20.

Phase Diagrams III

Fe-C System
 Questions
• What kind of microstructures can form
when heating and cooling steel?

2
 Learning Objectives
• Identify the key regions on the Fe-Fe3C
Phase Diagram (Austenite, Ferrite,
Cementite)
• Explain the formation of the microstructure
Pearlite.
• Apply the lever rule in different stages
during cooling, and at concentrations
above and below the eutectic value.
3
Right – from “Sustainable Materials with Both Eyes Open”
4 - update
 Pure Iron Above
1538oC
Liquid
• Pure iron experiences two changes in crystal
structure.
1394-
1538oC
• From 1394-1538oC iron exists as a BCC
 Ferrite
phase called  ferrite. BCC

• From 912-1394oC it experiences a

polymorphic transformation to austenite, 912-
1394oC
or  iron
– FCC crystal structure  iron
Austenite
– Unstable at room temp. FCC

• At room temperature to 912oC it exists Below

as ferrite, or  iron. 912oC
– BCC crystal structure  Ferrite
– relatively soft BCC
5
 Fe-Fe3C Phase Diagram
• Only part of the phase
diagram is shown.
• The left axis is pure iron.
• On the right the phase
diagram only extends to 6.70
wt%C
• At this concentration the
intermediate compound
iron carbide, or cementite
(Fe3C) is formed
• Cementite is hard, brittle, and
not used on its own.
• This portion of the Fe-C Phase
diagram is sufficient to
describe all of the steels and
cast irons used today (many
are less than 2% C)
• We refer to percentage of C or
% Fe3C or % cementite, as they
NB: the -phase Ferrite is is Fe3C
are all equivalent. Pure Fe cementite
very close to pure Fe (only
6
0.02% C) 6.70 wt% C
 Fe-Fe3C Phase Diagram
Single-Phase Regions
• ,  phase (BCC)
•  phase (FCC)
• Liquid
Two-Phase Regions
•  + Fe3C
•+
•  + Fe3C
•  + Liquid
Area of interest
for steels Fe3C
• Fe3C + Liquid Pure Fe cementite
7
6.70 wt% C
 Development of Microstructures in Iron-Carbon
Alloys - Pearlite
• Various microstructures can be
produced in steel alloys depending on
– carbon content 
– heat treatment Austenite
• Equilibrium (slow) cooling from the 
region through the eutectoid
composition of 0.76 wt% C

   + Fe3C (Pearlite)

• Pearlite has a laminar form, appearing

like “mother-of-pearl” pattern in mollusks
and pearls, and mechanically has
 + Fe3C
properties in between the soft, ductile
ferrite and the brittle, hard cemetitie.

8
 Development of Microstructures in Iron-Carbon
Alloys – Pearlite (cont)
Q: What is the %  and Fe3C in eutectoid
pearlite?
• Apply the Lever Rule:

𝐶𝑆1 − 𝐶0 Austenite
𝑊𝑆2 =
𝐶𝑆1 − 𝐶𝑆2
𝐶𝐹𝑒3𝑐
𝐶𝐹𝑒3𝐶 − 𝐶0 6.7 − 0.76 = 6.7 %
𝑊𝛼 = = = 0.89
𝐶𝐹𝑒3𝐶 − 𝐶𝛼 6.7 − 0.0022 (𝐶𝑒𝑚𝑒𝑛𝑡𝑖𝑡𝑒)

𝐶0 − 𝐶𝑆2
𝑊𝑆1 =
𝐶𝑆1 − 𝐶𝑆2
𝐶0
= 0.76%  + Fe3C
0.76 − 0.022
𝑊𝐹𝑒3𝐶 = = 0.11
6.7 − 0.022

C = 0.022 %
9 - UPDATED
 Formation of Pearlite
0.022 wt%C

0.76 wt% C 6.7 wt%C

• Schematic representation of the • Micrograph of eutectoid

formation of pearlite from austenite steel, showing pearlite
• direction of arrows indicates carbon microstructure.
diffusion –  ferrite (light)
• This is almost identical to Eutectic Structure for
– Fe3C (dark)
Pb-Sn (lecture #19), except here Ferrite layer is
~8x thicker than Cementite layer (almost equal
in Pb-Sn formation) 10
 Hypo-eutectoid Composition (wt% C <0.76)
• For example, consider a composition
between 0.002 and 0.76 wt% C

