Engineering Materials

Student Notes

Note
This document contains the important points discussed in the pre-recorded courseware. It will help in revising the
important concepts related to Engineering Materials course.

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Lecture 10 Notes
Focus Topics:
 Eutectic Phase Diagram
 Eutectic Reaction and Microstructural Changes
 Gibb’s Phase Rule
KEY POINTS
Eutectic Phase Diagram
Eutectic is a three-phase invariant reaction in which one liquid phase solidifies to
produce two solid phases.

 The eutectic reaction is similar to solidification for pure components in that the
reaction proceeds to completion at a constant temperature. However, the solid
product of eutectic solidification is always two solid phases, whereas for a pure
component only a single phase forms. Because of this eutectic reaction are
termed eutectic phase diagrams; components exhibiting this behaviour comprise
a eutectic system. Such a reaction is noted on the lead–tin phase diagrams.
 Low melting temperature alloys are prepared having near-eutectic compositions.
A familiar example is the 60–40 solder, containing 60 wt% Sn and 40 wt% Pb.
The alloy of this composition is completely molten at about 185oC, which makes
this material especially attractive as a low-temperature solder, because it is
easily melted.
 For the lead–tin system the solid-solution phases are designated by 𝛼 and 𝛽; in
this case, 𝛼 represents a solid solution of tin in lead and, for 𝛽, tin is the solvent
and lead is the solute. The eutectic invariant point is located at 61.9 wt% Sn and
183oC.
Determination of Phases Present for a 40 wt% Sn–60 wt% Pb alloy at 150oC.

Located temperature–composition point on the

phase diagram. It is within the α + β region, both
α and β phases will coexist.

Computation of Phase Compositions and Relative Phase Amount for a 40 wt%

Sn–60 wt% Pb alloy at 150oC

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Two phases are present at located point, so it

becomes necessary to construct a tie line
across the 𝛼 + 𝛽 phase field at 150oC. The
composition of the 𝛼 phase corresponds to the
𝛼
tie line intersection with the 𝛼 + 𝛽 solvus phase
boundary is about 11 wt% Sn, denoted as C𝛼.
Similarly for the 𝛽 phase, which will have a
composition of approximately 99 wt%Sn,
denoted as C𝛽

It is necessary to employ the lever rule to find out Relative Phase Amount. If C1
denotes the overall alloy composition, mass fractions may be computed by
subtracting compositions, in terms of weight percent tin, as follows
W𝛼= (C𝛽 – C1) / (C𝛽 - C𝛼) = 99-40/ 99-11 = 0.67 = 67 wt%.
W𝛽= (C1 – C𝛼) / (C𝛽 - C𝛼) = 40-11/ 99-11 = 0.33 = 33 wt%.

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.

Case I: It is for compositions ranging between a pure component and the maximum solid
solubility for that component at room temperature. For the lead–tin system, this
includes lead-rich alloys containing between 0 and about 2 wt% Sn for the 𝛼 phase
solid solution, and also between approximately 99 wt% Sn and pure tin for the
𝛽 phase.
 For example, consider an alloy of
composition Co as it is slowly cooled from
a temperature within the liquid phase
region, say, 350oC; this corresponds to
moving down the dashed vertical line.
 The alloy remains totally liquid and of
composition Co until cross the liquidus
line at approximately 330oC, at which
time the solid 𝛼 phase begins to form.

While passing through this narrow L+ 𝛼 phase region, solidification proceeds with
continued cooling more of the solid 𝛼 forms. Liquid and solid phase compositions

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are different, which follow along the liquidus and solidus phase boundaries,
respectively.
Solidification reaches completion at the point where crosses the solidus line. The
resulting alloy is polycrystalline with a uniform composition of Co, and no
subsequent changes will occur upon cooling to room temperature.

Case II: It is considered for compositions that range between the room temperature
solubility limit and the maximum solid solubility at the eutectic temperature. For the
lead–tin system, these compositions extend from about 2 wt% Sn to 18.3 wt% Sn for
lead-rich alloys and from 97.8 wt% Sn to approximately 99 wt% Sn for tin-rich alloys.

 For example, consider an alloy of composition

Co as it is cooled along the dashed vertical line.
 Just above the solvus intersection, the
microstructure consists of 𝛼-grains of
composition Co.
 Upon crossing the solvus line, the 𝛼 solid
solubility is exceeded, which results in the
formation of small 𝛽 phase particles; these are
indicated in the microstructure.

 With continued cooling, these particles will grow in size because the mass
fraction of the 𝛽 phase increases slightly with decreasing temperature.

