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Acta mater.

48 (2000) 2765±2775
www.elsevier.com/locate/actamat

MASSIVE TRANSFORMATION IN THE Fe±Ni SYSTEM


A. BORGENSTAM and M. HILLERT{
Department of Materials Science and Engineering, KTH, SE-10044 Stockholm, Sweden

(Received 9 March 2000; accepted 12 April 2000)

AbstractÐThe critical limit for the massive g 4 a transformation in the Fe±Ni system has been measured
by isothermal heat treatment of di€usion couples. The position of the a/g interface at the end of the treat-
ment could be identi®ed but some growth occurred during the quench. Growth is probably hindered at the
beginning of the quench by a redistribution of Fe and Ni at the interface during the isothermal treatment.
During the quench it often happens that the a/g interfaces develop jagged shapes and even very ®ne plates
although there should usually be no orientation relationship. The critical limit agrees fairly well with classi-
cal results for the formation of equiaxed ferrite from continuous cooling of homogeneous specimens. At
1023 K it coincides with the a=a ‡ g phase boundary. At lower temperatures it moves inside the a ‡ g two-
phase ®eld. The driving force for the massive transformation increases at decreasing temperature and the
limiting composition never approaches the T0 line. 7 2000 Acta Metallurgica Inc. Published by Elsevier
Science Ltd. All rights reserved.

Keywords: Massive transformation; Microstructure; Thermodynamics; Iron alloys; Interface

1. INTRODUCTION it had been established that there is no obvious


Alloys may transform without a change in compo- orientation relationship between parent and product
phases, the interface is usually smoothly curved and
sition from the parent phase to a new one, so-called
it may cross a grain boundary in the parent phase.
partitionless transformation. This usually requires
It was thus concluded that the massive transform-
high cooling rates because slower cooling would, at
ation proceeds by the migration of highly disor-
least at higher temperatures, give time for long-
dered, incoherent interfaces. However, long planar
range di€usion and changes of composition in the
boundary segments and ledge-like growth may
transformed region. For the g 4 a transformation in
sometimes appear occasionally and then disappear
iron with a substitutional alloying element, which is
again according to a cinematographic study by
the subject of the present paper, the temperature is
Kittl and Massalski [3]. Aaronson et al. [4] con-
about half the melting point or less and long-range
nected the observations of planar segments with the
di€usion may be neglected under many circum-
theoretical expectation of some orientation relation-
stances. There are two well-known types of parti- ship between a nucleus, formed at a grain bound-
tionless transformation in solids, the martensitic ary, and both parent grains. Thus they envisaged a
and massive types. However, in iron alloys without growing massive crystal as being bounded in some
interstitials there may also be a partitionless, acicu- areas by disordered interfaces and in the remaining
lar type, probably related to the bainitic transform- areas by ledged, partially coherent interfaces. This
ation in Fe±M±C alloys, which occurs without aspect was further elaborated by Plichta et al. [5].
partitioning of the substitutional elements [1]. The On the other hand, Perepezko and Massalski [6]
massive type will be considered in the present work. showed that a polycrystalline specimen of the
It is usually easy to distinguish in the microscope parent phase can transform into a single crystal of
because the massive type got its name from the fact the product phase by a massive transformation,
that the growing grains are blocky or massive and which is clear evidence that the growth process in
the whole of the parent phase transforms as the the massive transformation is not dependent on any
reaction proceeds. orientation relationship even if it can proceed if
The early work on the massive transformation there is some.
was reviewed by Massalski in 1968 [2]. At that time Karlyn et al. [7] studied the massive b 4 a trans-
formation in Cu±Zn alloys by ®rst retaining the
high temperature b phase by quenching and then
{ To whom all correspondence should be addressed. studying the rate of reaction on up-quenching to

1359-6454/00/$20.00 7 2000 Acta Metallurgica Inc. Published by Elsevier Science Ltd. All rights reserved.
PII: S 1 3 5 9 - 6 4 5 4 ( 0 0 ) 0 0 1 0 2 - 6
2766 BORGENSTAM and HILLERT: MASSIVE TRANSFORMATION IN THE Fe±Ni SYSTEM

