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THE KINETICS OF GRAIN BOUNDARY NUCLEATED REACTIONS*

JOHN W. CAHNt

Rate laws are derived for transformations in which the new phase nucleates on grain boundary surface,
grain edges, or grain corners, and in which the new phase grows with constant radial velocity. Time-
dependent and time-independent nucleation rates are treated. At high nucleation rates (relative to
growth rates and grain sizes) the rate law assumes a form independent of the nucleation rate, and the
half-time of the transformation becomes approximately 0.1 D/G, where D is the grain diameter and (2 the
radial growth velocity, independently of which sites are responsible for nucleation. St low nucleation
rates the rate law approaches that given by randomly distributed nucleation sites. The conditions which
determine which type of site will produce the most nuclei, and hence determine the form of the rate law,
are discussed.

LA CINETIQUE DES REACTIONS DE GERMINATION z4UX FRONTIERES


INTERGRANULAIRES
Des lois de vitesse de germination sont Btablies pour des transformations au tours desquelles la
nouvelle phase apparait aux surfaces intergranulaires aux bords et aux coins de grains, et
croit iL vitesse radiale constante. On Btudiee Bgalement les vitesse de germination influencPes ou non par
le facteur temps. Pour des vitesses de germination &e&es (comparativement aux vit,esses de crossiance
et aux dimensions des grains) la loi est indbpendanto de Is vitesse de germination et la demi-durbe de
transformation est approximativement 0,l D/G, avec D = diametre du grain et, G = vitesse radiale de
croissance, quelque soient les endroits ob seffectue la germination.
Pour des vitesses de germination faibles, la loi se rapproche de celle valable lorsque la germination
seffectue k partir de sites distribuks au hasard. Laubeur discute encore les conditions determinant
les types de sites de nucleation dormant lieu au plus grand nomhre de germes, et par suit,e la forme de la
loi de la vitesse de croissance.

DIE KINETIK VON REAKTIONEN MIT KEIMBILDUNG AN DEN KORSGRENZES


Fiir Umwandlungen, bei denen die neue Phase an Korngrenzflhchen, Kanten oder E&en van
KGrnern entsteht und bei denen die neue Phase mit konstanter Radialgeschwindigkeit w&chst, werden
Gesetzmiissigkeiten fiir die Umwandlungsgeschwindigkeit abgeleit,et. Dabei werden zeitabh&ngige und
zeitunabhiingige Keimbildungsgeschwindigkeiten behandelt. Bei hohen Keimbildungsgeschwindig-
keiten (im Vergleich zur Wachstumsgeschwindigkeit und dor KorngrGsse) nimmt die Gesetzmiissigkeit,
der Umwandlungsgeschwindigkeit eine van der Keimbildungsgeschwindigkeit unabhgngige Form an
und die Halbwertszeit der Umwandlung wird-unabhkngig davon, an welchen St&en die Keimbildung
erfolgt-niiherungsweise 0,l D/G, wobie D der Korndurchmesser und G die radiale Wachstumsgeschwin-
digkeit sind. Bei kleinen Wachstumsgeschwindigkeiten niihert sich die Gesetzmiissigkeit der Umwsnd-
lungsgeschwindigkeit derjenigen fiir regellose Verteilung der Keimhildungsstellen. Schliesslich werden
die Bedingungen diskutiert. die dafiir massgebend sind, an welcher Art van Keimbildungsstellen die
meisten Keime entstehen und die somit den Verlauf der Umwandlungsgeschwindigkeit bestimmcn.

It has recently been suggested by Clemm and (junctions of 4 grains), and will be progressively greater
Fisher(l) that the nucleation energy at a junction of as, one considers edges (junctions of 3 grains), grain
grain boundaries could be less than at a plane boundary surfaces, and the interior of grains. It is
boundary, and that these junctions might be favored the purpose of this paper to explore the suggestion
sites for nucleation. However, there are two factors of Clemm and Fisher, by deriving the rate laws associ-
opposing this purely energetic consideration. One ated with reactions nucleating at such sites, developing
factor results from the ease with which these sites can t.he limits under which a particular site is favored, and
transform, and might lead to a situation where these examining some of the characteristics of such a
sites lie wholly in transformed material at a time early reaction.
