Scripta Materialia 50 (2004) 285–289

www.actamat-journals.com

A novel experimental approach to identifying kinetic transitions

in solid state phase transformations
a,*
C.R. Hutchinson , A. Fuchsmann a, H.S. Zurob b, Y. Brechet a

a
Laboratoire de Thermodynamique et Physico-Chimie M etallurgiques, Institut National Polytechnique de Grenoble, Domaine Universitaire,
St. Martin d’Heres Cedex, 38402, France
b
Department of Materials Science and Engineering, McMaster University, Hamilton, ON, Canada L8S 4L7
Received 11 February 2003; received in revised form 18 September 2003; accepted 23 September 2003

Abstract
A Fe–1Ni/Fe–5Ni (wt.%) diffusion couple carburised to 0.1 C (wt.%) has been used to examine the kinetic transitions during the
c ! ðc þ aÞ transformation that occur with changes in Ni content. The wide range of applicability of such a combinatorial approach
for studying transitions in behaviour in metallurgical phenomenon is emphasised.

2003 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: Phase transformations; Steels; Diffusion couple

1. Introduction A problem which is especially important both from a

An understanding of the kinetics of solid state phase
transformations requires knowledge of the effects of
both temperature and composition. Whereas experi-
mental studies of the effect of temperature are relatively
rapid, studies of the effect of composition are much
more time consuming and costly since they require the
casting of different alloy compositions. It is especially
difficult when the relevant critical compositions sepa-
rating different modes of behaviour are unknown. It is
therefore of great practical and fundamental interest to
define a simple and rapid procedure for investigating the
effect of composition on the kinetics of solid state phase
transformations. A similar situation occurs in solid state
chemistry where the products depend sensitively on
composition. One of the strategies followed in this field
is to develop samples which contain gradients in com-
position. These have been used to great effect, for ex-
ample, in the experimental determination of phase
diagrams [1]. We propose here a simple procedure using
diffusion couples for investigating the composition-
induced transitions in behaviour observed in solid state
phase transformations.
*
Corresponding author. Tel.: +33-4-76-82-66-10; fax: +33-4-76-82-
66-44.
E-mail address: hutch@ltpcm.inpg.fr (C.R. Hutchinson).
1359-6462/$ - see front matter
2003 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.scriptamat.2003.09.051
practical viewpoint (control of microstructure) and from
a fundamental viewpoint (coupling of interface migra-
tion with thermodynamics and kinetics) is the diffusional
formation of ferrite (a) from austenite (c) in so-called
Fe–C–X systems (where X is one of Mn, Ni, Cr, Mo, Si
etc.). Particularly characteristic features of Fe–C–X
systems are the very large differences in the diffusivities
of C and X in the c at typical temperatures of interest
and the often large solubility ranges for X in the a and c.
These features mean that, under suitable conditions, it is
possible to observe the formation of a unaccompanied
by bulk X redistribution and with a decrease in the
Gibbs free energy of the system, even though a greater
decrease would result from full equilibrium partitioning
of X. Such a possibility was first suggested by Zener [2]
in 1946 in connection with the pearlite transformation
but applies equally to the formation of a. The observa-
tions of a formation both with and without partitioning
of X is now experimentally well established [3–5]. Sev-
eral theoretical treatments have been developed to de-
scribe the kinetics of a formation under partitioning
(local equilibrium, LE) and non-partitioning (LENP [6–
10] and paraequilibrium (PE) [6,11]) conditions but the
emphasis has more recently shifted towards the devel-
opment of a coherent treatment that can describe the
transition between the different modes of growth [12]. In
particular, the need for experimental investigations of
this transition has been emphasised [13].
286 C.R. Hutchinson et al. / Scripta Materialia 50 (2004) 285–289

