Acta mater. Vol. 46, No. 13, pp.

4671±4690, 1998
# 1998 Acta Metallurgica Inc.
Published by Elsevier Science Ltd. All rights reserved
Printed in Great Britain
PII: S1359-6454(98)00144-X 1359-6454/98 $19.00 + 0.00

A MODEL FOR THE SINTERING OF SPHERICAL

PARTICLES OF DIFFERENT SIZES BY SOLID STATE
DIFFUSION
J. PAN{, H. LE{, S. KUCHERENKO and J. A. YEOMANS
School of Mechanical and Materials Engineering, University of Surrey, Guildford GU2 5XH, U.K.

(Received 30 September 1997; accepted 29 March 1998)

AbstractÐIn this paper the numerical scheme developed by Pan and Cocks (Acta metall. 43, 1395±1406,
1995) is used to simulate the co-sintering process of two spherical particles of di€erent sizes by coupled
grain-boundary and surface di€usion. The numerical analysis reveals many interesting features of the co-
sintering process. For example, it is found that the shrinkage between the two particles is not a€ected sig-
ni®cantly by the size di€erence of the two particles as long as the di€erence is less than 50%. Based on the
numerical results, empirical formulae for the characteristic time of the co-sintering process and for the
shrinkage rate between the two particles are established. The empirical formulae can be used to develop
constitutive laws for early-stage sintering of powder compacts which take into account the e€ect of particle
size distribution. To demonstrate this, a densi®cation rate equation for compacts with bimodal particle size
distributions is derived. # 1998 Acta Metallurgica Inc. Published by Elsevier Science Ltd. All rights reserved.

