THE UNIVERSITY OF DODOMA

CH 3107

MATERIAL SCIENCE
 PHASE DIAGRAMS OF ALLOYS
• Phase Diagrams are charts which show how
different Phases can exist together under
certain conditions
• Three obvious Phases are the three states of
matter: Solid, Liquid, and Gas but different
Phases also exist when two or more liquids or
solids come into contact with each other and
form distinctive Crystalline Structures.

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Definition of terms
Component
• Is a pure metal and/or compound of which an alloy is
composed.
• For example, in a copper–zinc brass, the components
are Cu and Zn
System
• First, “system” may refer to a specific body of material
under consideration (e.g., a ladle of molten steel).
• Or it may relate to the series of possible alloys
consisting of the same components, but without
regard to alloy composition (e.g., the iron–carbon
system).
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Solid solution
• A 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.
Solubility limit
• A maximum concentration of solute atoms
that may dissolve in the solvent to form a solid
solution

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Phase
• A phase may be defined as a homogeneous
portion of a system that has uniform physical
and chemical characteristics.
• Every pure material is considered to be a
phase so also is every solid, liquid, and
gaseous solution.
• For example, in a saturated sugar solution
system, the sugar–water syrup solution is one
phase, and solid sugar is another.
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• If more than one phase is present in a given system,
each will have its own distinct properties, and a
boundary separating the phases will exist across in
which there will be a discontinuous and abrupt
change in physical and/or 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.
• Example; when water and ice are present in a
container, two separate phases exist; they are
physically dissimilar (one is a solid, the other is a
liquid) but are chemically identical.
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• Also, when a substance can exist in two or more
polymorphic forms (e.g., having both FCC and BCC
structures), each of these structures is a separate
phase because their respective physical
characteristics differ.
Homogeneous and Heterogeneous system
• Sometimes, a single-phase system is termed
homogeneous system.
• Systems composed of two or more phases are
termed heterogeneous or mixtures systems.
• Most metallic alloys, ceramic, polymeric, and
composite systems are heterogeneous.
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Microstructure
• In metal alloys, microstructure is characterized
by the number of phases present, their
proportions, and the manner in which they
are distributed or arranged.
• The microstructure of an alloy depends on
such variables as the alloying elements
present, their concentrations, and the heat
treatment of the alloy (i.e. the temperature,
the heating time at temperature, and the rate
of cooling to room temperature)
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 UNARY PHASE DIAGRAM
• This is the one component phase diagram
• Perhaps the simplest and easiest type of phase diagram
to understand.
• Composition is held constant (i.e. the phase diagram is
for a pure substance).
• This means that pressure and temperature are the
variables.
• The unary phase diagram sometimes also called a
pressure–temperature (or P–T) diagram is represented as
a two-dimensional plot of pressure (ordinate, or vertical
axis) versus temperature (abscissa, or horizontal axis).
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• A good example is the phase diagram for
water (exists as solid, liquid and gas)

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• Each of the phases will exist under equilibrium
conditions over the temperature–pressure ranges of
its corresponding area.
• Furthermore, the three curves shown on the plot
(labeled aO, bO, and cO) are phase boundaries.
• At any point on
one of these
curves, the two
phases on either
side of the curve
are in equilibrium
(or coexist) with
one another.
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• Equilibrium between solid and vapor phases is along
curve aO, likewise for the solid-liquid, curve bO, and
the liquid-vapor, curve cO. Also, upon crossing a
boundary (as temperature and/or pressure is altered),
one phase transforms to another.
• Eg. at 1 atm pressure, during
heating the solid phase
transforms to the liquid
phase (i.e., melting occurs) at
the point labeled 2 on Figure.
This point corresponds to a
temperature of 0°C.
• The reverse transformation
(liquid-to-solid, solidification)
takes place at the same point
upon cooling
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• At the intersection of the dashed line with the liquid-vapor
phase boundary [point 3 in the Figure), at 100°C] the liquid
transforms to the vapor phase (or vaporizes) upon heating.
• Condensation occurs for cooling at the same point.
• Solid ice sublimes or vaporizes upon crossing the curve
labeled aO as well as the vapour or steam.

