Densification and grain growth during

sintering of nanosized particles

Z. Z. Fang and H. Wang
The sintering of nanosized particles is a scientific and technological topic that affects the
manufacture of bulk nanocrystalline materials and the understanding of the stability of
nanoparticles. Owing to their extremely small size and the high surface to volume ratio,
nanoparticles during sintering exhibit a number of distinctively unique phenomena compared to
the sintering of coarse powders. Particularly, it is generally found that the sintering temperatures
of nanosized particles are dramatically lower than that of their micrometre or submicrometre sized
counterparts. Research has also shown that the grain growth during nanosintering consists of an
initial dynamic grain growth stage that occurs during heating up and the normal grain growth
stage that occurs mostly during isothermal holding. For nanoparticles, the effect of the initial grain
growth cannot be ignored because that it is sufficient to cause the material to lose nanocrystalline
characteristics. This review aims to bring to focus the understanding of the fundamental issues of
nanosinteirng, including the thermodynamic driving force of nanosintering, non-linear diffusion
and the kinetics of nanosintering, and the relationships between agglomeration, densification and
grain growth. This review will also examine the effects of microstructure and processing variables.
Keywords: Nanoparticle sintering, Sintering, Densification, Grain growth, Coarsening, Size effect

Introduction which in turn results in different kinetic rates of

Since the emergence of nanoscaled science and technol-
ogy, the sintering of nanosized particles has been a topic
of both scientific and technological importance.
Sintering is a phenomenon that occurs in a broad range
of nanomaterials processes, including the synthesis of
nanoparticles and fabrication of bulk nanocrystalline
materials. Moreover, sintering is an important factor in
determining the stability of nanomaterials, nanoscaled
coatings and nanodevices. In some cases, sintering of
nanosized particle is not desired; in others, sintering is
required. For example, sintering should be prevented for
nanosized catalysts, while nanosized powders must be
sintered to manufacture bulk nanocrystalline materials.
Owing to the importance of the sintering of nanopar-
ticles, a large body of literature on nanosintering has
been accumulated and published over the past two
decades. Although sintering nanoparticles shares the
same basic principles as that of sintering coarser
particles, a number of issues and challenges are unique
to nanosintering. For example, the thermodynamic
driving force for nanosintering is extremely large, calling
into question the use of conventional sintering doctrines
based on linear diffusion theories. Non-linear diffusion
behaviour leads to different kinetic rates of diffusion,
Department of Metallurgical Engineering, University of Utah, 135 S. 1460
E. Room 412, Salt Lake City, UT 84112, USA
*Corresponding author, email zak.fang@utah.edu
sintering.
In the context of engineering processes, sintering
implies the bonding of one solid particle to another. The
sintering process can be regarded as consisting of two
intertwined processes: densification and grain growth.
Another unique issue of nanosintering is that nanopar-
ticles almost always experience extremely rapid grain
growth during sintering, rendering the loss of nanocrys-
talline characteristics at the fully sintered state. With
respect to manufacturing bulk nanocrystalline materials
from nanoscaled particles, the objective of nanosintering
is to achieve maximum densification while retaining
nanoscaled grain sizes. This goal, however, has been
very difficult to reach. In fact, it is a glaring technolo-
gical challenge for many materials. Fundamentally,
there are two main reasons for this technological
impasse. One is that the same factors that result in
densification also cause grain growth. In other words,
both densification and grain growth processes share the
same driving force and mass transport mechanisms.
Moreover, in many cases, grain growth is required in
order to break the local interfacial energy balance
necessary to sustain continuous elimination of pores.1
The literature on nanosintering can be classified into
two groups: those focused on the densification and grain
growth behaviour during sintering at the nanoscale; and
those focused on innovative sintering technologies and
processes. Fundamental studies included molecular
dynamics (MD) simulation at the atomic scale, the
kinetic studies of sintering using non-linear diffusion

ß 2008 Institute of Materials, Minerals and Mining and ASM International

Published by Maney for the Institute and ASM International
326 International Materials Reviews 2008 VOL 53 NO 6 DOI 10.1179/174328008X353538
 Fang and Wang Densification and grain growth during sintering of nanosized particles

theories, and the modelling of kinetic behaviour based
on a generalised parabolic model of grain growth. In
addition, efforts have been directed toward the study of
the grain growth of nanosized particles.
Innovative sintering technologies include the two step
sintering technique and various pressure assisted sinter-
ing techniques. The two step sintering technique was
designed to decouple the densification and grain growth
processes that occur during conventional pressureless
sintering. Pressure assisted sintering techniques were
designed to achieve full densification while retaining
nanoscaled grain sizes. Conventional pressure assisted
processes, including hot pressing (HP) and hot isostatic
pressing (HIP), have been used for sintering and
consolidation of nanosized powders. Other unique
processes such as microwave sintering and spark plasma
sintering (SPS) are widely applied in the research of
sintering of nanoparticles.
Since the early 1990s, two comprehensive reviews have
been conducted that deal with the topic of nanosintering
or processing of nanosized particles.2,3 The issues of
nanosintering and the difficulties of manufacturing bulk
nanocrystalline materials from nanoscaled powders are
discussed in other reviews that cover broader topics of
nanomaterials.4,5 Collectively, these reviews provide a
strong foundation for understanding the status of
technologies and science issues involved in sintering of
nanosized particles. Since that time, however, significant
progress in the field has been made. This review will focus
on the progress toward understanding the unique
behaviours of nanoparticles, particularly the size depen-
dent properties and their effects on nanosintering. The
authors anticipate that this focus will aid the community’s
efforts to find solutions to controlling and optimising
densification and grain growth. Specifically, we will
extract information from published studies, both experi-
mental and theoretical, and organise the information a
way that highlights the differences in the sintering of
nanoparticles versus that of coarser particles, as well as the
relationship between grain growth and densification. The
review is presented in two main sections: densification of
nanoparticles and grain growth during nanosintering.
Each section will include a discussion of the thermo-
dynamic driving force and kinetic behaviours.
Densification during sintering of
nanosized particles
In general, the sintering of nanosized or nanocrystalline
powders follows the same path as larger grain powders.
However, compared to conventional micrometre sized
or submicrometre sized particles, the densification
behaviour of nanoparticles during sintering is notably
different with respect to the rate of densification and the
temperature range at which densification occurs. The
densification of nanoparticles is strongly affected by
agglomeration of particles, pores and other processing
variables. Although many of these factors also impact
the sintering of conventional micrometre sized particles,
the effects are more dramatic and magnified in the case
of nanosized particles. The densification behaviour of
nanosintering can be analysed from the perspectives of
both the thermodynamics and the kinetics of the
process.
Thermodynamic driving force of nanosintering
The thermodynamic driving force for sintering particles
of any size is the reduction of surface energy. Based on
conventional sintering theories, the driving force of
sintering can be given by6


1 1
s~ck~c z (1)
R1 R2
where c is the surface energy of the material, k is the
curvature of a surface, which is defined by k~ R11 z R12 (for
a convex surface, it is taken to be positive; for a concave
surface, it is taken to be negative), and where R1 and R2
are the principal radii of the curvature. The driving force
for the sintering of nanosized particles is, therefore,
inversely proportional to the size of the particles. This
relationship would lead to a much higher driving force for
the sintering of nanosized particles compared to micro-
metre sized particles. For example, based on equation (1),
the driving force for a 10 nm particle is two magnitudes
higher than that for a 1 mm particle.
The large driving force of nanosintering can be even
higher than the result of equation (1) if the non-linear
dependency of vacancy concentrations on the particle
size is considered. During sintering, mass transport,
usually mediated by vacancies, is driven by the
difference in vacancy concentration DCv5Cv2Cv0,
where Cv is the vacancy concentration for a surface
with curvature of k, and Cv0 is vacancy concentration
for a flat surface. Based on Gibbs–Thomson equation7


ckV
Cv ~Cv0 exp { (2)
kT
where V is the atomic volume, k is Boltzmann’s constant
and T is the absolute temperature. For micrometre sized
particles, the term

ckV/kT%1,
 equation (2) becomes
ckV
linear, Cv &Cv0 1{ , therefore
kT
ckV
DCv &{Cv0 (3)
kT
However, when particle size approaches nanoscale, the
linear approximation is no longer valid. The correct
expression for the driving force of mass transport should
be given as


ckV
DCv ~Cv0 exp { {Cv0
kT

 
ckV
~Cv0 exp { {1 (4)
kT
Equation (4) shows that the driving force for mass
transport during sintering is a non-linear function of
the surface curvature, and it increases exponentially
when particle size decreases to nanoscale. Figure 1
DCv
schematically illustrates the relationship of versus
Cv0
ckV 1
{ ~
, where d* is related to the particle size. This
kT d
non-linear relationship of the driving force for nano-
sintering is expected to have a dramatic effect on the
kinetics of sintering.
The driving force of nanosintering is also affected by
specific surface energy c. The value of c may change as a
function of the particle size. Campbell et al.8 studied the

International Materials Reviews 2008 VOL 53 NO 6 327

Fang and Wang Densification and grain growth during sintering of nanosized particles
1 Schematic comparison of vacancy concentration as
function of particle size between linear approximation
and non-linear equation
effect of size dependent nanoparticle energetics on
catalyst sintering. By using microcalorimetric measuring
the heat of adsorption of Pb onto MgO (100), they
showed that the surface energy increases substantially as
the radius decreases below y3 nm (Fig. 2).
Independently, Nanda et al.9 showed that the surface
energy of nanoparticles is significantly higher than that
of the bulk, as demonstrated by studying size dependent
evaporation of Ag nanoparticles.
From another aspect, the surface energy is also a
function of the crystal orientations, which could affect
the driving force of nanosintering. Groza2 pointed out
2 Illustration of discrepancy between measured differential
heat of adsorption of Pb onto MgO(100) and prediction
based on constant c model: surface energy increases
substantially as radius decrease below y3 nm (Reprinted
with permission from American Association for the
Advancement of Science)
328 International Materials Reviews 2008 VOL 53
3 Oriented attachment of nanosized titania under hydro-
thermal conditions (Reprinted with permission from
Elsevier)
that because nanocrystals have significant surface area,
the problem of anisotropy becomes even more critical.
Although there are numerous studies reporting that
nanoparticles have anisotropic faceted morphology, direct
correlation of their effect on surface energy and sintering
are not available in the literature and, understandably,
very difficult to perform. One phenomenon that has been
reported regarding nanocrystals with faceted morphology
is that they form oriented attached assembly as shown in
Fig. 3.10 The oriented attachment of nanoparticles could
affect the coalescence of these particles and the densifica-
tion and grain growth during sintering.
Kinetic behaviour of nanosintering
Sintering temperature
Notably, the sintering of nanosized particles occurs at
lower temperatures than the sintering of conventional
micrometre sized or submicrometre sized powders, as
shown schematically in Fig. 4. Sintering temperature is,
in general, a loose concept, referring to the entire
temperature range of densification. In order to be
specific and quantitative, the starting temperature is
often used for comparison. However, because sintering
and densification are continuous kinetic processes,
rigorously speaking, a single point of demarcation for
the starting temperature of sintering does not exist.
Based on typical experimental behaviour, the starting
temperature can be defined as the temperature at which
the rapid densification stage initiates, as marked on
Fig. 4. In general, the densification versus temperature
plot shifts to the left (lower temperature) when
nanosized powders are used rather than micrometre
sized powders. For example, several studies on the
sintering of nanoyitrium stabilised zirconia (YSZ) have
4 Schematic diagram illustrating different onset tempera-
tures of sintering of nano- and micrometre sized particles
NO 6
 Fang and Wang
5 Per cent of densification of WC–Co as function of continuous heating temperature for various initial particle sizes:
After Ref. 17
shown that the sintering temperature of nanocrystalline
ZrO2 initiates at a temperature 200 degrees lower than
that of the microcrystalline powders.11–13 An even
greater temperature difference of sintering, 400uC, was
reported by Mayo14 for nanosized titania compared to
commercial TiO2 powders. Similar results were observed
when sintering nanoceria15 and nano-titanium nitride
powders.16
A comprehensive study on the sintering of nanotung-
sten carbide and cobalt (WC–Co) powders was con-
ducted by Muheshwari et al.17 Figure 5 shows the per
cent of densification as a function of the continuous
heating temperature for various initial particle sizes.
Clearly, the entire sintering temperature decreases
steadily as the initial average particle size decreased
from 30 mm to 10 nm. It seems, however, that there is
little difference between the onset temperatures of the
sintering of particles greater than 1 mm.
Relatively speaking, fewer systematic studies exist on
the densification behaviour of nanosized metal powders
than on nanoceramic powders.18–20 A direct and
systematic study of the sintering of nanocrystalline Fe
and Cu powder was reported by Dominguez et al. in
1998.21 Compared to micrometric powder, the rapid
densification of nano-Fe and Cu powders started at
y200uC lower temperatures. A reduction of the sinter-
ing temperatures was also reported for nanotung-
sten.22,23 The reported sintering temperature of
nanosized tungsten powders produced by high energy
mechanical milling was dramatically decreased from
conventional temperature of 2500 to 1700uC. More
surprisingly, Oda et al. showed that the nanosized
tungsten powders could be sintered even at 1000uC by
using SPS. The authors’ own recent work on sintering of
nanosized tungsten powder demonstrated that nano-
tungsten with y20 nm initial sizes can be sintered up to
.98% relative density without pressure at 1100uC in a
hydrogen atmosphere.24
General sintering theories hold that a material’s
sintering temperature is often correlated with the
material’s melting point. It has long been known that
Densification and grain growth during sintering of nanosized particles
the melting temperature of very fine particles decreases
with the size of particles.25–40 In the case of nanosin-
tering, the decreasing onset temperature of sintering
can be understood, therefore, on the basis of the
lower melting temperature of nanoparticles. Troitskii
et al.41 studied the initial sintering temperature of
different sized TiN powders and found the relationship
between initial sintering temperature Tis and particle
size r is
Tis (r)~T(?)exp½{c(r0 {r)=r (5)
where T(‘) is the initial sintering temperature of coarse
particles; c is a constant determined by the properties
of the material and the energetic state of the surface
layer; r9 is arbitrary size.
Jiang and Shi42 ascribed the size dependent initial
sintering temperature of nanosized particles to the
decreased melting temperature of nanosized particles
based on the relationship
Tis (r)~0:3Tm (r)
 
