Iron Carbon System PDF

Module 23
Iron Carbon System I
Lecture 23
Iron Carbon System I

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NPTEL Phase II : IIT Kharagpur : Prof. R. N. Ghosh, Dept of Metallurgical and Materials Engineering || |
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Keywords : Ferrite (), Austenite (), Ferrite (d): three different forms of iron, solubility of carbon in
different forms of iron, cementite, graphite, Fe – Fe3C meta‐stable phase diagram, pearlite, ledeburite,
hypo‐eutectoid steel, hyper‐eutectoid steel, hypo‐eutectic white cast iron, hyper‐eutectic white cast
iron
Introduction
The last five modules were devoted to the solidification behavior of binary alloys. This is best
represented by its phase diagram. We are now familiar with a wide range of simple and complex phase
diagrams. However while introducing this we only considered hypothetical cases. Now let us consider a
specific binary alloy of considerable importance. We are going to talk about iron ‐ carbon system. Iron
can exist in two different crystalline forms. These are BCC and FCC. This is known as allotropy. Carbon
too has several allotropic forms. However the form which is of relevance to this system is graphite. It has
a hexagonal structure. This is considered to be the most stable state of carbon. An atom of carbon atom
is significantly smaller than that of iron. Therefore it can be accommodated within the interstitial sites of
iron lattice resulting in an interstitial solid solution. Solubility carbon is likely to be limited. Apart from
this iron has a strong affinity to form carbide. The most common form is cementite. Its chemical formula
is Fe3C. This is truly a meta‐stable. However the rate of decomposition of Fe3C into Fe and C is extremely
slow. In most of the common grades iron – carbon alloy excess carbon is present as cementite. Let us
first look at the Fe‐Fe3C meta‐stable phase diagram and in a later module we shall discuss about iron –
graphite phase diagram as well. The alloys belonging to this system is popularly known as steel or cast
iron. We would soon learn about the difference between the two.
Solidification of pure iron:
Fe : crystal structure
T
Liquid Solubility of carbon in Fe =
1539 f(structure, temperature)
 BCC
1394
 FCC
Where is the carbon Slide 1
910 located in iron lattice?
Paramagnetic BCC
770
Ferromagnetic

2 time

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The sketch in slide 1 is a typical cooling curve of pure iron. Solidification begins with nucleation and
growth of crystals of iron at 1539°C. It is BCC (body centered cubic). At 1394°C it transforms into FCC
(face centered cubic) structure. This is stable till 910°C where it again transforms into BCC. Each of these
transformations appears as steps on the cooling curve. Apart from this there is another transformation
which may not get detected by thermal analysis. This is the transformation from paramagnetic to
ferromagnetic state. It occurs at 770°C. This is known as its Curie temperature. The property which is
most sensitive to detect it, is magnetic permeability. The three different forms of iron are known as
ferrite (), stable until 910°C, austenite (), stable from 910°‐1394°C and ferrite (), stable from1394°–
1539°C. Note that the BCC form of iron is known as ferrite. Therefore in order to distinguish between
the two, the high temperature form is termed as delta ferrite. If carbon atoms are introduced into iron
these are likely to occupy the interstitial sites because the atoms carbon are much smaller than those of
iron atoms. The interstitial sites in BCC and FCC are shown in slide 2. The solubility of carbon in iron is a
function of temperature and crystal structure.
Solubility of carbon is higher in BCC or FCC?
Interstitial sites in iron lattice

c c
Slide 2
b b
a a FCC
BCC
Lattice site
Interstitial site
Slide 2 shows the lattice sites occupied by iron atoms and possible interstitial sites for carbon atoms in
both BCC & FCC structures. The interstitial sites shown here are known as octahedral sites. The sketches
in slide 2 show only the positions of iron atoms and the interstitial sites in one unit cell. The sites located
within the cell belong exclusively to a unit cells but those lying on the faces, the edges or the corners are
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shared by the neighboring unit cells as well. BCC has eight corner sites for iron atoms. Each of these is
shared by 8 neighboring unit cells. The contribution of corner site is thus 1/8. The atom at the centre
belongs exclusively to this unit cell. Therefore the number of iron atoms / unit cell = 8 x (1/8) + 1 = 2. Let
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us use the same approach to estimate the number of interstitial sites /unit cell for BCC structure. The
sketch in slide 2 shows the locations of interstitial sites. There are 6 sites at the centers of 6 faces. Each
face is shared by two unit cells. There are 12 sites at each of the 12 edges. Each of these is shared by 4
neighboring cells. Therefore the number of interstitial sites / unit cell in BCC crystal = 12 x (1/4) + 6 x
(1/2) = 6. Note that it is 3 times the number of Fe atoms in a unit cell. Look at the sketch for FCC unit cell
in slide 2. Count the number of lattice sites. Follow the same approach to show that the number of Fe
atoms / unit cell = 6 x (1/2) + 8 x (1/8) = 4. In the same way the number of interstitial sites / unit cell in
FCC structure = 1 + 12 x (1/4) = 4. Note that in FCC structure the ratio of the number of interstitial site to
the number of lattice sites = 1. Now that we know about the possible sites carbon atoms could occupy
is it possible to guess which of these is likely to have higher solubility?
F
D C
F
O
A B D
Fig 1
A O C
E
B

