Iron-Iron Carbide

Phase Diagram

PIYUSH VERMA
3rd year undergraduate,
Department of Metallurgical and Materials Engineering
Indian Institute of Technology, Kharagpur

Topic for today

Fe-Fe3C Phase
Diagram
(For a plain C steel)
(plain because no element presence other than C in
Iron)
(A base for understanding how different phases of iron
evolves)

Why steel is important

It is the Gold-standard against which emerging structural materials

are compared.
Moving standard: exciting discoveries being made in the context of

iron and alloys, now and then.

Most successful and cost-effective structural material.
Overwhelming dominance of steel : Due to variety of microstructures

and properties generated by the solid-state transformation and

processing.

Steels-Microstructure and Properties

By
Honeycombe & Bhadeshia)

Some facts
Presence of carbon in iron has such a great effect that even

0.1-0.2 wt% (approx 0.5- 1.0 at % i.e. 5-10 C atoms in

1000 Fe atoms) produces strengthening effect on ferritic
iron, fact, known to smiths for over 2500 years ago, since
iron heated in a charcoal fire can easily absorb carbon
through solid-state diffusion.
Carbon nano-tubes are 100 times more stronger than steels

but cannot be used in engineering scale because of

inevitable defects which arise as these tubes are grown.
Inner core of earth may consist of pure phase of iron (apart

from ,,,) in shape of double HCP.

Pure Fe Phase Diagram

bcc
fcc

bcc

hcp

Iron-Iron Carbide
Phase Diagram

What is a phase?
A homogeneous portion of the system that has a
uniform chemical and physical characteristics.

Every pure material is a phase : elements,

compounds.

Example

solid sugar is a solid phase and sugar-syrup

solution is a liquid phase

Both have different chemical composition: one is

pure sugar (C12H22O11) and the other is a solution
of sugar and water (H2O)

Every teaspoon of the sugar-syrup is always of

same composition

Liquid steel
Austenite + Liquid

nt
i
o
ic p
t
c
e
Eut

Austenite
Eu
t

ec
t

Ferrite
Pro-eutectoid
Ferrite+Pearlite

oi
d

Liquid+Cementite

Pro-eutectic Austenite
Cementite + Ledeburite
+ Ledeburite
po
in
t

Pearlite+

Some features of Fe-Fe3C Phase Diagra

It is a Binary Alloy phase diagram.

Binary because here only two elements, Fe

and C are considered.
The phase-diagram is only applicable for

the equilibrium cooling, meaning a very

slow cooling.
(By equilibrium we mean very minute change
in the system-parameters/compositions etc
for a long period of time)

Each Vertical Green Line represents

a different Carbon wt% Fe-C alloy

 Each C wt% on the X-Axis is a

different alloy system

Phases of iron in Fe-Fe3C Phase Diagram

-Ferritic (alpha phase)-BCC crystal lattice

-Austenite (gamma phase)-FCC crystal lattice

- (delta phase)-BCC crystal lattice

Fe3C Cementite phase - Orthorhombic

Carbon goes into the interstitial sites

Tetrahedral site in BCC

Octahedral site in BCC

Octahedral sites in FC

Carbon goes into the octahedral sites (both in BCC

and FCC) to avoid strain due to surrounding Fe atoms in
Tetrahedral sites.
(Strain due to C in octahedral site is less than tetrahedral
sites due to its large size)
Solubility of C in Austenite is larger than Ferrite
because Octahedral site is larger in FCC than BCC.

Ma

Maximum solubility of C in -Ferritic phase is 0.022 wt%, in -

Austenite phase is 2.1 wt%, in -phase 0.015

M wt%.
ax
im
um

um
xim

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so

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lit
i
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er
f
f

so
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 It means that by heating Iron we can add more C in it and get

a homogenous solution, as the solubility of Austenite (which is

stable at higher temperature) is more than the ferrite
phase( which is stable at room temperature)
If we cool the iron( when it is in austenite phase) then due to

less solubility at lower temperature, C atoms will come out of

the Fe Matrix in the form of precipitates , so that the solution
will be no more homogeneous.

 Ferrite is softest whereas Cementite is the most hardest

and brittle phase in the entire phase diagram

Because presence of C enhances strength and the maximum

solubility of C in ferrite is only 0.02 wt% whereas in Cementite it

is 6.67 wt% (& which is constant)
Cementite is only a metastable phase, which will decompose

into Ferrite and graphite if heated between 650-700 for several

years.
(A metastable phase may persist indefinitely and often,
experiencing only slight and imperceptible changes as time
progresses)

Hypoeutectoid Steel

Eutectoid Steel

Hypereutectoid Steel

Determination of phase amounts

at different temperatures
LEVER RULE

MECHANISM OF PHASE
TRANSFORMATION

Two types of transformation processes in

- phase transition (Ferrite-AusteniteFerrite)
RECONSTRUCTIVE
TRANSFORMATION

DISPLACIVE OR SHEAR
TRANSFORMATION

1. Involves diffusion of atoms

(both solute-Fe and the
solvent)

1.No diffusion

2.No resultant stress in the

microstructure

2. Results in combination of
elastic and plastic strain in
the matrix(microstructure)

3.No resultant shape change

in the sample

3. Resultant shape change of

the bulk sample

4.Stable above 835C (in

steels)

4.Stable below 835C (in

steels)

Austenite to Pearlite transformation

Pearlite : A grain containing alternate lamellae of

ferrite and Cementite.

In pearlite the width ratio of to Cementite

lamellae (Fe3C) is generally

8: 1 .
Pearlite forms through diffusion of C atoms out

from austenite making left out Fe atoms in

austenite to rearrange and transform their crystal
structure from FCC to BCC (Ferrite). C diffusing
out forms Cementite(Fe3C 6.67 wt% C ) .

Dependence of Eutectoid Composition

References
Steels-Microstructure and Properties

Honeycombe & Bhadeshia

(Introduction and the Crystal Structure part)
Materials Science and Engineering-William

Callister
(Fe-Fe3C Phase diagram part)
Pictures-Google

Thank You

Common Doubts

Yes, the Fe-Fe3C is just a part of the Fe-C phase diagram, the entire

Fe-C phase diagram extends to the right hand side upto 100 wt% C, which is
pure Carbon phase called Graphite. (Fe-C phase diagram has got not so
significant use in steel industry, thats why its generally not shown).
Ferrite is a phase, Austenite is a phase, Cementite is a phase but pearlite is
not a phase, pearlite is just a colony of 2 phases-ferrite & Cementite in a
grain.
We discussed the solution of Fe & C and definitely not a mixture.
Solution is homogenous in its composition and properties everywhere
whereas a mixture is not. (Sugar-Syrup is a solution and clay in water is a
mixture).
The width of the precipitate at the grain boundary varies as a grain
boundary can be a high-angle grain boundary or a low-angle grain boundary,
High angle grain boundaries are highly preferential sites for nucleation of
precipitates due to their high incoherency.(Different orientation of grains)
Different Heat-Treatment processes changes the microstructure
differently for the same alloy composition. We discussed the phase
diagram and microstructures for a Slow cooling process. Quenching (Oil
and water) is a fast cooling process and it produces martensite (another
phase of iron) along with other phases depending on the processing
parameters.