Materials Science and Technology

ISSN: 0267-0836 (Print) 1743-2847 (Online) Journal homepage: https://www.tandfonline.com/loi/ymst20

Kinetics of martensite formation in plain carbon

steels: critical assessment of possible influence of
austenite grain boundaries and autocatalysis

S. M. C. van Bohemen & J. Sietsma

To cite this article: S. M. C. van Bohemen & J. Sietsma (2014) Kinetics of martensite
formation in plain carbon steels: critical assessment of possible influence of austenite grain
boundaries and autocatalysis, Materials Science and Technology, 30:9, 1024-1033, DOI:
10.1179/1743284714Y.0000000532

To link to this article: https://doi.org/10.1179/1743284714Y.0000000532

© 2014 The Author(s). Published by Informa Published online: 21 Mar 2014.

UK Limited, trading as Taylor & Francis
Group.

Submit your article to this journal Article views: 2932

View related articles View Crossmark data

Citing articles: 10 View citing articles

Full Terms & Conditions of access and use can be found at

https://www.tandfonline.com/action/journalInformation?journalCode=ymst20
 Kinetics of martensite formation in plain
carbon steels: critical assessment of possible
influence of austenite grain boundaries and
autocatalysis
S. M. C. van Bohemen1 and J. Sietsma2
The kinetics of the martensitic transformation in Fe–0?80C has been determined from dilatometry
data and shows no significant variation when the cooling rate is changed by two orders of
magnitude. All kinetic data can be adequately simulated by the Koistinen and Marburger (KM)
equation using a specific start temperature TKM and rate parameter am. This finding supports the
suggestion that the transformation is athermal, and moreover, the absence of a time dependence
strongly indicates that autocatalytic nucleation does not contribute to the transformation kinetics in
plain carbon steels on measurable time scales. Furthermore, dilatometry experiments with
different austenitising conditions were conducted to examine the effect of the prior austenite grain
size on the overall kinetics of martensite formation. The present results indicate that the progress
of martensite formation beyond a fraction f50?15 is independent of the prior austenitising
treatment. It is therefore concluded that austenite–austenite grain boundaries have no significant
effect on the overall nucleation and growth of athermal martensite, which is consistent with a
model proposed by Ansell and co-workers.
Keywords: Martensitic phase transformation, Nucleation, Kinetics, Dilatometry

This paper is part of a special issue on Adventures in the Physical Metallurgy of Steels

Introduction which are comparable to the Ms temperature of alloys

Although much research has been performed on
martensite formation in steels,1–6 the exact mechanisms
by which martensite nucleates and grows are not yet
understood. Experimental investigations and their inter-
pretation have proven to be complicated since the
growth of martensite is very fast, and therefore each
nucleation event directly leads to the formation of a
typical volume of the new phase. Regarding the
transformation kinetics, three different types of beha-
viour have been identified. These kinetic modes are
athermal, isothermal, and burst kinetics. Although some
common features of the three kinetic modes are known,
a unifying kinetic theory does not yet exist.7–9 Moreover,
there seems to be no general consensus regarding some
fundamental aspects of the transformation.10,11
Athermal martensite is usually observed in low-alloy
carbon steels.8 As argued by Entwisle,7 the apparent
independence of martensitic athermal transformation on
time might be explained by extrapolating the typical
isothermal transformation kinetics observed at low tem-
peratures in Fe–Ni–Mn alloys to the higher temperatures
1
Tata Steel RD&T, IJmuiden, The Netherlands
2
Delft University of Technology, Delft, The Netherlands
*Corresponding author, email s.m.c.vanbohemen@gmail.com
exhibiting athermal kinetics. Such a translation would lead
to transformation times of less than 1 ms and thus not
resolvable with conventional experimental capabilities.7
Isothermal martensite is typically formed in high-Ni
iron based alloys at sub-zero temperatures.9 The
isothermal transformation can be preceded by the
formation of a volume fraction of athermal or burst
martensite formed during cooling to the holding
temperature.12 In some alloys with Mn addition a truly
isothermal transformation has been reported.7
In the formation of burst martensite, which is
probably the least-understood transformation mode,
the transformation occurs abruptly at a certain tem-
perature during cooling of the austenite.9,13,14 The
fraction formed at the burst temperature can vary from
a few percentage to more than 50 vol.-%, and this burst
transformation can take place within a millisecond. This
chain reaction of the formation of plates is usually
regarded as an extreme form of autocatalysis.9
In the comprehensive review by Raghavan9 it is
argued that the present understanding of the martensite
kinetics is largely confined to the isothermal mode, with
a limited extension of the concepts to the athermal and
burst modes. In the case of athermal martensite, the
nucleation is often believed to take place at structural
imperfections in the parent phase and these defects are