E
(a) (b)
Fig. 1(a): Shows the lattice and the interstitial sites in a BCC unit cell. Circles are the lattice sites. The
black dots are the interstitial sites. In a lattice several of such cells are stacked one after the other. F
represents the body center site in a unit cell just above the one shown in the sketch. The figure ABCDEF
formed by joining the lattice sites as illustrated is an octahedron. There is an interstitial site at its center
marked as O. All the interstitial sites are identical. Note that AB = BC = CD = DA = = the lattice
parameter. The other edges of the octahedron AE = BE = CE = DE = AF = BF = CF = DF = √3/2. It is not a
regular octahedron. The interstitial site in BCC structure is not symmetrical. The gap along EF is shorter
than that along AC or DB. It is 2 √3 /2. The lattice parameter of BCC iron called ferrite is
0.286nm. The shortest gap is equal to 0.038nm.
Fig. 1(b): Shows the lattice and the interstitial sites in a FCC unit cell. Circles are the lattice sites. The
black dots are the interstitial sites. In a lattice several of such cells are stacked one after the other. The
figure ABCDEF formed by joining the lattice sites as illustrated is an octahedron. There is an interstitial
site at its center marked as O. All the interstitial sites are identical. Note that AB = BC = CD = DA = AE =
√
BE = CE = DE = AF = BF = CF = DF = , where = the lattice parameter. It is a regular octahedron. The
4 interstitial site in FCC structure is symmetrical. The gap along EF is equal to that along AC or DB. It
is 2 √2 /2. The lattice parameter of FCC iron called austenite is 0.362nm. The interstitial gap is
equal to 0.106nm. It is much larger than the interstitial gap in ferrite.
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FCC has higher packing density than BCC. Yet the solubility of carbon is FCC is higher. This is because the
interstitial sites in FCC are bigger than that in BCC. There are two types of interstitial sites known as
octahedral and tetrahedral. In FCC the tetrahedral sites are surrounded by four close packed atoms. The
gap is extremely small, whereas in BCC the four atoms are more widely spaced. The tetrahedron is not
symmetric. The shortest dimension (size) of tetrahedral sites in BCC lattice was derived in module 5. This
is nearly same or marginally lower (0.036nm) than that of the octahedral site (0.038nm). The number of
such sites is much more than that of the octahedral sites. Although the packing density in BCC is lower
than that of FCC, the gaps are equally distributed between two types of interstices making these
significantly smaller than that of FCC. This is why the solubility of carbon which is an interstitial solute is
significantly lower in ferrite (BCC) than that in austenite (FCC). Apart from this the interstitial site in BCC
is asymmetric. When a carbon atom goes into the interstices the atoms along one of the axes are
pushed further apart. This results in a tetragonal distortion. We shall talk about it in one of the
subsequent modules.
Phases in iron – carbon binary system:
Iron can exist in three different crystalline forms each having limited solubility of carbon. The stability of
these depends on temperature and composition. The two high temperature forms of iron are  ferrite
which is BCC (stable above 1394°C) and austenite (stable above 910°C) which is FCC. The room
temperature form of iron is  ferrite which is BCC. The solubility of carbon in ferrite is limited. The
maximum solubility is around 0.025wt% as against this the solubility of carbon in austenite is a little
more. It is about 2wt%. Apart from this iron carbon system may have iron carbide (Fe3C) called
cementite. It has 6.67% carbon. It is considered as an inter‐metallic compound having relatively more
complex crystal structure than those of ferrite and austenite. It is a meta‐stable phase. It may exist for
indefinite periods of time at room temperature. However on prolonged thermal exposure at 600°C or
beyond it transforms into ferrite and graphite. Therefore iron carbon alloys of commercial importance
may be considered as a binary alloy of iron and cementite. Let us first look at its phase diagram. It is
also known as iron cementite meta‐stable phase diagram. Although it is a binary system there are 5
different phases including the liquid. This is likely to have more than one invariant reaction involving 3
phases.
5
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Iron – cementite phase diagram
1539 +L Peritectic
 isotherm L
Eutectic
1394
+ isotherm
+L L + Cm
 1148
910 Hypoeutectic Hyper-eutectic

