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Peritectic Reaction and Solidification in Iron-Nickel Alloys

N.J. McDONALD and S. SRIDHAR

A high-temperature confocal scanning laser microscope (CSLM) has been used to study austenite ()
precipitation and growth on -ferrite during peritectic reaction and solidification in the Fe-Ni system.
The two stages of the peritectic transition involving the liquid phase—the reaction, which sees austen-
ite grow along the ferrite/liquid boundary, and the direct solidification of austenite—were observed.
It was found that, for both the hypoperitectic (4.2 pct nickel) and hyperperitectic (4.7 pct nickel) alloys,
the reaction rate increases with increased undercooling. It was also observed that the reaction rates
were faster in the hypoperitectic alloy. However, for both grades, the solidification rate was found to
be a function of local-temperature gradients rather than undercooling. Comparisons to available mod-
els are made, and a description of possible rate-controlling phenomena is given.

I. INTRODUCTION transformation. The direct solidification of  is the final

THE peritectic reaction,   L  , is extremely impor-
tant for a number of material systems. These include copper
and aluminum alloys as well as magnetic and electronic
materials.[1] It is perhaps most important to understand for
iron-based alloys solidified in nonequilibrium processes.
In processes such as ingot casting, it is assumed that steel
compositions that fall within the peritectic range will even-
tually pass through the austenite phase and negate the
delta-ferrite phase that formed earlier.[2] However, in
processes such as continuous casting, the volume change
associated with the peritectic transition causes the shell to
pull away from the mold, leading to a decrease in heat flux,
which, in turn, leads to thin spots. These thin areas on the
surface of the casting then have a higher chance of crack-
ing or causing a breakout.[3] Currently, this problem is
prevented by reducing the rate at which the casting is pulled
from the mold, to ensure adequate wall thickness.[4]
A magnification of the peritectic region of a binary-phase
diagram is shown in Figure 1(a). The peritectic composition
is Cp at the temperature Tp and is the composition at which
all ferrite () will convert to austenite (). The peritectic
region is described as any alloy with a composition that
falls between C and CL, as shown in Figure 1(a). Hypoperi-
tectic alloys are those between C and Cp, while hyperperi-
tectic alloys have a composition range of Cp to CL.[2]
It should be noted that the equilibrium partition coefficient
(keq  CS /CL) for the iron-nickel system—shown in Figure
1(b)—is less than unity, so the product is not an intermetallic
species.[1] The peritectic transition is here defined as all
stages between the initial formation of austenite and the final
solidification. Kerr et al.[5] have split this transition into three
distinct regimes: reaction, transformation, and solidification.
The peritectic reaction requires that all three phases be in
contact with one another while the  grows, while the
peritectic transformation starts at the point where  and liquid
are not necessarily in contact and  grows by the -to-
N.J. McDONALD, Graduate Student, and S. SRIDHAR, Assistant Pro-
fessor, are with the Department of Materials Science and Engineering,
Carnegie Mellon University, Pittsburgh, PA 15213. Contact e-mail:
sridhars@andrew.cmu.edu
Manuscript submitted December 3, 2002.
stage.
Early descriptions of the peritectic transition followed the
phase diagram depicted in Figure 1. Under equilibrium con-
ditions, at the peritectic composition Cp, ferrite forms at
some temperature below its liquidus and solidifies until it
reaches the peritectic temperature Tp. At Tp, the austenite
phase nucleates and all three phases ( / /L) are in equilib-
rium with each other, according to Gibbs’ phase rule at con-
stant temperature and pressure. All of the solidification is,
thus, completed by Tp. What this explanation fails to account
for is the driving force required for the peritectic reaction.
Kerr and Kurz[1] state that, for hypoperitectic alloys, solid-
ification will be complete by Tp but that, due to slow solid-
state diffusion, there will be more retained ferrite than that
predicted by the phase diagram, along with the new austen-
ite. For hyperperitectic alloys, all of the ferrite will be used
in the reaction at Tp, but solidification will not be complete
until the solidus of austenite is reached.
Hillert,[6] Kerr et al.,[5] Fredriksson,[7] and Chuang et al.[8]
have proposed more detailed theories that are summarized as
follows. Considering the isothermal case, at some tempera-
ture below Tp, austenite will begin to form along the ferrite/
liquid boundary dividing the two phases. Hillert[6] explained
that the peritectic phase will grow along the solid/liquid bound-
ary due to the phase-diagram requirement that both ferrite and
liquid be available to form austenite. The undercooling pro-
vides a driving force because the liquid in equilibrium with
austenite contains more of the solute than that in equilibrium
with the ferrite. Once the reaction is complete and the /L
boundary has been covered by , the only mode left for the
dissolution of -ferrite is by solid-state diffusion. The  can
continue to grow by direct solidification into the liquid.
During the peritectic-reaction stage, it can be assumed
that the surface tensions of the three phases are balanced
at the triple point.[6,9] This would give a shape for the growing
austenite phase as shown in Figure 2. In order to satisfy the
condition of equilibrium ( F  0), Eqs. [1] and [2] must
be satisfied.
  L cos (1)  L cos (2) [1]
L sin (1)  L sin (2) [2]