1. INTRODUCTION component during the sintering process [4].

Sintering is a crucial step for the fabrication of a
ceramic component from a powder compact. Two
things occur during sintering: grain growth and
densi®cation. The driving force for the microstruc-
tural changes is the excess free energy associated
with the large free-surface area of the ®ne powders.
The actual mechanism of matter redistribution
depends on the material system, the particle size,
the sintering temperature and the level of external
pressure, if such pressure is applied. Coupled grain-
boundary and surface di€usion is often the domi-
nant mechanism for the sintering of a ®ne particle
compact which is subjected to a moderate
pressure [1, 2]. This is a mechanism where grain-
boundary di€usion transports matter to the junc-
tions between grain-boundaries and pore surfaces,
and surface di€usion redistributes that matter onto
the pore surfaces. A typical example of sintering by
this mechanism is the pressureless sintering of
alumina powder with a particle size of about 3±
8 mm at 14008C. In this paper we concentrate on
this coupled di€usion mechanism only.
Considerable e€orts have been made to under-
stand the sintering process. Constitutive laws have
been developed that enable ®nite element analysis
to be performed for the sintering process [3]. The
analysis can predict the history of stress, strain,
relative density and grain size at any location of a
{To whom all correspondence should be addressed.
{Current address: Department of Engineering, University
of Cambridge, Cambridge CB2 1PZ, U.K.
4671
However, the current generation of densi®cation
laws assume uniform particle size and ignore the
fact that most of the commercial powders consist of
particles with a wide range of sizes. There have
been relatively few studies examining the e€ect of
particle size distribution on sintering. Patterson and
Benson [5] did an experimental study on the e€ect
of powder size distribution on sintering. Ting and
Lin [6] derived a shrinkage rate equation for pow-
der compacts taking into account the e€ect of par-
ticle size distributions. Grain growth was also
considered in their model. Ting and Lin did not in-
vestigate the detailed kinetics of the co-sintering
process between particles of di€erent sizes. It was
simply assumed that the sintering rate equation
between two particles of di€erent sizes takes exactly
the same form as that between two particles of
single size. For bimodal powder mixtures,
German [7] proposed a simple model for prediction
of the sintered density vs mixture composition from
the knowledge of the densi®cation of the large and
small powders. Probably the ®rst theoretical study
of the co-sintering process between a pair of spheri-
cal particles of di€erent sizes was made by Coble [8]
who used the approximiate geometric relationships
for identical particles to derive an approach rate
equation for the non-identical particles. Recently
Tanaka [9] re-investigated this problem. Assuming
that the two particles maintain their truncated
spherical shape during the co-sintering process,
Tanaka obtained the rate equations for the sintering
and coarsening of the two-particle system. More
4672 PAN et al.: A MODEL FOR THE SINTERING OF SPHERICAL PARTICLES
recently Parhami et al. [10] investigated a similar
problem using a variational approach. Three
degrees of freedom were used to de®ne the geome-
try of a representative unit of a row of particles of
two di€erent sizes. Using the classical Rayleigh±
Ritz method, a numerical solution was obtained for
the co-sintering process. It is important to realize
that the selected degrees of freedom in these models
limit the co-sintering process to a speci®c kinetic
route which can be very di€erent from the actual
one. For example, it was assumed that the main
parts of the two particles remain spherical during
the sintering process. This is not quite correct since
surface di€usion is often not fast enough for the
two particles to maintain the near-equilibrium
shape. The accuracy of these models can only be
found when they are compared with a full solution.
The main purpose of this paper is to investigate
the sintering kinetics of two spherical particles of
Fig. 1. The co-sintering process of two particles in contact with each other (schematic drawings).
di€erent sizes by means of computer simulation.
Such a computer simulation was made possible by
a numerical scheme developed recently by Pan and
Cocks [11]. Ignoring the interaction between the
pair of particles and the particles surrounding
them, the two particles can be considered as a
representative unit of a powder compact. The nu-
merical analysis is shown to reveal many interest-
ing features of the co-sintering process. Based on
the numerical results, empirical formulae are estab-
lished in order to describe the various aspects of
the co-sintering process analytically. These empiri-
cal formulae can be used to develop constitutive
laws for early-stage sintering taking into account
the e€ects of particle size distributions. To demon-
strate this, a densi®cation rate equation is derived
for powder compacts with bimodal particle size
distributions based on the empirical formula.
 PAN et al.: A MODEL FOR THE SINTERING OF SPHERICAL PARTICLES
Experimental work is underway to verify the major
®ndings of this numerical study.
2. DRIVING FORCE FOR SINTERING
Figure 1(a) shows the representative unit that is
considered in this work. The total free energy of the
system is
… …
E ˆ gs dAs ‡ ggb dAgb …1†
s gb
where gs and ggb are the speci®c energies of the free
surface and the inter-particle boundary (the grain-
boundary), respectively. The tendency to reduce E
is the driving force for a shape change of the sys-
tem. For the two-particle system, it is obvious that
E reaches its minimum value when the two particles
become one perfect sphere.
There are several mechanisms by which matter
redistribution can be achieved. These include vis-
cous ¯ow, lattice di€usion, evaporation and con-
densation, and coupled grain-boundary and surface
di€usion. As mentioned in the Introduction
(Section 1), only the last mechanism is considered
here. The shape evolution is controlled by the
kinetic law as well as by the driving force. A
comprehensive discussion about the roles played
by driving forces and kinetic laws, respectively, in
the microstructral evolution has been given by Sun
et al. [12].
Where the grain-boundary meets the free surface,
the equilibrium between the surface tensions of the
two particles and the grain-boundary tension has to
be maintained. As shown in Fig. 1(b), this require-
ment of equilibrium tends to ``bend'' the grain-
boundary towards the small particle with ends
pinned at the junction. The grain-boundary then
moves towards the smaller particle to ¯atten itself.
The combination of these two mechanisms results
in migration of the boundary towards the smaller
particle as long as the junction itself moves. The
¯attening of the grain-boundary is assumed to be
much faster than the movement of the junction.
3. THE KINETIC LAW
The usual linear kinetic law (Fick's law) is
assumed for grain-boundary and free-surface di€u-
sion. The di€usive ¯ux j, de®ned as volume of mat-
ter ¯owing across unit area perpendicular to the
¯ux direction per unit time, is assumed to depend
linearly on the gradient of the chemical potential m
of the di€using species:
Dd
jˆÿ rm …2†
kT
where D is di€usivity, d is the thickness of the
layer through which the material di€uses, k is
Boltzmann's constant and T is the absolute tem-
perature.
4673
Along the grain-boundary, the gradient of the
chemical potential is directly related to the gradi-
ent of stress, s, acting normal to the grain-
boundary [13], i.e.
m ˆ ÿOs …3†
where O is the atomic volume. Along the free
surface, the gradient of the atomic chemical poten-
tial is related to the gradient of the free-surface
curvature [13], i.e
m ˆ ÿOgs k …4†
Here gs is the surface tension and k is the principal
curvature of the surface.
In equation (2), Dd should be replaced by
Dgbdgb for grain-boundary di€usion and by Dsds
for free-surface di€usion. The subscripts ``gb'' and
``s'' represent grain-boundary and free surface,
respectively.
4. NUMERICAL SCHEME AND NON-
DIMENSIONALIZATION
The coupled grain-boundary and surface di€u-
sion problem is generally too dicult to solve ana-
lytically. Cavity growth and sintering are two
opposite phenomena. Under many practical circum-
stances both processes can be controlled by the
coupled di€usion mechanism. For cavity growth, a
steady state solution was obtained by Chuang and
Rice [14] and later a self-similar solution was
obtained by Chuang et al. [15]. For the sintering
problem of uniform particles, Svoboda and Riedel
obtained an analytical solution for the so-called
``small scale'' di€usion problem [16]. For more gen-
eral situations, numerical methods have to be used.
Pharr and Nix [17] studied the cavity growth pro-
blem while Bross and Exner [18] studied the sinter-
ing problem using similar numerical methods at
almost the same time. More recent studies of sinter-
ing using numerical analysis include the work by
Bouvard and McMeeking [19] and Zhang and
Schneibel [20]. These e€orts have considerably
improved our understanding of sintering kinetics.
However, there is a common problem to all these
previous studies: surface di€usion was assumed to
be symmetric about the grain-boundary and conse-
quently the sintering of particles of di€erent sizes
cannot be studied using these numerical schemes
since matter di€uses from the smaller particle to the
larger one when the two particles in contact are of
di€erent sizes.
Recently, a general numerical method has been
developed by Pan and coworkers [11, 21], which can
be used to simulate microstructural evolution con-
trolled by solid state di€usion and grain-boundary
migration. Using this numerical method, the evol-
ution history of a prescribed network of grain-
boundaries with internal and external free surfaces
can be followed. The grain-boundaries and the free
4674 PAN et al.: A MODEL FOR THE SINTERING OF SPHERICAL PARTICLES