Slide 3
  + Cm

727
Eutectoid
Hypo Hyper isotherm
eutectoid eutectoid
0 0.8 2.0 %C 4.3 6.67

Slide 3 gives a schematic Fe‐Fe3C phase diagram. It has 3 invariant reactions (transformation). These are
given in slide 4. The one occurring at 1495°C is the peritectic reaction. The delta ferrite reacts with liquid
to form austenite. The one at 1148°C is known as the eutectic reaction where the liquid transforms into
a mixture of austenite and cementite. The eutectic is known as Ledeburite. The one at 727°C is known as
eutectoid transformation where austenite decomposes into a mixture of ferrite and cementite. This is
known as Pearlite. On the basis of this diagram iron – carbon alloys having less than 2.0% carbon are
known as steel, whereas those having more than 2.0% carbon are known as cast iron. This classification
is based on their ability to undergo large plastic deformation. Steel is ductile but cast iron is brittle.

Slide 4

Steel:
It is an iron carbon alloy where most of the carbon is present as meta‐stable iron carbide called
cementite. The upper limit of carbon content is 2%. Phase diagram helps us guess the structure of alloys
6 and their properties. Let us look at what kinds of structure steel could have depending on its
composition. We would only consider the structure that develops under equilibrium rate of cooling. The
steel on solidification is expected to have fully austenitic structure. It may be assumed to be
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homogeneous since the rate of cooling is considered to be slow. Depending on its composition we may
have 3 types of structures. (i) % carbon < 0.02 (ii) 0.02 < % carbon < 0.8 (iii) 0.8 < % Carbon < 2.0.
L

1539
L
L + 

+ L L
1495 
1394  
+ L
T°C T  Fig 2

910 
  + Cm 
727

 + Cm
 + Cm
0 0.02 0.8 2.0 Wt% C time
(i) Figure 2 explains the solidification behavior of steel having less than 0.02% carbon with the
help of a set of schematic diagrams. The sketch on the left shows a part of the equilibrium
diagram (Fe‐Fe3C) with the location of the alloy by a vertical dotted line. It intersects the
liquidus, solidus, and a set of solvus curves. These are projected on to the cooling curve
shown on the right with the help of a set of horizontal lines. The cooling curve exhibits
inflection points at each of these intersections. Solidification begins with precipitation of a
few grains of  ferrite. The top most microstructure corresponds to this stage. The
solidification takes place by nucleation and growth. The composition of the liquid and the
solid keeps changing during this stage. When solidification is complete the entire liquid is
replaced by  ferrite having the same composition as that of the alloy. This is shown by the
second schematic structure from the top in Fig 2. The structure remains unchanged until the
temperature crosses the boundary between  /  phase fields. Thereafter austenite
precipitates from  ferrite. The grain corners and boundaries are the preferred sites where
grains of austenite nucleate. The third microstructure from the top in Fig 2 represents its
main features. It consists of grains of  (white) and a few grains of  (grey). There is partition
of carbon between these two phases. Bulk of the carbon goes into austenite. The
composition of the two keeps changing as the temperature drops. The volume fraction of 
increases at the cost of . When the %carbon in austenite becomes equal to that of the steel
 ferrite disappears. The structure now consists of 100% austenite. Note the main features
of the fourth microstructure from the top in Fig 2. The grain size is finer than that of 100% 
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ferrite. The structure remains as 100% austenite until the temperature drops below the line
representing the boundary between  and  phase fields of the equilibrium diagram.
This is where  ferrite starts precipitating from austenite. The grain boundaries and the
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grain corners are the preferred sites for precipitation. The fifth sketch from the top of Fig 2
is a typical representation of its microstructure at this stage. Ferrite grains are shown as
white and austenite grains are shown as grey. This continues through nucleation of new
grains and growth of the existing ones until the temperature drops below the line between
 and  phase fields of the phase diagram. At this stage the structure is 100% ferrite ().
The 6th sketch in Fig 2 is a typical representation of the microstructure. This remains
unchanged till the temperature drops below the solvus. At this stage excess carbon
precipitates as cementite. The last sketch in Fig 2 is a typical representation of its
microstructure. The amount of cementite keeps increasing as the room temperature drops.
It can be estimated by lever rule. From the phase diagram it is evident that the steel at room
temperature would consist of ferrite with a few specks of cementite. If % carbon in the steel
is 0.01 the amount of cementite is given by (0.01/6.67)x100 = 0.15%. The grains are
relatively finer than that after solidification. L

