Congruent phase transformation

Congruent transformation: no change in composition upon phase

transformation.
Incongruent transformation: phase transformation where at least one of the
phases go through composition change.

At what overall
composition does Mg2Pb
melt congruently?

MetE 201 47
 Intermetallic compounds
Intermediate (intermetallic) compounds: discrete metal compounds rather
than solutions (i.e. distinct chemical formula).
AxBy: in solution x and y can vary
in compounds x and y are fixed (always fixed composition of A and B).
Mg-Pb phase diagram

Can be considered as two

phase diagrams put
together back to back.

Mg-Mg2Pb phase diagram Mg2Pb-Pb phase diagram

MetE 201 48
 Intermetallic compounds: Example
A 50wt% Pb/50wt% Mg
alloy is heated to
300oC. The mass
fraction of each phase
is 0.5.
1. What are the phases
present?
2. What are the
compositions of the
phases?

MetE 201 49
 Ceramic phase diagrams
Al2O3-Cr2O3 MgO-Al2O3

MetE 201 50
 Gibbs Phase Rule
Number of non-compositional
variables (Temperature &
Pressure)
Number of phases
present

P+F=C+N
Degree of freedom (externally
controllable parameters: i.e. T, Number of
P, and C) components

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 Gibbs Phase Rule
e.g. Cu-Ag phase diagram
P+F=C+N
Cu and Ag are the only components ->
C=2

Temperature is the only non-

compositional variable here (i.e. fixed
pressure). -> N = 1 (but in general N =
2)

When 2 phases are present -> P = 2

which leads to F = C+N-P = 2+1-2 = 1

When only 1 phase is present -> P = 1

which leads to F = 2

What does this mean? Why should

you care?

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 Gibbs Phase Rule
In the previous example of Cu-Ag phase diagram, when F = 1, only one
parameter (T or C) needs to be specified to completely define the system.

e.g. (for α+L region)

If T is specified to be 1000oC,
compositions are already
determined (Cα and CL).

Or

If composition of the a phase is

specified to be Cα then both T and
CL are already determined.

Cα CL
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 Gibbs Phase Rule
When F = 2, both T and C have to be specified to completely define
the state of the system.

e.g.(for α region)
If T is specified to be 800oC, Cα can
be any where between 0 to ~8 wt%
Ag)

Or

If composition of the a phase is

specified to be Cα = 3 wt%, then T
and can be any where between
~600 to 1100oC.

Cα

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 Gibbs Phase Rule
Where in the Cu—Ag diagram, is there a 0 degree of
freedom? (i.e. T, P, and C are all fixed)

MetE 201 55
 Iron-Carbon System
Typical metal (e.g. Cu) Iron
T T(oC)

Liquid
Liquid
1538
δ-Fe(BCC)
Tm 1394
γ-Fe (FCC)
Solid 912
α-Fe (BCC)

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 The Iron-Carbon System

1538oC
Melting δ 1495oC
1400
δ-ferrite high temperature 1394oC

Temperature (oC)
BCC iron 1200 1148oC
Peritectic 2.11
γ 4.30
γ-Austenite- FCC iron 1000
912oC
Eutectic
800
α-ferrite- BCC iron 727oC
α 0.77
Eutectoid 0.022
600
Cementite-Fe3C Fe3C
1 2 3 4 5 6 6.70
Composition, wt %C

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 Iron-Carbon System
Eutectic point

Eutectoid

Note: only goes out to 6.7

wt% C (100 wt% Fe3C
intermediate compound)

FCC γ-phase has highest C concentration (2.14 wt% C) whereas BCC α-

phase has low solubility (0.022 wt% C). Recall FCC is close packed (i.e.
larger APF). Why is C more soluble in FCC?
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 The Iron-Carbon System

α+γ Hypoeutectoid Hypereutectoid

800oC γ γ + Fe3C 727oC
0.77 Cementite, Fe3C
600oC 0.022
α, Ferrite α + Fe3C

1 2 3 4 5 6 6.7
Wt% C

• Hypoeutectoid Steels- Compositions to the left of the eutectoid

compositions
• Hypereutectoid Steels- Compositions to the right of the eutectoid
compositions

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 Eutectoid cooling

cool
γ (0.76 wt% C) α (0.022 wt% C)
heat + Fe3C (6.7 wt% C)

Pearlite structure

Layered structure forms due to the same reason as eutectic structure formation.
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 Formation of Pearlite in a Eutectoid Steel
α+γ
γ
800oC γ + Fe3C 727oC
6.70 − .77
0.77 Cementite, Fe3C =fα = 0.888
600oC 6.70 − 0.022
0.022
α, Ferrite α + Fe3C 0.77 − 0.022
=fFe3C = 0.112
6.70 − 0.022
1 2 3 4 5 6 6.7
Wt% C

α-Fe γ C
γ Fe3C Fe
Alternate lamellae
of a-Fe and Fe3C
make up the structure
Short range diffusion
of pearlite.
of carbon and iron along
the boundary separating
Advancing interface austenite from pearlite
MetE 201
 The Iron-Carbon System

α+γ
γ For hypoeutectoid compositions
800oC γ + Fe3C 727oC
For hypereutectoid compositions
0.77 Cementite, Fe3C
600oC 0.022
α, Ferrite α + Fe3C

1 2 3 4 5 6 6.7
Wt% C

• Proeutectoid Ferrite- Ferrite that forms prior to the eutectoid ferrite

• Proeutectoid Cementite- Cementite that forms prior to the eutectoid
cementite

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 Hypoeutectoid Alloys
Cooling below eutectoid
composition.
c: homogeneous γ solid.

d: α + γ coexistence. α-phase nucleate

at the grain boundaries (Why?).

e -> f:
- crossing eutectoid isotherm will cause all
remaining γ-phase into eutectoid structure.
- α-phase that formed prior to eutectoid isotherm
are called proeutectoid ferrite.

Co − 0.022
Fraction of pearlite = W p =
0.76 − 0.022
0.76 − Co
Fraction of proeutectoid α = Wα ' =
0.76 − 0.022

MetE 201 63
 Hypereutectoid Alloys
Cooling above the
eutectoid composition
Compositions and wt% can be
found similarly as hypoeutectoid
cooling.

Instead of proeutectoid α,
proeutectoid cementite appears.

MetE 201 64
 Example problem
For 0.35 wt% C, at T just
below eutectoid
isotherm, determine:

a) Fractions of total ferrite

and cementite phases.

b) Fractions of proeutectoid
ferrite and pearlite.

c) Fraction of eutectoid
ferrite.

MetE 201 65
 Influence of other alloying elements

Changes eutectoid T

Changes eutectoid
composition

Useful processing info to control microstructure.

MetE 201 66
 Concepts to remember
• Phases, physical states, chemical composition, phase equilibrium.
• Phase diagrams tell us about:
– Number and types of phases present.
– Composition of each phase.
– Mass fraction (wt%) of each phase.
• Binary isomorphous systems.
• Intermediate phases and compounds.
• Binary eutectic systems.
• Microstructure evolution in cooling (equilibrium vs. non-equilibrium).
• Eutectic, eutectoid, and peritectic reactions.
• Hyper- and hypoeutectic & hyper- and hypoeutectoid alloys
• Fe-C phase diagram.
• Phase diagrams help us to determine the equilibrium
microstructures which in turn determines the properties of
materials!

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