Phase Diagrams:

The Iron- Iron Carbide (Fe-Fe3C)Diagram or

Iron-carbon (Fe-C) equilibrium diagram

Presented by:
Dr. R. D. Palhade,
Professor, Department of Mechanical Engineering,
SSGMCE, Shegaon
Pin-444203

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 (Fe-C) equilibrium diagram

Iron, Allotropy
If the change in crystal structure is reversible then that
polymorphic change is called as allotropy

This is the ability of some elements to exist in more than one

crystalline structure. Steel can exist as BCC when cold and as
FCC when heated above a certain temperature, depending on its
carbon content.

Polymorphism: in which change of crystal structure occur due to

either increase in pressure or temperature is called as
polymorphism
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Cooling curve for pure Iron
Allotropy of pure Iron:

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 Pure iron when heated experiences 2 changes in crystal
structure before it melts.
 At room temperature the stable form, ferrite (α iron) has a
BCC crystal structure.
 Ferrite experiences a polymorphic transformation to FCC
austenite (γ iron) at 912 ˚C (1674 ˚F).
 At 1394˚C (2541˚F) austenite reverts back to BCC phase δ
ferrite and melts at 1538 ˚C (2800 ˚F).
 Iron carbide (cementite or Fe3C) an intermediate compound is
formed at 6.67 wt% C.
 Typically, all steels and cast irons have carbon contents less
than 6.67 wt% C.
 Carbon is an interstitial impurity in iron and forms a solid
solution with the α, γ, δ phases.
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 Introduction to Iron-Carbon phase diagram
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Objectives: Iron-carbon (Fe-C) equilibrium diagram

1. Explain and use the terms hypoeutectoid, hypereutectoid,

proeutectoid, and pearlite.
2. Identify the major phases on the Fe-C diagram and explain their
chief characteristics.
3. Identify the proeutectoid phase for a given alloy.
4. Steel with other elements in small amounts are called plain
carbon steel and their structure and properties can be
discussed with the help of Fe-C diagram
5. Some time some elements added in steels to increase some of
required properties, these steels are called alloy steel-this
discussed with modified Fe-C diagram

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 General classes of steels

1. Low carbon (mild steels): <0.3% C - high ductility, low

strength, for general use, sheets, plate.
2. Medium carbon steel: 0.3-0.6% C – higher strength, higher
hardness, less ductility, gears, axles, railroad, etc.
3. High carbon steels :>0.6% C – hard, strong, brittle, tool steel,
springs, cutting tools

Heat Treatments
 Both microstructure and composition affect a material’s
properties. Heat treatment is one way to manipulate
microstructure.
 These changes to microstructure are caused by phase
transformations and changes in grain size. These effects are
both thermodynamically and kinetically driven.

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The Iron-Carbon Diagram

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Critical Temperature:
 The temperature at which the phase changes occur during heating and
cooling are called critical temperature
 The critical temperature at different stages shown on diagram A0, A1,
A2, ---etc.
Sr. Critical temp Temperature Significance during heating
No. in 0C
1. A0 210 Cementite changes ferromagnetic to
{critical temp of Fe3C} paramagnetic character
2. A1 727 Pearlite starts transforming into
{lower critical temp} austenite
3. A2 768 Ferrite becomes paramagnetic
{curie temp of ferrite}
4. A3 727-912 Completion of ferrite to austenite
{Upper critical temp. for transformation
hypo-eutectoid steel}
5. Acm 727-1147 Completion of cementite to austenite
{upper critical temp for (100%)
hyper-eutectoid steel}
6. A4 1400-1492 Completion of austenite to δ-ferrite
transformation
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 Introduction to Iron-Carbon phase diagram
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An iron-carbon equilibrium diagram forms a basis for
differentiating among
 Iron (0.008 % C or less)
 Hypo-eutectoid steels (0.008 to 0.8 % C)
 Hyper-eutectoid steel (0.8 to 2.0 % C)
 Hypoeutectic cast iron (2 to 4.3 % C) &
 Hypereutectic cast iron (above 4.3 % of C)

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Temperature

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Wt. % of carbon

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 Micro-constituents of Iron and Steel (The phased diagram
includes four solid phases)

General Properties:
1. α -Ferrite - Iron with a little Carbon. Fairly Soft.
2. γ -Austenite - FCC Iron with much Carbon Ductile.
3. Fe3C -Cementite - Hard ceramic material.
4. δ-Ferrite- This has no real practical significance in
engineering.