2Sm (?) 1
~0:3Tm (?) exp { (6)
3k (r=r0 ){1
where Tm(‘) is the melting temperature of the bulk
material, Svib(‘) is the bulk melting entropy, r is particle
radius, r053h (where h is atomic diameter) for nano-
particles, k is Boltzman constant. Figure 6 shows the
predicted size dependent initial sintering temperature of
some metallic powders by using equation (6).42 Note
that the significant changes of the initial sintering
temperature do not occur until the particle size is less
than y20 nm.
Scaling law: dependence of nanosintering on particle size
In conventional sintering theories, the dependence of
densification behaviour on the size of particles is
described by the scaling law. In 1950, Herring44 first
introduced the scaling law as follows
Dt2 ~ln Dt1 (7)
International Materials Reviews 2008 VOL 53 NO 6 329
Fang and Wang Densification and grain growth during sintering of nanosized particles
6 Theoretical prediction of initial sintering temperature
Tis(r) for selected metals in terms of equation (6):
experimental initial sintering temperature of W, Ni and
Ag are also plotted in figure for comparison:18,43 After
Ref. 42
where l5R2/R1, R1 and R2 are particle radius, n depends
on specific diffusion mechanisms of the densification.
Specifically, n51 for viscous flow, 2 for evaporation and
condensation, 3 for volume diffusion and 4 for surface
diffusion or grain boundary diffusion. The scaling law
states that the time required to sinter powders with a
particle radii of R1 and R2 is proportional to the ratio of
the particle radius. Although the densification behaviour
of nanopowders can be qualitatively understood on the
basis of the scaling law, few direct analyses of
experimental data exist in the literature. The few studies
that did apply the scaling law used the following
expression to analyse the activation energies of the
sintering of nanopowders45,46



d1 Q 1 1 powders, the densification of a powder compact depends
nln ~ { (8)
d2 R T2 T1
where d1, d2 are particle sizes, T1 and T2 are
corresponding sintering temperatures, R is the gas
constant and Q is the activation energy. By using the
above equation, some studies obtained activation energy
values that are closer to grain boundary diffusion, while
others obtained values closer to volume diffusion, which
is believed to be unlikely at low temperatures. These
discrepancies in the values of activation energies
obtained using this method, therefore, raise questions
on the validity of the scaling law for sintering of
nanoscale particles.
The derivation of scaling law is based on an
assumption that the particle size of two different
powder systems used for comparison does not change
during sintering and microstructural changes remain
geometrically similar for the two systems. This
assumption points out the key limitations of using
the scaling law: it is difficult to maintain the conditions
in the assumption in real powder systems.47 During
nanosintering, particle size changes rapidly and some
characteristics of nanoparticles, such as agglomeration
and the non-uniformity of green density, increase the
difficulty of maintaining similar microstrutural evolu-
tions during sintering. In addition, the classic scaling
law was derived from linear equations; thus the validity
of the scaling law during nanosintering is questionable.
The non-linear diffusion behaviour of nanosintering48
and the size dependent diffusion activation energies49
will change the expression for calculating the diffusion
330 International Materials Reviews 2008 VOL 53 NO
7 Densification behaviour of nanocrystalline TiO2 with
three different agglomerate sizes: note that the larger
the agglomerate size, the higher the sintering tempera-
ture (agglomerate size in bold, crystallite size in light).
For the non-agglomerated (N/A) powder, sintering time
is 120 min;52 for the 80 and 340 nm agglomerate pow-
ders, sintering time is 30 min:53,54 After Ref. 3
flux. Furthermore, the scaling law considers different
mechanisms separately. In practice, multiple mechan-
isms of sintering may occur simultaneously, especially
in nanosintering.
Effect of green density, agglomeration on nanosintering
In the practice of nanosintering, the densification
behaviour of nanoparticles are affected not only by the
intrinsic nature of the nanoscale size of the particles, but
also by the processing conditions and related difficulties,
such as green density and agglomeration.
First, similar to powder compacts of micrometre sized
significantly on the green density of the compact. Green
density must be sufficiently high in order to achieve
adequate densification under similar sintering condi-
tions. On the other hand, the finer the particle sizes, the
lower the green density of powder compacts assuming
the compaction pressure is the same. Therefore, it is
generally observed that the sintering of nanosized
powders is affected by compaction pressure.2,50,51
It has been widely recognised that agglomeration of
nanoparticles has a critical impact on the sintering of
nanoparticles. Owing to the extremely fine size and the
strong interactive force between particles, nanoparticles
tend to form agglomerates. The size and strength of the
agglomerated particles affect the densification rate. The
most direct investigation of the agglomeration of
densification was summarised by Mayo3 whose data
was based on numerous published experimental results
as shown in Fig. 7.
In essence, a powder compact can be viewed as
consisting of a bilevel hierarchical structure: the
compact is made of agglomerates which are made of
nanosized particles. There is, therefore, a bimodel pore
size distribution. The pores existing within agglomerates
are finer than the pores between agglomerates. The
densification of an individual agglomerate is relatively
easy, while the elimination the interagglomerate pores is
more difficult. By tracking the evolution of pore size
distributions, Peterson et al.55 studied the sintering of
fine grain cemented tungsten carbide and cobalt system
(WC–Co). They showed that during the intermediate
stage of sintering, the considerable densification
6
 Fang and Wang
8 Derjaguin–Landau–Verwey–Overbeek (DLVO) potential
(green line) is sum of attraction potential and repulsion
potential (Reprinted with permission from Nature
Publishing Group)
obtained is primarily connected to removal of small
pores rather than shrinkage of larger ones.
From the perspective of achieving full densification
and elimination of pores, it is logically desirable to de-
agglomerate powders or to avoid the formation of
agglomerates in the first place. Fundamentally, the
formation of agglomerates is attributed to balance of
the interparticle forces, specifically the van der Waals
force, which acts to bind particles, and the electrostatic
repulsion which opposes agglomeration. Figure 8 illus-
trates potential energy between nanoparticles as a
function of the distance between them.56 Agglomerates
of particles form when either the primary or the
secondary minimum condition is met. Agglomerates at
the secondary minimum are kinetically stable while
agglomerates at the primary minimum are thermodyna-
mically stable. Figure 9 shows that lowering the particle
surface charge by increased ion binding or increasing the
salt concentration could induce two particles to come
into adhesive contact at the primary minimum.57
To de-agglomerate, however, opposite measures must
be taken in order to stabilise a colloidal solution. In
other words, the repulsive forces must be boosted to
achieve a balance between the attractive and repulsive
forces such that the dispersion of particles can be
stabilised. Methods for nanoparticle dispersion include
electrostatic charge stabilisation, steric stabilisation, or a
combination of the two. Details on the principles of
stabilising colloidal solutions can found elsewhere.58
These techniques can be implemented in the processes,
including mixing and milling of the powders that are
necessary prior to sintering of these materials.
To sinter nanoparticles for the fabrication of bulk
engineering components, a colloidal solution must be
dried; agglomerates will inevitably form. Ideally, the
agglomerates are soft and the interagglomerate pores are
small. Lange provided a more extensive discussion on
ceramic powder processing techniques for avoiding
agglomeration and achieving uniform pore distributions
within a powder compact.59
Effect of pores on nanosintering
A common thread for the effect of green density and
agglomeration on sintering is the effect of pores on
densification.60
Densification and grain growth during sintering of nanosized particles
a surfaces repel strongly; small colloidal particles remain
‘stable’. b surfaces come into stable equilibrium at sec-
ondary minimum if it is deep enough; colloids remain
kinetically stable. c surfaces come into secondary mini-
mum; colloids coagulate slowly. d the ‘critical coagula-
tion concentration’. Surfaces may remain in secondary
minimum or adhere; colloids coagulate rapidly. e sur-
faces and colloids coalesce rapidly
9 Schematic energy versus distance profile of DLVO
interaction: After Ref. 57
A compact consists of particles and pores, and each
pore has a volume, shape and a coordination number.
The pore coordination number is defined as the number
of touching particles surrounding and defining each void
space. A pore’s surface morphology is determined by the
dihedral angle and the pore’s coordination number. In
general, for a given dihedral angle, a critical coordina-
tion number nc, exists that defines the transition of the
pore surface morphology from convex (n.nc) to
concave (n,nc). Kingery and Francois61 first recognised
that only those pores with n,nc are able to shrink
during sintering because the concave surface morphol-
ogy with negative chemical potential is thermodynami-
cally unstable. As a result, atoms will diffuse to the pore
surface and fill the void space. Figure 10 illustrates the
stability of pores and their dependence on both the
dihedral angles and the coordination number. For any
10 Relationship between dihedral angle and critical pore
coordination number: After Ref. 61
International Materials Reviews 2008 VOL 53 NO 6 331
Fang and Wang Densification and grain growth during sintering of nanosized particles
given dihedral angle, which is dictated by the material, a
critical coordination number exists below which the
pores will shrink and above which the pores will grow.
The effects of green density and agglomeration on
densification can be explained by the pore coordination
number theory. Higher green density and less agglom-
eration result in fine and uniform pores that shift the
pore coordination number distribution from high values
to low values, i.e. more pores fall into the category
below the critical pore coordination number. These
pores are easily removed during sintering and, thus, lead
to denser products. As for the large pores that are
thermodynamically stable and have coordination num-
bers higher than the critical value, a process by which
the coordination number can be reduced during sinter-
ing is essential, since the pores will again become
unstable and the densification will then continue.
Particle rearrangement and grain growth are the two
processes that can play this role, creating a dilemma, of
course, and difficulty for any attempt to achieve
maximum densification without grain growth.
Densification mechanisms during nanosintering
Calculations of activation energy
In order to understand the mechanisms of sintering,
activation energy is commonly used to indicate the
internal mechanistic process. In most cases, activation
energy can be calculated from isothermal experimental
data. A derivation by Johnson et al.62 resulted in a
densification equation based on two sphere models and
both volume and grain boundary diffusion mechanisms.
The initial stage sintering of a powder compact is
described by Theunissen et al.63
 

(Dl=l0 ) {mEa
~const exp (9)
T RT
where m is a constant characteristic for the sintering
mechanism, i.e. 1/2 for volume diffusion and 1/3 for
grain boundary diffusion, Ea is the apparent activation
energy for densification, Dl/l0 is the relative shrinkage
during continuous heat-up and R and T are the gas
constant and absolute temperature respectively.
Linearisation of the equation results in63
 
(Dl=l0 ) {mEa
ln ~ zconst (10)
T RT
On plotting (2ln[(Dl/l0)/T]) versus 1/T, a straight line
with slope mEa/R is obtained when only one single
mechanism is operative.
Obviously, isothermal relationships of densification as
a function of time at several temperatures are required
to obtain relatively reliable data of activation energy. An
inherent assumption of this approach is that the
mechanisms of densification, or any other process of
interest, should not change within the temperature range
of the experiments. Otherwise, the calculated value does
not represent a single mechanism; rather, it is an
effective activation energy that results from multiple
mechanisms.
As stated earlier, densification and grain growth
during sintering of nanopowders take place rapidly
during the heating-up process. In order to capture the
changes during continuous heating, the Dorn method64
can be used to calculate activation energy. To determine
the activation energy of creep, Dorn allowed a sample to
332 International Materials Reviews 2008 VOL 53 NO
deform under a constant tensile stress at temperature T1
and then rapidly raised or lowered the temperature to a
new value T2 where the sample was allowed to further
deform. The deformation rates corresponding to the
temperatures are then determined for the time in which
the temperature is changed. According to this method,
the activation energy of the responsible mass transport
phenomenon can be determined using the relationship
 
RT1 T2 T1 (d e1 =d t)
Q~ ln (11)
T1 {T2 T2 (d e2 =d t)
where T1 and T2 and are the temperatures of the sample
before and after rapid heating, (de1/dt) and (de2/dt) are
the respective shrinkage rates immediately before and
after the temperature rise, R is the universal gas
constant, and Q is the activation energy. The tempera-
ture difference between T1 and T2 should not exceed
50uC.
To evaluate activation energies of kinetic processes
during continuous heating, a number of other methods
can be found in literature.65–67
Analysis of mechanisms of densification
Using the various methods described above, activa-
tion energies for sintering various nanosized powders
were reported. For example, a very low activa-
tion energy for densification is observed in initial
sintering: y234 kJ mol21 for nanocrystalline Al2O3 and
96?2 kJ mol21 for nanocrystalline TiO2,68 268 kJ mol21
for nanocrystalline ZnO,69 66?2 kJ mol21 for nanocrystal-
line nickel,70 82 kJ mol21 for nanocrystalline a titanium
and 49 kJ mol21 for nanocrystalline b titanium.71
Using these activation energy values to deduce
sintering mechanisms has inherent shortcomings with
respect to accuracy, because in almost all cases, multiple
mechanisms may be operating simultaneously.
Especially during the early stages of sintering, when no
one clearly dominant mechanism can be identified, the
activation energy values calculated using the kinetic data
gives an effective activation energy value that is the
combined effect of multiple mechanisms.
It can be seen from the data, however, that the
majority of studies point toward lower activation
energies for early stages of sintering. This is reasonable
for the obvious reason of the huge surface areas and the
expected high activity of nanoparticles. Surface diffusion
is one of the most cited mechanisms that contribute to
the sintering of nanosized particles. However, in
conventional sintering theories, surface diffusion is
believed to induce initial neck formation between
particles, but not densification. In principle it is correct
that surface diffusion will cause the bonding of particles
to each other, but not the dimensional shrinkage (i.e. the
densification) of a monosized spherical particle compact.
This seemingly conflicting theory on the effects of
surface diffusion on sintering of nanoparticles can be
understood from a perspective of the indirect role of
surface diffusion to densification.
First of all, the rapid and active surface diffusion may
lead to grain boundary slip and rotation of particles that
may result in the rearrangement of particles, hence the
increased density of the compact. The possibility of
grain boundary slip and rotation was mentioned in
numerous sintering studies.2,3,63 Evidence of nanoparti-
cle coalescence via surface diffusion was presented in
6
 Fang and Wang
11 Particle chain sintered with no reorientation: gap
between particles (.1) was filled by surface diffusion
that has also roughened the middle particle’s surfaces
(.2)73 (Reprinted with permission from Materials
Research Society)
Shi’s study on barium titanate72 and Bonevich and
Marks study of Al2O3,73 using TEM. Figure 11 shows
the formation of the neck between two Al2O3 particles
after sintering at 1000uC for just a fraction of a second.
This study shows that surface diffusion is the predomi-
nant mechanism for sintering, as evidenced by the fact
that the faceted interfaces are similar to ledge growth,
and the sintered particles retain their initial adhesion
structure with no reorientation occurring during sinter-
ing. The driving force for sintering can be considered a
chemical potential difference between facet surfaces and
the neck region.
The indirect role of surface diffusion on densification
can also be understood based on theories of the
relationship between coarsening and sintering of parti-
cles.1,72,74,75 As discussed earlier, effects of pores on
nanosintering, according to theories first proposed by
Kingery and Francois and further elaborated by Lange
et al.,60,61 a pore will shrink during sintering only if the
coordination number of the pore is smaller than a
critical value n,nc because only then is the surface of the
pore concave. Thermodynamic driving force dictates
that mass will diffuse from convex surfaces to concave
surfaces. Initial sintering of a compact will develop an
equilibrium configuration at which the driving force for
further sintering is zero. Grain growth, or coarsening,
will perturb the equilibrium configuration to reinitiate
neck growth (sintering) and densification. In other
Densification and grain growth during sintering of nanosized particles
words, when the coordination number reaches a critical
value, the pore is at equilibrium. The shrinkage of the
pore (i.e. sintering) can not progress until the equili-
brium condition can be tipped in favour of sintering by
grain growth. With respect to the densification mechan-
isms of nanoparticles, surface diffusion can cause
coarsening of nanoparticles which, in turn, contributes
to the process of densification. Therefore, it can be
stated that by inducing coarsening, surface diffusion will
contribute indirectly to densification. Further discussion
on the relationship between grain growth and densifica-
tion will be given later.
Surface premelting is another mechanism that could
lead to rapid densification at low temperature during
nanosintering. Owing to a large surface to volume ratio
in nanoparticles, surface premelting can happen at low
temperature, and as a result, particle rearrangement is
facilitated by sliding, rotation, or viscous flow. Alymov
et al.18 calculated the dependence of the melting point of
a particle as a function of its size using the following
equation
Tm =T0 ~
 