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02-584A-10.qxd 31/7/03 9:18 PM Page 1932
(a)
(b)
Fig. 1—(a) Schematic of peritectic region of binary alloy. (b) Peritectic
region of the iron-nickel phase diagram.[2]
(a) (b)
Fig. 2—(a) Schematic of peritectic reaction.[6] (b) Surface energy terms.[9]
Where all terms are as described in Figure 2(b). The arrows
in Figure 2(a) show the rejection of the nickel solute by the
growing austenite phase. The growth of the ferrite phase
ahead of the advancing austenite was attributed to the neg-
ative curvature of the ferrite/liquid boundary.[6]
Most theoretical predictions of the rate of the peritectic
reaction have involved the iron-carbon system.[8,10] These
studies assumed that the interstitial diffusion of carbon was
rate controlling and furnished results based on this. It was
found that the peritectic reaction occurs very rapidly and
is complete within 2 °C to 4 °C of the equilibrium temper-
ature. Zener,[11] while studying the kinetics of austenite
decomposition, proposed a theory for the diffusion-controlled
propagation of a phase boundary involving a change in both
composition and lattice type. Hillert[12] then modified this
model by examining the effect of pressure caused by inter-
facial energy on equilibrium compositions and by develop-
1932—VOLUME 34A, SEPTEMBER 2003
ing the rate equations for a new phase growing as a plane
front facing the parent phase. These rate equations, which
provided for diffusion in one direction only, were then fur-
ther modified for the growth of a plate- or needle-shaped
phase. Bosze and Trivedi[13] assumed that this new phase
would grow at its maximum velocity and have a radius one-
half the thickness of the plate. Fredriksson and Nylen[14]
applied Bosze and Trivedi’s model to Cu-Sn, Ag-Sn, and
Al-Mn peritectic systems, and Shibata et al.[15] used the same
model to attempt to describe observations in Fe-0.14 pct C
and Fe-0.42 pct C.
For substitutionally diffusing solute atoms, such as nickel,
the diffusion rates in the solid  and  phases are expected
to be slow. Therefore, diffusion is likely the rate-controlling
mechanism for substitutional systems in the reaction and
transformation steps. Fredriksson and Stjerndahl[10] pointed
out that, as a consequence of this, only small amounts of
the alloying element can move between the austenite and
the ferrite. This could lead to a large amount of the retained
primary phase after the reaction stage is completed.
Despite the importance of the peritectic phase transition,
little attention—particularly experimental—has been paid to
it. Reasons for this may be the difficulty in observing such
a high-temperature phenomenon or the fast rate of reaction.
However, the feasibility of using a confocal scanning laser
microscope (CSLM) to carry out solidification experiments
has been shown recently by a number of researchers.[15,16,17]
This work employs a high-temperature CSLM to directly
observe the solid/melt interface of peritectic Fe-Ni alloys
at various undercoolings near the peritectic temperature. The
specific objectives are to (1) quantify the rates of the peri-
tectic reaction and solidification of hypo- and hyperperitec-
tic Fe-Ni alloys and (2) compare the measured rates to model
predictions.
II. EXPERIMENTAL APPARATUS
AND MATERIALS
A. Materials
The iron-nickel system, as shown in Figure 1(b), displays
