The IronIron Carbide (FeFe3C) Phase Diagram

In their simplest form, steels are alloys of Iron (Fe) and Carbon (C).

The Fe-C phase diagram is a fairly complex one, but we will only consider the steel part of
the diagram, up to
around
d 7% C
Carbon.
b

Phases present
-ferrite,
-ferrite,
-ferrite,
Fe3C (iron carbide
or cementite)
Fe-C liquid solution

School of Mechanical and Building Sciences, VIT University, Vellore

Phases in FeFe3C Phase Diagram

-ferrite - solid solution of C in BCC Fe
Stable form of iron at room temperature.
The maximum solubility of C is 0.022 wt%
Transforms
T
f
t FCC -austenite
to
t it att 912 C
-austenite - solid solution of C in FCC Fe

Fe3C (iron carbide or cementite)

This

intermetallic

compound

is

metastable, it remains as a compound

indefinitely at room T, but decomposes
(very slowly, within several years) into Fe and C (graphite) at 650 - 700 C

The maximum solubility of C is 2.14 wt %.

Transforms to BCC -ferrite at 1395 C
Is

not

stable

below

the

Fe-C liquid solution

eutectic

temperature (727 C) unless cooled

rapidly
-ferrite - solid solution of C in BCC Fe
The same structure as -ferrite
Stable only at high T, above 1394 C
Melts at 1538 C

-ferrite

School of Mechanical and Building Sciences, VIT University, Vellore

austenite
2

Changes in Crystal Structure

Pure iron when heated experiences two changes in crystal structure before it melts.

At room temperature the stable form, ferrite ( iron) has a BCC crystal structure.

Ferrite experiences a polymorphic transformation to FCC austenite ( iron) at 912 C (1674 F).

At 1394C
1394 C (2541F)
(2541 F) austenite reverts back to BCC phase ferrite and melts at 1538
1538C
C (2800F)
(2800 F).

Iron carbide (cementite or Fe3C) an

intermediate compound is formed
at 6.7 wt% C.

Typically, all steels and cast irons have

carbon contents less than 6.7 wt% C.

Carbon is an interstitial impurity in iron

and forms a solid solution with the
, , phases.

School of Mechanical and Building Sciences, VIT University, Vellore

A few comments on FeFe3C system

C is an interstitial impurity in Fe. It forms a solid solution with , , phases of iron

Maximum solubility in BCC -ferrite is limited (max. 0.022 wt% at 727 C) which can be
p
byy the shape
p and size of the BCC interstitial p
positions,, which make it difficult to
explained
accommodate the carbon atoms. BCC has relatively small interstitial positions. Even though
present in relatively low concentrations, carbon significantly influences the mechanical
properties of ferrite

Maximum solubility in FCC austenite is 2.14 wt% at 1147 C - FCC has larger interstitial
positions

Mechanical properties: Cementite is very hard and brittle - can strengthen steels.
Mechanical properties also depend on the microstructure, that is, how ferrite and cementite
are mixed.

Magnetic properties: -ferrite is magnetic below 768 C, austenite is non-magnetic

School of Mechanical and Building Sciences, VIT University, Vellore

Classification - Types of ferrous alloys

Three types of ferrous alloys:

Iron:
less than 0.008 wt % C in ferrite at room T
Steels:
0.008 - 2.14 wt % C (usually < 1 wt % );
-ferrite + Fe3C at room T
Cast iron:
2.14 - 6.7 wt % (usually < 4.5 wt %)

School of Mechanical and Building Sciences, VIT University, Vellore

Invariant Reactions in FeFe3C System

In binary phase diagrams, a horizontal line always indicates an invariant reaction.

Three invariant reactions are present in IronIron Carbide (FeFe3C) Phase Diagram.

