Module 2.

Binary Phase Diagram

1. Binary phase diagram and Gibbs free
energy, a review
2. The Phase Rule
3. Binary Phase Diagram
a. Isomorphous system
b. Isomorphous system with miscibility gap
c. Eutectic system
d. Peritectic system
e. Monotectic system
f. Complex phase diagrams

Reading: Chapter 1.5 Porter and Easterling

Learning Outcomes
After learning this module, students are expected to:

1. Be able to derive a binary phase diagram from the concept of equilibrium in

terms of ΔG (C3).
2. Understand the concept of Phase Rule (C2).
3. Be able to calculate the phase amount of a binary system by using the
Lever Rule (C3).
4. Be able to illustrate the phase transformation in an isomorphous system
(C4)
5. Be able to illustrate the phase transformation in an isomorphous system
with miscibility gap (C4).
6. Be able to illustrate the phase transformation in a eutectic system (C4)
7. Be able to illustrate the phase transformation in a peritectic system (C4)
8. Be able to illustrate the phase transformation in an monotectic system (C4)
9. Be able to illustrate the phase transformation in a complex system involving
solid-to-solid reaction (C4)

Dept. Metallurgy and Materials

University of Indonesia
Binary phase diagram and Gibbs free energy, a review

 A binary phase diagram is a

temperature - composition
map which indicates the
equilibrium phases present
at a given temperature and
composition.
 The equilibrium state can be
found from the Gibbs free
energy dependence on
temperature and
composition.

 We have discussed the

dependence of G of a one
component system on T:

Dept. Metallurgy and Materials

University of Indonesia
Binary phase diagram and Gibbs free energy, a review

 We have also
discussed the
dependence of the
Gibbs free energy from
composition at a given
T:

Dept. Metallurgy and Materials

University of Indonesia
 Binary solutions with unlimited solubility
 Let’s construct a binary phase diagram
for the simplest case: A and B
components are mutually soluble in any
amounts in both solid (isomorphous
system) and liquid phases, and form
ideal solutions.
 We have 2 phases – liquid and solid.
Let’s consider Gibbs free energy curves
for the two phases at different T.
 T1 is above the equilibrium melting
temperatures of both pure components:
T1 > Tm(A) > Tm(B) > the liquid phase
Gstep 2 = Gstep 1 + ΔGmix
will be the stable phase for any
composition. Gstep 1 = XA GA + XB GB

Dept. Metallurgy and Materials

University of Indonesia
 Binary solutions with unlimited solubility
Decreasing the temperature below T1 will have two effects:
• GAliquid and GBliquid will increase more rapidly than GAsolid and GBsolid liquid.
Why?
• The curvature of the G(XB) curves will decrease. Why?
Eventually we will reach T2 – melting point of pure component A, where
GAliquid = GBsolid

Dept. Metallurgy and Materials

University of Indonesia
 Binary solutions with unlimited solubility
For even lower temperature T3 < T2
= Tm(A) the Gibbs free energy
curves for the liquid and solid phases
will cross.

As we discussed before, the

common tangent construction can
be used to show that for
compositions near cross-over of
Gsolid and Gliquid, the total Gibbs
free energy can be minimized by
separation into two phases.

Dept. Metallurgy and Materials

University of Indonesia
 Binary solutions with unlimited solubility
As temperature decreases below T3, GAliquid and GBliquid continue to
increase more rapidly than GAsolid and GBsolid .
Therefore, the intersection of the Gibbs free energy curves, as well as
points X1 and X2 are shifting to the right, until, at T4 = Tm(B) the curves
will intersect at X1 = X2 = 1
At T4 and below this
temperature the Gibbs free
energy of the solid phase
is lower than the G of the
liquid phase in the whole
range of compositions –
the solid phase is the only
stable phase.

Dept. Metallurgy and Materials

University of Indonesia
Dept. Metallurgy and Materials
University of Indonesia
Binary solutions with unlimited solubility
Example of isomorphous system: Cu-Ni (the complete solubility
occurs because both Cu and Ni have the same crystal structure, FCC,
similar radii, electronegativity and valence).