in the reaction and, hence, be no longer available to In a polycrystalline material, nucleation is assumed
nucleation. The other factor, affecting the nucleation to occur with characteristic frequencies on four t,ypes
rate, is the number of atoms associated with each type of sites. We shall designate the homogeneous nuclea-
of nucleation site. This will be least for corners tion frequency per unit volume as I,, the specific
grain boundary nucleation frequency per unit area as
*Received November 18, 1955. I,, the specific edge nucleation frequency per unit
eneral Electric Research Laboratory, Schenectady,
&w%ork. length as I,, the specific corner nucleation frequency
ACTA METALLURGICA, VOL. 4, SEPTEMBER 1956 449

1
450 ACTA METALLURGICA, VOL. 4, 1956

per corner as 1,. We should also like t*o define nuclea- for considerable distance from a growing particle,
tion frequencies per unit volume for each type of Johnson and Mehlc2) derived the rate law for grain
site, r;,, lir,, &,, SC. If S, L, C are respectively the boundary nucleation by assuming that the trans-
boundary area, edge length, grain corner number formation product could not grow across grain
(all per unit volume), then SV = I,; 8, = I$; boundaries. It will be necessary t.o examine this
8, = I,L; NC = ICC. The total rate of nucleation assumpt,ion in detail. At high nucleation rates many
per unit volume AT= Szl + gir, + Se -+- gC. nuclei per grain will form and the reaction will be
In order to compare expressions complaining 8, L, substantially eomplete when Gt is of t.he order of the
and C, it will be necessary to express them approxi- grain diameter. At low nucleation rates the reaction is
mately in terms of CL
grain diameter. If we assume that far from complete at that time. If one assumes that
all grains are equally large tetrakaidecahedra arranged the transformation product cannot grow across
so that they fill space [a body-centered-cubic array boundaries, then the fraction transformed will be
orient,ed so that the square faces are in (100) planes, equal to the fraction of the grains in which a nucleus
and hexagonal faces in (111) planes] and call the has formed, with a correction for that fraction of the
distance between
square faces D, then the edge untransfor~ned volume which is in grains which are in
length will be D/242. The number of grains per unit the process of transforming. This correctSion becomes
volume are 2/O, and a constant fraction of the untransformed volume at
5 = 3.350-l, time greater than the time it takes a nucleus starting
at time 0 to consume its grain, that is, at t > D/G.
I; = 8.5D-2, (1)
(This is true whether the nucleation rate is high or low,
C = 12.OD-3.
except that when it is high, at t = DIG the reaction is
While the act,ual numerical constants in equations close to completion.) Indeed, Johnson and Mehls
(1) are to be taken as approxiinate, the functional analysis at t > D/G reduces t,o
dependence on D is assumed to be exact,
1 - X = (1 + K)e-~B21~t,
DERIVATION OF THE RATE LAWS
where E is the constant* which denotes the fraction of
Nucleation and growth reactions fall into two the untransformed material which is in grains in the
broad classes. The first,
termed discontinuous, process of transforming. One predicts, therefore, that
will be treated in this report. In this class of reactions, where grain boundaries are not crossed by the growing
the transformation product which nucleates and grows transformed material, and where K is small, a plot of
has the same average composition as the untrans- log log (l/l - z) vs. log t would rapidly approach
formed material, and, except for a short distance slope unity whenever t > I)/@.
from the advancing interface, the untransformed An alternate assumption, and one which will be
material has the original composition. One can assume treated here, is that grain boundaries offer no resistance
that, after a time, steady-state conditions are achieved to a growing nodule. It is believed that this assump-
in which both the growth rate and the specific tion is a better approximation to the true situation.
nucleation rate are
independent of time. This Wherever grain boundaries stop a nodule, nucleation
assumption will be treated first. In the last section we on the other side appears to be greatly enhanced, and
shall trea,t the case where, for some reason, steady- this situation should be better approximated as
state conditions are not achieved in the nucleation
rate during a significant part of the reaction time.
The other class, to be discussed more fully in a
subsequent paper, is where the transformation
product is of a different composition and the untrans-
formed material is gradually changing composition.
Here the nucleation rate in the untransformed
material may be a strong function of time and distance where 6 = g ; z and y EUPC
dummy variables;
from a growing transformed region, because the (1 + ?/)2-a
and w = exp (4nb [ -(I -Y -z)
nucleation rate is a strong function of composition. 1 4Y 1
In the case of grain boundary nucleated reactions 1+?/+z
+(1+Y--~ogY+(l+Y)log~+
(and incidentally, for reactions which nucleate on
+ z lo_ (1 + z/P - x2
dislocations), the high diffusivity in a boundary could 0
4 II
be expected to affect furt,her nucleation drastically K is a function of b only. For small b, K is proportional to 6.
