Acta Materialia 52 (2004) 2953–2963

www.actamat-journals.com

Effective diffusion coefficients in solid-state sintering

Andrey L. Maximenko, Eugene A. Olevsky *

Department of Mechanical Engineering, San Diego State University, 5500 Campanile Dr., San Diego, CA 92182-1323, USA
Received 14 January 2004; received in revised form 14 January 2004; accepted 27 February 2004
Available online 27 March 2004

Abstract

A numerical analysis of the sintering neck growth rate between rigid spherical particles of the same size is carried out. The
contributions of the surface, grain-boundary and volume diffusion transport into sintering kinetics during the first and the second
stages of sintering are estimated. It is shown that the three-dimensional problem of the matter redistribution during sintering can be
reduced to a two-dimensional problem if the effective diffusion coefficients are introduced. The effective diffusion coefficients are the
grain-boundary diffusion coefficients that include the contribution of volume diffusion. The effective diffusion coefficients are sen-
sitive to the stage of sintering: they have different form during the first and the second stages. During the second stage of sintering,
the unified effective diffusion coefficient is determined. It is demonstrated that the effective diffusion coefficients can be used also for
the description of the pressure-assisted sintering.
Ó 2004 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: Sintering; Grain-boundary diffusion; Surface diffusion; Volume diffusion; Interparticle neck

1. Introduction sion coefficients are, in general, different from each

Solid-state sintering is a thermally activated process of
the matter transport driven by high surface energies of the
aggregates of fine particles. Diffusion matter redistribu-
tion decreases the area of internal surfaces in powder
compacts and as a rule leads to their consolidation. In
technological processes, sintering is often aided by an
external compressive pressure. In this case, the process is
termed ‘‘pressure-assisted sintering’’ to distinguish it from
‘‘free sintering’’ without any external loading. A consol-
idation technology, sintering is widely used in all branches
of powder metallurgy and ceramic production. The pre-
diction of consolidation kinetics and of the contributions
of different matter transport mechanisms into densifica-
tion is one of the core problems in sintering theory.
During solid-state sintering, diffusion transports
matter along free surfaces and volumes of particles,
along grain boundaries between them, and through a
vapor phase around them. In all these cases, the diffu-
*
Corresponding author. Tel.: +1-619-594-6329; fax: +1-619-594-
3599.
E-mail address: olevsky@engineering.sdsu.edu (E.A. Olevsky).
other. Resulting diffusion fluxes are related to each other
through the common driving force dictated by an ex-
ternal loading and by the geometry of a powder aggre-
gate; however, they vary in magnitudes and directions
[1]. The prediction of sintering kinetics depends on
correct estimations of matter transport along different
diffusion paths. Despite the appreciable practical sig-
nificance of the classical models of sintering (e.g. [2–4]),
they, as a rule, belong to the pre-‘‘computer-simulation’’
age; now, many well-known sintering problems can be
revisited on the basis of new opportunities in modeling.
Different types of diffusion processes during solid-
state sintering are not equal in difficulty arising in their
modeling. The analysis of grain-boundary diffusion
tends to be straightforward and it has been studied ex-
tensively [1]. In recent years, a significant improvement
has been achieved in the computer modeling of surface
diffusion. From the mathematical point of view, the
prediction of the matter transport by surface diffusion is
a highly non-linear problem that, in general, does not
have simple analytical solutions. The development of
effective numerical methods enabled a number of im-
portant findings on the kinetics of sintering by coupled