Liquidus line separates

liquid from liquid + solid
Solidus line separates solid
from liquid + solid

Dept. Metallurgy and Materials

University of Indonesia
Terminology
 Component: chemically recognizable species (Fe and C in carbon steel, H2O and
NaCl in salted water), which are mixed initially. A binary alloy contains two
components, a ternary alloy – three, etc.
 A phase is a portion of a system that has uniform properties and composition and
physically and chemically distinct material with a given chemical composition and
structure.
 For solids: Chemically and structurally distinct
 For liquids: Miscibility
 For gases: Always 1 phase
 Solvent: in an alloy, the element or compound present in greater amount
 Solute: in an alloy, the element or compound present in lesser amount.
 Solid Solution are made of a host (the solvent or matrix) which dissolves the
minor component (solute). The ability to dissolve is called solubility.
 homogeneous
 maintains crystal structure
 contains randomly dispersed impurities (substitutional or interstitial)

Dept. Metallurgy and Materials

University of Indonesia
Terminology, cont….
 Second Phase: as solute atoms are added, new compounds /
structures are formed, or solute forms local precipitates.
 Liquidus: Temperature at which alloy is completely liquid or
solidification begins
 Solidus: Temperature at which alloy is completely solid or
liquefaction begins.
 Solubility Limit of a component in a phase is the maximum
amount of the component that can be dissolved in it (e.g. alcohol
has unlimited solubility in water, sugar has a limited solubility, oil is
virtually insoluble). The same concepts apply to solid phases: Cu
and Ni are mutually soluble in any amount (unlimited solid
solubility), while C has a limited solubility in Fe.
 Isomorphous: when the two components have complete liquid
and solid solubility (unlimited solid solubility).

Dept. Metallurgy and Materials

University of Indonesia
The Phase Rule
 Propounded by W. Gibbs (1928), underlies the study of
phase equilibria and is of basic importance in the
representation of such equilibria by means of equilibrium
phase diagrams.

P + F = C +2 (for P and V variable)

F=C–P+2

 P = number of phases, C = number of components, F =

degrees of freedom.

 For P = fixed: P + F = C + 1
F = C – P +1

Dept. Metallurgy and Materials

University of Indonesia
One-Component Phase Diagrams

Dept. Metallurgy and Materials

University of Indonesia
Two-Component Phase Diagrams
Isomorphous system
( complete solubility over the
composition range)

F=C–P+1
If pressure is fixed (1 atm)

In a two-phase field need to

specify either the temperature
or the composition of one of the
phases.

Dept. Metallurgy and Materials

University of Indonesia
Champions aren’t made in gyms.
Champions are made from something they
have deep inside them—a desire, a dream,
a vision. They have to have last-minute
stamina, they have to be a little faster,
they have to have the skill and the will.
But the will must be stronger than the
skill.” (Muhammad Ali)

Dept. Metallurgy and Materials

University of Indonesia
Binary Phase Diagram
 Isomorphous system
 Isomorphous system with miscibility gap
 Eutectic system
 Peritectic system
 Monotectic system
 Complex phase diagrams
 Phase equilibria involving solid-to-solid
reactions
Dept. Metallurgy and Materials
University of Indonesia
Isomorphous System: Binary solutions with unlimited
solubility
In one-component system melting occurs at a well-defined
melting temperature.

In multi-component
systems melting occurs
over the range of
temperatures, between
the solidus and liquidus
lines. Solid and liquid
phases are in equilibrium
in this temperature
range.

Dept. Metallurgy and Materials

University of Indonesia
 Isomorphous System: Binary solutions with unlimited
solubility
Let’s derive development of microstructure in isomorphous
alloys, Cu-35Ni, during equilibrium (very slow) cooling.
Work in pairs!

Dept. Metallurgy and Materials

University of Indonesia
How does
phase
rule work
in this
system?

Dept. Metallurgy and Materials

University of Indonesia
Interpretation of Phase
Diagrams
 For a binary system of known composition and
temperature that is at equilibrium, at least three kinds
of information are available:
 Phase present
 Composition of the phases
 Percentage or fraction of the phase
 Phase present is determined by locating the
temperature-composition point on the diagram and
notes the phase(s) which the corresponding labeled
phase field (see example of copper-nickel phase
diagram).

Dept. Metallurgy and Materials

University of Indonesia
Phase Present

Dept. Metallurgy and Materials

University of Indonesia
Phase Compositions
 For one phase, the composition is
simply the same as the overall
composition of the alloy. For example,
point A in Cu-Ni phase diagram, the
composition is 60 wt% Ni – 40 wt%
Cu.
 For two-phase region, the composition
is determined from the tie line, which
extend across the two-phase region
and terminate at the phase boundary
lines on either side.

 For example, composition of 35 wt% Ni – 65 wt% Cu alloy at 1250C,

located at point B and lying within the a + L region. The problem is to
determine both the a and liquid phase.
 After constructing the tie line, the liquidus meets the composition
axis at 32 wt% Ni – 68 wt% Cu (CL), and for the solidus-tie line
intersection, we find Ca at 43 wt% Ni – 57 wt% Cu.

