Iron-Iron Carbide

(Fe-Fe3C) Phase Diagram

Presented by Dr. Nur Farhana HAYAZI

Date: 10 November 2023
Email: [Link]@[Link]

Ref: The background microstructural image was originally from Struers website, and it shows the Aluminum-silicon cast,
color etched with molybdic acid with a magnification of 200x
 Iron-Iron
Carbide
(Fe-Fe3C)
Phase Diagram

Reference :
W. F. Smith, & Javad Hashemi, Foundation of
Materials Science and Engineering, page 379-389.
2
 Content
• Introduction
• Classification of Ferrous Alloy
• Carbon Steel and its content
• Fe - Fe3C Phase Diagram
• Solid Phases in the Fe - Fe3C Phase
Diagram
• Invariant Reactions
• Slow Cooling of Plain Carbon Steel
• Development of Microstructures in
Eutectoid Plain Carbon Steels 3
 Introduction
• Steels are the most complex and widely used
engineering materials because of:
❑ the abundance of iron (Fe) in the earth’s crust
❑ high melting temperature of iron (1534oC)
❑ wide range of mechanical properties and associated
microstructures produced by solid-state phase
transformations by varying the cooling rate from the
austenitic condition.
• The Fe-Fe3C phase diagram is a very useful foundation
on which analysis of all steel heat treatment processes is
dependent. 4
Classification of Ferrous Alloy
AISI/SAE Steel - Numbering System

6
7
 Carbon Steel and its content

*As the carbon content percentage rises, steel has the ability to become
harder and stronger through heat treatment; however, it becomes less
ductile. Regardless of the heat treatment, a higher carbon content
reduces weldability.
 Iron-iron Carbide (Fe - Fe3C) Phase
Diagram
- Of all binary alloy systems, the one that is possibly the most
important is carbon and iron. Both steel and cast irons,
primary structural materials are essentially iron-carbon alloys.
- Iron-carbon alloys containing a very small amount (about
0.03% to about 1.2% C, 0.25 to 1% Mn and a minor amount of
other elements are termed ‘plain carbon steel’ (ANSI, ASTM).
- A portion of the Fe-Fe3C phase diagram is shown in Slide 12.
-The Fe-Fe3C diagram contains the following FOUR (4) solid
phases:
1)  ferrite 3) cementite (Fe3C)
2) austenite () 4)  ferrite 11
This figure shows a
portion of Fe-Fe3C
phase diagram.

Video 1 – Iron-Iron Carbide Phase

Diagram ----- [Link]
UinlgsYA?si=m4wilg5bxtYYsvuJ

Video 2 – Iron-Iron Carbide Phase

Diagram ------
[Link]
G47jx4sG-6AhatNf

12
13
 SOLID PHASES IN THE Fe – Fe3C PHASE DIAGRAM
1) - Ferrite @  -iron
• An interstitial solid solution of carbon in the BCC iron crystal lattice.
• Carbon is slightly soluble in  ferrite, reaching a maximum solid solubility of
0.02% at 723oC.
•The solubility of carbon in  ferrite decreases to 0.005% at 0oC.
• The ferrite is a more open or less dense structure than the other structural
modifications of iron

BCC structure
- Properties : soft and ductile

Microstructure
of –ferrite
(90x).

15
2) Austenite () @  -iron
• is the interstitial solid solution of carbon in  iron.
• has an FCC crystal structure and a much higher solid solubility
than for carbon than  ferrite.
• The solid solubility of carbon in austenite is a maximum of 2.08%
at 1148oC and decreases to 0.8% at 723oC.

FCC structure - Properties: soft and ductile

Microstructure
of  –ferrite
(90x).

16
3) -ferrite @ -iron
• is the interstitial solid solution of carbon in  iron.
• has a BCC crystal structure like  ferrite but with a greater
lattice parameter.
• The maximum solid solubility of carbon in  ferrite is 0.09% at
1465oC.
- Properties: soft and ductile.

It has a BCC crystal

structure like - Ferrite
but with a greater lattice
constant.

17
4) Cementite (Fe3C)
- is the metastable Fe-C intermetallic compound.
- orthorhombic crystal structure.
- has a negligible solubility limits and a composition of 6.67% C
and 93.3% Fe.
-The hardest structure that appears on the Fe-Fe3C phase
diagram.
- It plays an important role in the hardening of many
commercials' steels.
- Properties: hard and brittle.