1359-6454/$30.00 Ó 2004 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.actamat.2004.02.042
2954 A.L. Maximenko, E.A. Olevsky / Acta Materialia 52 (2004) 2953–2963
grain-boundary and surface diffusions. These diffusion
mechanisms are dominant for the low-temperature sin-
tering of fine powders. The numerical modeling verified
traditional assumptions of the sintering simulations and
gave new insights on such sintering-related processes as
highly non-equilibrium regimes of initial neck growth
[5,6], the development of internal stresses [7], the pore–
grain-boundary separation [8,9], and the neck develop-
ment under tensile loading [10]. The modeling of the
surface and grain-boundary diffusions during sintering is
a two-dimensional problem since only matter fluxes
upon surfaces are considered. An incorporation of the
bulk diffusion into sintering models renders a full-scale
three-dimensional problem.
A general framework for the analysis of the bulk dif-
fusion has been developed by Herring [11]. From the
mathematical standpoint, the analysis of bulk diffusion
matter fluxes is similar to the analysis of heat fluxes in a
steady-state heat conduction problem [12]. The methods
of the solution of this problem are well established. In our
case, the main difficulty in the use of standard methods is
that the three-dimensional boundary-value problem for
the determination of the bulk diffusion matter fluxes has
to be solved at every time step of the numerical procedure
employed in the sintering modeling. A straightforward
solution of the three-dimensional problem dramatically
extends the time of sintering calculations. In order to
circumvent this difficulty, different analytical approxi-
mations for the bulk diffusion fluxes have been used by
different authors. In some of these approximations, the
solution of the boundary-value problem has been replaced
by the analysis of the diffusion ‘‘leakage’’ of the material
from boundaries into the adjacent infinite volume [2]; in
other approximations, the effect of bulk diffusion has been
taken into account by adopting the same functional form
for the evolution of sintering parameters as for the cou-
pled grain-boundary and surface diffusion and by the re-
placement of the grain-boundary diffusivity with some
effective parameter [3,4,10]. The results of these approxi-
mations are useful from the practical point of view but
their applicability range is usually unclear. Another idea is
the utilization of some commercial finite-element software
using the similarity between diffusion and heat conduction
problems [12,13]. In prospect, this approach seems to be
the simplest. Unfortunately, the majority of commercial
finite-element software does not include modules for
modeling grain-boundary and surface diffusion. The pre-
sent paper is an attempt to simultaneously model the
grain-boundary, the surface and the bulk diffusion for the
classical problem of the sintering of spherical particles.
2. Problem formulation
The modeling is dedicated to the numerical analysis
of the sintering neck growth rate between rigid spherical
Fig. 1. Schematics of the considered unit cell of sintered material.
particles of the same size (Fig. 1). During sintering,
plane circular necks of the radius x between particles of
the radius R are developed. Free surfaces of particles
meet at the dihedral angle w at the edge of the neck
between them. The coordination number of powder
packing is incorporated into the model through the
packing angle u. The packing angle defines the spherical
sector of the particles corresponding to the considered
neck. For example, for the cubic packing of spherical
particles, the packing angle is u ¼ p=4 (see Fig. 1); for
the row of particles, it is equal to p=2. In numerical
calculations of the neck development, it is sufficient to
consider only a part of the particles within the spherical
angle u with the symmetry boundary conditions super-
imposed at the conical boundaries of the spherical sector
[5,6]. From the physical point of view, the introduction
of the packing angle replaces the influence of the pro-
pinquitous necks on the development of the neck under
consideration by the influence of the continuous band of
contacts located around the equator of the particles
forming the neck. As a result of this simplification, the
problem of the neck development becomes axially
symmetrical about the center-to-center line OO1 (see
Fig. 1). The considered geometry of the neck develop-
ment corresponds to the first and the second stages of
sintering [14] when single necks are discernible. The final
stage of sintering with close porosity cannot be de-
scribed by this model.
As aforementioned, three different paths of diffusion
matter redistribution are considered in the sintering
modeling. The diffusion matter flux Js along free sur-
faces of particles is driven by the gradient of the surface
curvature
ds Ds Xcs dK
Js ¼
; ð1Þ
kT ds
where Ds is the surface diffusivity, ds is the thickness of
the surface layer in which the diffusion takes place, K is
the sum of the principal curvatures at the edge of the
neck, k is the Boltzmann’s constant, cs is the specific
 A.L. Maximenko, E.A. Olevsky / Acta Materialia 52 (2004) 2953–2963 2955

surface energy, X is the atomic volume, s is the curvi- l ¼
cs K: ð9Þ

linear coordinate along the particle surfaces. The cur-
vature is assumed to be positive when the center of the Another boundary condition is defined at the contacts
curvature is outside of the particle volume. The grain- between the particles and it is the result of the as-
boundary diffusion flux is described with the equation sumption of the flatness of the contact area between two
similar to (1) identical particles. If the contact remains flat at each
moment of time, the displacement rates are the same for
Dg dg X dl
Jg ¼
; ð2Þ every element of the contact area
kT dr
mg ðrÞ þ mv ðrÞ ¼ const: ð10Þ
where l is the volume density of the chemical potential
at the grain boundary, Dg is the grain-boundary diffu- A similar boundary condition has been widely used for
sivity, dg is the grain-boundary diffusion width, r is the the modeling of the grain-boundary diffusion [5,6]. In
coordinate along the neck radius (Fig. 1). our case, an additional contribution due to the volume
The non-uniformity of the surface or the grain- diffusion appears in the left-hand side of (10). The
boundary diffusion fluxes leads to the deposition of matter displacement rates at contacts between particles
matter with the displacement rate m normal to the con- define the shrinkage rates of the considered unit cell of
sidered surface, which is equal to the material. The shrinkage rate w_ can be defined as a
rate of the distance change between the centers of par-
1 dðrJs Þ ticles (see Fig. 1)
ms ¼ ;
r ds ð3Þ w_ ¼ mg ðrÞ þ mv ðrÞ; ð11Þ
1 dðrJg Þ
mg ¼
; where dot in the left-hand side of (11) means the de-
r dr
rivative with respect to time. In the dimensionless
for free surfaces and grain boundaries, respectively. The computer calculations, the time of the process has been
condition of the flux continuity at the edge of the neck normalized by the characteristic time of surface diffusion
demands [5,10] ss [5] where
Jg ¼ 2Js at r ¼ x: ð4Þ kTR4
ss ¼ : ð12Þ
Another condition relating the grain-boundary and the ds Ds Xcs
surface matter transport is the condition of continuity of Sometimes it is convenient to use also characteristic
the chemical potential at the edge of the neck [5,6] times of the grain-boundary diffusion sg and the volume
ljr¼x ¼ cs Kjr¼x : ð5Þ diffusion sv
The diffusion matter flux from free surfaces or grain kTR4
sg ¼ ;
boundaries into the volume of the particles can be given dg Dg Xcs
ð13Þ
in the form [12] kTR3
sv ¼ :
Dv X ol Dv Xcs
Jv ¼
; ð6Þ
kT on In the time scale related to the time ss , the kinetics
where Dv is the volume diffusion coefficient, n is the di- of sintering do not depend directly on the different
rection of the outer normal to the surface element. A diffusivities but rather on the relative rates n, f of the
positive volume diffusion flux corresponds to the with- grain-boundary and volume diffusions compared to the
drawal of a material from particle surfaces; and the dis- surface diffusion
placement rate of surfaces mv due to volume diffusion is dg D g
n¼ ;
mv ¼
Jv : ð7Þ ds D s
ð14Þ
Note, that according to the definition (6), the volume RDv
f¼ :
diffusion matter flux Jv has different units than Jg , Js . ds Ds
According to the approach developed in [11], the volume In case of pressure-assisted sintering, the normal com-
diffusion during sintering can be considered through a ponent r of the external stress at the neck between par-
steady-state approximation when the chemical potential ticles has to be taken into account. In our calculations
in the bulk of particles obeys the Laplace equation the stress r is not a macroscopic stress in the particle
Dl ¼ 0: ð8Þ packing. It is a local stress resulting from the stress
concentration of a macroscopic stress in the neck area
For an unambiguous solution of the Eq. (8), the [5]. In a dimensionless form this stress can be used as
boundary conditions for the density of the chemical
potential have to be defined. At free surfaces of the rR