various temperatures. They observed massive trans- 3 at.% in a wide range of temperature. The g 4 a
formation to a within the a one-phase ®eld, only. transformation in some binary Fe systems may be
They proposed that this was not due to slow mas- better suited because there the distance between the
sive growth inside the a ‡ b phase ®eld but due to two lines increases towards lower temperatures.
the diculty of the reaction to get started there. Furthermore, it is easier to prevent di€usional
They proposed that the massive transformation in transformations because the parent phase is not
their alloys initiates at small pre-existing a particles b.c.c., as in Cu±Zn, but f.c.c. with a lower di€usiv-
which have rejected Zn into the surrounding b ity, and the homologous temperature is lower.
matrix. There would be no driving force for parti- Thus, the partitionless transformations have been
tionless growth from such Zn enriched regions extensively studied in the Fe±Ni system, which will
inside the a ‡ b phase ®eld. They predicted that also be used in the present study. However, pre-
massive growth might take place in the two-phase vious studies have employed the rapid quenching
®eld if it could only be initiated. They reported that technique and the present work will introduce an
this prediction had been con®rmed in a double-pul- isothermal, composition gradient technique.
sing experiment [8] where massive growth was ®rst The rapid quenching technique is a very ecient
allowed to start inside the a one-phase ®eld. It was method of studying partitionless transformations in
then observed to continue when the temperature Fe alloys. One identi®es the temperatures for arrests
was increased just inside the a ‡ b phase ®eld. in the cooling curves and studies how they vary
Hawbolt and Massalski [9] investigated the same with the cooling rate. Usually the arrest tempera-
alloy system by studying thermal arrests in cooling ture for a certain transformation ®rst decreases with
curves and reported that the massive transformation increasing cooling rate but then levels out to a pla-
can occur some tenths of a per cent Zn inside the teau. Several plateaus have been found and each
a ‡ b phase ®eld, which is in close agreement with one has been related to a particular mode of the
the results from the double-pulsing experiment. In a g 4 a transformation, all of them partitionless due
following study, Massalski et al. [10] detected mas- to the low temperature and short time. Figure 1 is
sive transformation up to approximately 38.75 at.% taken from a compilation of data for the Fe±Ni
Zn which was supposed to be 0.45 at.% inside the system [1] and it shows that there is some confusion
a ‡ b phase ®eld. They proposed that the critical among the data [14±18]. However, four modes are
limit for the massive transformation is not related identi®ed and they were denoted I, II, III and IV
to the a=a ‡ b phase boundary but to the T0 line by Mirzayev et al. [17]. Plateaus III and IV were re-
below which the driving force for the partitionless lated to lath and plate martensite, respectively.
transformation turns positive. They estimated that Plateau I is usually related to equiaxed ferrite and
some 150 K of undercooling are required to bring plateau II to acicular ferrite. Swanson and Parr [15]
about a massive transformation in this system. only observed two plateaus and they are roughly
On the other hand, Plichta et al. [11] studied represented by the two dashed curves in Fig. 1.
three binary Ti systems and reported that the mas- They related the upper one of them to massive fer-
sive reaction took place solely in the (metastable) a rite, as did Wilson [18] who in addition found an
region and not in the (extended) a ‡ b range.
When examining the experimental information
from the Cu±Zn system, Hillert [12] found that the
critical limit for the massive transformation,
reported by Hawbolt and Massalski [9] and
Massalski et al. [10] could coincide with the coher-
ent a=a ‡ b phase boundary. He also showed that
the growth rates reported by Karlyn et al. [7] do
not necessarily extrapolate to positive values inside
the coherent a ‡ b phase ®eld. Thus, it seemed poss-
ible that the critical limit for the massive transform-
ation is closely related to the a=a ‡ b phase
boundary and not to the T0 line. It should be men-
tioned that Hillert [13] had previously pointed out
that the a=a ‡ b phase boundary would be the limit
for partitionless growth if local equilibrium between
parent and product phases prevails at the migrating
interface.
It may seem that the Cu±Zn system is not very
well suited for studying the position of the critical
limit for the massive transformation relative to the Fig. 1. Plateau temperatures for various partitionless
a=a ‡ b phase boundary or the T0 line because the transformations in the Fe±Ni system, determined from
distance between those two lines is only about rapid cooling experiments [14±18].
BORGENSTAM and HILLERT: MASSIVE TRANSFORMATION IN THE Fe±Ni SYSTEM 2767

