Eutectic diagram

Eutectic phase diagram describes behavior of the alloys,

two components of which are completely soluble in
liquid state and entirely insoluble in solid state.
This diagram has two liquidus curves, starting from the
freezing points of the two metals and intersecting in a
minimum point – eutectic point.

05/30/2022 Dr R Haldar 1
05/30/2022 Dr R Haldar 2
 Binary-Eutectic Systems
LIQUIDUS

ALL LIQUID

SOLIDUS

05/30/2022 Dr R Haldar 3
Eutectic or invariant point – Liquid and two solid phases co-exist
in equilibrium at the eutectic composition CE and the eutectic
temperature TE.
Eutectic isotherm - the horizontal solidus line at TE.
Eutectic reaction – transition between liquid and mixture of two
solid phases (α+β) at eutectic concentration CE. The melting point
of the eutectic alloy is lower than that of the components.
(eutectic = easy to melt in Greek).

At most two phases can be in equilibrium within a phase field.

Three phases (L, α & β) may be in equilibrium only at a single
point along the eutectic isotherm. Single phase regions are
separated by 2-phase regions.

05/30/2022 Dr R Haldar 4
 Eutectic Point

Concentration of B in A
05/30/2022 Dr R Haldar 5
Consider solidification of an alloy with concentration C. When the
alloy temperature is higher than TL , single liquid phase exists
(point M on the diagram).
When the temperature reaches the value TL (point M1 on the
liquidus curve) solidification starts. The primary crystals, forming
in this case are the crystals of the metal “A”.
Further cooling of the alloy causes enrichment of the liquid phase
with the metal “B” according to the liquidus curve and when the
alloy temperature reaches a certain intermediate value T
(position MT ), liquid phase of composition Cy and solid phase,
consisting of “A” crystals, are in equilibrium.
At the temperature equal to TE (eutectic temperature) formation
of the primary crystals stops and the remaining liquid phase ,
having composition CE (eutectic composition), transforms to an
intimate mixture of small “A” and “B” solid crystals. This is the
eutectic phase transformation.
05/30/2022 Dr R Haldar 6
 Binary Equilibrium Diagrams with components
having complete mutual solubility in the liquid state
and limited solubility in Solid State.

This kind of phase diagram is a “hybrid” of the diagram

with complete solid and liquid solubility and the eutectic
diagram.

05/30/2022 Dr R Haldar 7
05/30/2022 Dr R Haldar 8
Up to a few percent of composition, it is possible for one element
to remain dissolve in another while both are in the solid state.
This is called solid solubility and the solubility limit normally
changes with temperature.
 The alpha phase is the region of solid solution where some of B
atoms have dissolved in a matrix of A atoms.
 The beta phase is the region where a small percentage of A
atoms have dissolved in a matrix of B atoms.

Some elements have zero solid solubility in other elements. An

example is aluminum/silicon alloys, where aluminum has zero
solid solubility in silicon.

05/30/2022 Dr R Haldar 9
At alloy compositions and temperatures between the liquidus
temperature and the eutectic temperature, a mushy mix of
either alpha or beta phase will exist as solid masses within a
liquid mixture of A and B. These are the alpha plus liquid and
the beta plus liquid areas on the phase diagram. The region
below the eutectic line, and outside the solid solution region,
will be a solid mixture of alpha and beta.

05/30/2022 Dr R Haldar 10
05/30/2022 Dr R Haldar 11
05/30/2022 Dr R Haldar 12
05/30/2022 Dr R Haldar 13
05/30/2022 Dr R Haldar 14
05/30/2022 Dr R Haldar 15
05/30/2022 Dr R Haldar 16
05/30/2022 Dr R Haldar 17
05/30/2022 Dr R Haldar 18
 .
Cooling of liquid lead – tin system

In this case of lead-rich alloy (0 - 2 wt%

of tin) solidification proceeds in the
α+ L same manner as for isomorphous
alloys (e.g. Cu-Ni)
Temperature ͦC

L α+L α

α+β

05/30/2022 Dr R Haldar 19
Wt % Sn
 α
β

05/30/2022 Dr R Haldar 20
05/30/2022 Dr R Haldar 21
05/30/2022 Dr R Haldar 22
05/30/2022 Dr R Haldar 23
05/30/2022 Dr R Haldar 24
05/30/2022 Dr R Haldar 25
 TL Liquid

Concentration of B in A
05/30/2022 Dr R Haldar 26
 Composition of the Phases
Consider solidification of an alloy with concentration C. When the
alloy temperature is higher than TL, single liquid phase exists (point
M on the diagram).
When the temperature reaches the value TL (point M1 on the
liquidus curve) solidification starts. According to solidus curve the
first solid crystals (primary crystals) of the α-phase have
composition C1.
Further cooling of the alloy causes changing of the liquid phase
composition according to the liquidus curve and when the alloy
temperature reaches a certain intermediate value T (position MT ),
liquid phase of composition Cy and solid α-phase of composition Cx
are in equilibrium.