ß 2014 Institute of Materials, Minerals and Mining

Published by Maney on behalf of the Institute
Received 25 September 2013; accepted 28 February 2014
1024 DOI 10.1179/1743284714Y.0000000532 Materials Science and Technology 2014 VOL 30 NO 9
 van Bohemen and Sietsma
stimulated to grow into martensite crystals at different
degrees of undercooling below Ms.8 However, the nature
of the defect sites at which heterogeneous nucleation
occurs is still not well understood. In addition to
nucleation at pre-existing defects, the overall transfor-
mation rate can, in principle, be enhanced by so called
autocatalytic nucleation: the stimulus of nucleation by
previously formed martensite crystals. In addition the
mechanism of this type of nucleation is not fully
understood.
Based on the considerations discussed in Ref. 15 it
seems plausible to assume that the freshly formed
martensite strengthens the surrounding austenite during
its formation, and that this mechanical stabilisation
impedes the plastic accommodation of the subsequent
transformation. When a martensite lath or plate is
formed, dislocations are generated in the surrounding
austenite by plastic deformation due to the volumetric
and shear strains.9 On the one hand, it is sometimes
assumed that the dislocations produced in the austenite
during transformation can assist the subsequent nuclea-
tion of martensite, which is known as autocatalytic
nucleation.16–19 However, the dislocations induced in
the austenite due to prior transformation can also retard
the subsequent transformation to martensite, which is
known as mechanical stabilisation.4,20–23 The dislocation
debris interferes with the movement of the glissile
interface that constitutes the growth. When the strain
build-up in the remaining austenite accompanying the
transformation exceeds a critical value, the further
transformation at a certain temperature below Ms is
suppressed.22 In this sense mechanical stabilisation can
play an essential role in the athermal character of the
martensitic transformation in low-alloyed carbon
steels.15
When the athermal martensitic transformation is
interrupted at a temperature below Ms by stopping the
cooling, the remaining austenite is often observed to
decompose; however, there is not yet consensus on the
exact transformation mechanism and the classification
of this isothermal transformation product in low-alloyed
steels. It has frequently been argued that isothermal
martensite forms below Ms.24,25 In contrast, in another
investigation26 it was shown that below Ms the remain-
ing austenite continues to decompose isothermally with
a certain rate, which is in agreement with the kinetics of
bainite formation above Ms. Based on this it was
concluded that isothermal bainite can be formed below
Ms, which was supported by SEM images showing a
mixed martensite–bainite microstructure.26 A renewed
literature survey was conducted by the present authors
which shows that the isothermal decomposition to
bainite below Ms was already suggested by Davenport
and Bain in 1930,27 although no experimental evidence
was shown. Some years later Howard and Cohen1
investigated the transformation kinetics and microstruc-
tures formed both above and below Ms in plain carbon
steels with approximately 1 wt-%. Based on their data,
TTT diagrams were constructed displaying isothermal
kinetics below and above Ms and they concluded that
‘the bainite formation below Ms takes place at a rate
more or less predictable from the normal shape of the
bainite curves extending down from above Ms’, which is
fully consistent with interpretation of the results for Fe–
0?66C discussed elsewhere.26 Howard and Cohen found
Kinetics of martensite formation in plain carbon steels
no evidence for isothermal martensite formation in steels
with 0?75–1?35 wt-%C at temperatures below Ms.1
In the first part of the present work the possible time
dependence of the martensitic transformation will be
investigated by applying different cooling rates to Fe–
0?80C samples. In the analysis of the results special
attention will be paid to the influence of possible
instrumental effects like thermal gradients across the
sample length. Furthermore, the influence of autotem-
pering on dilatometry results is discussed. In the second
part the kinetics of the transformation are determined
from the dilatometry data and compared with simula-
tions using the Koistinen Marburger (KM) equation.28
In the final part of this investigation it is attempted to
get more insight into the role of the austenite grain size
and grain boundaries in the nucleation and growth of
martensite. Although it is known that microstructural
features such as the grain size can cause variations in the
Ms temperature,29–35 little systematic work has been
conducted to quantify the effect of the grain size on the
progress of the transformation below Ms. In the present
paper, dilatometry measurements are analysed to
quantify the effect of the austenite grain size on both
the Ms temperature and the kinetics of the transforma-
tion below Ms.
Experimental
Steel Fe–0?80C used in this study has a chemical
composition that is close to the eutectoid composition
as shown in Table 1. The dilatation of the samples as a
function of temperature and time was measured using a
Bähr 805A/D dilatometer.36 Cylindrical dilatometric
samples were machined of 10 mm in length and 5 mm
in diameter. The temperature was controlled using a
thermocouple spot-welded onto the middle of the
sample. In order to get an estimate of the thermal
gradient in the axial direction of the sample a second
thermocouple was welded approximately 4 mm from the
centre of the sample. In Fig. 5 of Ref. 36, a schematic
drawing of the sample in the dilatometer is presented,
which shows the position of the two thermocouples.
Results of repeated heat treatments with different
samples sometimes showed differences in the tempera-
ture at which the onset of expansion during cooling
appeared (the martensite-start temperature), and these
differences seemed to correlate with changes in the
thermal gradient along the sample length. Despite these
differences in Ms the characteristics of the dilatometry
curves below Ms were very similar. In contrast to these
irreproducible variations in Ms, repeated heat treat-
ments with the same sample did not show any
anomalous results. It is noted that Tsuzaki et al.
observed similar differences when different samples
were used.37 Analysis showed that these systematic
errors are probably due to inaccuracies in the spot-
welding of the thermocouples on the sample, and the
exact position of the thermocouple wires relative to the
nozzles of the He quench gas spray system. In order to
avoid these errors and to ensure an unambiguous
Table 1 Chemical composition of steel Fe–0?80C/wt-%
C Mn Si Ni Cr Cu P S
Fe–0.80C 0.80 0.61 0.3 0.2 0.3 0.23 0.012 0.04
Materials Science and Technology 2014 VOL 30 NO 9 1025
van Bohemen and Sietsma Kinetics of martensite formation in plain carbon steels