equiaxed ferrite plateau in close agreement with pla- ated at the position where the massive
teau I. transformation had stopped before the quench,
An attempt will now be made to evaluate the when that could be seen. Otherwise, the measure-
critical limit for massive growth under isothermal ments were taken where the a/g interface was as
conditions by using specimens with a composition planar as possible. Those values are presented in
gradient. The transformation can thus start well Table 1 together with information on the Ni gradi-
inside the one-phase ®eld where the initiation is ent at the point of measurement.
easy. It will be allowed to proceed isothermally into
the gradient and come to a natural stop at some 3. MICROSTRUCTURAL OBSERVATIONS
composition. The critical question is whether that
position can be observed after a ®nal quench to Typical microstructures are presented in Figs 2±
room temperature. The present authors have 11. Figure 7 was taken at low magni®cation and
recently used this technique in a study of the limit shows that the massive transformation g 4 a started
for growth of martensite in the Fe±C system [19] in the high Fe part of the specimens (below the pic-
and in that case the martensite formed at the exper- ture, not shown) and proceeded roughly perpendi-
imental temperature could be recognized because it cularly into the Ni gradient until the growing a
had been tempered before quenching. Of course, grains came to a halt at a certain Ni content, higher
that will not happen in the present case. Instead it the lower the isothermal temperature was. Above
was expected that some redistribution of Fe and Ni the front of the a phase there is a thick layer of
would occur at the interface when it has come to a martensite with variable microstructure extending
stop and that should prevent further growth for further into the Ni gradient. This specimen was
some time during the quench, in accordance with heavily etched in order to bring out the martensite.
the proposal by Karlyn et al. [7]. The a phase at the bottom of the picture is thus
An additional advantage with the isothermal, fairly dark but closer to the front it has not been
composition gradient technique is that the growing attacked as much due to the higher Ni content. The
crystals reach new parent grains with which they ®rst martensite is again dark, probably due to the
can hardly share a speci®c orientation relationship. high dislocation density. The many black dots are
One may thus expect to obtain information on the probably pores, some of which were present in the
critical limit for the migration of incoherent inter- original Ni alloy which was produced in the labora-
faces. tory. In the composition gradient they have grown
considerably, probably due to a Kirkendall e€ect
during the di€usion treatment.
2. EXPERIMENTAL

Di€usion couples were prepared by pressing


together two rods of pure Fe and an Fe±32 mass%
Ni alloy, each with a 2  2 mm 2 cross section, and
annealing the couple for 400 h at 1500 K. After
cooling the couple was sectioned into 6 mm long
specimens. They were austenitized in ¯owing argon
at 1323 K and dropped into a lead pot of a tem-
perature in the range of 700±1050 K and then
quenched in iced brine after various times.
The specimens were sectioned perpendicularly to
the original interface, prepared metallographically
and etched in 4% nital. After the microstructure
had been examined, the composition pro®le perpen-
dicular to the original interface was recorded with
an EDS instrument and the Ni contents were cali-
brated by comparing with a pro®le measured by a
microprobe equipped with a wavelength dispersive
spectrometer, which was regarded as a more accu-
rate instrument. The correction was very slight,
though.
Evidently, in the lead pot the massive transform-
ation must have started in the high Fe part and in
specimens treated isothermally at higher tempera-
tures the microstructure revealed very well how far
Fig. 2. Specimen from 5 s at 1023 K, showing extensive
it had proceeded into regions of higher Ni before growth during the quench, on top of the uniform massive
the quench. In specimens treated at lower tempera- layer formed at 1023 K (lower part of picture).
tures it was less evident. The Ni content was evalu- Magni®cation 200  :
2768 BORGENSTAM and HILLERT: MASSIVE TRANSFORMATION IN THE Fe±Ni SYSTEM

Table 1. Maximum nickel content in massive a and nickel gradient in same position

Temperature (K) Time at.% Ni at.% Ni/mm

1 2 3 4 5 Aver.

777 2 min 8.78 9.04 9.14 8.99 0.083


832 2 min 8.00 8.49 8.25
873 2 min 6.08 6.30 6.19 0.083
2h 6.10 6.35 6.61 6.86 7.27 6.64 0.096
7h 5.99 6.07 6.03 0.081
878 30 s 5.91 6.16 6.40 6.16 0.075
15 min 6.26 6.55 6.56 6.46 0.085
2h 6.43 6.43 0.089
7h 6.34 6.75 6.55 0.116
894 2 min 5.46 5.84 5.92 5.74 0.092
923 2 min 4.77 5.07 4.92 0.100
953 2 min 3.04 3.24 3.25 3.31 3.21 0.051
971 5s 3.26 3.46 3.36 0.083
2h 4.30 4.51 4.41 0.084
973 2h 3.46 3.76 3.61 0.057
1023 5s 2.12 2.21 2.16 0.086
2 min 1.97 2.16 2.06 0.075
7h 2.09 1.91 2.00 0.076

