Diffusionless Transformation

Edited from Class Materi of Prof.Dr..Bondan Tiara Sofyan,MSi

 Diffusionless Transformation

◼ Introduction
◼ Diffusive vs. Displacive Transformation of Pure Iron (Fe)

◼ Role of Dissolved Carbon in Fe Transformation

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Materials Tetrahedron
Processing
Performance

Microstructure Properties

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Introduction
◼ The conventional example of diffusionless
transformation is martensitic transformation
in steel.
◼ Faster cooling gives “non-equilibrium
microconstituents”…
❑ Bainite
❑ Martensite
❑ And more!
◼ To know what microconstituents are present,
you must look at cooling curve diagrams

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 Microconstituents vs. Cooling Rate

◼ Spheroidite: Spherical “globs” of Fe3C in Ferrite

In creasing Cooling Rate

◼ Pearlite: Layers of  ferrite and Fe3C

❑ Course Pearlite
❑ Fine Pearlite

◼ Bainite: 200 – 500 C Transformation

◼ Martensite: Rapid Cooling

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Bainite
◼ Upper (550-350°C)
❑ Rods of Fe3C

◼ Lower (350-250°C)
❑ Fe3C Precipitates in
Plates of Ferrite
◼ It is still Ferrite and
Cementite! It’s just acicular.

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Martensite

◼ Diffusionless
transformation
of FCC to BCT (more
volume!)
◼ Lenticular structure
◼ Very hard & very brittle.

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TTT Diagrams

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Full TTT Diagram

The complete TTT

diagram for an
iron-carbon alloy of
eutectoid
composition.
A: austenite
B: bainite
M: martensite
P: pearlite

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CCT Diagram

◼ Phase Transformations and Production of

Microconstituents takes TIME.
◼ Higher Temperature = Less Time.
◼ If you don’t hold at one temperature and allow time
to change, you are “Continuously Cooling”.
◼ Therefore, a CCT diagram’s transition lines will be
different than a TTT diagram.

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Slow Cooling

Time in region
indicates amount of
microconstituent!

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Medium Cooling

Cooling Rate, R, is
Change in Temp /
Time °C/s

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Fast Cooling

This steel is very

hardenable… 100%
Martensite in ~ 1
minute of cooling!

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Diffusive Transformation of FCC to
BCC in Pure Fe
Above 914° C pure
Fe is face centered
cubic (FCC).
Below 914° C the
thermodynamically
stable phase of pure
Fe is body centered
cubic (BCC).
Note that the speed
of the “interface” in
this transformation
is zero at 914° C.

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Nucleation in the Diffusive Transformation of
f.c.c.-> b.c.c. in Pure Fe
Nucleation is very
important
The more nuclei : The
more Volume
Transformed
In a diffusive
transformation:
Volume transforming
per second increases
linearly with the
number of nuclei.

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 Grain Boundary Nucleation
◼ The grain boundaries in the f.c.c. pure Fe are the most
common site for nucleation of the b.c.c. phase.

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 Diffusive Transformation of
f.c.c.-> b.c.c. in Pure Fe

The overall rate of

transformation depends both
on nucleation and growth

The semi-schematic diagram

below shows that the rate of
transformation starts below
the equilibrium temperature,
914°C, and increases until
approximately 700°C.
The slowing rate of diffusion
dominates below 700°C.
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Displacive Transformation of
f.c.c. -> b.c.c. in Pure Fe
◼ If we quench f.c.c. Fe from
914°C at a rate of about
105°Cs-1, we expect to
prevent the diffusive
◼ The TTT diagram for the
diffusive f.c.c.->b.c.c.
transformation from taking
place.
◼ In reality, below 550°C the
Fe will transform to b.c.c.
by a displacive
transformation.