1{2Q{1 r{1
s ssl =(r{d)zslg r{1 (1{rs =rl ) (12)
where T0 is the bulk melting point of the solid, Q is its
latent heat of fusion. ssl and slg are the interfacial
surface tensions between the solid and the liquid and
between the liquid and its vapour respectively, and rs
and rl are the densities of the solid and liquid
respectively, r is the radius of particle and d is the
thickness of melted layer on a particle surface.
Given that the sintering temperature is proportional
to the melting point, it is generally understood that as
the melting point decreases, the sintering temperature
decreases. It has been demonstrated that the melting of a
particle with diameter d will result in coagulation with its
neighbours and will become the centre of a new, larger
particle. In an independent study of the sintering of
nanometric Fe and Cu, Dominguez et al.21 attributed
the initial densification to surface melting mechanisms
because the activation energies that were obtained from
either constant heating or isothermal experiments were
too small to ascertain lattice diffusion mechanisms. In
fact, Dominguez et al. claimed that the activation energy
measured during the course of their experiments is very
small, compared to the values published for the self-
diffusion of the metal in a liquid state. Therefore, it was
reasoned that the presence of a liquid-like layer on the
surface of the nanometric particles during sintering
could simultaneously explain such phenomena as high
diffusivity and enhanced grain growth at a narrow
temperature range.
Although surface melting is a reasonable mechanism
for sintering nanosized particles, no direct experimental
evidence supporting the formation of liquid phase has
been published to date. In fact, because the formation of
any liquid at temperatures below equilibrium melting
point will be thermodynamically unstable, there could
be only transient liquid, making experimental verifica-
tion of the presence of liquid phase even more difficult.
A more generally applicable theory that explains the
rapid densification of nanoparticles is based on the
hypothesis of non-equilibrium high concentration of
vacancies at the interparticle grain boundaries. In 1974,
International Materials Reviews 2008 VOL 53 NO 6 333
Fang and Wang Densification and grain growth during sintering of nanosized particles
Vergnon et al. studied the ‘initial stage for the sintering
of ultrafine particles TiO2 and Al2O3’.68 Using flash
sintering and isothermal experimental techniques, it was
shown that during the first 20 s, a fraction of the total
observed shrinkage, up to 95%, was registered.68 There
was an initial loss of surface area, before the shrinkage
starts during the heating of the compact to the desired
temperature, a process which requires only a few
seconds. It was reasoned that this almost instantaneous
loss of the surface area corresponds to the formation of
junction zones between particles of the compact. The
fast formation of the junctions between particles, before
the shrinkage onset, involves the creation of a high
concentration of vacancies inside these junctions. The
shrinkage of the compact results then from a decrease of
the distance between the centres of particles due to
annihilation of the trapped vacancies in the junction
zone. Because the concentration of trapped vacancies
inside the junction zone largely exceeds the thermo-
dynamic equilibrium concentration, the diffusion can be
considered as independent of time and controlled only
by the probability of jumping of ions, as long as the
concentration of vacancies exceed the equilibrium
content. Any further sintering, after the initial non-
equilibrated concentration of vacancies is exhausted,
corresponds with the diffusion of equilibrated vacancies.
Furthermore, based on the theory that excessive
concentration of vacancies exist (c.1024), Trusov
et al.20 stipulated that there is a possibility of liquid-
like merging (coalescence) of particles into large ones.
Liquid-like coalescence, as well as slippage, causes the
compact shrinkage of ultrafine particles.
In another study focusing on size dependent grain
growth kinetics observed in nanocrystalline Fe, Krill
et al.76 also established their model on the basis of
existence of excess volume at the grain boundaries.
The ‘excess’ volume is in the form of vacancies, which
leads to a non-equilibrium vacancy concentration. The
issues of grain growth of nanoparticles during sintering
will be further discussed in latter sections of this
review.
Finally, the rapid densification mechanisms of nano-
particles is also related to the preferential crystalline
orientations. It has been observed that in loose nanocrys-
talline powders, the first neck formation occurs, not
randomly between particles, but by the orderly mating of
parallel, crystallographically aligned facets on the particle
surfaces.73,77 Some nanocrystalline powder compacts also
appear to reflect a kind of ordered structure resulting from
less than random type matings of particles during the
initial stage of sintering.78
Kinetic theories, modelling and simulations of
nanosintering
Given the unique physics that present when sintering
nanoparticles, considerable work has been reported on
the theoretical modelling of thermodynamics and the
kinetics of sintering of nanosized particles. In one of the
more significant studies, Pan recognised that the rapid
kinetic rate of sintering is a direct result of the large
driving force for sintering of nanosized particles, and
revised the two sphere sintering model by using non-
linear diffusion law.48 Because the diffusion is the result
of jumping atoms, the flux of diffusion as a function of the
frequency of jumping f, volume atomic concentration
334 International Materials Reviews 2008 VOL 53 NO
Csolid, and the atomic spacing a can be given by


2D aF
J~ sinh (13)
aV 2kT
where D is the diffusion coefficient, V is the atomic
volume, a is the atomic spacing, F is the driving force for
diffusion, k and T are the Boltzmann constant and
absolute temperature respectively. Pan pointed out that
this equation reduces to linear diffusion law, when
aF(kT, sinh (aF/2kT)<aF/2kT. However, when particle
sizes are in the range of nanometres, the linear approx-
imation is no longer reasonable. Then, the diffusion
equation becomes a non-linear equation that can only be
solved via numerical methods. Applying this approach to
sintering two particles, the ratio of the neck to particle
radius as a function of the length of time at a given
temperature was calculated and shown by Fig. 12. The
differences between prediction by linear solutions and
non-linear solutions are significant during the initial stage
of sintering and diminish as sintering time increases. The
distinction between linear and non-linear solutions also
diminishes as particle size increases.
The rapid rate of sintering due to the rapid rate of
diffusion is also supported by recent studies which
indicate that the coefficient of diffusion D, is size
dependent as shown49
D(r,T)~
  
{E(?) {2Svib (?) 1
D0 exp exp (14)
RT 3R r=r0 {1
where D0 is pre-exponential constant, E(‘) is bulk
activation energy, Svib(‘) is bulk melting entropy, r is
particle radius, r053h (where h is atomic diameter) for
nanoparticles, R is ideal gas constant and T is absolute
temperature.
The dependence of the coefficient of diffusion on
particle size is attributed to that, as the size of the
nanocrystals decreases, the activation energy of diffu-
sion decreases and the corresponding coefficient of
diffusion increases based on the Arrhenius relationship
between them. Together these theories, based on non-
linear diffusion law and the increase of the coefficient of
diffusion with decreasing particle size convincingly
argue for the rapid formation of necks bonding with
neighbouring particles.
With the development of modern tools of computa-
tional materials science, considerable effort has been
made toward numerical simulation of the sintering of
nanoparticles. One of the most notable works was
published by Zhu and Averback in 1995,79,80 who
simulated the sintering of YSZ using the MD approach.
Molecular dynamics simulations of sintering have been
conducted in numerous other materials as well.81–86 The
basic approach toward simulating sintering using MD
method involves tracking the motion of atoms under
stress caused by surface or interfacial energy. The
kinetics of sintering is given as the rate of decreasing
distance between two atoms in the middle of two
particles in contact. It was shown that sintering
nanoparticles at the atomic level can be accomplished
by dislocation motion and grain boundary rotation, as
well as other mechanisms. It was further predicted that
the sintering time of nanoparticles would be in the range
of a few hundred picoseconds. Although the predicted
6
 Fang and Wang
a R55 nm; b R510 nm; c R5100 nm; d R51000 nm
12 Comparison between linear solution (broken line) and non-linear solutions (solid line) for shrinkage between two
spherical particles as functions of time (Reprinted with permission from Taylor & Francis)
sintering time is far from engineering reality, the results
of the simulation can be used as a basis for under-
standing the initial bonding or formation of the necks
between nanoparticles.
Owing to the limitations of studying sintering by using
atomic scale simulation, multiscale simulation is con-
sidered a promising approach. Pan87 categorised the
simulations of sintering in three levels: atomic level,
particle level and component level. The primary method
of atomic level simulation is MD, as mentioned earlier.
In particle level simulation, which is also classified as
mesoscale simulation,88 classic sintering models6,62,63,89–101
based on mass transport between two or multiple
particles provide the basis of simulation. The kinetics of
sintering densification depends on the kinetics of specific
diffusion mechanisms that control the rate at this stage
of the process. In Pan’s review, the typical numerical
methods used in particle level simulations include the
finite difference method, the variational calculus, and
the finite element method. To model the evolution of the
microstructure during sintering, however, Monte Carlo
method is often a popular choice.102–106 The finite
element method is the primary method for simulation at
the component level, which is chiefly concerned with
macro scale shrinkage, distortion and dimensional
accuracy control.
Overall, most published studies of sintering simula-
tions were not nanoscale specific, except for the MD
simulations described above. Although these methods
are arguably applicable to sintering of nanosized
Densification and grain growth during sintering of nanosized particles
particles, especially during the later stages of sintering,
further details on simulation of sintering is beyond the
scope of this review, which focuses on the size dependent
characteristics of sintering of nanoparticles.
Grain growth during nanosintering
Issues of grain growth during nanosintering
A primary motivation for studying sintering of nano-
sized particles is rooted in the issue of rapid grain
growth during sintering. In many cases, particularly
when the goal is to produce nanocrystalline bulk
materials, the objective of nanosintering is to achieve
full densification as well as the retention of nanoscaled
grain structure in the sintered material. Research has
generally shown that after sintering, nanosized particles
lose nanoscale characteristics because grain size grows to
greater than 100 nm. Therefore, understanding and
controlling grain growth is a critical scientific and
technical issue of nanosintering.
In a systematic study of the stability of nanosized
metal powders, Malow and Koch107–109 reported that
the rate of grain growth of nanocrystalline Fe powders
made by ball milling is initially very rapid (,5 min)
when annealed at various temperatures. Grain growth
then stabilises during extended isothermal holding (up to
142 h). During isothermal holding, grain growth follows
a generalised parabolic grain growth law and is similar
to that found in bulk materials. It is noted, based on
Fig. 13, that at the first data point of the isothermal
International Materials Reviews 2008 VOL 53 NO 6 335
Fang and Wang Densification and grain growth during sintering of nanosized particles
13 Evolution of grain size as function of annealing time at three annealing temperatures for nanocrystalline iron: grain
size was determined by Scherrer equation (Reprinted with permission from The Minerals, Metals & Materials Society)
annealing curves at higher annealing temperatures
(825 K), the grain sizes are already several times (3–
66) greater than the original as milled grain size
(y8 nm). In other words, grains grow rapidly during
heat-up, prior to reaching the preselected isothermal
holding temperature.
In another study of the grain growth of nanocrystal-
line Fe using in situ synchrotron X-ray diffraction
techniques, Krill et al.76 further demonstrated that grain
growth of nano-Fe particles is comprised of three steps:
the ‘initial growth spurt’, a linear growth stage and the
normal parabolic stage, as shown in Fig. 14. Once again,
the normal parabolic stage can be modelled using the
classic grain growth parabolic law, however the ‘initial
growth spurt’ of nanocrystalline Fe during annealing
was not captured by isothermal studies.
Grain growth during nanosintering is also a strong
function of temperature. Figure 15 shows the relation-
ship between grain size and temperature during the heat
treatment of nanocrystalline cobalt powder.110 It is
obvious that the grain growth is initially slow at very low
14 Size dependent grain growth kinetics observed in
nanocrystalline Fe (Reprinted with permission from
American Physical Society)
336 International Materials Reviews 2008 VOL 53 NO
temperatures and that it accelerates dramatically when
the temperature is above an apparent critical tempera-
ture range. Figure 16 provides another example of the
relationship between grain size and temperature during
heating up of nanocrystalline WC–Co powder at a
heating rate of 10uC min21.111 It shows that the original
20 nm grain size has increased almost 45 fold to 900 nm.
This ‘explosive’ grain growth occurs almost instantly
during heat-up, with no significant holding time. Similar
behaviour has also been reported for sintering of other
nanocrystalline ceramics, as well as for metallic pow-
ders.112–118 It appears that a critical temperature exists,
above which the grain growth accelerates dramatically
as a function of temperature.
The unique issues of grain growth during sintering can
be studied by examining the grain size versus relative
density relationship. In one of the earliest studies of the
sintering and grain growth of nanosized ceramic
powders in 1990s, Owen and Chokshi119 and Averback
et al.120 showed that oxides densify without significant
grain growth until the density reaches y90% of the bulk
density. Then the grain growth becomes very rapid. This
phenomenon is observed in many different materi-
als.2,3,121,122 A typical relationship between grain size
15 Change of mean grain size (linear intercept) with
annealing temperature, measured in pure nanocrystal-
line Co (Reprinted with permission from Elsevier)
6
 Fang and Wang Densification and grain growth during sintering of nanosized particles

I: early stage of grain growth; II: late stage of grain

16 Grain size versus temperature during heating up of
nanocrystalline WC–Co powder at heating rate of
10uC min21: After Ref. 111
and density during nanosintering is schematically shown
in Fig. 17. This relationship implies that the grain
growth during sintering consists of two stages: the early
stages of sintering, before the powder compact reaches
90% relative density; and the late stages of sintering,
when relative density is greater than 90%. It is believed
that the late stages of grain growth can be viewed as
‘normal’ grain growth, similar to that found in bulk
materials by boundary migration, but incorporating the
effect of pinning by closed pores. In contrast, the early
stage of grain growth during sintering is often referred to
as ‘coarsening’.
Figure 18 shows another example of grain growth
versus densification during the sintering of nanocrystal-
line Y2O3 materials.123 This work demonstrated that the
normal grain growth stage during sintering, the mechan-
ism of which will be discussed later in this section, can be
growth
17 Relationship between grain growth and densification
during nanosintering
controlled. The result also shows that at the starting
point for the normal grain boundary controlled grain
growth, grain size has grown to 4–6 times the initial
grain size of the nanopowder. This part of grain growth
is attributed to coarsening.
Another approach for studying the relationship of
densification versus grain growth was summarised by
German et al. in a recent study on sintering of nanosized
tungsten powder.124 The dynamics of densification and
grain growth is described by the continuum theory of
sintering98 as follows
d r 9ch
~ (15)
d t 4gG
where r is sintered density, h is porosity, c is the surface
tension, g is the effective porous body viscosity and G is
grain size. In order to apply the above equation, the
relationship between the grain size and densification is
described by another relationship