At the highest temperatures it was easy to see there is no doubt about its approximate position.
where the a phase stopped during the isothermal Specimens from 971 and 973 K showed the same
treatment because there was a distinct di€erence two types of structure after 5 s (Fig. 5) and 2 h
from the structure formed during the ®nal quench.
As an example, Fig. 3 from 2 min at 1023 K shows
a thin layer of a very ®ne structure which evidently
represents a further growth of the a grains. Figures
4(a)±(c) show further examples from the same speci-
men. The specimen treated for 7 h at the same tem-
perature showed the same structures but the
specimen treated for only 5 s showed much more
extensive growth during the quench, Fig. 2. Here it
is more dicult to see exactly the ®nal position of
the a front during the isothermal treatment but

Fig. 3. Specimen from 2 min at 1023 K, showing a thin


layer formed by resumed growth (upwards) during the Fig. 4. Three more observations of the thin layer formed
quench. Magni®cation 1250  : in the specimen shown in Fig. 3.
BORGENSTAM and HILLERT: MASSIVE TRANSFORMATION IN THE Fe±Ni SYSTEM 2769

[Figs 6(a)±(d)], respectively. Figure 5 shows the That specimen looked almost as the front of the
same extensive growth during the quench as Fig. 2 outgrowth shown in Fig. 2, which had formed
but the position before the quench is better de®ned during the quench. It should again be stressed that
in this particular region. The structures in Fig. 6 re- the data in Table 1 were taken from the most pla-
semble those in Fig. 4 but it is more dicult to see nar segments found in each specimen. No data are
the internal structure that was so evident in Fig. 4. included from 696 K because of the diculty in
Figure 7 was taken at a much lower magni®cation identifying the position of the front before the
on the same specimen to show the general appear- quench and the large scatter obtained when an
ance which was the same in all the specimens. attempt to measure was made.
For some reason, the specimen from 2 min at
953 K had rather few planar segments and Fig. 8 4. COMPARISON WITH RESULTS FROM
shows a drastic example of a non-planar segment. CONTINUOUS COOLING
Similar shapes but less pronounced were sometimes
observed in the other specimens, as well. The speci- The results in Table 1 are compared with the
men from 923 K again showed many planar seg- phase diagram in Fig. 12. The experimental
ments but occasionally there were exceptions. points represent the maximum Ni content in the
Figure 9 shows a step in the planar front and that regions transformed to massive a. There is some
was also noticed at the higher temperatures. These experimental scatter. However, it is evident that
two cases will be further discussed in Section 7. the massive growth at 1023 K does not extend
The thin a layers, representing further growth very far into the a ‡ g two-phase ®eld, if at all.
during the quench in Fig. 6, could be seen down to At lower temperatures it extends deeper and dee-
873 K but at lower temperatures it was not possible per into the two-phase ®eld. However, in the
to distinguish the a layer formed during the quench examined temperature range it does not seem to
and it was not even certain that there was any such approach the T0 line, i.e. the line where a and g
layer. Jagged shapes were often observed and, due
to the suspicion that they could sometimes originate
from the quench, measurements were taken on the
most planar segments of the front.
In a specimen from 2 min at 832 K the front was
generally rather jagged and, even though it was dif-
®cult to decide whether that was due to further
growth during the quench or not, it was concluded
that it originated from the isothermal growth when-
ever it was connected to the formation of subgrain
boundaries in the a phase as in Fig. 10. In a speci-
men from 2 min at 777 K some segments were even
very acicular, Fig. 11, and that tendency was predo-
minant in a specimen treated for 2 min at 696 K.

Fig. 5. Specimen from 5 s at 971 K, showing extensive


growth (upwards) during the quench, starting from a fairly Fig. 6. Specimen from 2 h at 973 K, showing several
¯at a/g interface established at 971 K. Magni®cation examples of thin layers formed by resumed growth during
500  : the quench. Magni®cation 1250  :
2770 BORGENSTAM and HILLERT: MASSIVE TRANSFORMATION IN THE Fe±Ni SYSTEM