surfaces can take any arbitrary shape. As a demon- and

strating example of the numerical scheme, the dA
co-sintering process of two cylinders of di€erent dA ˆ 2
r2
radii was simulated [11].
In this work, the numerical scheme described in Then equation (2) becomes
Ref. [11] is used with some straightforward modi®-
cations to consider the axisymmetric problem of the jgb ˆ rs …9†
two spherical particles instead of the two cylinders
for the grain-boundary di€usion and
considered previously. The underlying principle
used in this study is exactly the same as that js ˆ D s rk …10†
described in Ref. [11], i.e. the chemical potential at
the junction between the grain-boundary and the for the free-surface di€usion, in which
free surface is taken as an unknown. Matter conser- Ds ds
vation in the vicinity of the junction is used to D s ˆ …11†
Dgb dgb
determine the chemical potential. As soon as this
chemical potential is known, the central ®nite di€er- Two non-dimensionalized groups of the material
ence scheme is used to determine the migration vel- properties have emerged from the above analysis:
ocity of the free surface. The approach velocity D s , which represents the relative importance of the
between the two particles is obtained analytically two di€usion processes, and g gb , which determines
for the di€usion problem in the circular disk of the dihedral angle, C, through the equation
contact between the two particles. The pro®le of the g gb
system is then updated using the direct Euler inte- cos C ˆ …12†
2
gration scheme and the entire procedure is repeated
for a required number of time steps. Rather than The numerical results are presented using D s and C
repeat the details of the numerical scheme here, as the input material properties. To apply the
emphasis is placed on the physical merits of the results to any real material system, data required by
numerical analysis. equation (5) as well as D s and g gb need to be avail-
It proves convenient to discuss the numerical able so that equation (6) can be used to transform
results in terms of non-dimensionalized groups of the non-dimensionalized results into those for the
material properties that control the sintering kin- material system concerned.
etics. A reference ``strain rate'' is de®ned as:
Dgb dgb O gs
e_ gb ˆ …5†
kT r42 5. OVERVIEW OF THE COMPUTER SIMULATION

where r2 is the initial radius of the large particle. In The computer simulations presented cover a wide
this paper, all the lengths are scaled by r2 and the range of di€erent combinations of r1/r2, D s , C, and
various physical variables are non-dimesionalized in s 1 , which represent the ratio of particle radii, the
the following way: ratio of surface di€usivity over grain-boundary dif-
k ˆ kr2 , fusivity, the dihedral angle and the normalized
average stress applied on the grain-boundary, re-
sr2 spectively. The ratio of particle radii, r1/r2, is varied
s ˆ
gs between 0.1 and 1.0 and D s is varied between 0.01
j and 100. Three di€erent values of the dihedral
j ˆ angle, i.e. C = 458, C = 608 and C = 758, and
e_ gb r22
three levels of the applied stress are used. Table 1
summarizes all the di€erent cases. In total about
_ ˆ W_
W
e_ gb r2 150 simulations were performed covering the
various di€erent cases.
t ˆ e_ gb t …6† Ideally, the numerical analysis should start from
zero contact area between the two particles.
where W_ is the approaching velocity between the Numerically, however, the analysis has to start
two particles and t is the time. The free energy E from a small initial contact area. In the numerical
can be non-dimensionalized as
… …
E
E ˆ 2 ˆ dA s ‡ g gb dA gb …7†
r2 gs s gb
Table 1. An overview of the computer simulation
r1/r2 D s C s 1
in which
0.1, 0.2, 0.3, 0.01, 0.1, 458, 608, 758 0.0, 5.0, 50.0
ggb 0.5, 0.7, 0.9, 1.0, 100.0
g gb ˆ …8†
gs 1.0
 PAN et al.: A MODEL FOR THE SINTERING OF SPHERICAL PARTICLES 4675

