http://scophy.

com/
What is the best composition for solder?

http://sentryair.com/
How is ultrapure Si for computer chips
produced?
http://people.seas.harvard.edu/~jones/
 Phase
Diagrams
 Cu melts at 1085C,
Ni melts at 1453C.
What is the melting point of a 50 wt% Cu + 50wt% Ni alloy?
Phase Diagram of Cu-Ni System
Liquid, L idu s Tm Ni 1453
L iq u
Liquid, L
Temperature, C

TL , Liquidus temp.
(Tm Cu + Tm Ni )/2 L+ Melting completes
Tm Cu50 Ni50
1269
TS , Solidus temp.
Melting begins

Tm Cu 1085 idu s
so l

Solid solution,

0 50 100

Cu Composition (Wt% Ni) Ni

 Equilibrium phase diagram
or
Equilibrium diagram
or
Phase diagram

A diagram in the space of relevant

thermodynamic variables (e.g., T
and x) indicating phases in
equilibrium is called a phase
diagram.
 Phase Diagram of Cu-Ni
System
Phase?
Liquid, L Tm Ni
1453
A chemically
Temperature, C

L+
Tm Cu
homogeneous,
1085 physically
Solid solution,
distinct and
mechanically
0
Cu
50
Composition (Wt
100
Ni
separable part
% Ni) of a system is
called a phase.
 Phase

Three phases of matter:

solid, liquid and gas.

Solids with different crystal structures

are different solid phases (usually
designated by different Greek letters ,
, etc. on the phase diagrams).
 Components
The independent chemical species (element or
compound) in terms of which the composition of
the system is described are called components.

Liquid, L Tm Ni Cu and Ni are

1453 components of this
Temperature, C

L+
diagram.
Tm Cu
1085
Two-component
Solid solution, phase diagram
or
0 50 100 a binary phase
Cu Composition (Wt Ni diagram
% Ni)
 Components and phases

Some more examples:

System components phases

Water H 2O liquid

Water +ice H 2O Liquid+solid

shikanji nimbu, chini and pani liquid solution

Mild steel Fe + C + Fe3C

A single component phase diagram:
Unary diagram

A two-component phase diagram:

Binary diagram

A three-component phase diagram:

Ternary diagram
CONSTITUTION POINT
Any given point (x,T) on the
phase diagram represents
an alloy of composition x
held at equilibrium at
temperature T

Point A:
60 wt% Ni at 1100C

Point B:
35 wt% Ni at 1250C

Cu-Ni binary phase diagram Callister, Fig. 9.2

The Three questions
For any given constitution point (x,T)
one can use the phase diagram to
answer the following:
1. What phases are present?
2. What are the compositions of the
phases?
3. What are the relative amounts of
the phases (phase proportions or
phase fractions)?
The Three questions
For any given constitution point (x,T)
one can use the phase diagram to
answer the following:
1. What phases are present?
2. What are the compositions of the
phases?
3. What are the relative amounts of
the phases (phase proportions or
phase fractions)?
Q: What phases are present at a
given constitution point?

Answer:
Mark the constitution point on the
phase diagram and read the phase
field it falls in.
What are the phases present at points A and B?

Point A
60 wt% Ni at 1100C
Phases present:

Point B

35 wt% Ni at 1250C
Phases present: + L
 V. Raghavan, Materials Science
1-2-1 rule and Engineering

Liquid, If we move
Tm Ni
L 1453
horizontally from one
single phase (1) to
L+ another single phase
L
Temperature, C

Tm Cu (1) we will encounter

1085 a two phase region
(2) in between. This
Solid solution, two phase region is
the mixture of two
100
single phases on
0 50
either side.
Cu Composition Ni
(Wt% Ni) True for all
binary diagrams
The Three questions
For any given constitution point (x,T)
one can use the phase diagram to
answer the following:
1. What phases are present?
2. What are the compositions of the
phases?
3. What are the relative amounts of
the phases (phase proportions or
phase fractions)?
Composition?

Composition is given as percentage of components

Weight percent: Percentage by mass

Atom percent: Percentage by number of atoms

Alloy composition (C0): Percentage of the component

in the whole alloy

Phase composition (Cphase) : Percentage of component

in a phase
Compositions for the constitution Point A:
60 wt% Ni at 1100C

Q: Alloy composition, C0 ?

Ans: C0 = 60 wt%Ni

Q: Phase composition, C?

Ans: C = 60 wt%Ni

For single phase alloys

Alloy composition =
phase composition
Compositions for the constitution point Point B:
35 wt% Ni at 1250C
Phases present: + L

Q: Alloy composition, C0 ?