Dept. Metallurgy and Materials

University of Indonesia
Phase Amounts
 For single phase, the alloy is composed
entirely at of that phase, i.e. the phase
fraction is 1.0, or 100%.
 For two-phase region, the amount is again
determined with the aid of tie line in
conjunction with a procedure called lever
rule, in which the fraction of one phase is
computed by taking the length of tie line
from the overall alloy composition to the
phase boundary for the other phase, and
dividing by the total tie line length.

 In the employment of the lever rule, tie line segment lengths may be
determined either by direct measurement from the phase diagram using
linear scale, or by substracting composition as taken from the composition
axis.

Dept. Metallurgy and Materials

University of Indonesia
Phase Amounts, cont…

Concept of tie line

Dept. Metallurgy and Materials

University of Indonesia
Phase Amounts, cont…

Dept. Metallurgy and Materials

University of Indonesia
Isomorphous System: Binary solutions with unlimited
solubility
Cored vs Equilibrium Solid Phases
Ca changes as we solidify
Cu-Ni case:
First a to solidify has Ca = 46wt%Ni
Last a to solidify has Ca = 35wt%Ni

Fast rate of cooling: Slow rate of cooling:

Cored structure Equilibrium structure
Dept. Metallurgy and Materials
University of Indonesia
Isomorphous System: Binary solutions with unlimited
solubility

Mechanical Properties: Cu-Ni System

• Effect of solid solution strengthening on:
-Tensile Strength (TS) and Ductility (%EL, %AR)

Dept. Metallurgy and Materials

University of Indonesia
Dept. Metallurgy and Materials
University of Indonesia
 Application
Cu-Ni Alloy compositions (wt. %)
C70600 C71500 C71640 C72200
Element Range Range Range Range
NI 9.0 - 11.0 29.0 - 33.0 29.0 - 32.0 15.0 - 18.0
Cr - - - 0.3 - 0.7
Fe 1.0 - 1.8 0.4 - 1.0 1.7 - 2.3 0.5 - 1.0
Mn 1.0 max 1.0 max 1.5 - 2.5 1.0 max
Zn 1.0 Max 1.0 max - -
Pb 0.05 max 0.05 max 0.01 max -
Si - - - 0.03 max
C - - 0.06 max 0.03 max
Ti - - - 0.03 max
S - - 0.03 max -
Cu Balance Balance Balance Balance

Dept. Metallurgy and Materials

University of Indonesia
 Application
Seawater cooled heat exchangers
Two basket type
strainers in a large
desalination plant

Find out the real microstructure

of Cu-Ni alloys!

Dept. Metallurgy and Materials

University of Indonesia
Binary Phase Diagram
 Isomorphous system
 Isomorphous system with miscibility gap
 Eutectic system
 Peritectic system
 Monotectic system
 Complex phase diagrams
 Phase equilibria involving solid-to-solid
reactions
Dept. Metallurgy and Materials
University of Indonesia
Isomorphous System with Miscibility Gap

What’s miscibility? ………………….

Let’s consider a system in which the liquid phase is

approximately ideal, but for the solid phase we
have ΔHmix > 0  What does it mean?

Dept. Metallurgy and Materials

University of Indonesia
At low temperatures, there is a region where the solid solution is
most stable as a mixture of two phases α1 and α2 with
compositions X1 and X2. This region is called a miscibility gap.

Dept. Metallurgy and Materials

University of Indonesia
Congruent Melting Minimum

Deviation from ideal behavior

Dept. Metallurgy and Materials

University of Indonesia
Congruent Melting Maximum

Deviation from ideal behavior

Dept. Metallurgy and Materials

University of Indonesia
 Binary Solutions with a Miscibility Gap

Ordered Au3Cu Disordered Au3Cu

Dept. Metallurgy and Materials

University of Indonesia
Exsolution Perthite structure

Orthoclase  orange
Albite  yellow

Albite Orthoclase

Dept. Metallurgy and Materials

University of Indonesia
Binary Phase Diagram
 Isomorphous system
 Isomorphous system with miscibility gap
 Eutectic system
 Peritectic system
 Monotectic system
 Complex phase diagrams
 Phase equilibria involving solid-to-solid
reactions
Dept. Metallurgy and Materials
University of Indonesia
 Binary Solutions: Eutectic System
For an even
larger ΔHmix
the miscibility
gap can extend
into the liquid
phase region. In
this case we
have eutectic
phase
diagram.

