IIT Delhi

APL 102
Ferrite

Austenite

Ferrite

Pearlite

Phase diagrams : Iron – Carbon (Fe – Fe3C) System

Concepts: Intermetallics, Steels, Cast iron, Pearlite, Eutectoid steel, Zone refining

Lecture 23
 Recap
IIT Delhi

Gibbs Phase Rule

Phase diagram – Key concepts
F=C–P+2 Gas
P↑F↓
Single phase regions
F = C – P + 1 (Pressure is constant) F=1–1+2=2
Liquid

Temperature (ºC) →
Two phase coexistence lines
Liquidus F=1–2+2=1
 (BCC)
1535
1410
 (FCC) Triple points:
3 phase coexistence
Tm
Solidus F=1–3+2=0
 (BCC)  (HCP)

Pressure (GPa) →
 Recap
IIT Delhi
Phase diagram – Key concepts
Tie-line rule & Lever Rule Type II Phase diagrams:
Cooling Eutectic, Eutectoid, Peritectic & Peritectoid
Arm of the lever T(°C)
proportional to
Arm of the lever
proportional to
L
L: C wt%Sn
Hypo or Hyper
the liquid
o Proeutectic
the solid 300 L
 or 
T0 L+
L+S L+ 
Fulcrum of the lever
200
TE  183°C
T →

Tie line
100 +
S : 97.8wt%Sn
: 18.3wt%Sn
Eutectic
A C1 C0 %B → C2 B 0
0 20 40 60 80 100 Mixture of
18.3 CE 97.8
C0  C1 C2  C0 Co, wt% Sn +
f liquid at T0 
C2  C1
f solid at T0

C2  C1
Pb-Sn system 61.9
IIT Delhi

Complex Diagrams
Some observations…..
 Complex diagrams may have some additional features:
IIT Delhi
 Often one could find more than one 3 phase equilibria;
 Congruent melting system
Congruent melting system
 Intermetallic compound
 Complex Diagrams
IIT Delhi

An alloy typically melts over a range of temperatures. However, there are

special compositions which can melt at a single temperature like a pure metal.
One of these is the congruent melting composition

α and γ are A-rich and B-rich Solid solutions, respectively:

known as Terminal or primary SS

β is also SS of A and B but it forms in the middle of the diagram:

known as Intermediate SS or Intermetallic phase or Intermetallic compound
(very narrow composition range)
IIT Delhi
Question for thought

What is the most successful structural material?

Fe – based…. Steels, Iron etc.,

IIT Delhi

An important phase diagram

Fe – Fe3C phase diagram
 Fe – Fe3C Phase diagram
IIT Delhi

 Some phase diagrams are technologically important and via these further aspects
of the utility of phase diagrams can be learnt.

 The Fe-C (or more precisely the Fe – Fe3C) diagram is an important one.
Cementite (Fe3C is a metastable phase and ‘strictly speaking’ should not be
included in a phase diagram. But the decomposition rate of cementite is small
and hence can be thought of as ‘stable enough’ to be included in a phase
diagram. Hence, we typically consider the Fe – Fe3C part of the Fe-C phase
diagram.

 Another technologically important phase diagram is the Al-Cu system (especially

the Al rich end of the phase diagram) which we will see later.
 Important Phases of the diagram
IIT Delhi

Ferrite (α): SS of C in BCC Fe

Soft phase, BCC, 0 K - 910 °C (Pure Fe)
C is located at (0, 0, 1/2), 0.19 Å Delta (δ) ferrite:
Size of the C atom: 0.71 Å SS of C in BCC Fe
Solubility is max. 0.02 wt.% at 725 °C

1410 °C to 1535 °C
Austenite (): SS of C in FCC Fe Solubility is max. 0.1 wt.% at 1493 °C

Soft phase, FCC, 910 °C to 1410 °C (Pure Fe)

C is located at (0, 0, 1/2) or (1/2,1/2,1/2);
Void size (0.52 Å)
Solubility is max. 2.1 wt.% at 1150 °C
IIT Delhi

Cementite (Fe3C): undergo congruent melting, fixed composition

Complex orthorhombic structure: 25 at. % C = 6.67 wt.% C

Beyond 6.67 wt.% C all alloys of Fe-C are useless

Up to 2 wt.% C: Steels

2 – 6.67 wt.% C: Cast Iron

IIT Delhi

Complete Diagram: Fe – Fe3C

IIT Delhi
Question for thought

What is the difference between steels and cast iron?