18 a increasing grain size of Y2O3 with density in normal sintering. (Heating schedule shown in inset). Even with fine
starting powders (30 nm), the final grain size of dense ceramics is well over 200 nm regardless of whether dopant
was used. The shaded area indicates the grain size regime commonly defined as nanostructured materials. At lower
densities, the mean grain (particle) size was estimated on the fracture surface. At higher densities, the grain size was
obtained by multiplying by 1?56 the average linear intercept length of at least 500 grains. b grain size of Y2O3 in two
step sintering. (Heating schedule shown in inset.) Note that the grain size remains constant in the second sintering
step, despite density improvement to 100% (Reprinted with permission from Nature Publishing Group)

International Materials Reviews 2008 VOL 53 NO 6 337

Fang and Wang Densification and grain growth during sintering of nanosized particles

n{1
dG G0
~xK h{(n{1)=2
dt G nanoscale, this part of grain growth must be con-
where x is a material constant, K is the reference grain
growth rate, G0 is the initial particle size, and n is a
material constant. By solving equations (15) and (16),
both the density and grain size can be evaluated.
Yet another parametric approach for studying the
relationship between the densification and grain growth
is based on the master sintering curve method, which
describes the sintering densification as follows125,126


dr cV dDb Cb Dv Cv
~ z 3 (17)
3r d t kB T G4 G In general, when the relative density is greater than 90%
where c is surface energy, kB is Boltzmann constant, Db
and Dv are grain boundary and volume diffusivity, T is
absolute temperature and V is atomic volume, G is mean
grain diameter. Cb and Cv are scaling parameters, which
relate the driving force, mean diffusion distance, and
other geometric features of the microstructure on which
the sintering rate depends on mean grain diameter G. By
rearranging the above equation, equation (17) becomes
ðr ðt

½G(r)n cVD0 Q Typically, because the properties of sintered materials
d r~ exp { dt (18)
r0 3rC(r) 0 kT RT
where r0 is the green density of powder compact, Q is
apparent activation energy, R is the gas constant. For
volume diffusion, D05(Dv)0 and n53; for grain bound-
ary diffusion, D05(dDb)0 and n54. Grain size G is given
as a function of the density. Once again, if the
relationship between the grain size and density is known,
the model would be complete. Using this approach, Park
et al.127 further expressed the relationship of grain size as
functions of time and temperature as follows
ðt

Q dG M
G 3
~G03 z3 K0 exp { dt
RT
0
where G is grain size, G0 is initial grain size, K0 is pre-
exponential factor, Q is activation energy; R is gas
constant and T is absolute temperature. The advantage
of the above relationship is that it is not limited to
isothermal conditions. It can be applied to continuous
heating conditions. However, the above relationships
were developed for general situations using the equal
size two sphere model without explicitly considering the
effects of nanoscale particle sizes.
In short, from a kinetic perspective of grain growth
as a function of time, the experimental observations as
described above suggest that the grain growth of
nanosized particles during sintering can be treated as
consisting of two steps: a dynamic grain growth
process that occurs during heating-up and at the
beginning of isothermal duration; and the static grain
growth during isothermal holding. From another
perspective of the interrelations of grain growth to
densification, the grain growth during sintering con-
sists of two stages: first, when the relative density is
lower; and second, when the relative density is greater
than 90%. It should be emphasised that although the
late stage of grain growth, when relative density is
greater than 90%, accounts for the majority of total
grain growth, early stage grain growth that occurs
during heating (when relative density is still lower than
338 International Materials Reviews 2008 VOL 53 NO
90%) is significant and sufficient to reach beyond
nanoscale. Thus, if grain size is to be maintained at
(16)
trolled. However, it appears from the search of open
literature that although the early stage of grain growth
process is critical to nanosintering, few published
studies to date focus on this aspect of grain growth.
In the following sections, we will examine the issues of
grain growth during nanosintering in both the ‘normal’
and ‘initial’ stages.
Normal grain growth during nanosintering when
relative density .90%
during sintering of micrometre sized particles, bonding
between powder particles by neck growth is well
developed and the majority of pores within a sintered
body are closed. Grain growth during the continued
sintering densification process is akin to that of bulk
materials during heat treatment, although the remaining
pores can still hinder the kinetic rate of grain growth
during this stage. Consequently, this stage of grain
growth is referred to as ‘normal’ grain growth.
depend on their final grain sizes, the final stage of grain
growth during sintering has received, therefore, the most
attention.
Grain growth law: kinetics of normal grain growth
Classic treatment of grain growth in solid materials was
reviewed in several studies.7,47,128,129 It is generally
believed that the mechanism of grain growth in bulk
materials is by curvature driven grain boundary migra-
tion, and the rate of grain growth is inversely propor-
tional to grain size130
(19) ~ (20)
dt G
where M is a constant. By integrating over time, the
classic parabolic grain growth law is
G(t)2 {G02 ~kt (21)
where k5k0 exp(2Q/RT) is the rate constant of grain
growth that is a function of the mobility of grain
boundary, k0 is a constant, Q is activation energy for
grain boundary migration, R is gas constant, and T is
absolute temperature.
In practice, accounting for the fact that the experi-
mental observed grain growth data do not always fit
equation (21) with the exponent equals to two, the
parabolic grain growth law is usually generalised as
G(t)n {G0n ~kt (22)
Equation (22) is thus termed as generalised parabolic
grain growth model.131 When n is variable, grain growth
kinetics can be better described by equation (22).
Considering the effect of factors such as segregation
of impurities on grain boundaries that mitigate grain
growth, the dependence of grain size on time is further
modified as132–134
 
G0 {G(t) G? {G0
zln ~kt (23)
G? G? {G(t)
where G‘ denotes the grain size when the grains cease to
6
 Fang and Wang
19 Temperature and time evolution of the volume
weighted average crystallite diameters of nano-Fe; the
lines represent fit with different kinetic grain growth
models. Broken lines represent fit with the general-
ised parabolic grain growth model; solid lines repre-
sent fit with the grain growth model with impediment;
broken dotted lines represent fit with size dependent
impediment (Reprinted with permission from American
Chemical Society)
grow at tR‘. This is also termed as grain growth model
with impediment.131
In the process of grain growth, the volume fraction of
grain boundaries decreases; therefore, the concentration
of solute and impurity atoms segregated to the grain
boundary is expected to increase, resulting in a grain size
dependent retarding force on grain boundary migration.
On this basis, Michels et al.135 proposed a grain growth
model with size dependent impediment.131
 2 2
1=2
G(t)~ G? { G? {G02 expð{ktÞ (24)
In a detailed study of the grain growth of nanocrystal-
line Fe prepared by pulsed electrodeposition, Natter131
applied all three grain growth models to the data of
grain size versus time, as shown by Fig. 19. It was noted
that the generalised parabolic growth model appropri-
ately fits the data at low temperature, with unrealisti-
cally large grain growth exponents n.10. The growth
model with impediment yields the best fit among the
three models considered.
Using the adjustable parameters contained in these
models, the authors calculated the rate constants and,
hence, the activation energies for grain growth of
nanocrystalline Fe. It was concluded that, although the
generalised parabolic model yielded a good fit with
variable n values, the calculated activation energy based
on that fit was unreasonably high (220 kJ mol21) for
what is assumed to be grain boundary diffusion in
nanocrystalline Fe. Therefore, it was declared by the
authors that the generalised parabolic model failed.
Densification and grain growth during sintering of nanosized particles
The activation energies calculation, based on the rate
constant deduced from the impediment model, yielded
an activation energy value of 170 kJ mol21, which is in
agreement with other published values for grain
boundary diffusion.136,137 Thus, based on the calculated
activation energies, the authors summarised that the
grain growth model with impediment was a good
candidate for describing the isothermal kinetics of grain
growth of nanocrystalline metals.
As discussed earlier in this article, an approach that
uses activation energy values to gain insight about the
grain growth or densification mechanisms is inherently
limited because the models contain varying parameters
which can result in mathematical flexibility that would
enable the model to fit almost any data. It is very
difficult, however, to assign physical meaning to the
parameters n and k. The fact that the grain growth of
nanoparticles during sintering may be attributed to
multiple mechanisms makes the matter even more
complicated.
In a different approach to applying the generalised
parabolic grain growth models, Liu et al.138 analysed
grain growth data in separate ‘domains’, meaning
different stages of grain growth at different sequential
time periods. For each time period, a fixed value of n52
and/or 3 is used in modelling. The overall grain growth
equation is expressed as follows
G(t)2 {G02 ~
8 9
>
> k1 t t¡t1 >
>
>
> >
>
>
> k1 tzk2 (t{t1 ) t2 wtwt1 >
>
>
> >
>
>
> >
>
>
< >
=

(25)
>
>  tn{1 wtwtn{2 >
>
>
> >
>
>
> >
>
>
> k1 tzk2 (t{t1 )z    >
>
>
> >
>
>
: >
;
zkn (t{tn{1 ) tn wtwtn{1
According to this model, the rate constant k and the
activation energies change as grain growth progresses.
Specifically, the activation energies increase as grain size
increases. This is attributed to the increasing segregation
of impurities on grain boundaries which reduces grain
boundaries, hence the driving force for grain growth.
Within each growth time period, or ‘domain’, the
activation energies and rate constants k hold constant.
Compared to conventional parabolic models, this model
takes into account the effect of the changes in
thermodynamic properties on the kinetics of grain
growth. The assumption of the model is that the grain
growth is fully accomplished by grain boundary diffu-
sions. Direct evidence of the mechanisms of grain
growth of nanoparticles during sintering is, however,
still sorely needed.
Effect of pores on grain growth in late stages of sintering
As in sintering of coarser particles, in the final stage of
sintering nanoparticles, grain growth will be affected by
remaining pores that pin the grain boundaries and
reduce the kinetic rate of grain growth. The effect of
pores on grain growth during the final stage of
conventional sintering are reviewed by Rahaman and
Kang.47,129
In the final stage of sintering, isolated spherical pores
are situated at the grain boundaries, and in particular, at
International Materials Reviews 2008 VOL 53 NO 6 339
Fang and Wang Densification and grain growth during sintering of nanosized particles
triple junctions. Therefore it is expected that a large
number of pores exist in a system with nanosized grains.
Pores are considered to be a second phase with an
inhibiting force against boundary movement. Owing to
the presence of large number of pores in the system at
the beginning of the final stage of nanosintering, the
boundary is at first dragged by the pore and the rate of
grain growth is slow. But as sintering proceeds, both the
number and the size of the pore decrease as a result of
densification. When the density reaches the specific value
at which the boundary is able to break away from
inhibition of the pore (i.e. pore/boundary separation
occurs), grain growth will accelerate dramatically.
Ostwald ripening during liquid phase sintering
The generalised grain growth law describes another
category of grain growth which is based on Ostwald
ripening. The theory of Ostwald ripening was originally
developed for the coarsening of precipitates in two phase
materials. The mechanism of the coarsening of second
phase particles is solution and reprecipitation. During
liquid phase sintering, the solution reprecipitation
mechanism is responsible for increased average grain
size due to the growth of larger particles at the expense
of smaller particles. The term ‘coarsening’ is also used in
a more general sense to describe the increase of grain
sizes, as well as particle sizes, during sintering. At
isothermal conditions, the kinetics of grain growth by
solution reprecipitation is also given by the polynomial
law as follows
G(t)n {G0n ~kt
where n is the grain growth exponent. Usually n53 for
diffusion controlled processes and n52 for interface
controlled processes. Published reports on grain growth
during liquid phase sintering of nanosized tungsten
carbide particles generally have found that the equa-
tion (26) is applicable with varying n values to nanosized
particles during isothermal sintering.139 Efforts to apply
this equation to the initial grain growth stage, however,
failed to yield meaningful results.139
Two step sintering: decoupling of grain growth from
densification
As an example of understanding and controlling normal
grain growth during nanosintering, Chen and Wang
developed a clever approach to decouple grain growth
from densificaton of nanosized particles,123 using a
pressureless sintering process to fully densify nanocrys-
talline Y2O3. In a simple two step process, the compact
is briefly heated to 1310uC; the temperature is then
lowered to 1150uC and held at that temperature for an
extended period of time. As a result, the material can be
sintered to full density with minimum grain growth. If
the lower temperature is applied at the onset, complete
densification would not be possible. It is reasoned, then,
that suppression of the final stage grain growth is
achieved by exploiting the difference in kinetics between
the grain boundary diffusion and the grain boundary
migration. Grain growth requires grain boundary
migration which requires higher activation energy than
grain boundary diffusion. At a temperature that is high
enough to overcome the energy hurdles for grain
boundary diffusion, but low enough to deactivate grain
boundary migration, the densification will proceed via
grain boundary diffusion without triggering significant
340 International Materials Reviews 2008 VOL 53 NO
grain growth. This phenomenon was further studied in
multiple publications of Kim et al.140,141
It is noted, once again, that in this successful work to
decouple grain growth from densification by exploiting
differences in grain boundary mechanisms, the authors
explicitly showed that at the beginning of the second
sintering step, the grain size increases 4–6 times larger
than the original size of the powder, which is attributed
to coarsening during the first sintering step (Fig. 18).
The following section will focus on coarsening, or in
other words, the initial grain growth of nanoparticles.
Initial grain growth – coarsening – of
nanoparticles during early stages of sintering
(relative density ,90%)
The above discussion provides evidence of an initial
stage of grain growth. This part of grain growth occurs
in the beginning of the sintering, often during heating up
when the relative density is less than 90%. In conven-
tional sintering of micrometre sized powders, the
contribution of the initial grain growth to the final
grain size is relatively minor, compared to that of the
normal grain growth during late stages of sintering. For
nanosintering, however, the amount of the initial grain
growth is significant and sufficient in many cases to
cause the material to lose its nanocrystalline character-
istics. Further, the initial grain growth can be described
by the generalised classic parabolic grain growth law
only if very large values of growth exponent is used,
which represent no physical processes. This implies that
(26) the mechanism of grain growth in the initial stage may
be different from that of the normal grain growth stage.
Neck formation and coarsening of contacting nanoparticles
To understand initial grain growth, the key issue is the
interaction between ultrafine particles at the start of
sintering. According to classical sintering theories by
Kuczynski,100 Kingery,96 Coble142 and Johnson,143
necks will form and grow between adjacent particles,
which are assumed to have equal diameter. Densification
is modelled as the approach of the centres of the two
particles. In this situation, no grain growth occurs at the
beginning of sintering. In practical fine or ultrafine
powder material systems, however, there are always
wide particle size distributions. The densification and
grain growth behaviour will be markedly different.
Figure 20 illustrates that when very fine particles are in
contact, where the particle sizes are not uniform,
interparticle diffusion will lead to coarsening of parti-
cles, in addition to formation of the neck. Large
particles will grow at the expense of small particles.
The coarsening of particles can be understood using the
criteria shown by equation (27), which was first
expressed by Lange1 based on Kingery’s initial concept
of pore stability.61
1
Rc ~{ (27)
cos we
where Rc is called critical particle size ratio for boundary
migration and we is the dihedral angle relating surface
energy and grain boundary energy. Lange explained that
when the size ratio between two particles is larger than
the critical size ratio Rc, grain boundary migration will
occur, resulting in grain growth. When actual size ratio
is less than Rc, boundary migration will yield an increase
6
 Fang and Wang
a just in touch without formation of interface; b when
r1/r2,Rc; c r1/r25Rc; d r1/r2.Rc
20 Linear array of two spheres of initial radii of r1 and r2
(r1.r2): After Ref. 74
in the grain boundary area and is energetically
unfavourable. In this situation, interparticle mass
transport will happen first, in order to increase the size
ratio between adjacent particles. This coarsening process
will not stop until the size ratio R5r1/r2 reaches Rc.
Then grain boundary migration will take over because
the condition for grain boundary migration is now
energetically satisfied.
The studies by Lange and Kingery aimed to explain
the stability of pores in the intermediate stage of
sintering. Shi further applied the critical size ratio
criteria to the initial sintering of ultrafine particles.74,75
It was shown that the driving force for neck growth and
interparticle diffusion are given respectively is as follows