simulations, the radius of the initial contact area
has been taken as 0.1r1.
The total volume of the two particles should
remain constant throughout the co-sintering process
but numerical errors cause volume ¯uctuations
during the simulation. In all the simulations per-
formed, the maximum ¯uctuation of the total
volume was within 4% of the initial volume of the
small particle. This indicates the high accuracy of
the numerical scheme.
The co-sintering process can be divided into two
distinct stages, i.e. the stages before and after the
grain-boundary disappears. Once the grain-bound-
ary disappears, the system becomes one particle
which evolves eventually into a perfect sphere as
shown in Fig. 1. The second stage, which is comple-
tely controlled by surface di€usion, is of little prac-
tical interest since at this stage the interaction
between the system and the surrounding particles
becomes signi®cant. All the simulations were there-
fore terminated as soon as the grain-boundary
migrates out of the system.
6. CHARACTERISTICS OF SHAPE EVOLUTION OF
THE TWO-PARTICLE SYSTEM
One of the purposes of the numerical study is to
understand how the two-particle system evolves.

Fig. 2. Computer-simulated co-sintering process of two particles in contact with each other: r1/r2=0.5,
D s =1.0 and C = 608. (a) t ˆ 0, (b) t ˆ 1:153  10ÿ2 , (c) t ˆ 21:95  10ÿ2 , (d) t ˆ 28:19  10ÿ2 .
4676 PAN et al.: A MODEL FOR THE SINTERING OF SPHERICAL PARTICLES

Based on such an understanding, a simpler model
of the system can be proposed and approximate sol-
utions can be obtained using the variational
approach described by Parhami et al. [10].
It is obvious that the closer the sizes of the two
particles, the greater is the in¯uence of the smaller
particle on the shape evolution of the entire system.
This can be seen by comparing the numerical result
from the case of r1/r2=0.5 with that of r1/r2=0.1 as
shown in Figs 2 and 3, respectively. In these
examples C = 608 and D s =1. For r1/r2=0.5 the
large particle changes its shape rapidly from a
sphere into a bulb. For r1/r2 =0.1, however, the
large particle manages to maintain its original
shape.
Varying D s (the ratio of surface di€usivity to
grain-boundary di€usivity) changes whichever of
the two di€usion processes dominates the co-sinter-
ing process. It is the slower process that controls
the overall rate, for example, when D s =100 grain-
boundary di€usion dominates and when D s =0.01
surface di€usion dominates. Figures 4 and 5 show
the cases for D s =0.01 and 100, respectively, which
can be compared with Fig. 2 where D s =1. In these
examples, C = 608 and r1/r2=0.5. It can be
observed that although D s varies over a range of
®ve orders of magnitude, the pattern of the shape
evolution remains similar. The grain-boundary dif-
fusion-controlled case shows a slightly smaller
grain-boundary during the entire process. These ob-

Fig. 3. Computer-simulated co-sintering process of two particles in contact with each other: r1/r2=0.1,
D s =1.0 and C = 608. (a) t ˆ 0, (b) t ˆ 1:227  10ÿ4 and (c) t ˆ 2:9  10ÿ4 .
 PAN et al.: A MODEL FOR THE SINTERING OF SPHERICAL PARTICLES 4677

Fig. 4. Computer-simulated co-sintering process of two particles in contact with each other: r1/r2=0.5,
D s =0.01 and C = 608. (a) t ˆ 0, (b) t ˆ 0:8078, (c) t ˆ 10:56 and (d) t ˆ 20:05.

servations are also true for other ratios of particle
radii. The numerical results suggest that D s mainly
in¯uences the rate of the process not the pattern of
evolution.
The dihedral angle has a dramatic e€ect on the
pattern of the shape evolution. This is clearly
demonstrated by comparing Fig. 6, where C = 458,
with Fig. 2, where C = 608, for r1/r2=0.5 and by
comparing Fig. 7, where C = 458, with Fig. 8,
where C = 608, for r1/r2=0.9. In these examples,
D s =1.0. It can be seen that a smaller dihedral
angle helps the small particle to maintain a more
rounded shape throughout the co-sintering process.
As mentioned in the Introduction (Section 1), in
e€ort to model the co-sintering process, Tanaka [9]
assumed that the two particles maintain their trun-
cated spherical shape as matter is transferred from
the small particle to the large one while Parhami et
4678 PAN et al.: A MODEL FOR THE SINTERING OF SPHERICAL PARTICLES

Fig. 5. Computer-simulated co-sintering process of two particles in contact with each other: r1/r2=0.5,
D s =100 and C = 608. (a) t ˆ 0, (b) t ˆ 0:6  10ÿ3 , (c) t ˆ 7:171  10ÿ3 and (d) t ˆ 9:687  10ÿ3 .

