Pb-Sn Cooling Curve

Pb-Sn Eutectic Reaction

Binary Eutectic Alloy System Generic Diagram

Definition:

L (eutectic)
a b

a = A-rich solid solution (B solute, A host)

b = B-rich solid solution (A solute; B host)
Three single-phase regions:
a solid phase
b solid phase
L liquid phase

Three 2-phase regions:

(a + L); (b + L); (a + b)

Composition

8-4

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display

Binary Eutectic Alloy System

In binary eutectic alloy systems, components have limited solid

solubility in each other. Example: Pb-Sn alloy, Cu-Ag alloy.

Regions designated as alpha phase (a) and beta phase (b) at each
ends are called terminal solid solutions because they appear at the
ends of the phase diagram.

Eutectic composition freezes at a lower temperature than all other

alloy compositions.

Eutectic temperature is the lowest temperature at which the liquid

phase can exist, when cooled slowly.

Eutectic composition and eutectic temperature define the eutectic

point.

When liquid of eutectic composition is slowly cooled to eutectic

temperature, the single liquid phase transforms into two solid phases.

Foundations of Materials Science and Engineering, 5th Edn. Smith and Hashemi

The Eutectic Reaction

Eutectic reaction is called invariant reaction because it

occurs under equilibrium conditions at a specific
temperature and alloy composition that can not be varied.

Eutectic reaction has zero degree of freedom (F = 0)

F + P = C + 1 = F + 3 = 2 + 1.

At eutectic point, three phases are in equilibrium, i.e. one

liquid phase (L) is in equilibrium with two solid phases
(a and b)

Eutectic isotherm is the horizontal solidus line at TE. There is

no liquid below TE.

General eutectic reaction:

Liquid

Eutectic temp.
Cooling

a solid solution + solid solution

Binary Eutectic Alloy System: Cu-Ag

Invariant or eutectic point

Eutectic isotherm

Cu-Ag equilibrium phase diagram. This diagram is characterized by the limited solid
solubility of each terminal phase (a and b). The eutectic invariant reaction at 71.9% Ag
and 779C is the most important feature of this system. At eutectic point, a (8.0% Ag),
b (91.2% Ag) and liquid (71.9% Ag) can coexist.

Binary Eutectic Alloy System: Pb-Sn

Alpha phase is Pb-rich solid

solution; at 183C a
maximum of 19.2 wt % Sn can
be dissolved in it.
Beta phase is Sn-rich solid
solution; at 183C a
maximum of 2.5 wt % Pb can
be dissolved in it.

Solvus is the phase boundary below isothermal liquid + proeutectic solid

phase. Also phase boundary separating terminal solid solution from two-phase
region of solid solutions. Solvus shows the maximum solid solubility of
solute in a solid solution.
Pb-Sn equilibrium phase diagram. Eutectic composition is at 61.9% Sn and
183C. At eutectic point, a (18.3% Sn), b (97.5% Sn) and liquid (61.9% Sn) can
coexist.

8-8

Slow Cooling At Eutectic Composition

Pb-Sn system

T(C)
Liquid at 300C.
At TE liquid solidifies by
eutectic reaction into two
solid phases a (19.2% Sn)
and b (97.5% Sn)
Further cooling from TE to
room temperature, solid
solubility of solute in a and b
phases decreases, as
indicated by solvus line.

300

L
L+a
a

200

183C

TE

100

ab

20

40

18.3

L: 61.9% Sn

Lb b

b: 97.5 wt% Sn
a: 18.3 wt%Sn

60
80
CE = 61.9

100
97.5

C, wt% Sn

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display

Slow Cooling of 60% Pb 40% Sn Alloy

Liquid at 3000C.
At about 2450C first solid
forms proeutectic or
primary a, contains 12%
Sn.
Slightly above 183C
composition of alpha
follows solidus and
composition of Sn varies
from 40% to 61.9%.
At eutectic temperature,
all the remaining liquid
solidifies.
Further cooling lowers alpha Sn content and beta Pb.
10

Foundations of Materials Science and Engineering, 5th Edn. Smith and Hashemi

Slow Cooling At Hypoeutectic Composition (cont.)

Primary a (i.e. proeutectic a) phase is formed in the (a + L) region, while
the eutectic structure that includes layers of a and b phases is formed upon
crossing the eutectic isotherm.

