ENG31 1000 Engineering Materials I

2(2-0-4)

CHAPTER 4
Phase Diagrams of Metals
CHAPTER 4: Phase Diagrams of Metals ENG31 1000 Engineering Materials I
2(2-0-4)

4.1 Gibbs’ Phase Rule

Introduction to phase diagram and Gibbs’ phase rule

4.2 Binary Phase Diagrams

Isomorphous, eutectic, eutectoid, peritectic, peritectorid, monotectic

4.3 Fe-Fe3C Phase Diagram

Phase, calculation and interpretation
Learning Outcomes
✓ Classify phase transformation reactions of alloy systems provided.
✓ Identify phases and composition present in the binary phase diagrams of various alloys.
✓ Calculate the amounts of phases according to the given composition and temperature.
✓ Explain microstructure-property evolution according to Fe-Fe3C phase diagram.
CHAPTER 4: Phase Diagrams of Metals 3
4.1 Gibbs’ Phase Rule – Introduction to phase diagram
▪ Definition: Phase is all the same kind
❑ A physically homogeneous and distinct portion of a material system
❑ A region in a thermodynamic system that physical properties (i.e., density, index of
refraction, magnetization and chemical composition) of a material are essentially uniform.

vapor vapor

ice
water
water
CHAPTER 4: Phase Diagrams of Metals 4
4.1 Gibbs’ Phase Rule – Introduction to phase diagram
❑ Phase : region that possesses homogeneous/uniform physical and chemical characteristics.

1 phase 2 phases 2 phases

Complete soluble Partial soluble Complete insoluble
CHAPTER 4: Phase Diagrams of Metals 5
4.1 Gibbs’ Phase Rule
▪ Gibbs’ Phase Rule is general principle governing systems in thermodynamic equilibrium.

P + F = C+ 2

P is number of phases
C is number of components
F is degree of freedom
CHAPTER 4: Phase Diagrams of Metals 6
4.1 Gibbs’ Phase Rule
▪ Example: P + F = C+ 2

solid–liquid boundary: melting

P+F=C+2
2+F=1+2
F = 1 (one degree of freedom)

solid–liquid-vapor point
P+F=C+2
3+F=1+2
F = 0 (zero degree of freedom)
CHAPTER 4: Phase Diagrams of Metals 7
4.1 Gibbs’ Phase Rule
▪ Example: P + F = C+ 2

P+F=C+2
1+F=1+2
F = 2 (two degree of freedom)
CHAPTER 4: Phase Diagrams of Metals 8
4.1 Gibbs’ Phase Rule
▪ In the equilibrium materials system, the pressure is generally constant (one atmosphere),
therefore the Gibbs’ phase rule becomes P + F = C+ 1
▪ For binary mixtures of two chemically independent components, C = 2 so that F = 4 − P

At point A: 2 + F = 1 + 1
B C zero degree of freedom

At point B: 2 + F = 2 + 1
A
one degree of freedom

At point C: 1 + F = 2 + 1
two degree of freedom
CHAPTER 4: Phase Diagrams of Metals 9
4.1 Gibbs’ Phase Rule
▪ When metal is alloyed, there are different ways solid solution can be formed.
atom of metal A
(solvent atom)

atom of metal B
(solute atom)

disordered ordered disordered

substitutional solid solution substitutional solid solution interstitial solid solution

