Eutectic Systems

• The simplest kind of system with two solid phases is called a eutectic system.
• A eutectic system contains two solid phases at low temperature. These phases
may have different crystal structures, or the same crystal structure with different
lattice parameters.
• Examples:
– Pb (FCC) and Sn (tetragonal) - solder systems
– Fe (BCC) and C (graphite - hexagonal) - cast irons
– Al (FCC) and Si (diamond cubic) - cast aluminum alloys
– Cu(FCC) and Ag(FCC) – high temperature solder

Cu/Ag Eutectic System

• Copper and Silver are both FCC, but their lattice parameters and atomic radii
are very different, so they have limited solubility in the solid state.
• There are two solid stable phases α and β, and at high temperatures there is a
eutectic reaction where the solids α, β and the liquid coexist.

L(CE) ←⎯ ⎯ ⎯
Heating
α(CαE) + β(CβE)
⎯ Cooling
⎯ ⎯→
Cu – Ag System
Cu: α phase
Ag: β phase
Eutectic means “easily
melted” in Greek
Point E: invariant point
(eutectic point)
BG line: isotherm line

AB: Solidus line

FG:
BC: Solvus line
GH:
AE: Liquidus line
EF:
BEG: Solidus line,
isotherm line
TE: eutectic isotherm
Eutectic isotherm
Invariant or
eutectic point
 Eutectic Reaction:
L(CE) Cooling α(CαE) + β(CβE)
Heating
For copper-silver system:
L(71.9wt%Ag) Cooling α(8.0wt%Ag) + β(91.2wt%Ag)
Heating

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 - horizontal solidus line at TE.

 Binary Eutectic System
Eutectic reaction – transition from liquid to mixture of two solid phases,
α + β at eutectic concentration CE.
At most two phases can be in
equilibrium. Three phases (L,
α, β) may be in equilibrium
only at a few points along the
eutectic isotherm. Single-
phase regions are separated
by 2-phase regions.
 Binary Eutectic System
Compositions and relative amounts of phases are determined
from the same tie lines and lever rule, as for isomorphous alloys-
-demonstrate

•A

•B

•C
 Example
For Point C: 40wt%Sn-60wt%Pb alloy at 150oC
a) What are the phases present?
b) What are the compositions of the phases present?
c) Mass fraction?
d) Volume fraction at 150oC?
Knowing that the densities of Pb and Sn are 11.23 and
7.24g/cm3, respectively
a) At C, α and β phases
coexist
b) Draw Tie Line at 150oC:
For α-phase:
Cα = 10%
→10wt%Sn–90wt%Pb
For β-phase:
Cβ = 98%
→98wt%Sn–2wt%Pb •C
c) Mass fraction:

Cβ − C1 98 − 40
Wα = = = 0.66
Cβ − Cα 98 − 10
C1 − Cα 40 − 10
Wβ = = = 0.34
Cβ − Cα 98 − 10
.
 Wα
d) volume fraction: vα ρα
Vα = =
vα + vβ Wα Wβ
+
Where: ρα ρβ

100 100
ρα = = = 10.64 g .cm − 3
CSn (α ) CPb (α ) 10 90
+ −3
+
ρ Sn ρ Pb 7.24 g .cm 11.23 g.cm − 3
100 100
ρβ = = = 7.29 g .cm − 3
CSn ( β ) CPb ( β ) 98 2
+ −3
+
ρ Sn ρ Pb 7.24 g.cm 11.23 g.cm − 3

Wα 0.66
vα ρα 10.64
Vα = = = = 0.57
vα + vβ Wα W 0 . 66
+
0 . 34
+ β
ρα ρ β 10.64 7.29
Vβ = 1 − Vα = 1 − 0.57 = 0.43
 L Development of microstructure in
⇓ eutectic alloys (I)
L+α
⇓
Several types of microstructure formed in
α
slow cooling an different compositions.
Cooling of liquid lead/tin system at different
compositions.