Fig. 8. Specimen from 2 min at 953 K, showing a very


jagged segment of the a/g front. Magni®cation 500  :

stant and rather low cooling rate. Those data are


similar to values one can read for low cooling rates
in diagrams from the rapid quenching studies by
Fig. 7. Typical structure of the specimens shown at low Izumiyama et al. [16] and Mirzayev et al. [17]. It is
magni®cation …100). This specimen was from 2 h at thus evident that they are all related to the for-
973 K. The Ni content increases from very low at the bot- mation of equiaxed ferrite. The fair agreement
tom to about 30% at the top. The lower part has trans-
formed to massive a and the middle part to martensite. between the present results and those by Jones and
The top part is still g. Pumphrey supports the conclusion that all this in-
formation is due to the same mode of transform-
have the same Gibbs energy. Even though there is ation, i.e. equiaxed ferrite and massive a are
identical. If that is correct, the results of the con-
an experimental uncertainty in the values, and the
tinuous cooling experiments have not been much
calculation of the T0 line is also subject to some
a€ected by a slow nucleation process. On the other
uncertainty, this conclusion seems safe. It should be
hand, the nature of the plateau related to massive
mentioned that the phase diagram and the T0 line
ferrite by Wilson [18] and roughly represented by
were calculated from a CALPHAD assessment of
the upper one of the two dashed curves in Fig. 1,
the Fe±Ni system [20].
and probably identical to the transformation
Figure 13 compares the present results (dashed
line) with the line for plateau I from rapid quench-
ing in Fig. 1 (now represented by a dash-dotted
line). That line has been related to the formation of
equiaxed ferrite, which should be identical to the
massive a studied in the present work. The fact that
the present results fall at higher temperatures (or
higher Ni contents if a constant temperature is con-
sidered) is expected for at least two reasons. First,
in rapid quenching the arrest occurs at a tempera-
ture where the rate of formation is high enough to
balance the rate of heat extraction. Evidently, the
upper limit for massive growth should be at a some-
what higher temperature. Secondly, the arrest tem-
perature decreases with increasing cooling rate and
seems to level out to a plateau in a range of high
cooling rates. All the data in Fig. 1 represent such
plateaus and somewhat higher arrest temperatures
have been observed at lower cooling rates except
for the martensitic transformations which are not
time dependent. Fig. 9. Specimen from 2 min at 923 K, showing planar seg-
Figure 13 also presents arrest temperatures ments at di€erent positions in the composition gradient.
obtained by Jones and Pumphrey [21] using a con- Magni®cation 500  :
BORGENSTAM and HILLERT: MASSIVE TRANSFORMATION IN THE Fe±Ni SYSTEM 2771

Fig. 10. Specimen from 2 min at 832 K, showing a jagged


segment connected with the formation of subgrain bound- Fig. 11. Specimen from 2 min at 777 K, showing a very
aries in the a phase (lower part of picture). Magni®cation acicular segment. The a phase (lower part of picture)
500  : shows very strong substructure. Magni®cation 200  :

described as massive by Swanson and Parr [15], is does not di€er much from what has here been
uncertain. called the ideal massive type.
The maximum Ni content for massive growth, The fact that the massive transformation in the
established in the present work, coincides well with Cu±Zn system does not seem to extend much into
the value used by Massalski et al. [22], 8.7% Ni, the two-phase ®eld was explained by Karlyn et al.
when applying continuous cooling to establish that [7] with reference to the inability of a nucleus to
the massive transformation can occur outside the break through the pile-up of alloy element sur-
one-phase ®eld for a which is retrograde and has a rounding it. Hillert [12] gave an alternative expla-
maximum of 4.6% Ni. nation by calculating the steady-state width of the
spike of the alloy element in front of the interface,
if it would migrate, and ®nding that it is not negli-
gible as compared with atomic distances. The two
5. NATURE OF THE MASSIVE TRANSFORMATION
phases could then be reasonably close to local equi-
In the Fe±Ni system the volume di€usivity is so librium with each other during migration and, even
low that it is easy to prevent di€usion. Various if initiated, partitionless growth would not proceed
types of partitionless transformations can thus be if the initial parent phase is substantially inside the
observed depending on the orientation relationship
between grains of the parent and product phase.
The result obtained without any special orientation
relationship, and thus with an incoherent interface,
may be de®ned as the ideal massive type. This is
probably the one studied with the isothermal, com-
position gradient technique in the present work.
The very strict orientation relationship, which
would be expected to give rise to WidmanstaÈtten
precipitate if there were time for long-range di€u-
sion, may be responsible for the acicular type that
causes plateau II in Fig. 1. The orientation of a
crystal nucleated at a grain boundary would prob-
ably be related to both parent grains in most cases.
The orientation relationship to each one would then
be less strict and one can expect to ®nd a wide spec-
trum of partially coherent interfaces. The resulting
types of partitionless transformation should simply
be regarded as intermediate cases. In view of the
results by Plichta et al. [5] partially coherent inter-
Fig. 12. Limit of massive growth of ferrite in the Fe±Ni
faces may be very common if the gradient technique system according to the present results (triangles and
is not used. However, the close agreement, demon- dashed line), compared with calculated phase boundaries
strated in Fig. 13, indicates that the result generally and the equal Gibbs energy curve, the so-called T0 line.
2772 BORGENSTAM and HILLERT: MASSIVE TRANSFORMATION IN THE Fe±Ni SYSTEM