1 a measured dilatation as a function of temperature due to martensite formation during cooling of Fe–0?80 samples with
different rates. Right-hand y-axis shows measured temperature difference between two thermocouples (DT) and b dila-
tometry data plotted against temperature corrected for thermal gradients

analysis, all experiments were conducted with the same austenite grain size on the kinetics of martensite
sample. formation in Fe–0?80C. The five austenitising treatments
In the experiments with varying cooling rates, the discussed in detail in this paper are listed in Table 3.
sample was heated with 10uC s–1 to a temperature of After austenitising in the range 800–1050uC, the samples
900uC, and austenitised for 2 min at a pressure of less were cooled with the natural cooling conditions
than 561025 mbar. Subsequently, the sample was explained above.
cooled using He gas to 500uC with an average cooling
rate between 800 and 500uC of approximately 75uC s–1. Results
Below 500uC the cooling rate was decreased gradually to
approximately 15uC s–1 at 400uC with the aim to Influence of cooling rate on dilatometry
minimise the temperature differences in the sample measurements
before the transformation to martensite starts. The The dilatation curves measured as a function of
dilatation signal as a function of temperature indicated temperature for the five investigated cooling rates are
that no ferrite or bainite formation occurred at the shown in Fig. 1a. It is seen that the three dilatometry
cooling rates employed. curves for cooling with He quench gas, the cooling rates
To investigate the possible effect of the cooling rate on 2, 5 and 12uC s–1, are mutually not very different, but
the transformation kinetics, the sample was cooled from they are distinctly different from the two dilatation
approximately 400uC to room temperature with five signals measured for the slowest cooling rates (0?2uC s–1
different cooling rates in the range of 0?2 to 12uC s–1 (see and natural cooling). This difference between the
Table 2). For cooling rates higher than 2uC s–1, He experiments with and without He quench gas can be
quench gas was applied; the lowest cooling rates attributed to the thermal gradients in the sample, which
required induction heating. A number of experiments are depicted in the same figure. The right-hand y axis of
were conducted with natural cooling subsequent to the
initial fast cool. This gave highly reproducible results,
not only for the experiments with the same sample but Table 3 Experimental details and results of experiments
also in the case that different samples were used. with varying austenitising treatments*
Therefore, the natural cooling conditions are considered
Taus/uC taus/min Dc/mm Ms/uC TKM/uC am/K21 cR/vol.-%
to give results that are least susceptible to inaccuracies
due to temperatures differences in the sample. Natural 800 1 12¡4 221 218 0.0122 11¡2
cooling in an He atmosphere results in a cooling rate of 850 2 25¡5 225 218 0.0122 …
approximately 2uC s–1 close to Ms and decreases 900 2 40¡8 230 218 0.0122 10¡2
gradually to 0?3uC s–1 just above room temperature. 1000 2 65¡15 235 218 0.0122 11¡2
1050 12 130¡25 238 218 0.0122 11¡2
Experiments with different austenitising conditions
were conducted to examine the effect of the prior *Taus, austenitising temperature; taus, austenitising time.

Table 2 Experimental details and results of experiments with varying cooling rates

Cooling rate
between Ms DT at TKM from am from Ms from cR
and RT/uC s–1 Ms/uC KM fit/uC KM fit/K21 slope/uC XRD/vol.-%

12.5 20 247 10¡2

5 18 248
2 17 245
Natural 2 218 0.0122 230 10¡2
0.2 2 218 0.0122 226

1026 Materials Science and Technology 2014 VOL 30 NO 9

 van Bohemen and Sietsma
2 a dilatation due to tempering of fully martensitic sample at 180uC as a function of time: length decrease of about 2–
2?5 mm in some tens of seconds and b dilatation as a function of temperature showing tempering characteristics dur-
ing heating of samples which were made martensitic with different cooling rates as shown in Fig. 1
Fig. 1a shows the temperature difference DT measured
between the centre and the edge of the sample. It is seen
that DT is less than 3uC near Ms for the experiments
without active cooling. In contrast, DT is quite large for
the experiments using He quench gas: DT is approxi-
mately 18uC near Ms, and increases somewhat for the
higher cooling rates (see Table 2). It should be noted
that the maximum thermal gradient in the sample may
even be somewhat larger than measured with the two
thermocouples. For the measurements with active cool-
ing it is also seen that just below Ms the thermal gradient
decreases more strongly: the DT curve exhibits a small
dip. This behaviour may be due to the release of latent
heat accompanying the martensitic transformation. The
regions near the edge of the sample with the lowest
temperature will transform first, and the local heat
release increases the temperature, which reduces DT.
Based on above observations it is concluded that the
dilatometry curves measured during active cooling of
samples do not always give a very accurate measure of
the kinetics of the transformation. The Ms temperature,
as determined from the change in slope of these
dilatometry curves,38 is about 15uC higher than the Ms
temperature evaluated from the more accurate measure-
ments performed without the use of He quench gas (see
Table 2).
The average sample temperature of quenched samples
is lower than the temperature recorded with the control
thermocouple in the middle of the sample. An estimate
of the average sample temperature is needed to correct
for the influence of thermal gradients on the dilatometry
curves. In the present work it is assumed that the
average sample temperature can be approximated by T–
KDT. Figure 1b shows the dilatometry data plotted
against this corrected temperature. Owing to this
correction all five dilatometry curves are very similar
in the temperature range 160–240uC. Although the
correction for thermal gradients indicates that the
cooling rate has no influence on the kinetics of
martensite formation at the beginning of transformation
(see Fig. 1b), it is seen that in the final stage of
transformation (below 160uC) the dilatation becomes
significantly smaller with decreasing cooling rate. This
Kinetics of martensite formation in plain carbon steels
difference in kinetics is thought to be related to
autotempering of martensite: the tempering of the as
formed martensite during subsequent slow cooling.
Tempering of martensite, and therefore also autotem-
pering, is accompanied with a volume decrease.39
Moreover, this thermally activated process is stronger
for the lower cooling rates. In fact, there are two
simultaneous effects on the measured dilatation due to
autotempering. At the relatively low temperatures at
which the martensite is formed, the so called first stage
of tempering is probably dominant,40 which means
partitioning of carbon to dislocations or the remaining
austenite. In addition, carbide formation takes place,
and both processes involved in tempering result in a
negative change in length39 and can thus explain the
smaller dilatation for the lower cooling rates. The
magnitude of the dilatation due to tempering will be
discussed later in this section.
Furthermore, at very low temperatures the carbide
formation may become very sluggish, and consequently
the austenite is stabilised when carbon partitions from
the supersaturated martensite to the austenite. Such
chemical stabilisation of the austenite implies that the
transformation shifts to lower temperatures. The resul-
tant decrease in the transformation kinetics also results
in a smaller dilatation signal. In relation to this, it is
noted that in the literature the stabilisation of austenite
due to a lower cooling rate or interrupted cooling
has sometimes been called thermal stabilisation of
austenite.41
In order to further test this explanation of the
differences in dilatation in terms of the degree of
autotempering taking place during cooling, both iso-
thermal aging and heating experiments were conducted
to obtain an estimate of the dilatation owing to the
tempering of martensite. To investigate tempering under
isothermal conditions, a sample of Fe–0?80C was first
fully transformed to martensite by quenching in liquid
nitrogen, and subsequently heated with 20uC s–1 to
180uC in the dilatometer and isothermally annealed at
that temperature for 5 min. The result shown in Fig. 2a
indicates that the sample length decreases approximately
2–2?5 mm in some tens of seconds. This estimate of the
Materials Science and Technology 2014 VOL 30 NO 9 1027
van Bohemen and Sietsma Kinetics of martensite formation in plain carbon steels