Case III: The third case involves solidification of the eutectic composition, i.e. 61.9
wt% Sn.
 Consider an alloy having this composition that is cooled from a temperature
within the liquid-phase region (e.g., 250oC) down the dashed vertical line.
 As the temperature is lowered, no changes occur until we reach the eutectic
temperature, 183oC. Upon crossing the eutectic isotherm, the liquid transforms
to the two 𝛼 and 𝛽 phases. During this transformation, there must necessarily be
a redistribution of the lead and tin components.
 The microstructure of the solid that results from this transformation consists of
alternating layers (sometimes called lamellae) of the 𝛼 and 𝛽 phases that form
simultaneously during the transformation. Subsequent cooling of the alloy from
just below the eutectic to room temperature will result in only minor
microstructural alterations

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Microstructure of a lead–tin alloy of eutectic

composition.

Case IV: Final microstructural case for this system includes all compositions other
than the eutectic, when cooled cross the eutectic isotherm. Consider, for example, the
composition Co, which lies to the left of the eutectic; as the temperature is lowered,
we move down the vertical dashed line.
 The microstructural development between L and L+ 𝛼 is similar to that for the
second case, such that just prior to crossing the eutectic isotherm, the 𝛼 and
liquid phases are present having compositions of approximately 18.3 and 61.9
wt%Sn, respectively.
 As the temperature is lowered to just below the eutectic, the liquid phase, which
is of the eutectic composition, will transform to the eutectic structure (i.e.,
alternating 𝛼 and 𝛽 lamellae); insignificant changes will occur with the 𝛼 phase
that formed during cooling through the 𝛼 + 𝐿 region.
 Thus, the 𝛼 phase will be present both in the eutectic structure and also as the
phase that formed while cooling through the phase field.
 To distinguish one from the other that which resides in the eutectic structure is
called eutectic 𝛼. while the other that formed prior to crossing the eutectic
isotherm is termed primary 𝛼.
 It is possible to compute the relative amounts of both eutectic and 𝛼 crystals by

Just above TE,

C𝛼 = 18.3 wt%Sn and CL = 61.9
wt%Sn
𝑆
W𝛼 = = 50wt%; W L = (1- W𝛼) =
𝑅+𝑆
50wt%;
Just below TE,
C𝛼 = 18.3 wt%Sn and Cβ = 97.8
wt%Sn
𝑆
W𝛼 = = 73 wt%; W β = (1- W𝛼) =
𝑅+𝑆
27 wt%;
applying lever rule using a tie line.

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Gibbs Phase Rule

The Gibbs phase rule is a simple equation that relates the number of phases (P)
present in a system at equilibrium with the number of degrees of freedom (F), the
number of components (C), and the number of non-compositional variables (N).
P+F=C+N
 Ex. applying it to binary temperature composition phase diagrams, the pressure
is constant (1 atm), the parameter N = 1 as temperature is the only non-
compositional variable. Equation now takes the form,
P+F=C+1
Furthermore, the number of components C is 2,
P+F=2+1=3
Consider the case of single-phase fields on the phase diagram (e.g., 𝛼, 𝛽, and
liquid regions). Because only one phase is present, P = 1 and
F=3-P=3-1=2
This means that to completely describe the characteristics of any alloy that exists
within one of these phase fields, we must specify two parameters, i.e.,
composition and temperature.
 For the situation wherein two phases coexist, for example, 𝛼 + L, 𝛽 + L, and 𝛼 +
𝛽 phase regions, the phase rule stipulates that we have but one degree of
freedom because
F=3-P=3-2=1
Thus, it is necessary to specify either temperature or the composition of one of
the phases to completely define the system
 For binary systems, when three phases are present, there are no degrees of
freedom, because
F=3-P=3-3=0
This means that the compositions of all three phases as well as the temperature
are fixed. This condition is met for a eutectic system by the eutectic isotherm.
HYPOEUTECTIC AND HYPEREUTECTIC
Hypoeutectic alloy is an alloy with a composition between that of the left-hand end of
the tie line defining the eutectic reaction and the eutectic composition. As a
hypoeutectic alloy containing between 19% and 61.9% Sn.
An alloy composition between that of the right-hand end of the tie line defining the
eutectic reaction and the eutectic composition is known as a hypereutectic alloy. In
the Pb-Sn system, any composition between 61.9% and 97.5% Sn is hypereutectic.

Eutectic: Microstructure consists of

alternating layers of a lead rich 𝛼-
phase solid solution (dark layers),

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and a tin-rich 𝛽-phase solid solution

(light layers)

Hypoeutectic: Microstructure is
composed of a primary lead-rich 𝛼
phase (large dark regions) within a
lamellar eutectic structure

Hypereutectic: Microstructure is
composed of a primary Tin-rich 𝛽
phase (large light regions) within a
lamellar eutectic structure

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