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• All three phase boundary curves intersect at a common
point, labeled O, (at 273.16K and 6.04 x 10–3 atm in this
system). This means that at this point only, all of the solid,
liquid, and vapor phases are simultaneously in
equilibrium with one another
• Appropriately, this, and any
other point on a P–T phase
diagram where three phases
are in equilibrium, is called a
triple point or an invariant
point.
• Any deviation from this point
by a change of temperature
and/or pressure will cause at
least one of the phases to
disappear.
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 BINARY PHASE DIAGRAMS
• Binary phase diagrams are maps that
represent the relationships between
temperature and the compositions and
quantities of phases at equilibrium, which
influence the microstructure of an alloy.
• In this phase diagram, pressure is held
constant and normally 1 atm.
• It is normally comprises of those phase
diagrams that contain two components
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 Effect of Temperature & Composition
• Altering T can change # of phases: path A to B.
• Altering C can change # of phases: path B to D.
B (100ºC,C = 70) D (100ºC,C = 90)
1 phase 2 phases
water-sugar 100
system
80 L
Temperature (ºC)

(liquid)
60 +
L S
( liquid solution (solid
40 i.e., syrup) sugar)
20 A (20ºC,C = 70)
2 phases
0
0 20 40 60 70 80 100
C = Composition (wt% sugar)
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• Binary phase diagrams are helpful in
predicting phase transformations and the
resulting microstructures, which may have
equilibrium or non-equilibrium character.
• Many microstructures develop from phase
transformations, the changes that occur when
the temperature is altered (ordinarily upon
cooling).
• This may involve the transition from one
phase to another, or the appearance or
disappearance of a phase
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 BINARY ISOMORPHOUS SYSTEMS
• These involves the system having two components
with the same crystalline forms
• Consider copper–nickel system
• In this system, temperature is plotted along the
ordinate, and the abscissa represents the
composition of the alloy, in weight percent (bottom)
and atom percent (top) of nickel.
• The composition ranges from 0 wt% Ni (100 wt% Cu)
on the left to 100 wt% Ni (0 wt% Cu) on the right

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 Copper – Nickel phase diagram

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• Three different phase
regions, or fields,
appear on the diagram.
– an alpha (α) field,
(solid)

– a two-phase (α + L)
– a liquid (L) field,

field (solid + liquid).

• Each region is defined
by the phase or phases
that exist over the
range of temperatures
and compositions
delimited by the phase
boundary lines.
02/09/2025 CH 325 20
 separating L and α+L phase
• In this phase diagram, the line

field is called the liquidus line

and liquid phase is present at
all temperatures and
compositions above this line.

between the α and α+L

• The solidus line is located

regions, below which only the

solid phase exists
• The solidus and liquidus lines
intersect at the two
composition extremities which
correspond to the melting
temperatures of the pure
components.

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• Example in Cu-Ni alloy phase diagram, the
melting temperatures of pure copper and
nickel are 1085°C and 1453°C respectively.

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• For any composition other than pure
components, this melting phenomenon will occur
over the range of temperatures between the
solidus and liquidus lines; both solid and liquid
phases will be in equilibrium within this
temperature range.
• For example, upon heating an alloy of
composition 50 wt% Ni–50 wt% Cu, melting
begins at approximately 1280°C; the amount of
liquid phase continuously increases with
temperature until about 1320°C, at which the
alloy is completely liquid.
02/09/2025 CH 325 23
INTERPRETATION OF PHASE DIAGRAM
• For a binary system, at least three kinds of
information are available:
(1) the phases that are present
(2) the compositions of these phases
(3) the percentages or fractions of the
phases.

