ON THE MECHANISM OF SERRATED GRAIN

BOUNDARY FORMATION XN Ni-BASED SUPERALLOYS

A. K. KOUL’ and G. H. CESSINCER’

‘Structures and Materials Laboratory, Montreal Road, National Research Council, Ottawa,
Canada KIA OR6 and “Central Laboratory, Brown Boveri & Cie, CH-5401 Baden, Switzerland

(Recehed I5 Dccrn3hrr 1982)

Abstract-Grain boundary serration is studied as a function of cooling rate in a number of Ni-based

superalloys. e.g. IN 738, Nimonic 115 and Nimonic 105. The mechanism is related ta y’ precipitation in
these alloys and a higher y’ solvus temperature than the M,C, solvus temperature appears to be a
prerequisite for the development of serrations. A model based on the grain boundary primary y’ particle
movement causing the displacement of the local grain boundary segment and initiating serrated grain
boundary formation has been proposed.

R&m&--Nous avons ttudii la formation de joints de grams dentelis en fonction de la viteaae de

refroidissement dans un certain nombre de superalliages a base de nickel, comme par exemple IN 738.
Nimonic I IS et Nimonic 105. Dans ces alliages, le mecanisme est lie a la precipitation de y ’ et une
temperature du solvus de y’ plus Clev& que celle du solvus de M& semble une condition prcalable a
la formation des deutelures. Nous proposons un mod&k dam ie quel le mouvement des partioules
intergranulaires primaires de y’ provoque le d&placement local d’un segment du joint de grains et entraine
la formation d’un joint de grains deatelt.

Zuaammeuf~An einer Rcihe van Superlegierungen auf Nickelbasis, LB. IN 738, Nimonic 115und
Nimonic 105, wird die Korngmnzenfacettierung in Abhlngigkeit von der Abkiihlmtc untersucht. Der
Mechanismus hHngt mit dem y’-AusseheidungsprozeB in diesen Legierungen zusammen. Es seheint, daR
Vorbedingung !Iir die Ausbildung der Famtten eine y’-Solvustemperatur ist. die h&her als die
M&Z,-Solvustemperatur ist. Ein Modell wird vorgesehlagen, das von den y’-Teiichen an der prim&n
Komgrenze ausgeht. Die Rewegung dieser Teilchen an der prim&n Komgrenze ausgeht. Die Beweguug
dieter Teilchen an der prim&en Korngrenze ausgeht. Die Bewegung dieser Teikhen emeugt eine
Verschiebung des lokalen Komgrenzbereiches und verursacht die Bildung der facettierten Komgrenee.

1. ~~RODU~ION the grain boundary segment bb is shorter than the

segment aa in Fig. i, the localized boundary dispkce-
Furnace cooling treatments designed to generate
ment occurs due to the lower energy configuration of
serrated or zig-zag grain boundaries have long been
the segment bb, thus forming a serrated grain bound-
used to improve the stress-rupture properties of ary. However, no quantitative measurements of
20-I IP austenitic stainless steel [l-3]. More recently,
controlled furnace cooling treatments have been used
to develop serrated grain boundary structures in
wrought and powder processed Ni-base superalloys,
e.g. Nimonic 115, IN 792, Rem! 95 and Astroloy, in
order to improve the high temperature impact
strength and creep ductility in these materials [4-g].
The beneficial elfects of serrated grain boundaries on
the stress-rupture properties of investment cast Ni-
base superall superalloys, e.g. IN 738. have also been
pointed out in the literature ]9]. These grain boundary
serrations are said to impede grain boundary
sliding, thereby improving the overall high tem-
perature creep properties [4-91.
In 20-I II’ austenitic stainless steel, the precip-
itation of coarse grain boundary M2,C6 carbides was
held responsible for the creation of grain boundary Fig. I. A model for serrated brain boundary formation
based on M&, precipitation. Straight grain boundaries
serrations [l-3). Grain boundary M,,C, precipitates
(a-a) formed on solution treatment and serrated grain
arc assumed to grow from one grain into the matrix boundaries (b-b) formed after M2& precipitation (Refs
of the adjacent grain such as indicated in Fig. I. Since H-31).
1061
1062 KOUL and GESSINGER: ON SERRATED GRAIN BOUNDARY FORMATION

Fig. 3. Experimental technique employed to determine

Migratory forces octlng on 0 groin serration wavelength (i) and amplitude (A).
(0 1 boundary during slow cooling from
solution treofment temparotura

SECONDARY y’ forces involved in the creation of these serrated grain

PRIMARY y’ PAR’ICLES
boundaries will be dealt with at a fundamental level.

