DIVERGENT PEARLITE IN A MANGANESE EUTECTOID STEEL*

JOHN W. CAHNt and W. C. HAGELT

An unusual structural feature, diverging lamellae, has provided new insight to the influence of com-
position on transformations in steel. Samples from a high-purity ternary alloy of iron containing 5.2 per
cent manganese and 0.6 per cent carbon were austenitized, isothermally transformed within the tem-
perature range 500-675C, and quenched. Neither pearlite growth rate nor interlamellar spacing
remain constant with time, but they vary over several orders of magnitude during the course of a single
isothermal reaction. The nodules initially grow rapidly and possess a fine spacing; with longer times,
growth rate decreases and interlamellar spacing increases. Nodules approaching impingement are
characterized by a very slow growth rate and coarse spacing at the advancing interface. This is quite
different from the time-invariant behavior observed in plain-carbon steels. It is shown that manganese
diffusion is too slow to give a zone of manganese-enriched au&mite, and so an austenite of continuously
changing carbon content must cause the observed phenomenon.

PERLITE DIVERGENTE DANS UN ACIER EUTECTOIDE AU MANGANESE

De lobservation dun aspect structural inhabituel, a savoir des lamelles de perlite divergentes, on a pu
deduire une nouvelle conception de linfluence de la composition sur les transformations des aciers. Les
auteurs ont observe des Qchantillons dun alliage ternaire ferreux et de haute purete contenant 5.2% de
Mn et 0,6% C. Ces Bchantillons sont austenitises, subissent une transformation isotherme dans une gamme
de temperatures comprises entre 500 et 675C et sont enfin trempes. On a observe que la vitesse de
croissance perlitique, ou lespacement interlamellaire, ne restait pas constant au tours du temps mais
quil varait au contraire considerablement au tours dune meme reaction isotherme. Les germes initiaux
croissent rapidement et possedent une structure lamellaire t&s fine; lorsque le temps saccroit, la vitesse
de croissance decroit et lespacement interlamellaire augmente.
Lorsque les differentes nodules arrivent a un stade de croissance ou ils se touchent presque lun lautre,
on observe que la vitesse de croissance devient t&s faible et que lespacement interlamellaire saccroit
considerablement a Iinterface de contact. Ce comportement est t&s different de celui observe dans les
aciers au carbone oh lon nobserve pas une influence du temps de maintien sur les deux facteurs etudies
ci-dessus. Les auteurs montrent que la diffusion du manganese est trop lente pour produire une zone
austenitique enrichie en manganese. Des lors, cest une variation continuelle de la teneur en carbone de
laustenite qui provoque le phenomene observe.

DIVERGENTER PERLIT IN EINEM EUTEKTOIDEN MANGEN-STAHL

Ein ungewohnlicher Strukturzug-divergente Lamellen-ergab neue Einsicht in den EinfluR der
Zusammensetzung auf die Umwandlungen von Stahl. Proben einer hochreinen ternliren Legierung von
Eisen mit 5.2 Prozent Mangan und 0.6 Prozent Kohlenstoff wurden ins Austenit-Gebiet gebracht, im
Temptaturbereich 500-675C isotherm umgewandelt und abgeschreckt. Weder die Waohstumsge-
schwindigkeit des Perlit noch der Abstand zwisohen den Lamellen bleiben im Lauf der Zeit konstant,
sondern sie iindern sich im Verlauf einer einzigen isothermen Reaktion urn einige GrGDenordnungen. An-
fiinglich wachsen die Knotchen schnell mit geringem Lamellenabstand; nach langeren Reaktionszeiten
nimmt die Wachstumsgeschwindigkeit ab und der Lamellenabstand zu. Kurz vor einem ZusammenstoB
von Knotchen tritt an der voranschreitenden Grenzfliiche sehr geringe Wachstumsgeschwindigkeit mit
groben Lamellen auf. Das ist vijllig verschieden von dem zeitlich konstanten Verhalten einfacher Kohlen-
stoffstiihle. Es wird gezeigt, da6 die Diffusion des Mangan zu langsam ist, urn eine Mangan angereicherte
Zone im Austenit zu ergeben. Infolgedessen mu6 das beobachtete Phiinomen durch Austenit mit stetig
veriinderlichem Kohlenstoffgehalt verursacht sein.