1 1
Dmn ~cs V { (28)
X r


1 1
Dmc ~2cs V { (29)
r1 r2
where Dmn and Dmc are chemical potential for neck
formation and mass transport between two particles, cs
is surface energy, V is atomic volume, X is radius of the
neck and r is radius of particles (r1 and r2 are radii of
two particles with different sizes).
Equation (29) indicates that if a difference in the
radius of curvature exists, mass transport would take
place from the area of larger curvature to the area of
smaller curvature. This process is related to the particle
coarsening.
Considering equations (28) and (29) together, both
the neck growth and coarsening, driven by the surface
tension between the particles, can take place concur-
rently. However, the magnitude of the driving force for
the two processes is different. Assuming the interface
energy is not considered, then |Dmn|.|Dmc|, which implies
that neck formation takes place before coarsening.
On the other hand, if the interface energy between
particles is considered in the analysis of the driving
forces as an energy barrier to neck growth, Shi74 showed
that equation (28) becomes


’ 1 1
Dmn ~cs V { {cb f ðr,w,we Þ (30)
X r
where cb is boundary energy, w is the contact angle and
we is the equilibrium dihedral angle. From a thermo-
dynamic point of view, when w5we, the driving force for
the neck growth is zero. Intuitively, it is possible under
certain conditions when w,we, driving force for coarsen-
ing may equal that for neck growth. Hence, coarsening
by interparticle mass transport may take place signifi-
cantly prior to the achievement of the equilibrium
dihedral angle and the beginning of grain boundary
migrations.
Densification and grain growth during sintering of nanosized particles
a configuration when r1/r2,Rc (boundary cannot move);
b configuration resulted from mass transport between
particles before boundary motion; c transient configura-
tion after boundary motion where r1/r2 becomes .Rc; d
final configuration either directly by mass transport or
by combined mass transport and boundary motion
21 Particle configuration change after formation of di-
hedral angle shown in Fig. 20: After Ref. 74
Considering the coarsening mechanisms described
above, the initial grain growth can, therefore, be
described by a two step qualitative growth model.144
When particles of different sizes are in contact, the first
step in grain growth is coarsening due to interparticle
mass transport via the growth of larger particles into
smaller particles, which result in the increase of the
material’s average grain size regardless of whether the
size ratio r1/r2 is larger or smaller than Rc. During
the coarsening and sintering progress, the size ratio
between particles can increase. When the condition of
size ratio r1/r2.Rc is reached, grain boundary migration
will occur, leading to the second step of grain growth by
the grain boundary migration. Figures 20 and 21
schematically illustrate the two step process.
The differences in grain growth kinetics at different
stages of sintering suggest differences in grain growth
mechanisms, which would also be a function of specific
material systems. The mechanism for normal grain
growth is widely believed to be grain boundary
migration. However, as indicated in the above discus-
sion, the mechanism of coarsening, or initial grain
growth, could be different depending on the specific
situation with regard to relative particle size ratios and
dihedral angles. Possible mechanisms of initial grain
growth are discussed in the following sections.
Initial grain growth mechanisms
Based on conventional grain growth theories, several
possible grain growth mechanisms for grain growth
during nanosintering exist, including: grain boundary
migration, surface diffusion, solution reprecipitation
and coalescence. Understandably, surface diffusion is
expected to be a highly probable mechanism, due to the
extremely fine particle sizes.
It has been demonstrated that surface diffusion leads
to grain growth of nanosized particles. In a study of the
sintering BaTiO3, Shi et al. observed that the contacting
particles become one particle via surface diffusion as
shown in Fig. 22.72 Surface diffusion transported the
atoms from the dissolving small particle to be redepos-
ited on the surface of the larger particle. This is direct
evidence of the role of surface diffusion in the
coarsening of nanoparticles at the beginning of sintering.
Although surface diffusion induced grain growth is not a
widely recognised grain growth mechanism, it could play
an important role in the initial grain growth. It is noted
that surface diffusion causes coarsening of larger
International Materials Reviews 2008 VOL 53 NO 6 341
Fang and Wang Densification and grain growth during sintering of nanosized particles

22 Observations of grain growth in BaTiO3 powder at different temperatures from a 940uC, b,c 950uC to d–o 960uC:
grains grow by through reduction of smaller grains and enlargement of larger ones; distance between particle centres
decreases simultaneously (Reprinted with permission from Springer Science and Business Media)

particles by consuming small particles, i.e. grain growth
without requiring either grain boundary migration,
rotation, or grain boundary diffusion.
Considering that the initial grain growth during
sintering is the result of the coarsening of nanoparticles
due to interparticle diffusions, there are other inter-
particle diffusion mechanisms, other than surface diffu-
sion, that could also contribute to coarsening of
particles. In particular, there is a relaxation period for
migration, redistribution and annihilation of the defects
due to the fact that nanoparticles are usually not at
equilibrium states and are likely to contain excess
amounts of various defects that are created during the
production of nanoparticles.145,146 Owing to the non-
equilibrium structure of nanoparticles, diffusivity is
dramatically enhanced during the relaxation pro-
cess,147–150 which may contribute to dynamic grain
growth at the beginning of sintering. Dynamic grain
growth usually dominates during the heat-up stage and
for the first few minutes after reaching a preset
isothermal holding temperature. Therefore, rapid
dynamic grain growth accounts for the experimental
observation that the first data point during isothermal
holding is several times of that of the initial grain size.
The relaxation time depends on materials, nanoparticle
production methods and temperature.
The role of grain boundary migration should also be
considered in discussing the initial grain growth during
nanosintering. As discussed earlier, for single phase
materials at late stages of sintering when relative density

342 International Materials Reviews 2008 VOL 53 NO 6

 Fang and Wang Densification and grain growth during sintering of nanosized particles

a one particle’s ‘grain’ has grown, outlined, and has distinct grain boundary; b grain boundary migrated into small particles
23 Alumina particles cluster sintered at 1200uC (Reprinted with permission from Materials Research Society)

is great than 90%, grain boundary migration is the most evidence of coalescence is, however, very difficult to
logical mechanism of grain growth as that found in bulk identify. Fang et al.111 studied the grain growth of nano-
single phase materials. Grain boundary migration has WC during sintering and found the growth of nanosized
also been observed during early stages of sintering tungsten carbide grains within aggregates via coalescence,
nanosized Al2O3.73 Figure 23 shows that when the as shown in Fig. 24. It has been speculated that when
nanosized Al2O3 particles were subjected to high nanoscale is approached, atomic mechanisms become
temperatures in a flash sintering set-up, instant grain more obvious. For example, the rotation and alignment of
growth was observed and grain boundary migration was nanosized grains may be easier than coarse grains.2
believed to be part of the process. This confirms the Kumar and Fang’s analysis of the sintering of WC–Co
analysis of the coarsening of nanoparticles that when composites suggests that the lattice shift along low energy
r1/r2 is greater than Rc, grain boundary migration will CSL grain boundaries is a viable mechanism for materials
take place. with high degree of crystallographic anisotropy.155
Coalescence is another grain growth mechanism that
is often cited to qualitatively explain rapid grain growth. Effects of agglomerates on initial grain growth
Coalescence is a term that is often loosely used to Another important factor in grain growth mechanisms
describe various phenomena. For example, coalescence during nanosintering is the role of agglomerates in grain
is sometimes used interchangeably with the term growth. Agglomerates are defined as loosely packed
‘sintering’ to describe the growth of particles during
particle synthesis and growth process.151–154 For clarity
in this article, coalescence is used strictly to describe the
increase of grain size due to the merging of two grains by
eliminating the common grain boundaries between
them. Differing from other grain growth processes,
which may also be described as the merging of two
grains, the two original grains should not demonstrate
significant change from their morphology prior to
coalescence.
The term coalescence, as defined above, describes a
unique way of grain growth, which can be accomplished
only through various diffusion mechanisms. Possible
mechanisms for coalescence include grain boundary
diffusion, dislocation climb along grain boundaries, or 24 Coalescence of two platelet shaped grains of nano-
even grain rotations. In liquid phase sintering systems, it crystalline WC–Co compact heated up to 1200uC at
is believed that the solution reprecipitation mechanism heating rate of 10uC min21 and held for 1 min: After
may also help facilitate the coalescence of grains. Direct Ref. 111

International Materials Reviews 2008 VOL 53 NO 6 343

Fang and Wang Densification and grain growth during sintering of nanosized particles

25 Schematic diagrams of a agglomerated and b aggre- 27 Microstructure of same sample as Fig. 26 at 1200uC:
gated powder (Reprinted with permission from Maney agglomerates were transformed into individual grains
Publishing)

agglomerates was characterised as ‘nucleation’ sites. A

particles forming fractals, while aggregates are particles key point of these observations, with respect to the issue
packed together in a more defined equi-axial shape. of grain growth during nanosintering, is the fact that
Figure 25 is a schematic illustration of the differences grains grow within agglomerates, probably with a
between agglomerates and aggregates. Mayo3 pointed relatively lower energy barrier and thus rapidly during
out that grain size is often related to the size of the initial stages of sintering.
agglomerates at the beginning of sintering. As Mayo
To explain the effect of agglomerates, Lange60
summarised, the larger the agglomerate size, the higher
classified the structure of a powder compact as a
the sintering temperature required to eliminate large
hierarchical structure of agglomerates, domains, and
interagglomerate pores. By contrast, the crystallite size
primary particles, as shown by Fig. 28. Defining the
has little effect on the temperature required to reach full
coordination number as the number of particles
density. The same temperatures, however, promote
surrounding the pore, Lange explained that pores within
grain growth to such an extent that the grain size can
domains have the lowest coordination number, pores
easily balloon to the agglomerate size.
between domains have higher, and pores between
Fang et al. observed a similar phenomenon. Figure 26
agglomerates have the highest coordination number.
shows an agglomerate of WC–10Co when heated to
800uC within a powder compact, while Fig. 27 shows the Figure 29 shows schematically the volume distribution
structure when the same compact is heated to 1200uC. It of the three classes of pores as a function of coordina-
can be seen that the original agglomerates, within which tion number. When N,Nc, a pore is unstable.
the WC grains are visible at 800uC, no longer exist at Otherwise, grain growth, or coarsening of particles
1200uC. Instead, the individual grains with sizes similar within agglomerates, will be necessary for elimination of
to those of the agglomerates at lower temperatures the pore and continuation of the sintering. This explains
constitute the microstructure. It is thus deduced that the the correlation between grain growth and the size of
densification and grain growth processes during nano- agglomerates.
sintering, progressed via consolidation and grain growth
within individual agglomerates, and then proceeded to
the consolidation and elimination of porosities between
agglomerates. This mechanistic process of sintering was
also observed and discussed by Petersson and Agren.55
The process that first takes place within individual

28 Schematic diagram of hierarchical structure of

26 Densification and grain growth within individual agglomerates (large circle), domains (small circle) and
aggregated particles before bulk densification primary particles (dots within small circles)

