Diffusionless Transforma/ons

50 µm

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A. S. C. M. D’Oliveira

vDiffusionless transformations
Characteristics of Diffusionless Transformations

Any diffusionless
transformation Martensite
product

Any transformation in which (from start to completion of the

transformation) individual atomic movements are less than one
interatomic spacing.

Associated with systems exhibiting alloptropic transformations

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 vDiffusionless transforma/ons
Characteristics of Diffusionless Transformations

Evidences of a diffusionless transformation?

Ø Low T – even intersticial diffusion is difficult

Ø Very high transformations velocities (in steels~1100ms-1); not
compatible with diffusion mechanisms
Ø Chemical composition of martensite is the same of the mother phase

The regimented manner in which atoms change position in this transformation has led to it
being termed military, in contrast to diffusion-controlled transformations which are termed
civilian.

Atoms move less than one interatomic distance as a block vs individual movement of atoms by at least one
interatomic distance
A. S. C. M. D’Oliveira

vDiffusionless transformations
Characteristics of Diffusionless Transformations

BCT

Martensite grows independently of thermal activation;

Starts at Ms; the amount of martensite that forms does not

depend on the exposure time at temperature;

50 µm
Is the formation of martensite plates a random process? A. S. C. M. D’Oliveira

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vDiffusionless transformations
Characteristics of Diffusionless Transformations

The formation of martensite appears to be a random

process but is not

Ø The martensitic phase (α`) is often in the shape of a lens

and spans initially an entire grain diameter.

Ø The density of plates does not appear to be a function of the

grain size of the γ-austenite .

A. S. C. M. D’Oliveira

vDiffusionless transformations
Characteristics of Diffusionless Transformations

At least macroscopically, the transformed regions appear coherent with the

surrounding austenite; the intersection of plates or lenses with the surface of the
specimen does not result in any discontinuity.

Where the plates intersect the surface of a polished specimen

they bring about an elastic deformation, or tilting of the surface

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 vDiffusionless transformations
Characteristics of Diffusionless Transformations

A fully grown plate spanning a whole grain may form within ~10-7 s
which means that the α’/γ interface reaches almost the speed of sound in the solid.

Martensite is thus able to grow independently of thermal activation;

some Fe-Ni alloys do exhibit isothermal growth characteristics.

The volume fraction of martensite increases by the systematic

transformation of the austenite remaining between the plates that
have already formed.

The first plates form at the Ms (martensite start temperature).

This temperature is associated with a certain driving force for the
diffusionless transformation of γ into α’.

A. S. C. M. D’Oliveira

vDiffusionless transformations
Large undercooling

- Diffusionless transformations require higher driving force

than diffusional transformations
- Diffusionless transformations products maintain the chemical
composition of the mother phase

To, T under which the new phase can form with a reduction in the system
free energy

•Why does martensite forms well below To?

A driving force is require to supply energy for:
i) Interfacial energy of the nucleus (small)
ii) elastic energy associated with transformation distortion (large)

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 vDiffusionless transforma/ons
Characteristics of Diffusionless Transformations
In low-carbon steels, Ms = 500°C
but increasing C contents progressively decrease the Ms temperature.

The Mf temperature (martensite finish) corresponds to that

temperature below which further cooling does not increase
the amount of martensite.

In practice the Mf may not correspond to 100% martensite, and some retained austenite can be left even below
Mf.
The retention of austenite in such cases may be due to the high elastic stresses between the last martensite plates
to form

A. S. C. M. D’Oliveira

vDiffusionless transformations
Characteristics of Diffusionless Transformations

In steels:
The cooling rate is such that the majority of C atoms in solution in the FCC γ-Fe remains in
solution in the α -Fe phase. Steel martensite is thus simply a supersaturated solid
solution of C in α -Fe
FCC BCC

How does the CFC lattice changes into a CCC lattice without atomic diffusion?
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 vDiffusionless transformations
The Solid Solution of C in Fe

FCC

There are two possible positions for accommodating

interstitial atoms:

- tetrahedral sites which is surrounded by four atoms

- octahedral sites which has six nearest neighbours.