1539
L
+ L L L
1495

1394
+ L
T°C T 
  Fig 3
910

  + Cm 
727

Pearlite
 + Cm


0 0.02 0.8 2.0 Wt% C time

(ii) Figure 3 explains the solidification behavior of steel having greater than 0.02% carbon but
less than 0.8% carbon with the help of a set of schematic diagrams. The sketch on the left
shows a part of the equilibrium diagram (Fe‐Fe3C) with the location of the alloy by a vertical
dotted line. It has around 0.18% carbon. It intersects the liquidus and a set of lines denoting
either phase field boundaries or isotherms representing 3 phase equilibrium. These are
projected on to the cooling curve shown on the right with the help of a set of horizontal
lines. The cooling curve exhibits inflection points or steps (discontinuity) at each of these
intersections. Solidification begins with the precipitation of a few grains of  ferrite. The first
microstructure from the top corresponds to this stage. Solidification takes place by the
nucleation of new grains and the growth of the existing ones. The composition of the liquid
and the solid keeps changing during this stage. When the temperature reaches 1495°C
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peritectic reaction sets in. This is an invariant reaction. The liquid having 0.55% carbon
reacts with  ferrite having 0.08% carbon to form austenite () having 0.18% carbon. The
amount of is just enough to consume the remaining liquid. The alloy on solidification
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consists of austenite () having 0.18% carbon. This is shown by the second schematic
structure from the top in Fig 3. The structure remains unchanged until the temperature
crosses the boundary between  /  phase fields. Thereafter ferrite () precipitates from
( austenite. The grain corners and boundaries are the preferred sites where grains of
ferrite nucleate. The ferrite precipitating from austenite is known as pro‐eutectoid ferrite.
The third microstructure from the top in Fig 3 represents its main features. It consists of
grains of pro‐eutectoid  (white) and a few grains of  (grey). There is partition of carbon
between these two phases. Bulk of the carbon goes into austenite. The composition of the
two keeps changing as the temperature drops. The volume fraction of  increases at the
cost of . When % carbon in austenite reaches 0.8% eutectoid reaction sets in. This is an
invariant reaction. As long as it continues the temperature remains constant. During this
stage both cementite and ferrite start precipitating from austenite at the same time. The
product is an intimate mixture of two phases. It is known as pearlite. It consists of parallel
layers (plates) of ferrite and cementite. Figure 4 gives a series of sketches showing various
stages involved in the formation of pearlite. When a cementite plate nucleates as in (Fig.
4(a)) at an austenite boundary it takes carbon from its neighboring area. This results in a
change in local carbon profile as shown in the sketch. Just beside cementite % C = 0.02
whereas at a distance far from this it approaches 0.8 % C (this is the composition of the
eutectoid). When this becomes low enough a ferrite plate nucleates. Figure 4 (b) illustrates
this. Note the change in carbon concentration as a function of distance. Figure 4 (c) shows
the arrangement of ferrite cementite plates in a colony of pearlite. The width of the two is
approximately proportional to % ferrite and % cementite in eutectoid steel having 0.8%
carbon. Using lever rule % cementite in pearlite =100 x (0.8‐0.025) / (6.67‐0.025) = 12%
(approximately). Therefore % ferrite = 88%. The ratio of the two is approximately equal to
1:7. This means the width of the ferrite plate will be seven times the width of cementite
plate. On completion of the eutectoid reaction the structure consists of pro‐eutectoid ferrite
and pearlite. Note the main features of the fourth microstructure from the top in Fig 3.
When the temperature drops below the eutectoid temperature, excess carbon from ferrite
() precipitates as cementite. This is known as tertiary cementite (Why this is called tertiary
will be clear from subsequent part of this module). However the change in structure below
the eutectoid temperature is too little to detect. Steels having carbon within 0.02 – 0.8
consist of ferrite and paerlite. They are known as hypo‐eutectoid steel.