¼
r : ð15Þ
particles the chemical potential l has the value of cs
2956 A.L. Maximenko, E.A. Olevsky / Acta Materialia 52 (2004) 2953–2963

All possible sintering conditions can be taken into potential is that at h ¼ hj it is exactly equal to lj , so the
consideration through the variation of the five dimen- approximation is uniformly close to the chemical po-
sionless parameters: n, f, r

, w, u. tential throughout all h. Of course, accuracy of the ap-
proximation between the values h ¼ hj depends on the
number N . Fourier expansion (17) can be transformed
into the expansion with respect to Legendre polynomials
3. Numerical determination of volume diffusion fluxes
with the use of the following formula:
A numerical approach for the modeling of the surface X i
cosð2ihÞ ¼ dil P2l ðcos hÞ: ð21Þ
and grain-boundary diffusions was described in [10]. l¼0
Modeling of the surface and grain-boundary diffusion Relationship (21) contains finite number of terms equal
operates only with values of the chemical potential at to the order of the corresponding cosine. Coefficients dil
particle surfaces. Modeling of volume diffusion necessi- can be found numerically by the inversion of the Fourier
tates the determination of the chemical potential in the expansion of the Legendre polynomials
particle volumes. Spherical functions have been used for
the approximation of the chemical potential in the vol- X
l
P2l ðcos hÞ ¼ Clm cosð2mhÞ; ð22Þ
ume of particles m¼0
XN
r n
s where the exact forms of the coefficients Clm are delin-
l¼ an Pn ðcos hÞ; ð16Þ
n¼0
R eated in a multitude of Legendre polynomials-relevant
works [16]. After substitution of (21) into expansion (17)
where rs , h are the spherical coordinates related to the we obtain a relationship for the values of the chemical
center of a particle (see Fig. 1), Pn ðcos hÞ are Legendre potential at the spherical surface with unit radius
polynomials, an are unknown coefficients and N is the
number of terms. Spherical functions are the solutions X
N X
N X
i
lðhÞ ¼ lj pij dil P2l ðcosðhÞÞ: ð23Þ
of Eq. (8). If values of the chemical potential are known j¼1 i¼1 l¼0
at some spherical surface, the coefficients an can be
procured from the well-known integral formulas for the At the same surface the derivative of the potential in the
coefficients of the Legendre polynomial expansions. direction normal to the surface is
However, this simple approach turned out to be inef- ol XN XN Xi
fective due to the non-uniform convergence of the ob- ðhÞ ¼ lj pij 2ldil P2l ðcosðhÞÞ: ð24Þ
ors
tained expansions at the particle surfaces. As an j¼1 i¼1 l¼1