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

tin) solidification proceeds in the same
manner as for isomorphous alloys (e.g. Cu-
Ni) that we discussed earlier.
 Development of microstructure
L in eutectic alloys (II)

α +L At compositions between
room temperature solubility
α limit and the maximum solid
solubility at the eutectic
α +β temperature, β phase
nucleates as the α solid
solubility is exceeded at
solvus line.
 Development of microstructure in eutectic alloys (III)
Solidification at the eutectic composition (I)
No changes above eutectic temperature, TE. At TE liquid
transforms to α and β phases (eutectic reaction).

L → α +β
 Development of microstructure in eutectic alloys (IV)
Solidification at the eutectic composition (II)
Compositions of α and β phases are very different →
eutectic reaction involves redistribution of Pb and Sn
atoms by atomic diffusion. Simultaneous formation of α
and β phases results in a layered (lamellar)
microstructure:called eutectic structure.
Formation of
eutectic structure
in lead-tin system.
Dark layers are
lead-reach α
phase.
Light layers are
the tin-reach β
phase.
 Development of microstructure in eutectic alloys (V)
Compositions other than eutectic but within the range
of the eutectic isotherm

Primary α phase is formed in the α + L region, and the

eutectic structure that includes layers of α and β phases
(called eutectic α and eutectic β phases) is formed upon
crossing the eutectic isotherm.
 L
⇓
α+L
⇓
α+β
 Development of
microstructure in eutectic
alloys (VI)

Microconstituent – element
of microstructure having a
distinctive structure. For
case described on previous
page, microstructure
consists of two
microconstituents, primary
α phase and the eutectic
structure.

Although the eutectic structure consists of two phases, it

is a microconstituent with distinct lamellar structure and
fixed ratio of the two phases.
Compositions of α and β phases are very
different → eutectic reaction involves
redistribution of Pb and Sn atoms by atomic
diffusion. Simultaneous formation of α and β
phases results in a layered (lamellar)
microstructure:called eutectic structure.
Formation of eutectic structure in lead-tin
system.
Dark layers are lead-reach α phase.
Light layers are the tin-reach β phase.

Relative amounts of microconstituents?

Eutectic microconstituent forms from liquid having eutectic
composition (61.9 wt% Sn)
Treat the eutectic as if it were a separate phase and apply lever rule
to find relative fractions of primary α phase (18.3 wt% Sn) and
eutectic structure (61.9 wt% Sn):
We = P / (P+Q) (eutectic)
Wα’ = Q / (P+Q) (primary)
Equilibrium Diagrams Having Intermediate Phases or Compounds

Terminal solid solution:

a solid solution that exists
over a composition range
extending to either
composition extremity of
a binary phase diagram
Equilibrium Diagrams Having Intermediate
Phases or Compounds
Intermediate solid
solution:
Copper-zinc
α and η: two
terminal solid
δ solution
β β, γ, δ, & ε are
intermediate
α γ phases
ε
 Intermetallic Compounds

Ex: magnesium-
lead phase
diagram:
Intermetallic
compound:
Mg2Pb can exist
by itself only at
the precise
composition of
19wt%Mg –
81wt%Pb
Eutectoid Reaction (Invariant Point E at 560oC)
Copper-zinc

cooling
δ γ +ε Eutectoid reaction
heating
Peritectic Reaction (Invariant Point P at 598oC)
Copper-zinc

cooling
δ+L ε Peritectic reaction
heating
The Iron - Iron Carbide (Fe-Fe3C) Phase Diagram
 Reactions Phases Present
Peritectic L + δ = γ
at T=1493oC and 0.18wt%C L

δ ferrite delta
Eutectic L = γ + Fe3C Bcc structure
at T=1147oC and 4.3wt%C Paramagnetic