al. [10] modi®ed Tanaka's model by introducing a
cylindrical disk between the two spheres. From the
computer simulations presented above it can be
seen that the actual shape evolution of the two-par-
ticle system is very di€erent from those assumed by
Tanaka and Parhami et al. In fact the two-particle
system can be better approximated by a system that
consists of two truncated spheres connected by a
truncated cone, as shown in Fig. 9(a). The approxi-
mate system is completely determined by ®ve geo-
metric parameters: the radii of the large and small
truncated spheres, r1 and r2, the radii of the top
and bottom sections of the truncated cone, r1 and
r2, and the height of the truncated cone, h. Matter
conservation requires that only four of the ®ve par-
ameters are independent; the system therefore has
four degrees of freedom. The system starts from
h = 0 and r1=r2=r0, where r0 is the initial neck
 PAN et al.: A MODEL FOR THE SINTERING OF SPHERICAL PARTICLES 4679

Fig. 6. Computer-simulated co-sintering process of two particles in contact with each other: r1/r2=0.5,
D s =1.0 and C = 458. (a) t ˆ 0, (b) t ˆ 7:948  10ÿ2 , (c) t ˆ 65:49  10ÿ2 and (d) t ˆ 80:77  10ÿ2 .

size. By comparing the numerical results for all the
di€erent cases, it is found that for r1/r2 larger than
0.5, the junction between the truncated cone and
the large truncated sphere can be regarded as a
smooth one. As a consequence, the degrees of free-
dom of the approximate system can be reduced to
three as shown by Fig. 9(b). For r1/r2 less than 0.5,
the approximate model with four degrees of free-
dom, shown by Fig. 9(a), is more appropriate.
7. TIME TO DISAPPEARANCE OF THE GRAIN-
BOUNDARY
A characteristic time describing the co-sintering
process is the time taken for the inter-particle
boundary (i.e. the grain-boundary) to migrate out
of the system. In the following discussions, this
characteristic time is referred as to td (which is non-
dimesionalized by e_ gb ). Once the grain-boundary
has disappeared, grain growth is complete as far as
4680 PAN et al.: A MODEL FOR THE SINTERING OF SPHERICAL PARTICLES

Fig. 7. Computer-simulated co-sintering process of two particles in contact with each other: r1/r2=0.9,
D s =1.0 and C = 458. (a) t ˆ 0, (b) t ˆ 12:68 (c) t ˆ 15:25 and (d) t ˆ 16:39.

the two particles are concerned and it is experimen- log±log plots. The numerical results can be best
tally dicult to distinguish the system from its sur- ®tted using the following empirical formula
rounding particles in a powder compact.    4:63
ggb r1
The dependence of td on relative di€usivity D s td ˆ 0:15
D sÿ0:85
…13†
gs r2
and the ratio of particle radii r1/r2 is shown in
Figs 10±12, for C = 458, C = 608 and C = 758, re- which is plotted in Figs 10±12 using solid and
spectively. The interesting feature of the numerical dashed lines to compare with the numerical results.
results is that td depends linearly on r1/r2 on the Using equations (5) and (6) we obtain
 PAN et al.: A MODEL FOR THE SINTERING OF SPHERICAL PARTICLES 4681

Fig. 8. Computer-simulated co-sintering process of two particles in contact with each other: r1/r2=0.9,
D s =1.0 and C = 608. (a) t ˆ 0, (b) t ˆ 0:7869, (c) t ˆ 5:242 and (d) t ˆ 5:84.

    Equation (14) suggests that the in¯uence of grain-

kT Dgb dgb 0:85 ggb
td ˆ 0:15

boundary di€usivity on the characteristic time is
Ogs Dgb dgb Ds ds gs
much weaker than that of surface di€usivity. This is
 4:63
r1 expected since it is the local surface di€usion of


r42 …14†
r2 matter from the small particle to the large one that
controls the grain-boundary migration. The grain-
boundary is pinned at the junction between the
grain-boundary and the free surface, and can only
4682 PAN et al.: A MODEL FOR THE SINTERING OF SPHERICAL PARTICLES

Fig. 9. An approximate model of the two-particle system (a) using four independent degrees of freedom
and (b) using three independent degrees of freedom.

migrate when the junction moves by surface di€u-
sion. Grain-boundary di€usion has little in¯uence
on this process. It does, however, control the neck
growth and shrinkage between the two particles
which will be discussed in the Section 8. Equation
(14) also suggests that the in¯uence of the size of
the large particle on the characteristic time is much
weaker than that of the small one. This is simply
because the grain-boundary always migrates
through the small particle.
Equation (14) breaks down when r1/r2
approaches unity for which td should be in®nity in

Fig. 10. The time to disappearance of the grain-boundary at various values of the relative di€usivity
and ratio of particle radii. The symbols represent the numerical results; the solid and dashed lines rep-
resent the empirical formula of equation (13). C = 458.
 PAN et al.: A MODEL FOR THE SINTERING OF SPHERICAL PARTICLES 4683

Fig. 11. The time to disappearance of the grain-boundary at various values of the relative di€usivity
and ratio of particle radii. The symbols represent the numerical results; the solid and dashed lines rep-
resent the empirical formula of equation (13). C = 608.