Liquid  a1 (solid) + a2 (solid) Dept. Metallurgy and Materials

University of Indonesia
 Eutectic System

Liquid  a (solid) +  (solid)

Dept. Metallurgy and Materials

University of Indonesia
Eutectic System

Dept. Metallurgy and Materials

University of Indonesia
 Please do the
exercise
a.Label all the phase fields.
b.Determine the isothermal
reaction at 175 oC.
c.Sketch the evolution of
microstructure during
equilibrium cooling of Pb-
40Sn at T = 300, 209, just
above 175, just below 175,
and 100 oC.
d.Calculate the phase fraction
at each temperature above.
e.Determine the composition
of each phase at each
temperature above.

Dept. Metallurgy and Materials

University of Indonesia
 All liquid

209 oC

Proeutetic a solidifying

175 oC

Dept. Metallurgy and Materials

University of Indonesia
Microstructure development in two-phase alloy: a
hipoeutectic Pb – 40% Sn alloy
 Liquid at 3000C.
 At about 2090C first solid
forms – proeutectic solid.
 Slightly above 1750C
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.

•(They try to move to equilibrium)

Dept. Metallurgy and Materials

University of Indonesia
Microstructure development in two-
phase alloy: a hipoeutectic Pb-30% Sn

Dept. Metallurgy and Materials

University of Indonesia
Microstructure development in the
eutectic Pb-51.9% Sn

Dept. Metallurgy and Materials

University of Indonesia
Pb-70Sn Pb-61.9Sn

Pb-60Sn Pb-50Sn
Dept. Metallurgy and Materials
University of Indonesia
Microstructure Above and Below the Eutectic
Temperature for an Off-Eutectic Alloy

Just above TE Just below TE

Dept. Metallurgy and Materials

University of Indonesia
Various Eutectic Structures
 Structure depends on
factors like
minimization of free
energy at α / β
interface.
 Manner in which two
phases nucleate and
grow also affects
structures.

Dept. Metallurgy and Materials

University of Indonesia
 SEM microstructures in
longitudinal section for the
Cu-12wt. % Ag wires (a)
drawn to n=7.0 and
annealed at (b) 300, (c) 400
and (d) 500 oC for 1 h

Ref: http://www.paper.edu.cn
Optical microstructures of the Cu-12wt. % Ag Dept. Metallurgy and Materials
alloy (a) as-cast and (b) homogenized. University of Indonesia
Sketch the
evolution of
microstructure
during equilibrium
cooling of:
•Al-8Si,
•Al-12Si
•Al-20Si
•Al-50Si
Find out the alloys’
AISI designation!

Dept. Metallurgy and Materials

University of Indonesia
8 % Si 20 % Si 100 % Si

0 % Si 12 % Si 50 % Si Dept. Metallurgy and Materials

University of Indonesia
Dept. Metallurgy and Materials
University of Indonesia
Dept. Metallurgy and Materials
University of Indonesia
Al-8Si-2Cu-0.12Mg
0 wt. % Sr 0.02 wt. % Sr

Dept. Metallurgy and Materials

University of Indonesia
Pb-1.7Sb, Pb-6.5Sb, Pb-11.5Sb, Pb-12.25Sb !

Dept. Metallurgy and Materials

University of Indonesia
 Pb-1.7 % Sb

Dept. Metallurgy and Materials

University of Indonesia
6.5 % Sb 11.5 % Sb
(eutectic)

12.25 % Sb
Dept. Metallurgy and Materials
University of Indonesia
Binary Phase Diagram
 Isomorphous system
 Isomorphous system with miscibility gap
 Eutectic system
 Peritectic system
 Monotectic system
 Complex phase diagrams
 Phase equilibria involving solid-to-solid
reactions
Dept. Metallurgy and Materials
University of Indonesia
Peritectic System
Peritectic Reaction: A three-phase reaction by which, on
cooling, two phases (one of them liquid) react to give a
single new solid phase.