2.‘EXPERIMENTAL MATERIALS AND METHODS

L In order to broaden the scope of the investigations,

ORIGINAL GRAIN BOUNOARY
Sarroted grain boundaries formed
(bl cooling from solution treatment to
portiol solution treotment temperatures
Fig. 2. A model showing serrated grain boundary formation
on cooling from solution treatment through y’ precipitation
range to PST (Refs [5] and [q).
M& carbide length and the amplitude of serrations
have been presented to demonstrate the viability of
this hypothesis.
In contrast, slow cooling through the y’ precip
itation range is considered essential to form serrated
grain boundaries in Ni-base superalloys [7-IO]. The
mechanism of serrated grain boundary formation is
thought to be associated with the heterogeneous
nucleation of y’ at the grain boundaries, and the
migration of grain boundary sections in between the
primary y’ particles as shown in Fig. 2(a) and (b).
These grain boundary segments supposedly continue
to migrate until y’ forms homogeneously throughout
the grain at a lower temperature. If the material is
cooled rapidly through the y’ precipitation range, the
heterogeneously formed y’ particles are small and the
boundary migration is limited [7-81. However, it is
not clear why the grain boundary segments in be-
tween the primary 7’ particles should be mobile when
cooling from a high temperature. The observations
indicate that the basic mechanisms of serrated grain
boundary formation are but imperfectly understood.
This paper therefore aims to present some system-
atic observations and explanations on the influence of
varying cooling rates on the serrated grain boundary
formation in Ni-base superalloys. Also, the driving
the materials used in this study were investment cast
on IN 738, wrought Nimonic I15 and Nimonic 105.
Samples were solution treated at a specific tem-
perature for a given length of time and furnace cooled
at a rate of O.S”C/min, 1.33”C/min or 2.33”C/min to
a selected intermediate temperature below the y’
solvus and then immediately water quenched to arrest
the precipitation reactions. One sample from each of
the three materials was used for microstructural
analysis. The details of various solution treatment
temperatures and times, including the intermediate
cooling temperatures for each material are given in
Table 1. The selected solution treatment temperature
for each material was well above their y’ and M&
solvus temperature, whereas the intermediate cooling
temperature was chosen well below the y’ solvus
temperature. All heat treatments were carried out at
atmospheric pressure in a muffle furnace fitted with
a proportional controller and Data Trak pro-
grammer.
IN 738 and Nimonic 115 samples were etched in
8% Br-92% CH,OH solution, whereas Nimonic 105
was etched in 40% HCl-20% Hr0,-400/, H,O solution
to reveal the grain boundaries for quantitative metal-
lography. In specimens showing serrated grain
boundaries, the serrations were quantified in terms of
the amplitude (A pm) and a wavelength (A pm) such
as defined in Fig. 3. These serration parameters were
measured manually off the grain boundary tracings
made from the optical micrographs. A centre line was
drawn through a chosen set of tracings and parame-
ters A and A were determined with reference to this
centre line alone, Fig. 3. A number of micrographs
per heat treatment condition were examined and

Table 1. Selected solution treatment and cooling conditions used on difkent alloys

Selected solution Intermediate

Treatment cooling M,& ’
Temperature Time Temperature Solvus &us
Material (“0 (h) (“C) (“G) (“0
IN-738 I200 2 1090 IO00 1160-1175
Nimonic I I5 II75 1.5 1000 1080-l IO0 Il40-I I60
Nimonic 105 1170 2 loo0 I lo&l 150 1020-1060
 KOUL and GESSINGER: ON SERRATED GRAIN BOUNDARY FORMATION 1063

treated and controlled furnace cooled at a rate of

0.5”-2.33”C/min, revealed very sharp but straight
rain boundaries at all cooling rates, Fig. 8. An
additional Nimonic 105 specimen was cooled at a
much slower rate of 0. I “C/min from 1170” to IOOO‘C,
with the same result.
Electron microscopy of the solution treated and
water quenched specimens of IN 738 and Nimonic
I I5 showed straight grain boundaries with some
cuboidal primary y’ particles precipitated at the grain
boundaries, Fig. 9. The controlled furnace cooled
specimens, however, revealed serrations with primary
y ’ particles nearly elliptical in shape associated with
all serration peaks, Figs 10 and 11. These primary y’
(a) particles were always present on the concave side of
the serrations in both alloys. The particles remained
confined to their parent grains, Figs 10 and 11. In
contrast, Nimonic 105 contained a fair proportion of
grain boundary M2J6 carbides on most of the grain
boundaries, together with a fine y’ distribution within
the grain interiors.