CARX: GHAIN BOUNDARY

contSinued growth and ncrt as the relatkely rare from a plane or edge, assuming that these are only
~~~~~~~n~~ of original ~~oleat,ion. impinging with nodules origin&ing from the same
fn the study of pea,rlite, for instance, where the plane OPedges. One next considers a random distri.
parameter b is small, a plot of Iog Iog (l/i - 2) vs, bution of planes or edges each giving rise tn a certain
lag the usudy results in a slope of 4 or more? which transformed v&me, and considers irn~i~~e~nent
is &e dope one WRUIdsxpe& from rand~mI~ d&k=i- a~~~~~~ L&se volnmes.
but.ed nodules growing with no res~rietian to their For the case of corner ~I~cIeat.iu~~,
it is just. assumed
%%~a1size except inlping~n~ent with one another, that tShe corners are randomly distributed, and
The occurrence of a,slope of more than 4 appears ta be limited in number.
due to t.ransienLeffects in nucleation.
The derivation of t,he rate laws center around tke
pmblem of ~~inge~~el~t:. The newly formed grain is
assumed to grow at cor~tsnt radiaI velocity until it
impinges on another growing grain. ft then st~3p3
growiq along the area of e#nta.i.&1%KiIl be e~i~~eR~e~~~
ta use a device used by Avrami,@) a.nd Johnson and
Mehl called extended volume fraction &X4.This is the
sum of the volumes of all grains, divided by the total
~olumc, ~s~~~i.~~gthat the grain5 never stop growing
and t*hatnew grains keep nucleating at the same rate
in transfornl~ as well us untransf~r~~ed material,
XT, can esmd unity, 1-f nucleators is randomly
dis~ri~~uted,then the a&al volume fraction X is
rigoronsly given by
xEZZ.2 -@--X6

It) +I1 be necessary La define an extended area


fraction and an extended line fraction. The extended
area fra~caiionYe is the sum of aff areas of ~~~~rsee~io~
af the extended grains with a plane divided by the
total area of the plane. If t*hese ~n~rsectio~~s are
randomly distributed on the plane, tie actual area
-0 X>l
fraction
Y-l: 1. -&?-ye
distributed on R
The exkended Iine fraction Z, is the snm of all lengths p = 1- g-IV*,
of a line intercep%d by exkended grains divided by the The v&me oecnpied by nodules ~~iginat,ing fsom &
length of the line. ITfthese ~l~t~r~e~~~~~~s
are modernly uni% area of B is &en
~istrib~~~edon the line, the actual Iine fraction Pm

For the case of grain boundary and grain edge The exknded volume fraction due to a b~und~y area
n~~cleat~ reactinns, two types of ~rn~~ngel~en~wiU be S per unit volume
treated separat,ely. Thie first type is impingement;
among nodules ~r~ginati~~~from the same pIma OF where
sdge. For example, if this ~oenrs early in the reaction,
the individual nodules would cease growing parallel to
the plane or edgee, further growth only occurring
~~r~en~~~~a~ $0 the edge or plane. Armeq3re8sion is
derived for bhe total volume of the nodules o~gina~ing
462 ACTA METALLURGICA, VOL. 4, 1956

and if this boundary area is assumed randomly time at a time between t and t + dt is e-c dt. The
distributed in the specimen extended volume fraction at time t is therefore

X = 1- exp [-b,-13f,(a,)] (3) t4?7


x, = c - G3(t - T)~ exp ( -1,~) &-
fs(a,) was evaluated numerically, using Simpsons I0 3
id&
and = b~-3~(u~} W
Grain Edge Nucleation X = 1 - exp [ -b,3f,(a,)]
Consider a straight-line edge E of infinite extent where a, = I,t
having a specific nucleation rate I,. Consider an
arbitrary line P parallel to E at SLdistance T. A
nodule starting to grow at time r from E will intercept
on P a length ~~(~~)= ac3 - 3ac2 + &z, - 6 (1 - e-Q),
2[Gz(t - ~~~- +]lfi when G(t - T) > r, which is the same as the expression derived and
0 G(t - T) < r. tabulated by Avrami for a limited number of randomly
distributed nucleation sites.c4) The three functions
The extended length fraction at time t due to nodules f(a) are tabulated in Table 1.
starting at a time between 7 and r + dr is

aZ, = 21, aT [G2 (t - 7)s - ry G(t - T) > r, DISCUSSION

= 0 G(t - 7) ( T. It will be noticed that all of the above rate laws can
be plotted as log log (111 - XI) vs. log t to give
Integrating with respect to t and substituting x for
characteristic master curves, Figs. 1-3, in which two
r/Q& we get
parameters are undetermined as additive scale factors.
