UNIT II: PHASE DIAGRAMS

Phase A Phase B

Silver atom
Copper atom

• When we combine two elements...

what equilibrium state do we get?
• In particular, if we specify...
--a composition (e.g., wt%Cu - wt%Ag), and
--a temperature (T)
then...
How many phases do we get?
What is the composition of each phase?
How much of each phase do we get?
 THE SOLUBILITY LIMIT
• Solubility Limit:
Max concentration for
which only a solution
occurs.

• Ex: Phase Diagram:

Water-Sugar System
Question: What is the
solubility limit at 20C?
65 wt% sugar
Answer: 65wt% sugar.
If Comp < 65wt% sugar: syrup
If Comp > 65wt% sugar: syrup + sugar coexist

• Solubility limit increases with T:

e.g., if T = 100C, solubility limit = 80wt% sugar.
EFFECT OF T & COMPOSITION (Co)
• Each point on this phase diagram represents equilibrium
• Changing T can change # of phases: path A to B
• Changing Co can change # of phases: path B to C

B
C

A
 WATER-SALT PHASE DIAGRAM

Solubility limit

Reduction in
freezing point
 Gibb’s Phase Rule or Phase Rule

Phase Rule: F=C-P+2

F: Degrees of Freedom
C: No of Components
P: No of Phases
1: Temperature
2: Composition
P=1 atm
 COMPONENTS AND PHASES
• Components:
The elements or compounds which are mixed initially
(e.g., Al and Cu, or water and sugar)
• Phases:
The physically and chemically distinct material regions
that result (e.g.,  and , or syrup and sugar)

Aluminum-
Copper
Alloy

Adapted from
Fig. 9.0,
Callister 3e.
 What We get from Phase Diagram?

•Types of Phases

•Composition of Each Phase

•Amount of each phase in wt% (By Lever Rule)

 THE LEVER RULE: A PROOF
• Sum of weight fractions: WL W 1
• Conservation of mass (Ni): C
o
 W L C L  W C 
• Combine above equations:

WL  C  C o  S
W 
CL 
Co R

C CL R S C CL R S

• A geometric interpretation:
moment equilibrium:
CL Co C 
WL R  W S
R S

WL W  1W

solving gives Lever Rule

 Cu – Ni PHASE DIAGRAM
• Tell us about phases as function of T, Co, P
• For this course:
--binary systems: just 2 components.
--independent variables: T and Co (P = 1 atm is always used)
T(°C)
160 0 2 phases:
• Phase
Diagram for Cu- L (liquid)
150 0
Ni system L (liquid)  (FCC solid solution)
140 0 3 phase fields:
• Isomorphous L
system: i.e., uidus 
130 0 liq
L
+ L+ 
complete du
s
oli

solubility of one 120 0 s
 Adapted from Fig. 9.2(a),Callister 6e.
component in (Fig. 9.2(a) is adapted from Phase
another 110 0
(FCC solid Diagrams of Binary Nickel Alloys , P. Nash
(Ed.), ASM International, Materials Park,
solution) OH (1991).
Note change in 100 0
melting point 0 20 40 60 80 10 0 wt% Ni
 PHASE DIAGRAMS: Composition and Types of
Phases
• Rule 1: If we know T and Co, then we know:
--the types of phases present.

• Examples:
A:
1 phase ()

B:
2 phases (L + )

Cu-Ni
phase
diagram
PHASE DIAGRAMS: composition of phases
• Rule 2: If we know T and Co, then we know:
--the composition of each phase. Cu-Ni
system
Examples:
• C0 = 35 wt% Ni
• At 1300 C:
– Only liquid (L)
– CL = C0 (= 35 wt% Ni)
• At 1150 C:
– Only solid ()
– C = C0 (= 35 wt% Ni)
• At TB:
– Both  and L
– CL = Cliquidus (= 32 wt% Ni)
– C = Csolidus (=43 wt% Ni)
 PHASE DIAGRAMS: Weight fractions of phases
• Rule 3: If we know T and Co, then we know:
--the amount of each phase (given in wt%). Cu-Ni
• C0 = 35 wt% Ni system
• At 1300 C:
– Only liquid (L)
– WL = 100 wt%, W = 0 wt%
• At 1150 C:
– Only solid ()
– WL = 0 wt%, W = 100 wt%
• At TB:
– Both  and L
– WL = S/(R+S) =
(43-35)/(43-32) = 73 wt%
– W = R/(R+S) =
The lever rule
(35-32)/(43-32) = 27 wt%
 NON-EQUILIBRIUM PHASES
• C changes as we solidify.
• Cu-Ni case: First  to solidify has C = 46wt%Ni.
Last  to solidify has C = 35wt%Ni.