same atomic size different atomic size

CHAPTER 4: Phase Diagrams of Metals 10
4.1 Gibbs’ Phase Rule Fe+C - Steel
▪ For a given chemical composition, different atomic arrangements of a mixture results in
different phases (phase I and phase II) that are related to different properties.
CHAPTER 4: Phase Diagrams of Metals 11
4.2 Binary Phase Diagrams
▪ Isomorphous Binary Phase Diagram
- Construction of Phase Diagram
- The Lever Rule
- Solubility
▪ Binary Eutectic Phase Diagram
▪ Binary Peritectic Phase Diagram
▪ Binary Monotectic Phase Diagram
▪ Phase diagrams for Intermediate Phases and Intermetallic Compounds
CHAPTER 4: Phase Diagrams of Metals 12
4.2 Binary Phase Diagrams
▪ Isomorphous Binary Phase Diagram: Ex: Cu-Ni system
❑ Cu-Ni system shows complete solubility
because both metals have similar crystal
structure (FCC) nearly the same radii, Liquid
electronegativity and valence. Liquidus line
❑ The liquidus line separates the liquid
phase from solid or solid + liquid phases. solidus line
That is, the solution is liquid above the
liquidus line. Solid solution (a)
❑ The solidus line is that below which the
solution is completely solid (does not Ni
contain a liquid phase.) Cu
CHAPTER 4: Phase Diagrams of Metals 13
4.2 Binary Phase Diagrams
▪ Isomorphous Binary Phase Diagram: Ex: Cu-Ni system

❑ Point A: L
only liquid phase Liquid
A
B
❑ Point B: a C
L a
liquid and solid mixture a
Solid solution (a)

❑ Point C: a a
a a Ni
only solid phase a Cu
a
CHAPTER 4: Phase Diagrams of Metals 14
4.2 Binary Phase Diagrams
▪ Isomorphous Binary Phase Diagram: The Construction of Phase Diagram
❑ Cooling curves : pure metal vs an alloy

Cooling curve of pure metal

Cooling curve of an alloy

CHAPTER 4: Phase Diagrams of Metals 15
4.2 Binary Phase Diagrams
▪ Isomorphous Binary Phase Diagram: The Construction of Phase Diagram
❑ Cooling curves : pure metal vs an alloy
CHAPTER 4: Phase Diagrams of Metals 16
4.2 Binary Phase Diagrams
▪ Isomorphous Binary Phase Diagram: The Construction of Phase Diagram
❑ Cooling curve of Cu-Ni alloy system
CHAPTER 4: Phase Diagrams of Metals 17
4.2 Binary Phase Diagrams
▪ Isomorphous Binary Phase Diagram: Lever Arm Rule

❑ Definition: The Lever Rule is a tool used

to determine the mole fraction (xi) or the
mass fraction (wi) of each phase of a
binary equilibrium phase diagram.

❑ Used to determine the fraction of liquid

and solid phases for a given binary
composition and temperature between
the liquidus and solidus lines.
CHAPTER 4: Phase Diagrams of Metals 18
4.2 Binary Phase Diagrams
▪ Isomorphous Binary Phase Diagram: The Lever Rule
❑ Tie-line method: find the phase
- draw the composition line (vertical x)
intersect the tie line
- draw an isothermal line to intersect
the phase lines.
❑ Read concentration of each solid and
liquid phase.
- Concentration of solid (% B at ws)
- Concentration of liquid (% B at wL)
CHAPTER 4: Phase Diagrams of Metals 19
4.2 Binary Phase Diagrams
▪ Isomorphous Binary Phase Diagram: The Lever Rule XS + X L = 1
❖ Lever rule: find the amount of phase
- the phase fractions are inversely
proportional to the length to the boundary
for the particular phase.
- let B is the fraction of liquid and A is
the fraction of solid, thus A B
𝐴 w0 − wL
𝑊𝑒𝑖𝑔ℎ𝑡 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑠𝑜𝑙𝑖𝑑 = XS =
𝐴+𝐵 or wS − wL

wS − w0
𝐵 or XL =
𝑊𝑒𝑖𝑔ℎ𝑡 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑙𝑖𝑞𝑢𝑖𝑑 = wS − wL
𝐴+𝐵
CHAPTER 4: Phase Diagrams of Metals 20
4.2 Binary Phase Diagrams
▪ Isomorphous Binary Phase Diagram: Lever Arm Rule XS + X L = 1