__- 1+2/l-9 Thus, instead of a family of curves obtained by
d1-~2-~210g--~-~- - x<l,
2 I
Johnson and Mehl, a single curve is obtained. The
parameters of Johnson and Mehl are related t,o the
zzz.z 0 x> 1. parameters a and 6 in the following way: The bs are
The volume occupied by nodules originating from a equivalent to Johnson and Mehls shape factor 1, in
unit length of E is that they can both be expressed as 8jD4/G times a
1 geometrical constant. The us are respectively
v,z m2?7rZ ar = 2rG2t2 ~(1 - eeze) ax. (4) proportional to bs13Z, b,l12Z, and b,Z. All curves have
10 s0 slope 4 when a is small and approach the equation
Randomly distributing an edge length L in zt unit X = 1_ p/3&GP
volnme will give
which is identical with that, obtained for randomly
X = 1- exp f-b,-lf,(u,)]
placed nucleation sites. In the vicinity of a = 1, the
where
curves change slope. This change of slope is due to a
process which we shall call site saturation. In the case
of corner nucleation it occurs because there are only a
limited number of corners. In the case of grain
boundary and edge nucleation it occurs because the
nucleation sites are not randomly distributed, but
$,(a8) was evaluated, using Simpsons rule. are in the vicinity of other nucleation sites. Hence,
they have a greater probability of being transformed.
Comer Nucleation Therefore, the fraction of boundary area or edge
Here there is no problem about impingement length transformed is larger than the volume fraction
between nodules starting from the same corner. transformed, and the nucleation rate which is pro-
The first nucleus is the only one which will determine portional to the untransformed area or length drops
how much volume will contribute to the extended off faster than the untransformed volume. In the
volume. If the specific nucleation rate per corner is I,, limit of a > 1, nucleation is so small conlpared to the
then the fraction of corners nucleating for the first untransformed volume fraction that the curves can be
CAHN: GRAIN BOUNDARY SUCLEATED REACTIOXS 463

approximated by ones derived on the assumption 10 O-


that all nucleation occurred everywhere at time zero.
For small values of the parameter b, the increase in
probability for a boundary to be transformed com- t 1O-

pared to the rest of the material is small and the site


-7
saturat,ion will not occur until the sample is almost I-
PI l-
completely transformed. It will occur early in the .?
reaction if b is large. Substituting the approximate
d
values of S, L, and C into the expressions for b, we get II
0 1.1
2
0

O*(11-

O-0( )l-
0.1

Frc. 2. Master curve for transformations which ntcleaLe


100 on grain edges.
or

10
t which is independent of grain size.
At very large values of b the sites would saturate
-, t: , very early in the reaction, and furt.her nucleation
0
would cease. For a grain boundary nucleated reaction
?
the t,ransformed region would occupy an ever-
2
y; 0.1 thickening slab of material with the original boundary
at its center. The rate law would then be of the form
2
e
001
which is wha,t equation (3) approaches. Sirnila.rl~,
one would expect that for edge-nucleated reactions
O.OOll
0.1 10 1 100
as -
FIG. 1. Master curve for t,ransformations which nucleat,e which is the limit of equation (5) for large values of b.
on grain boundary surfaces.

The requirement that site saturation occurs early in


the reaction can be obt,ained from the Figs. l-3 by
finding a value of b for which the reaction would bend
in the vicinity of half reaction. From this, one gets
that whenever
g, > 6 x lo3 G/D4,

Ii,, > lo3 G/D, W


Or

site saturation can be expected to occur early in the


reaction.
The time at which saturation occurs is
t Z (I *~2)-1/3 a, -
Fm. 3. Xaster curve for transformations which nncloate
zzzz(f,G)-13,
on grain corners.
454 ACTA METALLURGICA, VOL. 4, 1956

the transition to saturation be observable. Even then,


especially for corner nucleation, the kinetic data will
not curve much in the observed range, but will appear
to give a fairly straight line of intermediate slope.