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 Martensite Plates form in f.c.c.
Lattice
◼ The displacive transformation
of f.c.c. -> b.c.c. in pure Fe is
shown schematically.
◼ Lens shaped crystals of b.c.c.
Fe nucleate at the grain
boundaries of the f.c.c. Fe and
grow out into the f.c.c. crystal.
◼ The lens shaped crystals stop
when they hit the next grain
boundary.
◼ This kind of transformation is
called a Martensitic
Transformation.
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Free Energy - Composition: T0
,
product ∆Gg→ T1
g,
parent

G Common
tangent
∆Gg→ T1>T2
T2
T2 corresponds to
figure 6.3b in P&E.
Diffusionless transformation impossible at T1,
Diffusionless transformation possible at T2;
“T0” is defined by no difference in free
Edited from Class Materi of Prof.Dr..Bondan Tiara Sofyan,MSi X
energy between the phases, ∆G=0.
Driving Force Estimation

◼ The driving force for a martensitic

transformation can be estimated in exactly
the same way as for other transformations
such as solidification.
◼ Provided that an enthalpy (latent heat of
transformation) is known for the
transformation, the driving force can be
estimated as proportional to the latent heat
and the undercooling below T0.

∆Gg→ = ∆Hg→ ∆T/T0.

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 T near T0
Phase
relationships

equilibrium
diffusionless

Note that the Ms

line is horizontal
in the TTT diagram;
also, the Mf line.

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Crystal Structures of f.c.c. Fe and
b.c.c. Martensite
◼ The details of how pure
f.c.c. iron transforms by
translation is shown below.

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Microstructure of Martensite
◼ The microstructural characteristics of martensite are:
- the product (martensite) phase has a well defined
crystallographic relationship with the parent (matrix).
- martensite forms as platelets within grains.
- each platelet is accompanied by a shape change
- the shape change appears to be a simple shear parallel
to a habit plane (the common, coherent plane between the
phases) and a uniaxial expansion (dilatation) normal to the
habit plane. The habit plane in plain-carbon steels is close
to (225), for example (see P&E fig. 6.11).
- successive sets of platelets form, each generation
forming between pairs of the previous set.
- the transformation rarely goes to completion.
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Microstructures

Martensite formation
rarely goes to
completion because
of the strain associated
with the product
that leads to back
stresses in the
parent phase.

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Mechanisms
◼ The mechanisms of military transformations are not
entirely clear. The small length scales mean that the
reactions propagate at high rates - close to the speed of
sound. The high rates are possible because of the
absence of long range atomic movement (via diffusion).
◼ Possible mechanisms for martensitic transformations
include
(a) dislocation based
(b) shear based
◼ Martensitic transformations strongly constrained by
crystallography of the parent and product phases.
◼ This is analogous to slip (dislocation glide) and twinning,
especially the latter.
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Edited from Class Materi of Prof.Dr..Bondan Tiara Sofyan,MSi
 Phenomenological
theory of martensitic
transformation

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The Martensite in Steel is Not
Cubic
◼ The crystal structure of 0.8% Carbon
martensite is shown below.
◼ To make room for the carbon atoms the lattice
stretches along on crystal direction. This
produces a face centered tetragonal unit cell.
◼ Note that only a small proportion of the labelled
sites actually contain a carbon atom.

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Self-accommodation by variants
◼ A typical feature of martensitic transformations is that
each colony of martensite laths/plates consists of a stack
in which different variants alternate. This allows large
shears to be accommodated with minimal macroscopic
shear.

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Fe-C Interstitial Solid Solution in  & Martensite
The Carbon atoms cannot fit into interstitial spaces in the
BCC ferrite structure like they can in the FCC Austenite
and produce a BCT ( schematically shown below).
Note in the BCT the Carbon atoms force the unit cell to be
alongated in the c-direction. The largest interstitial void
in BCC iron has a diameter of 0.072-nm.

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 Isothermal Transformation
Experiments

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Nucleation paths
◼ It is important to remember that the actual
outcome is always the process that leads most
rapidly to the change for which a
(thermodynamic) driving force exists.
◼ Different transformations are observed for the
same material because different types of
transformation occur most rapidly for different
undercoolings. In carbon steels, for example,
austenite decomposes to pearlite most rapidly
for small undercoolings but to martensite for
large undercoolings.

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Nucleation paths

◼ Anisotropy in the interfacial energy forces

growing grains to adopt anisotropic shapes in
order to minimize high energy orientations of
the interface.
◼ Anisotropy in growth rates has a similar effect.
◼ Heterogeneous nucleation on surfaces, pre-
existing interfaces (grain boundaries),
dislocations etc. is very important.
◼ Elastic energy plays a major role in
constraining nucleation.
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Edited from Class Materi of Prof.Dr..Bondan Tiara Sofyan,MSi