Theory of Grain Growth in Porous Compacts

F. A. Nichols
Citation: Journal of Applied Physics 37, 4599 (1966); doi: 10.1063/1.1708102
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Journal

of

Applied Physics
Volume 37, Number 13

December 1966

Theory of Grain Growth in Porous Compacts

F. A.

NICHOLS

Bettis Atomic Power Laboratory,* Pittsburgh, Pennsylvania

(Received 16 May 1966)

Following a suggestion by Kingery and Francois, the theory of grain growth in porous compacts controlled by the migration of pores with the boundaries is developed for all possible transport processes. Contrary to the assumption of these authors, it is shown that the cubic rate law reported for both U02 and
AhOa compacts, if it is due to pore migration, must be interpreted as being controlled by vapor transport
through the pore with the pressure maintained at 2'y/r, where 'Y is the surface tension and r the pore radius.
Available data for U02 and AbOa are analyzed according to this model and found to give satisfactory
agreement, with the calculated activation energies being reasonably close to the heats of vaporization for the
two oxides. An interesting prediction of the model is that the compact should in fact show a decrease in
density during grain growth. This behavior has been observed in the case of U02 but apparently has not yet
been reported for AI,Oa.

I. INTRODUCTION

HE rate of grain growth in crystals is often

analyzed by assuming that the grain boundaries
move toward their center of curvature at a rate proportional to the curvature. l The boundary curvature is in
turn assumed to be inversely proportional to the grain
diameter. Then equating the time rate of change in
grain diameter to the boundary velocity, one obtains
dD/dt=k'/D,

(1)

where D is the grain diameter, t is the time, and k' is a

constant. Upon integration this yields
JJ2-D02=kt,

(2)

where Do is the grain diameter at t=O and k is a constant. Equation (2) is observed to describe grain growth
in most metals only at very high temperatures, with
large deviations occurring at lower temperatures. This
is presumably due to the effect of impurity particles
which act as a drag on the boundaries at low temperature but tend to dissolve at high temperature. This
view seems to be supported by the fact that Eq. (2) is
found to apply in ultra-pure metals even at low temperatures. 1 2 The role of impurity atoms in solution on

* Operated for the U. S. Atomic Energy Commission by

Westinghouse Electric Corporation.
1 J. E. Burke and D. Turnbull, Progress in Metal Physics, Bruce
Chalmers, Ed. (Pergamon Press, London, 1952), Vo!' III, p. 220.
2 P. Niessen and W. C. Winegard, J.lnst. Metals 94,31 (1966).

boundary mobility has been discussed theoretically by

Cahn 3 and Niessen and Winegard2 have discussed the
effect of the distribution coefficient (i.e., the ratio of
solute in the solid to solute in the liquid when both
phases are in equilibrium), suggesting that the disordered structure of a random high-angle boundary resembles that of a melt.
The purpose of the present paper is to discuss the
kinetics of grain growth in the presence of inclusions
which are dragged along with the moving boundaries.
Kingery and Francois4 have suggested that grain growth
in porous ceramic compacts is controlled by the migration of pores along with the boundaries. These authors
note that pore migration can be accomplished by
evaporation-condensation, surface diffusion or volume
diffusion but state, without justification, that for a pore
of constant shape the rate of pore migration is inversely
proportional to the pore diameter. We shall see this is
not generally correct and specifically the assumption is
valid only for the very special mechanism of vapor
transport with the pressure in the pore maintained at
2,,(/ r, where "( is the surface tension and r is the pore
radius. The results are applied to the case of grain
growth in U0 2 5 and AhOa6 compacts where the cubic

J. W.

Cahn, Acta Met. 10,789 (1962).

W. D. Kingery and B. Francois, J. Am. Ceram. Soc. 48, 546
(1965).
6 J. R. MacEwan, J. Am. Ceram. Soc. 45, 37 (1962).
6 R. L. Coble, J. App!. Phys. 32, 793 (1961).
3
4

4599
Copyright 1967 by the American Institute of Physics.

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4600

F.

A.

NICHOLS

time dependence predicted by Kingery and Francois has

been observed and the activation energies calculated
from available data are found to be in reasonable agreement with the heats of vaporization for the two oxides.
The results presented here for volume- and surfacediffusion transport should apply to the case of solid impurity particles being dragged by the boundaries.