02/09/2025 CH 325 24
Phase present
• Phase is determined by just locates the temperature–
composition point on the diagram and notes the
phase(s) with which the corresponding phase field is
labeled.
Example:
To determine the
phase of alloys of
composition 60 wt%
Ni–40 wt% Cu at
1100°C and 35 wt%
Ni–65 wt% Cu at
1250°C
(the point marked A and
B respectively)
02/09/2025 CH 325 25
• An alloy of composition
60 wt% Ni–40 wt% Cu
at 1100°C (point A):

α region, only the

since this is within the

single phase will be

present (solid “α”
phase.
• An alloy of composition
35 wt% Ni–65 wt% Cu
at 1250°C (point B) will
consist of both solid
and liquid phases
(α+L phase).
02/09/2025 CH 325 26
 Determination of Phase Compositions
• The first step in the determination of phase
compositions (in terms of the concentrations
of the components) is to locate the
temperature–composition point on the phase
diagram.
• Different methods are used for single- and
two-phase regions

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If only one phase is present
• The composition of one phase is simply the
same as the overall composition of the alloy.
• For example, consider the 60 wt% Ni–40 wt%
Cu alloy at 1100°C (point A in the Figure).

α phase is present, having a composition of

• At this composition and temperature, only the

60 wt% Ni–40 wt% Cu.

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For a two-phase region
• In a two-phase regions, one may
imagine a series of horizontal lines
known as a tie line, or isotherm, one at
every temperature.
• These tie lines extend across the two-
phase region and terminate at the phase
boundary lines on either side.
• Full procedures are summarized in the
next slide
02/09/2025 CH 325 29
NB: To compute the equilibrium composition of
the two phases, the following procedure is used:
1. A tie line is constructed across the two-phase
region at the temperature of the alloy.
2. The intersections of the tie line and the
phase boundaries on either side are noted.
3. Perpendiculars are dropped from these
intersections to the horizontal composition
axis, from which the composition of each of
the respective phases is read.

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• The three procedures are shown in the figure

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 Example:
• Consider again the 35
wt% Ni–65 wt% Cu
alloy at 1250°C
located at point B in
Figure.
• Thus, the problem is
to determine the
composition (in wt%

α and liquid phases.

Ni and Cu) for both the

• The tie line has been

α+L phase region, as

constructed across the

shown in Figure.
02/09/2025 CH 325 32
 Example:
• The perpendicular from
the intersection of the tie
line with the liquidus
boundary meets the
composition axis at 31.5
wt% Ni–68.5 wt% Cu,
which is the composition
of the liquid phase, CL.
• Likewise, for the solidus–

composition for the α

tie line intersection, a

solid-solution phase, Cα is
42.5 wt% Ni–57.5 wt%
Cu.
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 Determination of Phase Amounts
• The relative amounts (as fraction or as
percentage) of the phases present, may also
be computed with the aid of phase diagrams.
• Again, the single- and two-phase situations
must be treated separately.

02/09/2025 CH 325 34
If only one phase is present
• Since only one phase is present, the alloy is
composed entirely of that phase; that is, the
phase fraction is 1.0 or, alternatively, the
percentage is 100%.
• From the previous example for the 60 wt% Ni–

next slide), only the α phase is present;

40 wt% Cu alloy at 1100°C (point A in Figure,

hence, the alloy is completely 100% α.

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02/09/2025 CH 325 36
For a two-phase region
• For two-phase region the tie line must be
utilized in conjunction with a procedure that is
often called the lever rule (or the inverse lever
rule).
• The procedure for the use of lever rule to
determine fraction or percent of the phase
present are listed next slide.

02/09/2025 CH 325 37
Procedures
1. The tie line is constructed across the two-phase region at the
temperature of the alloy.
2. The overall alloy composition is located on the tie line.
3. 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.
4. The fraction of the other phase is determined in the same
manner.
5. If phase percentages are desired, each phase fraction is
multiplied by 100.
• When the composition axis is scaled in weight percent, the
phase fractions computed using the lever rule are mass/weight
fractions—the mass (or weight) of a specific phase divided by
the total alloy mass (or weight).
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 1250°C both α and liquid phases are present
• Consider example in Figure below in which at

for a 35 wt% Ni–65 wt% Cu alloy.

