Phase Diagrams

• There is a strong correlation between

microstructure and mechanical properties, and the
development of microstructure of an alloy is related
to the characteristics of its phase diagram.
• Phase diagrams provide valuable information about
melting, casting, crystallization, and other
phenomena.
• Solid Solution consists of atoms of at least two
different types; the solute atoms occupy either
substitutional or interstitial positions in the solvent
lattice, and the crystal structure of the solvent is
maintained.

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Phase
• A phase may be defined as a homogeneous
portion of a system that has uniform physical
and chemical characteristics.
– A phase must be homogeneous in its crystal
structure and atomic arrangement.
– A phase must have the same physical and chemical
properties throughout.
– A phase must have a definite interface between its
surroundings.
– A phase must be mechanically separable.
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 Gibbs Phase Rule
• This rule represents a criterion for the number of
phases that will coexist within a system at
equilibrium, and is expressed by the simple
equation
F=C-P+2
F is the degrees of freedom: number of variables that
can be changed independently without altering the
number of phases that coexist at equilibrium.
C is the number of components,
P is the number of phases present,
2 implies that both variables the pressure and the
temperature are able to change.
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•Triple point: F=0

•At a melting point
on the line between
single-phase fields,
a solid and a liquid
phase may co-exist:
F=1.
• A point within one
of the single-phase
fields represents a
system that is
bivariant

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 • for most metals, vapor pressure is disregarded
and it is customary to use isobaric (constant
pressure) phase diagrams in which the
composition (concentration) of component
metals is plotted against temperature.

F=C-P+1

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Equilibrium
• A system is at equilibrium if its free energy is at a
minimum under some specified combination of
temperature, pressure, and composition.
• The characteristics of the system do not change
with time but persist indefinitely; that is, the
system is stable.
• A change in temperature, pressure, and/or
composition for a system in equilibrium will result
in an increase in the free energy and in a possible
spontaneous change to another state whereby the
free energy is lowered.
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 Solubility
• The amount of one substance that can be dissolved
(solute) into another (solvent) is its solubility.
• For a binary alloy:
 unlimited solubility,
 limited (partial) solubility, and
 no solubility.
 A single intermediate phase.
 A mixture of two intermediate phases.
 A solid solution and an intermediate phase mixed
together.

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Unlimited Solubility
• For two substances to have unlimited solubility, any
amount of either substance must be able to
dissolve completely into any amount of the other
substance.
• After the solution is thoroughly mixed, only one
phase is produced.
• This system is termed isomorphous because of
this complete liquid and solid solubility of the two
components.

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 Limited Solubility
• For limited solubility only a certain amount of one
substance may completely dissolve into the other
substance.
• Solubility limit: maximum concentration of solute
atoms that may dissolve in the solvent to form a
solid solution.
• The addition of solute in excess of this solubility
limit results in the formation of another solid
solution or compound that has a distinctly different
composition.
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 Immiscibility
• When two substances are insoluble, almost none of
either substance will dissolve in the other.
• Most materials will dissolve at least a tiny amount
of another component, but when the maximum
amount is small this is often described as insoluble.

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Equilibrium phase diagrams

• Equilibrium phase diagrams represent the relationships
between temperature and the compositions and the
quantities of phases at equilibrium.
• For a binary system of known composition and
temperature that is at equilibrium, at least three kinds
of information are available:
– the phases that are present,
– the compositions of these phases, and
– the percentages or fractions of the phases
• Atmospheric pressure.

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 Binary Isomorphous System
• liquidus line: the
geometrical locus of
the temperatures
indicating the start of
the freezing.
• Solidus line: the
geometrical locus of
the temperatures
indicating the end of
freezing, or complete
solidification.
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• At the melting points of pure

components:
F = 1-2+1=0, i.e. F=0 which
means we have zero degree
of freedom, or these
represent invariant points.
• Within the two-phase region
(L + SS) :
F = 2-2+1 = 1, there is a one
degree of freedom.
• In a single-phase region
(either L or SS) :
F = 2-1+1 = 2, there are two
degrees of freedom.