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The various phases existing in Fe-C diagram are as:
Micro-constituents of Iron and Steel (The phased diagram includes
four solid phases)

(a) Ferrite (α)

 Ferrite is an interstitial solid solution of carbon in low temp. BCC
α- iron phase with very limited solubility for carbon.
 At 0% C this is pure iron.
 The maximum solubility of carbon in iron is 0.025% at 727oC &
At 0 oC temperature the solubility falls to 0.008%.
 Ferrite is the softest structure that appears on the Fe-C
equilibrium diagram.
 It can be extensively cold worked without cracking.
 The carbon atoms are located in the crystal interstices.
Ferrite has:
 tensile strength 2800 kg/cm2 (approx.)
 Elongation 40 % in 50 mm
 Hardness less than Rockwell C 0 or Rockwell B 90
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(b) Austenite (γ)
 Austenite is the interstitial solid solution of carbon and/or
other alloying elements (e.g. Mn, Ni, etc.) in FCC γ- iron.
 Carbon is in interstitial solid solution where as Mn, Ni, Cr, etc.
are substitutional solid solution with iron.
 This has a FCC crystal structure with a high solubility for
carbon compared with α ferrite.
 The solubility reaches a maximum of 2.14 % at 1147 oC The
solubility decreases to 0.8 % at 727 oC.
 The difference in solubility between the austenite and α
Ferrite is the basis for the hardening of steels.
 Austenite is normally not stable at room temperature.

Austenite has:
Tensile strength 10500 kg/cm2
Elongation 10% in 50 mm
Hardness Rockwell C 40 (Approx.) Introduction to Iron-Carbon phase diagram
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Though carbon is present in relatively low concentrations, it
significantly influences the mechanical properties of ferrite:
(a) α ferrite, (b) austenite.

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(c)Cementite (Fe3C)

 Cementite or iron carbide, chemical formula Fe3C.

 This is an intermetallic compound of iron and carbon,
which contains 6.67 % C and 93.3 % Fe.
 Cementite is a hard and brittle interstitial compound of low
tensile strength.
 Its crystal structure is orthorhombic crystal structure with
each unit cell has 12 Fe atoms and 4 C atoms.
 It is ferromagnetic up to 2100C and becomes paramagnetic

Cementite has:
 Tensile strength 350 kg/cm2 (Approx.)
 High compressive strength

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(d) δ Ferrite

 This is a interstitial solid solution of carbon in iron and has a

BCC crystal structure.
 The maximum solubility or C in Fe is 0.1% at 1492oC.
 This has no real practical significance in engineering.

(e) Ledeburite

 Ledeburite is the eutectic mixture of austenite & cementite.

 It contains 4.3 % carbon, it is formed at about 11470c

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(f) Pearlite
 The Pearlite micro-constitute consists of alternate lamellae of
ferrite and cementite.
 Pearlite is the product of austenite decomposition by an
eutectoid reaction.
 Pearlite is an eutectoid mixture containing about 0.8 % C, is
formed 7270C

Pearlite has:
Elongation 20 % in 50 mm
Hardness Rockwell C 20

120 mm
Result: Pearlite =
alternating layers of
a and Fe3C phases
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(h) Martensite
 Martensite is a metastable phase of steel, formed by
transformation of austenite below Ms temperature.
 Martensite is a interstitial supersaturated solid solution of
carbon in α-iron and has BCC tetragonal lattice.
 Martensite, normally is a product of quenching.
 Martensite possesses an acicular or needle like structure.

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(i) Troostite
 Troostite (Nodular) is a mixture of radial lamellae of ferrite
and cementite and therefore differs from pearlite only in the
degree of fitness and carbon content which is the same as
that in the austenite from which is formed.
 In steel heat treatment, the troostite, i.e. the microstructure,
consisting of ferrite and finely divided cementite is
produced on tempering martiensite below apporx. 450 C
(g) Bainite
 Bainite is the constituent produced in a steel when austenite
transforms at a temperature below that at which pearlite is
produced and above that at which martensite is formed.
 Bainite is decomposition product of austenite, consisting of
an aggregate of ferrite & carbide.

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(a) Upper bainite (gray, feathery plates) ( 600).
(b) Lower bainite (dark needles) ( 400). (From ASM
Handbook, Vol. 8, (1973), ASM International, Materials
Park, OH 44073.)

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(j) Sorbite
 Sorbite is microstructure consisting of ferrite and finely
divided cementite, produced on tempering martensite
above approximately 4500C.
 The constituent also known as Sorbitic Pearlite, is produced
by the decomposition of austenite when cooled at a rate
slower than that which will yield a troostitic structure and
faster that that which will produce a pearlitic structure.
 Difference between Pearlite, Sorbite and Troostite: are all
ferrite-cementite mixtures having a lamellar structure and
distinguishable from each other in eutectoid steel only by
theirs of dispersion.
The diagram contains three different transformations:
Invariant Reactions
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 Fe-Cementite diagram Eutectic
L →  + Fe3C
Peritectic L
L+→ 1492ºC

L+ 
0.1 %C  2.06 1147ºC

Eutectoid  + Fe3C
 → a + Fe3C
727ºC
a

0.025 %C a + Fe3C
T →

Fe Fe3C
0.16 0.8 4.3 6.7
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%C →
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The diagram contains three different transformations:
Invariant Reactions:
1. Peritectic reaction

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2. Eutectic reaction

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3. Eutectoid reaction

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Microstructural development for eutectoid steel (of composition 0.77
wt % C). The resulting (low-temperature) sketch

Explain the microstructural

change during transformation L
upon equilibrium cooling.
Calculation of each phase. γ

727oC
Explain the mechanical
α + Fe3C
properties of cast iron.