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• In the employment of
the lever rule, tie line
segment lengths may be
determined either by
direct measurement
from the phase diagram
using a linear scale,
preferably graduated in
millimeters, or by
subtracting
compositions as taken
from the composition
axis.
02/09/2025 CH 325 40
• The tie line has been
constructed that was

determination of α and
used for the

L phase compositions.
• Let the overall alloy
composition be located
along the tie line and
denoted as Co and mass
fractions be
represented by WL and
Wα for the respective
phases.
02/09/2025 CH 325 41
• From the lever rule, WL
may be computed by
using tie line length as

• It may be also be
computed by
substracting
compositions as

02/09/2025 CH 325 42
• From the lever rule, W𝜶
may be computed by
using tie line length as

• It may be also be
computed by
substracting
compositions as

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• Composition need be
specified in terms of
only one of the
constituents for a binary
alloy.
• For the computation
above, weight percent
nickel will be used (i.e.,
C0 = 35 wt% Ni, CL = 31.5
wt% Ni, and Cα = 42.5
wt% Ni)

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• Therefore the fraction or percent of the phase
present for 35 wt% Ni–65 wt% Cu alloy at
1250°C is computed as;

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NB:
• Identical answers are obtained if compositions
are expressed in weight percent copper
instead of nickel (Try as your homework).
• Thus, the lever rule may be employed to
determine the relative amounts or fractions of
phases in any two-phase region for a binary
alloy if the temperature and composition are
known.

02/09/2025 CH 325 46
DEVELOPMENT OF MICROSTRUCTURE
IN ISOMORPHOUS ALLOYS
• Many microstructure develop from phase
transformation, the changes that occur when
the temperature is altered.
• This may involve the transition from one
phase to another or the appearance or
disappearance of the phase.

02/09/2025 CH 325 47
Equilibrium Cooling
• At this point it is instructive to examine the
development of microstructure that occurs for
isomorphous alloys during solidification.
• Consider the copper–nickel system (Figure in
next slide), specifically an alloy of composition
35 wt% Ni–65 wt% Cu as it is cooled from
1300°C (a ppoint marked “a” in the figure).

02/09/2025 CH 325 48
02/09/2025 CH 325 49
• Cooling of an alloy of
the above composition
corresponds to moving
down the vertical

°C, point a, the alloy is

dashed line. At 1300

completely liquid (of

composition 35 wt%
Ni–65 wt% Cu) and
has the microstructure
represented by the
circle inset in the
figure.

02/09/2025 CH 325 50
• As cooling begins, no microstructural or

the liquidus line (point b, ≈1260°C).

compositional changes will be realized until we reach

• At this point, the first α solid begins to form, which

has a composition dictated by the tie line drawn at

as α(46 Ni)];
this temperature [i.e., 46 wt% Ni–54 wt% Cu, noted

• The composition of liquid is still approximately 35 wt

that of the solid α.

% Ni–65 wt% Cu [L(35 Ni)], which is different from

• With continued cooling, both compositions and

relative amounts of each of the phases will change.

02/09/2025 CH 325 51
 fraction of the α
• Furthermore, the

phase will increase

with continued
cooling.
• Note that the overall
alloy composition (35
wt% Ni–65 wt% Cu)
remains unchanged
during cooling even
though there is a
redistribution of
copper and nickel
between the phases.
02/09/2025 CH 325 52
 • At 1250°C, point
c in Figure, the

the liquid and α

compositions of

phases are 32 wt
% Ni–68 wt% Cu
[L(32 Ni)] and 43
wt% Ni–57 wt%
Cu [α(43 Ni)],
respectively.

02/09/2025 CH 325 53
• The solidification
process is virtually
complete at about
1220°C, point d.

the solid α is
• The composition of

approximately 35 wt%
Ni–65 wt% Cu (the
overall alloy
composition)
• Composition of the
last remaining liquid
is 24 wt% Ni–76 wt%
Cu.
02/09/2025 CH 325 54
• Upon crossing the
solidus line, the
remaining liquid
solidifies; the final

polycrystalline α-phase
product then is a

solid solution that has a

uniform 35 wt% Ni–65
wt% Cu composition
(point e in the Figure).
• Subsequent cooling will
produce no
microstructural or
compositional
alterations.
02/09/2025 CH 325 55
Non-equilibrium Cooling
• Consider non-equilibrium solidification for
isomorphous alloys with a composition of 35
wt% Ni–65 wt% Cu alloy from 1300°C.
• To simplify this discussion it will be assumed
that diffusion rates in the liquid phase are
sufficiently rapid such that equilibrium is
maintained in the liquid.