alternative approach, the Lanczos approximation for- Formula (24) is the main relationship that has been used
mulas [15] have been used for the coefficients of Fourier for the evaluation of the chemical potential derivatives
expansion. For example, if parameter h belongs to the and diffusion fluxes normal to the surface of spherical
interval ½0; p particles. The Legendre polynomials in (24) have been
X
N calculated through Eq. (22). The modeling indicates that
l¼ ci cosð2ði
1ÞhÞ; ð17Þ particle shapes steadily digress from the initial spherical
i¼1 shape. In the numerical assessments of (24), the values lj
the coefficients of the expansion (17) ci can be obtained have been calculated at the current distorted particle
as surfaces and then shifted to the spherical surface along
X
N the radial direction.
ci ¼ pij lj ; ð18Þ According to boundary conditions (9), the values of
j¼1 the chemical potential at free surfaces can be derived
directly through the assessment of the surface curvature.
where lj are the values of the chemical potential corre-
The values of the chemical potential at contacts between
sponding to the coordinates hj
particles are unknown. They have been determined from
hj ¼ ðj
1ÞDh j ¼ 1; N ; boundary condition (10). After substituting into Eq. (10)
p ð19Þ the relationships between the displacement rate and the
Dh ¼ :
N
1 derivatives of the chemical potential (3), taking into
The coefficients pij have the analytical form [15] account Eq. (7) with the use of the approximation for
the chemical potential (23), boundary condition (10) has
cosð2ði
1Þðj
1ÞDhÞ been transformed by collocation method into the set of
pij ¼ 2C : ð20Þ
N
1 linear equations with respect to the potentials lj at the
The constant C in (20) is equal to 0.5 if i ¼ 1, i ¼ N or contact between particles. For the unique solution these
j ¼ 1, j ¼ N ; and it is equal to 1 in all other cases. The equations have to be supplemented with the equation of
specific feature of expansion (17) for the chemical stress balance at the neck [17]
 A.L. Maximenko, E.A. Olevsky / Acta Materialia 52 (2004) 2953–2963 2957

Z x  
rx2 w 4. Effective diffusion coefficients during the first stage of
lðrÞr dr
þ xcs sin ¼ 0: ð25Þ sintering
0 2 2

This equation does not depend on the peculiarities of the Sintering process is naturally divided into three
considered diffusion mechanisms. The results of the stages. The first stage is the early stage of a highly non-
calculations demonstrate that, in general, for the com- equilibrium neck growth. During the second stage in-
bined matter transport by the grain-boundary and vol- dividual necks between particles are still discernible, but
ume diffusions, the distribution of the chemical potential the process of the neck growth can be treated as a quasi-
at contacts between particles is not a quadratic function equilibrium process. The boundary between the first and
anymore in opposite to the case of the independently the second stages seems somewhat vague, however, in
functioning grain-boundary diffusion. The chemical the considered model it can be clearly detected from the
potential distribution depends on the relative activity of form of the functions relating the dimensionless neck
the different diffusion paths. The distributions of the radius x=R with the accumulated shrinkage ðR
wÞ=R.
dimensionless potential density l
¼ lR=cs as a function These functions for different n and f ¼ 0 (see Fig. 3) and
of the radial coordinate r for x=R ¼ 0:1 and of the dif- different f for n ¼ 0 (see Fig. 4) include two parts. The
ferent combinations n, f are given in Fig. 2. As soon as initial parts of the curves are sensitive to n, f values.
the values of the chemical potential are known at the Later on, with neck increase all the curves gradually
contacts between particles, they are known everywhere converge into one unified curve. Both Figs. 3 and 4 have
at particle surfaces and the volume diffusion fluxes can been obtained for a cubic packing of particles. The
be estimated from (6) and (24). The packing angle has merger point with the unified curve indicates the onset
been introduced into the volume diffusion modeling of the second stage of sintering. Therefore, during the
through the selection of the initial Fourier expansions second stage of sintering the neck radius and the accu-
(17) with the periodicity corresponding to the packing mulated shrinkage are uniquely determined by the
angle u. equilibrium functions, which are, in our calculations,
The proposed method for the consideration of vol- slightly dependent on the n=f ratio. The comparison of
ume diffusion is an approximation. The error becomes the ‘‘equilibrium neck radius–accumulated shrinkage’’
greater when the shapes of particles considerably differ curves for the independently functioning grain-bound-
from spherical shapes. The level of the numerical error ary and volume diffusion mechanisms are given in
has been estimated through the level of the violation of Fig. 4, where the equilibrium curve from Fig. 3 is shown
the mass balance during diffusion processes. Calcula- as a dotted line. In general, Figs. 3 and 4 indicate that
tions have been stopped when the mass balance error the peculiarities of the matter redistribution during the
exceeded 0.02 of the initial particle mass.

0.80
x/R
200.00
_ 2
µ (R-w)/R=0.25(x/R)
ξ=0.1,ζ=0
0.60
Dimensionless chemical potential

100.00
ξ=0,ζ=1 ξ=0.01
Neck radius

xs /R ξ=0.1
0.40
ξ=1
0.00

0.20
-100.00

(R-w)/R
0.00
r
-200.00 0.00 0.04 0.08 0.12 0.16 0.20
0.00 0.04 0.08 0.12 Shrinkage
Distance from the neck center
Fig. 3. Neck radius as a function of accumulated shrinkage for sin-
Fig. 2. Dimensionless chemical potential at the neck between particles tering by coupled grain-boundary and surface diffusion. The dotted
as a function of the distance from the center of the neck for the neck line shows quadratic approximation of the accumulated shrinkage as a
radius x=R ¼ 0:1. function of neck radius.
2958 A.L. Maximenko, E.A. Olevsky / Acta Materialia 52 (2004) 2953–2963