10 2. Experimental procedure
isoactivity line
for C in γ
Binary alloys of composition Fe–1Ni and Fe–5Ni
8
(wt.%) were cast and hot-rolled at IRSID Laboratories,
Metz, France. Samples of dimensions 40 mm · 40
6 γ mm · 10 mm were taken from each alloy and the broad
(wt. %) Ni

surfaces were polished to a 1 lm finish using standard

PE
Ph
ase
4 Bo
un
LE-P da
ry
/LE-N
P Bo
unda
2 ry
0 ONERA Laboratories, Paris, to form the diffusion
0 0.2 0.4 0.6
(wt. %) C
Fig. 1. Isothermal section of the Fe–C–Ni phase diagram sectioned at
700 C. The bold solid line represents the c=ðc þ aÞ equilibrium phase
boundary. The PE and LE-P/LE-NP boundaries are also indicated and
the range of Ni contents sampled in the diffusion couple are bounded
by the full circles.
In this paper, we report the development of a novel
procedure for the investigation of the effect of compo-
sition on solid state phase transformations and apply it
to the study of the transitions in a formation using a Fe–
1Ni/Fe–5Ni (wt.%) diffusion couple carburised to 0.1 C
(wt. %). The technique allows for the simultaneous ob-
servation of the c ! ðc þ aÞ transformation in the
continuous spectrum of Ni contents between 1 and 5
(wt.%) at a given temperature. The range of Ni contents
being investigated and their relation to the LENP and
PE phase boundaries in the Fe–C–Ni phase diagram at
700 C is shown in Fig. 1. The LENP 1 and PE 2 phase
boundaries were evaluated using the Thermo-Calc
software package. The transitions in a formation are
discussed and the wide applicability of the technique is
emphasised.
metallographic techniques. To create a good bond be-
tween the two alloys, the two polished surfaces were
held together under a pressure of
15 MPa for
5 min
at
900 C using a pneumatic press equipped with an
induction coil. The bonded samples were then treated at
1400 C for 72 h under primary vacuum conditions at
0.8 1
couple. The Ni concentration profile was measured us-
ing a CAMECA SX50 electron probe microanalyser
(EPMA) and the plot in Fig. 2 illustrates that the width
of the diffusion zone is
600 lm after the elevated
temperature heat treatment. Since the thickness of the a
layers to be studied is of the order of
10–100 lm, a Ni
diffusion zone of 600 lm is insufficient to perform an
investigation of the composition dependence of the
c ! a transformation. To increase the width of the Ni
diffusion zone, the diffusion couples were then reduced
from
20 mm in thickness to
1 mm by multiple cold-
rolling passes of very small reduction to encourage ho-
mogeneous deformation. The deformation resulted in
the geometrical spreading of the Ni diffusion zone from

600 lm to
1 cm. The rolled samples were given a
further homogenisation treatment at 1400 C for 96 h to
remove any small scale fluctuations in the Ni profile
arising from shear banding during rolling. The couples
were then carburised to a C content of
0.1 C (wt.%)
using a CO2 /CO gas mixture. Samples of binary Fe–1Ni
and Fe–5Ni alloy were included in the carburisation
6

1 5
The LENP boundary separates the ðc þ aÞ two phase field into
two regions: below the LENP boundary a growth under LE conditions
is possible without bulk partitioning of the alloying element (X) 4
(wt. %) Ni

between the a and c but above the boundary a growth must be

accompanied by bulk partitioning of X. The boundary is found by
3
identifying the bulk composition (C, X) where the activity of C in the c
at the c=a interface, determined from the LE tie-line found assuming
that the a inherits the bulk X content of the alloy, has the same activity 2
as the C in the c of bulk alloy composition. Such conditions represent
the limit where there would be no driving force for C diffusion from the
1
a to the c and growth could only proceed with bulk X partitioning
between the a and the c [6–10].
2
PE is a constrained type of LE which treats all substitutional 0
elements as immobile and thus reduces a multicomponent system Fe– -800 -600 -400 -200 0 200 400 600 800
C–X to a pseudo-binary system M–C. The substitutional elements Fe Position (µm)
and X are replaced by an ‘‘average’’ component M with thermody-
namic properties such that the Gibbs energy functions of the pseudo- Fig. 2. Plot of the experimentally measured Ni concentration as a
binary system M–C are identical to the Gibbs energy functions of the function of position after treating the bonded Fe–1Ni/Fe–5Ni (wt.%)
corresponding vertical section of the Fe–C–X system [6,11]. couple for 72 h at 1400 C.
 C.R. Hutchinson et al. / Scripta Materialia 50 (2004) 285–289
treatment for the purpose of measuring the C content.
The contents, measured by combustion analysis, were
found to be 0.114 and 0.112 C (wt.%), respectively.
The carburised diffusion couples were austenitised at
1100 C for 5 min followed by transformation for var-
ious times in a salt bath at 700 C before quenching into
water. Metallographic samples were prepared using
standard techniques and the samples were etched using a
2% nital solution.
3. Results and discussion
A diffusion couple treated for 2 min at 700 C has
been chosen for illustration processes. A montage of
optical micrographs taken from within the zone con-
taining the Ni concentration gradient is shown in Fig.
3a. Superimposed on the image is a plot of the experi-
mentally measured Ni concentration as a function of
position. In the field of view captured by Fig. 3a, the Ni
concentration falls from
3.6 (wt.%) at the left side of
the figure to
2.6 (wt.%) at the right hand side. This
variation in Ni content occurs over a distance of
4.5
mm. The a phase etches lightly in this micrograph and
can be seen to form a network along the prior c grain
boundaries. A smooth and continuous transition from
significant fractions of a formation at the right hand side
of the image (corresponding to a Ni concentration of

