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5. THE IRON-CARBON EQUILIBRIUM DIAGRAM

INTRODUCTION
The Iron-carbon diagram is the basis of two very important groups of alloys: steels and cast
irons (also termed ferrous alloys). Their importance derives from the following:
i) the relative abundance of iron which forms about 5% of the earth's crust.
ii) the ease with which the iron ore can be reduced to the metal. The reduction can be done
using carbon (which is cheap and is also the alloying element) as the reducing agent.
iii) their wide range of properties which makes them very versatile.

For this reason, ferrous alloys are relatively cheap and are the first choice as structural
material unless other considerations (weight, corrosion resistance, etc.,) dictate otherwise.
Their main disadvantage is their high susceptibility to atmospheric corrosion.

ALLOTROPIC FORMS OF IRON
Iron exhibits temperature based polymorphism (see chapter two): up to 912C, it has a bcc
crystal structure and this polymorph is termed iron. Between 912C and 1400C, the
structure changes to fcc - the polymorph being termed -- iron. The last polymorph, -- iron,
which also has a bcc structure, exists between 1400C and 1535C, (the melting point of
iron). Thus on heating, the volume change of iron with temperature will have the shape
shown below.














Fig 5.2 The variation of volume with temperature when iron is heated

There is normal thermal expansion up to 912C when a sudden drop occurs. This results due
to the closer packing of the fcc structure. A sudden rise in volume takes place at 1400C
when the structure reverts to bcc. This is followed by normal thermal expansion up to
melting at 1535C. Another important temperature is the Curie point, 769C at which iron
losses its magnetism (changes from ferromagnetic to paramagnetic).

Carbon dissolves interstitially in all the above polymorphs of iron. It has a maximum
solubility of 0.02% in --Fe at 723C. The resulting solid solution is given the special name
ferrite and designated by . The solubility in --Fe reaches a maximum of 2.06% at 1146C,
the resulting solid solution being given the name austenite and is designated by .

The higher solubility of carbon in --Fe (despite its higher atomic packing factor compared to
-Fe) results from the fact that the interstices in fcc are fewer but each one is bigger than
V
o
l

912
1535 1400
Temp (
o
C)
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those in the bcc (which are more but smaller). A Carbon atom taking the (1/2, 0, 1/2)
position in a bcc lattice causes more distortion than one taking the (1/2, 1/2, 1/2) position in
an fcc). Finally, dissolves up to 0.1% carbon at 1492C. This solution, has no
technological importance and hence has no special name. It is designated by .

In addition to the above solid solutions, iron and carbon form an inter-metallic compound
Fe
3
C which is termed cementite or carbide. From equation
Ax wt at y wt at
y wt at
B Wt
. . . .
. .
% .
+
=
B
B
,
the weight percentage of carbon in Fe
3
C is 6.67%.

EUTECTIC, EUTECTOID AND PERITECTIC DECOMPOSITION IN THE
FE-C SYSTEM
Like most systems with an inter-metallic compound, only the part of the Fe-C diagram
between Fe and Fe
3
C has technological importance. In the Fe-Fe
3
C system, the peritectic
reaction takes place at 1492C (0.3%C) when reacts with excess liquid to form . The
eutectic reaction takes place at 1146C and 4.3%C when the liquid precipitates alternate
layers of and cementite. The cementite which results from the eutectic reaction is termed
primary cementite and the eutectic is termed ledeburite. The eutectoid reaction takes place at
723C, 0.8%C when iron changes polymorph from -Fe (fcc) to -Fe (bcc). Since the
solubility of carbon in -Fe is much higher than in -Fe, the excess carbon diffuses out of
solution to form Fe
3
C. Thus we have precipitating alternate layers of and cementite. The
product of the eutectoid reaction is termed pearlite.
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With the information given above, the iron-carbon (or more correctly the Iron-Fe
3
C) diagram
looks as shown in fig. 5.2. Due to the importance of ferrous alloys all engineers must be well
conversant with the Fe-C diagram.

STABLE AND METASTABLE FE-C SYSTEMS
The Fe-Fe
3
C system described above is termed the metastable system. Under certain
conditions (slow cooling rate in presence of other elements especially silicon) Fe
3
C does not
form and graphite (carbon) precipitates instead. Fe
3
C already formed may also break down
to and free carbon in the form of graphite. The Fe- graphite system is referred to as the
stable system. In the stable system, only carbon in excess of 0.8%C can form graphite. The
rest will stay as Fe
3
C similar to the case in the metastable system.