peritectic attributes between 3.4 and 6.2 wt pct nickel. This
system has been chosen since it is less prone to surface
oxidation than other Fe-based peritectic systems. Two alloys,
one containing 4.2 wt pct and the other 4.7 wt pct, were pre-
pared in an induction furnace using iron pieces (99  pct)
and nickel shot (99.9  pct). These compositions were cho-
sen to represent both hypo- and hyperperitectic cases. Sam-
ples for the CSLM experiments were taken using a quartz
tube, while the master alloys were molten and then sent for
chemical analysis to confirm the compositions.
B. High-Temperature CSLM
The CSLM 1LM21H*, equipped with a gold-image hot
*ILM21H is a trademark of the Lasertec Corporation, Yokohama, Japan.
stage, is a tool for observing high-temperature phenomena
in situ under controlled thermal fields and gas atmospheres.
It has been described in detail in the literature previ-
ously.[18,19] To summarize, a He-Ne laser beam (1.5 mW,
METALLURGICAL AND MATERIALS TRANSACTIONS A
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632.8 nm) is scanned two-dimensionally (5.7  60 Hz)
and sent through a beam splitter and an objective lens
before hitting the surface of the sample. The deflected
beam is then sent back through the objective lens and
polarized through another half-mirror before passing
through a pinhole and reaching the light sensor. The main
advantage to this microscope and the associated appara-
tus is that high-contrast systems can be viewed due to
the pinhole’s ability to shut out flare. Also, high resolu-
tion can be obtained because the light passes through an
objective lens twice. The signals from the light sensor are
then displayed on a television screen and can be recorded
by a video cassette recorder or sent to a computer for
future analysis. Images can be captured at a rate of 30
frames per second.
The sample itself is placed in a high-purity alumina
(Al2O3) cylindrical crucible that has dimensions of 5.5 mm
o.d.  3 mm i.d.  3 mm height. To prevent any damage
to the apparatus, a second alumina crucible measuring 11 mm
o.d.  10 mm i.d.  2.5 mm height is placed underneath the
first. Both of these crucibles are then rested on a platinum
pan wired with one thermocouple, as shown in Figure 3(a).
The thermocouple leads are attached to jacks inside a box
that is sealed with an o-ring to maintain the necessary
(a)
Tunder) refers to the temperature below the
(b)
Fig. 3—(a) Schematic of alumina crucible and platinum holder. (b) Inte-
rior of gold-plated image furnace including crucible and hold.
METALLURGICAL AND MATERIALS TRANSACTIONS A
atmospheric conditions once operation begins. The entire
apparatus slides into the side of a gold-plated image furnace,
as shown in Figure 3(b). The halogen lamp at the bottom
of the furnace provides heat to the sample, which is directed
externally by a programmable controller. The laser beam
enters through a port that is covered in an airtight manner
by a quartz plate and o-ring. A wide range of atmospheres
can be maintained in the furnace through a gas inlet and
vacuum pump.
C. Experimental Procedure
The samples were pickled in hydrochloric acid for short
periods and then washed with acetone prior to placement
in the alumina crucible and sample holder described
earlier. No polishing was considered necessary, as the sam-