2.6 (wt.%)) to only very small amounts of thin grain
boundary a at the left hand side of the micrograph in
Fig. 3 (corresponding to a Ni concentration of
3.6
(wt.%)) can be seen.
From the practical viewpoint of microstructure con-
trol in steel processing, it would be very useful to have
a reliable quantitative description of the kinetics of a
formation and their dependency on temperature and
composition. The observations of very slow a growth
accompanied of X diffusion and fast a growth unac-
companied by X diffusion have already been made [3–5],
but the conditions describing the transition from one
mode to the other with changes in Ni content or tem-
perature are not well understood. One model that has
been proposed to describe the two different growth
modes in Fe–C–X based systems is the LE model. This
model assumes that LE conditions exist at the moving
a=c boundary at all times. The slow growth mode, oc-
curring at small undercoolings, is referred to as the LE-P
mode and implies a partitioning of the slow diffusing
species between the c and a. The fast growth mode,
occurring at larger undercoolings, is referred to as LE-
NP and apart from a thin spike at the growth interface,
the X content is similar in both the parent and daughter
phases. Thermodynamic considerations allow a parti-
tioning of the (c þ a) two phase field into two regimes
where one or the other LE growth mode may be ex-
pected. These regimes are separated by the LE-P/LE-NP
287
boundary labelled in Fig. 1. For a C content of 0.1%, the
LE-P/LE-NP boundary lies at
2.9 (wt.%) Ni. The
position of this boundary is also marked on the optical
micrograph of the diffusion couple shown in Fig. 3a.
Those compositions to the left of this boundary fall
above the LE-P/LE-NP boundary in the phase diagram
shown in Fig. 1 and therefore within the LE-P regime,
whilst those to the right of the boundary in Fig. 3a, fall
within the LE-NP regime. The rate of a growth within
the LE-P regime is effectively controlled by the diffusion
of Ni in c. At 700 C, the diffusivity
pffiffiffiffiffiffiffiffi of Ni in c at 700 C
is
3 · 1020 (m2 /s) and a 4Dt calculation assuming
t ¼ 120 s, illustrates that the diffusion distance of Ni is
or the order of 4 nm. At 700 C and for a reaction time
of 120 s, the LE-P model predicts that no a formation
should be observed in Ni compositions larger than