Ans: C0 = 35 wt%Ni

Q: Phase compositions,
C , C L?
For two-phase alloys

Alloy composition
phase composition
C CL C0

Tie Line Rule

The Three questions
For any given constitution point (x,T)
one can use the phase diagram to
answer the following:
1. What phases are present?
2. What are the compositions of the
phases?
3. What are the relative amounts of
the phases (phase proportions or
phase fractions)?
Composition of phases in the two-phase region
Tie Line Rule

L

Tie Line

CL= 31.5 wt% Ni

C= 42.5 wt% Ni
 Tie Line Rule

Whenever the constitution point falls in a two phase

field (say and ) the phase compositions C and C
are determined using the Tie-Line rule as follows:

1. Draw a horizontal (isothermal) tie-line passing

through the constitution point and ending at the two
phase boundaries /+ and / + .

2. The composition corresponding to the intersection of

the tie line with the boundary with single phase , i.e.,
/+ is the composition of the phase C.
Similarly the intersection of the tie-line with the
other boundary / + gives the composition C of the
other phase .
The Lever Rule: A Mass balance Proof Prob. 7.6
Wt of alloy = W

L Wt of in alloy W = fW

Wt of L in alloy WL = fLW

Wt of Ni in alloy = W C0/100

Wt of Ni in = fWC/100

Wt of Ni in L = fL WCL/100

Wt of Ni in alloy = Wt of Ni in + Wt of Ni in L

C f + C L fL = C 0 C C0 opposite lever arm

fL
C C L total lever arm
f + fL = 1
 Lever Rule: relative amounts of phases in
two-phase field
Tie-Line as a lever with
constitution point as the fulcrum

Total lever arm = C CL

L side arm = C0 CL

Side arm = C C0

Lever Rule
mL opposite lever arm C C0 42.5 35
fL 0.68
m0 total lever arm C C L 42.5 31.5
Development of Microstructure during
solidification

35 32 3
f 0.273
43 32 11
f L 1 f 0.727

Single phase
polycrystalline
Solder alloy?

An alloy of Pb and Sn

What is best composition of the

solder alloy?

Requirements:
1. should melt easily
2. should give a strong joint
 Solder alloy 1-2-1 rule Eutectic diagram

327
Liquidu
s L
us

us
d

ui d
Liq 232
o li

us
s

l id
183

so
Eutectic horizontal
solvus

solvus
Eutectic
point

Pb Sn
62
Eutectic Eutectic
temperature Wt % Sn composition
Pb: monatomic fcc
Sn: monatomic bct

: Pb rich substitutional solid

solution of Pb and Sn
crystal structure: monatomic FCC

: Sn rich substitutional solid

solution of Pb and Sn
crystal structure: monatomic BCT
 Woods metal tea
party
Bi 50.0 wt%
Pb 25.0 wt%
Cd 12.5 wt%
Sn 12.5 wt%

An eutectic alloy with m.p. of 70C

100 g US$ 181
Anti-Fire Sprinklers
Eutectic
reaction

Invariant
reaction
cool
L 183C

62 18 97
wt%Sn wt%Sn wt%Sn

Eutectic mixture

Callister Figs. 9.11, 12 375 X

 L
(40 wt% Sn)

18 wt% Sn

L+

L (62 wt% Sn) Eutectic mixture

+
Primary
18 wt% Sn

Eutectic Eutectic (97 wt %

(18 wt % Sn) Sn)

Hypoeutectic alloy

Microstructure of hypoeutectic alloy

 Eutectc mixture

Proeutectic
or Primary

18 62 97

Amount of total and total at a temperature just below 183C

Tie line just below 183C (red)

97 40 57 f total 1 0.72 0.28

f total 0.72
97 18 79
 Eutectc mixture

Proeutectic
or Primary

18 62 97

Amount of proeutectic at a temperature just below 183C

= Amount of at a temperature just above 183C

Tie line just above 183C (green)

62 40 22 f eut 1 0.5 0.5
f pro 0 .5
62 18 44
 Eutectc mixture EXPERIMENT 5

Proeutectic
or Primary

18 62 97

Let the fraction of proeutectic in micrograph fpro = 0.25

Let the composition (wt% Sn) of the alloy be C 0

Tie line just above 183C (green)

62 C0 C0 51 wt % Sn
f pro 0.25
62 18
Optimum composition for solders

For electronic application

Eutectic solder
62 wt% Sn
18 62 97

Minimum heating

For general application

Hypoeutectic solder
Cheaper Allows adjustment of joint during
solidification in the L range
Modern Trend