CLASSIFICATION OF FERROUS ALLOYS

PLAIN CARBON STEELS
The products of the eutectoid reaction are termed steels. They have less than 2.06%C and
have the distinct characteristic that they can be heated to a single solid phase . This makes
them suitable for hot working processes like forging, hot rolling, etc. The properties of steels
can be varied over a wide range by controlling the rate of the decomposition of austenite to
ferrite and cementite, and by adding other alloying elements in addition to carbon. This
accounts for the very widespread use of steel.


Fig 6.2 Fe-Fe
3
C equilibrium phase diagram

Peritectic
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A steel which contains only carbon as alloying element (with up to 1% Mn) is termed a plain
carbon steel. If any other alloying elements are added, it is termed an alloy steel. The
following terminology is commonly used when dealing with plain carbon steels:
i) Ingot iron -- carbon content less than 0.05%. Hence high ductility.
ii) dead soft mild steels -- carbon content between 0.05% and 0.15%.
iii) mild steels - carbon content between 0.15% and 0.3%. These have adequate
plasticity, good machineability and weldability. Mild steel is therefore the most
commonly used structural material and is used for making structural shapes: I--
beams, channels and angles.
iv) medium carbon steels -- carbon content between 0.3-0.5%.
v) high carbon steel -- carbon content higher than 0.5%.

5.5.2 Hypo and Hyper-eutectoid Steels
As stated above, steels are the product of the eutectoid reaction in the Fe-C system. The
eutectoid reaction gives simultaneous precipitation of and cementite from . The resulting
product, which consists of alternate layers of and cementite is termed pearlite (from its
appearance of alternate black and white streaks when viewed under the microscope). A steel
with 0.8%C will consist entirely of pearlite when cooled under equilibrium conditions and is
termed an eutectoid steel. A steel with carbon content below 0.8% is termed a hypo-
eutectoid steel. If cooled under equilibrium conditions, the microstructure of hypo-eutectoid
steels will consist of a mixture of ferrite (which precipitates before the eutectoid reaction and
is termed pro-eutectoid ferrite) and pearlite. The ferrite and cementite in pearlite are termed
eutectoid ferrite and eutectoid cementite respectively. A steel with carbon content in excess
of 0.8%C is termed hyper-eutectoid steel and will consist of pro-eutectoid or secondary
cementite (usually precipitated at the grain boundaries of austenite -- the prior-austenite grain
boundaries) and pearlite. Fig. 5.3, which is an enlargement of the steel part of the Fe-C
diagram and fig. 6.4 showing schematically the grain structure of the various steels help to
illustrate these points. In fig. 5.3, points along PS are termed lower critical point, A
1
, those
along GS, the uper critical point, A
3
, while A
2
represents the Curie point. A
1
, A
2
and A
3

are also termed arrest temperatures.




















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Fig 5.3- Iron-carbon diagram
If the cooling rate is rather fast, pro-eutectoid (secondary) cementite will precipitate inside
the grains along certain preferred crystal plains -- forming a needle like network termed a
Widmamnstatten structure.










(A) (B) (C)










723
o
C
A
3

A
2

A
1

A
cm

+L
+

+ Pearlite

+L
+

+ C
P
e
a
r
l
i
t
e

1535
912
1134
0.86%C
2.01%C
P S
G
Ferrite
Pearlite
Cementite
Fig 5.4 The structures of (a) Hypoeutectoid (b) Eutectoid (c) Hyper-eutectoid steels
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5.5.3 Quantities of Phases in the Fe-C System
The ratios of the phases in the Fe-C system can be easily calculated using the lever rule. For
a hypo-eutectoid steel with x% carbon just below the eutectoid temperature:
ratio of pro-eutectoid ferrite:


2 0 . 0 - 8 . 0
x - 8 . 0


ratio of pearlite = ratio of just above eutectoid temperature:

2 0 . 0 - 8 . 0
2 0 . 0 - x


ratio of eutectoid ferrite:
e t i l r a e p . t a u q

8 8 . 0 =
2 0 . 0 - 7 6 . 6
8 . 0 - 7 6 . 6


eutectoid cementite:
= 0.12 of quantity of Pearlite

The total quantity (ratio) of ferrite:
=(6.67 - x)/( 6.67 - 0.02)
and that of cementite:
= (x - 0.02)/ (6.67 - 0.02 )
Similarly for a hyper-eutectoid steel containing x%C:
ratio of pro-eutectoid cementite:
= (x - 0.8)/ ( 6.67 - 0.8)
ratio of pearlite:
= (6.67 - x)/ (6.67 - 0.8)

The ratios of eutectoid ferrite and cementite can be calculated from the same equations as for
hypo-eutectoid steel. As the temperature changes, the ratios also change and hence for any
steel, a phase transformation diagram can be plotted. Such a diagram is shown in figure 6.5
for a 0.6% C steel. Phase transformation diagrams are easily constructed from the phase
diagram using the above equations as appropriate.

Decrease in the solubility of carbon in ferrite as the temperature is decreased leads to
precipitation of ternary cementite which segregate to the grain boundaries or form plate-like
needles inside the ferrite matrix. Quantities of phases in the metastable system and for
products of the eutectic reaction can be determined easily in a manner similar to what is done
above for steels.

5.5.4 Properties of Annealed Plain-Carbon Steels
The mechanical properties of plain carbon steels are affected by:
i) the size and number of phases present;
ii) the ratio of the phases (which is a function of the carbon content);
iii) shape and distribution of the minor phase.
Ferrite, being a solid solution is soft and ductile. Pearlite has moderate strength which
depends on the size of the lamellae. The size of the lamellae in turn depends on the cooling
rate. The slower the cooling rate, the coarser the lamellae and the lower the hardness
(approximately. 170 HB). Finer lamellae can have hardness up to 340 HB since slip is more
difficult in the finer structure. With other factors kept constant therefore, the strength
(hardness) of a steel will vary with carbon content as shown in fig. 5.5. As the carbon
content increases, the ratio of pearlite increases. Maximum hardness is achieved at 100%
pearlite (0.86%C).

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The shape and distribution of the minor phase also affects the properties. If the minor phase
(cementite in this case) is distributed as fine particles inside the ductile ferrite, the toughness
is increased. If the particles are larger or if they segregate to the grain boundaries, both the
hardness and toughness are reduced.

Steels are classified according to chemical composition of alloying ingredients:-
Carbon steels
Alloy steels
Stainless steels

Carbon Steels
Carbon steels as explained earlier contain mainly iron and carbon. Other elements such as
silicon, manganese, sulphur, phosphorous are considered as impurities. A deoxidizer can ce
added in order to remove the impurities.
Carbon is the most important element that determines the properties of steel
0.035% Tensile strength increases upto 0.83% Carbon

Properites:-
Good machinability
Deep hardening properties
Dont easily fail due to fatigue
Employed in forgings, crankshaft pins, gears, railway axels, connecting rods

High carbon steels
These contain over 0.6% C
They posses good machinability and high strength

The presence of silicon in carbon steels :-
Acts as a major deoxidizer
Promotes grain size
Imparts deep hardening properties
Facilitates carburization
0
0.5
1.0
%C
H
a
r
d
n
e
s
s

(b)
(a)
0.8
Fig 5.5 The
variation of
hardness with
carbon content in
plain carbon steels
(a) normalized
(b) quenched.
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ALLOY STEELS
These are steels with special alloying elements like Nickel, Chromium, Molybdenum,
tungsten, vanadium, titanium, aluminium, cobalt e.t.c.

Silicon and aluminium in excess of 0.5% and 1.5% respectively may be considered as
alloying elements.

Low Alloy Steels
Those that may require heat treatments
They have similar microstructure and may have the same contents as plain carbon steels.

High alloy steels
These dont require similar heat treatments as plain carbon steels

STAINLESS STEELS
These are iron based alloys having great resistance to corrosion due to addition of Nickel and
chromium. Oxidation of the chromium on the surface creates a protective oxide film (that
prevents further attack).
Stainless steels are selected for their excellent resistance to corrosion. All true stainless steels
contain a minimum of about 12 % Cr, which permits a thin, protective surface layer of
chromium oxide to form when the steel is exposed to oxygen. Chromium is also a ferrite
stabilising element. Chromium causes the austenite region to shrink, while the ferrite region
increases in size. For high-chromium, low-carbon compositions, ferrite is present as a single
phase up to the solidus temperature.
There are several categories of stainless steels based on crystal structure and strengthening
mechanism.