❑ Calculation of the amount of

solid phase for 53% Ni at 1300 oC
𝐴 53 − 45
𝑋𝑆 = = = 0.615
𝐴 + 𝐵 58 − 45

61.5% solid A B
❑ Calculation of the amount of
liquid phase for 53% Ni at 1300 oC
𝐵 58 − 53
𝑋𝐿 = = = 0.385
𝐴 + 𝐵 58 − 45
38.5% liquid
CHAPTER 4: Phase Diagrams of Metals 21
4.2 Binary Phase Diagrams
Isomorphous Binary Phase Diagram: L
(40% B)
a
Ex: phase and composition at 40 wt.% of B
L (40% B) S (78% B)

b
x
Liquid a
L (25% B) S (62% B)
Temperature

a a

40 L+S a a
a
c
b 78
a a

25
c 62
d L (14% B) S (40% B)
14 a a
40
a
e Solid a a d
a a

S (40% B)
0 20 40 60 80 100 a
a
A B a a
Wt.% B a
a
e
a
CHAPTER 4: Phase Diagrams of Metals 22
4.2 Binary Phase Diagrams
Solvent: host or major component in solution.
▪ Binary Phase Diagram: Solubility
Solute: dissolved, minor component in solution.
❑ Definition: solubility is the
maximum quantity of solute Ex : solubility of salt in water vs partial solid solution of one metal to another.
that can dissolve in a certain
quantity of solvent or quantity Solubility curve Solvus
of solution at a specified solid solution, a
temperature (or pressure).

Temperature
Unsaturated

Temperature
❑ Solubility limit can be extended liquid solution

solid solution, a + solid

by raising up the temperature. Saturated liquid solution + salt phase b

❑ Similarly, metal solid (B) can

be dissolved in another metal Undissolved salt Solid phase b
solid (A), giving the solubility
100% water % salt 100% Metal A % Metal B
line called solvus.
CHAPTER 4: Phase Diagrams of Metals 23
4.2 Binary Phase Diagrams
▪ Binary Phase Diagram: Solubility
❑ Definition: solvus line is a line that separates L
a homogeneous solid solution from a field of
several phases.

Temperature
❑ showing solubility of solute metal atoms in a+L

solvent metal atoms in a solid solution system.

❑ solid solubility limit changes as a function of a
temperature.
a+b

0 10 20 30
A B
Wt.% B
Substitution and interstitial solid solution
CHAPTER 4: Phase Diagrams of Metals 24
4.2 Binary Phase Diagrams ❖ eutectic = easy to melt in Greek
▪ Binary Eutectic Phase Diagram
𝑐𝑜𝑜𝑙𝑖𝑛𝑔
❑ Eutectic reaction is the reaction at 𝐿 𝛼+𝛽
Liquidus line
which liquid phase becomes two solid
L
phases. TA TB

❑ Eutectic temperature is the

Temperature
L+a L+b
temperature at which a particular a Solidus line b
TE
eutectic mixture freezes or melts,
normally lower than the melting point a+b

of either of the constituents. Solvus line

❑ Eutectic composition is the Eutectic

composition

composition defined where eutectic A Composition B

reaction taking place
CHAPTER 4: Phase Diagrams of Metals 25
4.2 Binary Phase Diagrams
▪ Binary Eutectic Phase Diagram
𝑐𝑜𝑜𝑙𝑖𝑛𝑔
❑ Eutectic mixture is homogeneous 𝐿 𝛼+𝛽
mixture of substances that melts or Liquidus line
solidifies at a eutectic temperature. TA L TB

❑ Primary phase is the phase solidifying

Temperature
L+a L+b
prior to eutectic reaction. a Solidus line b
TE

Primary phase a+b

Solvus line
Eutectic
composition

A B
eutectic mixture Composition
is a + b
CHAPTER 4: Phase Diagrams of Metals 26
4.2 Binary Phase Diagrams
▪ Binary Eutectic Phase Diagram: Phases and composition