DL D04= kl exp( -Q/ RT)t (volume diffusion),

II. THEORY
A grain boundary which is subjected to some driving
force can in turn exert a force on a particle located in
the boundary. This force, F, depends upon the grain
boundary tension 'Ygb, the particle radius r and the halfangle 0 of the cone with its apex at the particle center
and its base defined by the intersection of the boundary
with the particle, in accordance with the well-known
formula,7
(3)
F = 'Trr'Ygb sin20,
and is directed along the cone axis (the direction of
boundary motion). This force which is directly proportional to the particle radius r, is of course independent
of the mechanism by which the particle migrates, but
has a finite value only when 0>0, i.e., only when some
other force is driving the boundary. Clearly, 0= 90
(and hence F= 0) when the driving force on the boundary Fb=O. Since sin20 increases as Fb increases, we
assume for simplicity that sin20 a: F b and further make
the usual assumption that Fba: 1jD. Under these assumptions, we can write from Eq. (3)
F=KrjD,

fusion and vaporization, respectively. As the boundaries move during grain growth, the particles will
collide and hence enlarge along with the grains, Since
the average pore size r increases as grain growth proceeds, we make the reasonable assumption following
Kingery,4 that rn:D; then setting V in Eq. (5) equal to
dD/dt, the integrated equations become

(4)

Db_D ob=k 2 exp(-Q./RT)t

(surface, or interface, diffusion),

(vapor transport, p= constant),

(12)

fl3- D03= k4 exp( -Q./ RT)t

(vapor transport, p= 2'Y/r) ,

(13)

where kl' k2' k3, and k4 are rate constants. It is thus seen
that the only mechanism which agrees with the cubic
rate behavior observed for U0 2 and Ab03 compacts is
one of vapor transport with the pressure in the pores
maintained at p=2'Y/r.
It should be noted that Eqs. (10)-(13) apply only
under the assumption that the particles (or pores) migrate and remain on the boundaries. Hillert9 has treated
the case in which boundaries are freed to move as the
result of the dissolution of second phase inclusions and
obtained a rate equation equivalent to (13). For porous
ceramic compacts, however, it is more reasonable to
assume that the gas-filled pores remain on the boundaries, since the solubility of the inert gas is felt to be
quite limited.
ITI. COMPARISON WITH EXPERIMENT

V=BF=BKrjD,

A. U0 2

where B=mobility of pores. The mobility of pore migration is of course dependent upon the mechanism of
movement. Shewmon 8 has treated this problem in an
approximate fashion, assuming the particles to remain
spherical. If we assume his results to be valid here we
have
B= (Ajr) exp( -Qj RT) (volume diffusion),

(6)

B= (Cjrl) exp(-Qs/RT) (surface diffusion),

(7)

B= (D/r 3 ) exp(-Q./RT)
(vapor transport, p= constant),
and

(8)

B= (E/r2) exp( -Q./ RT)

(vapor transport, p=2'Y/r),

(9)

where A, C, D, and E are constants, and the Q's are the

activation energies for volume diffusion, surface dif7 R. E. Reed-Hill, Physical Metallurgy Principles (D. Van
Nostrand Co., Inc., Princeton, N. J., 1964), p. 208.
S P. G. Shewmon, Trans. Met. Soc. AlME 230, 1134 (1964).

(11)

D4- D04=k3 exp( -Q./ RT)t

where K is a constant, and the velocity of pore migration and hence boundary motion can be expressed as
(5)

(10)

Shewmon 8 discussed the relative importance of the

various transport mechanisms and showed that surface
diffusion dominates for small r, volume diffusion becomes important at intermediate values and eventually
r becomes large enough that only vapor transport is
important. With reasonable assumptions for the
parameters in Eqs. (6)-(9), the radius above which
vapor transport becomes dominant can be shown to be
in the micron-size range. For ceramic substances such
as U0 2 and Al 20 3 with relatively high vapor pressures,
vapor transport should certainly dominate for any pores
with r;;:: IJ.!. This means that the motion of the fabricated pores remaining after sintering of compacts of
these materials should be controlled by vaporization
rates.
MacEwan reported 5 that U02 sinters to an essentially constant density with little or no grain growth
and then grain growth occurs with no further increase
in density. He analyzed his results on the basis of
Eq. (2) but found that a plot of log(D2-D o2) vs logt
o M.Hillert, Acta Met. 13, 227 (1965).