Lead-free solders

Phase diagrams can help in

identification of such solders

Sn-Ag
 Gibbs Phase Rule

Thermodynamic variables:
P, T, Phase Compositions
(overall composition is not considered)

If there are C components then C-1 compositions

have to be specified for each phase

Therefore total number of composition variables:

P (C-1)

With Pressure and Temperature, total number of

variables = P (C-1) + 2
Gibbs phase rule states that one
cannot specify all of the above
P (C-1) + 2 variables independently in
a system at equilibrium

Degrees of Freedom F:
No. of thermodynamic variables
that can be specified independently
 Gibbs Phase Rule

F = Degrees of freedom
C = No. of components in the system
P = No. of phases in equlibrium

F=CP+2
If pressure and temp both are variables

F=CP+1
If pressure is held constant
 F=CP+1

C=2

F=3-P
F =2 At eutectic
reaction P=3
(L, , )

F =1 F=0

Invariant
reaction
 Mild steel
The Iron-carbon system
0-0.3 wt% C

Bicycle frame
Ship hull
1410
Car body
1150
Medium C steel
0.4-0.7 wt% C
910
steel Cast iron Rail wheel
725
rail axle
0.8
rails
0.02
High C steel
0.8-1.4 wt% C
Razor blades
scissors, knives
Phases in Fe-C system
Phase Symbol Description
Liquid L Liquid solution of Fe and C
-Ferrite Interstitial solid solution of C in
-Fe (high temperature bcc phase)
Austenite Interstitial solid solution of C in
-Fe (FCC phase of Fe)
Ferrite Interstitial solid solution of C in
-Fe (room temperature bcc phase)
Soft and Ductile
Cementite Fe3C Intermetallic compound of Fe and C
(orthorhombic system)
Hard and Brittle
Ferrite Austenite
 Invariant Reactions in Fe-C system
A horizontal line always indicates an invariant reaction
in binary phase diagrams

Peritectic Reaction
1493o C
(0.1 wt % C ) L (0.5 wt % C ) (0.18 wt % C )

Eutectic Reaction
1150 o C
L (4.3 wt % C ) (2.1 wt % C ) Fe3C (6.67 wt % C )

Eutectoid Reaction
725o C
(0.8 wt % C ) (0.02 wt % C ) Fe3C (6.67 wt % C )
You are expected to memorise this part of Fe-C diagram and the
associated eutectoid reaction.
Eutectoid Reaction
725o C

cool
Fe3C
0.8 0.02 6.67

Pearlite

725
 Eutectoid Reaction
725o C

cool
Fe3C
0.8 0.02 6.67

Pearlite

Ammount of Fe3C in Pearlite

Red Tie Line below eutectoid temp

0.8 0.02 0.78
f pearlite
F3C 0.117
6.67 0.02 6.65
Development of
Microstructure
in a
hypoeutectoid
steel
Proeutectoid
Ferrite EXPERIMENT 5

Pearlite

Microsructure of a hypoeutectoid steel, 0.38 wt% C

fpearlite below TE = faustenite above TE

Tie-Line above the eutectoid temperature TE

0.8 0.38 0.42
f pearlite 0.54
0.8 0.2 0.78
Development of
Microstructure
in a
hypereutectoid
steel
 Pearlite

Proeutectoid
cementite on
prior
austenite
grain
boundaries

Microsructure of a hypereutectoid steel, 1.4 wt% C

Fproeutectoid cementite=fcementite above TE

1.4 0.8 0.6

f proeutectoid cementite 0.10
6.67 0.8 5.87
 Phase vs. microconstituents

A phase or a mixture of phases which has a distinct

identity in a microstructure is called a
microconstituent

Pearlite is not a phase.

It is microconstituent which is a mixture of
two phases and Fe3C.
Eutectoid Hypoutectoid Hypereutectoid
steel steel steel
+Fe3C +Fe3C +Fe3C
Pearlite Pearlite + Pearlite +
proeutectoid ferrite proeutectoid
cementite
 T Principle of Zone Refining
L
Tm A

C < CL
T

+L

A C C0 CL Wt % B
SemiconductorTransistor was invented by

Bardeen, Brattain and Shockley

At AT&T Bell Labs

One needs ultrapure Si (impurity level few ppm)

Zone Refining was invented by Pfann at Bell Labs

as a process to obtain ultrapure Si

Basis for modern Si technology