1. INTRODUCTION progress of the pearlite reaction both above and below

Theoretically, and with experimental justification, the lower Ae,. Our purpose here is to report the
the growth of pearlite is usually treated as a steady- unusual structural and kinetic features observed.
state process. (l) However, an exception has been
uncovered which may well extend to many other 2. EXPERIMENTAL

compositions and in time prove important to an A 75 mm dia., 15 kg ingot was prepared by the
understanding of alloy-steel hardenability. From induction melting of electrolytic iron (99.94), electro-
thermodynamic reasoning, we previously developed(2) lytic manganese (99.9+), and rod carbon (99.9+) in
that if pearlite forms in certain ternary alloys above a magnesia crucible under 1 atm. of argon. Liquid
the lower Ae, temperature, it should not grow with a iron was first deoxidized for an hour with carbon and
steady rate. The remaining austenite was expected flowing hydrogen; then the furnace chamber was
to alter continuously until it reaches a composition pumped down to a pressure of about 40 ,u Hg. After
in equilibrium with ferrite and carbide, and the numerous cycles of melting and solidification, no
reaction stops. This was shown to occur for a hyper- further boiling took place. A purified atmosphere of
eutectoid high-manganese alloy. We later prepared argon was imposed, and the necessary amounts of
a similar alloy of lower carbon content, to eliminate manganese and carbon were added. The heat was
the formation of proeutectoid carbide, and followed the poured at 1465C under argon into a cast-iron mold.
After slow cooling and removing the hot top, the
* Received November 29, 1962. casting was next homogenized in a retort under argon
eneral Electric Research Laboratory, Schennectady,
NhG
. . for 24 hr at 1lOOC and quickly hot-forged and swaged,
ACTA METALLURGICA, VOL. 11, JUNE 1963 561
.562 ACTA METALLURGICA, VOL. 11, 1963

with intermediate heating, to 18 mm dia. barstock. necessitated a high degree of preparation care to
After furnace cooling, shorter lengths were cut, and prevent relief polishing, that resulted in the rounding
these in turn were tempered at 600C for 8 hr. On of each nodule. After polishing through 180-, 400-
taking machinings from each length for an overall and 600-grit silicon carbide papers, the specimens
sample, the final chemical analysis was reported in were lapped by 8 and 3 ,u diamond paste, followed by
wt. y0 as 5.2OM& 0.59 C, 0.010 S, 0.003 P, 0.005 Si, 3 and 0.1 ,u alumina on rotating cloths. Some repeats
0.008 0, 0.004 N, 0.001 H, less than 0.001 Cr, V, Co, were required using successive polishing and etching
Ni, Cu, Mg, W and MO-with the balance Fe. with a solution containing 25 g of picric acid in 475 ml
Discs measuring 5 mm in thickness were sliced from of ethyl alcohol. The most satisfactory final etchant
the bars and notched in two places to permit ease of for optical microscopy was found to be 5% of the
holding with Nichrome wire. Each was numbered above solution in ethyl alcohol, and still weaker for
separately for positive identification throughout the electron microscopy. Prior to viewing, the outer edges
study. Salt pots were used for both austenitizing and of each cross section were covered with tape to avoid
isothermal transformation; adequate thermocouple any regions of possible decarburization.
surveys were conducted to insure that the samples Tables l-3 list the quantities measured metallo-
were at their prescribed temperatures. Transfers were graphically or derived from metallographic measure-
made quickly by hand with the final quench in water. ments.
Temperature control varied &3C from the nominal 3. RESULTS

for times up to 4000 min. Two austenitizing treat- 3.1 Morphology

ments of 1 hr at 1060C anp 1 hr at 1180C were used A typical sequence for the development of divergent
to provide a grain-size difference. Samples were trans- pearlite is given in Fig. 1. As the reaction proceeds
formed from 500C to 675C with the major emphasis isothermally, the newly formed pearlite at the moving
given 6OOC, 625C and 650C. pearlite-austenite interface, starting as unresolvably
The fine-to-coarse spacing of divergent pearlite fine, becomes progressively coarser. This time

TABLE 1. Areas/Volume. Measured by counting number of intersections of feature with randomly placed test
circle.3z4 Units are reciprocal centimeters

Symbol Name Comments

A, Free pearlite surface area Pearlite-austenite interfaces not impinged (with either other
pearlite nodules or grain boundary) and therefore assumed
free to grow
B Starting austenite grain-boundary area Related to austenite grain size by equation
B0 Uncovered austenite grain-boundary area Grain boundaries free from pearlite
B, Singly covered austenite grain-boundary area Grain boundaries having pearlite on one side only
B, Doubly covered austenite grain-boundary area Grain boundaries having pearlite on both sides

TABLE 2. Other metallographically determined quantities

Symbol Name How measured

_
X Volume fraction Systematic point count(5)
1 Apparent spacing Length of period normal to lamellae
W Maximum nodule width Width of largest nodule found in plane of section

TABLE 3. Quantities derived from metallographic measurements

Symbol Name Defining equation Comments

Average growth rate (l/A,) dX Averaged (by area) instantaneous growth rate
a
__=

(VW Mean reciprocal square spacing Averaged (by area) * instantaneous spacing

Nodule shape factor A,/@, -+ 2R,) Ratio of free surface area to base area of nodules
Grain-boundary coverage $%& 2%)/2R Fraction of grain boundary covered by pearlite
d Grain diameter
M ASTM grain size 6:65(log B) - 12.14

* The factor of $j comes from a correction for the sectioning statistics. On a random plane I is always larger than or equal to
the true spacing S.
 CAHN AND HAGEL: DIVERGENT PEARLITE 563

FIG. 1. Fe-5.2 Mn-0,6C alloy austenitized for 1 hr at 1180C and transformed at 625C
for (a) 42, (b) 202, (c) 420 and (d) 2545 min showing divergency and slow growth as time
increases. 300 x _ Etched with 5% Picral.

sequence can also be deduced by examining the struc-
ture of a large nodule from a specimen reacted for long
times. After 2545 min at 625X, some of the interior,
i&e lamellae have begun to spheroidize. The pearlite
reaction eventually becomes so slow that there is
little change in pearlite volume fraction between
successive long-time samples, e.g. compare Fig. l(c)
with l(d). These samples were austenitized to give
a B* =7Ocm-r, ie. . a d = 4.78 x 1O-2 cm or a
M = 0.1. With samples austenitized for Z hr at
1060C to give a B = 170 cm-l (d = 1.97 x 10e2 cm
or M = 2.7), the overall reaction was more rapid
initially, but was retarded at approximately the same
fraction transformed. Complete transformation was
not observed for either series. This is evidence, in
corroboration with existing phase diagrams, that
625C is above the lower Ae, temperature for this
alloy.
At 6OOC, nodule width in the samples of B = 70
* Symbols defined in Tables l-3.
cm-r increased and much impingement occurred, as
seen in Fig. 2(a-c). Note that impingement seems to
be characterized by a coarse spacing. We deduce this
as evidence for soft impingement, i.e. impingement
characterized by a large decrease in growth rate just
prior to impingement. Complete transformation was
observed for long-time samples of l3 = 170 cm-l.
Therefore, this temperature seems to be below the
lower Ael. t
Little nodule growth took place at 650C, Fig. 3,
t Although we agree with the lower Ae, of Tofaute and
Linden, we are not convinced that this is the true equilib-
rium lower Ae, simply because the austenite had not been able
to achieve the equilibrium manganese content. The true
lower Ae, must lie somewhat below. This presents an inter-
esting paradox. We attempt to approach eq~jbrium by
starting with austenite; Tofaute and Linden start with
martensite. That these different approaches agree is normally
taken as proof of equilibrium. But it is not, since it is likely
that both suffer from the same lack of equilibrium par-
titioning ; they even use the same maximum time. Some
manganese partitioning did occur in Tofaute and Lindens
work, or else they would have found a pseudobinary diagram
with no 3-phase field.
564 ACTA METALLURGICA, VOL. 11, 1963

FIG. 3. Fe-5.2 Mn-0.6C alloy austenitized for 1 hr at

118OC and transformed at 65OC for 990 min. 300 x .
Etched with 5% Picral.

examined the sample of Fig. 3 and many others for

any indication of a ferrite gap.() Except for occasional
breaks in the continuity of a growing carbide plate,
perfect abutment, as shown by Fig. 4(a), was the
general case. If a gap does exist, the resolution of our
replica technique requires that it be less than one-
hundreth (rather than one-tenth) the true interla-
mellar spacing. Electron micrographs were taken of
the fine pearlite formed at 550C and 500C. Diverg-
ency is present down to the lowest temperature, Fig.
4(b), although the spacing variation from nodule
center to edge is not as great as at higher temperatures.

3.2 Growth kinetics and mechanism

3.2.1 Growth rate. The standard method(l) of deter-

mining pearlite growth rate is to examine the plane of
section for the largest nodule, measure its width and
obtain the growth rate from the time derivative of
width. The results of such a measurement are given
in Fig. 5. As can be seen, the growth rate is not
constant, but varies with time.
During the course of this measurement, it became
apparent that the standard method suffered from
FIG. 2. Fe-5.2 Mn-0.6C alloy austenitized for 1 hr at severe limitations and was really not applicable. In
1180C and transformed at 600C for (a) 41, (b) 200 and particular, we became interested in growth rate at
(c) 1617 min. 350 x . Etched with 5% P&al.
very late stages in the reaction long after impingement
had made it difficult to find the size of individual
but the initial spacing is larger. No pearlite was found colonies. It was also observed that even in the early
within 4000 min at 675C, irrespective of austenite stages the nodules were far from spherical or hemi-
grain size. spherical and seemed to have grown much faster along
Since this alloy possesses a relatively high harden- the boundary than normal to it. The largest apparent
ability, the advancing interface should be little nodule therefore is not one sectioned through its center
affected by a water quench. Therefore, we closely but one sectioned at a shallow angle to the boundary,
 CAHN AND HAGEL: DIVERGENT PEARLITE 565

FIG. 4. Electron micrographs of divergent pearlite in samples transformed for

(a) 990 miu at 660C and for (b) 1440 min at 5OOC. 13,500 X. Parlodion
replica of surface lightly etched with 5% Picral.

exposing its full length along the boundary. Further- and in time, the overall rate
more, because of early impingement along the bound-
ary, sooner or later one is reduced to examining grain-
boundary slabs and must choose the thinnest rather
than the thickest for a true thickness. This transition
dX
-=
0% s
Af
GdA

where the integral is taken over all the pearlite-

from looking for thickest to thinnest is rather sub- auatenite surface area free to grow with a local
jeative. An additional fault is that this method growth rate G that varies over surface and time.
measures a growth rate characteristic of the fastest Defining a growth rate averaged over A, at an instant
growing pear~te{z) which may not be eharac~risti~ of time
of the average.
We therefore explored several alternate growth-rate (2)
measurements in hope of developing one that is as
free from objections as possible. The method decided yields
upon seems to be so. It is based upon the realization
that, even if growth rate varies from nodule to nodule
; = t?Af.
566 ACT.4 METALLURGICA, VOL. 11, 1963

8
c p

70cmf
625C

-&--- 170cm

65OC
#

01 I t I I i I I I I I t I I
0 200 400 600 800 loo0 1200
TRANSFORMATION TIME - MINUTES

FIG. 5. Maximum nodule width vs. tr~sform~tion time. The points were determined by looking for the
largest nodule in & plane of section, and the short lines are superimposed a values.

The quantities A, and X c&n be measured by point
counting to a high degree of ~~~ur~ey,~~15~
1 ax
Since B=_---,
A, dt
the main experimental uncertainty in 0 comes from
differentiating X with respect to time. (In the standard
method, the differentiation of nodule width with
respect to time suffers from the same difficulty). It
is easier to obtain an accurate slope from 8 plot that
does not curve excessively; one such plot is shown in
Fig. 6. We evaluated dX{dt from the relationship
dX (1 - X) In (l/l - X) 112
---=
dt t
where m is the instantaneous slope of the log In
(l/l - X) vs. log t curve. The method proved easy
to use and required almost no subjective judgment.
We measure, by using equation (4), an average growth
rate defined by equation (2) with the only assumption
being that there are no variations from sample to
sample so that dX/dt can be obtained from a series of
samples.
Results of the above method give the growth rate
shown in Fig. 7. Since this is the growth rate itself,
it could be compared with the derivative obtained
from the curves in Fig. 5. We have made the com-
parison instead by plotting short lines of the slope
obtained by the new method on Fig. 5. Agreement is
(4) quite good considering the approximations in the
old method.
From these graphs we conclude: (1) that growth
rate varies by a factor of about 100 in the heat treat-
ment time; (2) that growth rate is approximately
proportional to the reciprocal of time. Of course, this
can not persist to zero time because the growth rate
must start with a finite velocity. However, only in
growth at 650C can any evidence be found of a
levelling off at early times, i.e. a linear region in Fig. 5
(5) and a bend over in Fig. 7.* (3) There is little variation
in growth rate with temperature during most of the
reaction compared with the large isothermal variation
with time. The large differences in nodule size are
created in the early stages. Thereafter, growth rates
are approximately equal over the 50C temperature
range, and the nodule-size curves are approximately
parallel.(4) Grain-size differences have little effect on
growth rates except ;ts the reaction nears completion.
At the time when the pearlite reaction in small
* The horizontal line in Fig. 7 (for the early stages, where
we hsve no data) w&s estimated by extrapolating to zero the
short-time maximum nodule widths of Fig. 5.
 CAHN AND HAGEL: DIVERGENT PEARLITE 567