4. DI!KUS!SION

On closely studying the electron micrographs

presented in Figs 9-11, the serrated grain boundary

(bl
Fig. 4. Optical micrographs showing serrated grain bound-
ary formation in IN-738. (a) Cooling rate of 2.33”C/min (b)
cooling rate of 0.5”C/min.

approximately 100 serrations per sample were mea-

sured.
This foil electron microscopy was carried out on all
heat-treated samples, where discs 3 mm in diameter
and 0.25 mm in thickness were electrolytically pol-
ished using Struer’s Tenupol polisher. The discs were
polished in a solution comprising of 94 parts acetic (a)
acid-6 parts perchloric acid, at a current density of
4mA/mm2 at room temperature.

3. RESULTS

IN 738 and Nimonic 115 specimens that were

furnace cooled at a rate of 0.5”-2.33”C/min revealed
profuse serrations, Figs 4 and 5, whereas the speci-
mens water quenched immediately after solution
treatment showed a straight grain boundary struc-
ture, Fig. 6. The serration amplitude and wavelength
increased in both alloys on decreasing the cooling
rate from 2.33” to O.S”C/min, Table 2. An increase in
wavelength with a decreasing cooling rate should be
noted. In Nimonic 115, however, both serration (b)
amplitude and wavelength appeared to have reached Fig. 5. Serrated grain boundary formation in Nimonic 115.
an optimum at a cooling rate of O.S”C/min, Fig. 7. (a) Cooling rate of 2.33’C/min, (b) cooling rate of
In contrast, Nimonic 105 specimens solution O.S’C/min.
I064 KOUL and GESSINGEK: ON SERRATED GRAIN BOUNDARY FORMATION

* tUitl?onir II5
E 0 tN 738

ir>, ,
d 9

0.5 1.0 I.5 2.0 25 3.0

Cooling rote %/min

c
A Nimonir II6
(b) 0 IN 738
E, z5

Cooling mto lC/rein

Fig. 7. Effect of cooling rate on the amplitude and wave-

lengths of serratlons in IN 738 and Nimonic 1IS. (a)
Amplitude variations, (b) wavelength variations.

(b) mation in Ni-base superalloys, Nimonic 105 was

Fig. 6. Straight and sharp grain boundaries formed on
solution treatment and water quenching of (a) IN 738, (b)
Nimonic I 15.
formation mechanism in IN 738 and Nimonic 115
appears vastly different from the one proposed for
20-l 1P austenitic stainless steels [l-3] in Fig. 1. On
cooling from the solution treatment temperature, y’
precipitation occurs well in advance of M.& precip-
itation in both nickel-base alloys [4-g], and this is also
indicated by their y’ and M& solvus temperatures
presented in Table 3. The resultant grain boundary
and the matrix y ’ precipitation would be expected to
inhibit the type of grain boundary migration required
by the mechanism proposed in Fig. 1. Therefore,
M&J6 precipitation may not necessarily participate in
the serrated grain boundary formation in Nimonic
115 and IN 738.
In order to elucidate the precise role of M&
precipitates on the serrated grain boundary for-
examined since its M2rCb solvus is higher than its y’
solvus temperature, Table 3. On cooling from, a
solution treatment temperature of 1170°C to lOOO”C,
the grain boundary Mr3Cb carbide precipitation pre-
cedes y’ precipitation at all cooling rates [4]. There-
fore, Nimonic 105 should have generated a serrated
grain boundary structure in accordance with the
mechanism proposed in Fig. 1. Instead, Nimonic 105
developed a straight grain boundary structure at all
cooling rates, Fig. 8, where grain boundary M&
particles were uniformly distributed. Grain boundary
M&Z6 precipitation would generally be expected to
inhibit the boundary migration rather than create a
serrated grain boundary such as proposed in Fig. 1
[ll]. This is perhaps why the grain boundary ser-
rations could not be generated in Nimonic 105, even
at a very slow cooling rate of O.l”C/min. If Nimonic
105 is considered a generalized reflection of serrated
grain boundary formation in other Ni-based super-
alloys, the mechanism is obviously very different
from the one proposed in Fig. 1.