6.67 6.67
% C % C
0.8 0.8 0.8 0.8
0.02 x 0.02 0.02 x 0.02
9 Fe3C Fe3C Ferrite

(a) Austenite (b) Austenite
boundary boundary Fig 4
| |  Pearlite
Fe3C colony
(c) Austenite (d) Structure

boundary

Hyper-eutectoid steel (0.8-2.0% C)

1539 L L

1394 L+ L
(a)
  
910   Slide 5
 

  Cm
723 
 
Cm 
P
0 0.8 2.0 Time

Cm
%C

(iii) Slide 5 explains the solidification behavior of steel having greater than 0.8% carbon but less
than 2.0% carbon with the help of a set of schematic diagrams. Such steels are known as
hyper‐eutectoid steel. The sketch on the left shows a part of the equilibrium diagram (Fe‐
Fe3C) with the location of the alloy as a vertical dotted line. It has around 1.0% carbon. It
intersects the liquidus, solidus, solvus and the eutectoid reaction isotherm representing 3
phase equilibrium. These are projected on to the cooling curve shown on the right with the
help of a set of horizontal lines. The cooling curve exhibits inflection points or a step
(discontinuity) at each of these intersections. Solidification begins with precipitation of a
few grains of  austenite. The top most microstructure corresponds to this stage. The
solidification takes place by nucleation of new grains and growth of the existing ones. The
composition of the liquid and the solid keeps changing during this stage. When the
temperature reaches that of the solidus the composition of the solid becomes equal to that
of the steel. The alloy on solidification consists of 100% austenite () having 1.0% carbon
(say). This is shown by the second schematic structure from the top in slide 5. The structure
remains unchanged until the temperature crosses the solvus, the boundary between  / +
Cm phase fields. At this stage cementite starts precipitating from austenite. It grows at the
cost of austenite. The % carbon in austenite keeps decreasing as the amount of cementite
increases. The grain boundary is the most favored site for precipitation. The fourth structure
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from the top in slide 5 gives a typical structure of steel at this stage. When % carbon in
austenite decreases to 0.8% eutectoid reaction sets in. This is an invariant reaction. As long
as it continues the temperature remains constant. During this stage both cementite and
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ferrite start precipitating from austenite at the same time. The product is an intimate
mixture of two phases. It is known as pearlite. The details about the pearlitic structure are
shown in Fig 4. Cementite is a hard and brittle phase. The presence of a continuous network
of cementite makes steel extremely brittle. There are methods to avoid the formation of
such a network to make it suitable for engineering applications. We shall learn about in one
of the subsequent modules.
Estimation of the amount of micro‐constituents in steel from phase diagram:
The micro‐constituents in steel are ferrite, austenite, cementite and pearlite. Out of these austenite
is not stable at room temperature. When we look at microstructures of steel we get an idea about
the distribution of various constituents. If the composition or % carbon in steel is known we can
estimate the volume fraction (weight fraction) of each the likely constituents.
L
T
(x) (y) 1145 Fig 5: Shows how to estimate the amounts of
910  micro‐constituents in steel at room temperature.
 + Cm The phase diagram gives approximate % C for

 727 various points of interest. These are denoted as a,

 + Cm b, c, d, & e. % C in a hypo‐eutectoid steel is x and
that in hyper‐eutectoid steel is y.
0
0.02 0.8 2.0 4.3 6.67
a b c d e
Figure 5 gives the relevant part of Fe‐Fe3C phase diagram. For practical purpose we may assume that the
solubility of carbon in ferrite is negligible. The general expressions for the amount of Pearlite (P),
Cementite (Cm), Pro‐ eutectoid Ferrite & Total ferrite () in a hypo‐eutectoid steel having x% C are as
follows.
% 100 100
.
.
% 100 100
.
% 100 100
.
. .
% 100 100
.
This truly gives weight % of various constituents. When you look at the microstructure you get an
estimate of volume %. However if the density of the phases are known weight % can be converted to
11 volume %. In the case of steel the density of ferrite is 7.87 g/cc and that of cementite is 7.662. Although
the difference is not much the amount of Cm seen in a microstructure (volume fraction) will be a little
more than weight fraction obtained from the lever rule.
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Microstructure of Fe‐Fe3C eutectic:
The slide 6 explains the solidification behavior of Fe‐Fe3C eutectic. This is the binary iron‐carbon alloy

having the lowest melting point. It solidifies as eutectic at 1148°C. It is known as Ledeburite.
Structure of eutectic (Ledeburite)
T L
T
cm Slide 6
cm
a b c d e time
%  in eutectic at TE = (de/ce) x100
% P in eutectic at RT = (de/be) x100