theory. In reality the symmetric con®guration of erty can destroy the symmetry. This was observed
two identical particles is unstable and a small per- in the numerical simulation for identical particles
turbation of the particle geometry or material prop- during which numerical errors destroy the sym-

Fig. 12. The time to disappearance of the grain-boundary at various values of the relative di€usivity
and ratio of particle radii. The symbols represent the numerical results. The solid and dashed lines rep-
resent the empirical formula of equation (13). C = 758.
4684 PAN et al.: A MODEL FOR THE SINTERING OF SPHERICAL PARTICLES

metry slightly and cause the grain-boundary to s1 r2

migrate towards one of the particles. s 1 ˆ
gs
In these examples, D s =1 and C = 608. The nu-
merical results can be ®tted using a modi®ed ver-
8. SHRINKAGE AND CONTACT SIZE sion of equation (15)
   
Based on their ®nite di€erence studies, Bouvard W_ r1 a b s 1 r2
and McMeeking [19] suggested the following ˆ 0:5 1 ‡ ‡
r2 e_ gb r2 …x=r2 †4 …x=r2 †2 gs
empirical formula to describe the relationship
_ and the radius …16†
between the approach velocity, W,
of the contact area, x, between two identical par-
which is plotted in the ®gures using solid and
ticles
dashed lines. Here a and b have been taken as 9
 
W_ a b s1 r and 8, respectively, which is consistent with the
ˆ ‡ …15† values used by Bouvard and McMeeking [19]. It
r_egb …x=r†4 …x=r†2 gs
can be seen that the numerical results con®rm
where r is the radius of the particles, s1 is the aver- equation (15) for the case of uniform particles. As
age stress transmitted onto the contact area, a is a the size of the small particle decreases, the approach
pure number which depends on D s and b is a pure rate decreases. This is incorporated in the empirical
number which is insensitive to D s and s1. formula given by equation (16) by introducing a
Figures 13±15 present the numerical results from factor 0.5(1 + r1/r2). The interesting feature of the
this study relating W _ to x for various values of r /
1 numerical results is that the particle ratio does not
r2 and for s 1 =0 (Fig. 13), s 1 =5 (Fig. 14), and have a signi®cant e€ect on the approach rate pro-
s 1 =50 (Fig. 15), respectively, where vided that r1/r2 is larger than 0.5. This is especially
the case when stress is applied as shown by Figs 14
_ ˆ W_
W and 15. As the matter redistribution from the grain-
r2 e_ gb
boundary to the neck is a local event in the early
x stages of the co-sintering process, the relative size
x ˆ of the two particles only comes into play at a later
r2
stage. The numerical results indeed indicate that W_
and depends on r1/r2 in the later stages. When stress is

Fig. 13. Relationship between the shrinkage rate and the contact radius at various values of the ratio of
particle radii. The solid and dashed lines represent the empirical formula of equation (16). C = 608,
D s =1 and s 1 =0.
 PAN et al.: A MODEL FOR THE SINTERING OF SPHERICAL PARTICLES 4685

Fig. 14. Relationship between the shrinkage rate and the contact radius at various values of the ratio of
particle radii. The solid and dashed lines represent the empirical formula of equation (16). C = 608,
D s =1 and s 1 =5.

applied, it tends to dominate the driving force for equation (16) breaks down for r1/r2 less than 0.5.
the co-sintering process and further weakens the in- The numerical results can be better ®tted by intro-
¯uence of r1/r2. From Figs 13±15 it can be seen that ducing a di€erent factor, 0.5(1 + (r1/r2))x for

Fig. 15. Relationship between the shrinkage rate and the contact radius at various values of the ratio of
particle radii. The solid and dashed lines represent the empirical formula of equation (16). C = 608,
D s =1 and s 1 =50.
4686 PAN et al.: A MODEL FOR THE SINTERING OF SPHERICAL PARTICLES

example, to equation (16) where x is an empirical
exponent. No attempt to do so has been made here
since such ®tting does not give any further insight
into the process.
Figure 16 shows the numerical results relating the
shrinkage W to the radius of the contact area x
between the two particles. Coble used a simple re-
lationship between the two variables [8]
 