Result:
Growth of a solid phase
occurs above TE

Primary or proeutectic a
growth stops at TE
Below TE, all remaining
liquid transforms into
eutectic structure by
eutectic reaction

Various Eutectic Structures

Micrograph of Pb-Sn
eutectic microstructure

rodlike

lamellar

acicular
globular

160 m

In eutectic reaction, both a and b phases are formed simultaneously,

resulting in a microstructure called eutectic structure. In Pb-Sn alloy,
eutectic reaction involves re-distribution of Pb and Sn atoms by atomic
diffusion.
In binary eutectic reaction, the two solid phases (a + b) can have various
structures as shown above. The most common is lamellar eutectic
structure of alternating layers of a and b phases.

12

Microstructure: Eutectic, Hypoeutectic and Hypereutectic

of Pb-Sn Alloy

300

T(C)

200

L+ a

L+b b

TE

(Pb-Sn System)

a+b
100

hypoeutectic: Co< 61.9wt% Sn

20

40

60

80

100

Co, wt% Sn

eutectic

a
a

a a

eutectic: Co = 61.9 wt% Sn

hypereutectic: Co > 61.9wt% Sn

b
b
Eutectic structure

b
b b
b
13

Microstructure Evolution of Pb-Sn Alloy:

Slow Cooling At Hypereutectic Composition
Growth of b solid phase occurs above TE
Growth of this primary b or proeutectic b stops at TE
Below TE, all remaining liquid transforms into eutectic structure.

8 - 14

Phase Diagram Analysis : Pb-Sn Eutectic Alloy

For a 40 wt% Sn-60 wt% Pb alloy at 150C, find...
--the phases present: a + b
T(C)
--compositions of phases:
CO = 40 wt% Sn
Ca = 11 wt% Sn
Cb = 99 wt% Sn

300

--relative amount of
each phase:

200

Wa =

C - CO
S
= b
R+S
Cb - C a

L (liquid)
a

L+ a

18.3
150
100

99 - 40
59
=
= 67 wt%
99 - 11
88
C - Ca
Wb = R = O
Cb - C a
R+S

L+b b

183C

61.9

97.5

S
a + b

40 - 11
29
=
= 33 wt%
99 - 11
88

0 11 20
Ca

40
Co

60
80
C, wt% Sn

99100
Cb

15

Phase Diagram Analysis : Pb-Sn Eutectic Alloy

For a 40 wt% Sn-60 wt% Pb alloy at 220C, find...
--the phases present: a + L
T(C)
--compositions of phases:
CO = 40 wt% Sn
Ca = 17 wt% Sn
CL = 46 wt% Sn

--relative amount of
of each phase:
CL - CO
46 - 40
=
Wa =
CL - Ca
46 - 17
6
=
= 21 wt%
29

300
L+a
220 a
200

L (liquid)

L+b b

S
183C

100

CO - Ca
23
=
WL =
= 79 wt%
CL - Ca
29

a + b

17 20
Ca

40 46 60
80
Co CL C, wt% Sn

100

16

Phase Diagram Analysis : Pb-Sn Eutectic Alloy

For a 40 wt% Sn-60 wt% Pb alloy slow-cooled to just below TE
Result: a crystals and eutectic microstructure

T(C)

L: Co wt% Sn

300

L
a

L
a

200

a L

L+a
R

TE

L+b b

a+b

100

primary a
eutectic a
eutectic b

20
18.3

40

60
61.9

80

Co, wt% Sn

100
97.8

Just above TE :
Ca = 18.3 wt% Sn
CL = 61.9 wt% Sn
Wa = S = 50 wt%
R+S
WL = (1- Wa) = 50 wt%
Just below TE :
Ca = 18.3 wt% Sn
Cb = 97.5 wt% Sn
Wa = S = 73 wt%
R+S
Wb = 27 wt%
17

SAMPLE PROBLEM 1
For a 75 wt.% Cu 25 wt.% Ag alloy at the following temperatures: (a) 1000oC,
(b) 800oC, (c) 780oC +DT, and (d) 780oC DT, state the:
i)phase(s) present.
ii)chemical composition of the phases.
iii)amount of each phase.
iv)Sketch the microstructure.

780C
7.9

8 - 18

PROBLEM 1

7.9

780C

25 wt%

~ 65 wt%

SOLUTION: PROBLEM 1
(a) At 1000oC:

(b) At 800oC:

(i) Phases present: 1 phase: L

(i) Phases present: 2 phases: L & a

(ii) Composition of phases:

CL = Co = 25 wt % Ag

(ii) Composition of phases:

L = 65 wt % Ag;
a = 7.9 wt % Ag

(iii) Amount of each phase:

WL = 100 wt %,
Wa = 0

(iii) Amount of each phase

65 25
Wa
x 100% 70.0%
65 7.9

(iv) Microstructure: All liquid

25 7.9
WL
x 100% 30.0%
65 7.9

(iv) Microstructure: proeutectic a + L

Proeutectic a
L

SOLUTION: PROBLEM 1 (continue)