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THEORY OF GRAIN GROWTH

yielded a set of lines with an average slope of 0.8,

whereas Eq. (2) would predict a slope of unity. The data
are replotted in Fig. 1 as log(D3-D o3) vs logt and
straight lines with unit slope are found to describe the
data very nicely. In a review of all available grain
growth data for U0 2 , Lyons et al. lO concluded that the
most reliable data (primarily that of MacEwan) are
best represented by a cubic equation.
More recently, Mansour and Whitell in studying the
sintering of U02 compacts, found that the density
reached ",98% of the theoretical density and then decreased to ",95% before again increasing at rates dependent upon the atmosphere employed. The rate of
the decrease in density, on the other hand, was independent of whether the experiment was carried out in
argon or nitrogen. They also measured pore sizes and
found the average pore size to increase with time. These
authors interpret their results on the basis of the diffusion of the gas from small pores to larger ones. This is
unlikely in view of the extremely low solubility to be
expected for the inert gases in U0 212 and also fails to
explain the equivalent rates of expansion in both atmospheres. On the other hand, it seems more probable
that the expansion occurs due to the migration and
coalescence of the pores as they are dragged by the
moving boundaries.
Mansour and White obtained limited data on grain
growth during their sintering studies at 1400C in
argon and a plot of log(D2- D02) vs logt yielded a slope
of 0.68. Since DoD in their experiments, the authors
pointed out that this indicates a cubic rather than a
parabolic time dependence.
The decreasing density reported by Mansour and
White has also been observed by Lafontain and Vanden
Bemden 13 in U0 2 and by Harrison, Foster, and Russell14
in U02-PU02 mixtures. The latter authors observed no
subsequent shrinkage. This constitutes rather clear evidence that the growth of pores is intimately involved in
the grain growth of U0 2 compacts. Kingery and
Francois4 also show metallographic evidence that the
pores remain on the grain boundaries and enlarge with
time as the grain size increases. All evidence then points
to the validity of Eq. (13).
The rate constants for U0 2 grain growth obtained
10 M. F. Lyons, D. H. Coplin, and B. Weidenbaum, "Analysis
of DO. Grain Growth Data from 'Out-of-Pile' Experiments,"
General Electric Co., Atomic Power Equipment Dept., San Jose,
Calif., Report No. GEAP-4411, dated November 1963.
11 Nayla A. L. Mam;our and J. White, Powder Met. 12, 108
(1963).
12 Some studies with DO. have employed a hydrogen atmosphere, in which case diffusion ot the gas from small to large pores
might seem reasonable. However, the activation energies reported
for grain growth [ef. I. Amato, R. L. Colombo, and A. Petruccioli
Balzari, J. Nucl. Mater. 18, 252 (1960) for a review of reported
"activatiun energies"] are much too high to be reasonably interpreted on this basis.
13 I. Lafontaine and E. Vanden Bemden, Special Report No.4
(Centre d'Etude de l'Energie Nucleaire and Societe Belge pour l'
lndustrie Nucleaire, Brussels).
14 J. D. L. Harrison, E. Foster, and L. E. Russell, in Powder
Metallurgy in the Nuclear Age, Plansee Proc. 1991, F. Benesovsky,
Ed. (Springer-Verlag, Vienna, 1962), pp. 140-65.

4601

IN POROUS COMPACTS
1000000

100000

10000

:.
<.>

T
2
1:5

1000

"'"
~I
0
0

100

2440C

C. 2206'C

2007 DC

X 1832'C
1680'C
10

elsss'c

0.1

10

100

1000

10000

TIME (HOURS)-

FIG. 1. Grain growth in DO. compacts.