The Half&me of a Reaction and Its Dependence on


Grain Size
The time required for a reaction to reach a certain
stage of completion is a convenient parameter for
cataloging the speed of a reaction. The relationships
involving the half-time will be discussed here, but

0.01
they can be generalized to the time for any fraction
0.1 1 10 100 1000 completion by substituting for ln 2, In (l/l - X),
where X is the desired fraction.
(2, M,,, W
Substituting 0.5 for X, and a = a(t,n), where tlls is
FIG. 4. Theoretical curves for half-times of transformations
which nucleate on grain boundary surfaces.
This Paper
Johnson and Mehl------

For corner nucleation equation (6) becomes

X = 1 _ e-- $CG3t3

which is what one expects for a limited number of


sites which nucleate at an early time.
The range from 17/o reaction to 99% reaction is
quite short, only a factor of 500 on the log (l/l - x)
scale. or 2.7 cycles on the log log (l/l - Z) scale.
Since this is the limit of observation, most kinetic
0.01
observations will be entirely in the straight-line
0.1 1 10 100 1000
extremes of Figs l-3. Saturation will usually occur
E
before 1% reaction, or not till after 99% reaction. LxGt,,2 -
G
Only in those reactions where parameter 6 is such that FIG. 6 Theoretical curve for half-times of transformations
which nucleate on grain corners.
the inequalities (7) are close to being equalities, will

the half-time, into equations (3), (5), and (6), we get


upon rearrangement

6 l/3 =fs(G
S
In2

b _fe(ae)
e
In2

,I,3 =fc(o
c
In2 .

These equations may be used to find the relationship


between the Is, CTI,
D, and t,,%,for the various types of
nucleation sites.
0.01 0.1 10 100 Of particular interest is the relationship between
($)%k,,, _ t 1,2 and grain size, keeping the Is and G fixed
(constant temperature).
FIG. 5 Theoretical curve for half-times of transformations
which nucleate on grain edges. Substituting the approximate expressions for
CARN: GRAIN ROUKJJARY NUCLEATED REACTIOXX 45.5

S, L, C into the bs and rearranging, we obtain should incrertse with the inverse diameter squared.*
At sufficiently la*rgegrain diameter, the grains have no
trouble nucleating, and the half.time is the time
required for the growing transformation product to
consume balf of its grain, which va.ries directly as the
d&meter.
The following conclusions can be drawn from t,he
curves: (1) If, and only if, site saturation occurs,
D = 4.18 [f&~~)]~~,
G4/2 is a8pproximately equal to O.lD. This corre-
since sponds to the upper portion of the curves, and is
independent of the type of nucleating site. (2) tr,, can
never be appreciably fess than 0.1 DIG for any reaction
where nucleat,ion occurs only on boundaries or
i~ltersect~ons of boundaries. (3) At su&iently tow
values of the parameter, b = ~~~4lG), the half-time is
given approximately by (&Gs)-rI, if the trsnsforma-
tion prodnct cnn cross boundaries. This is the same
result one would expect for homogeneous nucleation.
Since the fs are i~de~endeni~ of ,aa,in size, sub-
a plot of as against9.7 $,(a,); as against 8.8r~e.(~~)~~~3~
&it&ion into ($?Ga)--1~4 leads to the result tha,t t,,, is
of a, ngainst 4.18 ~C(uC)]1/3 is a plot of I) against Gi& proportional t.o the .ZW4 for boundary nucleation,
for the various types of nucleation, v&h D and G&, EPs for surface nucleat~ion,Df4 for corner nucleation,
plotted in the same units and Gfl to the appropriate as well as D1 for site saturat,ion and I>a for homo-
power as the scale factor. This is plotted in Figs. 4-6 geneous nueleiltion.
on a double log plot. The scale factor is now an
ndditive constant. Since it is the same additive
Rates if More Than One Ty-pe of&&? is Active
constant, the only permissible translation for the
Whenever more than one type of site i+ active,
master curves, if fG is unknown, is along a 45 line.
the impingement problem is considerably more
Also, points having a certain vahe of ~~~~!~~~~ are
oompficoted. Certa*inlimits can be discussed, however.
constrained to he on a certain 45 tine. A (~~~~~~~~)
Until one type of site begins t,o saturate, the rate law
axis is therefore indicated.
can be approximated by
l?igs. 4-6 can be used to obtain relationships
between Gtriz, D, and f/G, or any of their ~ornbin~t~o~s~
if the type of site responsible for nucleation is known.