344 International Materials Reviews 2008 VOL 53 NO 6

 Fang and Wang
29 Schematic of pore coordination number distribution of agglomerated powder indicating three classes of pores, i.e.
those within domains, those between domains and those between agglomerates (R stands for coordination number):
After Ref. 60
Techniques for controlling grain growth while
achieving full densification
The difficulty of controlling grain growth while achiev-
ing maximum density is rooted in the fact that both
grain growth and densification rely on thermally
activated diffusion mechanisms. As discussed through-
out this article, densification relies on grain growth to
break local balance of surface and grain boundary
energies that mitigate the elimination of pores. Further,
to achieve nanoscaled grain sizes in sintered materials, it
is necessary to control both the normal grain growth due
to grain boundary migration and the initial grain
growth, which is a crucial part of the overall grain
growth process.
Two step sintering technique
As mentioned earlier, two step sintering is a proven
effective strategy for controlling normal grain growth.
As shown by Fig. 18, in the two step sintering process,
the compact is briefly heated to a high normal sintering
temperature, and then cooled to and held at a lower
temperature. It is necessary for the first step to be carried
out at a higher temperature, in order to quickly achieve
a high relative density. The second isothermal step at the
lower temperature is selected so that the densification
can continue, whereas grain growth is limited because
grain boundary migration is suppressed. This significant
discovery proves that it is possible to decouple grain
growth from densification and, hence, to achieve full
densification while retaining nanoscaled grain sizes.
Use of grain growth inhibitors
The use of grain growth inhibitors is a common method
for controlling grain growth during sintering. For
example, with the addition of SiC to Al2O3,156 ZrO2 to
b0-Al2O3,157 and Al2O3 to cubic ZrO2,158 large grain
growth can be effectively prevented. The use of grain
growth inhibitor can also be found during sintering of
other materials.119,159–161
Grain growth inhibitors are widely used in manufac-
turing fine and ultrafine grained cemented tungsten
carbide (WC–Co) materials.162–164 When VC, or VC
combined with Cr2C3, is used in liquid phase sintering of
nanosized WC–Co powder, grain size after sintering is
dramatically finer than if grain growth inhibitors had
Densification and grain growth during sintering of nanosized particles
not been used. Maheshwari et al.17 found that the effect
of VC on grain growth during sintering of WC–Co
significantly inhibits the rapid grain growth during the
solid state as well as the liquid phase sintering stage.
However, the finest grain size that has been reportedly
achieved using grain growth inhibitors in pressureless
liquid phase sintering processes is approximately 100 to
200 nm or larger, which is significantly larger than the
goal of being smaller than 100 nm. One explanation for
the limited effect of grain growth inhibitors has to do
with the size of agglomerates. If the mixing and
distribution scale of grain growth inhibitors is larger
than the original nanoscaled grain sizes and closer to the
size of the agglomerate, then the grain growth inhibitors
are effective only in that same dimensional scale.
However, more fundamental studies are needed to
extend their effectiveness into true nanoscale.
Pressure assisted sintering
The use of pressure assisted processes is another
straightforward approach for minimising grain growth
while achieving maximum densification. A variety of
pressure assisted sintering processes have been used in
sintering nanosized powders, including HP, HIP, SPS
and sinter forging. It is generally believed that the
applied pressure is able not only to enhance densification
by increasing sintering driving force, assisting particle
rearrangement and promoting diffusional creep,2,165–167
but also to inhibit grain growth by decreasing the
diffusivity and thus the grain boundary mobility.165 The
total sintering driving force when an external pressure is
applied includes both the intrinsic curvature driven
sintering stress and the applied external stress. The
significance of the applied pressure on sintering depends
on the relative magnitudes of the two components. The
applied pressure is independent of the particle size, while
the intrinsic sintering pressure increases when the
particle size is reduced, and it can reach a very high
value as particle size is in nanoscale. In order to make
the effect of applied pressure on densification become
dominant, the applied pressure has to be larger than the
intrinsic curvature driven pressure.2,167 Therefore, a
threshold pressure, which is dependent on the particle
size, must be exceeded so that the applied pressure can
have a significant influence on sintering. The existence of
International Materials Reviews 2008 VOL 53 NO 6 345
Fang and Wang Densification and grain growth during sintering of nanosized particles
the threshold pressure had been confirmed experimen-
tally by Skandan et al. on sintering of nanosized zirconia
powder.13,168
The logic for this approach is based on the belief that
densification can be achieved at lower than normal
sintering temperatures with the aid of pressure. The
lower temperature would, of course, slow the kinetic rate
of grain growth. For example, Haji-Mahmood and
Chumbley169 investigated the consolidation of molybde-
num disilicide (MoSi2) using HIP. Nanosized powders
produced by mechanical attrition were hipped under
300 MPa pressure at temperatures ranging from 800 to
1500uC. The grain sizes before hipping ranged from 20
to 30 nm. After hipping the range of grain size was from
30 to 40 nm, which is the minimum grain growth
considering that the relative density of the samples were
from 80 to 90%. In another example, Hayashi and
Etoch170 studied sintering behaviour of nanosized Fe,
Co, Ni and Cu metal powders under pressures ranging
from 400 to 500 MPa. The nanosized powders were
fabricated by evaporation and condensation method in
an inert gas. The starting average particle size of Fe, Co
and Ni were y20 nm; that of Cu was y50 nm. The
results showed that sintering temperatures were effec-
tively decreased by increasing pressure. Under 400 MPa,
the sintering temperature for Fe, Co, Ni and Cu
powders were about 590, 640, 450 and 450 K respec-
tively, which were 380–620 K lower than those without
pressure. The minimum average grain sizes of Fe, Co, Ni
and Cu in the fully densified compacts after sintering
were about 80, 210, 120 and 400 nm, which were much
smaller compared to those obtained by pressureless
sintering.
Pressure induced phase transformation is a phenom-
enon that was observed in several ceramic materials
during the consolidation of nanosized powders under
high pressure. It was found that several materials,
including nanosized TiO2, undergo phase transforma-
tion from anatase to rutile when pressure is higher than
1 GPa during a pressure assisted consolidation pro-
cess.165,171 The grain size of the product phase (rutile) is
smaller than that of the parent phase (anatase) after
consolidation. Under such high pressure, sintering
temperature is as low as one-third of Tm. Further, the
transformed grain size of the rutile phase decreases as
temperature increases, which was explained as the
competition between nucleation and grain growth
Table 1 Transformation assisted consolidation processing of five material systems: After Ref. 174
Material system Starting powder Consolidated and sintered parts
TAC sintered structure
Anatase n-Rutile, n-Srilankite
TiO2
nanopowder
c-alumina n-a-alumina
Al2O3
nanopowder
Amorphous n-a or mixed a/b
Si3N4
nanopowder
Al2O3/13w/oTiO2 Plasma sprayed 2–4 phase: Al2O3 (a);
Al2O3/40w/oTiO2 powder (mm scale) TiO2 (anatase, rutile or
srilankite); Al2O3
(TiO2 (x, or b)
2–5 phase: Al2O3 (a);
TiO2 (anatase, rutile or
srilankite); Al2O3
(TiO2 (x, or b)
346 International Materials Reviews 2008 VOL 53 NO 6
processes during pressure induced transformation. For
consolidation of nanocrystalline TiO2, pressures as high
as 8 GPa was used.172 A new transformation from rutile
to srilankite phase starts at y5 GPa. The theory
regarding the effect of high pressure on the sintering
behaviour of these materials has two key points. One is
that the pressure reduces the nucleation barrier for a
phase transformation that is accompanied by volume
reduction, as in the case of anatase to rutile of TiO2, and
c to a phase for Al2O3. The second point is that the high
hydrostatic pressure reduces the diffusion rate and, thus,
grain growth rate.
The consolidation of nanosized powders by utilising
the pressure induced phase transformation was also
characterised as ‘transformation assisted consolidation’
(TAC).173 Transformation assisted consolidation has
also been used to densify several materials, including
Al2O3 and Si3N4, as shown in Table 1.174 The key
criteria for the suitability of this technique is that the
starting material must be a metastable phase, which
transforms into the desired stable phase in a controlled
way during pressing and sintering. The combination of
increased nucleation and controlled grain growth
produces fully consolidated material with nanosized
grain structure.
Sinter forging is another unique technique that has
been used to produce fully dense materials with
nanosized grains from nanosized ceramic or metal
powders. First of all, sinter forging, also termed powder
forging, is a routine process that has been used to
manufacture ferrous powder metallurgy automobile
parts. In this case, green compacts are first sintered via
a standard atmospheric sintering process, and then the
sintered compacts are placed in a forging die and forged
at an elevated temperature. The forging process results
in fully dense metal parts.
In recent years, the term ‘sinter-forging’ has been used
to describe the processing of nanoscaled powder
materials. However, sinter forging of nanosized powder
is somewhat different from conventional sintering
forging, although it shares the same traits of ‘forging’
and distinguishes the process from conventional HP. In
this process, powders are placed in a die without lateral
constraint. The die and powder are heated via techni-
ques similar to the HP process and a uniaxial load is
applied. During sintering forging, the powder compact is
allowed to ‘upset’, i.e. bulge laterally, and is densified
Percentage theoretical density Grain size, nm
95–99 10–30
95–98.2 49–73
85–96 25–40
Cannot be determined 10–30
(theoretical density
is not known)
 Fang and Wang Densification and grain growth during sintering of nanosized particles

30 Prediction of grain size as a function of density for sinter forging at 1100uC. Higher strain rates are able to eliminate
large pores before the smaller pores enter the final stage of densification and allow grain growth. Therefore, density
is increased while grain growth is minimised (Reprinted with permission from Elsevier)

under load at specific temperature. The process is often
conducted under a constant load or a constant loading
rate. In most of the published research regarding
sintering of nanosized powders using sinter forging
process, a typical hot press is adapted for experiments.
Load capacity and loading rate are thus comparable to a
conventional HP process. In a study on the consolida-
tion of nano-3Y-TZP (3 mol.-% yttria stabilised tetra-
gonal zirconia polycrystals) using sinter forging process,
the loading rate varied from 0?005 to 0?1 kN21, sintering
temperature was around 1000–1100uC. Maximum load
was not allowed to exceed 30 kN.175 For sinter forging,
two densification mechanisms were assumed to be
operating: stress assisted diffusion and plastic flow
induced elimination of pores. Figure 30 shows the
relationship of grain size versus density at different
strain rates, illustrating that finer sintered grain size can
be achieved by using a higher strain rate during sinter
forging. In another study on consolidation of nano-
TiO2, sinter forging was conducted using 20 MPa
pressure at 1573 K for 1?0 h.119 The results demonstrate
that the relative density of the samples increased from 94
to 98% due to the use the compressive stress during
sinter forging.
In a study of the consolidation of nanosized metal
powders using a sinter forging process, Ma et al.176
applied a ‘constrained sinter forging’ or ‘upset hot
forging’ process scheme to consolidate nanocrystalline
Fe and Fe–Cu alloyed powders. A schematic of their
two step sinter forging technique is illustrated in Fig. 31.
Powders were prepared using mechanical milling tech-
niques. The initial grain sizes of mechanical milled
powder were 5–20 nm. In the first step, a preform was
compacted at room temperature or elevated temperature
using a tungsten carbide die at a pressure of y1 GPa
for a few to 24 h. In the second step, a compact with

a green compact is made using first die set at room temperature; b,c full density is reached in second die set using
elevated temperature and pressure
31 Schematic showing two step consolidation process, using procedure for Fe consolidation as example: After Ref. 176

International Materials Reviews 2008 VOL 53 NO 6 347

Fang and Wang Densification and grain growth during sintering of nanosized particles

32 Relative density and average grain size of aluminium oxide in compacts quenched from sintering temperatures ran-
ging from 1000 to 1400uC when a heating rate of 100uC min21 and a pressure of 50 MPa are applied. Within tempera-
ture regime I there is no densification or grain growth, whereas in regime II densification occurs, accompanied by
very limited grain growth; within regime III fast grain growth occurs in a fully dense body (Reprinted with permission
from Elsevier)

70–80% of theoretical density after the first step was
consolidated in a second die with a larger diameter. It
was then pressed using high pressure (0?5–1 GPa) at the
desired temperature for 30 min to a few hours in a
laboratory hot press system. The final consolidation was
carried out at temperatures below 600uC. Full density
was reached for the sample consolidated at 500uC with
an average sintered grain size of 138 nm. Consolidated
samples with 80 nm grain size were achieved with 99%
relative density. It was noted that, compared with grain
sizes in as milled powders (5–20 nm), grain growth was
present in all consolidated samples approaching full
density. Nonetheless, consolidated nanocrystalline Fe
with grain sizes within the typical range of nanocrystal-
line (,100 nm) was achieved. The successful consolida-
tion with minimum grain growth during sinter forging is
attributed to two aspects of applied pressure: the plastic
strain controlled pore closure and the stress assisted
diffusion induced densification.
Spark plasma sintering is a new pressure assisted
sintering process that quickly gained popularity with
researchers looking for ways to consolidate materials
with nanoscale or simply very fine grain sizes, or with
other non-equilibrium microstructures. Spark plasma
sintering, a commercial version of several related
consolidation techniques, was developed primarily dur-
ing 1980s and 1990s. The other variations or terms of the
technique include plasma activated sintering, field
assisted sintering, and electroconsolidation, all of which
share the same basic process elements as conventional
HP. The main difference between the SPS process and a
hot press is that rather than using an external heating
source, a current (either or AC or pulsed) is allowed to
pass through the electrically conducting die, and the
sample itself if it is conductive. Further, the technique of
heating using the graphite die has been used in
conventional HP. Therefore, the real uniqueness of the
SPS process may lie in the claimed electric spark and
plasma that may be generated between particles as a
result of pulsed electric current. A comprehensive and
critical review of the SPS process is beyond the scope of
this paper. Readers can refer elsewhere.167,177 However,
due to the extensive body of research on the consolida-
tion of nanosized powders that have been conducted
using the SPS process, an examination of the effects of
SPS process characteristics on densification and grain
growth of nanosized powders is necessary.
Groza et al. conducted a series of studies on the
sintering of different materials using field assisted
sintering techniques, or SPS.178–182 In the sintering of
nanocrystalline TiN using field assisted technique179, a
constant uniaxial pressure of 66 MPa was used. Relative
densities ranging from 91?5 to 94?3% were achieved for
monolithic TiN powder. Initial average grain size of the
powder was 70 nm. The average grain size after sintering
was determined to be 150–200 nm, a moderate increase
by a factor of y2. By comparison, conventional vacuum
sintering conducted at 1500uC showed that the sample
had a final grain size of 0?5–1?0 mm with 5–7% porosity.
Shen et al. studied the sintering of nanocrystalline
aluminium oxide, barium/strontium titanites, and silicon
nitride using the SPS process.112,183,184 Figure 32 shows
the densification and grain growth of Al2O3 as functions
of temperature during SPS. It was found that grain
growth starts at a temperature that is slightly higher
than in the densification process. Above the critical
temperature, the grain growth rate, and hence the grain
size, increases rapidly, with results similar to vacuum
sintering of WC–Co (Fig. 33). It demonstrates again
that the initial grain growth during sintering of
nanosized powders is primarily temperature dependent.
In order to avoid excessive grain growth, the critical
temperature, which should vary depending on the
material, must not be exceeded.
Overall, the positive effects of SPS process for sinter-
ing of nanosized powder reflect its unique characteristics