BCC

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vDiffusionless transforma/ons
The Solid Solution of C in Fe
The size of the largest atoms that can be accommodated without distorting the surrounding matrix can be
calculated if it is assumed that the atoms are close-packed hard spheres

tetrahedral interstice d4 = 0.225 D

octahedral interstice d6 = 0.414 D

where D is the diameter of the parent atoms

In case of γ-Fe D=2.52Ǻ, (Room T)

d4= 0.568Ǻ e d6=1.044Ǻ,

The largest diameter of interstitial atoms that can be contained in tetrahedral and octahedral
interstices without distorting the lattice

Considerable distortion of the austenite lattice must

occur to contain carbon atoms in solution ;
However, dcarbon=1.54 Ǻ • the octahedral interstices should be the most favorable

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 vDiffusionless transformations
The Solid Solution of C in Fe
In a BCC lattice, there are 3 possible octahedral positions and six possible tetrahedral spaces for each unit
cell

d4 = 0.291D
d6 = 0.155D

Although there is more 'free' space in BCC than the close-packed lattices, the larger number of possible
interstitial positions means that the space available per interstitial is less than for the FCC.(d4=0.225D e d6 =
0.414D)

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vDiffusionless transforma/ons
The Solid Solution of C in Fe
In spite of d6<d4, measurements of carbon and nitrogen in solution in Fe show that these interstitials prefer to
occupy the octahedral positions in the BCC lattice.
Considerable distortion to the BCC lattice occurs!

Lattice distortion as a function of C content

the martensitic Fe-C lattice is

distorted to a BCT structure
c/a=1.005+0.045(wt%C)

The distortion of the lattice in one direction (z) causes a contraction in the two directions normal
to z(x, y); these measurements suggest a certain long-range order in the distribution of the carbon
interstitials
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 vDiffusionless transformations

Martensite Crystallography:
- Martensite plates show a crystallographic dependence of martensite plate formation.
- Within a given grain, all the plates grow in a limited number of orientations.
In Fe alloys, the orientation variants and even plate morphology turn out to be dependent upon alloy content,
particularly carbon or nickel

- if martensite is able to grow at speeds approaching the speed of sound, then some
sort of highly mobile dislocation interface is required… ( not dislocation glide!)
- the growth of habit plane of martensite is observed to be macroscopically
undistorted, i.e. the habit plane is a plane which is common to both the austenite and
martensite in which all directions and angular separations in the plane are
unchanged during the transformation.

A. S. C. M. D’Oliveira

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vDiffusionless transforma/ons
Where the plates intersect the surface of a polished specimen they bring about an elastic deformation, or
tilting of the surface; at least macroscopically, the transformed regions appear coherent with the surrounding
austenite.

The absence of plastic deformation in the form of a discontinuity at the

surface shows that the shape strain does not cause any significant
rotation of the habit plane.

If the habit plane had been rotated, plastic deformation would be

necessary to maintain coherency between the α’and γ and this would
have resulted in additional displacements of the surface

In order for the habit plane to be left undistorted, the martensite transformation appears to occur by a
homogeneous shear parallel to the habit plane

This transformation is also associated with -4% expansion, this implies that the dilatation must take
place normal to the habit plane, i.e. normal to the plate.
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vDiffusionless transformations

Can the BCT martensite lattice structure be generated by simple shear parallel to the habit
plane, together with a small dilatation normal to the plane?

The habit plane of a martensite plate remains undistorted

following the transformation ( as in twinning)

If the equivalent macroscopic shape change in the formation of a martensite plate is a twinning shear
occurring parallel to the habit (or twinning) plane, plus a simple uniaxial tensile dilatation perpendicular to
the habit plane.

v A strain of this type is termed: an invariant plane strain, because a shear parallel to the habit plane, or
an extension or contraction perpendicular to it, cannot change the positions or magnitude of vectors lying
in the plane.