two-phase ®eld. On the other hand, in the Fe±Ni inside the interface and, hence, the position of the
system the width of the spike would be orders of critical limit probably depend on how the chemical
magnitude smaller than atomic distances and the properties of the interface material and the trans-
spike should not exist. The partitionless transform- verse di€usivity in the interface vary with tempera-
ation could then proceed and closely approach the ture. These factors are not known at all and the
T0 line unless some other energy consuming process present kind of data may become a valuable source
interferes. That could be di€usion of Ni relative to of information. Modelling of this phenomenon has
Fe inside the migrating interface. That phenomenon only begun [23±26].
would be related to the solute drag e€ect on grain
growth in single-phase materials. The position of 6. RESUMED MIGRATION DURING QUENCHING
the critical limit for massive growth relative to the
phase boundary and the T0 line gives valuable in- Even though it was usually possible to identify
formation on the size of such an e€ect. In the pre- the position where the massive transformation had
sent case it is interesting to note that the critical stopped during the isothermal treatment, signs of
limit falls close to the a phase boundary at 1023 K. resumed migration during the following quench
The dissipation of Gibbs energy is thus roughly the were often found. The most evident cases were
same as in a well-developed spike in front of a mi- found after isothermal treatments for only 5 s (Figs
grating interface. At lower temperatures the critical 2 and 5) which may have been too short for an e-
limit moves further inside the two-phase ®eld and cient redistribution of Fe and Ni at the interface
eventually falls closer to the T0 line than to the a after it had stopped. It is even possible that 5 s was
phase boundary. From the position of the critical not even enough for the growth to come to a com-
limit one may evaluate the dissipation of Gibbs plete stop. Thus, the interface is able to continue its
energy inside the interface, assuming there are no migration soon after the temperature starts to
other sinks for driving force. In Fig. 14 it is plotted decrease by the quench. In Fig. 2 the additional
vs temperature and is found to increase at decreas- growth has proceeded further into the gradient for
ing temperature in spite of the fact that the critical almost 8 at.% and in Fig. 5 for almost 4 at.%.
limit moves further into the two-phase ®eld. There Related e€ects but much less pronounced were
is no tendency that it would ever decrease, which observed in many specimens treated for a longer
should be necessary if it would ever approach the time. Figures 3 and 4 from the specimen treated for
T0 line. On the other hand, it would decrease rela- 2 min at 1023 K show that the resumed migration
tive to the dissipation in a well-developed spike, has there resulted in a thin layer of a very ®ne
which is plotted as a second curve in Fig. 14. That structure, often suggesting the formation of a long
curve increases even faster with decreasing tempera- series of very thin parallel plates, Figs 4(a) and (b).
ture. The dissipation of Gibbs energy by di€usion The etching e€ect in the thin layers is probably due
to some defect structure left in the a crystal where
the ®ne plates have met side by side. It is proposed
that these thin layers have formed when the mi-

Fig. 13. Present results for the limit of massive growth of


ferrite in the Fe±Ni system (represented by the dashed
line), compared with the plateau temperature for equiaxed
ferrite, plateau I in Fig. 1 (represented by dash-dotted Fig. 14. The driving force for massive growth of ferrite,
line) and with the beginning of the g 4 a transformation at evaluated at the critical limit according to the present ex-
relatively slow cooling, according to Jones and Pumphrey periments, DGexpt
m , and evaluated under the assumption of
(squares). local equilibrium at the a/g interface, DGLE
m :
BORGENSTAM and HILLERT: MASSIVE TRANSFORMATION IN THE Fe±Ni SYSTEM 2773