2.9%. For Ni compositions less than this critical LE
amount, the LE model predicts that a formation should
be effectively controlled by C diffusion in the c and
growth is relatively rapid. A sharp transition between no
a formation and significant ferrite formation at a Ni
content of
2.9% is thus predicted from the LE model.
The optical micrograph in Fig. 3 clearly illustrates that
this is not the case and a smooth and continuous tran-
sition in a formation is observed. Furthermore, signifi-
cant a formation is observed in Ni compositions greater
than
2.9%, within the LE-P regime of the phase dia-
gram, and because of the diffusivity of Ni at these
temperatures, this growth must be unaccompanied by
bulk Ni partitioning. We do observe a transition to in-
significant fractions of a formation with increasing Ni
content, but this transitions occurs at Ni contents
greater than
3.5 (wt.%) Ni, which is significantly
higher than the LE prediction of
2.9 (wt.%). These
observations are consistent with the reports of Aaron-
son and Domain [4] and more recently Oi et al. [14] who
both reported a formation in alloy compositions lying
above the LE-P/LE-NP boundary at temperatures and
times where the bulk diffusion of Ni in c was negligible.
Such observations support the efforts being made to
develop models for a growth that consider significant
deviations from LE conditions at the moving interfaces.
Although, at the temperatures and times investigated
in this study, the Ni atoms can for all practical purposes
be considered immobile, this assumption is clearly not
valid for the Cffi atoms which move relatively rapidly in
pffiffiffiffiffiffiffi
the c. A 4Dt calculation, assuming t ¼ 120 s, gives
a diffusion distance of
20 lm for C. The practical
implication for the examination of solid state phase
transformations in carburised Fe–X diffusion couples, is
that the mobile C atoms partitioning from the a to the c
in those parts of the diffusion couple transforming most
quickly, could influence the transformation occurring in
other parts of the diffusion couple. In our case, a flux of
C from the Fe–1Ni end to the Fe–5Ni end of the cou-
ple will be observed. Whether this is an important or
 288
C.R. Hutchinson et al. / Scripta Materialia 50 (2004) 285–289
Fig. 3. (a) Optical micrograph of a formation within the Ni concentration gradient of the diffusion couple austenitized for 5 min at 1100 C followed by 2 min transformation at 700 C. The
experimentally measured Ni concentration profile is superimposed illustrating the transition in a formation with Ni content. (b) a growth kinetic measurements made from Fe–0.1C–2.8Ni and
Fe–0.1C–3.4Ni (wt.%) alloys treated at 700 C and designed on the basis of the diffusion couple experiment in (a).
 C.R. Hutchinson et al. / Scripta Materialia 50 (2004) 285–289
unimportant effect depends on the comparison between pffiffiffiffiffi
the average diffusion distance of the C atoms (
Dt)
and the spatial dimension of the gradient in the alloying
element, in this case Ni. During the duration of our
experiment C could diffuse on a length scale of
20 lm.
The Ni concentration gradient in our samples is
0.02
(wt.%) Ni per 100 lm. The change in Ni concentration
over a distance of 20 lm is 0.004 (wt.%), much less than
the experimental error in the Ni concentration mea-
surements, ±0.025 (wt.%) (the error is approximately
equal to the diameter of the circles used to denote the
experimental points in Fig. 3). We can therefore safely
assume that during our experiment the long range C flux
is negligible and that on the scale of the prior c grain size
(
100 lm) the transformation takes place at constant C
and Ni contents.
The purpose of our investigation was to observe the
nature of the variation in a fraction with changes in Ni
content and to use this for the selection of interesting
alloy compositions that could be cast and used for
conventional a growth kinetic measurements. Fig. 3b is
an example of such measurements that have been made
on alloys of compositions Fe–0.1C–2.8Ni and Fe–0.1C–
3.4Ni (wt.%) treated at 700 C and selected on the basis
of our diffusion couple experiments.
4. Conclusions
We have used a Fe–1Ni/Fe–5Ni (wt.%) diffusion
couple carburised to 0.1 C (wt.%) to study the kinetic
transitions during the c ! ðc þ aÞ transformation that
occur with changes in Ni content. A smooth and con-
tinuous transition in a fraction formed was observed
with increasing Ni content. Consistent with the obser-
vations of Aaronson and Domain [4] and Oi et al. [14], a
formation in compositions lying above the LE-P/LE-NP
boundary was observed.
In other systems where the diffusion distance of the
mobile species is small compared with the width of the
diffusion zone of the immobile species, it is anticipated
that useful kinetic data could also be extracted from the
289
diffusion couple experiments as well as information
concerning the composition-induced transitions in be-
haviour. This approach is very general in nature and
could be used for the investigation of transitions in be-
haviour in many types of solid state transformations
such as recrystallisation, grain growth, precipitation,
oxidation etc.
Acknowledgements
The financial support of IRSID Laboratoires and
CNRS (CRH) and the Natural Science and Engineering
Research Council of Canada (NSERC) (HZ) is grate-
fully acknowledged. The authors also acknowledge the
assistance of M. Thomas of ONERA Laboratoires,
Paris, for performing the high temperature heat treat-
ment, A. Mussi of GPM2, Grenoble for assistance in
rolling the samples, A. Crusci for performing the EPMA
and M. Kandel and D. Quidort or IRSID Laboratoires,
Metz for materials provision and performing the initial
hot-pressed bond.
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