JO, , I I r, I I ?I[ I , I,

170cm -'
a 600 C
. 625 C

I-

!.
x
-I
210 -

K?-
70 cm-'
0 603 C
A 625C
0
0 650 C

-@

Tl?ANSFORMATION TIME -MINUTES

FIG. 6. Isothermal transformation mrves for Fe-5.2 Mn-0.6C samples possessing
grain-surface areas of 170 and 70 cm-l.

grain-size samples is nearing completion, the rates are as a function of time since this spacing corresponds
different from those found in the large grain-size to the diffusion path length at the instant of time for
samples. This indicates the existence of what might which growth rate was measured. Again we were not
be termed soft impingement. It might be worthwhile certain that the spacing was constant over all surfaces
to emphasize again that this is a drop off in the rate at an instant of time. This is obscured by sectioning
of advance of uniwqinged pearlite-austenite interfaces. which always gives an apparent spacing 1 greater than
The overall rate drops off even faster because the or equal to the true spacing S, and so we decided to
interfacial area is also diminishing rapidly at the end measure an average spacing at the interface.
of the reaction. Since growth is probably faster wherever spacing is
3.2.2 Spacing. An important parameter of any smaller, we did not want a straight average, but instead
pearlite growth mechanism is the interlamellar spacing, decided to average a reciprocal square spacing which
for it is an indication of the diffusion distance involved. weights the smaller spacing more heavily in approxi-
In this steel it was immediately obvious that the mately the same way that growth rate should average
spacing is not constant with time at temperature. it. Thus, we traversed the specimen with random
Therefore, we needed to consider carefully what it lines. Wherever such a line intersected a free pearlite-
was about spacing that we wanted to know. Since austenite interface the apparent spacing 1was measured
growth rate varies in time, it would be desirable to there (the perpendicular repeat distance). The
measure spacing at the pearlite-austenite interface spacing was averaged by averaging l/P and multiplying
6
568 ACTA METALLURGICA, VOL. 11, 1963

70 cfn-
0600
A 625 %
o 650 %

650 C
r A

170 cl-n-
e600
A 625 C

lO-s1 I 1 III I I III I I L,

IO IO2 K?
TRANSFORMATION TIME --MINUTES
FIG. 7. Plot of average growth rate f? vs. time on a double logarithmic scale showing
transient nature of a.

by the appropriate geometric factor Z/3 to get a (l/P). volume diffusion coefficient of the ith component in
Fig. 8 shows how well this mean reciprocal square austenite. Each alloy element in a steel has a band
true spacing correlates with growth rate at 625C. width characteristic of its DiY. One can conclude that,
This is not unexpected and shows that spacing and if DiY/G for the fastest diffusing element is greater
growth rate are related, but leaves open the question than the grain size, steady-state conditions will rarely
of what determines them. be observed. Let us examine DiY/G for both carbon
3.2.3 The thickness of the austenite of altered com- and manganese at 600C. For carbon, using a DCy
position. Most derivations for pearlite growth rates = 0.22 exp (-33,000/RT),(8) D,YIG varies from 10 ,u
assume steady state has been reached. Clearly, if during the early stages of reaction to 1 mm at the
growth rate is not constant, this is not the case. later stages. This is therefore quite consistent with
Nevertheless, much can be learned by examining the observation of no steady-state growth. For
results using some of the relations derived for steady manganese, using a D,,Y = (0.486 + 0.011 x w/o Mn)
state. Growing pearlite will try to surround itself exp ( -66,000/RT),(g) DMnY/Gvaries from 0.002 to 0.2 A
with austenite of a composition that may be quite during the course of the reaction. When DJG is less
different from the original austenite. At steady state, than a few atom spacings it loses its meaning and the
this altered austenite forms a band surrounding each conclusion is clearly that there is no zone of austenite of
pearlite nodule of thickness DiYIG where DiY is the altered manganese composition ahead of the interface.
 CAHN AND HAGEL: DIVERGENT PEARLITE 569

r_

I -

B
4 6 8 lc? 2 4 6 8 IO- 2 4 6 8 I8
AVERAGE GROWTH RATE -cm see
FIG. 8. Correlation of (l/Se) vs. z at B = 70 cm- and T = 625C.