1. Peritectic reaction

1493 C

2. Eutectic reaction

1150 C

3. Eutectoid reaction

727 C

School of Mechanical and Building Sciences, VIT University, Vellore

Peritectic reaction - FeFe3C System

Peritectic, involves the following phase transformation.
PM

L(0.53%
(
C)) + ((BCC Ferrite of 0.1% C))

((FCC Austenite of 0.18% C))

N

The maximum solubility of carbon in BCC -iron is 0.1% (point M)

whereas in FCC -iron, it is greater. The presence of carbon
influences the allotropic changes. As carbon is increased or added
to the iron, the temperature increases from 1400C to 1493C at
0 1% carbon.
0.1%
b

School of Mechanical and Building Sciences, VIT University, Vellore

Peritectic reaction - FeFe3C System

Consider the portion NMPB in Peritectic Reaction

On cooling, the portion NM represents the beginning of the crystal

structure change from BCC iron to FCC iron for alloys

PM

containing less than 0.1%

0 1% carbon.
carbon

Line MP represents the beginning of crystal structure change by

means of peritectic reaction for the alloys between 0.1 & 0.18%
Carbon.

Line NP represents the end of crystal structure change for alloys

containing less than 0.18% C.

Portion PB represents the end of crystal structure by means of

peritectic reaction for the alloys between 0.18- 0.5% carbon. Here
the reaction takes place isothermally (i.e.) at constant temperature.

At the peritectic reaction point, liquid of 0.53% C combines with

ferrite of 0.1% C to form FCC austenite of 0.18% C
School of Mechanical and Building Sciences, VIT University, Vellore

Eutectic reaction - FeFe3C System

Eutectic Point is given by point E (refer fig.2) exists at 4.3% Carbon

L

and at the temperature of 1147C.

Horizontal line represents the eutectic temperature line and

g the eutectic
whenever an alloyy crosses the line must undergo
reaction

Any liquid that is present when this line is reached must solidify
now into very fine intimate mixture of two phases namely austenite
() and cementite (Fe3C).

The eutectic mixture has been given with the name LEDEBURITE
and the equation is given as
6.67%C
(4.3% C)
(FCC)
0.18% C

The eutectic mixture is not usually seen in the microscope because the austenite is not stable at
room temperatures and must undergo another reaction during cooling
School of Mechanical and Building Sciences, VIT University, Vellore

Development of Microstructure - FeFe3C System

An alloy of eutectoid composition (0.76 wt% C) as it is cooled from a temperature within the phase
region, say, 800 Cthat is, beginning at point a and moving down the vertical line xx`.

Initially, the alloy is composed entirely of the austenite

phase having
p
g a composition
p
of 0.76 wt% C ((Figure
g
a).
)
As the alloy is cooled, no changes will occur until the
eutectoid temperature (727 C) is reached.
Upon crossing this temperature to point b, the austenite
transforms to and Fe3C) .

This microstructure, represented schematically in

point b, is called pearlite (alternating layers or lamellae
of and Fe3C.

School of Mechanical and Building Sciences, VIT University, Vellore

10

Pearlite

Formation of pearlite structure

Nucleating at grain boundary,

upper-criticaltemperature line

growth by diffusion of C to achieve the compositions

of and Fe3C (with structural changes)
lamellae much thick ( relative layer thickness
is approximately 8 to 1)

Redistribution of carbon
by diffusion
Austenite 0.76 wt% C;
Ferrite - 0.022 wt% C
Cementite - 6.70 wt% C

School of Mechanical and Building Sciences, VIT University, Vellore

11

Hypoeutectoid Alloys

Composition C0 to the left of the eutectoid, between 0.022 and 0.76 wt% C; is termed a hypoeutectoid
(less than eutectoid) alloy.

At about 875C, point c, the microstructure will consist

entirely
y of g
grains of the p
phase ((Fig
g c))

Cooling to point d, at about 775C, both phase and

phase coexist (Fig d).

Cooling from point d to e, just above the eutectoid but

still in the + region, will produce an increased fraction
of the phase and a microstructure similar to fig e,
the particles will have grown larger.

As the temperature is lowered just below the eutectoid, to

point f, all the phase that was present at temperature Te
(and having the eutectoid composition) will transform
to pearlite,

School of Mechanical and Building Sciences, VIT University, Vellore

12

Hypoeutectoid Alloys

In the austenite range, it is a uniform interstitial solid solution. Upon slow cooling, nothing happens until
the line MO is crossed at point d. This MO line is known as the upper-critical-temperature line on the
hypoeutectoid side.