Liquid + Solid a  Solid 

Dept. Metallurgy and Materials

University of Indonesia
 Peritectic reaction: Liquid phase reacts with a solid phase to form a new
and different solid phase.
Liquid + α β
cooling
• Peritectic reaction occurs
when a slowly cooled alloy
of Fe-4.3 wt% Ni passes
through Peritectic
temperature of 1517C.
• Peritectic point is invariant.

cooling
Liquid(5.4 wt% Ni) + δ (4.0 wt% Ni) γ 4.3 wt % Ni

Dept. Metallurgy and Materials

University of Indonesia
The Use of Cooling Curves for Determining a Peritectic
Phase Diagram

Dept. Metallurgy and Materials

University of Indonesia
 Peritectic System
 At 42.4 % Ag & 14000C
Phases present Liquid Alpha
Composition 55% Ag 7%Ag
Amount of Phases 42.4 –7 55-42.4
55 – 7 55 - 7
= 74% = 26%
 At 42.4% Ag and 11860C – ΔT
Phase Present Beta only
Composition 42.4% Ag
Amount of Phase 100%

 At 42.4% Ag and 11860C + ΔT

Phases present Liquid Alpha
Composition 66.3% Ag 10.5%Ag
Amount of Phases 42.4 –10.5 66.3-42.4
66.3 – 10.5 66.3–10.5
= 57% =43%

Dept. Metallurgy and Materials

8-13 University of Indonesia
Rapid Solidification in Peritectic System
 Surrounding or Encasement: During peritectic reaction, L+ α  β , the beta
phase created surrounds primary alpha.
 Beta creates diffusion barrier resulting in coring.

Dept. Metallurgy and Materials

After F Rhines, “ Phase Diagrams in Metallurgy,”McGraw- Hill, 1956, p. 86. University of Indonesia
 Please do the
exercise
a.Label all the phase fields.
b.Determine the isothermal
reaction at T3.
c.Sketch the evolution of
microstructure during
equilibrium cooling of Alloy
3 at T1, T2, just above T3,
just below T3, T4.
d.Calculate the phase
fraction at each
temperature above.
e.Determine the composition
of each phase at each
temperature above.

Dept. Metallurgy and Materials

University of Indonesia
Binary Phase Diagram
 Isomorphous system
 Isomorphous system with miscibility gap
 Eutectic system
 Peritectic system
 Monotectic system
 Complex phase diagrams
 Phase equilibria involving solid-to-solid
reactions
Dept. Metallurgy and Materials
University of Indonesia
Monotectic Systems
 Monotectic Reaction: Liquid phase transforms into solid phase and another
liquid. L1 Cooling α + L2
• Two liquids are immiscible.
• Example: Copper – Lead
system at 9550C and 36% Pb.

Dept. Metallurgy and Materials

University
Metals Handbook,” vol. 8: “Metallography Structures and Phase Diagrams,” 8th ed., of Indonesia
American Society of Metals, 1973, p. 296.
Monotectic Systems

Dept. Metallurgy and Materials

University of Indonesia
Binary Phase Diagram
 Isomorphous system
 Isomorphous system with miscibility gap
 Eutectic system
 Peritectic system
 Monotectic system
 Complex phase diagrams
 Phase equilibria involving solid-to-solid
reactions
Dept. Metallurgy and Materials
University of Indonesia
 Intermediate Phases and Compounds

 Terminal phases: Phases occur at

the end of phase diagrams.
 Intermediate phases: Phases
occur in a composition range
inside phase diagram.
 Examples: Cu-Zn diagram has
both terminal and intermediate
phases.
 Five invariant peritectic points and
one eutectic point.

“Metals Handbook,” vol. 8: “Metallography Structures and Phase Diagrams,” 8th ed., American Society of Metals, 1973, p. 301

Dept. Metallurgy and Materials

University of Indonesia
Intermediate Phases in Ceramics

 In Al2O2 – SiO2
system, an
intermediate
phase called
Mullite is
formed, which
includes the
compound
3Al2O3.2SiO2.

After A. G. Guy, “Essentials of Materials Science, “McGraw-Hill, 1976 Dept. Metallurgy and Materials
University of Indonesia
Intermediate Compounds

 In some phase diagrams, intermediate compound are formed – Stoichiometric

 Percent Ionic/Covalent bond depends on electronegativeness
 Example:- Mg-Ni phase diagram contains
 Mg2Ni : Congruently melting compound
 MgNi2 : Incongruently melting compound.

Dept. Metallurgy and Materials

Metals Handbook,” vol. 8: American Society of Metals, 1973, p. 314. University of Indonesia
 Please do the Alloy 1

exercise T1

a.Label all the phase fields.

b.Determine the isothermal T2 T7
reaction at T3, T5, andT7. T3
c.Sketch the evolution of
microstructure during
T4
equilibrium cooling of Alloy
1 at T1, T2, just above T3,
just below T3, T4, just T5
above T5, just below T5 , T6

T6

Dept. Metallurgy and Materials

University of Indonesia
Dept. Metallurgy and Materials
University of Indonesia