A. S. C. M. D’Oliveira

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vDiffusionless transformations
Bain Model for FCC-> BCT
(an elongated unit cell of the BCC structure can be drawn within two FCC cells)

Transformation with a minimum of atomic movement, and b3

a3
the minimum of strain in the parent lattice

•contracting the cell 20% in the Z (a3) direction and

expanding the cell by 12% along the X and Y(a1 and a2) a2
axes . b1 b2
a1
(a) (b)

In the case of steels, the C atoms fit into z' axes of the BCC BAIN
cell causing the lattice to elongate in this direction STRAIN

Fe-1at%C, C occupies one position along the z' axis for

every 50 iron unit cells;
(c) (d)
Body-centered Body-centered
tetragonal cubic martensite
austenite
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vDiffusionless transforma/ons
Bain Model for FCC-> BCT
20%

12%

• Bain deformation results in the following correspondence of crystal planes and directions:
(111)γ <=> (011)α’
Minimum atomic movements [101]γ <=> [111]α´
[110]γ <=> [100]α´
[112]γ <=> [011]α’
Small shuffles of the C atoms must take place during the transformation

Bain transformation does not fulfil the requirements of bringing about a transformation
with an undistorted plane – invariant strain plane
A. S. C. M. D’Oliveira

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vDiffusionless transformations
Bain Model for FCC-> BCT

The key to the crystallographic theory of martensite transformations is to postulate an additional distortion
This new deformation can be in the form of dislocation slip or twinning

Shear (wrong New deformation ( correct

Uniaxial dilation crystal lattice) lattice; wrong morphology)

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vDiffusionless transforma/ons

Correct martensite morphology is obtained with a non-homogeneous macroscopic deformation.

An internally twinned martensite plate can form by having alternate

regions in the austenite undergo the Bain strain along different
contraction axes such that the net distortions are compensated.

By also adjusting the width of the individual twins, the habit plane of
the plate can even be made to adopt any desired orientation

The habit plane of the martensite plate can be defined

as a plane in the austenite which undergoes no net
(macroscopic) distortion
Local regions of strain energy associated with the α´/ γ
interface of twins;
Accommodation of large shear deformation with
a minimum macroscopic shear ( twin martensite)

A. S. C. M. D’Oliveira

398 Diffusionless transformations

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speeds of 800-1100 m/s have been measured (Nishiyama, 1978)6. The
nucleation event is thus very important in martensitic transformations be-
cause of its likely influence on the final form of the full-grown plate. This
implies that the nucleation of martensite influences the strength and tough-
ness of martensitic steels, since for a given austenite grain size, if the number
of nuclei is large, then the final grain size of the martensite will be finer and
hence the steel may be stronger.

vDiffusionless transforma/ons
Because of the great speed of growth of martensite, it is extremely difficult
to study this transformation experimentally. An example of Bunshah and
Mehl's (1953) resistivity measurements 7 is shown schematically in Fig. 6.13,
indicating that 0.' gives a lower resistivity than -y. The small initial increase in
Martensite nucleation:
resistivity is explained in terms of the initial strain of the austenite lattice by
the martensite nucleus. This suggests in turn that the initial nucleus should be
coherent with the parent austenite. This factor could be an important starting
- influence
point on thehow
when considering final form of
nucleation the full-grown plate
occurs.
- influences the strength and toughness of martensitic steels
6.3.1 Formation of Coherent Nuclei of Martensite
For a given austenite grain size, if the number of nuclei is large, then the final grain size of the martensite will
The total increase in Gibbs free energy associated with the formation of a
befully
finercoherent
and hence
inclusion the steel may
of martensite in a be stronger.
matrix of austenite can be
expressed as:
ÄG = A-y + VÄG - VÄG (6.5)
Resistivity measurements
s v
indicate that martensite gives a lower resistivity than austenite
where -y is the interfacial free energy, ÄG s is the strain energy, ÄG v the
volume free energy release, V the volume of the nucleus and A the surface

The small initial increase in resistivity is

Resistivity explained in terms of the initial strain of the
y austenite lattice by the martensite nucleus.

The initial nucleus should be

I
-----a
coherent with the parent
austenite
Time
Fig. 6.13 Resistivity changes during the growth of single plates of rnartensite across a A. S. C. M. D’Oliveira
grain in a Fe-Ni alloy. Frorn this it can be calculated that the velocity of growth is
ab out 1000 rn/so (After R. Bunshah and R.F. Mehl, Transactions AlME 197
22 (1953) 1251.)