• Upon cooling, the liquid solid

austenite  enters a two-phase region
   +
• Below 727°C (the eutectoid
isotherm) the remaining austenite
transforms to pearlite
   + Fe 3C

• Final structure is a mixture of

– Pro-eutectoid ferrite
– Pearlite

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 Hypo-eutectoid Composition (0.38 wt% C)

Dark regions:
White regions:
Pearlite
Proeutectoid
Ferrite Close-spaced
layers
Unresolved at this
magnification

Pearlite
wider-spaced
layers

91 m
 Computing the relative amounts of proeutectoid  and
pearlite
• Discussed briefly in Lecture 19, Slide 22.
• Use the Lever Rule in 2 stages, in
conjunction with a tie line
• For hypoeutectoid composition C'0,
fractions of pro-eutectoid  (primary ,
or  ’), and pearlite are:
U
W ' 
T +U
T
Wp 
T +U
•  (total) and Fe3C– Apply graphical
form of the Lever Rule just below the
Eutectoid temperature.
U +V + X
W 
T +U +V + X C’0

T hypoeutectoid
WFe3C 
T +U +V + X 13
 Hyper-eutectoid Composition (wt% C >0.76)
• Composition between 0.76 and 2.14
wt% C
• Upon cooling enter a two-phase
region
   + Fe 3C
• The pro-eutectoid cementite phase
has begun to form along the  grain
boundaries
• Final structure is a mixture of
– Pro-eutectoid cementite
– Pearlite

14
 Hyper-eutectoid Composition (1.40 wt% C)
White Pro- Pearlite ‘colonies’
eutectoid cementite
network

15
30 m
 Computing the relative amounts of proeutectoid
Fe3C and pearlite
For hypereutectoid composition C’1
Almost identical similar to the hypoeutectoid
reaction, again applying the lever rule in 2
stages.
• Apply graphical form of Lever Rule just
above Eutectoid Temperature
V
WFe3C ' 
V+X
X
Wp 
V+X
•  (total) and Fe3C – Apply graphical form
of Lever Rule just below Eutectoid
Temperature
X
W 
T +U +V + X
T +U +V C’1
WFe3C 
T +U +V + X hypereutectoid
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 Mechanical Properties of Steel
• The mechanical properties of steel are largely
dictated by the carbon content and phase
transformations they undergo upon cooling
• The proceeding preceding examples are for slow
cooled conditions, where the Fe-Fe3C phase
diagram is reasonably accurate.
• If we heat steel to the single phase austenite
region, and vary the cooling rate, we have an
additional effect on the microstructure.

17
 How do we change Cooling Rates?

Examples of ways to change external heat transport:

• Furnace cool – slow (equilibrium like)
• Air Cool – moderate (change in morphology length-scales)
• Oil quench – fast (change in morphology length-scales and
some non-equilibrium phases)
• Water Quench - very fast (non-equilibrium phases)

Note: the practical rates achieved will be dependent

on section thickness (internal heat transport)

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 Example: Railway Rails
• 46,000 km of rail in Canada, over 250,000 km in US.
• Much of it is at the eutectoid composition of 0.76 wt%C
• 100% Pearlite structure
• Pearlite is a natural ‘composite’
– Hard and Brittle Fe3C plates
– Soft and Ductile ferrite plates
• Pearlite displays good wear resistance for railway rails relative to other
compositions of pro-eutectoid ferrite and cementite
• New “ultra-quality” rail steels are hypereutectoid (i.e. higher carbon) **
• The strength of Pearlite is dictated by its interlaminar spacing, S (m)

Faster cooling rates = thinner

interlaminar spacing

S
**Reference - http://www.railjournal.com/index.php/track/next-generation
19
-super-premium-rail-steels-hit-the-tracks.html
 Pearlite

Coarse Pearlite Fine Pearlite 20

 Learning Objectives
• Identify the key regions on the Fe-Fe3C Phase
Diagram (Austenite, Ferrite, Cementite)
• Explain the formation of the microstructure
Pearlite.
• Apply the lever rule in stages during cooling at
concentrations above and below the eutectic
value.

21
 Updates to slides since initial
posting
• Page 4 – included graph of historical world steel production

• Page 9 – added text to the figure to clarify composition of ferrite and

cementite.

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