• Fast rate of cooling: • Slow rate of cooling:
Cored structure Equilibrium structure
Uniform C :
First  to solidfy:
35wt%Ni
46wt%Ni

Last  to solidfy:
< 35wt%Ni
 Pb-Sn EUTECTIC SYSTEM (1)
• For a 40wt%Sn-60wt%Pb alloy at 150C, find...
Pb-Sn
--the phases present T(°C) system

--the compositions of 3 00
L (liquid)
the phases
 L + 
2 00 183 癈 L+ 
--the relative amounts 18.3 61.9 97.8
of each phase 150

1 00 

0 20 40 60 80 10 0
Co
Adapted from Fig. 9.7, C o , wt% Sn
Callister 6e. (Fig. 9.7 adapted
from Binary Phase Diagrams , 2nd ed., Vol. 3, T.B. Massalski
(Editor-in-Chief), ASM International, Materials Park, OH,
1990.)
 EX: Pb-Sn EUTECTIC SYSTEM (2)
• For a 40wt%Sn-60wt%Pb alloy at 150C, find...
--the phases present: Pb-Sn
+ system
--the compositions of
the phases:
C = 11wt%Sn
C = 99wt%Sn
--the relative amounts
of each phase:
(lever rule)

59
W   67 wt %
88
29
W   33 wt %
Adapted from Fig. 9.7,
Callister 6e. (Fig. 9.7 adapted
88 from Binary Phase Diagrams , 2nd ed., Vol. 3, T.B. Massalski
(Editor-in-Chief), ASM International, Materials Park, OH,
1990.)
 MICROSTRUCTURES
IN EUTECTIC SYSTEMS-I
• Co < 2wt%Sn

• Result:
--polycrystal of  grains.

Adapted from Fig. 9.9,

Callister 6e.
 MICROSTRUCTURES
IN EUTECTIC SYSTEMS-II
• 2wt%Sn < Co < 18.3wt%Sn

• Result:
-- polycrystal with fine
 crystals.

Pb-Sn
system

Adapted from Fig. 9.10,

Callister 6e.
 MICROSTRUCTURES
IN EUTECTIC SYSTEMS-III
• Co = CE (Eutectic composition)
• Result: Eutectic microstructure
--alternating layers of  and  crystals.

Pb-Sn
system

Adapted from Fig. 9.12,Callister 6e.

(Fig. 9.12 fromMetals Handbook , Vol. 9,
Metallography and
9th ed.,
Microstructures , American Society for
Metals, Materials Park, OH, 1985.)
Adapted from Fig. 9.11,
Callister 6e.
 MICROSTRUCTURES
IN EUTECTIC SYSTEMS-IV
• 18.3wt%Sn < Co < 61.9wt%Sn
• Result:  crystals and a eutectic microstructure
Just above T E:
C  = 18.3wt%Sn
C L = 61.9wt%Sn
Pb-Sn W=
S
=50wt%
system R + S
W L = (1- W ) =50wt%

Just below T E:
C  = 18.3wt%Sn
C  = 97.8wt%Sn
S
W= =73wt%
R + S
Adapted from Fig. 9.14,
Callister 6e.
W  = 27wt%
 HYPOEUTECTIC & HYPEREUTECTIC

Adapted from Fig. 9.7,

Callister 6e. (Fig. 9.7
adapted fromBinary
Phase Diagrams , 2nd ed.,
Vol. 3, T.B. Massalski
(Editor-in-Chief), ASM
International, Materials
Park, OH, 1990.)

(Figs. 9.12 and 9.15

fromMetals
Handbook , 9th ed.,
Vol. 9,
Metallography and
Microstructures ,
American Society
for Metals, Materials
Park, OH, 1985.)

Adapted from Adapted from Fig. 9.15,

Fig. 9.15,Callister 6e. Adapted from Fig. 9.12, Callister 6e. (Illustration
Callister 6e. only)
 IRON-CARBON (Fe-C) PHASE DIAGRAM

• Pure iron: 3 solid

phases
– BCC ferrite ()
– FCC Austenite ()
– BCC 
• Beyond 6.7% C
cementite (Fe3C)
• Eutectic: 4.3% C
– L    Fe3C
– (L  solid  solid)
• Eutectoid: 0.76% C
–     Fe3C
– (solid  solid 
solid)
Fe-C PHASE DIAGRAM: EUTECTOID POINT

Pearlite microstructure:
Just below the eutectoid
point
 EUTECTOID POINT: LEVER RULE

• Just below the

eutectoid point:

• W = (6.7-0.76)/
(6.7-0.022) = 89%

• WFe3C = (0.76-0.022)/
(6.7-0.022) = 11%
HYPOEUTECTOID STEEL

Proeutectoid :
 phase formed at T > Teutectoid
HYPEREUTECTOID STEEL
Invariant Reactions
 Important Terms – Phase Diagrams
Eutectic:
A eutectic mixture is defined as a mixture of two or more
components which usually do not interact to form a new
chemical compound but, which at certain ratios, inhibit the
crystallization process of one another resulting in
a system having a lower melting point than either of the
components (Liquid to Solid)
Eutectoid:
Eutectoid refers to a homogeneous solid mixture that forms
from cooling two or more melted metals to a certain
temperature (Solid to Solid)
Eutectic Point: The eutectic temperature is the lowest
possible melting temperature for all of the mixing ratios of
the component substances in a eutectoid
 Important Terms – Phase Diagrams
(Contd..)
Hypo Eutectic: If the alloys composition places it to
the left of eutectic point then it is called
“Hypoeutectic”

Hyper Eutectic: If the alloys composition places it to

the right of eutectic point then it is called
“Hypereutectic”
 Important Terms – Phase Diagrams
(Contd..)
• Peritectic: Liquid + solid react to form another solid phase
• Peritectoid: Two solid phases react to form another solid

phase
• Monotectic: One liquid phase form another liquid phase and

solid phase
• Pro eutectoid: α phase formed at a temperature more than

eutectoid temperature
 Important Terms – Phase Diagrams
(Contd..)

Liquidus: Boundary between Liquid and Liquid + (α

or β) Solid Phases

Solidus: Boundary between Solid and Liquid + Solid

(α or β) phases

Solvus: Boundary between solid (α or β) and Solid

(α+β) Phases

Tie Line: The line joining Liquidus and Solidus

 Fe-C Phase diagram (Contd..)
• Ferrite : Alpha Phase (Fe2O3), Forms by Slow
cooling of Austenite associated with rejection of Carbon by
diffusion
• Austenite : Gama phase of Fe; Formed by diffusion of
carbon atoms from cementite to ferrite
• Delta Fe : Molten Iron cools down and solidifies at
1538 deg.C to form delta Fe
• Cementite : Fe3C
• Pearlite : Pearlite is a two phased, lamellar (or
layered) structure composed of alternating layers of ferrite( α)
and cementite (Fe3C) that occurs in some steels and cast
irons
 Carbon Steels
Type of Steel Carbon % age Structure Property/
Application
Mild Steel 0.1 to 0.2 75% Pro eutectoid ferrite High tensile and impact
and 25% Pearlite strength/
Rivets, car bodies,
Bridges, nails

Medium Carbon Steels 0.6 to 0.8 Pro eutectoid cementite Low hardnebility/
and Pearlite Saw cutters, hammers,
Rails

White Cast Iron (CI) >2 White CI – Pearlite and Very hard and brittle/
cementite cement mixers, ball mills

Gray Cast Iron (CI) >2 Graphite flakes and Brittle under tensile
ferrite loads/Pumps, IC
engines cylindrical
blocks

Malleable Cast Iron (CI) >2, Si ≥ 2.5 Spheroidal graphite (SG) Good ductility and
iron, Mg, Molten iron toughness/pipe fittings,
tools
Effect of Alloy Elements on Steel
 Applications of Phase Diagrams
• Zone Refining
• Making Cast Iron is easier and economical
• In cold countries, the depression of the freezing point of

water by the addition of salt is used to melt ice on roads

• Pb-Sn eutectic alloys are useful as soldering material
• Low melting eutectic alloys are used as safety devices in
fire
fighting equipment and petroleum storage tanks
• Gold-silicon eutectic finds uses in semi-conductor
Zone Refining (Pg No. 170 of V.Raghavan,
Material Science and Engineering)
 Zone Refining (Contd..)
• Objective : To Purify A
• Principle of phase separation is used for purifying A
• At the composition c0 the material starts solidifying at T1
• At the temperature below T1, a small quantity of solid
composition cs’ purer in A than c0 separates from the liquid
• Stop cooling further throw away the liquid part and remelt
the
left over solid
• This small quantity of liquid is purer at its concentration cs’
and it will now start solidifying at higher temperature T2
• The composition at T2 is cs”. Repeating the sequence of
operation a few times we can get pure A
 Zone Refining (Contd..)
Method:
• Material to be purified is in the form of a long rod
• Small length of this rod is melted with the aid of
induction coil
• The coil is moved slowly from one end to other end
of the rod
• The molten zone is continuously solidified and
fresh head is remelted
• Surface tension forces hold the molten zone
• The impurity level can be reduced to as low as
10**(-06)
• This technique produces ultra high purity materials –
semiconductor industries
Zone Refining (Contd..)
 SUMMARY
• Phase diagrams are useful tools to determine:
--the number and types of phases,
--the wt% of each phase,
--and the composition of each phase
for a given T and composition of the system.
• Alloying to produce a solid solution usually
--increases the tensile strength (TS)
--decreases the ductility.
• Binary eutectics and binary eutectoids allow for
a range of microstructures.
Thank You