Pb

Sn
L E L
TA TB
Pb m

Temperature
Sn
L+a L+b
a b TE 𝑐𝑜𝑜𝑙𝑖𝑛𝑔
Pb n 𝐿 𝛼+𝛽
b
Ex: Pb – Sn eutectic structure
a+b
a
Eutectic
composition

A Composition B
CHAPTER 4: Phase Diagrams of Metals 27
4.2 Binary Phase Diagrams
▪ Binary Eutectic Phase Diagram: Phases and composition
x y
L i L
f L a L L
g
L a
Liquidus
h
j

a a a a
Temperature

Temperature
a+L a+L
a a
a Solidus
a a
Eutectic k
Solvus
a b
a line
l
a+b

a+b

0 10 20 30 0 10 20 30 40 50
A B A B
Wt.% B Wt.% B
CHAPTER 4: Phase Diagrams of Metals 28
4.2 Binary Phase Diagrams
▪ Binary Eutectic Phase Diagram: Phases and composition

L o
o : Liquid phase TA o
z
L
p : primary a nucleation in liquid phase
p

Temperature
L+a
q : increasing primary a, p L+b
a q b TE
reducing liquid phase r a
a

r : the remaining liquid transforms into a a a

q
a a
eutectic structure via eutectic reaction a+b
(giving the eutectic structure r
surrounding primary a)
Primary a
A Composition B Eutectic (a+b)
CHAPTER 4: Phase Diagrams of Metals 29
4.2 Binary Phase Diagrams
▪ Binary Eutectic Phase Diagram:
phases and composition
❑ Ex: Cu – Ag system
Eutectic reaction: 𝑳 → 𝜶 + 𝜷
Eutectic temperature: 779 oC
= 0.232
Eutectic composition: 71.9 wt.% Ag
Eutectic mixture: a + b
CHAPTER 4: Phase Diagrams of Metals 30
4.2 Binary Phase Diagrams
▪ Binary Eutectic Phase Diagram:
phases and composition
❑ Ex: Cu – Ag system
Eutectic mixture: a + b
Composition of a : 8.0 wt.% Ag
Composition of b : 91.2 wt.% Ag
A B
❑ Fractions of a and b at eutectic
𝐵 91.2 − 71.9
𝑋𝛼 = = = 0.232
𝐴+𝐵 91.2 − 8.0

𝐴 71.9 − 8.0
𝑋𝛽 = = = 0.768
𝐴 + 𝐵 91.2 − 8.0
CHAPTER 4: Phase Diagrams of Metals 31
4.2 Binary Phase Diagrams
▪ Binary Eutectic Phase Diagram: The construction of binary eutectic phase diagram
100% Pb 20% Sn 40% Sn 61.9% Sn 80% Sn 100% Sn
❑ The cooling curve for Pb – Sn
eutectic phase diagram

https://slideplayer.com/slide/2683653/
CHAPTER 4: Phase Diagrams of Metals 32
4.2 Binary Phase Diagrams
▪ Binary Eutectic Phase Diagram: Phases and composition
❑ Ex: Pb – Sn system
Identify phases at different compositions
- 61.9% Sn (eutectic composition)
- 40% Sn

https://slideplayer.com/slide/2683653/
CHAPTER 4: Phase Diagrams of Metals 33
4.2 Binary Phase Diagrams
𝑐𝑜𝑜𝑙𝑖𝑛𝑔
▪ Binary Eutectic Phase Diagram: Phase identification 𝐿 𝛼+𝛽
❑ Ex: Pb – Sn system
Identify phases at 61.9% Sn

https://slideplayer.com/slide/2683653/
CHAPTER 4: Phase Diagrams of Metals 34
4.2 Binary Phase Diagrams Amount (fraction) of proeutectic a
▪ Binary Eutectic Phase Diagram: Phases and composition Amount (fraction) of liquid