% carbon in the eutectic is 4.3. Solidification occurs at a constant temperature. Immediately after
solidification the alloy consists of a mixture of austenite and cementite. % austenite = 100 x (e‐d)/(e‐c) =
100 x (6.67 – 4.3)/(6.67‐2.0) =52% (approx). The solubility of carbon in austenite decreases with
decreasing temperature. At the eutectoid temperature the solubility of carbon in austenite is only 0.8%.
Therefore as the alloy cools cementite precipitates from the austenite in the eutectic. % austentite at
the eutectoid temperature (just before the decomposition of austenite starts) = 100 x (e ‐ d)/(e – b) =
100 x (6.67 – 4.3)/(6.67 – 0.8) = 41% (approx). When the eutectoid reaction sets in the austenite having
0.8% carbon transform into pearlite. The eutectic after this transformation is known as transformed
Ledeburite. It approximately consists of 41% Pearlite in a matrix of cementite. Figure 6 shows the main
features of the eutectic that forms at 1148°C. It is initially a mixture of cementite and austenite. On
cooling the % cementite increases and the carbon content of austenite decreases till it reaches 727°C.
This is where the austenite having 0.8% carbon transforms into pearlite. Thereafter as per the phase
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diagram % ferrite within the pearlitic region would decrease as some cementite would precipitate out of
it. This is due to the decrease in the solubility of carbon in ferrite with decreasing temperature. However
the change is too little to be detected from the microstructure.
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Cm Cm


Pearlite

Fig. 6: Shows a schematic representation of the Fig. 7: Shows the structure of the eutectic Fe‐Fe3C

eutectic consisting of cementite as white matrix at room temperature. Note that volume fraction of
and austenite as grey particles at 1145°C. It is austenite has decreased and it has transformed

called ledeburite. into pearlite. It is called transformed ledeburite.

White cast iron:
If % carbon is greater than 2.0 but less than 6.67 the Fe‐Fe3C alloy is known as white cast iron. Such an
alloy can be easily cast into various shapes but it has poor ductility. The fracture surface has silvery
white luster. This is why it is known as white cast iron. On the basis of its microstructure there are two
types of white cast iron. These are (i) hypoeutectic white cast iron (2.0 < % C < 4.3) and (ii) hypereutectic
white cast iron (4.3 < %C < 6.67). Cementite (Fe3C) is the hardest constituent in the Fe – Fe3C system. Its
hardness is of the order of 1000HV (Vickers Hardness Number). This is why it has excellent wear
resistance. Recall that the % carbide in eutectic is around 60%. Hard materials are known to be brittle.
There is no wonder that white cast iron has poor ductility. Let us look at the evolution of microstructure
in hypo & hyper eutectic white cast iron. This has been explained with the help of a set of sketches given
in Fig 8 – 9.
x
1539
+ L L L
1495 
1394 L +Cm L
+ L
T°C T + L Ledeburite Fig 8
 
910
 + Cm
 Cm Transformed
727 Pearlite
Ledeburite
 + Cm

 + Cm
13
0 0.02 0.8 2.0 3.0 4.3 6.67 time

Wt% C
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Figure 8 describes the evolution of the microstructure in a hypoeutectic cast iron. The vertical dotted
line marked x is the location of the alloy with respect to the Fe‐Fe3C phase diagram. The sketch on the
right gives its cooling curve. Solidification begins with nucleation and growth of austenite grains. As it
cools the amount of austenite increases at the cost the liquid. The composition of the austenite and the
liquid keep changing. At the eutectic temperature the composition of liquid is 4.3 whereas that of the
austenite is 2.0. If %C in the cast iron is 3.0, % austenite at this temperature =100 x (4.3‐3.0)/(4.3‐2.0) =
57%. The balance 43% is liquid. On cooling this it solidifies as a mixture of austenite and cementite. The
eutectic is known as ledeburite. The austenite that forms before eutectic transformation is called pro‐
eutectic austenite or primary austenite. On subsequent cooling, the volume fraction of cementite
increases at the cost of austenite. At the eutectoid temperature the primary austenite and the austenite
in the eutectic transform into pearlite. The final structure would consist of relatively large nodule of
pearlite (originating from primay austenite) and a fine dispersion of tiny nodules of pearlite (originating
from the austenite in the eutectic) in a matrix of cementite.

x
1539
+ L L L
1495 Cm
1394 L +Cm L
+ L
T°C T + L Ledeburite Fig 9
 Cm
910
 + Cm
 Cm
727 Cm Transformed
 + Cm Ledeburite
 + Cm