3 a measured dilatation as a function of temperature due to martensite formation during natural cooling (open squares).
Solid lines represent thermal expansion of both austenite (fcc) and martensite (bcc); open circles describe dilatation of
fully martensitic sample during heating and b experimental volume fraction of martensite as a function of temperature
derived from Fig. 3a (open squares) can be described by KM equation (solid line) using TKM5218uC, am50?0122 K21.
Volume fraction of retained austenite at room temperature is approximately 0?10

magnitude of the length decreases owing to tempering is
in fair agreement with the differences observed between
dilatometry curves for natural cooling and cooling with
0?2uC s–1. The second contribution of autotempering to
the dilatation, the stabilisation of the remaining
austenite owing to autotempering during cooling,
cannot be simulated with an additional experiment,
but may also have contributed to the difference between
the two experiments without active cooling.
As discussed above, repeated heat treatments with the
same sample were conducted because this proved to yield
the most reproducible results. Thus all samples, for which
the dilatometry data for different cooling rates are shown in
Fig. 1, were heated with 10uC s–1 in a subsequent experi-
ment. Figure 2b shows that the degree of tempering of
samples depends on the cooling rate in the previous
experiment. As a reference, the solid line (red) shows the
thermal expansion of samples in the absence of tempering.
Samples cooled with He quench gas (open blue symbols)
show a stronger tempering behaviour during heating than
the samples that were cooled slowly (solid green symbols).
The susceptibility to tempering of a martensitic sample
during heating depends on the degree of autotempering that
occurred during cooling. Thus the relatively small temper-
ing during heating of slowly cooled samples indicates that
the martensitic microstructure was already autotempered to
a certain degree due to the slow cooling.
Kinetics of martensite formation
By applying different cooling rates it has been shown
that the progress of martensite formation has no time-
dependence, at least not on experimentally accessible
time scales, which confirms the athermal character of the
transformation. It seems to be widely accepted that the
extent of transformation as a function of temperature
can be well described by the Koistinen and Marburger
equation8,15,28
f ~1{exp½{am (TKM {T)
in which am is a rate parameter, and TKM is the
theoretical martensite-start temperature, which is typi-
cally somewhat lower than the conventional (experi-
mental) Ms determined as the onset of expansion during
cooling in a dilatometry experiment. As discussed
earlier, the experiments for continuous natural cooling
are most accurate and therefore the measured dilatation
during natural cooling after austenitising at 900uC (see
Fig. 1) is used for a further quantitative analysis using
the KM equation. These data are shown by the open
diamonds in Fig. 3a. The sample cooled to room
temperature was investigated by X-ray diffraction
(XRD) to confirm the presence of retained austenite
in the microstructure, and quantitative analysis of
the XRD pattern yielded a volume fraction austenite
of 0?10¡0?02, which is comparable to results of
previous investigations on steels with a similar carbon
content.28,42
The martensite transformation kinetics has been
evaluated from dilatometry data with the Lever rule
(the linear law of mixtures) applied to the data using the
non-linear equations for the thermal contraction of bcc
and fcc lattices (solid lines) derived in Ref. 43. The non-
linear thermal expansion of bcc phase43 is found to agree
well with the dilatation data measured during heating of
a Fe–0?80C sample that was made fully martensitic (see
open circles in Fig. 3a). This sample was produced by
rapid cooling to room temperature, followed by
quenching in liquid nitrogen. For comparison, to
demonstrate the importance of using the non-linear
expressions of thermal expansion, the dashed lines in
Fig. 3a represent linear approximations for thermal
expansion, which are seen to have a less adequate
agreement with the experimental data over the whole
temperature range. The fraction retained austenite of
10 vol.-% at room temperature, which was derived from
XRD measurements, specifies the relation between the
dilatation and the bcc phase fraction at room tempera-
(1) ture. This means that for the present analysis a length