Video 3 – Carbon Steel Crystal

Structure
([Link]
O8YROCpiLJkFO)

18
Cementite crystal structure
19
20
INVARIANT REACTIONS THAT TAKE PLACE IN BINARY PHASE DIAGRAM

Name of Equation Phase diagram

Reaction Characteristics

Peritectic  +L β

Eutectic L  + β

Eutectoid  β+

21
peritectic

eutectic

eutectoid

22
23
24
25
26
 INVARIANT REACTIONS IN THE Fe – Fe3C PHASE DIAGRAM
Peritectic Reaction
• At the peritectic reaction point, liquid of 0.53% C combines with  ferrite of 0.09% C
to form  austenite of 0.17% C. This reaction which occurs at 1495oC can be written
as
1495oC
Liquid (0.53% C) +  (0.09% C)  (0.17% C)
Eutectic Reaction
- At the eutectic reaction, liquid of 4.3% C forms  austenite of 2.08% C and the
intermetallic compound Fe3C (cementite) which contains 6.67% C. This reaction
which occurs at 1148oC can be written as
1148oC
Liquid (4.30% C)  austenite (2.08% C) + Fe3C (6.67% C)

Eutectoid Reaction
• At the eutectoid reaction point, solid austenite of 0.8% C produces  ferrite with
0.02% C and Fe3C (cementite) that contains 6.67% C. This reactions occurs at 723oC
can be written as

 austenite (0.8%C) 727oC  ferrite (0.02%C) + Fe3C (6.67% C)

27
- A plain carbon steel that contains 0.8% C is called a
‘eutectoid steel’ since an all eutectoid structure of -
ferrite and Fe3C is formed when austenite of this
composition is slowly cooled below the eutectoid
temperature.

•If a plain carbon steel contains less than 0.8% C it is

termed a ‘hypoeutectoid steel’.

•If a plain carbon steel contains more than 0.8% C it is

termed a ‘hypereutectoid steel’.

28
 DEFINITIONS
Eutectic:
the proportion of constituents in an alloy or other mixture that
yields the lowest possible complete melting point. In all other
proportions, the mixture will not have a uniform melting point;
some of the mixture will remain solid and some liquid. At the
eutectic, the solidus and liquidus temperatures are the same.

Eutectoid: transformation upon cooling from solid phase to 2

solid phases.

Eutectoid (plain carbon steel): a steel with 0.8% C.

Proeutectoid  ferrite :
 ferrite that forms by the decomposition of austenite at temperature
above the eutectoid temperature.

Eutectoid  ferrite :
 ferrite that forms during the eutectoid decomposition of austenite;
the  ferrite in pearlite.

Proeutectoid cementite (Fe3C) :

cementite that forms by the decomposition of austenite at
temperature above the eutectoid temperature.

Eutectoid cementite (Fe3C) :

cementite that forms during the eutectoid decomposition of
austenite; the cementite in pearlite.
30
SLOW COOLING OF PLAIN CARBON STEEL

i ) Eutectoid Plain-Carbon Steels

- When a sample of a eutectoid plain-
carbon steel (0.8% C) is heated to
about 750oC and held for a sufficient
time, its structure will become
homogeneous austenite. This
process is called ‘austenizing’.
If this eutectoid steel is then cooled
very slowly to just above the eutectoid
temperature, its structure will remain
austenitic or only has  phase only
(Fig. 9.7, point a).

Fig. 9.7 Transformation of an eutectoid

steel (0.8% C) with slow cooling.
 SLOW COOLING OF PLAIN CARBON STEEL
• Further cooling to the eutectoid
temperatureor just below it will cause
the entire structure to transform from
austenite () to a lamellar structure of
alternate plates of  ferrite and
cementite (Fe3C).
• Just below the eutectoid temperature,
at point b (Fig. 9.7), the lamellar
structure will appear as shown in Fig.
9.8. This eutectoid structure is called
‘pearlite’.
• Since the solubility of carbon in 
ferrite and Fe3C changes very little
from 723oC to room temperature, the
pearlite structure will remain essentially
unchanged in this temperature interval. Fig. 9.7 Transformation of an eutectoid
steel (0.8% C) with slow cooling.
 Pearlite :
a mixture of  ferrite and
cementite (Fe3C) phases in
parallel plates (lamellar
structure) produced by the
eutectoid decomposition of
austenite.

Fig. 9.8 Microstructure of a slowly cooled eutectoid steel. The microstructure

consists of lamellar eutectoid pearlite. The dark etched phase is cementite and the
white phase is ferrite. (Etch: picral; magnification 650x).

33
Development of Microstructures in
Eutectoid Plain Carbon Steels

34
ii) Hypoeutectoid
Plain-Carbon Steels

• When a sample of a
hypoeutectoid plain
carbon steel (0.4% C) is
heated to about 900oC
(Fig. 9.9, point a) for a
sufficient time, its
structure will become
homogeneous
austenite.