w 1 x 2
ˆ …17†
r 2 r
in which r is the initial radius of the particles. For
two identical particles, the numerical results con®rm
equation (17) when the neck radius is larger than
0.2r. For non-identical particles, the numerical re-
lationship can be ®tted using a modi®ed version of
equation (17)
  ÿz  2
W r1 1 x
ˆ 0:5 1 ‡ …18†
r2 r2 d r2
in which d and z are empirical parameters.
Equation (18) is plotted on Fig. 16 using z = 1.5
and d = 2.4 for comparision with the full numerical
results. The empirical ®tting breaks down when the
neck size is very small or when r1/r2 is less than 0.5.
Figure 17 presents the numerical results relating
the normalized shrinkage, W/r2, to the normalized
time, t_egb , for three di€erent values of r1/r2 and for
D s =1 and C = 608. Again it can be seen that the
size ratio of the two particles has almost no e€ect
on the shrinkage. This observation is true for the
entire range of values of D s and C covered in
Table 1. From Fig. 17, it can also be observed that
W/r2 is linearly dependent on t_egb on the log±log
scale which suggests the following empirical re-
lationship
W ÿ
1=n
ˆ lt_egb …19†
r2
where l and n are empirical parameters. It is found
that n is insensitive to D s and C and is within the
range between 3 and 4. The empirical parameter l
is found to be dependent on D s and C. For
example, l = 0.006316, 0.4453 and 1.1874 for
D s =0.01, 0.1, and 1.0, respectively when C = 608.
At any ®xed normalized shrinkage, the shrinkage
rate is linearly dependent on l. The numerical
results suggest that as surface di€usivity increases
over three orders of magnitude relative to grain-
boundary di€usivity, the shrinkage rate increases
over the same orders of magnitude.
Figure 18 presents the numerical relationship
between W/r2 and t_egb covering D s =0.01±10,
C = 458±758 and r1/r2=0.5±1.0. Equation (19) is
plotted on top of the numerical results using n = 4
and l = 1.1874. Equation (19) is invalid for D s lar-
ger than 10, i.e. the linear relationship between W/
r2 and t_egb on the log±log scale breaks down when
D s is larger than 10. This is shown in Fig. 19 for an
extreme case of D s =100.
Probably the most interesting numerical result
presented in this section is that for a wide range of

Fig. 16. Relationship between the shrinkage and the contact radius at various values of the ratio of par-
ticle radii. The solid and dashed lines represent the empirical formula of equation (18). C = 608, D s =l
and s 1 =0.
 PAN et al.: A MODEL FOR THE SINTERING OF SPHERICAL PARTICLES 4687

Fig. 17. The shrinkage as a function of time for various values of the ratio of particle radii. C = 608
and D s =1.

material parameters, the shrinkage and shrinkage
rate between the two particles are not signi®cantly
a€ected by the size di€erence between the two par-
ticles. This numerical ®nding simpli®es the task of
constructing densi®cation laws for powder compacts
when taking into account the e€ect of size distri-
butions. It means that the size distribution only in-
¯uences densi®cation (in the early stages) by
in¯uencing the initial density and the number of
contacts of a powder compact. The di€usion kin-
etics between the particles are not a€ected at least
in the early stages of the sintering process. This
conclusion is not valid if the size di€erence between
the particles is larger than 50%.
9. A DENSIFICATION RATE EQUATION FOR
POWDER COMPACTS WITH A BIMODAL
PARTICLE SIZE DISTRIBUTION
For a powder compact which consists of particles
of only two di€erent radii, Rl and Rs, for large and
small particles, respectively, nl and ns are the num-
ber fractions of the large and small particles. There
are three di€erent types of contacts between the
particles; nss, nll and nls represent the number frac-

Fig. 18. The shrinkage as a function of time. The shaded band represents the numerical results covering
D s =0.01±10, C = 458±758 and r1/r2=0.5±1.0. The solid line represents the empirical formula of
equation (19) using n = 4.
4688 PAN et al.: A MODEL FOR THE SINTERING OF SPHERICAL PARTICLES

Fig. 19. The shrinkage as a function of time for various values of the ratio of particle radii. C = 608
and D s =100.

tions of contacts between small and small, large nsll ‡ nsls ‡ nsss
and large, and large and small particles, respect- e_ ˆ ÿ W_ …24†
2nsll Rl ‡ nsls …Rl ‡ Rs † ‡ 2nsss Rs
ively. Turner [22] demonstrated that the number
fractions of the di€erent contacts can be expressed in which W_ is the shrinkage rate of a contact.
as Using equation (20) and equations (21)±(23), it can
 2 be shown that
n l Rl
nll ˆ
nl Rl ‡ ns Rs nsls V s 1 ‡ R s
s ˆ …25†
2nl Rl ns Rs nll 1 ÿ V s R 2s
ls ˆÿ
2
nl Rl ‡ ns Rs and
 2  2
ns Rs nsss V s 1
nss ˆ …20† ˆ …26†
nl Rl ‡ ns Rs nsll 1 ÿ V s R 3s