❑ Ex: Pb – Sn system
- at 40% Sn
At a : only liquid phase is present.
At b : first solid (a) is present → primary a.
At c : solid a increases with reducing temperature,
while liquid reduces.
At d : solid a increases even more while the liquid
continuously reduces till approaching eutectic
temperature (183oC).
At e : just crossing the eutectic temperature, the
remaining liquid transforms into eutectic structure
(alternate layers of a and b) surrounding the
primary a solid.
CHAPTER 4: Phase Diagrams of Metals 35
4.2 Binary Phase Diagrams
▪ Binary Eutectic Phase Diagram: Phases and composition
❑ Ex: Pb – Sn system
Alloy 1 Alloy 2
Microstructure at 61.9% Sn (eutectic) Microstructure at 40% Sn

a Primary a
b
Eutectic (a+b)
CHAPTER 4: Phase Diagrams of Metals 36
4.2 Binary Phase Diagrams 𝑐𝑜𝑜𝑙𝑖𝑛𝑔
▪ Binary Peritectic Phase Diagram: 𝐿+𝛼 𝛽

❑ Ex: Pt – Ag system

researchgate.net
CHAPTER 4: Phase Diagrams of Metals 37
4.2 Binary Phase Diagrams 𝐿(66.3%𝐴𝑔) + 𝛼(10.5%𝐴𝑔) → 𝛽
▪ Binary Peritectic Phase Diagram:
❑ Ex: Pt – Ag system Alloy 1 Alloy 2 Liquid
1800

1600 a
7 55 Liquid
Tie line b Tie line Alpha
1400 (1150 oC)

Temperature, oC
Liquid
L+a c 48 66.3
a (1186 oC) 77
very slow cooling of an alloy of 1200
d
peritectic composition through the 10.5 L+b
1000
peritectic temperature Beta
Liquid 800 a+b b
b
600
a a b 42.4

0 10 20 30 40 50 60 70 80 90 100% Beta
a a a b
a b 100% Ag Liquid
Pt Weight percent silver
Decreasing temperature
CHAPTER 4: Phase Diagrams of Metals 38
4.2 Binary Phase Diagrams 𝐿1
𝑐𝑜𝑜𝑙𝑖𝑛𝑔
𝛼 + 𝐿2
▪ Binary Monotectic Phase Diagram:
❑ Ex: Cu – Pb system
Two liquids are immiscible.
(completely insoluble in each other)
CHAPTER 4: Phase Diagrams of Metals 39
4.2 Binary Phase Diagrams Temp
Liquid
▪ Phase Diagrams for Intermediate Phases Congruent melting
and Intermetallic Compounds B+L
AB2 + L
- Intermediate phases are formed by two metals give intermetallic A+L AB2 + L
compounds, which is stoichiometric (distinct chemical formula) AB2 + B
A + AB2

A AB2 B
- Congruent melting occurs during melting of a compound when the
composition of the liquid that forms is the same as the composition Temp
of the solid.
Liquid

- Incongruent melting occurs when a solid substance does not melt Incongruent melting
Y+L
uniformly. So a new solid (of different composition) forms during
melting. X+L XY2 + L
XY2 + Y
X + XY2

X XY2 Y
CHAPTER 4: Phase Diagrams of Metals 40
4.2 Binary Phase Diagrams
▪ Phase Diagrams for
Intermediate Phases and Intermetallic compounds
Intermetallic Compounds
❑ Ex: Ti – Ni system
- Terminal solid solution phases occur at
the ends of phase diagram.
- Intermediate solution phases occur in TiNi

TiNi3
a composition range inside the phase
diagram.