0.60 _
wðn; 0; xÞ ¼ nwð1;
_ 0; xÞ;
ð27Þ
x/R _
wð0; f; xÞ ¼ fwð0;
_ 1; xÞ:

ζ=0.01 Relationships (27) are also approximations only, be-

ξ=0.01 cause for a non-equilibrium sintering the neck radius
0.40 does not define uniquely the whole particle shape and,
ζ=0.1
for example, wðn;
_ 0; xÞ, wð1;
_ 0; xÞ could correspond to
Neck radius

different particle shapes if two sintering processes with

different n were compared. However, for the considered
ζ=1 values of n; f < 5 the error in (26) and (27) always re-
mained within the range of several percents.
0.20
In order to find the combination of the diffusion pa-
rameters, that governs the shrinkage rate, the ratio
/ ¼ wð0;
_ 1; xÞ=wð1;
_ 0; xÞ ð28Þ
(R-w)/R has been estimated as a function of the neck radius. The
0.00 ratio of wð0;
_ f; 1Þ=wð1;
_ 0; xÞ as a function of the dimen-
0.00 0.01 0.02 0.03 0.04 0.05 sionless neck radius is given in Fig. 5 for different f. The
Shrinkage relative positions of the curves in Fig. 5 confirm the
Fig. 4. Neck radius as a function of accumulated shrinkage for sin-
linearity in (27). The ratio / has been estimated from the
tering by coupled volume and surface diffusions. The dotted line is the numerical results as
similar function for sintering by coupled grain-boundary and surface /  2:8x
0:05: ð29Þ
diffusions.
The second term in the right-hand side of (29) depends
on the initial particle shape during modeling and it is
first and the second stages are different and they have to considered to be negligible. After substitution of rela-
be analyzed separately. tionships (27) and (28) into Eq. (26) we obtain
During the first stage of sintering the interactions of _
wðn; f; xÞ ¼ wð1;
_ 0; xÞðn þ 2:8fx=RÞ
necks with each other are negligible and therefore the
topological character of this stage remains the same for Dweff dg
¼ wð1;
_ 0; xÞ : ð30Þ
any type of powder packing. The type of powder D s ds
packing determines only the duration of this stage. For The second equation in (30) defines the effective diffu-
example, the first stage of sintering ranges up to the sion coefficient of the shrinkage rate
relative neck radius of x=R  0:6 for the row of particles
(u ¼ p=2); x=R  0:45 for the simple cubic packing of
particles (u ¼ p=4); and x=R  0:33 for the fcc type of 8.00
Ratio of lattice and grain-boundary diffusion shrinkage rates

packing (u ¼ p=6). It is convenient to study the first φ

stage for the sintering of a row of particles because in
this case this stage has the longest duration.
The evolution rate of every geometrical parameter of 6.00

a sintering structure depends on some combinations of ζ=5

diffusion coefficients. These combinations can be differ-
ent for different parameters. As the most important
parameters, the shrinkage rate, the neck growth rate, 4.00

and the neck viscosity have been considered. The cal-

culations predict that in the case when all three diffusion
paths are active the shrinkage rate can be obtained as a
superposition of the shrinkage rates with a single-den- 2.00

sification mechanism and the same neck radius ζ=1

ζ=0.5
_
wðn; f; xÞ ¼ wðn;
_ 0; xÞ þ wð0;
_ f; xÞ: ð26Þ
0.00
In general, this result is not a foregone conclusion since
0.00 0.20 0.40 0.60 0.80
for each combination of n, f the chemical potential
Neck radius
distributions at the neck are different. For the same
particle shapes the linearity of the considered diffusion Fig. 5. Ratio of shrinkage rates / as a function of the dimensionless
process gives neck radius.
 A.L. Maximenko, E.A. Olevsky / Acta Materialia 52 (2004) 2953–2963 2959

x 1.00
Dweff ¼ Dg þ 2:8Dv : ð31Þ
dg φ1

Relationship (31) shows that the contribution of lattice

0.80
diffusion into the shrinkage rate linearly increases with
the neck radius. In case when the grain-boundary and

Relative neck growth rate

volume diffusion transports are both active, the shrink-
0.60
age of a powder compact can be estimated from the
analysis of the grain-boundary diffusion only with the ζ=5
grain-boundary diffusion coefficient equal to Dweff . Re-
lationship (31) also shows that, if Dv R is of the same 0.40