0 0.02 0.8 2.0 4.3 5.0 6.67 time

Wt% C

Figure 9 describes the evolution of the microstructure in a hyper‐eutectic white cast iron. The vertical
dotted line marked x is the location of the alloy with respect to the Fe‐Fe3C phase diagram. The sketch
on the right gives its cooling curve. Solidification begins with nucleation and growth of primary (pro‐
eutectic) grains of cementite. As it cools the amount of cementite increases at the cost the liquid. Note
that cementite has a fixed composition. However the composition of the liquid keeps changing. At the
eutectic temperature the composition of liquid is 4.3. If %C in the cast iron is 5.0, %liquid at this
temperature =100 x (6.67‐5.0)/(6.67‐4.3) = 70%. On further cooling it solidifies as a mixture of austenite
and cementite. The eutectic is known as ledeburite. The cementite that forms before eutectic
transformation is called pro‐eutectic cementite or primary cementite. On subsequent cooling, the
14 volume fraction of cementite increases at the cost of austenite within the eutectic. The cementite that
forms during this stage is called secondary cementite. At the eutectoid temperature the austenite in the
eutectic transforms into pearlite. The final structure consists of relatively large primary cementite and a
fine dispersion of tiny nodules of pearlite (originating from the austenite in the eutectic) in a matrix of
| |

cementite. The eutectic in cast iron at room temperature is known as transformed ledeburite. The
cementite present in iron carbon system has several distinct morphologies. In hyper‐eutectic white cast
iron has all of theses. Cementite precipitating from the liquid is called primary cementite, that
precipitating from austenite is called secondary cementite, and those precipitating from ferrite below
eutectoid temperature is called tertiary cementite. Apart from these cementite is also present as thin
plates within nodules of pearlite.
Summary:
In this lecture we have learned Fe‐Fe3C meta‐stable phase diagram. It gives a graphical representation of
the stability of different phases one may come across in such a system over a range of temperature (0°‐
1550°C) and compositions (0‐6.67%C). It has 3 invariant reactions. These are peritectic, eutectic and
eutectoid. Barring pure iron, cementite and the eutectic all alloys belonging to this system do not have a
definite melting point. We have learnt how to draw or guess the cooling curve of an alloy if its
composition were known. It helps in predicting the type of structure that evolves during solidification.
Iron carbon alloys having less than 2% carbon are known as steel whereas those having carbon more
than 2% but less than 6.67% are known as cast iron. At room temperature all iron carbon alloys are
made of ferrite and cementite. However the distribution and the amount of these may vary widely. On
the basis of the distribution of the two phases we can have 3 types of steel and two types of cast iron.
These are (i) terminal solid solution having only ferrite or at best extremely small amounts of tertiary
carbides (ii) hypo‐eutectoid steel (iii) hyper‐eutectoid steel (iv) hypo ‐ eutectic white cast iron and (v)
hyper‐ eutectic white cast iron. How the structure evolves in these during solidification has been
explained with illustrations. The iron cementite phase diagram at the end of this lecture gives an
overview of the structural features of each of the 5 types of alloys belonging to this system. However
while talking about the evolution of structure we do assume that cooling rate is slow. This indeed is a
major limitation of phase diagram. We have already seen the effect of non‐equilibrium cooling on
segregation during liquid to solid transformation. In Fe‐Fe3C system we do have a eutectoid
transformation where the effect of cooling rate is likely to be much more severe. We shall talk about it
in a subsequent lecture.
Exercise:
1. FCC is a more close packed structure yet solubility of carbon in austenite which is FCC is higher
than that in ferrite which is BCC. Why it is so?
2. Sketch the microstructure of 0.2% C steel. Calculate %Pearlite % cementite, % proeutectoid
ferrite and % total ferrite.
3. Estimate the ratio of the widths of ferrite and cementite plates in lamellar pearlite.
4. Sketch the temperarture – time diagram during the heating cycle of a 0.8% C steel. Use standard
Fe‐Fe3C phase diagram.
15 5. Estimate %Cm in Ledeburite just below eutectic and just above eutectoid temeratures. What is
its structure at room temperature?
Answer:
| |

1. There are 2 types of interstitial sites octahedral & tetrahedral. In FCC the former is significantly
larger than the latter. Whereas in BCC these are nearly same. The total open space is shared by
more number of sites. Therfore interstitial gap in BCC is much smaller than that of FCC. This is
why carbon which occupies interstitial site has higher solubility in austenite (FCC).

2. The stucture would consist of proeutectoid ferrite and pearlite. Assume solubility of carbon in
.
ferrite is negligible. Refer to phase diagram to get % Pearlite in 0.2% carbon steel =
.
.
100 25 Balance 75% is proeutectoid ferrite. % Cementite = 100 3% and total
.
ferrite = 97%.

3. Assume density of ferrite and cementite to be same (Note that in reality density of cementite is
. .
a little higher than that of ferrite). % ferrite in pearlite = 100 88. Balance 12% is
.
cementite. Therefore the ratio of the widths of the two = 12/88. This is approximately equal to
1:7.