02/09/2025 CH 325 56
02/09/2025 CH 325 57
• Let us begin cooling from a temperature of
about 1300°C (point a in the liquid region).
• This liquid has a composition of 35 wt% Ni–65
wt% Cu [noted as L(35 Ni) in the figure].
• No changes occur while cooling through the
liquid phase region (moving down vertically

1260°C, α-phase particles begin to form,

from point a). At point b (approximately

which, from the tie line constructed, have a

composition of 46 wt% Ni–54 wt% Cu [α(46
Ni)].
02/09/2025 CH 325 58
• Upon further
cooling to point c
(about 1240°C), the
liquid composition
has shifted to 29 wt
% Ni–71 wt% Cu.
• Furthermore, at this
temperature the

α
composition of the
phase that
solidified is 40 wt%
Ni–60 wt% Cu [α(40
Ni)].
02/09/2025 CH 325 59
• However, since diffusion in

relatively slow, the α

the solid (α) phase is

phase that formed at point

b has not changed
composition appreciably
(it is still about 46 wt% Ni)

α
and the composition of
the grains has
continuously changed with
radial position, from 46 wt
% Ni at grain centers to 40
wt% Ni at the outer grain
perimeters.
02/09/2025 CH 325 60
• Thus, at point c the

the solid α grains that

average composition of

have formed would be

some volume weighted
average composition,
lying between 46 and 40
wt% Ni.
• For the sake of
argument, let us take this
average composition to
be 42 wt% Ni–58 wt% Cu
[α(42 Ni)].
02/09/2025 CH 325 61
• At point d (about 1220°C)
and for equilibrium cooling
rates, solidification should
be completed.
• However, for this non-
equilibrium situation,
there is still an appreciable

remaining, and the α-

proportion of liquid

phase that is forming has a

composition of 35 wt% Ni

average 𝛼-phase com-

[α(35 Ni)]; also the

position at this point is 38

wt% Ni [α(38 Ni)]
02/09/2025 CH 325 62
• Non-equilibrium
solidification finally
reaches completion at
point e (about 1205°C ).

last α phase to solidify at

• The composition of the

this point is about 31 wt%

Ni.

of the α phase at
• The average composition

complete solidification is
35 wt% Ni.
• The inset at point f shows
the microstructure of the
totally solid material.
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 BINARY EUTECTIC SYSTEMS
Eutectic: relating to or
denoting a mixture of
substances (in fixed
proportions) that melts and
freezes at a single
temperature that is lower
than the melting points of
the separate constituents or
of any other mixture of
them (eutectic means easy
to melt in Greek).
02/09/2025 CH 325 64
Binary Eutectic Systems cont….

Three single phase

regions:
• α is the solid
solution of Ag in Cu
matrix,
• β is the solid
solution of Cu in Ag
matrix,
• L is liquid.
Three two-phase
regions:
• α + L, β + L, α + β
Solvus line separates one solid solution from a mixture of
solid solutions.
02/09/2025 CH 325 65
 Binary Eutectic Systems cont…

Eutectic or invariant point - Liquid and two solid phases co-exist

in equilibrium at the eutectic composition CE and the eutectic
temperature TE.
02/09/2025 CH 325 66
Eutectic isotherm - the horizontal solidus line at T .
Binary Eutectic Systems cont…

Eutectic reaction – transition between the phases at eutectic

point (or at concentration CE)
02/09/2025 CH 325 67
 Binary Eutectic Systems …
Compositions and relative amounts of phases are determined
from the same tie lines and lever rule, as for isomorphous
alloys.
Task:
For points A, B, and
C calculate
i) the compositions

(wt. %)
ii) relative amounts
(mass fractions)
of phases
present.

02/09/2025 CH 325 68
 Development of microstructure
in eutectic alloys
• Depending on composition, several different
types of microstructures are possible for the
slow cooling of alloys belonging to binary
eutectic systems.
• The discussion here will focus on iron-carbon
system with an example of iron-iron carbide
(Fe-Fe3C) phase diagram.