05/30/2022 Dr R Haldar 27
Hypo-eutectic alloys
If an alloy composition C is lower, than eutectic composition CE ,
solidification of the alloy starts from formation of the primary
crystals of α-phase according to the left branch of the liquidus
curve. These alloys are called hypo-eutectic.
Hyper-eutectic alloys
If an alloy composition C is higher, than eutectic composition CE ,
solidification of the alloy starts from formation of the primary
crystals of β-phase according to the right branch of the liquidus
curve. These alloys are called hyper-eutectic.
Eutectoid phase transformation is analogous to the
eutectic transformation, however it occurs with a solid
solution phase, breaking up into a mixture of two finely
divided phases of different compositions.
05/30/2022 Dr R Haldar 28
05/30/2022 Dr R Haldar 29
 C
(Invariant Point)
C

Can we have a 4-phase equilibrium in a binary system, or any

other system?
05/30/2022 Dr R Haldar 30
 Hypoeutectic & Hypereutectic Pb-Sn System

300
L
T(°C)
a L+ a
200 L+b b ( System)
TE

a+b
100

0 20 40 60 80 100 Co, wt% Sn

eutectic
hypoeutectic: Co = 50 wt% Sn 61.9

eutectic: Co = 61.9 wt% Sn Hypereutectic:)

a
a
a a b
a b
b b
a b
175 mm 160 mm b
eutectic micro-constituent

05/30/2022 Dr R Haldar 31
 Eutectic 40 Sn-60Pb

05/30/2022 70 Sn-30Pb Dr R Haldar 90 Sn-10Pb 32

05/30/2022 Dr R Haldar 33
05/30/2022 Dr R Haldar 34
05/30/2022 Dr R Haldar 35
 It is common to call the terminal solution on the
left side the alpha and the one on the right the
beta. So we have the alpha, the beta, and the
liquid phase. Thus the term three-phase
equilibria. We also have the α+β, α+L, and β+L.
The liquidus line in a binary eutectic is the curve
Ta-E-Tb. The solidus curve is the line Ta-a-E-b-Tb.
Note that the solubility curves slope inward, in
accordance with the fact that solubility increases
with temperature.

The simplest case is that of a compound of eutectic composition, denoted by line 1 on the
diagram. The eutectic reaction occurs at Te, the eutectic temperature, and is denoted by:
L alpha + beta
where L is the liquid phase. As the compound cool, it will reach Te. Here, the eutectic
reaction will proceed until all of the liquid has been consumed. At this point, the alpha
and beta will be in equilibrium with each other. Now the resulting solid will cool, where
the relative compositions of the phases will be controlled by the solubility curves ac and
bd.

05/30/2022 Dr R Haldar 36
 Hypo-eutectic alloys

These are ones whose

XB component is less
than the eutectic
composition.

There are three different cases worth noting, denoted by 2a, 2b,
and 2c. Lets look at 2a. This is the same case as for a two-phase
system. The solid starts to nucleate when the cooling crosses the
liquidus line and when it crosses the solidus line, there is no more
liquid. So we get the regular grain
05/30/2022
structure of a metal.
Dr R Haldar 37
The 2b case is more interesting. It begins in the same
way as 2a, freezing as an alpha solid solution. When it
crosses the ac solvus line, however, the beta phase starts
to deposit from the alpha phase. The beta phase can
precipitate at the alpha grain boundaries, at certain
crystallographic planes of the alpha phase, or around
inclusions and dislocations. the final case is illustrated by
2c. Here, upon crossing the liquidus line, the alpha phase
begins to deposit. When the composition reaches the
eutectic temperature, the remaining liquid undergoes
the eutectic reaction. The alpha phase is then present as
primary (that fraction present before the eutectic
reaction) and as one of the phases in the eutectic
mixture.
05/30/2022 Dr R Haldar 38
Hyper-eutectic alloys

3c 3b 3a

Hyper-eutectic alloys
are ones where the Xb
composition is greater
than the eutectic
composition.

They behave in a similar way to hypo-eutectics, the only change

being that now the dominant phase is the beta phase.