ples had not been machined and would be melted while
viewing.
A cycle of purging the furnace chamber using a vacuum
pump and backfilling with purified argon gas was used
to lower the oxygen potential in the furnace below its poten-
tial to oxidize the sample. The high-purity argon gas (99.99
 pct) was further deoxidized by passing it over heated cop-
per and magnesium chips plus drierite before pumping it
into the image furnace. The po 2 thus established was meas-
ured with an oxygen sensor as 10 9 atm. The tempera-
ture distribution in the furnace was measured by melting
pure iron (99  pct), moving the platinum holder horizon-
tally, and then recording the temperature. The temperature
was found to be even within 1.5 mm of the focal point and
then to decrease roughly linearly on either side at a gradi-
ent of 4 K/mm.
The experiment itself consisted of holding the
ferrite/liquid boundary just at or above the peritectic tem-
perature, as shown in Figure 4(a), and subsequently drop-
ping the temperature rapidly by a predetermined amount.
The melt was maintained at the undercooled temperature
for the duration of the observations. Figures 4(b) and (c)
show these later steps. Experiments on pure Fe samples
showed, as would be expected, that no growth along the
solid/liquid interface occurred, and there was only planar
movement toward the melt.
III. RESULTS AND DISCUSSION
A. Peritectic Reaction
The peritectic reaction was recorded at a number of under-
cooling temperatures. It should be stressed that the melt itself
is isothermal near the solid/melt interface (where the
peritectic reaction occurs), as shown in Figure 4(b). The
undercooling (
peritectic temperature ( |Tp Texperiment| ). This is the driving
force for the reaction stage.
1. Hypoperitectic (4.2 pct Nickel) case
Figure 5 shows the progression of the austenite phase
across the ferrite/liquid boundary at 3 °C of undercool-
ing below the peritectic temperature. Figure 5(d) contains
a description of the different phases being observed.
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Fig. 4—Schematic showing (a) the system held at or above Tp, (b) the system undergoing the peritectic reaction at 1 °C below Tp, and (c) the system under-
going solidification into an undercooled melt at 1 °C below Tp.
Fig. 5—(a) through (d) Peritectic reaction at 3 °C undercooling for hypoperi-
tectic alloy.
Similar results were observed for undercoolings of 1 °C
and 2 °C.
From Figure 5, the austenite phase can very clearly be
seen to be growing along the ferrite/liquid boundary.
The position of the advancing //L junction was measured
at three different undercooling temperatures (1 °C, 2 °C,
and 3 °C) and is plotted in Figure 6. From this it can be
1934—VOLUME 34A, SEPTEMBER 2003
Fig. 6—Progression of the austenite phase on the ferrite/liquid boundary
as a function of time for hypoperitectic alloy.
Fig. 7—Reaction rate as a function of undercooling for hypoperitectic alloy.
seen that the reaction proceeds linearly for each
undercooling and, by taking the slope of the position vs
time curve, that the reaction rate increases with increased
undercooling.
Figure 7 plots this change in reaction rate against
undercooling. Although only three points of undercooling
have been measured for this system, the plot appears to
METALLURGICAL AND MATERIALS TRANSACTIONS A
02-584A-10.qxd 31/7/03 9:18 PM Page 1935