02/09/2025 CH 325 69
 THE IRON–IRON CARBIDE (Fe–Fe3C)
PHASE DIAGRAM
• Pure iron, upon heating, experiences two
changes in crystal structure before it melts.

ferrite, or α iron, has a BCC crystal structure.

• At lower temperature the stable form, called

to FCC called austenite, or γ iron, at 912°C.

• Ferrite experiences a polymorphic transformation

• This austenite persists to 1394°C, at which

BCC phase known as δ ferrite, which finally melts

temperature the FCC austenite reverts back to a

at 1538°C. (consider the figure next slide)

02/09/2025 CH 325 70
 THE IRON–IRON CARBIDE (Fe–Fe3C) PHASE DIAGRAM

• Composition
axis extends
only to
6.70%
because all
steels and
cast irons
have carbon
contents less
than 6.70 wt
% C.

02/09/2025 CH 325 71
• In the BCC α ferrite, only
small concentrations of
carbon are soluble; the
maximum solubility is 0.022
wt% at 727°C.
• The limited solubility is
explained by the shape and
size of the BCC interstitial
positions, which make it
difficult to accommodate the
carbon atoms.
• Even though present in
relatively low concentrations,
carbon significantly
influences the mechanical
properties of ferrite.
02/09/2025 CH 325 72
• The maximum solubility
of carbon in austenite,
2.14 wt%, occurs at
1147°C.
• This solubility is
approximately 100 times
greater than the
maximum for BCC ferrite,
since the FCC interstitial
positions are larger.

02/09/2025 CH 325 73
• The δ ferrite is virtually
the same as α ferrite,
except for the range of

each exists. Since the δ

temperatures over which

ferrite is stable only at

relatively high
temperatures, it is of no
technological
importance.

02/09/2025 CH 325 74
• Cementite (Fe3C) forms when

in α ferrite is exceeded
the solubility limit of carbon

below 727°C (for

α+Fe3C phase region).

compositions within the

• Fe3C also coexist with the γ

phase between 727 and
1147°C.
• Mechanically, cementite is
very hard and brittle; the
strength of some steels is
greatly enhanced by its
presence

02/09/2025 CH 325 75
Eutectic reaction
• In iron-iron carbide phase diagram, two eutectic
points are present.
• It may be noted that one eutectic exists for the
iron–iron carbide system at 4.30 wt% C and
1147°C).
• The eutectic reaction for this point is

• The reaction indicates that liquid solidifies to form

austenite and cementite phases and vice versa.
02/09/2025 CH 325 76
• It may be noted that a eutectoid invariant
point exists at a composition of 0.76 wt% C
and a temperature of 727°C. This eutectoid
reaction may be represented by the reaction

• The reaction indicates the solid γ phase is

transformed into α and cementite and vice
versa for the heating

02/09/2025 CH 325 77
 Development of microstructure in eutectic alloys
(Lead-tin system)
Several different types of micro- L →α +L→α
structure can be formed in slow
cooling at different compositions.
Let’s consider cooling of liquid
lead – tin system at different
compositions.

In the case of lead-rich alloy (0-2

wt. % of tin), at composition C1,
solidification proceeds in the same
manner as for isomorphous alloys
(e.g. Cu-Ni) that we discussed earlier.
02/09/2025 CH 325 78
 Development of microstructure in eutectic alloys…..

At compositions C2
between the room
temperature solubility
limit and the maximum
solid solubility at the
eutectic temperature, β
phase nucleates as the α
solid solubility is
exceeded upon crossing
the solvus line.

02/09/2025 CH 325 79
 Development of microstructure in eutectic alloys (III)
Solidification at the eutectic composition
No changes above the eutectic temperature TE. At TE the liquid
transforms to α and β phases (eutectic reaction).

02/09/2025 CH 325 80
 Development of microstructure in eutectic alloys….
Compositions other than eutectic but within the range of the eutectic
isotherm
Primary α phase is
formed in the α + L
region.
The eutectic
structure includes
layers of α and β
phases (called
eutectic α and
eutectic β phases).
The eutectic
structure is formed
upon crossing the
eutectic isotherm.
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THE END
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Chapter 9 - 82