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 Construction of the Phase Diagram

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 • The area of the diagrams are called phase fields.
• On crossing any sloping line from one field to the
next, the number of phases will change by one.
• A phase which does not occupy a field by itself, but
appears only in a two phase field, is either a pure
metal or an intermediate phase (usually an
intermetallic compound) of invariable composition.

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Determination of Phase Composition

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 Determination of Phase Amount

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Development of Microstructure

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 Non Equilibrium Conditions

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• The distribution of the two elements within the

grains is non-uniform, a phenomenon termed
segregation.
• concentration gradients are established across the
grains.
• The center of each grain, which is the first part
to freeze, is rich in the high-melting element {e.g.,
nickel for this Cu-Ni system}, whereas the
concentration of the low-melting element increases
with position from this region to the grain
boundary.
• This is termed a cored structure.

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 • The properties of a cored structure are less than
optimal; as a casting having a cored structure is
reheated, grain boundary regions will melt first
inasmuch as they are richer in the low-melting
component. This produces a sudden loss in mechanical
integrity due to the thin liquid film that separates the
grains.
• Furthermore, 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.
• During this process, atomic diffusion occurs, which
produces compositionally homogeneous grains
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Mechanical Properties of Isomorphous

Alloys

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 Binary Eutectic Systems
• Eutectic Systems with no Solid Solution.
• Eutectic Systems with Limited Solid Solution.

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Eutectic Systems with no Solid Solution

• The two components, A & B,
are completely insoluble
in each other, and no solid
solution occurs.
• The solidus is a
horizontal line that
corresponds to the
eutectic temperature
and is called the
eutectic isotherm.
• Invariant point.
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 • The addition of either metal, lowers the melting point
of the other.
• The lowest attainable melting point, is at the eutectic
composition.
• Eutectic Liquid → Solid A + Solid B
• Every alloy completely solidified must be a mixture of
the two pure metals.
• Alloys to the left of the eutectic composition as
hypoeutectic alloys and those to the right as
hypereutectic alloys.

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 Alloy 1 will consist of
primary A (which
formed between T1 and
TE; i.e. before the
eutectic reaction) and
eutectic mixture (A +B).
A in the eutectic
mixture is called
secondary A.

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Eutectic Systems with Limited Solid

Solution

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 • The solid solubility limit line separating the α and
α + β phase regions is termed a solvus line.

• Eutectic Liquid → -solid solution + -solid solution

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• The phases separating

at such solvus lines are
given the notation
excess.
• They do not form
eutectic:
– They are not in the
lamellar form.
– It forms due to the
decrease in the solid
solubility and not due to
the solidification of
both phases

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 Dr. Yehia El Shazly

The microstructure of a
lead-tin alloy of eutectic
composition.
This microstructure consists
of alternating layers of a
lead-rich α-phase solid
solution (dark layers), and a
tin-rich β phase solid
solution (light layers).

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 Dr. Yehia El Shazly

The microstructure of a
lead-tin alloy of
composition 50 wt%
Sn-50 wt% Pb. This
microstructure is
composed of a
primary lead-rich α
phase (large dark
regions) within a
lamellar eutectic
structure consisting of a
tin-rich β phase (light
layers) and a lead-rich α
phase (dark layers).
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 Dr. Yehia El Shazly

• Important characteristics of eutectics

– A eutectic is a mechanical mixture of two solid
phases in lamellar shape.
– A eutectic has a constant composition, but it is
not a chemical compound.
– A eutectic freezes and melts at a constant
temperature.
– A eutectic has the lowest freezing point of all
alloys belonging to the system.
– A eutectic has the highest strength of the whole
system.
– The eutectic point is always nearer to the metal
of lower melting point.

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 Peritectic Systems
• A primary solid solution may react with the
remaining liquid in equilibrium with it, in a certain
proportion, to produce a new solid solution of
intermediate composition between them.
• Liquid + Solid Solution (1) → Solid Solution (2)
• Invariant reaction involving three phases at
equilibrium.