A knowledge of the parameter It for example is where .& is the sum of all the $%.
sufficient to determine the value of i~~~~~~~ and the Because of t,he geometry, when the boundaries
parameter a. An ex~rimenta~~y determined relat,ion- saturate, the edges and corners saturate too, regardless
ship among these parameters oan be used to determine of their specific nucleation rate. When the edges
what type of sit,e is xesponsible for nucleation. For saturate, the corners saturate too, while the boundaries
comparison, the curve obtained from Johnson and can continue to nucleate. When corners saturate,
Mehls equations is also plotted (Fig. 4-dotted curve). both edges and boundaries can continue to nucleate.
The agreement is very good along the upper portion The sat.uration of a type of site Emits ail further
(rl_IP~$). However, one sees immediately that one nucleation on sites of lower dimensional~ty. t_
consequence of the ass~l~ption tha~t the trans-
formation product cannot cross a grain boundary is *Another way of looking at it is that. w-hen the grains
that, at small enough grain size, the reaction rate become sufficiLtntly small, the volume nucleation rate will
increase as tho surface area or as l/t>, while the amount of
decreases as the grain size decreases. This is apparent transform&ion per nucleus will decrease as P. The over-all
if one considers the consequences of that assumption. rate will decrease as P, and the half-time will incres,se I~Rl/D*.
For grain-edge and grain-corner nucleat,ion the half-times
At sufficiently small grain size the time for half- will similarly depend on D- end Do instead of 2P2 and Da.
reaction will be that required for half of the grains to $For convenience, we shall refer to the dimensionalitg of Q
site as heing 0 for corners, 1 for edges, 2 for boundaries, 3 for
obtain at Last one nucleus. However, t;he area hmnogeneous nucleation. It is intended only as a notation,
a.vailable for each grain t,o receive a nucleus decreases and what foXlows does plot hold for nucleation on other types of
sites to which a ~~e~siona~~y can be assigned, such as
as the square of its diameter, and the half-time vacancies, dislacation, etc.
456 ACTA METALLURGICA, VOL. 4, 1956

What occurs when a site saturates depends therefore


on the hype of site as well as the relative values of
the 8s. The important site initially is the one whose
3 is the largest. Prom the inequalities (7) one can see
that only sites of lower dimension than this site can
saturate at an earlier time. If they do, they cease
nucleating, and their effect on the rat*elaw is one of
changing 2 in equation (9) to a lower value. When t.he
type of site with the largest contribut.ion to g
saturates, the rate law is approximated by a,dding the
extended volumes of sites, of higher dimensionality
only, to the extended volume of the site whose rj is
largest. If the 1?)7sare much smaller, these sites will
never oontr~bute much. If t,hey are of comparable
magnit~~de, the react,ion rate wiif eventualfy be
domil~at.ed by the new mode. The final stage will be
u 05 1.5 2.0
dominated by the mode of highest dimensional&y
I?-
where the inequalities (7) hold.
FIG. 5. Grain boundary nucletbtion
The half-time will beof the orderof O.lD,/G whenever _---_- Chin edze nucleation
one or more types of sites saturate early. If none ---- Grain coker nucleation
R,elative nucleation energies.
saturate, it will be given approximately by (J&P-1/4.
Therefore the half-time will depend on grain size in
a way characteristic of the mode which ~o~~tribut~ AF, could be expected to dif&r from t-hat of the other
most to t,he volume nucleation. types of sites.
The calculation of nucleation rate is critically
NUCLEATION RATES dependent on the assumption one has to make to
calculat-e AF*. However, to illustrate the relation-
It was noted in t~helast section that it is necessary
ships obt,ained, we shall use the calculations of Clemm
to know something about the relative nucleation
and Fisher,(l) who assumed no strain energy, and a
rates for the various types of sites in order to determine
surface energy which was independent of orientation
which rate law the system will follow. It is also
and ~ur~~a~ur~. One can express their value of
neeessay to know something about the nucleation
A.F, a,s AFj* = AjAFe*, where AFe* is the homo-
rate relat,ive to G/P in order to determine whether a
geneous nucleation energy and the param&er Aj
site will saturate.