Figure 9.9 Transformation of a 0.4% hypoeutectoid

plain carbon steel with slow cooling.
ii) Hypoeutectoid
Plain-Carbon Steels

• Then, if this steel is

slowly cooled to
temperature b in Fig.
9.9 (about 775oC),
proeutectoid ferrite will
nucleate and grow
mostly at the austenitic
grain boundaries.

Figure 9.9 Transformation of a 0.4% hypoeutectoid

plain carbon steel with slow cooling.
ii) Hypoeutectoid
Plain-Carbon Steels

• If this alloy is slowly

cooled from
temperature b to c in
Fig. 9.9, the amount of
proeutectoid ferrite
formed will continue to
increase until about
50% of the austenite is
transformed. While the
steel is cooling from b to
c, the carbon content of
the remaining austenite
will be increased from
0.4 to 0.8%. Figure 9.9 Transformation of a 0.4% hypoeutectoid
plain carbon steel with slow cooling.
ii) Hypoeutectoid
Plain-Carbon Steels

• At 723oC, if prolonged
cooling conditions
prevail, the remaining
austenite will transform
isothermally into pearlite
by the eutectoid
reaction;
austenite ferrite +
cementite

Figure 9.9 Transformation of a 0.4% hypoeutectoid

plain carbon steel with slow cooling.
ii) Hypoeutectoid
Plain-Carbon Steels

• The  ferrite in the

pearlite is called
‘eutectoid ferrite’ to
distinguish it from the
proeutectoid ferrite that
forms first above 723oC.
• Fig. 9.10 is an optical
micrograph of the
structure of a 0.35% C
hypoeutectoid steel that
was austenized and
slowly cooled to room
temperature.
Figure 9.9 Transformation of a 0.4% hypoeutectoid
plain carbon steel with slow cooling.
 Figure 9.9
Transformation of a
0.4% hypoeutectoid
plain carbon steel with
slow cooling.

Video 4 – Slow Coling of

Hypoeutectoid Steels
([Link]
g?si=HJUAMEByOV9EkhPb)

40
Figure 9.10
Microstructure of a
0.35% C
hypoeutectoid plain
carbon steel that is
slowly cooled from the
austenitic region. The
white constituent is
proeutectoid ferrite
while the dark
constituent is pearlite.
(Etchant: 2% nital,
magnification 500x).

41
iii) Hypereutectoid
Plain-Carbon Steels

• When a sample of a
hypereutectoid plain
carbon steel (1.2% C) is
heated to about 950oC
and held for a sufficient
time, its structure will
become essentially all
austenite (point a in Fig.
9.11).

Figure 9.11 Transformation of a 1.2% C

hypereutectoid plain carbon steel with slow cooling.
iii) Hypereutectoid
Plain-Carbon Steels

• Then, if this steel is

cooled very slowly to
temperature b in Fig.
9.11, ‘proeutectoid
cementite’ will begin to
nucleate and grow
primarily at the
austenite grain
boundaries.

Figure 9.11 Transformation of a 1.2% C

hypereutectoid plain carbon steel with slow cooling.
iii) Hypereutectoid
Plain-Carbon Steels

• With further slow

cooling to point c in Fig.
9.11 which is just above
723oC, more
proeutectoid
cementite will be
formed at the austenite
grain boundaries.

Figure 9.11 Transformation of a 1.2% C

hypereutectoid plain carbon steel with slow cooling.
iii) Hypereutectoid
Plain-Carbon Steels

• If conditions of
equilibrium are
maintained by the slow
cooling, the overall
carbon content of the
austenite remaining in
the alloy will change
from 1.2 to 0.8%.
• With further slow
cooling to 723oC or just
slightly below this
temperature, the
remaining austenite will
transform to pearlite by
the eutectoid reaction
as indicated in point d in Figure 9.11 Transformation of a 1.2% C
Fig. 9.11. hypereutectoid plain carbon steel with slow cooling.
Figure 9.12
Microstructure of a 1.2% C hypereutectoid plain carbon steel that is slowly
cooled from the austenitic region. The white constituent is proeutectoid
cementite while the dark constituent is coarse lamellar pearlite. (Etchant:
picral, magnification 1000x). 46
-The cementite formed by the eutectoid reaction is
called ‘eutectoid cementite’ to distinguish it from the
proeutectoid cementite formed at temperatures above
723oC.
- Similarly, the ferrite formed by the eutectoid reaction
is termed ‘eutectoid ferrite’.
- Fig. 9.12 is an optical micrograph of the structure of
a 1.2% C hypereutectoid steel that was austenized
and slowly cooled to room temperature.

47
 Transformation in relation to Fe-Fe3C diagram
austenite
ferrite
martensite

ferrite

Video 5 – Microstructure of Plain Carbon Steels

([Link] 48
 Interactive Fe-Fe3C diagram

[Link] 49