4. 0.8 % carbon corresponds to an eutectoid steel. It would first transform into austenite and then
it starts melting when the temperature reaches its solidus temperature. It becomes totally liquid
when temperature goes beyond its liquidus. Shematic heating curve is as follows:
liquid
L+

T

+cm: Pearlite
Time
. .
5. Assume % C in eutectic = 4.3. % Cm just below eutectic temperature = 100 49%and
. .
. .
just above eutectoid = 100 60%Between eutectic to eutectoid temperatures
. .
proeutectoid cementite precipitates from austenite in eutectic. On subsequent cooling the
austenite transforms into pearlite. At room temperatutre what we have is transformed eutectic.
16
| |

Iron – Cementite Meta‐stable Binary Phase diagram

0.08 1550
1539  + L =
L
+ L 0.55

1495
1394 0.18 L =  + Cm
 L +Cm
+ L
T°C

1146
910
 =  + Cm

  +Cm + Cm + LD Cm+ LD
727  727

 + Cm + P Cm + P P + TLD +Cm Cm + TLD

+ Cm Hypo‐eutectoid Hyper‐eutectoid Hypo‐eutectic Hyper‐eutectic
steel steel white cast iron white cast iron
0 0.02 0.8 2.0 4.3 6.67

Fe Cm
Wt% C

The above sketch is a little enlarged version of the phase diagram. Fe & Fe3C (also known as cementite)
are the two components. Nomenclature: P denotes Pearlite the product of eutectoid reaction in iron
carbon system. It is a mixture of ferrite and cementite. Ferrite = ,  = austenite,  = high temperature
ferrite, LD = Ledebutite: the product of the eutectic reaction. Note that austenite can form either by
peritectic reaction between  & L and also by direct precipitation from liquid when % C > 0.55. TLD =
transformed Ledeburite. Ledeburite is a eutectic mixture of austenite and cementite. At room
temperature austenite is not stable. It transforms into Pearlite. TLD therefore consists of tiny nodules of
pearlite in cementite matrix. It also describes the main structural features of five types of iron carbon
alloys. Low carbon steel consists of ferrite and tertiary cementite. Hypo‐eutectoid steel has ferrite, pro‐
eutectoid cememtite and pearlite. Hyper‐eutectoid steel has pro‐eutectoid cementite (secondary) and
pearlite. Hypo‐eutectic cast iron has pearlite, transformed ledeburite and pro‐eutectoid (secondary)
cementite. Hyper‐eutectic cast iron has primary cementite and transformed ledeburite. So far evolution
of microstructure that takes place during solidification of iron – carbon alloys has been explained with
the help of schematic microstructure. The following page gives a few typical microstructures of steel and
17 cast iron. These were prepared by some of my students and colleagues at I I T Kharagpur and CSIR‐NML
Jamshedpur.
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Typical microstructures of steel and cast iron
Fig A1: Microstructure of 0.15% carbon steel Fig A2: Microstructure of medium carbon steel
consisting of ferrite (bright) and pearlite (dark). consisting of ferrite (bright) and pearlite (dark).
Lamellar feature pearlite is not visible. (Curtsey G Amount of pearlite increases with % carbon.
Das CSIR‐NML Jamshedpur) (Curtsey G Das CSIR‐NML Jamshedpur).
Fig A3: Microstructure of a near eutectoid steel Fig A4: SEM image of 0.84% C steel having nearly

having a little pro‐eutectoid cementite in a matrix 100% pearlite. Lamellar feature is clearly visible.
of pearlite. In some of regions finer details of The dark region is pro‐eutectoid cementite.
pearlitic (lamellar) structure is visible. (Curtsey G Das CSIR‐NML Jamshedpur)
18
Fig A5: Microstructure of hyper‐eutectic white cast Fig A6: Microstructure of grey cast iron having
iron showing primary carbides (cm). The rest of the graphite flakes in a matrix consisting of mostly
region consists of a mixture of pearlite and ferrite and some amount of pearlite. (Curtsey G
cementite or transformed eutectic (ledeburite). Das CSIR‐NML Jamshedpur)
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Module 23

Iron Carbon System I

Iron Carbon System I

Interstitial sites in iron lattice

910 Hypoeutectic Hyper-eutectic

(c) Austenite (d) Structure

Hyper-eutectoid steel (0.8-2.0% C)

0 0.8 2.0 Time

The slide 6 explains the solidification behavior of Fe‐Fe3C eutectic. This is the binary iron‐carbon alloy

Structure of eutectic (Ledeburite)

0 0.02 0.8 2.0 4.3 5.0 6.67 time

0 0.02 0.8 2.0 4.3 6.67

Fig A3: Microstructure of a near eutectoid steel Fig A4: SEM image of 0.84% C steel having nearly

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