Table 2. Effect on cooling rate on serration parameters

Serration amplitude and wavelength in
Nimonic I IS IN 738
Cooling rate Amplitude Wavelength Amplitude Wavelength
“C/min Otm) (rm) (rm) (rm)
_~_.-___-... . ..--- __-
2.3 I.0 3.15 1.5 4.0
I .33 1.8 6.0 1.6 4.4
0.5 2.0 6.7 2.35 6.5
 KOUL and GESSINGER: ON SERRATED
f b)
Fig. 8. Straight and sharp grain boundaries formed in
Nimonic 105. (a) Cooling rate of 2.33OC/min, (b) cooling
rate of O.S”C/min.
A brief literature search of the conditions utilized
by different workers to produce serrated grain
boundary structures in a variety of Ni-based super-
alloys was carried out, and these results are presented
in Table 3 [4-lo]. The cooling rates vary anywhere
from air cooling in IN 792 to very slow furnace
Fig. 9. Cuboidal grain boundary primary y’ precipitated in
IN 738 on S.T. at lMo”C and water quenching.
GRAIN BOUNDARY FORMATION 1065
Fig. IO. Elliptical primary y’ associated with the serrations
in IN 738. Solution treated and cooled at a rate of
2.33”C/min.
cooling of 3”Cfmin in Nimonic 115. It is, however,
interesting to note that in any alloy where grain
boundary serrations were successfully produced, the
y’ solvus temperature was .always higher than its
M,C, solvus temperature, Table 3. Therefore, it was
only on cooling from the solution treatment tem-
perature through the y ’ precipitation range that these
serrated grain boundaries were formed. The mech-
anism thus appears to be related to y’ precipitation
rather than M& precipitation in these materials.
Figure 2 illustrates the primary y’ precipitation
dependence of serrated grain boundary formation
proposed by other workers in N&base superalioys
[S, 7,9]. However, on cooling from a higher tem-
perature to a lower temperature, the migration of the
boundary segments in between the primary y’ par-
ticles appears unlikely, considering the logistics of the
time and temperature dependence of the grain size in
any alloy system. A representative grain coarsening
schedule for the ~ready-h~t-~t~ Nimonic 115 is
presented in Fig. 12, and superimposed on it is a
typical cooling curve used in the present in-
vestigation. In any alloy, the grain size is usually
Fig. I I. Elliptical primary y’ associated with the grain
boundary serration in Nimonic II 5.
 KOUL and GESSINGER: ON SEKRATELI GRAIN BOUNDARY FORMATION

Table 3. A brief lileraturc search on Ni-Base superalloys with serrated grain boundaries
..’ Serrated grain Minimum
MI&
Si~lVUS SOIVUS boundaries cooling
Alloy temperature temperature fOl7Wd rate
type (‘>C) (“C) or not required

Nimonic I I5 1080-i 100 1140-1160 Yes 3”C/min.

IN 738 loo0 1160-I 175 Yes F.C.’
IN 792 1000-1050 IIOO-II50 Yes A.C.2
Rene 95 LOW 1120-1160 Yes F.C.
Astroloy L. C. 1000 1120 Yes F.C.
Nimonic I05 IIW-1150 1020-1060 No -

‘F.C.-furnace cool.
zA.C.-air cooling.