Thus, the change in austenite is entirely a change that an alloy element must segregate.
in carbon content and because carbon diffusion is so
great after a short time, it occurs throughout the
austenite grain.
3.2.4 The mechanism of diffu&on. In this section where concentrations Cari, Caci, Cci, Cfi are concentra-
we shall follow a sequence of steps outlined in Table 2 tions obtained from extrapolations from the phase
of Ref. 2. These steps make use of certain limits diagram.c2) This, of course, cannot be done very
imposed on the kinetics of the diffusion process by accurately, but as we shall see that does not matter.
the thermodynamic requirement for segregation. For both carbon and manganese at 6OOC, uoi lies
Although these relations were derived for steady between 0.1 and 10e3. That we get a finite value for
state, they should hold approximately for the non-
ar,Mnis a consequence of the high alloy content and the
steady state growth observed here. We begin by proximity of the Ae,. There is a thermodynamic
GX requirement that the manganese segegate. If it did
considering a kinetic parameter CQ= - which is
27rDi not, the pearhte would have a higher free energy than
a measure of the resistance to segregation. There the original austenite. At lower temperatures or
exists one such parameter for each alloy element and lower manganese contents, this ceases to be true and
each phase. Because GS is not constant, u( is time no thermodynamic requirement continues to be
dependent as well as temperature dependent. In the necessary.
range 600-625C we find u, ranging from 10-4-10-3 For carbon in austenite, ui is less than uo. This
and uMny ranging from 103-104. The former is much indicates that lateral diffusion of carbon is more than
smaller than unity indicating much diffusion of carbon adequate to accomplish segregation. Therefore, the
ahead of the pearlite-austenite interface; the latter lateral diffusion of carbon cannot be rate controlling.
is much larger than unity indicating little if any For manganese, the relation fails. Since the
diffusion in the autensite. manganese must segregate this means that there must
We next define a thermodynamic parameter for be another diffusion path. Estimating the contribu-
each component, ugi, which expresses the requirement tions from the ferrite leads one to the conclusion that
570 ACTA METALLURGICA, VOL. 11, 1963

this too is inadequate. We are thus f0rctd to the austenite is responsible. The conclusion we are led
conclusion that bulk diffusion in either austenite or to is that it is the carbon content (or some interstitial
pearlite is too small for these rates of growth and fast-moving impurity) that is responsible. The
spacings to accomplish the necessary manganese austenite is tending toward a composition where the
segregation. fast moving carbon atoms have approximately the
In recent years, it has been suggested(loY1l) that the same chemical potential everywhere, with ever de-
advancing pearlite-austenite interface couia provide creasing driving force for carbon diffusion. The
a diffusion path for segregation. Let us test if we have diffusion distance is no longer the interlameller
evidence for such a path here. A commonly used test distance but becomes of the order of the grain size.
for the relative effectiveness is to compare cliffusivities. In a previous paper, Cahn(13) pointed out that there
If D,lD > S/2nd where DB is the grain-boundary is more than one rate-determining process for this
diffusivity and 6 is the grain-boundary thickness, the type of reaction. Thus it appears that manganese
boundary is a much better path for the segregation. diffusion along the advancing boundary could be one
In practice, the measurement of grain-boundary of the rate-controlling reactions, but since the spacing
diffusivity always yields the product DBS and so it can adjust during the course of the reaction, man-
is simpler to note whether ganese-diffusion considerations alone a0 not determine
the rate. We are then left with considerations of such
D,d S
D> -. (7) factors as carbon-concentration changes extending
27r
over the entire austenite grain, the mobility of the
Unfortunately, we have no measurement for mangan- boundary, as well as factors that determine the
ese diffusion along austenite-pearlite interfaces. There spacing.
does exist a measurement(12) of iron diffusion along
ferrite grain boundaries. Using this value extrapol- 3.3 Nucleation phenomena

