Phase Diagrams

(for internal use only)

Habiburrahman (Zulfikri), S.Si., M.Sc., Ph.D.

Chemical Engineering Department,
Faculty of Engineering, Universitas Indonesia
Definitions and Basic Concepts
Components are pure metals and/or compounds of which an alloy is composed.
System may refer to
a) a specific body of material under consideration (e.g., a ladle of molten steel); or
b) the series of possible alloys consisting of the same components but without regard to
alloy composition (e.g., the iron–carbon system).
A phase is a homogeneous portion of a system that has uniform physical and chemical
characteristics. When two phases are present in a system, it is not necessary that there be
a difference in both physical and chemical properties; a disparity in one or the other set
of properties is sufficient. Ex: FCC iron and BCC iron are two different phases.
A single-phase system is termed homogeneous.
Systems composed of two or more phases are termed mixtures or heterogeneous
systems.
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Definitions and Basic Concepts: Example
A phase diagram of a
two-component
system: water and
sugar
Homogeneous (one
phase) on the left.
Heterogeneous (two
phases) on the right.
Solubility limit divide
the regions.
Solubility can be
pushed by raising
temperature.
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Unary phase diagrams
Curves aO, bO, and cO are
phase boundaries where two
phases on either side of the
curve are in equilibrium (or
coexist) with one another.
Process Transformation
Melting solid to liquid
Solidification liquid to solid
Sublimation solid to gas
Deposition gas to solid
Vaporization liquid to gas
Note: the logarithmic scale of the y-axis is common. Condensation gas to liquid

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Binary phase diagrams: isomorphous system
Three different phase regions, or fields,
appear on the diagram: an alpha (𝛼) field, a
liquid (L) field, and a two-phase 𝛼 + L field.
▪ The liquid L is a homogeneous liquid
solution composed of both copper and
nickel.
▪ The 𝛼 phase is a substitutional solid
solution consisting of both Cu and Ni atoms
and has an FCC crystal structure.
The copper–nickel system is termed
isomorphous because of this complete liquid
and solid solubility of the two components.
Note: solid solutions are commonly
designated by lowercase Greek letters

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Binary phase diagrams: phase composition
In all two-phase regions (and in two-
phase regions only), one may imagine a
series of horizontal lines, one at every
temperature; each of these is known as a
tie line, or sometimes as an isotherm.
At point B, the composition of the system
is 35 wt% Ni–65 wt% Cu.
The composition of the liquid phase (CL) is
31.5 wt% Ni–68.5 wt% Cu.
The composition of the solid phase (C𝛼) is
42.5 wt% Ni–57.5 wt% Cu.

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Binary phase diagrams: phase amounts (lever rule)
At point B, the composition of the system
(C0) is 35 wt% Ni–65 wt% Cu.
The composition of the liquid phase (CL) is
31.5 wt% Ni–68.5 wt% Cu.
The composition of the solid phase (C𝛼) is
42.5 wt% Ni–57.5 wt% Cu.
Liquid-phase mass fraction

𝛼-phase mass fraction

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Binary phase diagrams: multiphase alloys
For multiphase alloys, relative phase amount in terms of volume fraction is preferred since
a) Phase volume fractions may be determined from examination of the microstructure
b) The properties of a multiphase alloy may be estimated based on volume fractions.
In metal alloys, microstructure is characterized by the number of phases present, their
proportions, and the manner in which they are distributed or arranged.

Vα and Vβ are the volume fraction of phase α and β, respectively.

vα and vβ are the volume of the respective phase. 8
Isomorphous alloys: equilibrium cooling
The cooling occurs very slowly, in that phase
equilibrium is continuously maintained.
Composition (%) of the liquid and α phase:

Point α(Ni) α(Cu) L(Ni) L(Cu)

a - - 35 65
b 46 54 35 65
c 40 60 29 71
d 35 65 24 76
e 35 65 - -

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Isomorphous alloys: nonequilibrium cooling
In virtually all practical solidification situations,
cooling rates are much too rapid to allow these
compositional readjustments and maintenance
of equilibrium.
From b’ to c’, the composition of the 𝛼 grains
has continuously changed with radial position,
from 46 wt% Ni at grain centers to 40 wt% Ni at
the outer grain perimeters.
Thus, at point c′, the average composition of the
solid 𝛼 grains that have formed would be some
volume-weighted average composition lying
between 46 and 40 wt% Ni.
For example: 42 wt% Ni–58 wt% Cu [𝛼(42 Ni)]