Classes:-
Martensitic stainless steels
Cr 16%, 0.7 1.5% Carbon
These are hardenable and magnetic
They are referred to as chromium stainless steels
They are resistant to corrosion
Tempering at 500
o
C does not affect tensile strength.
They are used in the making of utensils
A 17% Cr-0.5%-C alloy heated to 1 200C forms 100% austenite, which transforms to
martensite on quenching in oil. The martensite is then tempered to produce high strengths and
hardnesses. The chromium content is usually less than 17% Cr; otherwise, the austenite field
becomes so small that very stringent control over both austenitising temperature and carbon
content is required. Lower chromium contents also permit the carbon content to vary from
about 0.1 % to 1.0%, allowing martensites of different hardnesses to be produced. The
combination of hardness, strength, and corrosion resistance makes the alloys attractive for
applications such as high quality knives, ball bearings, and valves.

Ferritic stainless steels
12 - 25% Cr
These are non-hardenable because - transformation temperature is raised by the presence
of chromium
Properties
Considerable ductility
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Excellent corrosion resistance
Relatively cheap
In order to resist corrosion at high temperatures, Cr can be increased to 30%
Used in kitchen ware, chemical equipment (can resist nitric acid)
Ferritic Stainless Steels
Ferritic stainless steels contain up to 30% Cr and less than 0.12% C. Because of the BCC
structure, the ferritic stainless steels have good strengths and moderate ductilities derived
from solid solution strengthening and strain hardening. Ferritic stainless steels have excellent
corrosion resistance and moderate formability and are relatively inexpensive.

Austenitic stainless steels
Contain Chromium and Nickel totaling up to 24% (Combined total)
They are non-hardenable and non-magnetic
Properties:-
Resistant to acids
Addition of tungsten and molybdenum increase strength at elevated temperatures
Selenium and sulphur improve machinability
Used in parts subjected to severe stresses at elevated temperatures.

Nickel, which is an austenite stabilising element, increases the size of the austenite field,
while nearly eliminating ferrite from the iron-chromiumcarbon alloys. If the carbon content is
below about 0.03%, the carbides do not form and the steel is virtually all austenite at room
temperature.

The FCC austenitic stainless steels have excellent ductility, formability, and corrosion
resistance. Strength is obtained by extensive solid solution strengthening, and the austenitic
stainless steels may be cold-worked to higher strengths than the ferritic stainless steels. The
steels have excellent low-temperature impact properties, since they have no transition
temperature. Furthermore, the austenitic stainless steels are not ferromagnetic. Unfortunately,
the high nickel and chromium contents make the alloys expensive.
Precipitation-Hardening (PH) Stainless Steels
The precipitation-hardening (or PH) stainless steels contain AI, Nb, or Ta and derive their
properties from solid-solution strengthening, strain hardening, age hardening, and the
martensitic reaction. The steel is first heated and quenched to permit the austenite to
transform to martensite. Reheating permits precipitates such as Ni3Al to form from the
martensite. High mechanical properties are obtained even with low carbon contents.

Duplex Stainless Steels
In some cases, mixtures of phases are deliberately introduced into the stainless steel structure.
By appropriate control of the composition and heat treatment, a duplex stainless steel
containing approximately 50% ferrite and 50% austenite can be produced. This combination
provides a set of mechanical properties, corrosion resistance, formability, and weldability not
obtained in any one of the usual stainless steels.

Effect of alloying elements
Generally tend to improve properties
Molybdenum, chromium, vanadium provide hardness
Nickel, chromium improve corrosion resistance.
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Vanadium, Molybdenum, chromium provide additional har abrasive particles to improve
wear resistance. They also act as deoxidisers and reduce blow holes in processed steel.
Sulphur, lead, phosphorous improve machinability
Manganese minimizes brittleness resulting form excess sulphur
Managenese molybdenum, chromium, nickel and silicon slow down the rate of
transformation of to pearlite upon cooling thus allowing thick sections to be hardened.



