The iron-carbon diagram (also called the iron-carbon phase or equilibrium diagram) is a graphic representation of the respective microstructure states depending on temperature (y axis) and carbon content (x axis).

1. Iron-Iron Carbon DIagram
Prof. D. K. MadhukarProf. D. K. Madhukar
Asst. Professor,
ME, S. I. E. M. - Siliguri

2. Allotropic Transformation in Iron
Iron is an allotropic metal, which means that it can exist in more than
one type of lattice structure depending upon temperature.
A cooling curve for pure iron is shown below:

3. 1) The Fe-C (or more
precisely the Fe-Fe3C)
diagram is an important one.
Cementite is a metastable
phase and ‘strictly speaking’
should not be included in a
phase diagram. But the
decomposition rate of
cementite is small and hence
can be thought of as ‘stable
enough’ to be included in a
phase diagram. Hence, we
typically consider the Fe-
Fe3C part of the Fe-C phase
diagram.
2) In the phase diagram,
temperature is plotted against
composition. Any point on the
diagram therefore represents a
definite composition and
temperature. The phase
diagram indicates the phases
present and the phase changes
that occur during heating and
cooling. The relative amounts
of the phases that exist at any
temperature can also be
estimated with the help of lever
rule.
Iron - CementIte phase DIagram

4. A portion of the Fe-C diagram – the part from pure Fe to
6.67 wt.% carbon (corresponding to cementite, Fe3C) – is
technologically very relevant.
 Cementite is not a equilibrium phase and would tend to
decompose into Fe and graphite. This reaction is sluggish
and for practical purpose (at the microstructural level)
cementite can be considered to be part of the phase
diagram. Cementite forms as it nucleates readily as
compared to graphite.
 Compositions up to 2.1%C are called steels and beyond
2.1% are called cast irons. In reality the classification
should be based on ‘cast ability’ and not just on carbon
content.
Heat treatments can be done to alter the properties of the
steel by modifying the microstructure→ we will learn
about this in coming chapters.

7. The important boundaries (the lines) separating phases have
some universally used abbreviations:
A1: Upper limit of the ferrite / cementite phase field
(horizontal line going through the eutectoid point).
A2: Temperature where iron looses its magnetism (so-
called Curie temperature).
Note that for pure iron this is still in the α-phase.
A3: Boundary between the γ austenite and the austenite/
ferrite field.
A4: Point in this case where α changes to δ at high
temperatures.
ACM: Boundary between the γ austenite and the austenite /
cementite field.

8. phases In Fe–Fe3C phase DIagram
 α‐ferrite ‐ solid solution of C in BCC Fe
• Stable form of iron at room temperature.
• Transforms to FCC g‐austenite at 912 °C
 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.
 δ‐ferrite solid solution of C in BCC Fe
• It is stable only at T, >1394 °C. It melts at 1538 °C
 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
 Fe‐C liquid solution

9. 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

10. 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 %)

11. Ferrite (α)
It is an interstitial solid solution of a small amount
of carbon dissolved in α iron.
The maximum solubility is 0.025%C at 723ºC and it
dissolves only 0.008%C at room temperature.
It is the softest structure that appears on the
diagram.
Ferrite is ferromagnetic at low temperatures but
loses its magnetic properties with the rise of
temperatures with major loss at curies temperatures,
768ºC and above this temperature, it becomes non
magnetic (paramagnetic).
The crystal structure of ferrite (α) is B.C.C
Tensile strength – 245 Mpa, Yield strength 118 Mpa
Elongation – 40-50% in 2 in. Ferrite (α)
Hardness - 95 VPN

12. Cementite (Fe3C)
Cementite or iron carbide, chemical formula
Fe3C, contains 6.67%C by weight and it is a
metastable phase.
It is typically hard and brittle interstitial
compound of low tensile strength (35 MPa)
but high compressive strength and high
hardness ~800VPN.
It is the hardest structure that appears on the
diagram.
It has a complex orthorhombic crystal
structure with 12 iron atoms and 4 carbon
atoms per unit cell.
It is slightly ferromagnetic up to 210ºC and
paramagnetic above it.
Melting point around 1227ºC