348 International Materials Reviews 2008 VOL 53 NO 6

 Fang and Wang
33 Grain size and densification of nanocrystalline WC–Co as function of sintering temperature at heating rate
10uC min21
which, as summarised by Nygren and Shen,185 include
rapid heat transfer; the application of a mechanical
pressure exceeding that used in normal HP processes;
the use of fast heating and cooling rates; and the use of a
pulsed direct current, implying that the samples are also
exposed to an electric field. In the authors’ opinion,
however, adequate data is not available in the literature
to support separating the effects of pressure and electric
field. Unfortunately, no data have been published that
compare the SPS process to the ‘hot press’ using the
same heating rate and pressure without the pulsed
current.
De-agglomeration
De-agglomerating the agglomerated particles prior to
sintering is another critical strategy for minimising the
initial dynamic grain growth. Based on the under-
standing that a pore’s stability is dependent on its
coordination numbers, a powder compact that has
uniformly distributed fine pores would have the most
efficient densification without relying on coarsening.
An ideal scenario for minimising grain growth while, at
the same time, achieving full densification is the
utilisation of green powder compacts composed of
monosized, spherical nanoparticles without agglomer-
ates. The pores within such a compact would be evenly
distributed and would have uniform size. To achieve
this type of green compact structure, Lange proposed a
methodology in which the powders would be treated
prior to sintering according to colloidal processing
principles.58 First, in order to de-agglomerate the
particles, dry powders are dispersed in fluid containing
a surfactant that produces interparticle repulsive
forces. After removing large particles that cannot be
de-agglomerated, the powder slurry is flocked by
changing the interparticle forces from repulsion to
attraction. As the result, the powder becomes a weak,
continuous network of touching primary particles.
Colloidally treated slurries could be used directly for
consolidation. The effects of de-agglomeration on the
density of green compacts and sintering of nanosized
particles are experimentally demonstrated in many
Densification and grain growth during sintering of nanosized particles
reported studies.59,186–191 In particular, Jae-Pyoung
Ahn et al.192 showed that the grain size of sintered
nano-SnO2 particles that have a dense green structure
are dramatically smaller than that of a compact with
loose structure.
Summary
Sintering of nanosized particles is a uniquely important
topic that is both scientifically and technologically
challenging. From a scientific perspective, the markedly
different sintering behaviour of nanosized powders
compared to micrometre sized powders, raises funda-
mental issues that cannot be fully comprehended based
on conventional theories of sintering. It is notable that
the driving force for sintering nanoparticles is signifi-
cantly higher than for micrometre sized particles. The
linear approximation used in conventional theories of
sintering, with regard to modelling the driving force and
the diffusion equations is no longer valid. In agreement
with the experimental observations, the rate of sintering
predicted by the non-linear diffusion model is much
higher than that predicted by the conventional linear
diffusion model.
With regard to the complex mechanisms of nanosin-
tering rapid densification of nanoparticles at relatively
low temperatures cannot be explained by the activation
energy values obtained from experiments. Several
possible mechanisms discussed in this article appear to
contribute to the initial densification including the rapid
diffusion rate due to non-equilibrium defect concentra-
tions in nanosized powders, the indirect role of mass
transport by surface diffusion, and the possible surface
melting of nanoparticles, all of which contribute to the
densification as well as coarsening of the nanoparticles.
From a technology perspective, proof that the
sintering temperature drastically decreases as particle
size decreases to nanoscale represents an actionable
knowledge that can be exploited in the production of
engineering materials from nanosized powders. As
reported in literature, the onset temperature of sintering
for most materials can be reduced by more than 200uC
International Materials Reviews 2008 VOL 53 NO 6 349
Fang and Wang Densification and grain growth during sintering of nanosized particles
depending on the particle size. For refractory metals
such as tungsten, the reduction of sintering temperature
is enabling. In other words, it is usually impossible to
sinter coarse tungsten powders at temperatures below
1800uC. With the reduction of the particle sizes to
20 nm, however, it is now feasible to sinter tungsten at
temperatures below 1200uC.
The greatest challenge for sintering nanosized pow-
ders is the ability to retain nanoscale grain sizes while
achieving full densification. The available literature
clearly demonstrates that the grain growth of nanosized
powders is characterised by two parts of grain growth:
the initial dynamic growth and the normal grain growth
which is reminiscent of that in bulk materials. The initial
grain growth is the result of the coarsening of particles
via the interparticle mass transport. For nanosized
powders, the initial grain growth causes the material to
lose nanocrystalline characteristics. Therefore, if at least
part of the goals of sintering is the retention of
nanoscaled grain sizes, the initial grain growth must be
controlled and minimised. On the other hand, in the
absence of the need to retain nanoscaled grain size,
the initial grain growth or coarsening is one of the
mechanisms that can be exploited to aid densification.
The methods for retaining grain growth include the
use of grain growth inhibitors, various high pressure hot
consolidation processes, and decoupling grain growth
from densification by manipulating different diffusion
mechanisms at different temperatures. The popular use
of SPS for consolidation of nanosized powders combines
the advantages of rapid heating rate and pressure.
However, regardless of the sintering technique used,
powder processing and green compact fabrication
techniques are crucial for controlling grain growth and
densification. In general, it is desirable to have minimum
agglomeration of particles, minimum pore size and
uniformly distributed pores. Even though the density of
a green compact usually decreases as the particle size
decreases, one must strive to increase green compact
density as high as possible to achieve maximum
densification with minimum grain growth.
Acknowledgements
The authors acknowledge the support by US
Department of Energy under Award no. DE-FC36-
04GO14041 with cost sharing by Kennametal Inc. and
Smith International Inc., and technical collaboration
with Idaho National Laboratory. The authors also
received support from US Army Research Laboratory
through a subcontract by Kennametal Inc. Several
graduate students’ thesis works are acknowledged
including Mr Praveen Maheshwari, Mr Xu Wang, and
Mr Vineet Kumar.
References
1. F. F. Lange and B. J. Kellett: J. Am. Ceram. Soc., 1989, 72, 735–
741.
2. J. R. Groza: ‘Nanocrystalline powder consolidation methods’, in
‘Nanostructured materials – processing, properties and potential
applications’, (ed. C. C. Koch), 1st edn, 115–178; 2002, Norwich,
NY, William Andrew Publishing/Noyes.
3. M. J. Mayo: Int. Mater. Rev., 1996, 41, 85–115.
4. V. Viswanathan, T. Laha, K. Balani, A. Agarwal and S. Seal:
Mater. Sci. Eng. R, 2006, R54, 121–285.
5. C. C. Koch: J. Mater. Sci., 2007, 42, 1403–1414.
350 International Materials Reviews 2008 VOL 53 NO 6
6. R. M. German: ‘Sintering theory and practice’; 1996, New York,
Wiley-Interscience.
7. D. A. Porter and K. E. Easterling: ‘Phase transformation in metal
and alloys’; 1992, London, CRC.
8. C. T. Campbell, S. C. Parker and D. E. Starr: Science, 2002, 298,
811–814.
9. K. K. Nanda, A. Maisels, F. E. Kruis, H. Fissan and S. Stappert:
Phys. Rev. Lett., 2003, 91, 106102.
10. R. L. Penn and J. F. Banfield: Geochim. Cosmochim. Acta, 1999,
63, 1549–1557.
11. H.-Y. Lee, W. Riehemann and B. L. Mordike: J. Eur. Ceram.
Soc., 1992, 10, 245–253.
12. H. Hahn: Nanostruct. Mater., 1993, 2, 251–265.
13. G. Skandan: Nanostruct. Mater., 1995, 5, 111–126.
14. M. J. Mayo: Mater. Design, 1993, 14, 323–329.
15. Y. C. Zhou and M. N. Rahaman: J. Mater. Res., 1993, 8, 1680–
1696.
16. T. Rabe and R. Waesche: Nanostruct. Mater., 1995, 6, 357–360.
17. P. Maheshwari, Z. Z. Fang and H. Y. Sohn: Int. J. Powder
Metall., 2007, 43, 41–47.
18. M. I. Alymov, E. I. Maltina and Y. N. Stepanov: Nanostruct.
Mater., 1994, 4, 737–742.
19. J. S. Lee and T. H. Kim: Nanostruct. Mater., 1995, 6, 691–694.
20. L. I. Trusov, V. N. Lapovok and V. I. Novikov: ‘Problems of
sintering metallic ultrafine powders’, in ‘Science of sintering’, (ed.
D. P. Uskokovic et al.), 185–192; 1989, New York, Plenum Press.
21. O. Dominguez, Y. Champion and J. Bigot: Metall. Mater. Trans.
A, 1998, 29A, 2941–2949.
22. R. Malewar, K. S. Kumar, B. S. Murty, B. Sarma and S. K. Pabi:
J. Mater. Res., 2007, 22, 1200–1206.
23. E. Oda, K. Ameyama and S. Yamaguchi: Mater. Sci. Forum,
2006, 503–504, 573–578.
24. H. Wang and Z. Z. Fang: ‘Study of size-dependant sintering
behavior of tungsten powders’, Proc. 2008 Int. Conf. on
‘Tungsten, refractory and hardmaterials VII’, Washington, DC,
USA, June 2008, Metal Powder Industries Federation, 2008,
05.72–05.77.
25. M. Attarian Shandiz, A. Safaei, S. Sanjabi and Z. H. Barber:
J. Phys. Chem. Solids, 2007, 68, 1396–1399.
26. P. Buffat and J. P. Borel: Phys. Rev. A, 1976, 13A, 2287–2298.
27. T. Castro, R. Reifenberger, E. Choi and R. P. Andres: Phys. Rev.
B, 1990, 42B, 8548–8556.
28. P. R. Couchman: Philos. Mag. A, 1979, 40A, 637–643.
29. P. R. Couchman and W. A. Jesser: Nature, 1977, 269, 481–483.
30. P. R. Couchman and C. L. Ryan: Philos. Mag. A, 1978, 37A, 369–
373.
31. Q. Jiang, S. Zhang and M. Zhao: Mater. Chem. Phys., 2003, 82,
225–227.
32. E. A. Olson, M. Y. Efremov, M. Zhang, Z. Zhang and L. H.
Allen: J. Appl. Phys., 2005, 97, 034304–034301.
33. W. H. Qi and M. P. Wang: Mater. Chem. Phys., 2004, 88, 280–
284.
34. J. Ross and R. P. Andres: Surf. Sci., 1981, 106, 11–17.
35. F. G. Shi: J. Mater. Res., 1994, 9, 1307–1313.
36. C. Solliard: Solid State Commun., 1984, 51, 947–949.
37. M. Wautelet: Solid State Commun., 1990, 74, 1237–1239.
38. M. Wautelet: Eur. J. Phys., 1995, 16, 283–284.
39. M. Wautelet: Phys. Lett. A, 1998, 246, 341–342.
40. P. Yang, Q. Jiang and X. Liu: Mater. Chem. Phys., 2007, 103, 1–4.
41. V. N. Troitskii, A. Z. Rakhmatullina, V. I. Berestenko and S. V.
Gurov: Poroshk. Metall., 1983, 22, 12–14.
42. Q. Jiang and F. G. Shi: J. Mater. Sci. Technol., 1998, 14, 171–172.
43. H. Ezaki, T. Nambu, M. Morinaga, M. Udaka and K. Kawasaki:
Int. J. Hydr. Energy, 1996, 21, 877–881.
44. C. Herring: J. Appl. Phys., 1950, 21, 301–303.
45. G. L. Messing and M. Kumagai: Am. Ceram. Soc. Bull., 1994, 73,
88–91.
46. M. F. Yan and W. W. Rhodes: Mater. Sci. Eng., 1983, 61, 59–66.
47. M. N. Rahaman: ‘Ceramic processing and sintering’, 2nd edn;
2003, New York, CRC.
48. J. Pan: Philos. Mag. Lett., 2004, 84, 303–310.
49. Q. Jiang, S. H. Zhang and J. C. Li: Solid State Commun., 2004,
130, 581–584.
50. E. Y. Gutmanas: Prog. Mater. Sci., 1990, 34, 261–366.
51. E. Y. Gutmanas, L. I. Trusov and I. Gotman: Nanostruct. Mater.,
1994, 4, 893–901.
52. M. F. Yan and W. W. Rhodes: Mater. Sci. Eng., 1983, 61, 59–66.
53. E. A. Barringer, R. Brook and H. K. Bowen: ‘The sintering of
monodisperse TiO2’, in ‘Sintering and heterogeneous catalysis’,
 Fang and Wang
(ed. G. C. Kuczynske et al. ), 1–21; 1984, New York, Plenum
Press.
54. D. C. Hague: ‘Chemical precipitation, densification, and grain
growth in nanocrystalline titania systems’, MSc thesis, The
Pennsylvania State University, Pittsburgh, PA, 1992.
55. A. Petersson and J. Agren: Acta Mater., 2005, 53, 1673–1683.
56. G. Malescio: Nature Mater., 2003, 2, 501–503.
57. J. N. Israelachvili: ‘Intermolecular and surface forces’; 1992,
London, Academic Press.
58. W. B. Russel, D. A. Saville and W. R. Schowalter: ‘Colloidal
dispersions’; 1992, Cambridge, Cambridge University Press.
59. F. F. Lange: J. Am. Ceram. Soc., 1989, 72, 3–15.
60. F. F. Lange: J. Am. Ceram. Soc., 1984, 67, 83–89.
61. W. D. Kingery and B. Francois: ‘Sintering of crystalline oxide, I.