At d, ferrite must begin to form at the austenite grain

boundaries. Since ferrite can dissolve very little carbon,
in those areas that are changing to ferrite the carbon
must come out of solution before the atoms rearrange
themselves to BCC

The carbon which comes out of solution is dissolved in

the remaining austenite, so that, as cooling progresses
and the amount of ferrite increases, the remaining
austenite becomes richer in carbon.

Its carbon content is gradually moving down and to the

right along the MO line. Finally, the line NO is reached at
point f.

School of Mechanical and Building Sciences, VIT University, Vellore

13

Hypoeutectoid Alloys

The ferrite phase will be present both in the pearlite and also as the phase that formed while
cooling through the and phase region.

The ferrite that is present in the pearlite is

called
ll d eutectoid
t t id ferrite,
f it
whereas the other, that formed above Te, is
termed proeutectoid ferrite (meaning pre- or
before eutectoid)

School of Mechanical and Building Sciences, VIT University, Vellore

14

Hypereutectoid Alloys

Compositions to the right of eutectoid (0.76 - 2.14 wt % C) hypereutectoid (more than

eutectoid -Greek) alloys.
+ Fe3C + Fe3C

H
Hypereutectoid
t t id alloys
ll
contain
t i proeutectoid
t t id cementite
tit
(formed above the eutectoid temperature) plus pearlite
that contain eutectoid ferrite and cementite.

School of Mechanical and Building Sciences, VIT University, Vellore

15

Hypereutectoid Alloys

In the austenite range, this alloy consists of a uniform FCC solid solution with each grain containing 1.0
percent carbon dissolved interstitially.
Upon slow cooling, nothing happens until the line OP is
crossed at point h. This line is called upper-criticalp
line on the hypereutectoid
yp
side.
temperature

The OP line shows the maximum amount of carbon that can

be dissolved in austenite as a function of temperature.

Above the OP line, austenite is an unsaturated solid

solution.

At h, the austenite is saturated in carbon. As the

temperature is decreased, the carbon content of the
austenite, that is, the maximum amount of carbon that can
be dissolved in austenite, moves down along OP line
towards point O.

Therefore, as the temperature decreases from h to i, the

excess carbon above the amount required to saturate
austenite is precipitated as cementite primarily along the
grain boundaries.

Finally, the eutectoid line is reached at i. This line is called

the lower-critical-temperature line on the hypereutectoid side
School of Mechanical and Building Sciences, VIT University, Vellore

16

Development of Microstructure - FeFe3C System

Eutectoid steel

Hypoeutectoid
yp
steel

Hypereutectoid
yp
steel

+Fe3C

+Fe3C

+Fe3C

Pearlite

Pearlite +
proeutectoid ferrite

Pearlite +
proeutectoid cementite

School of Mechanical and Building Sciences, VIT University, Vellore

17

Development of Microstructure - FeFe3C System

How to calculate the relative amounts of proeutectoid phase ( or Fe3C) and pearlite?

Application of the lever rule with tie line, that extends from the eutectoid composition (0.76 wt% C)

to ( + Fe3C) boundary (0.022 wt% C) for hypoeutectoid alloys and

to ( + Fe3C) Fe3C boundary (6.7 wt% C) for hypereutectoid alloys.

Fraction of phase is determined

by application of the lever rule
across the entire ( + Fe3C) phase.

School of Mechanical and Building Sciences, VIT University, Vellore

18

Development of Microstructure - FeFe3C System

Example for hypoeutectoid alloy with composition C0'

Fraction of pearlite:

T
C ' 0.022 C0' 0.022
= 0
=
T + U 0.76 0.022
0.74

WP =

Fraction of proeutectoid ferrite :

W ' =

U
0.76 C0'
0.76 C0'
=
=
T + U 0.76 0.022
0.74

School of Mechanical and Building Sciences, VIT University, Vellore

19

Development of Microstructure - FeFe3C System

Example for hypereutectoid alloy with composition C1'