1028 Materials Science and Technology 2014 VOL 30 NO 9

 van Bohemen and Sietsma
4 Change in length as a function of temperature due to martensite formation in Fe–0?80C during natural cooling of sam-
ples which were given different austenitising treatments. Inset shows magnification of dilatometry curves close to Ms
temperature
change DLa2cRT586 mm (see Fig. 3a) is caused by 100%
austenite-to-martensite transformation. Figure 3a shows
that the thermal expansion of 100% bcc phase (marten-
site) is significantly larger than the slope of the
dilatometry curve just above room temperature, which
indicates that the transformation is not finished at room
temperature.
The volume fraction of martensite as a function of
temperature as represented by the open triangles in
Fig. 3b shows the best agreement with the KM equation
using TKM5218uC, am50?0122 K21. The rate para-
meter found for Fe–0?80C is higher than the well known
value of 0?011 K21 obtained by Koistinen and
Marburger for plain carbon steels with 1 to 1?1 wt-%
carbon.28 The differences in the values of am for
different steels are thought to be related to their
chemical composition,44 in particular the carbon con-
tent.45 The rate parameter am50?0122 K21 derived from
the dilatometry data is comparable to the value
am50?0129 K21 predicted using the equation proposed
in.45
Figure 3b shows the volume fraction of martensite as
a function of temperature corresponding to the dilata-
tion signal shown in Fig. 3a. It is seen that the volume
fraction calculated with the KM equation (solid line) is
in very good agreement with the experimental result
except for some deviations near the start of the
transformation. The Ms temperature as derived from
the change in slope is approximately 230uC, which is
12uC higher than the value of TKM5218uC determined
from the best fit simulated with the KM equation. It is
noted that this gradual beginning of the transformation
can only partly be explained by temperature differences
in the sample. In principle, thermal gradients in the
sample lead to localised transformations as the sample
approaches the martensite-start temperature, and this
may effectively cause an apparent gradual beginning of
Kinetics of martensite formation in plain carbon steels
the transformation. However, for the experiment with
natural cooling the thermal gradient measured over the
sample length is very small, approximately 2uC near the
Ms temperature. A deviation of 12uC in the martensite
start temperature can only be caused by temperature
gradients of at least 12uC, whereas the experiments show
that the gradients are not more than 2uC. This means
that thermal gradients in the sample cannot fully explain
the gradual beginning of transformation, which is
different from the modelled kinetics. In the following
section it will be demonstrated that the temperature
range where the gradual start of the transformation
occurs is dependent on the austenitising treatment.
Effect of prior austenite grain size on
martensitic transformation
Figure 4 shows the dilatation curves measured during
cooling of five samples that were given different austenitis-
ing treatments in order to change the prior austenite grain
size. The estimated grain sizes of the samples are listed in
Table 3. Figure 4 shows that distinct differences are
observed in the early stage of transformation. The inset
of Fig. 4 shows that the Ms temperature derived from the
change in slope increases from Ms5221uC for Taus5800uC
to Ms5238uC for Taus51050uC (see Table 2). It is noted
that each experimental result is to some extent subject to
thermal gradients, but the measured temperature differ-
ence DT between the centre and the edge of the sample is
always smaller than 3uC in the temperature range of
transformation. Furthermore, DT is approximately the
same for all measurements. The observation that Ms
depends on the austenite grain size is consistent with
results reported previously for various steels.29–35
However, a systematic study of the effect of the austenite
grain size on the kinetics of martensite formation has not
been reported in the literature. Only a qualitative
description of this gradual beginning of transformation
Materials Science and Technology 2014 VOL 30 NO 9 1029
van Bohemen and Sietsma Kinetics of martensite formation in plain carbon steels
5 Volume fraction of martensite as a function of tempera-
ture derived from measured dilatation data shown in
Fig. 4 for Taus5800uC (open squares). Solid line repre-
sents progress of transformation calculated with KM
equation using TKM5218uC, am50?0122 K21
in relation to the austenitising treatment has been given by
Sastri and West.29
The small differences in the dilatometry curves of Fig. 4
at the final stage of transformation are possibly due to
different degrees of transformation plasticity for different
austenite grain sizes. Analysis of the sample length after
multiple thermal cycles on a single sample frequently
showed that the sample becomes about 2 mm shorter in the
case Taus5800uC, and approximately 8 mm shorter when
Taus51050uC. The final microstructures of four samples
with different prior austenite grain sizes were investigated
by XRD, and a similar volume fraction of retained
austenite was found in each sample as shown in Table 2.
The fraction of martensite as a function of temperature
was determined from the five dilatation curves shown in
Fig. 4 using the Lever rule as demonstrated earlier for
Taus5900uC (see Fig. 3). The fraction curve for the
smallest austenite grain size (Taus5800uC) is shown in
Fig. 5. The solid line through the data represents best fit to
the KM equation calculated with TKM5218uC,
am50?0122 K21. The Ms temperature as derived from
the change in slope is approximately 221uC, which is only
3uC higher than TKM5218uC. It is noted that this
deviation can be fully explained by temperature differ-
ences in the sample. It is therefore concluded that for
Taus5800uC the gradual beginning of the transformation
is not significant, whereas for Taus5850uC and higher a
distinct deviation is found (see Fig. 3).
The overall transformation kinetics for the other three
austenitising temperatures can also be well described
using KM equation by taking TKM5218uC, and
am50?0122 K21 (see Table 2). These model parameters
lead to the best agreement in the temperature range from
