Sie sind auf Seite 1von 4

THE INFLUENCE OF GRAIN BOUNDARIES ON THE NUCLEATION OF SECONDARY PHASES*

P. J. CLEMM and J, C. FISHERt

In calculating the critical energy required for the nucleation of grains at two, three and four grain junc-
tions it is necessary to know (1) the volume of the nucleus, (2) the surface area of the nucleus, and (3) the
matrix grain boundary area which has been absorbed by the nucleus. These three quantities have been
calculated as a function of (1) the dihedral angle between the surfaces bounding the nucleus and (2) the
radius of curvature of the bounding surfaces.
To illustrate the use of the calculated equations the critical energy for the nucleation of ferrite from
austenite at two, three and four grain junctions has been calculated.

L’INFLUENCE DES JOINTS INTERCRISTALLINS SUR LA GERMINATION DE


PHASES SECONDAIRES

Pour calculer la valeur critique de l’energie requise pour la germination des grains nouveaux aux jonctions
de grains, doubles, triples et quadruples, il est necessaire de connaitre (1) le volume du germe, (1) l’aire de
la surface du germe, (3) l’aire de la surface des joints de la matrice qui ont et6 absorb& par le germe. Ces
trois quantites furent calculees en fonction de (1) l’angle solide entre les surfaces qui limitent le germe,
(2) le rayon de courbure de ces memes surfaces.
En vue d’illustrer l’emploi des equations deduites de cette facon, on a calcule la valeur critique de l’energie
pour la germination de la ferrite B partir de l’austenite aux jonctions des grains, doubles, triples et quadruples.

DER EINFLUSS VON KORNGRENZEN AUF DIE KEIMBILDUNG SEKUNDARER PHASEN

Will man die zur Keimbildung von Kristallen an Zwei-, Drei- oder Vierkornpunkten notwendige kritische
Energie berechnen, so muss man (1) das Volumen des Keimes, (2) die Grosse der Oberflache des Keimes
und (3) die Griisse der von dem Keim absorbierten Korngrenzenthache der WirtskGrner kennen. Diese drei
Grijssen wurden als Funktion von (1) dem diedrischen Winkel zwischen den den Keim begrenzenden Flachen
und (2) dem Kriimmungsradius der begrenzenden Flachen berechnet.
Urn die Anwendungsmijglichkeiten der theoretischen Gleichungen zu illustrieren, wird die xur Keimbildung
von Ferrit aus Austenit an Zwei-, Drei- und Vierkornpunkten erforderliche kritische Energie berechnet.

In calculating the nucleation rate of a second phase B ing the new phase B; let the new grain boundary area
in a homogeneous solid matrix A the critical nucleus is formed between grains A and B be
spherical, and the critical energy that must be supplied
AAR= br2,
by thermal fluctuations (in the absence of strain energy)
is and let the volume of the new phase B formed be
~&TAB
w*=-, v= c13.
3Af,2 Here a, b, and c are coefficients that are functions of the
where W* is the critical energy, TAB is the interfacial or A-A and A-B grain boundary energies. Then the work
grain boundary energy between phases A and B, as- done in forming a nucleus of volume V is
sumed isotropic, and Afv is the difference in volume free
energy between phases A and B.’
W=YABAAB-YAAAAA+Afvl/,
or
In a polygrained metal, however, the nucleation of a
second phase is much more likely to take place at a
grain boundary or at the junction of several grains, The work of formation of the critical size nucleus corre-
since at these sites the grain boundary that is eliminated sponds to dW/&=O, for which
by formation of a nucleus provides an energy source
that can supply some of the needed critical energy for 4 (bYAB- W’A$
nucleation, thereby reducing the amount to be supplied c2Af,’ ’
by thermal fluctuations.
Let the grain boundary area that is eliminated be- The problem of grain junction nucleation then is
tween A-A grains in forming the nucleus of a new phase reduced to finding the coefficients a, b, and c, corre-
B at a grain junction of phase A be sponding to various types of grain junction.
AAA= ar2, TWO-GRAIN JUNCTIONS

where r is the radius of curvature of the surfaces bound- First, the case of a simple grain boundary or two-
grain junction will be considered. The grain boundary is
* Received August 4, 1954.
eneral Electric Research Laboratory, Schenectady, New
assumed to lie in a plane, and it is assumed that all
Yo!lz grain boundary energies are isotropic.
ACTA METALLURGICA, VOL. 3, JANUARY 19.55 70
CLEMM AND FISHER: NUCLEATION OF SECONDARY PHASES 71

PSR are the traces of the area AAB. Then

= * sin20r2,
or
a = T sin20.