gration was resumed at some low temperature grains, each one with a planar interface, sometimes
during the quench, when the driving force had have grown di€erently far into the Ni gradient,
increased to a high enough value to overcome the which is revealed by steps in the planar front.
resistance due to the redistribution of Fe and Ni at Figure 9 shows a typical example. This is an indi-
the interface when it stood still. The tendency to cation that even incoherent interfaces may have
form such layers in the specimen from 2 h at 973 K di€erent properties and give rise to di€erent
was weaker, probably because the supersaturation amounts of dissipation of Gibbs energy by interface
achieved on quenching is less due to the higher Ni di€usion.
content at the front. Figure 6 shows that the layers The fact that a/a grain boundaries and even sub-
are even thinner here and it was very dicult to see grain boundaries give rise to re-entrant angles is not
the internal structure. Both e€ects may have been surprising. Figure 4(a) shows an example. It is more
caused by the lower supersaturation. In the speci- surprising that this is not always the case, as illus-
mens treated below 873 K, the supersaturation trated in Fig. 4(b).
seems to have been too low to give such a layers.

8. COMPARISON WITH TERNARY ALLOYS


7. CRYSTALLOGRAPHIC FEATURES CONTAINING CARBON

In the specimen from 2 min at 1023 K there were The g 4 a transformation without partitioning of
thin layers consisting of very ®ne plates on almost the substitutional elements has been extensively stu-
all the massive grains and they can hardly be due to died in Fe alloys in the presence of carbon. It has
any orientation relationship to the parent grains. long been known that Mn and Ni have a strong
On the other hand, the fact that they often seem to retarding e€ect on the formation of a in spite of the
consist of parallel plates, whose direction varies fact that the theoretical thickness of a spike formed
from one a grain to the next, indicates that they are in front of the migrating a interface is well below
crystallographic features. This can be seen in atomic dimensions. Under such growth conditions
Fig. 4(b) although the magni®cation is not quite there are two possibilities. Either, the reaction is
sucient. The boundary to the right is an a/a grain completely di€usionless with respect to Mn and Ni
boundary. Those in the middle and to the left are and so-called ``paraequilibrium'', as de®ned by
subboundaries and they seem to have had only a Hultgren [27, 28], would prevail, i.e. local equili-
small e€ect on the direction of the ®ne plates. It brium for carbon across the interface but no move-
may be concluded that, even with a random orien- ments of Mn or Ni relative to Fe. In that case the
tation relationship between parent and product retarding e€ect of Mn or Ni could be directly calcu-
grains, the interface can ®nd a direction that is lated from the thermodynamic properties and
more favourable than others, but only if the driving should be rather low. However, experimental infor-
force is large enough. A planar interface may then mation seems to indicate that the retarding e€ect is
develop a more jagged shape and even turn into much stronger. As a second alternative, it was thus
plate-like growth. Figure 4(c) shows that a very proposed, e.g. by one of the present authors [13],
jagged shape formed during the quench although that the spike does not disappear but ``moves inside
the same a grain had a planar interface before the the interface'' if the volume di€usivity in the g
quench. The series of micrographs in Fig. 6 illus- phase is too low. There it could have a similar
trates that the further growth during the quench retarding e€ect as already explained for the binary
sometimes develops a layer of even thickness, some- Fe±Ni case in Section 5. It could be argued that
times small segments of even thickness and some- this requirement should always be satis®ed if the
times more triangular outgrowths, probably related atomic mobility inside the interface is high enough
to the jagged shapes discussed before. to allow the interface to migrate. However, it is
It is dicult to decide if the acicular structure to now realized that there may be a strong coupling
the left in Fig. 11 was formed isothermally or between the ¯uxes of substitutional elements across
during the quench. However, the similar structure phase interfaces [26]. This implies that much of the
in Fig. 2 was certainly formed during the quench atomic mobility that makes an interface migrate
and that is additional evidence that a planar inter- may be of a co-operative nature even though the
face can even form well-developed plates if the driv- interface has an incoherent structure. An indication
ing force is increased suciently by quenching. is that the mobility of interfaces in Fe and binary
It should be mentioned that there were usually a Fe alloys, predicted from the interfacial di€usivity
few grains in each specimen that certainly had a [29] with Turnbull's model [30], is only about a
very jagged shape already before the quench. hundredth of the experimental one. This implies
Figure 8 shows the most dramatic case. This is that the interface migrates with a process much fas-
most probably due to an orientation relationship ter than allowed by the atomic process of di€usion.
between the a and g grains which could occur oc- Thus, one should now be open to the possibility
casionally even though a gradient technique was that the dissipation of Gibbs energy due to a spike
used. It should also be mentioned that neighbouring inside the interface may be considerably lower than
2774 BORGENSTAM and HILLERT: MASSIVE TRANSFORMATION IN THE Fe±Ni SYSTEM