room temperature to Ms, although some discrepancies
are observed close to Ms depending on Taus. Figure 6
shows all five experimental fraction curves correspond-
ing to the inset of Fig. 4, and the best simulation for the
transformation kinetics. As demonstrated in Fig. 5, for
Taus5800uC the measured fraction curve agrees very
well with the calculated kinetics at each stage of the
transformation. With increasing austenite grain size
1030 Materials Science and Technology 2014 VOL 30 NO
6 Martensite fraction as a function of temperature corre-
sponding measured dilatation signals shown in inset of
Fig. 4. Black line represents transformation kinetics cal-
culated with KM equation using TKM5218uC, and
am50?0122 K21
the agreement with the KM model becomes poorer for
the early stages of transformation (see Fig. 6), and the
maximum deviations are observed for Taus51050uC.
Austenitising at Taus5800uC for 1 min resulted in
Dc<12 mm (Table 2). It was, however, not possible to
investigate the martensite kinetics for even smaller grain
sizes because for very small grain sizes it becomes
impossible to prevent bainite formation during the
fastest cooling. The kinetics of martensite formation
was also investigated for grain sizes somewhat smaller
and larger than the largest in Table 2, Dc5130 mm. It
was found that the dilatometry curve measured after
austenitising at Taus51050uC for 5 min (Dc<100 mm) or
18 min (Dc<150 mm) did not differ significantly from
the result for taus512 min shown in Fig. 4 although the
austenite grain size was different.
Based on abovementioned observations it is con-
cluded that the effect of the austenite grain size on the
start temperature is large when the grain size is small
and diminishes as the grain size increases. This effect on
Ms is consistent with the observations reported else-
where.29,30,32,35 In addition to the effect on Ms, it is seen
in Figs. 4 and 6 that the initial transformation rate
between Ms and TKM decreases when the austenite grain
size increases. Similar observations have been reported
by Sastri and West,29 and indicate that not only Ms, but
also the early stages of the martensitic transformation
just below Ms are dependent on the initial austenite
grain structure. The fraction curves in Fig. 6 also
indicate that the progress of martensite formation
beyond f50?15 (i.e. below 205uC) is nearly independent
of the prior austenitising treatment. It can therefore be
concluded that the major part (85%) of the overall
kinetics is not significantly influenced by the prior
austenite grain size.
Discussion
Autocatalytic nucleation
By applying different cooling rates it has been shown
in the foregoing that the martensite formation has no
9
 van Bohemen and Sietsma
time-dependence, at least not on experimentally acces-
sible time-scales (Fig. 1). This may imply that the
nucleation process takes place without thermal activa-
tion, i.e. the activation energy is zero in the temperature
range of transformation.9 This is called truly athermal
behaviour.9 However, the transformation kinetics may
also be too fast for experimental observation when the
activation energy is very small. In this case the
transformation would be thermally activated, and
therefore this kind of transformation is sometimes called
anisothermal.12 For most steels a distinction cannot be
made because of experimental limitations. Nevertheless,
the present results for Fe–0?80C confirm the athermal
character of the transformation as it is frequently
defined in literature, meaning that it is practically
impossible to measure time dependence, and thus the
volume fraction of martensite appears to vary only with
temperature below Ms.
Since martensite nucleation and growth events in
plain carbon steels take place too rapidly at any given
temperature to be measurable as a function of time, it is
not immediately evident that autocatalysis takes place
in athermal martensitic transformations. However, it
cannot be ruled out that autocatalysis plays a role on
very small time scales. Possibly martensitic laths, which
appear to be grouped into a single packet in the final
microstructure, are formed simultaneously in a very fast
transformation process/event in which autocatalytic
nucleation does play an important role.
In contrast to the present findings, a significant
cooling rate dependence of the kinetics was reported
by Tsuzaki et al. for lath martensite formation in a Fe–
15Ni alloy.37 For the lowest cooling rate they observed
steps in the transformation curve37 in the temperature
range 300–400uC, which are quite similar to fraction
curves observed for burst martensite formation,8,14 and
they concluded that the transformation has an isother-
mal character in addition to the athermal one. Similar
transformation behaviour has been reported for alloys
with higher Ni contents transforming below room
temperature.12 The observation of Tsuzaki et al. that
the progress of transformation depends on the cooling
rate,37 and thus has a time dependence, strongly
indicates that autocatalysis took place in the steel
studied by Tsuzaki et al. For example, kinetics of
isothermal martensite formation exhibits a typical S-
shaped transformation curve during isothermal holding,
which can be best understood and described under the
assumption of an autocatalytic contribution to the
overall nucleation kinetics. The autocatalytic nucleation
is accounted for in displacive models for isothermal
martensite and bainite by an additional autocatalytic
term in the total nucleation rate.7,18,46
The mechanism of autocatalytic nucleation is usually
assumed to be associated with the dislocations produced
in the austenite during transformation, which are
considered to assist the subsequent nucleation of
martensite.16,47 In this respect, autocatalysis can be
regarded as very similar to strain induced transforma-
tion with the strain generated by the transformation
itself. However, the dislocations induced in the austenite
due to prior transformation can also retard the
subsequent transformation to martensite,30 which is
known as mechanical stabilisation.23 The dislocation
debris interferes with the movement of the glissile
Kinetics of martensite formation in plain carbon steels
interface that constitutes the growth. If the strain in