ated to 600C we have DBd = 1.2 x lo-l4 cm3/sec or Very little reliable work exists on pearlite nucleation.
For a critical review, the reader is referred to Ref. 2.
-Dd _-
740 cm, which is many orders of magnitude
D y With the Fe-5.2 Mn-0.6C alloy, nucleation apparently
laF:er than the spacing. The grain-boundary resist- occurred exclusively on grain boundaries, but not all
ance to segregation ug is commonly taken(2T11) as grain boundaries were equally effective. Until very
late in the reaction, there always were some grain
GS2
(8) boundaries completely free from pearlite. Fig. 9 gives
OrB- 4rr=D,d a plot of fractional grain-boundary coverage vs.
and for 600C or, !Z 2 x 10-4, which is less than the volume-fraction transformed. The curve is much less
thermodynamically required maximum. Thus, we extreme than that reportecl(2) for the Fe-SCr-1C alloy
conclude that grain-boundary diffusion is probably where early in the reaction complete grain-boundary
the path for the thermodynamically necessary man- coverage is obtained. This is consistent with the
ganese segregation. Furthermore we note our finding, observations of Picklesimer et aZ.(14) who found that
that reciprocal square spacing is proportional to in their high-purity 1 per cent manganese steels almost
growth rate, shows that spacing and growth rate seem no nucleation occurs on grain boundaries, suggesting
to adjust during the course of the reaction to keep or, impurity catalysis of nucleation.
a constant. All of these relations were originally Several techniques for determining nucleation rate
derived for steady state, but as we have seen in view involve tedious methods of metallographically meas-
of the large inequalities they should also hold here. uring the true number of nodules in a unit volume of
Since the manganese content of austenite cannot specimen. Some of these methods depend on particle
be changing, what causes the tremendous decrease in shape. Since this came up in regards to the old growth
growth rate with time2 The manganese content of the rate method, we measured a nodule shape factor, i.e.
pearlite-austenite interface should reach secular the ratio of A, to the base area on the grain boundary.
equilibrium very rapidly. Certainly by the time it The results as given in Fig. 10 show that the true
has advanced by 1 ,u, it has swept through enough shape lies between hemispheres and slabs, making it
manganese and carbon to reach saturation. The difficult to develop a simple method for counting
answer appears to be in the changing austenite. This nodules except by successive polishing. Because of
is consistent with the evidence that we have for soft this and because of the feeling that nucleation is
impingement. The overlapping of diffusion zones of impurity sensitive anyway, we abandoned further
two nodules would give such behavior, if the changing attempts to measure nucleation rate.
 CAHN AND HAGEL: DIVERGENT PESRLITE 571

FIG. 9. Graph showing fraction of grain

boundaries occupied by pearlite as a func-
tion of volume-fraction transformed.

0600C
A 625C

70 cm'
0 600c
A 625%

0.2 0.4 06 0.8 la

VOLUME- FRACTION TRANSFORMED -

I
I I
I I
I I
I I

UNIMPINGED HEMISPHERES
2.0

1.6

A
A
0

EIG. 10. Shape factor vs. volume-fraction

transformed. Calculated curves for un-
impinged hemispheres and planar slabs
are provided.
572 ACTA METALLURGICA,
0.8 -
06 -
0 0.2 04
FRACTION OF GRAIN BOUNDARIES OCCUPIED-
FIG. 11. Square root of fraction doubly covered vs. fraction of grain boundaries
occupied. Calculated curves for nucleation catalysis or avoidance are provided.
The Smith-Hilled theory(15) of pearlite nucleation
requires that a grain boundary be free of pearlite if
pearlite is to nucleate. Once pearlite has grown on
one side of grain boundary, no new nodule can
nucleate on the other side. Thus the nodules on the
two sides ought to avoid each other to some degree.
This same avoidance should also occur if the austenite
on both sides of a boundary begins to alter due to the
presence of pearlite on just one side. On the other
hand, if pearlite on one side catalyses either the
nucleation or growth of pearlite on the other side we
should see a high degree of doubly covered boundaries.
Fig. 11 gives the surprising statistical result that
the two sides of a grain boundary appear to behave
completely independently of one another. We have
no explanation for this result. In Fig. 11 we plot
JB,/B vs. grain-boundary coverage (B, + 2B,)/2B.
If there is independence, these should be equal as is
shown. We also show the maximum curves of catalysis
(B, = 0) and avoidance (B, = 0 until half coverage;
thereafter B,, = 0).
3.4 Overall rate
Fig. 6 showed that in spite of all the aforementioned
complications, the overall-rate curves for an Fe-5.2
VOL. 11, 1963
A 625 C
A 625C
-1
0.6 0.a IO
Mn-0.6 C alloy do not differ greatly from those for
other steels when plotted as log In (l/l - X) vs. log t.
This points up again the danger of reasoning from
such curves alone. Almost all theories of overall rate
make use of either constant growth rates+) or a
growth rate that is initially proportional to t-l/z as
in diffusion-controlled precipitation. We have neither.
The slope m of a log In (l/l - X) vs. log t curve can
usually be used to obtain information about nucleation
or growth, and conversely it is easy to predict m when
given certain information about nucleation and
growth. Because growth rate decreases with time
the fact that the initial slope equals or exceeds 3 does
seem to indicate that we have some time-dependent
nucleation as is common(17) in other steels. But even
such a conclusion is not very strong. A theory of
overall rate must first explain the time dependence
of a and A,. Because we have obtained 0 from X,
it would be redundant to reverse the procedure and
calculate X from B and A,. A, is (as in other systems)
dependent on such geometrical factors as impingement
and distribution of nucleation sites as well as on
nucleation and growth rates.
For practical purposes, kinetic data are simply
reduced to a TTT diagram which gives approximately
 CAHN AND HAGEL: DIVERGENT PEARLITE 573