in a fully developed spike. It is an interesting ques- the present results and, as expected, fall close to the
tion how close the growth conditions can come to line extrapolated from the ternary information.
those for paraequilibrium. This was recently investi- It should be emphasized that in this kind of test
gated by an attempt to model the massive tranfor- one should compare information obtained with the
mation in an Fe±M alloy presented by Hillert and same kind of interface because the dissipation of
Schalin [25] and of the formation of ferrite in Fe± Gibbs energy could very well be quite di€erent for
M±C alloys by Liu and AÊgren [31] and Purdy and incoherent and partially coherent interfaces. It is
Brechet [32]. thus satisfactory that Oi et al. studied the formation
When studying the lengthening of WidmanstaÈtten of grain boundary allotriomorphs which may be
plates or bainite in high Ni steels, Goodenow et al. compared with the massive transformation in car-
[33] as well as Rao and Winchell [34] found appreci- bon-free alloys. There is much more information on
able growth rates although the Ni content was well the lengthening rate of WidmanstaÈtten plates or
above the solubility of Ni in a-Fe. Thus it is quite bainite but, unfortunately, it is dicult or even im-
clear that there could not have been a well-devel- possible to study the corresponding acicular growth
oped spike in the parent g. On the other hand, Rao of a in carbon free alloys (which forms at plateau II
and Winchell compared with growth rates predicted in rapid cooling) due to the competition from the
without a spike (based on a calculation similar to massive transformation.
one based on paraequilibrium [35]), ®nding that the
growth rates were much too low. After proposing 9. SUMMARY
several possible factors to explain their results they
The critical limit for massive growth of ferrite in
wrote ``Finally the possibility that the shu‚ing of
the Fe±Ni system can be studied isothermally using
nickel atoms slows down the interface must be
di€usion couples. By that technique one can make
admitted''. Evidently, they had an e€ect like the
sure that most of the interfaces studied are incoher-
solute drag in mind. It should also be mentioned
ent. The ®nal position of the interface can be
that Kinsman and Aaronson [36] proposed that the
detected after quenching even though some further
e€ect of some alloying elements on the growth rate
growth can occur during the quench.
of ferrite in Fe±M±C systems is due to an ``impur-
The critical limit for the massive growth seems to
ity drag e€ect'', later developed into a ``solute drag-
be related to the curve for the ®rst plateau tempera-
like e€ect'' [37]. Their proposal was not developed
ture studied by rapid quenching and presumably
in detail but it is evidently closely related to the pic- due to the formation of equiaxed ferrite. It falls
ture given above. A particularly interesting feature even closer to the temperature for the beginning of
is that they explained the strong e€ect of some car- the transformation observed with slower cooling
bide forming elements by a strong segregation to rates. It is thus con®rmed that equiaxed ferrite is
the a/g interface at locally high C contents. identical to the massive ferrite formed by the mi-
Over the years there have been several attempts gration of incoherent interfaces.
to locate the critical limit for the g 4 a transform- The critical limit coincides with the a phase
ation in ternary Fe±C±M alloys or commercial boundary at 1023 K but moves into the a ‡ g two-
steels and relate it to the lines for paraequilibrium phase ®eld at lower temperatures. However, it does
and local equilibrium with a spike. It is generally not approach the T0 line. The dissipation of Gibbs
agreed that the critical limit falls between those two energy at the critical limit increases at lower tem-
calculated lines, just as the present results for the peratures in spite of the fact that it moves further
Fe±Ni system falls between the T0 line and the and further into the two-phase ®eld.
a=a ‡ g phase boundary. As mentioned by Hillert The microstructures formed during the quench
[26], the calculation of the dissipation of Gibbs give strong indications that an incoherent and pla-
energy in front of and inside the migrating interface nar interface can develop into a jagged shape and
in a binary Fe±M system could easily be extended even form a series of parallel plates when the driv-
to ternary Fe±M±C systems by imposing the con- ing force increases during the quench. There is also
dition of constant carbon activity. Similar results some indication that the interaction between a mi-
should thus be expected. It should be very interest- grating a/g interface and an alloying element is not
ing to try to connect the limiting point for the mas- of the same strength for all planar, incoherent
sive transformation in an Fe±M system with the phase interfaces.
limiting line for the g 4 a transformation in the Fe±
M±C system at the same temperature. This is what AcknowledgementsÐThanks are due to Martin Schwind
Oi et al. [38] recently tried to do in a careful study for valuable experimental help.
of the growth of a in Fe±Mn±C and Fe±Ni±C
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