which is a function of the ratio K of bonndary energy
We will assume that the specific nucleation rates
to nucleus surface energy only. Fig. 7 is a plot of
are given by equations of the form
rlj versus t.his ratio. It will be noted that B decreases
moriotoni~ally as one goes to nu~l~a~io~~sites of
wt lower dinlensi~~~~ality. The expo~~e~~tial term in
equation (11) favors sites of lower d~tnensionali~y.
where Y is a frequency factor, p the density of sites,
The degree to which this occurs is a function of AFo*
AP* is the minimum free energy required to form a
as well as the differences in the As for the various sites.
nucleus, and AFd is the free energy of activat,ioil
Opposing the energy consideration is t.he density of
for a nucleus to continue to grow. If S is an effective
sites effect, which is (6/QAj, and which favors sites
grain boundary thickness and ~athe number of atoms
of higher dimensionality. The ratio of these two
per unit volume, p approximately equals ~(6/D)~-j.
opposing factors
Y and AFh can be assumed tzobe the same for a.11 sites.
The volume nucleation rate for each site is then
approximately

is a useful function. Forming the ratio of nucleation


rates on sites of dimensioI~~~1it.y
i and .i, we get that

where j is the dimensionality of t,he site. This can be


assumed to include hon~ogeneous nucleation, although
CAHN: GRAIN BOUNDARY NUCLEATED REACTIONS 457

Fig. S is not a plot of nucleation rat#es. It wiI1 be


useful to sketch in several const,ant nucleation rate
curves. If we assume vnexp (-AF,)/(kir) = lo30
cm-3 se&, D = 1O-2 cm, 6 = 10-s cm, we can obtain
four curves (Fig. 9). The lowest figure is that for
& = 1 cmW3see-l, which can be taken as a lower limit
of nucleation rate, the next three curves are those
which obey the inequalities (7). The curves for
saturation of sites of higher dimensionalities are
continued into regions of lower dimensionality, since,
after saturation of the lower site, the higher sites will
continue to nucleate and will saturate too if R is
large enough. From Fig. 9 it is apparent that under
certain conditions one might never see nucleation of
sites of lower dime~ionality, because the under-
cooling required to get appreciable nucleation might
place the reaction at a value of R where a higher mode
of nucleation predominates.
In order to estimate what to expect as a function of
undercooling, let us express APO* in terms of a
0 05 1.0 1.5 2.0
reduced temperature. 0 = TIT,,,, where T,,, is the
k-
FIG. 8. Regions showing which type of site has equilibrium temperature. AFo* is then approximately
the highest initial nucleation rate.

Al?,* = l?! __-?:--.._


_f__
and 3 (AII?)~kT,, (1 - 8)28
;j! log, $, = (i - j) R - (A$ - Aj)
0* 3 where AH is the heat of the reaction, and y is the
The requirement that &$ is greater than &+ is then nucleus surface energy. Then
that 3fAf02kT,,, log D/S
(i -j) R < JIi - Ai R =

f @(l - 0)s
167~y3
and the maximum R
(AH)2 Teq log D/S
R *,tax- -___-_ at 8 = l/S.
36ay3

If an interval of R can be found where these


inequalities hold for all j, then in this interval, sites j
will contribute most t,o the nucleation rate. For the
As determined from Fisher and Clemm, the sites
which will have the highest nucleation rate are t

the corners when R < A, - A,


the edges when A, - A, < R < A, - A,
the boundaries when A, - A, < R < 1 - A,
and homogeneous nucleation will predominate when
R > 1 - A,. Fig. 5 is a plot of these regions.
It is quite conceivable t,hat in an actual system
some sites will exist which will never contribute
significantly t,o N. If, for example,

A, > &-;/! k-
FIG. 9. Typical example showing conditions for bar+
edge nucleation would never predominate, and the detectable nucleation 1; nucleation sufficiently rapid for
corner saturation 2; edge saturation 3, boundary surface
area marked edge in Fig. S would be absent. saturation 4.
455 ACTA METALLURGICA, VOL. 4, 1956

R rises initially as the undercoo~ng squared reaehes Similarly, one can derive an expression for homo-
GM, at e = 8, and has a very long plateau. If R,,, geneous nucleation, using J, for the number of nuclei
is small for certain values of K, only modes of lower present at time zero. This leads to
dimensionality will ever predominate. If R,,, is large,
R in the regions of interest in Figs. 8 and 9 can be X,=l.-eq-:;IG3t3[Jv
taken as proportional to undercooling squared.