Furthermore Turner found that the number frac- where R s =Rs/Rl and V s is the volume fraction of
tions of the contacts in a string of two sizes of par- the small particles in the compact. Using
ticle can be given as equations (25 and 26), equation (24) can be rewrit-
ten as
2nll Rl
nsll ˆ …21†
2nll Rl ‡ nls …Rl ‡ Rs † ‡ 2nss Rs 1 ÿ
W_
e_ ˆ ÿ w R s ,V s …27†
2 Rl
nls …Rl ‡ Rs †
nsls ˆ …22† in which
2nll Rl ‡ nls …Rl ‡ Rs † ‡ 2nss Rs
ÿ

w R s ,V s ˆ
2nss Rs ÿ
2 ÿ
ÿ

nsss ˆ …23†
2nll Rl ‡ nls …Rl ‡ Rs † ‡ 2nss Rs R 3s 1 ÿ V s ‡ V s 1 ÿ V s 1 ‡ R s R s ‡ V s2
ÿ
2 ÿ
ÿ
2
where the superscript ``s'' denotes a string. R 3s 1 ÿ V s ‡ 0:5V s 1 ÿ V s 1 ‡ R s R s ‡ V s2 R s
In order to obtain the densi®cation rate equation, …28†
either equation (16) together with equation (18) or
equation (19) can be used. For simplicity, the latter Identifying r2 in equation (19) as Rl and substitut-
is used here, i.e. it is assumed that the normalized ing equation (19) into equation (27) gives
shrinkage rates for the three di€erent types of con-
1
tacts are the same. The line strain rate of the pow- e_ ˆ ÿ w…R s ,V s †…l_egb †1=n t…1ÿn†=n …29†
der compact is simply 2n
 PAN et al.: A MODEL FOR THE SINTERING OF SPHERICAL PARTICLES 4689

Referring to the relative density of the compact as ameter of the material which is advantageous as the
D and the densi®cation rate as D_ then constituent properties, especially the thermal di€u-
sivity, are dicult to measure accurately.
 1 It must be pointed out that equation (33) is only
D_ D 3
ˆ ÿ3_e …30† valid for the early stage of sintering during which
D D0
the interaction between di€erent contacts is insignif-
in which D0 is the initial density of the compact. icant and the contact number is not a€ected by
Combining equation (29) with equation (30) gives density changes of the compact although it would
be possible to release the second limitation. The
 1 conclusion that size di€erence does not a€ect the
D_ 3 ÿ  
D 3ÿ
1=n …1ÿn†=n
shrinkage between two particles can be used to
ˆ w R s ,V s l_egb t …31†
D 2n D0 develop densi®cation rate equations for powder
which can be integrated with respect to time giving compact with a known size distribution. This has
not been pursued here but rather equation (33) has
 1 been constructed to establish a macroscopic conse-
D0 3 1 ÿ  
ÿ
1=n 1=n quence of the numerical ®ndings so that exper-
1ÿ ˆ w Rs ,Vs l_egb t …32†
D 2 iments can be performed to verify the numerical
results. ÿ

Eliminating t from equations (31) and (32) and
Function w R s ,V s represents the di€erence in
noticing equation (5) results in densi®cation rate between a uniform powder com-
ÿ

0 11ÿn pact and a bimodal powder compact. w R s ,V s is
 1  1
D_ ÿ
1 D 3 B1 ÿ D 0 3C
plotted in Fig. 20 where the e€ects of volume frac-
ˆ Awn R s ,V s 4 @ A …33† tion and size of the small particles can be seen
D Rl D0 D
clearly.

in which A is the only parameter that depends on

material properties and temperature: 10. CONCLUSIONS
   
3…2†1ÿn Dgb dgb Ogs Particle size distribution can in¯uence the sinter-
Aˆ

l …34† ing process in two respects, i.e. grain growth and
2n kT
densi®cation. The two processes become strongly
As discussed in Section 8, l is an empirical par- coupled in the intermediate stage of the sintering
ameter which depends on Dsds/Dgbdgb and gs/ggb, process. In the early stage, however, they can be
and increases as Dsds/Dgbdgb increases. In practice treated separately. For early stage sintering,
A can be determined experimentally as a single par- equation (14) can be used to formulate a rate

Fig. 20. E€ect of the volume fraction V s and relative size R s of the small particles on the initial densi®-
cation rate of a powder compact with a bimodal particle size distribution.
4690 PAN et al.: A MODEL FOR THE SINTERING OF SPHERICAL PARTICLES
equation for grain growth, and equations (16) and
(19) can be used to formulate a rate equation for
densi®cation. The most interesting ®nding of this
numerical study is that the shrinkage and shrinkage
rate between two particles is not signi®cantly
a€ected by the size di€erence of the two particles as
long as the di€erence is less than 50%. The densi®-
cation rate equation, equation (33), for powder
compacts with bimodal particle size distribution, is
directly based on this numerical conclusion and
therefore can be used to verify the numerical ®nd-
ings experimentally.
AcknowledgementsÐThe authors wish to thank A. C. F.
Cocks for his invaluable suggestions throughout this
work. Parts of the numerical simulations were performed
by ®nal year project students including A. Sem, H. D.
Luong and C. Poth in the Department of Mechanical
Engineering of the University of Surrey. This research is
®nancially supported by the EPSRC (grant GR/K78102),
which is gratefully acknowledged.
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