Polymorphism and Allotropy

Polymorphism is a physical phenomenon where a material may

have more than one crystal structure (i.e. BCC, FCC & HCP). A material
that shows polymorphism exists in more than one type of space lattice
in the solid state.
If the change in structure is reversible with temperature or
pressure, then the polymorphic change is known as allotropy. The
prevailing crystal structure depends on both the temperature and the
external pressure. One familiar example is found in carbon: graphite is
the stable polymorph at ambient conditions, whereas diamond is
formed at extremely high pressures.
Iron too can exist in more than one crystal structure and the
change is reversible. The different allotropes of iron are designated with
Greek letters.
Low temperature iron is BCC and is called ALPHA iron ( Fe).
At 910C, Fe changes to GAMMA iron () Fe which is FCC.
Further heating until at 1400C, the FCC Fe, reverts to the BCC
form. This high temperature form is DELTA iron ( Fe) and it is stable
up to the melting point of iron (1537C).
By cooling, the reverse changes occur.

The five most important changes can be remembered :

Solid Solution

EutectIC

EutectOID

PeritectIC

PeritectOID

There are 5 phases in the iron carbon phase diagram, which are
liquid, ferrite, austenite, delta ferrite, and the fifth phase is the form in
which the insoluble carbon exists.
This may be the metastable interstitial compound Fe3C, or
the stable form graphite. This diagram is in fact a dual phase
diagram.
Since complete stability is difficult to achieve, Fe3C is the more
likely phase to form. However, under certain favorable conditions, the
higher carbon alloys can form graphite, giving the useful grey cast
irons.
In practice, iron carbon alloys are used with a limited carbon
content, so the iron carbon phase diagram extends only to the value of
C = 6.67%. This carbon content corresponds to the Fe3C in the

metastable system. Therefore, the right hand side boundary line of the
metastable phase diagram represents 100% Fe3C.
This diagram is therefore often referred to as the Fe-Fe3C system.
Cementite is a metastable phase, which on prolonged heating
breaks up into Iron+ Graphite. Thus, the diagram cannot be called an
Equilibrium diagram, but a Phase Diagram.

Fe-C Digram

Reactions occurring in the Fe-Fe3C system

Peritectic
Occurs at T = 1493C between 0.10 0.51%C.
Occurs between Liquid (L) and Delta-Ferrite () giving Austenite ().
L (0.5 %) + (0.1 %) ____ (0.18 %)
Since the range is very limited, this part of the diagram is of little
industrial importance in plain carbon steels.

Eutectic
Occurs at T = 1147C between 2.06 6.67%C.
The two phase product of the eutectic reaction
(i.e. austenite () + cementite (Fe3C)) is called
ledeburite.
L (4.3%) ___ (2.1%) + Fe3C (6.67%)
Eutectoid
Occurs at T = 723C between 0.025 6.67%C.
The two phase product of the eutectoid
reaction (i.e. ferrite () + cementite (Fe3C)) is
called pearlite.
(0.76%) ___ (0.022%)+ Fe3C (6.67%)

Phases in FeFe3C Phase Diagram

-ferrite - solid solution of C in BCC Fe
Interstitial solid solution of small amount carbon dissolver in B.C.C
iron
Stable form of iron at room temperature
The maximum solubility of C is 0.022 wt%
Transforms to FCC -austenite at 912 C
It has magnetic properties until 728 C and it looses this properties
above this temperature

-austenite - solid solution of C in FCC Fe

Interstitial solid solution of carbon dissolver in F.C.C iron
The maximum solubility of C is 2.14 wt %.
Transforms to BCC -ferrite at 1395 C
not stable below eutectic temperature (727 C) unless cooled
rapidly
-ferrite solid solution of C in BCC Fe
The same structure as -ferrite
Stable only at high T, above 1394 C, melts at 1538 C
It may exist in combination with the melt to about 0.5 %
It has B.B.C structure and is magnetic
Fe3C (iron carbide or cementite)
It is a chemical compound which contain 6.67 % carbon by weight
It is very hard and brittle structure
Its melting point is 1227 C , so it can't exist above this
temperature
It has low tensile strength but high compressive strength
This intermetallic compound is metastable, it remains as a
compound indefinitely at room T, but decomposes (very slowly,
within several years) into -Fe and C (graphite) at 650 - 700 C
Fe-C liquid solution
C is an interstitial impurity in Fe. It forms a solid solution with , ,
phases of iron
Maximum solubility in BCC -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:
The mechanical properties of crystalline solids are primarily
controlled by their microstructure, i.e. the proportions, properties,
shape and distribution of the phases present (the latter being the
most important).
The phases present at room temperature of plain carbon steels,
are essentially mixtures of ferrite and cementite.
Ferrite is almost pure iron, and has properties of a pure metal.
Therefore, it is soft, ductile and tough, and has low hardness and
strength. (These properties increase after alloying).
Cementite is an intermediate compound (also classified as a
ceramic), hence hard and brittle. It has low ductility and
toughness.
Pearlite contains mainly ferrite but being reinforced with platelets
of cementite in a sandwich fashion, will be considerably harder
and stronger than ferrite, but much less brittle than cementite

Magnetic properties:
-ferrite is magnetic below 768 C, austenite is non-magnetic

The effect of carbon content on the properties

For hypo eutectoid steels slowly cooled from the austenitic state,
the decreasing percentage of ferrite and the increasing percentage
of pearlite, results in an increase in tensile strength and hardness.
The ductility (percentage elongation) decreases.
For hyper eutectoid steels, increasing the amount of carbon,
decreases the percentage of pearlite and increases the percentage
of cementite. This increases the hardness. However, the tensile
strength and ductility are still low since the cementite still forms
along grain boundaries, making it easier for a crack to propagate
along a grain boundary.