05/30/2022 Dr R Haldar 39
Eutectic mixtures will have a characteristic microstructure.
These structures are called lamellar, globular, rod and
acicular, depending on the appearance of the two phases

Four eutectic structures:

A) lamellar B) rod-like C) globular D) acicular

05/30/2022 Dr R Haldar 40
 Copper –
Silver
phase
diagram

100

Cu Ag
Three single phase regions (α - solid solution of Ag in Cu matrix, β = solid
solution of Cu in Ag marix, L - liquid) Three two-phase regions (a + L, b +L, a +b)
Solvus line separates one solid solution from a mixture of solid solutions. It
shows limit of solubility
05/30/2022 Dr R Haldar 41
 Cu-Ag Eutectic system

T(°C)
1200
• 3 single phase regions L (liquid)
(L, a, b) 1000
• Limited solubility: a L + a
T 800 779°C L+b b
a: mostly Cu E
8.0 71.9 91.2
b: mostly Ag 600
• TE : No liquid below TE a + b
• CE : Min. melting TE 400

composition 200
0 20 40 60 CE 80 100
• Eutectic transition Co, wt% Ag
L(CE) (CE) + (CE)

05/30/2022 Dr R Haldar 42
05/30/2022 Dr R Haldar 43
 % Cu % Ag
Silver – Copper phase diagram Copper – Silver phase diagram

05/30/2022 Dr R Haldar 44
Peritectic diagram
Sometimes a solid solution phase, which has already been formed,
reacts with the residual liquid phase and form another solid
solution phase or intermetallic compound, having a composition
between the compositions of the liquid and the first solid. This is
peritectic transformation (peritectic reaction).

05/30/2022 Dr R Haldar in45

 Cooling Curves for Peritectic Reactions

05/30/2022 Dr R Haldar 46
05/30/2022 Dr R Haldar 47
Consider solidification of an alloy with concentration C.
When the alloy temperature is higher than TL , single
liquid phase exists (point M on the diagram).
When the temperature reaches the value TL (point M1 on
the liquidus curve) solidification starts. According to
solidus curve (point N1 )the first solid crystals (primary
crystals) of the α-phase have composition C1.
Further cooling of the alloy causes changing of the liquid
phase composition according to the liquidus curve and
when the alloy temperature reaches a certain
intermediate value T (position MT ), liquid phase of
composition Cy and solid α-phase of composition Cx are in
equilibrium.
05/30/2022 Dr R Haldar 48
At the temperature equal to TP (peritectic temperature)
formation of the α-phase crystals stops and the remaining
liquid phase , having composition CL reacts with α-phase
crystals , forming β-phase of composition CP (peritectic
phase transformation).
At this temperature remaining α-phase crystals have
composition Cα and all crystals of β-phase have
composition CP (peritectic composition).

05/30/2022 Dr R Haldar 49
 Pt – Ag Phase Diagram

05/30/2022 Dr R Haldar 50
Fe – Ni Phase Diagram

05/30/2022 Dr R Haldar 51
05/30/2022 Dr R Haldar 52
 Eutectoid & Peritectic
Cu-Zn Phase diagram Peritectic transition  + L 

Temperature ͦ C

Temperature ͦ F
Wt % Zn
Eutectoid transition  +

05/30/2022 Dr R Haldar 53
Eutectic diagram with intermetallic compound
Intermetallic compound (valence compound) is a phase,
having chemical composition equal to a fixed simple
ratio, like CuZn,Cu3Sn, Mg2Pb, etc.
Sometimes intermetallic compounds exist over a range
of composition, differing from the valence law.
Intermetallic compounds of this sort are called electron
compounds or intermediate solutions.
An example of a phase diagram with intermetallic
compound AB2 is shown in the figure below.
This diagram may be considered as a combination two
different diagrams: A- AB2 and AB2-B.

05/30/2022 Dr R Haldar 54
05/30/2022 Dr R Haldar 55
 Intermetallic Compounds

Note: intermetallic compound forms a line - not an area - because

stoichiometry (i.e. composition) is exact.
05/30/2022 Dr R Haldar 56
 Binary Monotectic Systems
A liquid phase transforms into a solid phase and another liquid
phase L1 α + L2

Cu-Pb System

05/30/2022 Dr R Haldar 57
 Phase Diagram with two eutectics

05/30/2022 Dr R Haldar 58
 It is possible to have several solid solution regions: eg
2 eutectic reactions and 3 solid solutions ( α, β and Ƴ )
 Upon cooling from T max at the alloy composition X
there is a phase change but no composition change
(Congruent Melting Point)

05/30/2022 Dr R Haldar 59
05/30/2022 Dr R Haldar 60
05/30/2022 Dr R Haldar 61
05/30/2022 Dr R Haldar 62