Fe3C

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 Iron-Carbon (Fe-C) Phase Diagram
• 2 important T(°C)
1600
points 
-Eutectic (A): 1400 L
L   + Fe3C   +L
1200 1148°C
A L+Fe3C
-Eutectoid (B): (austenite)

Fe3C (cementite)
R S
  a + Fe3C 1000  
   +Fe3C

a
800 727°C = T eutectoid
B
R S
600
a+Fe3C
400
0 1 2 3 4 5 6 6.7
(Fe) 0.76 4.30 Co, wt% C
120 mm
C eutectoid

Result: Pearlite = Fe3C (cementite-hard)

alternating layers of a (ferrite-soft)
a and Fe3C phases
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Microstructural development for a slowly cooled hypoeutectoid steel (of
composition 0.50 wt % C).

γ γ

γ+αpri
γ
(α is the continuous phase) 727oC

αpri
αpri+eut + Fe3Ceut
pearlite
As C ↓, αpri+eut↑, weaker or softer.

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 Study of various plain carbon steel on Fe-C Equilibrium Diagram
A] Hypo-eutectoid steel containing 0.32% C:

T(°C)
1600

1400 L
    +L (Fe-C
  1200 1148°C L+Fe3C System)

Fe3C (cementite)
(austenite)
  1000
   + Fe3C
a 800
a  r s 727°C
a
  aRS
w a =s/(r +s) 600
w  =(1- wa )
a + Fe3C
400
a 0 1 2 3 4 5 6 6.7
(Fe) Co , wt% C
0.76

C0
pearlite
w pearlite = w 
Hypoeutectoid
w a =S/(R+S) 100 mm
steel
w Fe3 =(1-w a )
C
pearlite Introduction to Iron-Carbon phase diagram
proeutectoid ferrite
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1. At very high temperature at point 1 the entire steel is in
liquid condition.
2. As the temperature decreases when the steel reduces at a
point 2 solidification starts which gives nuclei of δ-iron
phase. As the temperature further decreases the amount of δ
-iron goes increasing.
3. At any point 3, the amount of liquid and δ -iron can be
calculated by Appling the lever rule as % liquid = AB/AC &
% of δ-iron = BC/AC
4. Further decrease in temperature brings the steel at point 4
5. The properties of δ-iron transforms into austenite due to
hyperperitectic reaction. At any point 5, the steel in now
having liquid + austenite.
6. At point 6 all the liquid get converted into austenite. Further
decrease in temperature only shows austenite contents as
shown by point 7.
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7. At point 8, the austenite tries to convert into ferrite i.e. few
grains will now show the properties of ferrite.
8. At point 9 the steel shows the contents of austenite and ferrite
can calculated by applying lever rule, % of austenite =
XY/XZ. The ferrite which is available in this region is called
as pro-eutectoid ferrite.
9. At point 10, the steel is having pro-eutectoid ferrite with
austenite. This austenite then gets transforms into pearlite
(α+Fe3C), due to hypo-eutectoid reaction.

10. at point 11, α + α + Fe3C

(proecutectoid ferrite white Pearlite-dark).
11. After point 11, no further phase change takes place and only
the temperature is allow to come up to room temperature
hence, at room temperature also the microstructure will show
proeutectoid ferrite and pearlite.

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 Microstructural development for a slowly cooled hypereutectoid steel
or high carbon steel(of composition 1.13 wt % C).

γ γ
Primary Fe3C γ + Fe3C primary
Primary or
γ (Fe3C)primary
(Fe3C is the continuous phase) γ
• 727oC
αeut
(727+1)oC
(727-1)oC
(Fe3C)eut
eutectoid α
Primary or
αeut + Fe3Cpri+eut
Secondary or eutectoid Fe3C
As C ↑, Fe3Cpri+eut ↑→ stronger & brittle
Amount of phase calculation is important because it makes the
0.77
understanding of the mechanical property of the alloy. Explain the
property of hypereutectoid steel & with carbon.
Fe3C

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 Hypereutectoid Steel
T(°C)
1600

1400 L (Fe-C
    +L System)
 
1200 1148°C L+Fe3C

Fe3C (cementite)
(austenite)
  1000
   +Fe3C
Fe3C
  800 r s
  a R S
w Fe3C =r/(r +s) 600
a +Fe3C
w  =(1-w Fe3C )
400
0 1 Co 2 3 4 5 6 6.7
0.76

(Fe)
pearlite Co , wt%C
w pearlite = w 
w a =S/(R+S)
w Fe3C =(1-w a ) 60 mmHypereutectoid
steel
pearlite proeutectoid Fe3C
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Hypoecutectoid Line a-e; Cool From a to d.

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Proeutectoid – Forms before eutectoid

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Eutectoid Steel

NO Proeutectoid phase!

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Eutectoid Steel

Pearlite
Ferrite (white)
Cementite (dark)

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 Hypereutectoid Steel

Proeutectoid Cementite
(white)

Pearlite (striped)

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Effects of Carbon Content

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