Phase transformations. Kinetics.

Phase transformations (change of the microstructure) can be
divided into three categories:
Diffusion-dependent with no change in phase composition or
number of phases present (e.g. melting, solidification of pure
metal, allotropic transformations, recrystallization, etc.)
Diffusion-dependent with changes in phase compositions and/or
number of phases (e.g. eutectoid transformations)
Diffusionless phase transformation produces a metastable phase
by cooperative small displacements of all atoms in structure (e.g.
martensitic transformation)
Phase transformations do not occur instantaneously. Diffusiondependent phase transformations can be rather slow and the final
structure often depend on the rate of cooling/heating.

The process of phase transformation involves:

Nucleation of the new phase - formation of stable small particles
(nuclei) of the new phase. Nuclei are often formed at grain
boundaries and other defects.
Growth of new phase at the expense of the original phase

Superheating / Supercooling
Upon crossing a phase boundary on the composition temperature
phase diagram phase transformation towards equilibrium state is
induced.
But the transition to the equilibrium structure takes time and
transformation is delayed.
During cooling, transformations occur at temperatures less than
predicted by phase diagram: supercooling.
During heating, transformations occur at temperatures greater
than predicted by phase diagram: superheating.
Degree of supercooling/superheating increases with rate of
cooling/heating.
Metastable states can be formed as a result of fast temperature
change. Microstructure is strongly affected by the rate of cooling.
Below we will consider the effect of time on phase transformations
using iron-carbon alloy as an example.

Time Temperature Transformation TTT diagram

Let us consider eutectoid reaction as an example
eutectoid reaction:
(0.76 wt% C)


(0.022 wt% C)
+
Fe3C

 This diagram, note first that the eutectoid temperature 727 C is

indicated by a horizontal line; at temperatures above the eutectoid
and for all times, only austenite will exist.
The austenite-to pearlite transformation will occur only if an alloy is
supercooled to below the eutectoid; as indicated by the curves,
the time necessary for the transformation to begin and then end
depends on temperature.
To the left of the transformation start curve, only austenite (which
is unstable) will be present, whereas to the right of the finish
curve, only pearlite will exist. In between, the austenite is in the
process of transforming to pearlite, and thus both micro
constituents will be present.

 An actual isothermal heat treatment curve (ABCD) is superimposed

on the isothermal transformation diagram for a eutectoid iron
carbon alloy.
Very rapid cooling of austenite to a temperature is indicated by the
near-vertical line AB, and the isothermal treatment at this
temperature is represented by the horizontal segment BCD.
The transformation of austenite to pearlite begins at the
intersection, point C , and has reached completion at point D
At temperatures just below the eutectoid, relatively thick layers of
both the ferrite and Fe3C phases are produced; this
microstructure is called coarse pearlite, and the region at which it
forms is indicated to the right of the completion curve on Figure
11.5. At these temperatures, diffusion rates are relatively high,
such that during the transformation carbon atoms can diffuse
relatively long distances, which results in the formation of thick
lamellae.
With decreasing temperature, the carbon diffusion rate decreases,
and the layers become progressively thinner. The thin layered
structure produced until 540 C is termed fine pearlite.

If transformation temperature is low enough (540C) bainite

rather than fine pearlite forms.

For T ~ 300-540C, upper bainite consists of needles of ferrite

separated by long cementite particles
For T ~ 200-300C, 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 competitive;
transformation between pearlite and bainite not possible without
first reheating to form austenite

Martensite : Martensite forms when austenite is rapidly cooled

(quenched) to room T.
It forms nearly instantaneously when the required low temperature
is reached. It depends on the cooling temperature not the
diffusion.
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
Since martensite is metastable non-equilibrium phase, it does not
appear in phase Fe-C phase diagram
Austenite-to-martensite is diffusionless and very fast. The amount
of martensite formed depends on temperature only.

EXAMPLE PROBLEM
Using the isothermal transformation diagram for an ironcarbon
alloy of eutectoid composition , specify the nature of the final
microstructure (in terms of microconstituents present and approximate
percentages) of a small specimen that has been subjected to the
following timetemperature treatments.

In each case assume that the specimen begins at 760 C and

that it has been held at this temperature long enough to have achieved
a complete and homogeneous austenitic structure.
(a) Rapidly cool to 350 C, hold for 104 s, and quench to room
temperature.
(b) Rapidly cool to 250 C , hold for 100 s, and quench to room
temperature.
(c) Rapidly cool to 650 C , hold for 20 s, rapidly cool to 400 C ,
hold for 103 s, and quench to room temperature

Mechanical properties of bainite, pearlite, spheroidite

Fine pearlite is harder and stronger than coarse pearlite
Bainite is harder and stronger than pearlite
Mechanical properties of martensite
Martensite is the hardest, strongest and the most brittle. The
strength of martensite is not related to microstructure.

hypereutectoid (1.2%C) iron carbon alloy

hypo eutectoid (0.45%C)