LOG TRANSFORMATION TIME -

FIQ. 12. Schematic TTT diagrams for plain-carbon and high-manganese eutectoid steels showing
convergence and divergence of respective pearlite start and finish lines.

the time for the onset and end of the pearlite reaction not constant, the relation between time and grain
as a function of temperature. What factors determine diameter is no longer linear.
the difference in diagrams between plain-carbon and
alloy steels? 4. CONCLUSIONS
The major factor in explaining the difference in (1) For an Fe-5.2 Mn-O.6C alloy in the range of
overall rate between this steel and plain-carbon steels 600-650C we have found that pearlite growth rate
is the tremendous difference in growth rates and grain is not constant, but continually decreasing with time
sizes rather than in nucleation rates. Growth is, as at constant temperature. Impingement is soft.
we have seen, a very complicated phenomenon, but (2) There is a corresponding increase in spacing
it seems that requiring the alloy element to segregate with time so that GLP is constant.
is paramount in explaining slow growth. The large (3) Such variations in spacing within a nodule
time variation in growth rate in manganese steels persist down to 500C and we assume that this con-
seems to come from long-range carbon diffusion that tinues to imply a variable growth rate.
alters the carbon content of the entire austenite grain (4) We have not observed a ferrite gap.
until at last carbon activities in the three phases are (5) The diffusion geometry is such that the carbon
approximately equal throughout and growth becomes concentration in austenite is continuously changing
very slow. Above the lower Ae,, growth eventually throughout the specimen during most of the reaction
stops entirely and we are left with three-phase time. Yet, for the required manganese segregation
equilibrium. This extreme slowing down causes a only diffusion in the advancing pearlite interface is
divergence of the pearlite start and finish curves on sufficiently fast. The relation of growth rate to
a TTT diagram at high temperatures which is shown spacing is consistent with this manganese diffusion
schematically in Fig. 12, and which differs from the mechanism.
behavior of such curves for plain-carbon steels. (6) Nucleation is rapid enough to give many
The large grain size is also a factor. Because nodules per austenite grain, but there always are
pearlite nucleates at grain boundaries, the time to grain boundaries on which no pearlite nucleates.
completion is governed by the time for nodules to (7) The two sides of an austenite grain boundary
grow to the center of a grain. The larger the grain react independently of one another.
size, the longer this takes, and if the growth rate is Most of these effects have not been reported before.
574 ACTA METALLURGICA, VOL. 11, 1963

They seem to require a reexamination of many of the 6. gj TOFAUTE and K. LINDEN, Arch. Eisen. 10, 515 (1936/

basic precepts of pearlite theory when applied to alloy 7. L.

S.DARKEN and R. M. FISHER, Decomposition of Austen-
steels. ite by Diffuaional Processes, pp. 249-294. John Wiley, New
York (1962).
ACKNOWLEDGMENTS 8. C. WELLS, W. BATZ and R. F. MEHL, Trans. Amer. Inst.
Min. (Metall.) Engrs. 188, 553 (1950).
The authors are grateful for helpful discussions on 9. C. WELLS and R. F. MEHL, Trans. Amer. Inst. Min.
this topic with Professors B. Chalmers, J. E. Hilliard (Metall.) Engrs. 145, 315 (1941).
10. C. S. SMITH, Trans. Anzer. Sot. Metals 45, 533 (1953).
and D. Turnbull. 11. D. TURNBULL. Diffusion Short Circuits and Their Role in
Precipitation, pp. 203-211. Bristol Conference (1954).
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(1956). Vol. 1, Proc. 1st UNESCO Intl. Conf., p. 212 (1958).
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by Diffdonal Processes, pp. i31-196: John Giley, New 14. M. L. PICKLESIMER, D. L. MCELROY, T. M. KEGLY, E. E.
York (1962). STANSBURY and J. H. FRYE, Trans. Met. Sot. Amer. Inst.
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(Metall.) Engrs. 197, 81 (1953). 15. M. HILLERT, Decomposition of Austenite by Diffusional
4. J. E. HILLIARD, General Electric Report No. 62-RL- Processes, pp. 197-247. John Wiley, New York (1962).
3133M, October 1962. 16. J. W. CAHN, Acta Met. 4, 449 (1956).
5. J. E. HILLIARD and J. W. CAHN, Trans. Met. Sot. Amer. 17. F. C. HULL, R. A. COLTON and R. F. MBHL, Trans. Amer.
Inst. Min. (Metall.) Engrs. 221, 344 (1961). Inst. Min. (Metall.) Engrs. 150, 185 (1942).