from Fig. 1 (MacEwan and Lawson's data) are plotted

in Fig. 2 in Arrhenius fashion. The data show a linear
behavior and the calculated activation energy is 124
kcaljmole. This value compares favorably with the reported value for the heat of vaporization of U0 2,15 138
kcaljmole.
B. Ah03
6
Coble has studied the densification of Al 20 3compacts
and also obtained grain growth rates. The grain size
was found to increase as the cube root of time, but the
decrease in density discussed above for U0 2 was not observed and so this portion of the model is not substantiated for Ab03. Noting, however, that initial studies
with U0 2 also failed to reveal such shrinkage, it is possible that more refined techniques will yet reveal this
phenomenon in Al 20 3 compacts. Coble obtained an
activation energy of 153 15 kcaljmole from a plot of
the logarithm of the time required to reach a 3-J.I. grain
size vs liT.
The vaporization of U0 2 is primarily congruent in
nature, i.e., the primary vapor species is U0 2 This is
not the case for Al 20 3 and considerable discrepancies
exist in the older literature. The situation was summarized by Ackermann and Thorn,t6 who suggested
that more careful and complete experiments were required, taking into account the vapor species AI, AIO,
and AbO and also considering the possibility of coevaporation of the Knudsen cell liners. The recent investigation by Hasapis et alP treated all these possi16 R. J. Ackermann, R. W. Gilles, and R. J. Thorn, J. Chern.
Phys. 25, 1089 (1956).
16 R. J. Ackermann and R. J. Thorn, Progr. Ceram. Sci. 1,39
(1961).
17 A. A. Hasapis, A. J. Melveger, M. B. Panish, L. Reif, and
C. L. Rosen, "The Vaporization and Physical Properties of
Certain Rcefratories n Experimental Studies," U. S. Atomic
Energy Commission Rept. No. WADD-TR-60-463 (1961).

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F. A.

4602

NICHOLS

for the solid phase would be expected to be somewhat

higher than this, and so the v~lue !s in very good agre~
ment with the observed activatIOn energy for gram
growth. In view of the difficulties mentioned above connected with the vaporization studies of Ab03, however,
such close agreement could easily be somewhat
fortuitous.
IV. DISCUSSION
T

L--L~__~~__L-~~__L--L~~~~
C.~

0.4

0..5

0.6

IIT(X 10.-')-----_

FIG. 2. Cubic rate constants fo.r grain growth in VO.

compacts at various temperatures.

bilities and concluded that for the temperature range

employed (2200 to 2500 0K) the primary vaporization
process is
(14)
If this is correct, then the pertinent vapor pressure for
our purposes would be that of Al, since the rate of movement of an A1 20 3 surface will be controlled by the
vaporization of the less-volatile species. Hasapis reports
values for the vapor pressure of Al which vary from
7.9X 10-4 mm at 22000K to 3.2X 10-2 mm at 2500 0K.
Surprisingly, these values are quite comparable with
those for U0 2 which is well-recognized as a relatively
volatile oxide; recent values for U0 2 vapor pressures
are 9.9X 10-4 mm and 3.8X 10-2 mm at the same two
temperatures. IS
Since the vaporization studies of Ah03 are mostly
above the melting point (",2300 0K), the heat of vaporization of Al from the solid phase cannot be accurately
gauged. However, the value obtained from the slope of
the plot given by Hasapis is 147 kcal/mole. The value
18 C. A. Alexander, J. S. Ogden, and G. W. Cunningham, report
entitled "Thermal Stability of Zirco.nia and Tho.ria-Base Fuels,"
Battell~ Memo.rial Institute, Columbus, Ohio (1966).

The extremely low solubility of the inert gases normally employed as atmospheres in the sintering of
powder compacts seems to exclude a grain growth
mechanism controlled by the rate of dissolution of small
pores and growth of larger ones. Assuming this to be a
valid argument, we have derived the rate equations for
all possible transport mechanisms involving particles
or voids residing on the grain boundaries. The only
mechanism which predicts the cubic time dependence
observed for both U0 2 and A1 20 3 compacts is one of
vapor transport of matrix molecules through the pore,
with the pressure in the pore maintained by surface
tension effects at p= 2'Y/r. This is in agreement with the
experimental observation of an "end-point" density in
sintered compacts before the onset of grain growth.
The model implies a swelling of the compact during
grain growth. This arises from the p=2'Y/r relation,
which necessitates an increase in volume following the
coalescence of two pores. The predicted increase in
average pore size, and thedecrease in density, have been
reported for U0 2 by several investigators. This behavior has not yet been reported for Al 20 3.
The activation energies for grain growth calculated
on the basis of this model are within'" 10% of the heats
of vaporization of U0 2 and Al 20 3
Thus, the proposed model appears to be in good a~ree
ment with the most accurate data for these two OXIdes.
The predicted expansion during grain growth requires
further experimental investigation in the case of Al 20 3,
but appears to be lirmly established for U0 2
The grain-growth equations derived for surface and
volume diffusion-controlled migration of particles
should find application in the case of solid inclusions
and may afford explanations for some of the observed
deviations from the classical Eq. (2) in the case of metals
containing no pores, but containing very small solid
inclusions.
ACKNOWLEDGMENTS

This work was done under a contract with the U. S.

Atomic Energy Commission and permission to publish
these results is gratefully acknowledged.

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