established by the solution trea~ent temperature,
but it is possible for the boundaries to migrate at a
lower temperature when enough time, of the order of
a few hours, is allowed [I 11. Accounting for the
cooling schedules used in Nimonic 115 and IN 738
and those used by other workers in different N&based
superalloys, it is evident that the times spent at a
given temperature are far too short to influence the
boundary migration in these materials. Therefore, the
mechanism proposed in Fig, 2 may not be responsible
for serrated grain boundary formation in N&based
superalloys. Nevertheless, the mechanism is somehow
related to the y’ ~re~pitation on cooling from the
solution treatment temperature. Any proposed mech-
anism should account for an increase in the serration
amplitude and wavelength with a decreasing cooling
rate, Table 2 and Fig. 7. Also, the mechanism should
explain the variations in the required cooling rates to
initiate the formation of serrated grain boundaries in
different Ni-based superalloys, Table 3.
5. MODEL
either side of the grain boundary, Figs 10 and Il. It
appears that the primary y‘ particles precipitated
adjacent to the grain boundary have moved under the
influence of some driving force during cooling. The y ’
particle movement would also displace the local grain
boundary segment and create a serration such as
shown in Fig. 13. It is suggested that y ‘ nucleates on
one side of the grain boundary on cooling through
the y’ precipitation temperature range. Due to the
presence of a grain boundary, having a certain width
adjacent to the y’ precipitate, the coherency strains
on the boundary side of the y’ particle are easily
accommodated, Fig. 13. A net strain energy
differential between the interface A and B of the y’
particle, Fig. 13, provides a driving force to move the
y’ particle in the direction of the boundary. The y’
particle movement will however, be opposed and
finally stopped by the line tension of the boundary..
A model of this nature woutd predict the effect of
cooling rate to be similar to that observed in Fig. 7.
Also, the variations in the minimum required cooling
rates to produce serrations in different Ni-base super-

The primary y’ particles are elliptical and always

associated with a concave portion of the serration on t=o
~
““1 y’nucleoted on one side
of the groin boundory
270