Fig. 8—Example of austenite nucleation directly from liquid.

be linear over the undercooling range observed and follows

Eq. [3]:
R  (39.9Tunder 12.9)  4.2 [3]
Where R is the rate of austenite growth (m/s) and
Tunder
is the absolute difference between the actual and peritectic
temperatures (degrees Centigrade).
At larger undercoolings, some austenite precipitated directly
out of the liquid ahead of the solid/melt interface, thus hin-
dering any attempt to accurately measure the reaction rate.
An example of this is shown in Figure 8. This precipitation
may occur because the bulk melt is experiencing a greater

Tunder (hence, driving force) than the solid/liquid interface.
Fig. 9—(a) through (d) Peritectic reaction at 2 °C undercooling for hyper-
2. Hyperperitectic (4.7 pct Nickel) Case peritectic alloy.
Figure 9 shows the growth of austenite at 2 °C of under
cooling below the peritectic temperature. The phases are
described in Figure 9(d). It is interesting to note that the tips
of the growing austenite phase change shape as the reac-
tion progresses. Observations were also recorded at under-
coolings of 1 °C, 3 °C, and 4 °C of undercooling, which -
produced comparable images. Larger undercoolings resulted
in precipitation from the melt similar to that shown in Figure
8, which made quantification difficult.
As with the hypoperitectic sample, the position of the
//L junction was measured from an arbitrary starting point
and then normalized. The plot is shown in Figure 10 for
four different undercooling temperatures (1 °C, 2 °C, 3 °C,
and 4 °C). From Figure 11, it is clear that the austenite
grows at a linear rate which increases with undercooling,
and this dependency can be described by Eq. [4].
R  (30.3Tunder 16.1)  3.2
Where the symbols and units are the same as those described
in Eq. [3].
3. Comparison of Cases
The likely rate-controlling mechanisms for the peritectic
reaction include nucleation and growth. Nucleation does not
appear to be the controlling mechanism, since no further
nucleation was observed along the /L boundary ahead of
the advancing  phase. Growth is limited by driving force
METALLURGICAL AND MATERIALS TRANSACTIONS A
[4]
Fig. 10—Progression of the austenite phase on the ferrite/liquid boundary
as a function of time for hyperperitectic alloy.
and diffusion. If diffusion were rate controlling, then, as the
temperature of the system decreased, so too would be the
diffusion coefficient of the solute atom and, therefore, the
growth rate would be expected to decrease with increased
undercooling. However, undercoolings of 3 °C or 4 °C do
not correlate to a low-enough temperature to affect diffusion
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appreciably. With driving-force-controlled growth, there is
an increased driving force as the undercooling is increased,
which correlates to the trends observed in Figures 6, 7, 10,
and 11. This does not rule out that, as the undercooling
increases, there will eventually be a decrease in the reaction
rate due to entry into a diffusion-controlled regime. How-
ever, this could not be confirmed, because  growth along
the /L interface at higher undercoolings was prevented by
 precipitation from the melt (as shown in Figure 8).
As pointed out in Section I, Bosze and Trivedi[13] devel-
oped a model for  growth during the peritectic reaction.
Using the assumptions that the growing phase would be
platelike with a radius of one-half the thickness of the plate
and would grow at its maximum velocity, they developed
Eqs. [5] through [7]. These express the velocity as a func-
tion of the supersaturation.
CL CL

CL CL

¿ 
2 1 2
1  
2
9 D 2
R ¿
8 r
Where CL, CL, and CL are the compositions, at some
Tunder value below the peritectic temperature, of the liq-
uid at the /L boundary, liquid at the /L boundary, and
austenite at the /L boundary, respectively. Also, r is the
radius (in meters), D is the diffusion coefficient in liquid
(m2/s), and R is the reaction rate (m/s).
Applying the Bosze and Trivedi model to the current system,
one can determine whether or not the theory that diffusion is
rate controlling is correct. Figure 12 compares the rates cal-
culated from the model against those observed. Table I lists
the thermophysical properties used in all calculations.
Although the trends observed are confirmed using this
model—such as the rates observed in the hypoperitectic
system being faster than those for the hyperperitectic case—
the absolute values of reaction rates are not. There are a
number of possible explanations for this. First, diffusion-
coefficient data for molten alloys are accurate only within
one order of magnitude. Second, the assumptions made by
Zener and others involving no diffusion in the solid state
could be incorrect. Finally, since the CSLM is inherently
a surface-observation technique, there are surface effects
such as the presence of a gas/liquid and gas/solid bound-
[5] ary. Another surface phenomena that could affect the rate
of reaction is fluid flow, which, if present, could alter the
assumption about the diffusion field being small compared
to the radius of the growing tip. Such fluid flow would
[6] raise the effective diffusion coefficient by an undetermined
amount, thus increasing the calculated rates.
A noteworthy difference between the hypo- and
hyperperitectic cases is that the thickness of the growing
[7]
austenite phase was found to be larger in the former than
in the latter, as seen when comparing Figures 5 and 9. No
confirmed explanation can be offered for this effect.
However, it may be due to the fraction of solid at which the
reaction was witnessed or small changes in the thermal field
surrounding the crucible.