γ austenite
Eutectoid γ = α + Fe3C
at T=727oC and 0.77wt%C Fcc structure
Non-magnetic
ductile
α ferrite Fe3C cementite
Max. solubility of C Bcc structure Orthorhombic
in ferrite=0.022% Ferromagnetic Hard, brittle
in austenite=2.11% Fairly ductile
 Phases in Fe–Fe3C Phase Diagram
¾ α-ferrite - solid solution of C in BCC Fe
• Stable form of iron at room temperature.
• Transforms to FCC g-austenite at 912 °C
¾ γ-austenite - solid solution of C in FCC Fe
• Transforms to BCC δ-ferrite at 1395 °C
• Is not stable below the eutectic temperature (727 ° C)
unless cooled rapidly.
¾ δ-ferrite solid solution of C in BCC Fe
• It is stable only at T, >1394 °C. It melts at 1538 °C
¾ Fe3C (iron carbide or cementite)
• This intermetallic compound is metastable at room T. It
decomposes (very slowly, within several years) into α-Fe
and C (graphite) at 650 - 700 °C
¾ Fe-C liquid solution
 Comments on Fe–Fe3C system

C is an interstitial impurity in Fe. It forms a solid solution

with α, γ, δ phases of iron
Maximum solubility in BCC α-ferrite is 0.022 wt% at 727
°C. BCC: relatively small interstitial positions
Maximum solubility in FCC austenite is 2.14 wt% at 1147
°C - FCC has larger interstitial positions
Mechanical properties: Cementite (Fe3C is hard and brittle:
strengthens steels). Mechanical properties also depend on
microstructure: how ferrite and cementite are mixed.
Magnetic properties: α -ferrite is magnetic below 768 °C,
austenite is non-magnetic
Classification.
Three types of ferrous alloys:
Iron: < 0.008 wt % C in α-ferrite at room T
Steels: 0.008 - 2.14 wt % C (usually < 1 wt % )
α-ferrite + Fe3C at room T
Cast iron: 2.14 - 6.7 wt % (usually < 4.5 wt %)
 3

3
Eutectoid steel
 Microstructure of eutectoid steel
Alloy of eutectoid composition (0.76 wt % C) is cooled slowly:
forms pearlite, layered structure of two phases: α-ferrite and
cementite (Fe3C)
Mechanically, pearlite has properties
intermediate to soft, ductile ferrite and hard,
brittle cementite.
Hypoeutectoid steel
Hypoeutectoid
alloys contain
proeutectoid
ferrite (formed
above the
eutectoid
temperature) plus
the eutectoid
perlite that contain
eutectoid ferrite
and cementite.
Hypereutectoid steel
Hypereutectoid
alloys contain
proeutectoid
cementite
(formed above
the eutectoid
temperature) plus
perlite that
contain eutectoid
ferrite and
cementite.
How to calculate the relative amounts of proeutectoid phase
(α or Fe3C) and pearlite?
Use the lever rule and a tie line that extends from the eutectoid
composition (0.75 wt% C) to α (0.022 wt% C) for hypoeutectoid
alloys and to Fe3C (6.7 wt% C) for hypereutectoid alloys.

Example: hypereutectoid alloy, composition C1

X (6.7 − C1 )
Fraction of Pearlite = W P = =
(V + X ) (6.7 − 0.76 )
V (C1 − 0.76 )
Fraction of Proeutecto id Cementite = W Fe 3C = =
(V + X ) (6.7 − 0.76 )
 Example

For alloys of two hypothetical metals A and B, there exist an α, A-rich

phase and a β, B-rich phase. From the mass fractions of both phases of two
different alloys, which are at the same temperature, determine the
composition of the phase boundary (or solubility limit) for both α and β at
this temperature.

Fraction of α Fraction of β
Alloy Composition
phase phase

60wt%A – 40wt%B 0.57 0.43

30wt%A – 70wt%B 0.14 0.86

The problem is to solve for compositions at the phase boundaries
for both α and β phases (i.e., Cα and Cβ). We may set up two
independent lever rule expressions, one for each composition, in
terms of Cα and Cβ as follows:
C β − Co1 C β − 60
Wα1 = 0.57 = =
C β − Cα Cβ − Cα

C β − Co 2 Cβ − 30
Wα2 = 0.14 = =
Cβ − Cα Cβ − Cα

In these expressions, compositions are given in weight percent

A. Solving for Cα and Cβ from these equations, yield
Cα = 90 (or 90 wt% A-10 wt% B)
Cβ = 20.2 (or 20.2 wt% A-79.8 wt% B)