order as Dg dg , the change of the sintering dominant

mechanism and the sintering activation energy can be
observed during the neck growth.
For the neck growth rate during the first stage of
sintering, relationships similar to (26) and (27) are valid
for the differences x_
x_ 0 , where x_ 0 is the neck growth
rate by the surface diffusion matter transport without
any contribution of the grain-boundary and lattice
diffusion
x_ ðn; f; xÞ
x_ ð0; 0; xÞ
¼ ½_xðn; 0; xÞ
x_ ð0; 0; xÞ þ ½_xð0; f; xÞ
x_ ð0; 0; xÞ; ð32Þ
x_ ðn; 0; xÞ
x_ ð0; 0; xÞ ¼ nð_xð1; 0; xÞ
x_ ð0; 0; xÞÞ;
ð33Þ
x_ ð0; f; xÞ
x_ ð0; 0; xÞ ¼ fð_xð0; 1; xÞ
x_ ð0; 0; xÞÞ:
Similar to the procedure that has been used to define the
effective diffusion coefficient for the shrinkage rate, the
effective diffusion coefficient, which rules the neck
growth, has been obtained from the evaluation of the
ratio
/1 ¼ ½_xð0; 1; xÞ
x_ ð0; 0; xÞ=½_xð1; 0; xÞ
x_ ð0; 0; xÞ: ð34Þ
The calculations demonstrate that during the first stage
of sintering this ratio also can be approximated as a
linear function of x. The ratio
x_ ð0; f; xÞ
x_ ð0; 0; xÞ
/1 ðfÞ ¼ ð35Þ
x_ ð1; 0; xÞ
x_ ð0; 0; xÞ
as a function of x for different f is shown in Fig. 6. The
numerical approximation gives for the ratio /1
/1  0:4x: ð36Þ
Again, the free term in the approximation has been
omitted. The neck growth rate can be approximated as
x_ ðn; f; xÞ ¼ x_ ð0; 0; xÞ þ ½_xð1; 0; xÞ
x_ ð0; 0; xÞðn þ 0:4xfÞ;
ð37Þ
and the effective diffusion coefficient of the neck growth
can be introduced in the way similar to Eq. (30)
x very close to those obtained in [5]. Within the time scale
Dxeff ¼ Dg þ 0:4Dv : ð38Þ
dg
Despite a similar structure, the effective diffusion coef-
ficient estimated from the neck growth rate Dxeff differs
from the coefficient obtained based on the shrinkage
0.20
ζ=1
ζ=0.5
x/R
0.00
0.00 0.20 0.40 0.60 0.80
Neck radius
Fig. 6. Ratio of neck growth rates /1 as a function of the dimensionless
neck radius.
rate Dweff . However, comparable to the case of the
shrinkage rate, according to Eq. (38), the contribution
of volume diffusion into the neck growth is negligible for
small necks and it linearly increases with the neck size.
The effective diffusion coefficient Dxeff allows the predic-
tion of the neck growth rate from the consideration of
the grain-boundary and surface diffusion mechanisms
only with the grain boundary diffusivity replaced by
expression (38).
Another combination of the diffusion coefficients
should be present in the relationships for the neck vis-
cosity. The neck viscosity g appears as a parameter in
the stress–strain rate relationships for the shrinkage rate
of a neck under external stress [5]
!
w_
r¼g
e_ f : ð39Þ
R
The viscosity of a neck is the proportionality coeffi-
cient between the normal component of the external
stress at the neck r and the change of the shrinkage rate
due to the influence of this stress. Here e_ f stands for the
shrinkage rate without external loading. The numerical
modeling predicts simple relationships for the neck vis-
cosities as functions of neck radius. The neck viscosity
for the case of the grain-boundary and surface diffusion
coupled transport mechanisms has been obtained in [5].
Our results for this case are shown in Fig. 7, they are
related to the characteristic time sg (13) the neck vis-
cosity gg practically does not depend on n and can be
approximated as
2
gg ¼ gn  2:6ðx=RÞ : ð40Þ
2960 A.L. Maximenko, E.A. Olevsky / Acta Materialia 52 (2004) 2953–2963

0.16 1 2 3 relationship corresponding to the deformation by the

ηg two above-mentioned parallel mechanisms under the
influence of a common force
1 1 1
0.12 ¼ þ : ð42Þ
g gv gg
A comparison of approximation (42) with the results
Viscosity of the neck

of the direct numerical assessment of the neck viscosities

0.08 is given in Fig. 9. As expected, relationship (42) gives a
very good approximation for the neck viscosity. Ana-
1− ξ=1 lytical approximations (40) and (41) are shown in Fig. 9
2− ξ=0.1 as dotted lines. Eq. (42) gives
3− ξ=0.01
0.04 gg
¼ 2:7fx=R þ n: ð43Þ
g
The right-hand side of (43) includes a term similar to the
one in Eqs. (30) and (37). The effective diffusion Dgeff
0.00
defined from this term has the following form:
0.00 0.20 0.40 0.60 0.80
x
Dimensionless neck radius, x/R Dgeff ¼ Dg þ 2:7Dv : ð44Þ
dg
Fig. 7. Viscosity of the neck for sintering by coupled grain-boundary
and surface diffusion. Within the accuracy of the conducted calculations
one can see that
The neck viscosity gv during sintering governed by Dgeff ¼ Dweff : ð45Þ
the volume diffusion and the surface diffusion matter
transport is a linear function of the neck radius. Within The important consequence of equality (45) for the
the time scale related to the characteristic time sv (13) it effective diffusion coefficients is the independence of the
is not sensitive to the f value and can be given in the product
 2
form (see Fig. 8) R
r0 ¼ g_ef ; ð46Þ
gv ¼ gf  0:95x=R: ð41Þ x
If both the grain boundary and volume diffusions are from the parameters n, f. This result can be checked by
active, the viscosity of a neck can be derived from the the direct substitution of (30) and (43) into (46). The

