School of Physics & Materials Science, THAPAR UNIVERSITY

School of Physics & Materials Science, THAPAR UNIVERSITY

School of Physics & Materials Science, THAPAR UNIVERSITY
 Phases

Phase:
A homogeneous portion of a system that has uniform physical and chemical
characteristics.

1. Different physical states:

vapor, liquid, solid

2. Different chemical compositions

sugar solution

Question: What is the solubility limit at 20 C?

Answer: 65wt% sugar.

If Co < 65wt% sugar: syrup
If Co > 65wt% sugar: syrup + sugar.

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School of Physics & Materials Science, THAPAR UNIVERSITY
School of Physics & Materials Science, THAPAR UNIVERSITY
School of Physics & Materials Science, THAPAR UNIVERSITY
School of Physics & Materials Science, THAPAR UNIVERSITY
School of Physics & Materials Science, THAPAR UNIVERSITY
School of Physics & Materials Science, THAPAR UNIVERSITY
School of Physics & Materials Science, THAPAR UNIVERSITY
School of Physics & Materials Science, THAPAR UNIVERSITY
School of Physics & Materials Science, THAPAR UNIVERSITY
School of Physics & Materials Science, THAPAR UNIVERSITY
School of Physics & Materials Science, THAPAR UNIVERSITY
School of Physics & Materials Science, THAPAR UNIVERSITY
School of Physics & Materials Science, THAPAR UNIVERSITY
18
Phase Diagrams:
Determination of phase weight fractions
• Rule 3: If we know T and C0, then can determine:
-- the weight fraction of each phase. Cu-Ni
• Examples: T(ºC) system
Consider C0 = 35 wt% Ni TA A
tie line
At TA : Only Liquid (L) present 1300 L (liquid)
WL = 1.00, Wa = 0 B
At TD : Only Solid ( a) present TB R S
a
WL = 0, Wa = 1.00
1200 D (solid)
At TB : Both a and L present TD
S 43 − 35
WL =
20 3032 35 40 43 50
= = 0.73 CL C0 Ca wt% Ni
R +S 43 − 32

R
Wa = = 0.27
R +S
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 Development of microstructure in binary isomorphous system
Microstructures will vary on the cooling rate (i.e. processing conditions)
1. Equilibrium Cooling: Very slow cooling to allow phase equilibrium to be maintained during
the cooling process.
T(ºC) L (liquid) L: 35wt%Ni
a (T>1260 oC): start as
Cu-Ni homogeneous liquid solution.
130 0 A system b (T ~ 1260 oC): liquidus line
L: 35 wt% Ni reached. α phase begins to
a: 46 wt% Ni B nucleate. Cα = 46 wt% Ni; CL = 35
35 46
32 C 43
wt% Ni
D c (T= 1250 oC): calculate
24 36 L: 32 wt% Ni
composition and mass fraction of
a: 43 wt% Ni each phase.
120 0 E
L: 24 wt% Ni d (T~ 1220 oC): solidus line
a: 36 wt% Ni reached. Nearly complete
a solidification. Cα = 35 wt% Ni; CL =
(solid) 24 wt% Ni
e (T<1220 oC): homogeneous
110 0 solid solution with 35 wt% Ni.
35C0 wt% Ni
20 30 40 50
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 Development of microstructure in binary isomorphous system
2. Non-equilibrium cooling:
Fast cooling, but how fast? Fast w.r.t. diffusion
Since diffusion rate is especially low in solids, consider case where:
Cooling rate >> diffusion rate in solid
Cooling rate << diffusion rate in liquid (equilibrium maintained in liquids phase)

a’ (T>1260 oC): start as homogeneous liquid solution.

b’ (T ~ 1260 oC): liquidus line reached. α phase begins
to nucleate.
c’ (T= 1250 oC): solids that formed at pt b’ remain with
same composition (46wt%) and new solids with 42
wt% Ni form around the existing solids.
d’ (T~ 1220 oC): solidus line reached. Nearly complete
solidification. Cα = 46 wt% Ni; CL = 35 wt% Ni
e’ Previously solidified regions maintain original
composition and further solidification occurs at 35
wt% Ni.
f’ (T<1220 oC): Non-equilibrium solidification complete
(with phase segregation).

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 Cored vs. Equilibrium phases

• Ca changes as we solidify.
• Cu-Ni case: First a to solidify has Ca = 46 wt% Ni.
Last a to solidify has Ca = 35 wt% Ni.
• Slow rate of cooling: • Fast rate of cooling:
Equilibrium structure Cored structure
Uniform Ca:
35 wt% Ni First a to solidify:
46 wt% Ni
Last a to solidify:
< 35 wt% Ni

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School of Physics & Materials Science, THAPAR UNIVERSITY
School of Physics & Materials Science, THAPAR UNIVERSITY
 Eutectic point

Eutectic point: Where 2 liquidus lines meet

(pt. E).
Sometimes also referred to as invariant point.