250
E
a

P2=
,:
El
t
‘si
.E
PI0
tfionB
e
e 100

I70

AG between A and B provides the drivingforea

Ieo 12eo in the direction of the boundory
1000 lO!tO ,ioo I200
Tempemture PC)
Fig. 13. A schematic sprinting the model proposed for
Fig. 12. Grk coarsening characteristics of previously heat- serrated grain boundary formation in Ni-basedsu~ralloy~
treated Nimonic 115samples. based on y’ particle migration.
 KOUL and GESSINGER: ON SERRATED GRAIN BOUNDARY
alloys could be attributed to the variations in the y’
particie-mat~x misfit from one alloy to another, thus
changing the magnitude of the driving force available
to produce serrations. To simplify the analysis, we
have assumed the presence of a spherical y’ particle
of a constant diameter at a constant temperature
causing a serration, but the model will be modified
later to include growth of the y’ particle during
translatory motion on cooling. The precise details
and the calculations of the different energy parameter
are given below.
5.1. Force available fory'particle movement due to
strain energy d$erential
The free energy of a crystal containing a fully
coherent spherical precipitate, e.g. y’, has con-
tributions from (i) the coherency strain energy AG,V,
and (ii) the chemical interfacial energy y,,, [12]. The
sum of these two terms is given by
AG inherent) = AG, + yEt,x precipitate area. (1)
In the case of a spherical particle of volume Y and
radius r and a misfit 6, AG, is represented by
rr4,& V, where p is the shear modulus of the matrix.
Therefore, equation (1) can be rewritten as
AG t~he~nt) = 4~2,4~3~r3 -f- 47tr2*y,,.
If the same precipitate has a semicoherent or incoher-
ent interface that completely relieves the effects of
misfit (such as by the presence of a grain boundary
of finite thickness adjacent to the y ’ particle) there
will be no misfit energy. However, in the case of a
semicoherent interface there will be an extra struc-
tural contribution to the interfacial energy (y%,)due to
the structural distortion caused by the misfit dis-
locations. The free energy of a semicoherent precip-
itate is therefore given by
AG (s~i~herent) = 0 + 4%r2(y,&+ rd.
Therefore, for a given 6 there will be a minimum y’
particle radius above which AG (coherent) will exceed
AG (semicoherent), thus creating an energy
differential between two sides (A and B) of the y’
particle. These boundary conditions can be repre-
sented by [12].
4wr2(y, -l-y,?,)= 4pS2 )7rr3 t 4nr2y,.
Assuming the yrh term to be similar on both sides
of the y’ particle, then r = 3~,/4@~, and upon
substituting the IN 738 shear modulus value
u 10” N/m2 at 1lOO”C, a misfit value of -0.01 [I4
&d a Y,~,value of 0.10 N/m, an t value of 700 A
is obtained for the boundary conditions. Therefore
on furnace cooling the solution treated material
through the y’ precipitation range, a net y’ particle
free energy imbalance occurs between sides A and B
in Fig. 13, once the primary y’ particle precipitated
adjacent to the grain boundary has grown to a size
FORMATION 1067
in excess of 700 A in radius. The free energy of the
coherent side A is higher than the semicoherent
portion B in Fig. 13, once the particle radius exceeds
700 A.
The equilibrium state obtained on cooling to room
temperature after applying a controlled cooling treat-
ment, gives a primary y’ particle radius of 35OOA
when cooling at a rate of - 1.S”C/min. The coherency
strain energy difference of a primary y’ particle of
radius 3500 %r.between sides A and B in Fig. 13 can
be calculated by using the expression AG,<= 4 ~6’ V
AC,, (total) = AC, of side A + AG,r of side B.
Due to strain accommodation along side B of the
y’ particle in Fig. 13, the AG, of side B can be
approximated in zero. Substituting for parameters p,
S and V, the coherency strain energy difference of
7.75 x 10e6 ergs is obtained, which approximates to a.
force FE of -0.2 dynes acting on the y ’ particle.
5.2. Retarding force due to boggy energy
A net force (F,) of 0.2 dynes will move the y’
particle in the direction of the force and considering
the ordered nature of the y‘ precipitate, the moving
particle will also drag the localized grain boundary
segment such as indicated in Fig. 14. The boundary
segment, however, will exert a retarding force F2 due
(2)
to the grain boundary energy y and oppose the y’
particle motion.
The y’ particle shown in Fig. 14 will be attached to
the boundary along a length 2nr sin 8. The retarding
force component due to grain boundary energy is
given by y cos 8 and therefore, the y’ particle will feel
a back force of 27rr-ysin f3cos ff = nry sin 28,
or F2 = xry sin 20 (4)
where y’ is the grain boundary energy of the order of
N 300 ergs/cm2 I:121 and assuming a 6 value of w 45”
from Fig. 10, the retarding force (F2) approximates to
(3) -0.033 dynes. It must, however, be pointed out that
the forces F, and F2 will be acting along two different
planes pp’ and qq’ of the y ‘ particle in Fig. 13.
Therefore, in calculating the net force acting along y’
particle, the forces F, and F2 can not be simply
subtracted, and a detailed analyses of appropriately
treating these forces will be presented in the follo~ng
section.
Fig.14.A schematic representing the boundary y’-particle
contact and the forces involved.
1068 KOUL and GESSINGER: ON SERRATED
Fig. 15. A schematic showing the planes of action for forces
F, and Fz on a y’-particle.
5.3. y ’ Particle movement under the influence of forces
F, and F,
In order to check the validity of the model, it is
necessary to examine the distance x pm moved by a
grain boundary primary y’ particle under the
influence of two opposing forces F, and F,, acting at
an average approximated temperature of T K over a
time period of t seconds, and then compare the x
value with the experimentally determined serration
amplitude A value. Providing the calculated x value
and the experimentally determined amplitude A value
are of the same order of magnitude, then only the