Fig. 12—Comparison of observed and calculated reaction rates as a func-

Fig. 11—Reaction rate as a function of undercooling for hyperperitectic alloy. tion of undercooling.

Table I. Properties Used for the Calculation of

(a) Bosze and Trivedi Reaction Model

D1 (m2/s) [20] r(m)—hypoperitectic r(m)—hyperperitectic
2.0  10 9 10.0  10 6 5.0  10 6
(b) Growth into Undercooled Melt Solidification Model[9]
k1 (W/mK) (kg/m3)
hf (J/m3)  (m2/s)
35 7.25  103 1.93  109 6.0  10 6

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B. Peritectic Transformation
The second stage of the transition, namely, the solid-state
peritectic transformation, could not be resolved in the exper-
iments run. While the solid-state diffusion of substitutional
nickel is expected to be slower than that for interstitial car-
bon, the high temperatures of the present experiments should
allow it to occur over longer periods. The / interface was
held at temperature and observed for long periods of time,
but there was no noticeable change in either phase. The lack
of observation is, therefore, likely due to the difficulty in
resolution between the  and  phases.

C. Peritectic Solidification
As with the reaction stage, the solidification of austenite
into the melt was recorded at a number of undercooling tem-
peratures. It is difficult to separate the peritectic transition
into the three distinct stages outlined in the Introduction.
Quantifying the rate of austenite solidification illustrates these
complexities. Any measurement starting point is arbitrary,
because the austenite—even in the reaction stage—seems to
grow into the melt as well as grow along the ferrite/liquid
boundary. Therefore, the onset of the solidification stage was
considered when the growing austenite phases impinged on
one another and, thereby, separated the ferrite from the melt.
1. Hypoperitectic (4.2 pct Nickel) Case
Figure 13 is a typical example of the solidification of
austenite. In this case, the undercooling is 2 °C; however,
similar results were observed for all undercoolings mea-
sured. Figure 14 plots the austenite/liquid interface posi-
tion as a function of time for 1 °C, 2 °C, and 3 °C of under-
cooling. It is interesting to observe that the rate appears to
decrease slightly as time increases. There is also no clear
pattern relating the solidification rate to undercooling. This Fig. 13—(a) through (d) Austenite solidification at 2 °C undercooling for
hypoperitectic alloy.
is likely due to the fact that temperature gradients exist within
the CSLM image furnace. When comparing Figure 4 and
13, it is clear that unlike the  formed during the reaction
stage, the  phase formed during solidification is sufficiently
large to be affected by the temperature gradient within the
sample holder. The result of this is that—depending on the
position of the crucible holder within the furnace and the
solid/liquid interface relative to the crucible wall—the thermal
field surrounding the solidifying front may vary.
2. Hyperperitectic (4.7 pct Nickel) Case
To avoid the thermal discrepancies explained previously, care
was taken in the hyperperitectic case to record the solidification
rate within a repeatable thermal field. This involved maintain-
ing the crucible-holder position within the furnace as well as
attempting to keep the / interface in the same position rela-
tive to the crucible wall. Results similar to that of the hypoperi-
tectic case were recorded for undercoolings of 1 °C, 2 °C, and Fig. 14—Position of austenite/liquid phase boundary as a function of time
3 °C Figure 15 shows the progression of the austenite/liquid for hypoperitectic alloy.
boundary for three undercooling temperatures (1 °C, 2 °C, and
3 °C). It would appear that, under the thermal fields maintained,
austenite solidification is not dependent on the undercooling rate was as high as 4.5 m/s. The fact that neither the alloy
below the peritectic temperature. composition nor undercooling seem to play a role in the
changing solidification rates and that the thermal conditions
3. Comparison of Cases are of great importance would suggest that heat transfer
As discussed briefly earlier, the solidification rates seem controls the solidification of austenite.
to depend on the local thermal conditions. The rates vary There are many heat-transfer models available for solidi-
from 1.4 to 3.0 m/s. In some experiments (not shown), the fying metals.[9,21,22] Utilizing the assumptions that there is