1.00
0.60
η
η
v
ζ=10 ζ=1
0.80
ζ=0.01
ξ=0.1,ζ=0
Viscosity of the neck

0.40
Viscosity of the neck

0.60

0.40 ξ=0, ζ=1

0.20

0.20 ξ=0.1, ζ=1

x/R
x/R 0.00
0.00 0.00 0.20 0.40 0.60 0.80
0.00 0.20 0.40 0.60 0.80 Neck radius
Neck radius
Fig. 9. Viscosity of the neck for the combined grain-boundary, volume,
Fig. 8. Viscosity of the neck for sintering by coupled volume and and surface diffusion mechanisms: comparison of the numerical results
surface diffusion. with the prediction of the relationship (42).
 A.L. Maximenko, E.A. Olevsky / Acta Materialia 52 (2004) 2953–2963 2961

value of the parameter r0 is proportional to the sintering 10.00

•
stress [18,19] where sintering stress is a macroscopic •
Wς
isostatic stress producing the same densification effect as Wξ=0.01

the diffusion processes during free sintering without any 8.00

external loading. The independence of r0 from n, f
means independence of the sintering stress from char-

Ratio of shrinkage rates

acteristics of the diffusion processes during sintering. As 6.00
the first approximation, the sintering stress turns out to
be a function only of the geometrical parameters of ζ=1

powder packing and the neck radius. 4.00

ζ=0.5

5. The second stage of sintering and constrained sintering 2.00

There is a correlation between the neck size and ζ=0.1

accumulated shrinkage during the second stage of
sintering
R
w
x
¼f ; ð47Þ
R R
and, therefore, there is a correlation between time de-
rivatives w_ and x_ . Relationships between the shrinkage
and the neck radius are widely used in theories of sin-
tering. One of the most widespread relationships ap-
proximates the shrinkage ðR
wÞ=R as a quadratic
function of the neck radius [20]. The plot of this function
is given in Fig. 3 as a dotted line. One can see that the
quadratic approximation corresponds well only to the
first stage of sintering with n; f  1 . Unlike the qua-
dratic approximation, the equilibrium function (47)
during the second stage of sintering is not equal to zero
for zero shrinkage (see Figs. 3 and 4). It starts from
some minimum neck radius xs corresponding to the
transition to the second stage of sintering for small n, f
and, according to our calculations, the function (47) can
be approximated as some linear relationship at the be-
ginning of the second stage of sintering. The value of xs
is shown in Fig. 3. The correlation between the shrink-
age rate and the neck growth rate indicates the existence
of only one effective diffusion coefficient. For the as-
sessment of this coefficient, it is sufficient to calculate the
evolution of the shrinkage rates ratio / (28) during the
second stage of sintering. This ratio is given in Fig. 10 as
a function of the neck radius for the first and the second
stages of sintering and the packing angle u ¼ p=6. One
can see from this picture that both during the first and
the second stages, the ratio can be approximated as a
linear function of the neck radius. The linear approxi-
mations are given in Fig. 10 as dotted lines. However,
these linear approximations are different for different
stages. During the first stage, the ratio / increases with
the increase of the neck radius; during the second stage,
it slowly decreases. The rate of the decrease of the value
/ in our calculations depends on the type of powder
packing and it is proportional to the increase of the
neck curvature during the second stage. Experimental
0.00
0.00 0.10 0.20 0.30 0.40 0.50
Neck radius
Fig. 10. Ratio of shrinkage rates corresponding to the volume and
grain-boundary diffusion mechanisms through the first and the second
stages for fcc packing of particles. Dotted lines show linear approxi-
mations of the numerical data.
measurements of the internal surface curvature during
the second sintering stage show that the average pore
curvature is almost constant during this stage, because
the densification occurs primarily due to the decrease of
the amount of small pores [21,22]. As a result, the ef-
fective diffusion coefficient during the second stage of
sintering can be estimated as
C
Deff ¼ Dg þ Dv ; ð48Þ
dg
where C is a constant depending on the type of powder
packing. According to our modeling results for different
packing (see Fig. 11)
0:8 6 C 6 1:4: ð49Þ
During constrained sintering tensile stresses appear at
necks between particles. Low-tensile stresses just slow
the neck growth down, however, they do not prevent it.
For higher tensile stresses, the necks between particles
are stabilized at some level and the residual porosity re-
mains in a powder compact after sintering. If the tensile
stress is high enough the necks disintegrate [10]. At the
stages when the external stress dominates densification,
the constrained sintering has important common fea-
tures with the second stage of free sintering. Similar to
the case of the second stage of sintering, there is one-to-
one correspondence between the shrinkage rate and the
neck growth rate independent from n, f. For example,
the values of the accumulated shrinkage are given in
Fig. 12 as functions of the neck radius for tensile stress