Ti2Ni
- Stoichiometric intermetallic
compounds form, i.e., Ti2Ni, TiNi, TiNi3.
CHAPTER 4: Phase Diagrams of Metals 41
4.2 Binary Phase Diagrams
▪ Summary Name of reaction Equation Phase-diagram characteristic
L
L+a L+b
cooling
Eutectic L
heating
a+b
a+b

a
cooling a+b a+g
Eutectoid a heating b+g
b+g

L
cooling L1 + a L2 + b
Monotectic L1
heating
a + L2
a + L2

cooling L+a
Peritectic a+L heating b
a+b b+L
b

cooling a+b
Peritectoid a+b g
heating a+g g+b
g
CHAPTER 4: Phase Diagrams of Metals 42
4.3 Fe-Fe3C Phase Diagram
▪ Important Phases
❑ a solid solution - ferrite Peritectic
L
d
❑ g solid solution - austenite
g+L
❑ d solid solution - delta ferrite L + Fe3C
❑ Fe3C intermetallic - cementite g Eutectic
g + Fe3C
▪ Important Temperatures
❑ Melting point of Fe – 1538 oC a+g
❑ Peritectic temperature – 1493 oC Eutectoid
a + Fe3C
a
❑ Eutectic temperature – 1147 oC
❑ Eutectoid temperature – 727 oC
CHAPTER 4: Phase Diagrams of Metals 43
4.3 Fe-Fe3C Phase Diagram
▪ Steel (C < 2 wt.%)
❑ Hypo-eutectoid steel (C<0.83 wt.%)
❑ Hyper-eutectoid steel(0.83%<C< 2 wt.%)
▪ Cast iron (C > 2 wt.%)
▪ Cementite (C = 6.67 wt.%)

2%
Hypo-eutectoid Hyper-eutectoid
steel Cast Iron
CHAPTER 4: Phase Diagrams of Metals 44
4.3 Fe-Fe3C Phase Diagram
▪ Ferrite or a
❑ Interstitial solid solution
❑ BCC crystal structure

Temperature
1147 oC

❑ Stable at room temp 2.14%

g
❑ 0.008 %C is soluble at room temperature 912 oC

❑ C solubility increases to 0.022% at 727oC g + Fe3C

a+g 727 oC
a
0.022% 0.76%
a + Fe3C

Fe3C
0.008% 6.67%

BCC crystal structure a ferrite Fe Composition C

microstructure
CHAPTER 4: Phase Diagrams of Metals 45
4.3 Fe-Fe3C Phase Diagram
▪ Austenite or g
❑ Interstitial solid solution
❑ FCC crystal structure 1147 oC

❑ Stable at high temp g 2.14%

❑ Carbon is soluble up to 2.14 wt.% at 1147 oC 912 oC

Temperature
g + Fe3C
a+g 727 oC
a
0.022% 0.76%
a + Fe3C

Fe3C
0.008% 6.67%

FCC crystal structure g austenite Fe Composition C

microstructure
CHAPTER 4: Phase Diagrams of Metals 46
4.3 Fe-Fe3C Phase Diagram
▪ Delta ferrite or d
1538 oC L+ d
❑ Interstitial solid solution d 1493 oC
L
❑ BCC crystal structure 1394 oC
g+d
L+ Fe3C
L+ g 1147 oC
❑ Stable at high temperature

Temperature
a+g 2.14% 4.3%
912 oC g

727 oC g + Fe3C
0.76%
a 0.022%
a + Fe3C

Fe3C
6.67%
BCC crystal structure
Fe C
Gray, R.J, JOM (1978).
Composition
CHAPTER 4: Phase Diagrams of Metals 47
4.3 Fe-Fe3C Phase Diagram
▪ Cementite or Fe3C (C = 6.67 wt.%)
❑ Intermetallic compound
❑ Tetragonal crystal structure 1147 oC

❑ Stable at room temperature g 2.14%

❑ 6.67 %C 912 oC

Temperature
g + Fe3C
a+g 727 oC
a
0.022% 0.76%
a + Fe3C

Fe3C
0.008% 6.67%

Fe3C crystal structure Fe Composition C

CHAPTER 4: Phase Diagrams of Metals 48
4.3 Fe-Fe3C Phase Diagram
▪ Peritectic reaction 1538 oC L+ d
d 1493 oC
L
𝐿𝑖𝑞𝑢𝑖𝑑 0.53%𝐶 + 𝛿 0.009%𝐶 𝛾(0.17%𝐶) 1394 oC L+ Fe3C
14930 𝐶 g+d
L+ g 1147 oC
▪ Eutectic reaction