MORE GENERAL RATE LAWS

For the pear&e reaction it has been established


At high nucleat,ion rates and long times, equation ( 12)
that the nucleation rate is not constant,, but a function
reduces to
of time.f5s 6, This may be due to the fact that it takes
X = 1 - ,-2SGL
a finite time to establish a steady-stat,e nucleation
rate,(T) or as in the case of eutectoids it might be due and equation (13) reduces to
to the fact that two phases have to be nucleated, the
X = 1_ e-dG2tZ
second nu~leat~g in the changing environment of the
first growing by itself, or nucleating on an ever- Since
increasing surface of the first.(s)
Hull, Colton, and Mehl(Q have derived the rate law
for homogeneous nucleation, when the nucleation
rate can be expressed as a power series of time. at high nucleation rate and long times, equation (14)
It is fairly simple to generalize the derivations of reduces to
the rate laws given here to include a time-dependent
nucleation rate I as well as the prior existence of
nuclei, which instantan~usly start growing at These limits are identical w%h those previously
time 0. Let us call the number of such nuclei per derived for constant nucleation rate. Site saturation
unit area of boundaries J,, per unit length of edges J,, exists and leads to a rate law which is independent of
and the fraction of corners which have these nuclei the nucleation rate, whether constant or not.
J,. Then as before we will assume that only one type At the other extreme, far from saturation, equations
of site is active. (12), (13), and (14) reduce t,o equat,ion (15). This is
The deriva.tions lead to accomplished by expanding the exponentials in the
integrand into a power series and interchanging the
order of integration.
Far from saturation, then, the nucleation rate does
not enter as an average as has often been assumed,
but as a third moment about the time t. In other
words, the nuclei are weighted according to the cube
of the length of time they have been in existence.

for grain boundary nueleat~on; The determination of the n~~cleat,ion rate from a
rate law is therefore a very complicated problem.
X, = I - exp Even for equation (15), which has a simple solution
mathematically,
1 P log (1 - X)
x exp & = - s7Tc3-.-.-~-~~~
at4

x I,((1-g2- Y2]12dr))
dy]) (13) it is unlikely t,hat kinetic data can be obt,ained with
sufficient accuracy to make t,his solution useful.
for edge nucleation; and If the nucleation rate follows an expression of the
type
X,=1-exp(~CC$3~~-(l-J~)~
Ij = Njt

X 1,(1 --:I3 X exp (-llOdi) dr]) (14) it is possible to integrate equations (12-15). A plot of
log log (l/l - 2) against log t would be similar to
for corner nucleation. those of Figs. 13, except that the initial part of the
CAHN: GRAIN BOUNDARY NUCLEATED REACTIONS 459

curve would have slope 4 + n. The parameters a and where K = B,S, B,L, or B,C respectively for grain
b would become of the form boundary, edge, or corner nucleation. The dependence
a, = (BSG2)11(a+n). t of h/2 on grain size far from saturation would then be

B,
b,= ~
S:j+nGl+n

a, = (B,G)21(P+n) - t where j is the dimensionality of the site.

b, =
Be
Ll +nlZC;rl
+?I
REFERENCES
a = B l/(1+12) . t
c G
1. P. J. CLEMM and J. C. FISHER Acta Met. 3. 70-73 (1955).
b, =-
Bc 2. W. A. JOHNSONand R..F. MEHL Trans. Amer. Inst: Min.
(J(l+n)/3@+n Met. En+ 135, 416-442 (1939).
3. M. AVRAMIJ. Chem. Phys. 7, 1103-1112 (1939); 8,212-224
The half-time at saturation would be independent of (1940); 9, 177-184 (194-l).
4. J. E. BURKE and D. TURNBULL Progress in H&l Physics
the nucleat.ion rate, while the expected half-time at 3, 226 (1952).
low nucleation rates would be 5. E. SCHEIL and A. LANGEWEISE Arch. Eisen~hiittenw 11,
93 (1937).
6. F.C.HULL,R.A.COLTON,~~ R.F.MEHL Trans. Amer.
t,,, = Inst. Min. Net. Eng. 150, 185-207 (1942).
7. D. TURNBULL Trans. Amer. Inst. Min. Met. Eng. 175,
774 (1948).
8. J. C. FISHER, from ASM Symposium on Thermodynamics
in Physical Metallurgy, p. 201-241.

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