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vDiffusionless transformations

Nucleation of martensite is a balance between:

ΔG = Aγ+ VΔGs-VΔGv

Surface energy ( coherent interface)

Volume free energy, Gv
and
(reduces the energy of the
vs
Elastic deformation energy (martensite plate causes
system)
a deformation in austenite)
(Accounts for an increase in the energy of the system)

Balance between volume free energy and surface and elastic energy

• The strain energy of the coherent nucleus is much more important than the surface energy, since the
shear component of the pure Bain strain is as high as s = 0.32 which produces large strains in the
surrounding austenite

• The interfacial (surface) energy of a fully coherent nucleus is relatively smalI.

A. S. C. M. D’Oliveira

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vDiffusionless transformations
Nucleation of martensite

The number of nuclei increases substantially with increasing undercooling prior to transformation;

on the other hand,

the average number of nuclei is largely independent of grain size

In agreement with experimental observations, nucleation does not necessarily occur at grain
boundaries or at surfaces
Martensite nucleation is a heterogeneous
process.
Surfaces and grain boundaries are not significantly contributing to nucleation, then the
transformation is being initiated at other defects within the crystal.

most likely individual dislocations

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 vDiffusionless transforma/ons
The role of dislocations in Martensite Nucleation:
Dislocation in austenite may increase nucleation sites for martensite

Martensita ε

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vDiffusionless transforma/ons
Movement of partial dislocations <112>γ during twining generates a
Zener model thin BCC region from a FCC lattice

FCC
Shear of layer 3
followed by na
additional
dilatation to
bring about the
correct lattice
spacings

BCC
BCC lattice nucleus of only two atom layers thick.
Thicker nuclei could form at dislocation pile-ups, where the partial dislocations are forced closer together
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 vDiffusionless transforma/ons
Venable model
g -> ε -> α´?

g -> ε´

Low stacking fault energy alloys

Formation of matensite in stainless steels :

g -> ε or g -> α´ ε´ -> α´

ε and α´ form independently by different mechanisms

ε martensite structure thickens by inhomogeneous half-

twinning shears on every other {111} g plan
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vDiffusionless transformations
Dislocation Strain Energy Assisted Transformation

The nucleation barrier to form coherent nuclei can be reduced by the help of the elastic strain field of a dislocation

ΔG = Aγ+ VΔGs-VΔGv- ΔGd

dislocation interaction energy which

reduces the nucleation energy barrier

The strain field associated with a dislocation can in certain cases provide a favourable interaction with the
strain field of the martensite nucleus, reducing the total energy of nucleation

This theory combines the crystallographic characteristics of the inhomogeneous shear and the Bain
strain in terms of total strain energy at nucleation
It is in line with the majority of the known characteristics of martensite, including the initial straining
of the lattice due to the coherent nucleus and the fact that an inhomogeneous shear is necessary
for growth

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 vDiffusionless transformations
Martensite growth
Once the nucleation barrier has been overcome, the volume free energy becomes so large that
the martensite plate grows rapidly until it hits a barrier such as another plate, or a high angle
grain boundary

Very thin plates form with a very large a/c ratio and then thicken afterwards

Because of the very high speeds of growth, the interface between austenite and martensite must be a
glissile semicoherent boundary.
It consists of a set of parallel dislocations or twins with Burgers vector common to both phases, i.e.
transformation dislocations.
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vDiffusionless transformations
Martensite growth

Martensite plates changes from laths or needles (a>b>>c) to plates, in medium and high
carbon steels with high Ni content

Martensite growth:
• High T or low growth rates - grows by a sliding mechanism
• Low T and high growth rates - grows by twining mechanism

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vDiffusionless transformations
Factors affecting the growth of martensite:

Stabilization
samples cooled to some temperature intermediate between Ms
and Mf, held there for a period of time and then cooled again

Transformation does not immediately continue, the total

amount of transformed martensite is less than obtained by
continuous cooling throughout the transformation range.
Existing plates do not continue to grow after stabilization, but
new plates are nucleated instead
The degree of stabilization is a function of the time held at
temperature

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vDiffusionless transformations
Factors affecting the growth of martensite:

External stresses
Dependence of martensite growth on dislocation nucleation -> an externally applied stress will aid the
generation of dislocations and hence the growth of martensite. External stresses can also aid martensite
nucleation if the external elastic strain components contribute to the Bain strain
If plastic deformation occurs, there is an upper limiting value of Ms defined as the Md temperature

Role of grain size

Although grain size does not affect the number of martensite nuclei in a given volume, the final
martensite plate size is a function of the grain size.
Large grain sized material -> the dilatational strain associated with the transformation causes large
residual stresses to built up between adjacent grains and this can even lead to grain-boundary
rupture (quench cracking) and substantially increase the dislocation density in the martensite.
Fine grain-sized metals -> more self-accommodating and together with the smaller martensite plate
size, provides for stronger, tougher material.