Temperature
g 2.14% 4.3%

𝐿𝑖𝑞𝑢𝑖𝑑 4.3%𝐶 𝛾(2.14%𝐶) + 𝐹𝑒3 𝐶(6.67%𝐶) 912 oC

11480 𝐶
a+g 727 oC g + Fe3C
0.76%
▪ Eutectoid reaction a 0.022%
𝛾(0.76%𝐶) 𝛼 0.022%𝐶 + 𝐹𝑒3 𝐶(6.67%𝐶) a + Fe3C
7270 𝐶

Fe3C
6.67%

Fe C
Composition
CHAPTER 4: Phase Diagrams of Metals 49
4.3 Fe-Fe3C Phase Diagram
Eutectoid reaction 𝛾 ↔ 𝑝𝑒𝑎𝑟𝑙𝑖𝑡𝑒(𝛼 + 𝐹𝑒3 𝐶)
▪ Pearlite formation (eutectoid reaction)
❑ Austenite transforms into pearlite
(alternating layers of ferrite and 1147 oC
g
cementite) similar to eutectic structure. x
g g
g

Temperature
912 oC a
g

OM g + Fe3C
SEM
a+g 727 oC
a 0.022% b
a + Fe3C

a Fe3C
Fe3C
0.008% 0.76% 6.67%
Fe Composition C
CHAPTER 4: Phase Diagrams of Metals 50
4.3 Fe-Fe3C Phase Diagram 𝛾 ↔ 𝑝𝑟𝑖𝑚𝑎𝑟𝑦 𝛼 + 𝑝𝑒𝑎𝑟𝑙𝑖𝑡𝑒
▪ Hypo - eutectoid transformation
g g
❑ Austenite transforms into primary ferrite and pearlite at room temperature. g
g
a
At a : only austenite solid solution is present.
1147 oC
At b : proeutectoid ferrite (a) appears.
x g g
At c : proeutectoid a ferrite increases with reducing b
a
temperature, while g austenite reduces.

Temperature
a
At d : just crossing the eutectoid temperature, the
a+g g + Fe3C
remaining g austenite transforms into pearlite b g
structure (alternate layers of a and Fe3C) c 727 oC c
a d a
surrounding the primary a solid. 0.76%
a + Fe3C pearlite

ferrite (a) Fe3C d

0.008% 0.4% 6.67%
pearlite
Fe Composition C
Proeutectoid
ferrite, a
CHAPTER 4: Phase Diagrams of Metals 51
4.3 Fe-Fe3C Phase Diagram 𝛾 ↔ 𝑝𝑟𝑖𝑚𝑎𝑟𝑦 𝐹𝑒3 𝐶 + 𝑝𝑒𝑎𝑟𝑙𝑖𝑡𝑒
▪ Hyper - eutectoid transformation
g g
❑ Austenite transforms into primary cementite g
g
a
(Fe3C) and pearlite at room temperature. 1147 oC

At a : only austenite solid solution is present. x g

g b
At b : proeutectoid Fe3C appears. a
912 oC Fe3C
At c : proeutectoid Fe3C increases with reducing
temperature, while g austenite reduces. g + Fe3C
b g
a+g 727 oC c
At d : just crossing the a
c
0.022% 0.76% d Fe3C
eutectoid temperature, the a + Fe3C pearlite
remaining g austenite pearlite
transforms into pearlite Fe3C d
structure (alternate layers 0.008% 1.2% 6.67%
of a and Fe3C) surrounding Fe C
Composition
the proeutectoid Fe3C. Proeutectoid
Proeutectoid cementite,
cementite, Fe3C Fe3C
CHAPTER 4: Phase Diagrams of Metals 52
4.3 Fe-Fe3C Phase Diagram
▪ Steel microstructures