remaining austenite accompanying the transformation
exceeds a critical value,22 then mechanical stabilisation
suppresses further transformation. This mechanism is
assumed to control the kinetics of athermal martensite
formation in low-alloy carbon steels.15
Kinetics of athermal martensite
Figure 3 shows the kinetics of martensite formation as a
function of temperature below Ms. For steels in general,
the driving force at Ms is approximately 1700 J mol–1 of
which about 600 J mol–1 (Refs. 23 and 48) is considered
to be stored in the surrounding austenite as strain energy
after the formation of martensite crystals. The athermal
kinetics observed for low-alloy carbon steels (e.g. the
present results in Fig. 3) can be well explained with the
martensite model proposed in Ref. 15 in which it is
assumed that the shape deformation accompanying the
formation of a certain volume of martensite increases
the strength of the remaining austenite and stops the
transformation. This model explaining the athermal
nature of the martensitic transformation is consistent
with the ‘growth-resistance of austenite’ hypothesis
proposed by Edmondson and Ko.49 Since the resistance
of the remaining austenite against plastic deformation
increases due to the formation of a number of plates or
laths, an increase in driving force is required for the
transformation to recommence. Based on these assump-
tions the well known KM equation was derived,15 and
the rate parameter am was linked to the strain energy
stored in austenite. On the basis of fitting experimental
fraction curves to the KM equation it was found that the
rate parameter am decreases with increasing carbon
content.44,45 This empirical finding is possibly related to
dislocation strengthening of austenite which can be
expected to increase for higher carbon steels.
Austenite grain size dependence of martensite
kinetics
Since the first detailed investigation on the influence of
the prior austenite grain size on martensite formation,29
different explanations were proposed for the depression
of Ms with austenite grain refinement as shown in Fig. 4
for Fe–0?80C. At present the most plausible explanation
seems to be the mechanism based on Hall–Petch
strengthening of the austenite50 proposed by Ansell
and his co-workers.33–35 This explanation has been
supported by other investigators,30 and is adopted in
the present work. Ansell argued that the Ms temperature
is not directly affected by the austenite grain size, but
controlled by the austenite yield strength.34 Breinan and
Ansell used a high temperature tensile apparatus and
showed that an increasing austenite yield strength due to
grain refinement correlated with decreasing Ms tem-
peratures.33 The increasing resistance of austenite to
plastic deformation makes it more difficult to accom-
modate the shape change accompanying the martensitic
transformation.
The mechanism based on Hall–Petch strengthening50
proposed by Ansell et al. assumes that the grain interior
is locally soft compared to the grain boundary regions.35
The local strength of the austenite determines the
resistance against plastic deformation and thus the
strain energy involved in the formation of plates or
laths of martensite. It is well known that the austenite to
martensite transformation occurs when the change in the
Materials Science and Technology 2014 VOL 30 NO 9 1031
van Bohemen and Sietsma Kinetics of martensite formation in plain carbon steels
chemical free energy accompanying the transformation
is larger than the energy necessary to overcome the
resistance to volume deformation, strain energy and the
creation of new surfaces/interfaces. This means that
when the resistance of austenite to plastic deformation is
locally reduced, the transformation can occur at a higher
temperature. Thus with increasing austenite grain size
the non-chemical free energy opposing the transforma-
tion decreases, which leads to a higher Ms.35
Based on the micrographs seen in Fig. 10 of Ref. 15
and further consideration of the locally soft austenite
grain interior assumed in the Ansell model, it is
postulated that the initial formation of martensite occurs
preferably in the grain interior. The first-formed
martensite plates effectively divide the prior austenite
grain3,9,51 and strengthen the surrounding austenite, and
the subsequent formation of martensite plates in the
same geometrically partitioned austenite grain require a
larger driving force. In the model for athermal
martensite15 the local austenite strength determines the
transformation temperature of a certain region. The
transformation of such a region to martensite leads to an
increase in the strength of the surrounding austenite and
therefore each austenite region has a specific decom-
position temperature. Thus in this model the nucleation
at certain defects or grain boundaries is not considered
to be the rate-controlling step in the transformation, but
the resistance of the austenitic parent phase to the
growth of the nuclei.
This transformation induced stabilisation mechan-
ism,15 which controls the kinetics of martensite forma-
tion, can also aid to understand the evolution of
martensite formation in large grained structures com-
pared to fine grained structures. Figure 6 shows that the
effect of the austenite grain size on both Ms and the
initial rate of transformation is such that the degree of
transformation is similar for all measurements at
approximately 205uC, which corresponds to a volume
fraction martensite f50?15. This indicates that the
stabilisation in a large grained structure evolves in such
a way that at f50?15 the resistance of the remaining
austenite against plastic deformation becomes equal to
that for the fine grained structure. The subsequent
decomposition of austenite can be described accurately
by the KM equation. Apparently, the first-formed
martensite plates (or laths) in a large grained structure
have a relatively strong stabilisation effect on the
remaining austenite. Possibly this is due to the fact that
these martensite plates have a relatively large aspect
ratio. It is well known that the strain energy term
increases with increasing aspect ratio,18 and this may
explain that the first-formed martensite plates have a
stronger stabilising effect.
For isothermal martensite a similar study has been
undertaken by Raghaven and Entwisle using isothermal