It is the ‘C’ content that differentiates the two

 Fe-Fe3C Phase Diagram
IIT Delhi

Peritectic
L+→ Eutectic L
1493ºC
L →  + Fe3C
 Three Important reactions in the
L+
Fe-rich side of diagram:
1147ºC
 2.06
Eutectoid A3 Acm 1. Peritectic Reaction
 + Fe3C
 →  + Fe3C
A1 723ºC 2. Eutectic Reaction

Temp →

α + Fe3C
0.025
Of the three reactions the eutectoid 3. Eutectoid reaction
reaction is technologically important
Steels Cast Iron
Fe Fe3C
0.8 4.3 6.67
RT~0.008
0.16 Wt.% C →
IIT Delhi
Question for thought

What are the different steels that is available?

 Classification of steels
IIT Delhi

Plain Carbon Steels

Mild steels: 0 – 0.3 C
Applications: Nails, ship hulls, automobile, rivets etc.

Medium Carbon Steels: 0.35 – 0.7 C

Applications: Rails, Axles, wheels, Chisels

High Carbon steels: 0.8 – 1.4 C

Applications: Cutting wheels/tools, Blades, Razors, saws, scissors
 Classification of steels
IIT Delhi

Another way of classifying steels is based on Eutectoid composition (0.8 % C)

C < 0.8% C: Hypo-eutectoid steels

C > 0.8% C: Hyper eutectoid steels

C = 0.8% C: Eutectoid steels

 Fe-Fe3C Phase Diagram
IIT Delhi

Peritectic
Eutectic L
L+→ 1493ºC
L →  + Fe3C
 Three Important reactions in the
L+
Fe-rich side of diagram:
1147ºC
 2.06
Eutectoid A3 Acm 1. Peritectic Reaction
 + Fe3C
 →  + Fe3C
A1 723ºC 2. Eutectic Reaction

Temp →

α + Fe3C
0.025
Of the three reactions the eutectoid 3. Eutectoid reaction
reaction is technologically important
Steels Cast Iron
Fe Fe3C
0.8 4.3 6.67
RT~0.008
0.16 Wt.% C →
 The portion of the phase diagram, which is technologically relevant is shown in the figure below
IIT Delhi

Hypereutectoid steels
Hypoeutectoid steels

Eutectoid steels
IIT Delhi
Lets take an alloy of hypoeutectoid steel say 0.4%C steel

Understand the microstructure evolution of above steel

IIT Delhi γ

γγ γ

γ
γ γ

γ
Ferrite (α)
IIT Delhi γ

γγ γ

γ γ

γ
Ferrite (α)
IIT Delhi γ

γγ γ

γ γ

γ
Proeutectoid Ferrite
IIT Delhi γ

γγ γ

γ α γ
Fe3C

γ
Proeutectoid Ferrite
IIT Delhi
Pearlite is not a phase but it is a mixture of two phases:
Ferrite and Cementite (α and Fe3C)

Ferrite: 0.02 wt.% C at nearly 725 °C

Cementite: 6.67 wt.% C at nearly 725 °C
Our starting composition was 0.8 (Eutectoid composition)

A partition of C is going to take place

A carbon rich phase: cementite

A carbon depleted phase: Ferrite
 Microstructure of Hypoeutectoid steel
IIT Delhi

Ferrite
C1
C1
Austenite

Ferrite
For the formation of ferrite (α) where it is energetically
favourable??
Pearlite
Austenite grain boundaries

Eutectoid mixture is called pearlite

 Microstructure of Eutectoid steel
IIT Delhi

Grain boundary
C2  Fe3C

Pearlite a micro-constituent (Not a phase)

C2
 Pearlite is a micro-constituent with alternating
lamellae of cementite and ferrite

SEM micrograph of pearlite in

Eutectoid composition (0.8%C) steel

Also known as Eutectoid steel

 Microstructure of Hypereutectoid steel
IIT Delhi

C3

Pearlite

Pro-eutectoid SEM micrograph of pearlite in

Cementite along
prior Austenite
Hyper-eutectoid composition (1.0%
grain boundaries C) steel
IIT Delhi

Zone refining: A technique

that utilizes the concept of
phase diagrams
 Zone Refining
IIT Delhi
 Zone Refining
IIT Delhi

Ring heater moving from top to bottom

What solidifies first is purer than what solidifies next

Impurities concentrated in molten region

Several passes are required to get high purity material

- 10 passes reduce impurity to 10-6 times initial value

Wt.% B
Increasing number of passes
Distance (length of the rod)
IIT Delhi
Question for thought

In cold countries, why salt is added in road during/before

snowfall?

The freezing point of water is depressed and hence ice melts on roads
 Announcement
IIT Delhi

 Quiz: 27th September (Wednesday) @ 5:30 pm

Syllabus: After Minor 1 till 20th Sept. lecture