Fe3C
800 727°°C
VX
Amount of pearlite in 100 g 600 α + Fe3C
= (100 g)Wpearlite 400
0 1 2 3 4 5 6 6.7
Cα C0 Cγ C, wt% C
= (100 g)(0.512) = 51.2 g
52