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Fig. 15—Position of austenite/liquid phase boundary as a function of time
for hyperperitectic alloy.
one-dimensional heat transfer, that there is no temperature
gradient in the already-solidified austenite, and that there is
an undercooling in the liquid, an analytical solution to the
semi-infinite heat-transfer equations may be used. For the
case of a solid growing into an undercooled melt, the bound-
ary conditions are given in Eqs. [8] and [9]:
at x  , T  Tinf [8]
at x  0, T  T0 [9]
Where x is the position (in meters), T is the temperature
(in Kelvin), Tinf is the temperature at a maximum distance
from the solid/liquid interface into the liquid (in Kelvin),
and T0 is the temperature of the solid shell (in Kelvin).
Inserting these boundary conditions leads to an equation
which, when differentiated with respect to position, takes
the form of Eq. [10].
(T T0) x2
exp a b
dT
 [10]
dx 1
t 4
t the front to become nonplanar, thus making further meas-
Where  is the thermal diffusivity (m2/s) and t is the time
(in seconds).
Performing a heat balance at the solid/liquid interface and
substituting the thermal gradient in Eq. [10] into the result
gives an equation for the rate of solidification as a function of
time (Eq. [11]). It should be noted that x  0 at the interface.
kl (T )
R [11]
hf 1
t surface tensions of the three phases (ferrite/austenite/liquid)
Where kl is the thermal conductivity in the liquid (W/mK),
is the density (kg/m3),
hf is the latent heat of fusion per from the reaction stage of the peritectic transition, to witness
unit volume (J/m3),
T is the undercooling (Kelvin), and this three-phase equilibrium and measure the angles 1 and
R is the solidification rate (m/s). The values used for the
thermophysical properties are listed in Table I.
As discussed in Section II–C, pure iron samples were used
to measure the temperature gradients that exist in the image
furnace. It was found that, on average, a gradient of 4 K/mm
exists. This value was similar to that seen by other researchers.[15]
Knowing that the position of the solid/liquid interface relative
to the crucible wall changed from experiment to experiment,
1938—VOLUME 34A, SEPTEMBER 2003
Fig. 16—Comparison of observed and calculated positions of the
/L boundary.
Eq. [11] was applied to undercoolings ranging from 2 to 4 K.
This would correlate to 0.5 to 1.0 mm of liquid ahead of the
interface. The crucible diameter was 3 mm, so these values
are reasonable. Figure 16 compares the heat-transfer model
predictions to the observed hypoperitectic case.
It can be seen from Figure 16 that the observed position
of the /L interface as it advances falls within the range
predicted by the heat-transfer model. The hyperperitectic
case, not shown, also matches well with this model. Two
discrepancies between the predicted and observed values
require clarification. In the initial stages, the model predicts
a faster start to the solidification and a more dramatic slow-
ing as time progresses. This discrepancy may be caused
by the errors associated with measuring the small changes
in interface position at early times using the CSLM. In
later stages, there are no observations to correlate with
the approach to a steady-state rate as predicted by the heat-
transfer equations. This lack of data is caused by the ten-
dency of austenite to nucleate ahead of the front or for
urement of the position difficult and inconsistent.
The previous findings, coupled with the observed strong
dependence on thermal conditions mentioned earlier, suggest
that heat transfer controls the final stage of the peritectic tran-
sition, namely, the solidification of austenite, in this study.
D. The Mechanical-Equilibrium at the Three-Phase
Junction //L
As discussed in the Introduction, it can be assumed that the
are in mechanical equilibrium, according to Eqs. [1] and [2]
and as illustrated in Figure 2(b). It is possible, using images
2. With valid surface- and interfacial-energy information, this
could provide a means of independently verifying the phases
observed. Only the hypoperitectic case is discussed here,
