Libyan Academy for Postgraduate Studies, Biomedical Engineering- Genetic Engineering

Cont. Phase Diagrams

(Fe–Fe3 C Phase Diagram)

BEM 603
Lecture 11

Feb 23, 2022

Fall 2021/2022
The Iron–Iron Carbide (𝑭𝒆–𝑭𝒆𝟑 𝑪) Phase Diagram
❑ Of all binary alloy systems, the one that is possibly the most important is
that for iron and carbon.
❑ 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 6.7% Carbon.
❑ Several phases are resulted from iron-carbon system, which are:
➢ α-ferrite - solid solution of C in Fe (BCC)
▪ Stable form of iron at room temperature.
▪ The maximum solubility of C is 0.022 wt%.
▪ Transforms to FCC γ-austenite at 912 ˚C.
➢ γ-austenite - solid solution of C in Fe (FCC)
▪ The maximum solubility of C is 2.14 wt %.
▪ Transforms to BCC δ-ferrite at 1395 ˚C.
▪ It Is not stable below the eutectoid temperature (727 ˚C) unless cooled
rapidly.
The iron–iron carbide phase diagram
 ➢ δ-ferrite solid solution of C in Fe (BCC)
▪ The same structure as α-ferrite.
▪ Stable only at high T, above 1394 ˚C.
▪ Melts at 1538 ˚C.
➢ 𝐹𝑒3 C (iron carbide or cementite)
▪ This intermetallic compound is metastable, it remains as a compound
indefinitely at room temperature, but decomposes (very slowly, within
several years) into α-Fe and C (graphite) at 650 - 700 ˚C.

A few comments on 𝑭𝒆 − 𝑭𝒆𝟑 𝑪 system

❑ C is an interstitial impurity in Fe. It forms a solid solution with α, γ, δ
phases of iron.
❑ Maximum solubility in BCC α-ferrite is limited (max. 0.022 wt% at 727
˚C), BCC has relatively small interstitial positions.
❑ 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.
Classification of three types of ferrous alloys
❑ Iron: less than 0.008 wt % C in α−ferrite at room T
❑ Steel: 0.008 - 2.14 wt % C (usually < 1 wt % )
α-ferrite + 𝐹𝑒3 𝐶 at room temperature
Examples: cutting tools (tools for cutting other metals):
Fe + 1wt % C + 2 wt% Cr
Fe + 1 wt% C + 5 wt% W + 6 wt % Mo
❑ Stainless steel: (Medical tools, food
processing equipment, knives,
petrochemical equipment, etc.): 12-
20 wt% Cr.
❑ Cast iron: 2.14 - 6.7 wt % (usually <
4.5 wt %) heavy equipment casing.
Eutectic and eutectoid reactions in 𝑭𝒆 − 𝑭𝒆𝟑 𝑪 system
Development of microstructure in Iron - Carbon alloys
❑ Microstructure depends on composition (carbon content) and heat treatment.
In the discussion below we consider slow cooling in which equilibrium is
maintained.
(I) Microstructure of eutectoid steel
❑ When alloy of eutectoid
composition (0.76 wt % C) is
cooled slowly it forms pearlite (α +
cementite), a lamellar or layered
structure of two phases: α-ferrite
and cementite (𝐹𝑒3 𝐶).

❑ The layers of alternating phases in

pearlite are formed for the same
reason as layered structure of
eutectic structures: redistribution C
atoms between ferrite (0.022 wt%)
and cementite (6.7 wt%) by atomic
diffusion.
❑ Mechanically, pearlite has properties intermediate to soft, ductile ferrite
and hard, brittle cementite.

Photomicrograph of pearlite
microstructure consisting of alternating
layers of -ferrite (the light phase) and
𝐹𝑒3 𝐶 (thin layers appear dark).
(I) Microstructure of hypoeutectoid steel

❑ Compositions to the left of

eutectoid (0.022 - 0.76 wt % C) are
hypoeutectoid (less than eutectoid -
Greek) alloys.

❑ Microstructure of hypoeutectoid
steel contain proeutectoid ferrite
(formed above the eutectoid
temperature) plus the eutectoid
perlite that contain eutectoid ferrite
and cementite.
(I) Microstructure of hypereutectoid steel

❑ Compositions to the right of

eutectoid (0.76 - 2.14 wt % C) are
hypereutectoid (more than
eutectoid -Greek) alloys.

❑ The resulting microstructure

consists of pearlite and
proeutectoid cementite .
Example 1:
A 0.45%C hypoeutectoid plain-carbon steel
is slowly cooled from 950 C to a
temperature just slightly above 727 ˚C.
Calculate the weight percent austenite and
weight percent proeutectoid ferrite in this
steel.
0.76
Sol.

Austenite = (0.45 - 0.02) / (0.76 - 0.02)

= 58.1%

Proeutectoid Ferrite =(0.76 - 0.45) / (0.76 - 0.02)

= 41.9%
Example 2:
A 0.45%C hypoeutectoid plain-carbon steel is
slowly cooled from 950 C to a temperature just
slightly above 727 ˚C.
(a) Calculate the weight percent of proeutectoid
0.76
ferrite in this steel.
(b) Calculate the weight percent of eutectoid
ferrite and the weight percent eutectoid
cementite in this steel.
Sol.

Proeutectoid Ferrite = (0.76-0.45)/(0.76-0.02) = 41.9%

Cementite = (0.45-0.02)/(6.67-0.02) = 6.5%
Total ferrite = (6.67-0.45)/(6.67-0.02) = 93.5%
Eutectoid ferrite = total ferrite – proeutectoid ferrite = 93.5 – 41.9 = 51.6%
Example 3:
Consider 2.5 kg of austenite containing 0.65 wt% C, cooled to below 727ºC.
a) What is the pro-eutectoid phase?
b) How many kg each form of ferrite and cementite?
c) How many kg each form of pearlite and the pro-eutectoid phase?
Sol.
a) The pro-eutectoid phase forms prior to the eutectoid reaction, so that is the
α (ferrite) phase.
b) This involves using the inverse lever rule:

C) Remember, the pro-eutectoid α precipitates above 727ºC, while the

remaining 𝛄 is transformed at that temperature into pearlite. Therefore: