The Iron–Iron Carbide (Fe–Fe3C)

Phase Diagram

1
2
 Phases in Fe–Fe3C Phase Diagram
 a -ferrite
• solid solution of C in BCC Fe

• Stable form of iron at room temperature.

• The maximum solubility of C is 0.022 wt% at

727C
• Transforms to FCC γ -austenite at 912 C
• It is soft and ductile phase
• Can be cold worked without cracking

3
 Ƴ -austenite
• solid solution(interstitial) of C in FCC Fe

• The maximum solubility of C is 2.14 wt % at

1147C.
• Transforms to BCC - δ ferrite at 1395 C
• Is not stable below the eutectic temperature
(727  C) unless cooled rapidly & maximum conc.
of carbon at this temperature is 0.8 %.
• It is soft, ductile, malleable and non magnetic in
phase.
4
 d -ferrite
• solid solution of C in BCC Fe
• The same structure as a-ferrite
• It is soft and ductile phase
• Can be cold worked without cracking
• The maximum solubility of C is 0.09 wt% at 1493 C
• 1493 C is the temperature of peritectic transformation
• Stable only at high T, above 1394 C
• Melts at 1538 C

5
 Fe3C (iron carbide or cementite)
• It is intermetallic compound of iron and carbon

• Has carbon content of about 6.67 %

• It has a complex orthorhombic crystal structure having
12 iron atoms and 4 carbon atoms in a unit cell.
• It is hard and brittle phase
• It is metastable, it remains as a compound indefinitely at
room T, but decomposes (very slowly, within several
years) into a-Fe and C (graphite) at 650 - 700 C

6
 Ledeburite
• It consists of eutectic mixture of austenite
and cementite.
• Observed in cast irons containing 4.3 %
carbon
 Transformed ledeburite

• It consists of pearlite and cementite

• Pearlite = a - ferrite + cementite

• Cementite = Fe3C (iron carbide)

 Fe-C liquid phase

• It is the liquid solution of carbon in iron
7
Pure iron, upon heating, experiences two changes in crystal structure before it
melts.
• At room temperature the stable form, called ferrite, or α-iron, has a BCC crystal
structure.
• Ferrite experiences a polymorphic transformation to FCC austenite, or γ-iron, at
912 C. This austenite persists to 1394 C, at which temperature the FCC austenite
reverts back to a BCC phase known as δ-ferrite, which finally melts at 1538 C
• All these changes are apparent along the left vertical axis of the phase
diagram.

8
9
 The composition axis in Figure 9.24 extends only to 6.70 wt% C; at this

concentration the intermediate compound iron carbide, or cementite (Fe3C), is

formed, which is represented by a vertical line on the phase diagram.

Thus, the iron–carbon system may be divided into two parts: an iron-rich

portion, as in Figure 9.24, and the other (not shown) for compositions between

6.70 and 100 wt% C (pure graphite).

In practice, all steels and cast irons have carbon contents less than 6.70 wt% C;

10
• Carbon is an interstitial impurity in iron and forms a solid solution with

each of α and δ ferrites, and also with austenite

• In the BCC α -ferrite, only small concentrations of carbon are soluble; the

maximum solubility is 0.022 wt% at 727 C .The limited solubility is

explained by the shape and size of the BCC interstitial positions, which

make it difficult to accommodate the carbon atoms.

•The α -ferrite is virtually the same as δ -ferrite, except for the range of

temperatures over which each exists

11
• The austenite, or γ phase of iron, when alloyed with carbon alone, is not

stable below 727 C,

• The maximum solubility of carbon in austenite, 2.14 wt%, occurs at 1147 C

•This solubility is approximately 100 times greater than the maximum for

BCC ferrite, because the FCC interstitial positions are larger and, therefore,

the strains imposed on the surrounding iron atoms are much lower.

12
•Cementite (Fe3C) forms when the solubility limit of carbon in α-ferrite is

exceeded below 727 C for compositions within the αFe3C phase region).

• As indicated in Figure 9.24, Fe3C will also coexist with the γ phase between 727

and 1147 C.

•Mechanically, cementite is very hard and brittle; the strength of some steels is

greatly enhanced by its presence.

13
14
15
Transformation Reactions in Iron–Iron Carbide (Fe–Fe3C)
Phase Diagram

16
17
18
19
Critical Temperature Lines

20
 Development of Microstructure in
Iron–carbon Alloys
Microstructure depends on
1. composition (carbon content) and

2. heat treatment.
Assume slow cooling  equilibrium maintained

21
Microstructure of eutectoid steel

22
In the micrograph, the dark areas
are Fe3C layers, the light phase is a-
ferrite

23
• Pearlite, layered structure of two phases: a-ferrite and cementite (Fe 3C)

• Alloy of eutectoid composition (0.76 wt % C) Layers formed for same reason as in eutectic: Atomic
diffusion of C atoms between ferrite (0.022 wt%) and cementite (6.7 wt%)

• Mechanically, properties intermediate to soft, ductile ferrite and hard, brittle cementite.
24
 Microstructure of
hypoeutectoid steel
Compositions to the left
of eutectoid (0.022 - 0.76
wt % C) hypoeutectoid
(less than eutectoid
-Greek) alloys.
   +    + Fe3C

25
26
 Microstructure of
hypereutectoid steel
Compositions to
right of eutectoid
(0.76 - 2.14 wt % C)
hypereutectoid (more
than eutectoid
-Greek) alloys.
   + Fe3C   +
Fe3C
27
28
29
30
31
32