because the three-phase junction area of the hyperperitectic
samples was too small to resolve with the accuracy required
for measurement. Figure 17 shows a typical example of the
dihedral angle. A schematic is also provided to demonstrate
the terms used. It can be seen that the angle observed matches
METALLURGICAL AND MATERIALS TRANSACTIONS A
02-584A-10.qxd 31/7/03 9:18 PM Page 1939
Fig. 17—Hypoperitectic three-phase junction at 3 °C with a schematic[9]
superimposed.
reasonably well with the theoretical prediction of the inter-
face shape shown in Figure 2(b).
Interfacial-energy data vary widely for metallic systems;
however, using a value of /L interfacial energy, given by
Kurz and Fisher,[9] and taking the measured angles 1 and
2 to be 60 deg and 20 deg respectively, one can obtain a
value for the /L interfacial energy using Eq. [2]. Placing
these values in Eq. [1] gives a value for the / interfacial
energy of 600 mJ/m2. This is within the typical range of val-
ues given by Howe,[23] which is 200 to 800 mJ/m2.
Further measurements and more-refined surface-energy
data are needed before a conclusive statement can be made
about the three-phase junction viewed in the hypoperi-
tectic system. It is important to note that the system is not
truly described by Eqs. [1] and [2], due to the presence
of the inert gas phase through which all observations are
being made. Also, the dynamic nature of the growing
austenite phase causes the values of  1 and  2 to vary
slightly as the three-phase junction moves along the /L
boundary.
IV. CONCLUSIONS
The peritectic reaction and the direct solidification of
austenite have been observed on the surface of two iron-
nickel alloys: Fe-4.2 pct Ni and Fe-4.7 pct Ni.
1. The rate of reaction for both alloys was observed to increase
as the temperature dropped further below the peritectic tem-
perature. For the hypoperitectic (Fe-4.2 pct Ni) case, the
rates were measured at 1 °C, 2 °C, and 3 °C and followed
the expression R  (39.9
2. Using the Bosze and Trivedi diffusion-limited model, the
trends of increasing rate with undercooling and a faster
rate for the hypoperitectic system were confirmed. How-
ever, the values of the model are lower than those observed.
Possible explanations for this are (1) that fluid flow on the
surface is raising the effective diffusion coefficient and,
thus, the model is underpredicting the rates, or (2) the avail-
able melt-diffusion coefficients are of limited accuracy.
3. The solidification rate of austenite into the liquid was not
a function of the temperature below the peritectic over
the range studied. Instead, the rate depends on the posi-
tion of the sample holder within the furnace and also on
the position of the solid/liquid interface relative to the
crucible wall. Therefore, the rate depends on the thermal
field under which the solidification is being carried out.
4. Using an analytical solution to the semi-infinite heat-
transfer equation, it was found that the observed solidi-
fication rates fall within the predicted rates between
undercoolings of 2 to 4 K. These undercoolings are con-
sidered reasonable, since measured temperature gradients
in the CSLM are 4 K/mm and there can between 0.5 and
1.5 mm of liquid in front of the growing austenite. It can,
thus, be concluded that heat transfer controls the final
stage of the peritectic transition.
5. The three-phase //L junction on the melt surface was
witnessed and matched reasonably well with the shape
predicted by an assumption of mechanical equilibrium.
Given a solid/liquid interfacial energy for pure iron and
using the measured dihedral angles, one can employ the
equations of mechanical equilibrium to calculate a
solid/solid interfacial energy of 600 mJ/m2, which is
within the ranges reported in literature.
ACKNOWLEDGMENTS
The authors are grateful to the Center for Iron and Steel-
making Research and its member companies for financially
supporting this project. The authors also thank the profes-
sors, students, and staff of the CISR for contributing their
ideas and assistance with other aspects of this project.
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