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 Liquid (31% Pt) + -solid solution (86% Pt) → -solid solution (54% Pt)
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• There is no peritectic microconstituent corresponding

to eutectic structure.
• The peritectic reaction consumes two phases to
produce one different phase, a behavior just the
opposite of the eutectic reaction.

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Intermediate Phases
• The chemical
compositions are
intermediate between the
two pure metals.
• The crystal structures are
different from those of the
pure metals.
• when they have a fixed
simple ratio of the two
kinds of atoms →
intermetallic compounds
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 Eutectoid Reactions
• If one solid solution phase separates two solid
phases at a certain temperature and with a certain
composition , the reaction is said to be of the
eutectoid (or eutectic-like) type.
• The two solid phases form eutectoid structure,
similar to that of eutectic in being composed of
alternative lamellae of the two solid phases.
• Solid Solution →Solid Solution (1)+ Solid Solution (2)
• The cooling rate is a determining factor in the
eutectoid reactions upon which the properties
of the eutectoid depend.
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• Solid-state reactions differ in two important ways

from liquid reactions in the manner in which they
attain the equilibrium conditions predicted by the
phase diagram:
– Solid-state reactions occur much more slowly, and
rarely correspond in practice to true equilibrium
conditions.
– Solid phases consist of atoms arranged in certain
crystal structures, and new solid phases forming
from an existing solid phase tend to take definite
positions with respect to the existing crystal
structure.

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 Congruently and Incongruently phases

• Phase transformations may be classified according

to whether or not there is any change in
composition for the phases involved.
• Congruent transformations: those for which there
are no compositional alterations (allotropic
transformations and melting of pure materials).
• Incongruent transformations: at least one of the
phases will experience a change in composition.
(Eutectic and eutectoid and melting of an alloy that belongs
to an isomorphous system)
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For a 40 wt% Sn-60 wt% Pb alloy at 150°C (300°F)

a) What phase(s) is (are) present?
b) What is (are) the composition(s) of the phase(s)?
c) Calculate the relative amount of each phase
present in terms of (1) mass fraction and (2)
volume fraction. (At 150°C take the densities of Pb
and Sn to be 11.23 and 7.24 g/cm3, respectively.)
d) Determine the composition in Atom% of the
original alloy and each phase present. (atomic
weight of Sn=118.7 amu and of Pb=207.2)

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 Dr. Yehia El Shazly

a) At 150 °C; both α and β phases are present.

b) α composition is 10% Sn, 90% Pb, and β
composition is 98% Sn, 2% Pb.
c) (1) Mass fraction of α and β may be
computed using the lever rule:

W α=(98-40)/(98-10)=0.66
W β =(40-10)/(98-10)=0.34

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 (2) first we determine the density of each
phase using the following equation:

 
 
   
100
CSn( ) C Pb ( ) 
  
  Sn  Pb 

α=10.64 g/cm3
β=7.29 g/cm3

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To determine the volume fraction of α and β, we

use the following equation:

W
V 
V  
V  V W W

 

Vα=0.57
Vβ=0.43

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 d) To convert composition from wt% to at% we
use the following relation:

C1 A2
C1\  *100
C1 A2  C 2 A1

Original alloy composition :

Sn 53.8 at%; Pb 46.2 at%
α composition: Sn 16.2 at%; Pb 83.8 at%
β composition: Sn 98.8 at%; Pb 1.2 at%
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For the alloy of composition 33% Sn; calculate

a) the fraction of eutectic, liquid and primary α
at the eutectic temperature.
b) The fraction of total α and β.

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 Dr. Yehia El Shazly

a) The fraction liquid is equal to the fraction

eutectic at the eutectic temperature:
We=Wl=(33-18.3)/(61.9-18.3)=0.337
Wα= =(61.9-33)/(61.9-18.3)=0.663
b) The fraction of total α:
WTα=(97.8-33)/(97.8-18.3)=0.82
Wβ= (33-18.3)/(97.8-18.3)=0.18

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