MATERIAL SCIENCE

MODULE III
SOLID SOLUTIONS

Chapter IV – Iron – Carbon System

 Topics to be taken

▪ Allotropy of Iron/Cooling Curve of Iron

▪ Iron Carbon Phase Diagram

▪ TTT Curve

▪ Effect of Alloying Elements

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 Introduction

The iron-carbon phase diagram is important in engineering as it provides the basis for
understanding all cast irons and carbon steels and their heat treatment.

For structural and mechanical applications, steels and other alloys based on iron (the
ferrous alloys) are the dominant engineering alloys. They are intrinsically stiff, strong and
tough, and mostly low cost.

High density is a drawback for transport applications, allowing competition from light
alloys, wood and composites.

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 Allotropy of Iron

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▪  
Depending on pressure and temperature, many metals can exist in more than one crystalline form, a
phenomenon known as allotropy. For example, iron undergoes a series of allotropic transformations
during heating and cooling as shown in the diagram.
An allotropic transformation is a solid state phase transformation, and as such, occurs at a constant
temperature during either heating or cooling.
I. Under equilibrium cooling conditions, pure iron solidifies from the molten state at about 1540°C
(2800°F) and forms what is called delta iron (δ Fe) , which has a body-centered cubic (BCC) structure.
II. Delta iron is then stable on further cooling until it reaches 1395°C (2541°F), where it undergoes a
transformation to a face-centered cubic (FCC) structure called gamma iron / Austenite (γ Fe).
III. On still further cooling to 900°C (1648°F), it undergoes yet another phase transformation,
transforming from the FCC structure back to the BCC structure. This BCC structure is called alpha
iron/ ferrite (α Fe) to distinguish it from the higher-temperature delta iron.
IV. This last transformation, γFe αFe, is extremely important, as it forms the basis for the hardening of
steel.
Many other metals, as well as some nonmetals, also exhibit allotropic transformations. For example,
titanium, zirconium, and hafnium all exhibit a transition from a hexagonal close-packed (HCP) structure
to BCC on heating.

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THE IRON–IRON CARBIDE (Fe–Fe3C) PHASE DIAGRAM

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 Summary of Fe-C phase diagram

Fe-Fe3C phase diagram is characterized by five individual phases,: α–ferrite (BCC) Fe-C solid
solution, γ-austenite (FCC) Fe-C solid solution, δ-ferrite (BCC) Fe-C solid solution, Fe3C (iron
carbide) or cementite -an inter-metallic compound and liquid Fe-C solution and four invariant
reactions:

▪ peritectic reaction at 1495 C and 0.16%C, δ-ferrite + L↔ γ-iron (austenite)

▪ monotectic reaction1495 C and 0.51%C, L↔ L+ γ-iron (austenite)
▪ eutectic reaction at 1147 C and 4.3 %C, L↔ γ-iron + Fe3C (cementite) [ledeburite]
▪ eutectoid reaction at 723 C and 0.8%C, γ-iron ↔ α–ferrite + Fe3C (cementite) [pearlite]

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 Fe-C Alloy Classification
Fe-C alloys are classified according to wt.% C present in the alloy for technological convenience
as follows:
▪ Commercial pure irons% C < 0.008
▪ Low-carbon/mild steels 0.008 -%C -0.3
▪ Medium carbon steels 0.3 -%C -0.8
▪ High-carbon steels 0.8-%C -2.11
▪ Cast irons 2.11 < %C
▪ Cast irons that were slowly cooled to room temperature consists of cementite, look whitish –
white cast iron. If it contains graphite, look grayish –gray cast iron. It is heat treated to have
graphite in form of nodules –malleable cast iron. If inoculants are used in liquid state to have
graphite nodules –spheroidal graphite (SG) cast iron.

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 Micro constituents of Iron and Steel

▪ Austenite
▪ Ferrite
▪ Cementite
▪ Ledeburite
▪ Pearlite
▪ Bainite
▪ Martensite
▪ Troostite
▪ Sorbite

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 Effect of Alloying elements on Steel
▪ Carbon
▪ Nickel
▪ Chromium
▪ Molybdenum
▪ Vanadium
▪ Tungsten
▪ Manganese
▪ Copper
▪ Boron
▪ Aluminium
▪ Cobalt
▪ Silicon
▪ Titanium

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 Effect of Alloying elements on Cast Iron

▪ Chromium
▪ Copper
▪ Molybdenum
▪ Vanadium
▪ Nickel
▪ Magnesium
▪ Manganese
▪ Zirconium

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 TTT curve

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 Formation of Bainite Microstructure
▪ For T ~ 300-540°C, upper bainite consists of
needles of ferrite separated by long cementite
particles
▪ For T ~ 200-300°C, lower bainite consists of
thin plates of ferrite containing very fine rods
or blades of cementite
▪ In the bainite region, transformation rate is
controlled by microstructure growth
(diffusion) rather than nucleation.
▪ Since diffusion is slow at low temperatures,
this phase has a very fine (microscopic)
microstructure.
▪ Pearlite and bainite transformations are
If transformation temperature is low enough competitive; transformation between pearlite
(≤540°C) bainite rather than fine pearlite forms. and bainite not possible without first
reheating to form austenite
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 Upper Bainite Lower Bainite

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 Martensite
▪ Martensite forms when austenite is rapidly
cooled (quenched) to room T.
▪ It forms nearly instantaneously when the
required low temperature is reached. The
austenite-martensite does not involve diffusion
→ no thermal activation is needed, this is
called an athermal transformation.
▪ Martensite is metastable - can persist
indefinitely at room temperature, but will
transform to equilibrium phases on annealing
at an elevated temperature.
▪ Martensite can coexist with other phases
and/or microstructures in Fe-C system
Austenite-to-martensite is diffusionless and very fast.
The amount of martensite formed depends on ▪ Since martensite is metastable non-equilibrium
temperature only phase, it does not appear in phase Fe-C phase
diagram
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The strength and hardness of the different microstructures is inversely related to the size of the
microstructures (fine structures have more phase boundaries inhibiting dislocation motion).

Mechanical properties of bainite, pearlite

Considering microstructure we can predict that
▪ Fine pearlite is harder and stronger than coarse pearlite
▪ Bainite is harder and stronger than pearlite

Mechanical properties of martensite

▪ Of the various microstructures in steel alloys Martensite is the hardest, strongest and the most
brittle

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