5.6 CAST IRON
The products of the eutectic reaction (1146C, 4.3%C) are termed cast irons. They contain at
least 2.1% carbon. The eutectic reaction gives a simultaneous precipitation of and
cementite (in the metastable system) which is termed ledeburite. These alloys are suitable for
casting due to the low melting point (eutectic temperature); their castability (ability to fill
moulds), their high elastic modulus (rigidity) and their high damping capacity (ability to
absorb vibration energy). Some grades of cast iron also have good machineability.

5.6.1 White Cast Iron
If the precipitation takes place within the metastable system (this is favoured by a relatively
fast cooling rate, absence of silicon and nickel), then the structure will consist of ferrite,
cementite and pearlite at room temperature (the austenite originally precipitated at 1146C
undergoes the eutectoid reaction at 723C). Cast iron which contains all its carbon in the
form of cementite is termed white cast iron. Due to the hard cementite; white cast iron is
hard, brittle ( practically 0%) and virtually unmachineable. It may therefore be used only
in those applications where wear resistance is the prime requirement. As was the case with
steels, we can have hypo-- and hyper--eutectic white cast irons. In hyper--eutectic white cast
irons, the primary cementite (cementite precipitated before the eutectoid reaction) can only
be retained if the material is quenched. The cementite which precipitates as part of ledeburite
is termed ledeburitic or "free" cementite.

If the cooling rate is fairly slow and if appreciable amounts of silicon and/or nickel are
present in the melt, the carbon will precipitate within the stable system as graphite in the
form of graphite flakes. Cast iron which contains all its carbon as graphite is termed grey
cast iron ( the graphite gives a grey appearance to a broken piece of this form of cast iron).
The tendency to form graphite is also increased by increase in carbon content.

Grey cast iron is weak and has no shock-resistance. This results due to the tips of the
graphite flakes acting as areas of stress concentration. For the same reason, grey cast iron has
no notch sensitivity (i.e., the presence of notches does not severely reduce its strength). Grey
cast iron usually contains its iron as pearlite (plate 6.1). If however it is quenched after
solidification, the austenite forms martensite (see chapter nine) and we end up with
martensitic grey cast iron which is hard.

5.6.3 Malleable Cast Iron
The extreme properties of grey and white cast iron make their fields of application fairly
limited. Malleable cast iron is produced by heat treatment of white cast iron to reduce its
brittleness and hardness. There are two industrial processes used for the heat treatment: In
the "Blackheart" process, white cast iron is heated at about 900C for 2-3 days and cooled
very slowly in a neutral atmosphere. The cementite breaks down to ferrite plus spheroidal
graphite. Thus the final microstructure is ferrite + pearlite (from austenite) + spheroidal
graphite. In the "Whiteheart" process, the heating is done as above but in the presence of iron
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ore. Again the cementite breaks down as above but near the surface, the ore oxides the
carbon such that the structure at the surface becomes ferrite while the centre is ferrite +
pearlite + graphite nodules. Malleable cast iron has adequate ductility and toughness while
retaining adequate strength. It also has good machineability. Since the density of graphite is
less than that of cementite, formation of malleable cast iron is accompanied by expansion.
This is termed "growth" of cast iron.
The production of malleable iron requires several steps. Graphite nodules nucleate as the
white iron is slowly heated. During the first stage graphitization (FSG) cementite
decomposes to the stable austenite and graphite phases as carbon in Fe3C diffuses to the
graphite nuclei. Following FSG, the austenite transforms during cooling.

5.6.4 Other Types of Cast Iron
Other commercially available forms of cast iron include spheroidal cast iron and alloy cast
iron. In spheroidal cast iron (also called nodular or ductile cast iron) magnesium and nickel
are added to the melt. Cementite then solidifies in the form of spherical nodules inside a
matrix of ferrite and pearlite. The resulting structure is tougher and harder. In alloy cast iron,
other alloying elements are added to achieve specific properties. Chromium, nickel or
molybdenum are added to increase the strength and wear resistance, 15-25% Ni is added to
produce wear resistant cast iron, etc.




















Fig 5.6 The variation of microstructure of cast iron with carbon content and silicon content.












2 4 6
%
C

%Si
White
Pearlite +
Ferrite
Ferrite
Mot Pearlite



4



3



2



1