13. Pearlite (α + Fe3C)
• Pearlite is the eutectoid mixture
containing 0.80 %C and is formed
at 723ºC on very slow cooling.
• It is very fine plate like or
lamellar mixture of ferrite and
cementite. The fine fingerprint
mixture called pearlite is shown in
below figure.
• Tensile strength – 120,000 psi or
825Mpa
• Elongation – 20 percent in 2 in.
• Hardness – HRC 20, HRB 95-100,
or BHN 250-300

14. Austenite (γ)
• It is an interstitial solid
solution of a small amount of
carbon dissolved in γ iron.
• The maximum solubility is
2.1%C at 1147ºC.
• The crystal structure of
Austenite (γ) is F.C.C
• Tensile strength – 150,000 psi
or 1035 Mpa
• Elongation – 10% in 2 in.
• Hardness - 40 HRC and
Toughness is high.

15. Ledeburite (γ+ Fe3C)
• Ledeburite is the eutectic
mixture of austenite and
cementite.
• It contains 4.3%C and is formed
at1147ºC
• Structure of ledeburite contains
small islands of austenite are
dispersed in the carbide phase.
• Not stable at room temperature

16. δ -Ferrite
• Interstitial solid solution of carbon
in iron of body centered cubic
crystal structure. (δ iron ) of
higher lattice parameter (2.89Å)
having solubility limit of 0.09 wt%
at 1495°C with respect to austenite.
• The stability of the phase ranges
between 1394-1539°C.
• This is not stable at room
temperature in plain carbon steel.
• However it can be present at room
temperature in alloy steel especially
duplex stainless steel.

17. perIteCtIC reaCtIon
• The invariant peritectic reaction in Fe-Fe3C diagram is given by
• Fe-0.16%C steel is a peritectic steel because only this steel undergoes
above reaction completely.
• Peritectic reaction is of some importance during freezing of steels
(carbon from 0.1 to 0.51% particularly under fast cooling conditions,
when micro segregation may result, otherwise no commercial heat
treatment is done in this region.
• Unfortunately these temperatures are attained during heating of steels
for forging or rolling etc., then severe overheating and burning results in
steels turning them to scrap form.

18. Fe-4.3%C alloy is called eutectic cast iron as it is the lowest melting point alloy,
which is single phase liquid (100%) of 4.3% carbon at the eutectic temperature,
1147°C just attained and undergoes eutectic reaction completely at this constant
eutectic temperature to give a mixture of two different solids, namely austenite
and cementite, solidifying simultaneously. The eutectic mixture called Ledeburite.
As Fe-C alloys having more than 2.11% carbon are classed as cast irons, the Fe-C
alloys having carbon between 2.11 and 4.3% are called hypo eutectic cast irons,
where as those having carbon between 4.3% and 6.67% are called hypereutectic
cast irons. Alloys of Fe with 4.3% carbon is called eutectic cast iron.
euteCtIC reaCtIon

19. Eutectoid Reaction
• During cooling austenite of 0.8% at constant eutectoid temperature, 727°C undergoes
eutectoid transformation to form a mixture of ferrite (C%=0.02%) and cementite i.e., there
are alternate lamellae of ferrite and cementite .
• This eutectoid mixture of ferrite and cementite is called PEARLITE, because of its
pearly appearance under optical microscope.
• The weight % of these phases are thus 8:1. The densities are (α-7.87 gm/cm3) and (Fe3C-
-7.70 gm/cm3) are quite comparable. Thus the Volume % also approx 8:1. Thus ferrite
lamilla is 8 times thicker than cementite lamilla. As the two boundaries of cementite plate
are close together, they may not resolved separately under the microscope, instead of two
lines, it appears a single dark line.
The invariant Eutectoid reaction in Fe-Fe3C diagram is given by

20. Limitations on Fe-Fe3C phase diagram
Fe-Fe3C diagram represents behavior of steels under equilibrium
conditions, whereas the actual heat treatments of steels are normally
under non-equilibrium conditions.
The diagram does not indicate the character of transformation of
austenite such as to bainite, or martensite.
The diagram does not indicate the presence of metastable phases like
martensite, or bainite.
It does not indicate the temperature of start of martensite Ms or
bainite Bs .
It does not indicate the kinetics of the transformation of austenite to
martensite, bainite or even pearlite.
It does not indicate the possibilities of suppressing the pearlitic or
bainitic transformations