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Isomorphous alloys: nonequilibrium cooling
The distribution of Cu and Ni within the grains is
nonuniform. The center of each grain is rich in the
high-melting element (Ni).
As the system having cored structure are reheated,
grain boundary regions melt first.
This produces a sudden loss in mechanical integrity
due to the thin liquid film that separates the grains.
This melting may begin at a temperature below the
equilibrium solidus temperature of the alloy.
Coring may be eliminated by a homogenization heat
treatment carried out at a temperature below the
solidus point for the particular alloy composition to
promote atomic diffusion producing
compositionally homogeneous grains.
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Isomorphous alloys: mechanical properties

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Binary eutectic systems
The 𝛼 phase solid solution rich
in copper, silver is the solute.
The 𝛽-phase solid solution rich
in silver, copper is the solute.
Solid solubility limits:
• a solvus line (ex: BC and GH)
• a solidus line (ex: AB and FG)
As silver is added to copper, the
temperature at which the
alloys become totally liquid
decreases along the liquidus
line, line AE; thus, the melting
temperature of copper is
lowered by silver additions.

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Binary eutectic systems
The 𝛼 phase solid solution rich
in copper, silver is the solute.
The 𝛽-phase solid solution rich
in silver, copper is the solute.
Eutectic (easily melted) reaction:

Why is 8.0% + 91.2% is not 100%?

E is the eutectic point.
CE and TE are the eutectic composition
and temperature. 14
Binary eutectic systems: Phase Compositions
For a 40 wt% Sn–60 wt% Pb alloy at
150°C (point B), both 𝛼 and 𝛽
phases will coexist.
The composition of the 𝛼 phase (C𝛼)
is 11 wt% Sn–89 wt% Pb.
The composition of the 𝛽 phase (C𝛽)
is 98 wt% Sn–2 wt% Pb.
Mass fraction of each phase:

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Binary eutectic systems: Phase Compositions
Volume fraction
Density of each phase of each phase:

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Binary eutectic systems: microstructure devel
Case 1 Case 2

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Binary eutectic systems: microstructure devel
Case 3: Cooling from the eutectic
composition.

Eutectic
structure forms
upon cooling.

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Binary eutectic systems: microstructure devel
Case 4: Cooling from the eutectic
composition.

To distinguish one 𝛼 from the

other, two microconstituents are
introduced
• eutectic 𝛼 resides in the eutectic
structure
• primary 𝛼 the ones formed prior
to crossing the eutectic isotherm

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Binary eutectic systems: microstructure devel
The mass fraction of the eutectic alpha, We

The mass fraction of the primary 𝛼, W𝛼′

The mass fraction of total 𝛼, W𝛼

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Diagrams with intermediate phases/compounds
There are six different
solid solutions—two
terminal (𝛼 and 𝜂) and
four intermediate (𝛽, 𝛾,
𝛿, and 𝜀).
The 𝛽′ phase is termed
an ordered solid
solution, one in which
the copper and zinc
atoms are situated in a
specific and ordered
arrangement within
each unit cell.
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Diagrams with intermediate phases/compounds
The intermetallic compound Mg2Pb
has a composition of 19 wt% Mg–
81 wt% Pb (33 at% Pb) and is
represented as a vertical line.
The solubility of Pb in Mg is rather
extensive (large composition span
for the 𝛼-phase field).
The solubility of Mg in Pb is
extremely limited.
This phase diagram may be thought
of as two simple eutectic diagrams
joined back-to-back, as such, the
compound Mg2Pb is really
considered to be a component.
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Eutectoid and Peritectic Reactions
Eutectoid reaction:

Peritectic reaction:

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Congruent phase transformations

Phase transformations for which there are no

compositional alterations are said to be
congruent. Example: allotropic
transformations and melting of pure materials.
Eutectic and eutectoid reactions, melting of an
alloy that belongs to an isomorphous system
represent incongruent transformations.
There is a congruent melting point for the 𝛾
solid solution that corresponds to the point of
tangency for the pairs of liquidus and solidus
lines, at 1310°C and 44.9 wt% Ti.

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The Gibbs phase rule

P is the number of phases present.