Proeutectoid Fe3C + g 1147 oC

Ferrite + pearlite Pearlite pearlite 2.14%

Temperature
a+g g + Fe3C
727 oC
a 0.022% 0.76%
a + Fe3C

Hypo-eutectoid steel Eutectoid steel Hyper eutectoid steel Fe3C

Microstructures of carbon steels [3] 0.008% 6.67%
Fe Composition C
Hypo-eutectoid steel Hyper-eutectoid steel
CHAPTER 4: Phase Diagrams of Metals 53
4.3 Fe-Fe3C Phase Diagram
▪ Estimation of tensile properties in carbon steels

Tensile strength of ferrite = 28 kg/mm2

Tensile strength of pearlite = 80 kg/mm2
At 0.4 % C Ferrite ~ 50%
Pearlite ~ 50%
From rule of mixture
Tensile strength of 0.4%C steel = Sferrite Vferrite + Spearlite Vpearlite
= 28(0.5) +80(0.5)
~ 54 kg/mm2
CHAPTER 4: Phase Diagrams of Metals 54
4.3 Fe-Fe3C Phase Diagram
▪ Tensile properties in carbon steels
❑ Tensile strength increases with increasing
carbon content till reaching 0.8 %C (hyper

Tensile, hardness properties

– eutectoid steel).
❑ A slight reduction in tensile strength
beyond 0.8%C is due to the brittle nature
of Fe3C network along the boundary of
pearlite colonies. cementite

% Phases
ferrite
❑ Hardness increases with increasing C even pearlite

at C > 0.8%, as subjected to compression % CARBON eutectoid

Microstructure
(not under tension)
variation
CHAPTER 4: Phase Diagrams of Metals 55
Summary
❑ Phase diagram shows the presence
of phases according to composition
Steels for safety-critical parts,
and temperature. especially for maintaining a
passenger survival space in crash
❑ Fraction of phase can be events.

calculated by the Lever Rule High - strength steels with a good

❑ Phases of metal alloys influence

balance of strength, formability,
energy absorption and durability.

properties such as physical,

mechanical and chemical Steels with excellent formability
(eg. for deep drawing)

properties.
Stress vs % elongation for different steel types [S. Keeler]
CHAPTER 4: Phase Diagrams of Metals 56
Checklist - terminology
Austenite Incongruent melting Phase equilibrium
Cementite Intermediate solid solution Phase transformation
Composition Intermetallic compound Primary phase
Congruent melting Interstitial solid solution Proeutectoid cementite
Equilibrium Isomorphous Proeutectoid ferrite
Eutectic mixture Lever rule Solidus line
Eutectic reaction Liquidus line Solubility limit
Eutectic structure Monotectic Solvus line
Eutectoid reaction Pearlite Substitutional solid solution
Ferrite Peritectic reaction Terminal solid solution
Hypereutectoid alloy Phase Tie line
Hypoeutectoid alloy Phase diagram
CHAPTER 4: Phase Diagrams of Metals 57
References
• W.D. Callister, Fundamental of materials science and engineering/ an interactive e. text., 2001,
John Willey & Sons, Inc., New York, ISBN 0-471-39551-x.
• W.F. Smith and J. Hashemi, Foundations of Materials Science and Engineering, Mcgraw Hill
International Edition, Singapore, ISBN 007-125690-3.
• Y.Z. Tian, et.al, Microstructures, strengthening mechanisms and fracture behavior of Cu-Ag
alloys processed by high-pressure torsion, Acta Materialia 60 (2012) 269–281.
• Gray, R.J., Sikka, V.K. & King, R.T. Detecting Transformation of Delta-Ferrite to Sigma-Phase in
Stainless Steels by Advanced Metallographic Techniques. JOM 30, 18–26 (1978).
• S. Keeler, M. Kimchi, P. J. Mooney, Advanced high strength steels application guidlines version
6.0, World Auto Steel (2017), p 314.