¼ 100 and different n, f. One can see from this picture
r
that during the stage of the neck reduction under tensile
2962 A.L. Maximenko, E.A. Olevsky / Acta Materialia 52 (2004) 2953–2963

2.00
•
mined by the applied external stress and the viscosity of
Wς the neck. The effective viscosity of neck can be obtained
•
ςWξ=0.1 from relationship (42). However, it should be noted that
1.60 the viscosities gg , gv during the neck reduction stage are
slightly higher than the same viscosities during the neck
growth stage. The evolution of the viscosities during
Relative shrinkage rate

1.20 φ = π/4 tensile loading is given in Fig. 13. The increase of both
viscosities gg , gv during the neck reduction stage main-
tains their ratio close to its value during the neck growth
stage. As a result, relationship (44) for the effective dif-
0.80
fusion coefficient can be used also for the neck reduction
φ = π/6
stage under tensile loading.
In experimental investigation of the constrained sin-
0.40
tering of metal powders on rigid substrates in some
cases, it has been detected that the activation energy of
x/R the densification during constrained sintering is consid-
0.00 erably different from the activation energy of free sin-
0.00 0.20 0.40 0.60 tering [23]. This phenomenon can be explained as a
Neck radius result of the difference in activation energy during the
Fig. 11. Influence of the packing angle on the transition from the first first and the second stages of sintering and the sintering
to the second stage of sintering. Dotted lines show linear approxima- anisotropy of constrained films. During sintering of
tions of the relative shrinkage rates during the second stage of sinter- films the shrinkage rate in direction normal to the film
ing. surface is higher than the free shrinkage rate. The ratio
of the shrinkage rates is equal to ð1 þ mp Þ=ð1
mp Þ,
where mp is the viscous analogy of the elastic Poisson
0.04
ratio [20]. Active growth of necks in planes parallel to
(R-w)/R the film surface leads to the rapid completion of the first
stage of sintering for these necks. As a result, the acti-
0.00 vation energy measured during constrained sintering is,
in fact, the activation energy of the second stage of
sintering. The activation energy of the free sintering for
-0.04 ξ=0.1, ζ=1 the same density levels corresponds to the first stage of
Shrinkage

sintering because of the smaller necks between particles.

ξ=0.1, ζ=0 The role of volume diffusion increases during the second
-0.08
ξ=0, ζ=1
4.0E-1

ηg , η
v
-0.12

3.0E-1
Dimensionless viscosity

x/R
-0.16
0.04 0.08 0.12 0.16 0.20
Neck radius
2.0E-1
Fig. 12. Accumulated shrinkage as a function of the neck radius under
tensile loading. η (ζ=1, σ=100)
v

1.0E-1 ηg (ξ=0.1, σ=30)

loading the shrinkage rate is a linear function of the neck
growth rate. An approximation gives
w_ 
0:7_x: ð50Þ
x/R
This relationship can be useful for the modeling of the 0.0E+0
0.05 0.10 0.15 0.20 0.25 0.30
damage development during constrained sintering be-
Neck radius
cause it provides some assessment of the moment when
the neck between two particles disappears under tensile Fig. 13. Neck viscosity during neck growth and neck reduction stages
loading. The shrinkage rate w=R
_ in Eq. (50) is deter- under tensile loading as a function of the neck radius.
 A.L. Maximenko, E.A. Olevsky / Acta Materialia 52 (2004) 2953–2963
stage of sintering and the activation energy of the
constrained sintering should be close to the activation
energy of volume diffusion. This conclusion has been
confirmed experimentally in [23].
6. Conclusions
The numerical analysis of an axisymmetrical two-
particle unit cell allows the evaluation of the contri-
butions of the surface, grain-boundary and volume
diffusion transport into sintering kinetics during the first
and the second stages of sintering. The three-dimensional
problem of the matter redistribution during sintering
can be reduced to the two-dimensional one if the effec-
tive diffusion coefficients are introduced. The effective
diffusion coefficients are the grain-boundary diffusion
coefficients that include the contribution of volume
diffusion. In general, the effective diffusion coefficients
are different for the evolution of different sintering pa-
rameters: during the first stage of sintering, the effective
diffusion coefficient of the neck growth is different from
the effective diffusion coefficient of the shrinkage rate.
The effective diffusion coefficients are sensitive to the
stage of sintering: they have different form during the
first and the second stages. During the second stage of
sintering the unified effective diffusion coefficient has
been defined. The effective diffusion coefficients can be
used for the description of the pressure-assisted sintering
in the case of compressive or tensile loading.
Acknowledgements
The support of the NSF Division of Manufacturing
and Industrial Innovations (Grant DMI-9985427), NSF
Division of Civil and Mechanical Systems (Grant CMS-
0301115), and NSF Division of Materials Research
(Grant DMR-0313346) is gratefully appreciated.
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