resistivity measurements on a Fe–Ni–Mn alloy with
grain diameters in the range 10 to 100 mm.6 They found
that the incubation time increases with decreasing
austenite grain size, which was in agreement with their
model calculations. Based on this it was concluded that
grain boundaries and grain corners are not preferred
nucleation sites,6 which is in agreement with the
conclusion drawn from the present study of athermal
martensite formation. This standpoint seems to be
widely accepted; only Kajiwara argued that certain
1032 Materials Science and Technology 2014 VOL 30
types of austenite grain boundaries provide potential
nucleation sites for martensite formation.30
Conclusions
It is demonstrated that the martensite transformation
kinetics is not dependent on the cooling rate, which
means that the transformation can be regarded as
athermal for the experimentally accessible cooling
conditions in the range of 0?2–12uC s–1. The finding
that the progress of transformation is independent of the
cooling trajectory below Ms and thus exhibits no time
dependence strongly indicates that autocatalytic nuclea-
tion does not play a vital role in the overall transforma-
tion kinetics in plain carbon steels. The methodology of
cooling has been found to have a significant influence on
temperature gradients within a dilatometry sample,
which in turn can lead to experimental deviations in
the acquired dilatometry data. Furthermore, the influ-
ence of autotempering of the as formed martensite has
been discussed. It is concluded that experiments with
natural cooling conditions in the temperature range of
transformation are most reliable, and the kinetic data
thus obtained can be accurately simulated by the KM
equation using a specific (alloy dependent) start
temperature TKM and rate parameter am. Dilatometry
experiments with different austenitising conditions were
conducted to examine the effect of the prior austenite
grain size on the overall kinetics of martensite forma-
tion. In contrast to the known sizable effect on Ms, the
present results indicate that the kinetics of martensite
formation beyond f50?15 is independent of the prior
austenitising treatment. It is therefore concluded
that austenite–austenite grain boundaries have no effect
on the overall nucleation and growth of athermal
martensite.
References
1. R. T. Howard and M. Cohen: Trans. AIME, 1948, 176, 384–397.
2. B. L. Averbach and M. Cohen: Trans. AMS, 1949, 41, 1024–1036.
3. J. C. Fisher, J. H. Hollomon and D. Turnbull: Trans. AIME, 1949,
185, 691–700.
4. E. S. Machlin and M. Cohen: Trans. AIME, 1951, 191, 267–274.
5. E. S. Machlin and M. Cohen: Trans. AIME, 1952, 194, 489–499.
6. V. Raghavan and A. R. Entwisle: Special Report No. 93, 30, The
Iron and Steel Institute, London, UK, 1965.
7. A. R. Entwisle: Metall. Trans., 1971, 2, 2395–2407.
8. C. L. Magee: ‘The nucleation of martensite’, in ‘Phase transforma-
tions’, 115–144; 1970, Metals Park, OH, ASM.
9. V. Raghavan: in ‘Martensite’, (ed. G. B. Olson and W. S. Owen),
202–225; 1992, Metals Park, OH, ASM.
10. X. Q. Zhao and B. X. Liu: Scr. Mater., 1998, 38, 1137–1142.
11. K. Otsuka, X. Ren and T. Takeda: Scr. Mater., 2001, 38, 145–152.
12. M. Lin, G. B. Olson and M. Cohen: Metall. Mater. Trans. A, 1992,
23A, 2987–2999.
13. H. K. D. H. Bhadeshia: J. Mater. Sci., 1982, 15, 383–386.
14. R. Brook and A. R. Entwisle: J. Iron Steel Inst., 1965, 203, 905–
912.
15. S. M. C. van Bohemen and J. Sietsma: Metall. Mater. Trans. A,
2009, 40A, 1059–1068.
16. G. B. Olson and M. Cohen: Metall. Trans. A, 1975, 6A, 791–795.
17. G. B. Olson and M. Cohen: Metall. Mater. Trans. A, 1976, 7A,
1897–1923.
18. H. K. D. H. Bhadeshia: ‘Bainite in steels’; 2001, London, The
Institute of Materials.
19. T. Y. Hsu: Mater. Sci. Eng. A, 2006, A438–A440, 64–68.
20. J. R. Strife, M. J. Carr and G. S. Ansell: Metall. Trans. A, 1977, 8A,
1471–1483.
21. H. K. D. H. Bhadeshia: Mater. Sci. Eng. A, 1999, A275, 58–66.
22. S. Chatterjee, H. S. Wang, J. R. Yang, and H. K. D. H. Bhadeshia:
Mater. Sci. Technol., 2006, 22, 641–644.
NO 9
 van Bohemen and Sietsma
23. S. Chatterjee and H. K. D. H. Bhadeshia: Mater. Sci. Technol.,
2007, 23, 1101–1104.
24. I. A. Yakubtsov and G. R. Purdy: Metall. Mater. Trans. A, 2012,
43A, 437–446.
25. D. Kim, S. Lee and B. C. de Cooman: Metall. Mater. Trans. A,
2012, 43A, 4967–4983.
26. S. M. C. van Bohemen, M. J. Santofimia and J. Sietsma: Scr.
Mater., 2008, 58, 488–491.
27. E. S. Davenport and E. C. Bain: Trans. AIME, 1930, 90, 117–131.
28. D. P. Koistinen and R. E. Marburger: Acta Metall., 1959, 7, 59–60.
29. A. S. Sastri and D. R. F. West: J. Iron Steel Inst., 1965, 203, 138–
149.
30. S. Kajiwara: Metall. Trans. A, 1986, 17A, 1693–1702.
31. C. Hayzelden and B. Cantor: Acta Metall., 1986, 34, 233–242.
32. M. Umemoto and W. S. Owen: Metall. Trans., 1974, 5, 2041–2046.
33. E. M. Breinan and G. S. Ansell: Metall. Trans., 1970, 1, 1513–1519.
34. T. J. Nichol: Metall. Trans. A, 1977, 8, 1877–1883.
35. P. J. Brofman and G. S. Ansell: Metall. Trans. A, 1983, 14, 1929–
1931.
36. T. A. Kop, J. Sietsma and S. van der Zwaag: J. Mater. Sci., 2001,
36, 519–526.
Kinetics of martensite formation in plain carbon steels
37. K. Tsuzaki, T. Maki and I. Tamura: Scri. Met., 1987, 21, 1693–
1698.
38. H. S. Yang and H. Bhadeshia: Mater. Sci. Technol., 2007, 23, 556–
560.
39. E. J. Mittemeijer, L. Cheng, P. J. Vanderschaaf, C. M. Brakman
and B. M. Korevaar: Metall. Trans. A, 1988, 19A, 925–932.
40. T. Waterschoot, K. Verbeken and B. C. de Cooman: ISIJ Int.,
2006, 46, 138–146.
41. E. R. Morgan and T. Ko: Acta Metall., 1953, 1, 36–48.
42. A. R. Marder and G. Krauss: Trans. ASM, 1967, 60, 651–660.
43. S. M. C. van Bohemen: Scr. Mater., 2013, 69, 315–318.
44. S. M. C. van Bohemen and J. Sietsma: Mater. Sci. Technol., 2009,
25, 1009–1012.
45. S. M. C. van Bohemen: Mater. Sci. Technol., 2012, 28, 487–495.
46. S. M. C. van Bohemen: Philos. Mag., 2012, 93, 388–408.
47. M. Suezawa and H. E. Cook: Acta Metall., 1980, 28, 423–432.
48. J. W. Christian: in ICOMAT ’79, (ed. G. B. Olson and M. Cohen),
145–154; 1979, Boston, MA, MIT.
49. B. Edmondson and T. Ko: Acta Metall., 1954, 2, 235–241.
50. J. P. Hirth: Metall. Trans., 1972, 3, 3047–3067.
51. G. Ghosh and G. B. Olson: J. Phys. IV, 2003, 112, 139–142.
Materials Science and Technology 2014 VOL 30 NO 9 1033