=4x(1-cose)r2,
and
b=&(l-co@.
Further,

The critical nucleus of the newly formed phase B will


have the shape of a symmetrical lens as shown in Fig. 1.
=13*(2-3
cose+cos%)1-7,
The dihedral angle at the edge of the lens is determined and
by equilibrium of the interfacial energies. 2R
Letting the grain boundary energy between the two A c=$2-3 cosO+cosW).
grains be YAA ergs/cm3 and the grain boundary energy
between A and B grains be TAB ergs/cm”; then the These equations may be represented in somewhat
forces exerted by the grain boundaries on a length of the more convenient form if we let
perimeter of the lens are as shown in Fig. 2, which is
YAA
k=cose=-
hALi’

rAe DYNES/CM

FIG. 4.
FIG. 2.
Then
a=?r(l-k2),
drawn perpendicular to the lens perimeter at point P.
For equilibrium at point P, or at any other point along b=h(l-k),
the edge, the angle 0 must be such that
c=;(?-3k+k3).
YAA
cos e=--
hAB THREE-GRAIN JUNCTIONS

Here the volume of the newly formed phase particle


Figure 3 shows a diametrical cross section of the lens
will be bounded by three equivalent spherical surfaces
where PR is the trace of the area AAA and PQR and
as shown in Fig. 4.
The dihedral angle at the edge between two surfaces
will again be determined by the force diagram illus-
trated in Fig. 2.
For the three-grain junction the area and volume
coefficients are as follows :
a=3/3(1-k*)-k(3--4K)t,

b= 12(+-k/3),

FIG. 3.
,-2ci+;(3--IY)+-/31(3--y)
1,
72 ACTA METALLURGICA, VOL. 3, 1955

where The numerical quantities used in the calculations are


1 as follows :2 *
a!= arc sin
2(1-k+ YAA Austenite-austenite 850 ergs/cm2
TAB Austenite-ferrite 600 ergs/cm2
k Afv (Austenite--+ferrite), -4.3.5X lo* ergs/cm3.3
The results when plotted are as shown in Fig. 6,
showing clearly that four-grain junctions are the most
FOUR-GRAIN JUNCTIONS
favored nucleation sides for ferrite nucleation (W* is the
smallest), three-grain junctions next most favored,

/-
Here the volume of the newly formed phase will be
bounded by four equivalent spherical surfaces. It is a followed by two-grain junctions, and finally grain
spherical tetrahedron, as sketched in Fig. 5. The area interiors.
Another conclusion which may be derived from the
equations for a, b, and c and from the force diagram of

0
Fig. 2 is that when TAA/2TA&? exceeds the following
critical values the forces at the grain edges will no longer
be in equilibrium and there will be a continuous free
0’ energy decrease as the new phase grows from zero size.4

YAA
21/AB(=W

FIG. 5. CC
grain interior

and volume coefficients are 2-grain junction 1

Vz
o=J(&(l--e)-K[ (l-k’-;)‘?]/, 3-grain junction
-2(= Oe8@)

4-grain junction (2/3)*( =0.817).


,_24(%,-,),
Whenever YAA/i?YAB exceeds these critical values the
growth of a new phase will be controlled not by nuclea-
tion but only by its growth rate and the amount of grain
c=2( +)+kK[ (1-k’--$)‘$K]
boundary present per unit volume.

-2&(3-k2) , Y

7
1 !? W l I MAX. ENERGY 1

where GRAlN INTERIOR : I.913 I IO-’ ERGS


0 2 GRAIN JUNCTION : 0220x IO-’ ERGS
I
0 3 GRAIN JUNCTION : O.O4?aGxlO~’ ERGS
. 4 GRAIN JVNCTlON : 0.0096a10~ ERGS
$
_ 0.25 r

K
$J= arc sin
2(1-k2)+’

fl-k(3-K2)i
6 = arc cos
K(l-k2)t ’

To illustrate the use of these equations, the energy


required to form a ferrite grain in an austenite matrix
can be calculated and plotted as a function of the radius
of curvature of the nucleus surfaces for the case of a
RACIUG OF CURVATURE OF BOUNDING SURFACES
ferrite grain nucleating OF FERRITE NUCLEUS

1. Entirely within an austenite grain FIG. 6. Energy of ferrite nucleus formation as a


function of surface curvature.
2. At a two austenite grain junction
3. At a three austenite grain junction * The temperature at which these values were determined is in
4. At a four austenite grain junction. the neighborhood of 1000°K.
CLEMM AND FISHER: NUCLEATION OF SECONDARY PHASES 73

ACKNOWLEDGMENTS REFERENCES

The authors wish to extend their thanks


to Dr. J. H. 1. M. Vollmer, “Kinetik der Phasenbildung,” Theodor Stein-
kopff, Dresden, 1939.
Hollomon for suggesting the to Dr. R. L.
problem, 2. L. H. Van Vlack, “Intergranular Energy of Iron and Some Iron
Fullman for helpful discussions of the geometry involved Alloys,” Trans. A.I.M.E. 191, 251 (1951).
3. J. C. Fisher, “Influence of Boron on the Hardenability of
and to Mrs. N. V. Doyle for performing the numerical Steel,” R.L. 1031, General Electric Research Laboratory,
calculations. January 1954.