F is the number of degrees of freedom or the number of externally controlled
variables (e.g., temperature, pressure, composition) that must be specified to
define the state of the system completely.
C represents the number of components in the system.
N is the number of noncompositional variables (e.g., temperature and pressure)

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The Gibbs phase rule: example

Pressure is constant, temperature is

the only noncompositional variable.
N=1
C = 2 as we have Cu and Ag
For the case of single-phase fields
on the phase diagram (e.g., 𝛼, 𝛽,
and liquid regions), P = 1.
F = 2, which means that to
completely describe the
characteristics within one of these
phase fields, we must specify two
parameters—composition and
temperature.
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The Gibbs phase rule: example

For the case of two-phase fields (𝛼 + L, 𝛽 + L,

and 𝛼 + 𝛽), F = 1
It is necessary to specify either temperature or
the composition of one of the phases to
completely define the system.
For a fixed T1, the overall alloy composition
could lie anywhere along the tie line
constructed at temperature T1 and still give C𝛼
and CL compositions for the respective 𝛼 and
liquid phases.
At eutectic point, F = 0, no degrees of freedom.
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The Fe—Fe3C phase diagram
Pure Iron:
• At room temperature, the
phase is 𝛼-iron (ferrite)
having BCC crystal structure.
• At 912°C (1674°F), a
polymorphic transformation
to FCC austenite, or 𝛾-iron
occurs.
• At 1394°C (2541°F), a
polymorphic transformation
to BCC 𝛿-ferrite.
• At 1538°C (2800°F), 𝛿-ferrite
melts.
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The Fe—Fe3C phase diagram
In practice, all steels and cast
irons have less than 6.70 wt% C.
Carbon is an interstitial impurity
in iron and forms a solid
solution with iron.
In the BCC 𝛼-ferrite, the
maximum solubility of carbon is
0.022 wt% at 727°C (1341°F).
In the FCC austenite, the
maximum solubility of carbon is
2.14 wt% at 1147°C (2097°F).
The FCC octahedral sites are
larger than the BCC tetrahedral
sites. 29
The Fe—Fe3C phase diagram
Cementite (Fe3C) forms when
the solubility limit of carbon in
𝛼-ferrite is exceeded below
727°C (1341°F)
Mechanically, cementite is very
hard and brittle; the strength of
some steels is greatly enhanced
by its presence.
Strictly speaking, cementite is
only metastable. if heated to
between 650°C and 700°C for
several years, it gradually
transforms into 𝛼-iron and
graphite, which remains upon
subsequent cooling to room
temperature.
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The Fe—Fe3C phase diagram
One eutectic exists for the iron–
iron carbide system, at 4.30
wt% C and 1147°C (2097°F)

A eutectoid invariant point

exists at a composition of 0.76
wt% C and a temperature of
727°C (1341°F)

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The Fe—Fe3C phase diagram
Three types of ferrous alloys:
• Pure iron contains less than
0.008 wt% C and (ferrite
phase at room temperature).
• Steels contain between 0.008
and 2.14 wt% C. in practice,
carbon concentrations rarely
exceed 1.0 wt%
• Cast irons contain between
2.14 and 6.70 wt% C. They
normally contain less than 4.5
wt% C.

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The Fe—Fe3C phase diagram: cooling
The microstructure at point b, is called pearlite because
it has the appearance of mother-of-pearl when viewed
under the microscope at low magnifications.
The pearlite exists as grains, often termed colonies.
Carbon atoms diffuse
away from the 0.022-
wt% ferrite regions
and to the 6.70-wt%
cementite layers, as
the pearlite extends
from the grain
boundary into the
unreacted austenite
grain.
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The Fe—Fe3C phase diagram: cooling
Consider a composition C0 to the left of the eutectoid,
between 0.022 and 0.76 wt% C; this is termed a
hypoeutectoid (“less than eutectoid”) alloy.
Cooling from point d to e, just above the eutectoid but
still in the 𝛼 + 𝛾 region, enlarges the size of 𝛼 particles.
At this point, the compositions of the 𝛼 and 𝛾 phases
determined by constructing a tie line at the
temperature Te are the 0.022 wt% C and 0.76 wt% C,
respectively.
The ferrite present in the pearlite is called eutectoid
ferrite, whereas the other, which formed above Te, is
termed proeutectoid (meaning “pre- or before
eutectoid”) ferrite.

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The Fe—Fe3C phase diagram: cooling

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The Fe—Fe3C phase diagram: cooling

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THANK YOU

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