(c) At 780oC + DT:

(d) At 780oC - DT:

(i) Phases present: 2 phases: L & a

(i) Phases present: 2 phases: a & b

(ii) Composition of phases:

L = 71.9 wt % Ag
a = 7.9 wt % Ag

(ii) Composition of phases:

a = 7.9 wt % Ag
b = 91.2 wt % Ag

(iii) Amount of each phase:

(iii) Amount of each phase

71.9 25
Wa
x 100% 73.3%
71.9 7.9

91.2 25
Wa
x 100% 79.5%
91.2 7.9

25 7.9
WL
x 100% 26.7%
71.9 7.9

91.2 71.9
Wb
x 100% 20.5%
91.2 7.9

(iv) Microstructure:

(iv) Microstructure:

Proeutectic a

Proeutectic a
L

eutectic a
eutectic b

SAMPLE PROBLEM 2
If 750g of 80 wt.% Ag 20 wt.% Cu alloy is slowly cooled from 1000oC to just below
780C (i.e. cooled to 780oC DT), determine:
i)How many grams of liquid and proeutectic beta are present at 800C?
ii)How many grams of liquid and proeutectic beta are present at 780C + T?
iii)How many grams of alpha are present in the eutectic structure at 780C T?
iv)How many grams of beta are present in the eutectic structure at 780C T?

780C
7.9

8 - 22

SOLUTION: PROBLEM 2
(a) At 800oC:

(b) At 780oC + DT:

(i) Phases present: 2 phases: L & b

(i) Phases present: 2 phases: L & b

(ii) Composition of phases:

L = 79 wt % Ag; b = 92 wt % Ag

(ii) Composition of phases:

L = 71.9 wt % Ag
b = 91.2 wt % Ag

(iii) Amount of each phase:

92 80
WL
x 100% 92.3%
92 79

91.2 80
WL
x 100% 58%
91.2 7.9

80 79
Wb
x 100% 7.7%
92 79

(iv) Mass of each phase:

(iii) Amount of each phase

L = (750g)(0.923) = 692.3g

b = (750g)(0.077) = 57.7g

80 71.9
Wb
x 100% 42.0%
91.2 71.9

(iv) Mass of each phase:

L = (750g)(0.58) = 435g
b = (750g)(0.42) = 315g

SOLUTION: PROBLEM 2 (continue)

(c) At 780oC - DT:

(d) At 780oC - DT:

(i) Phases present: 2 phases: a & b

(i) Phases present: 2 phases: a & b

(ii) Composition of a phase:

a = 7.9 wt % Ag

(ii) Composition of b phase:

b = 91.2 wt % Ag

(iii) Amount of a phase:

(iii) Amount of b phase

91.2 80
Wa
x 100% 13.45%
91.2 7.9

80 7.9
Wb
x 100% 86.55%
91.2 7.9

Note this amount is the total b, which

includes
both proeutectic b and eutectic b

% total a = % eutectic a
(iv) Mass of a phase:

(iv) Mass of eutectic b:

a = (750g)(0.1345) = 100.8g

% eutecticb % Total b - % proeutectic b

= 86.55% - 42%
= 44.55%

Eutectic b = (750g)(0.446) = 334.5g

SAMPLE PROBLEM 3
An alloy of 75 wt.% Pb 25 wt.% Sn alloy is slow-cooled from 300oC to 27C.
Determine:
a) Whether this alloy is hypoeutectic or hypereutectic. Hypoeutectic
b) The composition of the first solid to form. 12% Sn
c) The amount and composition of each phase present at 183C + T
d) The amount and composition of each phase present at 183C T
e) The amount of each phase present at room temperature. Assume solid solubility
of Sn in Pb is 1% at room temperature.

SOLUTION: PROBLEM 3
(c) At 183oC + DT:
(i) Phases present: 2 phases: a & L

(d) At 183oC - DT:

(i) Phases present: 2 phases: a & b

(ii) Composition of each phase:

a = 18.3 wt % Sn; L = 61.9 wt % Sn

(ii) Composition of each phase:

a = 18.3 wt % Sn; b = 97.8 wt % Sn

(iii) Amount of each phase

(iii) Amount of each phase

97.8 25
Wa
x 100% 91.6%
97.8 18.3

25 18.3
WL
x 100% 15.4%
61.9 18.3
61.9 25
Wa
x 100% 84.6%
61.9 18.3

(amount of total a phase)

(e) At room temperature:

100 25
Wa
x 100% 75.8%

1001

25 1
Wb
x 100% 24.2%
1001

25 18.3
Wb
x 100% 8.4%
97.8 18.3

(amount of total b phase)