Fraction of pearlite:

WP =

X
6.70 C1'
6.70 C1'
=
=
V + X 6.70 0.76
5.94

Fraction of proeutectoid cementite:

WFe3C =

V
C ' 0.76
C ' 0.76
= 1
= 1
V + X 6.70 0.76
5.94

School of Mechanical and Building Sciences, VIT University, Vellore

20

10

Determination of relative amount of ferrite, cementite and pearlite

School of Mechanical and Building Sciences, VIT University, Vellore

21

Determination of relative amount of ferrite, cementite and pearlite

School of Mechanical and Building Sciences, VIT University, Vellore

22

11

Determination of relative amount of ferrite, cementite and pearlite

School of Mechanical and Building Sciences, VIT University, Vellore

23

Influence of other Alloying Elements - Teutectoid changes

The microstructural development of ironcarbon alloys it has been assumed that, upon
cooling, conditions of metastable equilibrium have been continuously maintained; that is,
sufficient time has been allowed at each new temperature for any necessary adjustment in
phase compositions and relative amounts as predicted from the FeFe
Fe Fe3C phase diagram
diagram.

These cooling rates are impractically slow and

really unnecessary; in fact, on many occasions
nonequilibrium conditions are desirable. Two
nonequilibrium effects of practical importance are

1. the

occurrence

of

phase

changes

or

transformations at temperatures other than those

predicted by phase boundary lines on the phase
diagram, and
2. the existence at room temperature of non-

Fig 1: The dependence of eutectoid

equilibrium phases that do not appear on the

temperature on alloy concentration for

phase diagram.

several alloying elements in steel

School of Mechanical and Building Sciences, VIT University, Vellore

24

12

Influence of other Alloying Elements - Ceutectoid changes

Additions of other alloying elements (Cr, Ni,Ti, etc.) bring about rather dramatic changes in
the binary ironiron carbide phase diagram, Fig 1. The extent of these alterations of the
positions of phase boundaries and the shapes of the phase fields depends on the particular
alloying element and its concentration.
concentration

One of the important changes is the shift in position of

the eutectoid with respect to temperature and to carbon
concentration. Fig 1 and 2, which plot the eutectoid
temperature and eutectoid composition (in wt% C) as a
function of concentration for several other alloying
elements. Thus, other alloy additions alter not only the
temperature of the eutectoid reaction but also the relative
fractions of pearlite and the proeutectoid phase that form.
Steels are normally alloyed for other reasons, howeverusually either to improve their corrosion resistance or to Fig 2: The dependence of eutectoid
render them amenable to heat treatment

composition (wt% C) on alloy concentration

for several alloying elements in steel.

School of Mechanical and Building Sciences, VIT University, Vellore

25

Definitions of structures

Cementite (Fe3C)
Contains 6.67% wt of Carbon
Hard, Brittle Interstitial compound
Tensile strength 5000 psi approx. and has high compressive strength
Crystal structure is orthorhombic

Austenite ()
Interstitial solid solution of carbon
Has FCC crystal structure can accommodate more carbon than ferrite
Max. solubility of carbon in this phase is 2% at 1148 C
C and lowers to 0.8% at 723 C
C
Tensile strength 1,50,000 psi; Elongation 2% in 2
Hardness 40 HRC
Not normally stable at room temperatures

School of Mechanical and Building Sciences, VIT University, Vellore

26

13

Definitions of structures

- Ferrite
Interstitial solid solution of carbon in BCC crystal lattice
As indicated in the Iron- Iron carbide equilibrium diagram, carbon is only slightly soluble
i -Ferrite
in
F it and
dh
has th
the solubility
l bilit off 0
0.025%
025% att 723 C
Softest structure that appears on the diagram
Average Props : TS 40000 psi, Hardness 90BHN

Pearlite ( + Fe3C)
Eutectoid mixture containing 0.8% Carbon and is formed at 723 C on very slow cooling
Microstructure has veryy fine plate
p
like / lamellar structure
Average Props : TS 120000 psi, Hardness 20HRC

School of Mechanical and Building Sciences, VIT University, Vellore

27

14