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26

Binary-Eutectic Systems
has a special composition
2 components with a min. melting T.
Cu-Ag
Ex.: Cu-Ag system T(ºC) system
• 3 single phase regions 1200
(L, a, b) L (liquid)
1000
• Limited solubility:
a: mostly Cu
a L + a 779ºC L+b b
TE 800 8.0 71.9 91.2
b: mostly Ag
• TE : No liquid below TE 600

• CE : Composition at a+b
400
temperature TE
200
• Eutectic reaction 0 20 40 60 CE 80 100
L(CE) a(CaE) + b(CbE) C, wt% Ag
cooling
L(71.9 wt% Ag) a(8.0 wt% Ag) + b(91.2 wt% Ag)
heating
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27

EX 1: Pb-Sn Eutectic System

• For a 40 wt% Sn-60 wt% Pb alloy at 150ºC, determine:
-- the phases present
Pb-Sn
Answer: a + b T(ºC) system
-- the phase compositions
Answer: Ca = 11 wt% Sn 300
Cb = 99 wt% Sn L (liquid)
-- the relative amount
a L+ a
of each phase 200 183ºC L+b b
18.3 61.9 97.8
Answer: 150
W =
S
=
Cb - C0 R S
100
a R+S Cb - Ca a+b
99 - 40 59
= = = 0.67
99 - 11 88
R C0 - Ca 0 11 20 40 60 80 99100
Wb = = Ca C0 Cb
R+S Cb - Ca C, wt% Sn
40 - 11 29
= = = 0.33
99 - 11 88
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31

EX 2: Pb-Sn Eutectic System

• For a 40 wt% Sn-60 wt% Pb alloy at 220ºC, determine:
-- the phases present: Pb-Sn
Answer: a + L T(ºC) system
-- the phase compositions
300
Answer: Ca = 17 wt% Sn L (liquid)
CL = 46 wt% Sn L+a
-- the relative amount 220
200
a R S L+b b
of each phase 183ºC
Answer:
100
Wa =
CL - C0
=
46 - 40 a+b
CL - Ca 46 - 17
6 0 17 20 40 46 60 80 100
= = 0.21 Ca C0 CL
29 C, wt% Sn
Adapted from Fig. 9.8,
C0 - Ca 23 Callister & Rethwisch 8e.
WL = = = 0.79
CL - Ca 29
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Microstructural Developments
in Eutectic Systems I
• For alloys for which T(ºC)
400
L: C0 wt% Sn

C0 < 2 wt% Sn L
• Result: at room temperature a
300 L
-- polycrystalline with grains of
a phase having L+ a
a
composition C0 200 (Pb-Sn
TE a: C0 wt% Sn
System)

a+ b
100

0 10 20 30
C0 C , wt% Sn
2
(room T solubility limit)

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 Microstructural Developments
30

in Eutectic Systems II
L: C0 wt% Sn
• For alloys for which 400
T(ºC)
2 wt% Sn < C0 < 18.3 wt% Sn L
• Result: L
at temperatures in a + b range 300 a
L+a
-- polycrystalline with a grains a: C0 wt% Sn
and small b-phase particles 200 a
TE
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)

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31
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
a+b b: 97.8 wt% Sn 160 m
a: 18.3 wt%Sn

0 20 40 60 80 100
18.3 CE 97.8
61.9 C, wt% Sn
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 Lamellar Eutectic structure
Eutectic reaction:
During this transformation, there is a redistribution of the Pb and Sn components, (a and
b phases have different compositions, different from liquid composition)
This redistribution is accomplished by atomic diffusion.
Resulting microstructure consists of alternating layers (lamellae) of the a and b phases
that form simultaneously during the transformation.

a - b layered eutectic growing into and replacing the liquid phase.

Redistribution of Pb and Sn occurs by diffusion in the liquid just ahead of
the eutectic–liquid interface.
Pb atoms diffuse toward the a-phase layers because this phase is Pb-rich
(18.3 wt% Sn–81.7 wt% Pb);
Conversely, the direction of diffusion of Sn is in the direction of
the b, Sn-rich (97.8 wt% Sn–2.2 wt% Pb) layers.
The eutectic structure forms in these alternating layers because, for this
lamellar configuration, atomic diffusion of Pb and Sn need only occur
over relatively short distances.

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 Microstructural Developments
33

in Eutectic Systems IV
• For alloys for which 18.3 wt% Sn < C0 < 61.9 wt% Sn
• Result: a phase particles and a 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
200
a R S L+b b 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
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 Hypoeutectic & Hypereutectic
34

300
L
T(ºC)
a L+ a
200 L+b b (Pb-Sn
TE

a+b System)
100

0 20 40 60 80 100 C, wt% Sn
eutectic
hypoeutectic: C0 = 50 wt% Sn 61.9 hypereutectic: (illustration only)

eutectic: C0 = 61.9 wt% Sn

a b
a b
a a b b
a b
a b
175 m 160 m
eutectic micro-constituent

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Determination of composition from cooling curve

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