feasibility of the present model can be acknowledged
with some degree of certainty.
The forces F, and F2 acting on the grain boundary
primary y ’ particle create a chemical potential
difference VP, which in turn leads to a net flux of
vacancies by diffusion [l4-161. As a result of this
diffusional flux, the y’ particle can move a distance x
pm in a given time t by three possible mechanisms:
(i) Interfacial-grain boundary diffusion
(ii) Volume diffusion through the particle
(iii) Dissolution of y’ particle on one side, where
volume diffusion of the solute takes place through the
matrix and the diffused species reprecipitate on the
opposite side of the particle.
However, the occurrance of interfacial-grain
boundary diffusion is more likely since Dgb >>D. and
the diffusion path is much shorter via the particle
interface than through the y-matrix. Therefore, the
movement dx of a y’ particle in a time interval dt
under the influence of a chemical potential gradient
VP is described by
ds 2 Dgb6,
-=-Vp (5)
dt kTr
where 6, is the diffusion thickness assumed to be of
the order of lattice spacing -4 x IO-*cm, Tis the y’
precipitation temperature .range - 1430 K. r is the y’
particle radius -3500 x IO-” cm, Dgb is the grain
boundary ditfusion coefficient similar of Ni
to that
_ I .34 x IO -’ Cm’/s and k is the Boltzmann’s con-
stant _ I.38 x IO.-“ergs/K.
In calculating the 011 for they’ particle, it is evident
from Fig. 15 that two opposing but normal stresses
proportional to forces F, and F? are acting along the
GRAIN BOUNDARY FORMATION
planes pp’ and qq’ respectively. Under the influence
of a normal stress, the chemical potential of vacancies
is changed by an amount equal to the product of the
magnitude of the stress and the atomic volume. Since
F, and F2 are acting in opposite directions, the
respective chemical potential gradients VP,, and V/J,
developed by these forces will also oppose one an-
other. Hence, the net chemical potential gradient VP
is defined by VP~, - VpF2and the equation (5) takes
the form
; = F .(Vpc, -V/J,)
where
VC(~,= stress due to force F, x atomic volume
= F,
XSf
area of pp’ plane x 2r
vpF, 2$= 4.75 x 10-r’ dynes.
Similarly,
V’Fz -- stress due to force F2 x atomic volume
4 x s;
= area of plane qq’ x 2r
F2G
= 2xr3 sin%
where 8 = 45” from Fig. 10 and VpF, = 1.57 x
lo-” dynes. Therefore, VP = VpF, - Vcl,, = 3.18
x IO-” dynes.
Substituting for VP and other variables in equation
(6). dx equals 4.9 x IO-scm/s. However, the time
allowed for y’ precipitate to migrate within a tem-
perature range of 1160’-1000°C at a rate of
l.S”C/min equals 6400 s. Therefore, the y’ particle
would move a distance of 3.13 pm within a time
period of 6400 s. An x value of 3. I3 pm compares
favourably with the observed serration amplitude A
of N 1.6 pm in both alloys.
An increase in the serration wavelength with a
decreasing cooling rate, Table 2 and Fig. 7, can be
attributed to the precipitation of fewer primary y’
particles adjacent to the grain boundary, since the
matrix supersaturation effects are maintained for a
longer period of time. These particles further grow
and coalesce, where their coalescence will only
influence the driving force for onward migration that
determines serration amplitude rather than the wave-
length. On top of this outward particle migration, the
grain boundary primary y’ particles change their
shape from a cuboidal to ellipical morphology with
a decreasing cooling rate, Figs 9 and IO. This shape
change decreases the overall energy of the system,
even though its effects have not been calculated in the
above mentioned model for simplicity purposes.
These observations clearly indicate that the grain
 KOUL and GESSINGER: ON SERRATED
boundary y’ particle migration is responsible for
serrations in these alloys.
It is possible that a similar mechanism is operative
in 20-I 1P austenitic stainless steels as well, since Ni
combines with P to form compounds similar in
morphology and distribution to that of y ’ [l-3]. Such
compounds were not considered in the interpretation
of the results on high P austenitic stainless steels.
5. CONCLUSIONS
The mechanism of serrated grain boundary for-
mation is related to y’ precipitation in Ni-base super-
alloys. A higher y’ solvus temperature than the M&,
solvus temperature appears to be a prerequisite for
the development of serrations. The serration ampli-
tude and wavelength increases with a decreasing
cooling rate until an optimum is reached. The min-
imum required cooling rate to initiate the formation
of serrations varies anywhere from air cooling to a
very slow furnace cooling from one alloy to another.
A model based on the grain boundary primary y’
particle movement causing the displacement of the
local grain boundary segment and initiating the ser-
rated grain boundary formation has been proposed.
The net strain energy differential between the matrix
side and the boundary side of the particle matrix
interface provides a driving force for the movement
of primary y’ particles in the direction of the bound-
ary. The simplified theoretical analysis and the ex-
perimentaly determined serration amplitude values
correlate well with the model presented. Previously
established models based on MI& precipitation and
boundary migration in between the primary y’ par-
ticles are not considered responsible for the serrations
on cooling from a higher temperature to a lower
temperature.
GRAIN BOUNDARY FORMATION 1069
Ackndwledgemenrs-This paper was written while one of
the authors (Dr G. H. Gessinger) was on leave of absence
from Brown Boveri & Co. at NRC, Ottawa, Canada. The
authors appreciate the helpful discussions with Professor H.
Gleiter, Professor E. Hornbogen, and Drs R. Singer and T.
Duerig. The authors are also grateful to Dr W. Wallace of
NRC for providing the materials and laboratory facilities to
conduct this investigation.
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