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 vDiffusionless transformations
Tempering of Ferrous Martensites

25-100º -> Carbon segregation to dislocations and boundaries; pre- precipitation clustering and ordering
100- 200°Cè Transition-carbide precipitation, diam. 2 nm (first stage of tempering) ε (Fe2.4C)
Hardness: 65 RC è60-63 HRC

200-350°Cè Retained austenite transforms to ferrite and cementite (second stage) - Associated with
tempered martensite embrittlement
250-350°Cè Lath-like Fe3C precipitation (third stage) Hardness: 62 RC è50 HRC

350-550°Cè Segregation of impurity and alloying elements - Responsible for temper embrittlement
400- 600°Cè Recovery of dislocation substructure. Lath-like Fe3C agglomerates to form spheroidal Fe3C -Lath
structure maintained Hardness: 20-45 HRC

500-700°Cè Formation of alloy carbides. (secondary hardening or fourth stage) - Occurs only in steels
containing Ti, Cr, Mo, V, Nb, or W; Fe3C may dissolve
600-700°Cè Recrystallization and grain growth; coarsening of spheroidal Fe3C - Recrystallization inhibited in
medium- carbon and high-carbon steels; equiaxed ferrite formed

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vDiffusionless transformations
Tempering – tool steels

Alloy carbides - replace the less stable cementite which dissolves as a finer alloy carbide dispersion forms.
Fe3C – alloy carbide:
By in situ transformation - the alloy carbides nucleate at several points at the cementite/ferrite interfaces, and
grow until the cementite disappears and is replaced by a finer alloy carbide dispersion.
By separate nucleation and growth - the alloy carbides nucleate heterogeneously within the ferrite on
dislocations, lath boundaries, and prior austenite grain boundaries. The carbides then grow at the expense of
cementite.

Secundary hardnening

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 vDiffusionless transforma/ons
Secundary hardnening

Some alloying elements can delay the hardness reduction and even enhance strenghening during tempering
(ex: Mo, V, W, Cr, Ti, Nb)
These elementsfForm stable carbides (MoC, VC, WC,...) that coarsen at higher T than cementite

Com elementos de liga

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vDiffusionless transformations

Effect of retained austenite

In steels, especially those containing more than 0.4% C, austenite is retained after quenching. On ageing in the range 200-
300 °C this austenite decomposes to bainite. In some high-alloy steels austenite can be stabilized to such low temperatures
that the martensite partially reverts into austenite on heating. Very thin regions of retained austenite may even be present
between laths in low-carbon steel, and this is thought to improve the toughness of these steels independently of tempering
treatments.

Recovery, Recrystallization and Grain Growth

As-quenched lath martensite contains high-angle lath boundaries, low-angle cell boundaries within the laths, and dislocation
tangles within the cells. Recovery usually occurs above 400°C and leads to the elimination of both the dislocation tangles and
the cell walls. The lath-like structure, however, remains. The ferrite can recrystallize at high temperatures in low-carbon
steels, (see, e.g., Fig. 6.32) but the process is inhibited in medium to high-carbon steels by the grain boundary pinning
caused by carbide precipitates. In the latter steels recovery is followed by grain growth.

Temper embrittlement
The aim of tempering martensite is to improve ductility. However, in some steels tempering in, or slow cooling through, the
range 350-575ºC , can lead to embrittlement. This has been attributed to the segregation of impurity atoms such as P, Sb
or Sn to prior austenite grain boundaries. Some steels also show an embrittlement on tempering between 230 and 370ºC.
This may be caused by the formation of carbides with a critical plate-like shape.

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