Interactions between grain boundaries and pores’, in ‘Sintering
and related phenomena’, (ed. G. C. Kuczynske et al.), 471–498;
1967, New York, Gordon and Breach Science Publishers.
62. D. L. Johnson: J. Appl. Phys., 1969, 40, 192–200.
63. G. S. A. M. Theunissen, A. J. A. Winnubst and A. J. Burggraaf:
J. Eur. Ceram. Soc., 1993, 11, 315–324.
64. J. J. Bacmann and G. Cizeron: J. Am. Ceram. Soc., 1968, 51, 209–
212.
65. C.-R. Li and T. B. Tang: J. Mater. Sci., 1999, 34, 3467–3470.
66. T. Ozawa: J. Therm. Anal., 1970, 2, 301–324.
67. J. H. Flynn and l. A. Wall: Polym. Lett. 1966, 4, 191.
68. P. Vergnon, M. Astier and S. J. Teichner: Polymer preprints,
Division of Polymer Chemistry, American Chemical Society,
1974, 299–307.
69. K. G. Ewsuk, D. T. Ellerby and C. B. DiAntonio: J. Am. Ceram.
Soc., 2006, 89, 2003–2009.
70. B. B. Panigrahi: Mater. Sci. Eng. A, 2007, A460–461, 7–13.
71. V. V. Dabhade, T. R. Rama Mohan and P. Ramakrishnan:
Mater. Sci. Eng. A, 2007, A452–453, 386–394.
72. J.-L. Shi, Y. Deguchi and Y. Sakabe: J. Mater. Sci., 2005, 40,
5711–5719.
73. J. E. Bonevich and L. D. Marks: Mater. Res. Soc. Symp. Proc.,
1993, 286, 3–8.
74. J. L. Shi: J. Mater. Res., 1999, 14, 1378–1388.
75. J. L. Shi: J. Mater. Res., 1999, 14, 1389–1397.
76. C. E. Krill, III, L. Helfen, D. Michels, H. Natter, A. Fitch,
O. Masson and R. Birringer: Phys. Rev. Lett., 2001, 86, 842–845.
77. A. H. Carim: ‘Microstructure in nanocrystalline zirconia powders
and sintered compacts’, in ‘Nanophase materials: synthesis,
properties, applications’, (ed. G. C. Hadjipanayis and R. W.
Siegel), 283–286; 1994, Dordrecht, Kluwer Academic Publishers.
78. J. Y. Ying, L. F. Chi, H. Fuchs and H. Gleiter: Nanostruct.
Mater., 1993, 3, 273.
79. H. Zhu and R. S. Averback: J. Eng. Appl. Sci. A, 1995, 204A, 96–
100.
80. H. Zhu and R. S. Averback: Mater. Manuf. Process., 1996, 11,
905–923.
81. Z. Xing, W. Shaoqing and Z. Caibei: J. Mater. Scie. Technol.,
2006, 22, 123–126.
82. V. N. Koparde and P. T. Cummings: J. Phys. Chem. B, 2005,
109B, 24280–24287.
83. K. Tsuruta, A. Omeltchenko, R. K. Kalia and P. Vashishta:
Europhys. Lett., 1996, 33, 441–446.
84. J. S. Raut, R. B. Bhagat and K. A. Fichthorn: Nanostruct. Mater.,
1998, 10, 837–851.
85. C. Win-Jin, F. Te-Hua and C. Jun-Wei: Microelectr. J., 2006, 37,
722–727.
86. D. Hai, M. Kyoung-Sik and C. P. Wong: J. Electr. Mater., 2004,
33, 1326–1330.
87. J. Pan: Int. Mater. Rev., 2003, 48, 69–85.
88. E. A. Olevsky, V. Tikare and T. Garino: J. Am. Ceram. Soc.,
2006, 89, 1914–1922.
89. M. F. Ashby: Acta Metall., 1974, 22, 275–289.
90. W. Beere: Acta Metall., 1975, 23, 139–145.
91. R. L. Coble: J. Appl. Phys., 1961, 32, 787–792.
92. H. E. Exner: Powder Metall., 1980, 23, 203–209.
93. H. E. Exner and E. Arzt: ‘Sintering processes’, in ‘Physical
metallurgy’, (ed. R. W. Cahn and P. Haasen), 4th edn, 2628–2662;
1996, Amsterdam, Elsevier Science.
94. H. E. Exner and T. Kraft: ‘Review on computer simulations of
sintering processes’, Proc. 1998 World Cong. on ‘Powder
metallurgy’, Shrewsbury, UK, October 1998, European Powder
Metallurgy Association, 278–283.
95. J. Frenkel: J. Phys., 1945, 9, 385–391.
96. W. D. Kingery and M. Berg: J. Appl. Phys., 1955, 26, 1205–1212.
Densification and grain growth during sintering of nanosized particles
97. J. K. Mackenzie and R. Shuttleworth: Proc. Phys. Soc. B, 1949,
12B, 833–852.
98. E. A. Olevsky: Mater. Sci. Eng. R, 1998, R23, 41–100.
99. G. W. Scherer: J. Amer. Ceram. Soc., 1977, 60, 236–239.
100. G. C. Kuczynski: J. Met., 1949, 1, 169–178.
101. H. E. Exner: Rev. Powder Metall. Phys. Ceram., 1979, 1, 11–251.
102. H. Matsubara: J. Ceram. Soc. Jpn, 2005, 113, 263–268.
103. L. R. Madhavrao and R. Rajagopalan: J. Mater. Res., 1989, 4,
1251–1256.
104. M. Braginsky, V. Tikare and E. Olevsky: Int. J. Solids Struct.,
2005, 42, 621–636.
105. V. Tikare, M. Braginsky and E. A. Olevsky: J. Am. Ceram. Soc.,
2003, 86, 49–53.
106. A. Luque, J. Aldazabal, A. Martin-Meizoso, J. M. Martinez-
Esnaola, J. G. Sevillano and R. Farr: Model. Simul. Mater. Sci.
Eng., 2005, 13, 1057–1070.
107. T. R. Malow and C. C. Koch: ‘Grain growth of nanocrystalline
materials – a review’, Proc. TMS Ann. Meet. on ‘Synthesis and
processing of nanocrystalline powder’, Anaheim, CA, USA,
February 1996, TMS, 33–44.
108. T. R. Malow and C. C. Koch: Mater. Sci. Forum, 1996, 225–227,
595–604.
109. T. R. Malow and C. C. Koch: Acta Mater., 1997, 45, 2177–2186.
110. X. Song, J. Zhang, L. Li, K. Yang and G. Liu: Acta Mater., 2006,
54, 5541–5550.
111. Z. Fang, P. Maheshwari, X. Wang, H. Y. Sohn, A. Griffo and
R. Riley: Int. J. Refract. Met. Hard Mater., 2005, 23, 249–257.
112. Z. J. Shen, H. Peng, J. Liu and M. Nygren: J. Eur. Ceram. Soc.,
2004, 24, 3447–3452.
113. S. Okuda, M. Kobiyama, T. Inami and S. Takamura: Scr. Mater.,
2001, 44, 2009–2012.
114. D. J. Chen and M. J. Mayo: Nanostruct. Mater., 1993, 2, 469.
115. W. Dickenscheid, R. Birringer, H. Gleiter, O. Kanert, B. Michel
and B. Guenther: Solid State Commun., 1991, 79, 683–686.
116. G. Hibbard, K. T. Aust, G. Palumbo and U. Erb: Scr. Mater.,
2001, 44, 513–518.
117. R. Klemm, E. Thiele, C. Holste, J. Eckert and N. Schell: Scr.
Mater., 2002, 46, 685–690.
118. F. Zhou, J. Lee and E. J. Lavernia: Scr. Mater., 2001, 44, 2013–
2017.
119. D. M. Owen and A. H. Chokshi: Nanostruct. Mater., 1993, 2,
181–187.
120. R. S. Averback: Z. Phys. D, 1993, 26D, 84–88.
121. J. G. Li and Y. P. Ye: J. Am. Ceram. Soc., 2006, 89, 139–143.
122. R. Vassen: CFI/Ber. DKG, 1999, 76, 19–22.
123. I. W. Chen and X. H. Wang: Nature, 2000, 404, 168–171.
124. R. M. German, J. Ma, X. Wang and E. Olevsky: Powder Metall.,
2006, 49, 19–27.
125. J. D. Hansen, R. P. Rusin, T. Mao-Hua and D. L. Johnson:
J. Am. Ceram. Soc., 1992, 75, 1129–1135.
126. H. Su and D. L. Johnson: J. Am. Ceram. Soc., 1996, 79, 3211–
3217.
127. S. J. Park, J. M. Martin, J. F. Guo, J. L. Johnson and R. M.
German: Metall. Mater. Trans. A, 2006, 37A, 3337–3346.
128. H. V. Atkinson: Acta Metall., 1988, 36, 469–491.
129. S.-J. L. Kang: ‘Sintering: densification, grain growth and
microstructure’; 2005, Burlington, MA, Butterworth-Heinemann.
130. J. E. Burke and D. Turnbull: Prog. Met. Phys., 1952, 3, 220–292.
131. H. Natter, M. Schmelzer, M. S. Loeffler, C. E. Krill, A. Fitch and
R. Hempelmann: J. Phys. Chem. B, 2000, 104B, 2467–2476.
132. E. A. Grey and G. T. Higgins: Acta Metall., 1973, 21, 309–321.
133. J. E. Burke: Trans. Metall. Soc. AIME, 1949, 180, 73–91.
134. J. E. Burke: Trans. Metall. Soc. AIME, 1950, 188, 1324–1328.
135. A. Michels, C. E. Krill, H. Ehrhardt, R. Birringer and D. T. Wu:
Acta Mater., 1999, 47, 2143–2152.
136. H. Mehrer: ‘Diffusion in solid metals and alloys’; 1990, Berlin,
New York, Springer-Verlag.
137. P. Guiraldenq and P. Lacombe: Acta Metall., 1965, 13, 51–53.
138. F. Liu, G. C. Yang, H. F. Wang, Z. Chen and Y. H. Zhou:
Thermochim. Acta, 2006, 443, 212–216.
139. X. Wang, Z. Z. Fang and H. Y. Sohn: Int. J. Refract. Met. Hard
Mater., 2008, 26, 232–241.
140. H.-D. Kim, Y.-J. Park, B.-D. Han, M.-W. Park, W.-T. Bae,
Y.-W. Kim, H.-T. Lin and P. F. Becher: Scr. Mater., 2006, 54,
615–619.
141. Y.-I. Lee, Y.-W. Kim, M. Mitomo and D.-Y. Kim: J. Am. Ceram.
Soc., 2003, 86, 1803–1805.
142. R. L. Coble: J. Am. Ceram. Soc., 1958, 41, 55–62.
143. D. L. Johnson and I. B. Cutler: J. Am. Ceram. Soc., 1963, 46, 541–
545.
International Materials Reviews 2008 VOL 53 NO 6 351
Fang and Wang Densification and grain growth during sintering of nanosized particles
144. C. Greskovich and K. W. Lay: J. Am. Ceram. Soc., 1972, 55, 142–
146.
145. R. A. Andrievski: J. Mater. Sci., 2003, 38, 1367–1375.
146. R. Wuschum, S. Herth and U. Brossmann: ‘Diffusion in
nanocrystalline metals and alloys – a status report’, in
‘Nanomaterials by severe plastic deformation’, (ed. M.
Zehetbauer and R. Z. Valiev), 755–766; 2002, Weinheim, Wiley-
VCH.
147. L. G. Kornelyuk, A. Y. Lozovoi and I. M. Razumovskii: Diffus.
Defect Data A, 1997, 143A, (1), 1481.
148. R. Wuerschum, K. Reimann and P. Farber: Diffus. Defect Data
A, 1997, 143A, (1), 1463.
149. V. N. Perevezentsev: ‘Theoretical investigation of nonequilibrium
grain boundary diffusion properties’, in ‘Nanomaterials by severe
plastic deformation’, (ed. M. Zehetbauer and R. Z. Valiev), 773–
779; 2002, Weinheim, Wiley-VCH.
150. A. Nazarov: Phys. Solid State, 2003, 45, 1166–1169.
151. K. Nakaso, M. Shimada, K. Okuyama and K. Deppert: J. Aerosol
Sc., 2002, 33, 1061–1074.
152. K. E. J. Lehtinen and M. R. Zachariah: J. Aerosol Sci., 2002, 33,
357–368.
153. W. Koch and S. K. Friedlander: J. Aerosol Sci., 1989, 20, 891–894.
154. D. Mukherjee, C. G. Sonwane and M. R. Zachariah: J. Chem.
Phys., 2003, 119, 3391–3404.
155. V. Kumar, Z. Fang, S. Wright and M. Nowell: Metall. Mater.
Trans. A, 2006, 37A, 599–607.
156. F. F. Lange and M. Claussen: ‘Some processing requirements for
transformation-toughened ceramics’, in ‘Ultrastructure processing
of ceramics, glasses, and composites’, (ed. L. L. Hench and D. R.
Ulrich), 493; 1984, New York, Wiley.
157. D. J. Green: J. Mater. Sci., 1985, 20, 2639–2646.
158. F. J. Esper, K. H. Friese and H. Geier: ‘Mechanical, thermal, and
electrical properties in the system of stabilized ZrO2(Y2O3)/alpha -
Al2O3’, in ‘Science and technology of zirconia II’, 528–536; 1984,
Stuttgart, CRC.
159. T. K. Gupta: J. Am. Ceram. Soc., 1972, 55, 276–277.
160. T.-G. Nieh and J. Wadsworth: J. Am. Ceram. Soc., 1989, 72,
1469–1472.
161. R. S. Averback, H. Hahn, H. J. Hofler, J. L. Logas and T. C.
Shen: ‘Kinetic and thermodynamic properties of nanocrystalline
materials’, Proc. Symp. on ‘Interfaces between polymers, metals
and ceramics’, San Diego, CA, USA, April 1989, Materials
Research Society, 3–12.
162. C. W. Morton, D. J. Wills and K. Stjernberg: Int. J. Refract. Met.
Hard Mater., 2005, 23, 287–293.
163. R. K. Sadangi, L. E. McCandlish, B. H. Kear and P. Seegopaul:
Int. J. Powder Metall., 1999, 35, 27–33.
164. O. Seo, S. Kang and E. J. Lavernia: Mater. Trans., 2003, 44,
2339–2345.
165. S. C. Liao, W. E. Mayo and K. D. Pae: Acta Mater., 1997, 45,
4027–4040.
166. B. J. Kellett and F. F. Lange: J. Am. Ceram. Soc., 1988, 71, 7–12.
352 International Materials Reviews 2008 VOL 53 NO 6
167. Z. A. Munir, U. Anselmi-Tamburini and M. Ohyanagi: J. Mater.
Sci., 2006, 41, 763–777.
168. G. Skandan, H. Hahn, B. H. Kear, M. Roddy and W. R. Cannon:
Mater. Lett., 1994, 20, 305–309.
169. M. S. Haji-Mahmood and L. S. Chumbley: Nanostruct. Mater.,
1996, 7, 95–112.
170. K. Hayashi and H. Etoh: Mater. Trans. JIM, 1989, 30, 925–931.
171. L. Shih-Chieh, K. D. Pae and W. E. Mayo: Nanostruct. Mater.,
1997, 8, 645–656.
172. S. C. Liao, Y. J. Chen, W. E. Mayo and B. H. Kear: Nanostruct.
Mater., 1999, 11, 553–557.
173. B. H. Kear, J. Colaizzi, W. E. Mayo and S. C. Liao: Scr. Mater.,
2001, 44, 2065–2068.
174. J. Colaizzi, W. E. Mayo, B. H. Kear and S.-C. Liao: Int. J. Powder
Metall., 2001, 37, 45–54.
175. D. C. Hague and M. J. Mayo: Mater. Sci. Eng. A, 1995, A204, 83–
89.
176. E. Ma, D. Jia and K. T. Ramesh: ‘Nanophase and ultrafine-
grained powders prepared by mechanical milling: full density
processing and unusual mechanical behavior’, Proc. Symp. on
‘Powder materials: current research and industrial practices’,
Indianapolis, IN, USA, November 2001, TMS, 257–266.
177. J. R. Groza and A. Zavaliangos: Rev. Adv. Mater. Sci., 2003, 5,
24–33.
178. G. Aldica, P. Badica and J. R. Groza: J. Optoelectr. Adv. Mater.,
2007, 9, 1742–1745.
179. J. R. Groza, J. D. Curtis and M. Kramer: J. Am. Ceram. Soc.,
2000, 83, 1281–1283.
180. V. Y. Kodash, J. R. Groza, K. C. Cho, B. R. Klotz and R. J.
Dowding: Mater. Sci. Eng. A, 2004, A385, 367–371.
181. V. Sandu, G. Aldica, P. Badica, J. R. Groza and P. Nita:
Superconduct. Sci. Technol., 2007, 20, 836–842.
182. L. A. Stanciu, V. Y. Kodash and J. R. Groza: Metall. Mater.
Trans. A, 2001, 32A, 2633–2638.
183. J. Liu, Z. Shen, M. Nygren, B. Su and T. W. Button: J. Am.
Ceram. Soc., 2006, 89, 2689–2694.
184. Z. J. Shen, Z. Zhao, H. Peng and M. Nygren: Nature, 2002, 417,
266–269.
185. M. Nygren and Z. Shen: Solid State Sci., 2003, 5, 125–131.
186. O. Vasylkiv and Y. Sakka: Scr. Mater., 2001, 44, 2219–2223.
187. O. Vasylkiv and Y. Sakka: J. Am. Ceram. Soc., 2001, 84, 2489–
2494.
188. F. F. Lange: Curr. Opin. Solid State Mater. Sci., 1998, 3, 496–500.
189. L. Bergstrom, K. Shinozaki, H. Tomiyama and N. Mizutani:
J. Am. Ceram. Soc., 1997, 80, 291–300.
190. C. Duran, Y. Jia, Y. Hotta, K. Sato and K. Watari: J. Mater.
Res., 2005, 20, 1348–1355.
191. P. Bowen, C. Carry, D. Luxembourg and H. Hofmann: Powder
Technol., 2005, 157, 100–107.
192. J.-P. Ahn, M.-Y. Huh and J.-K. Park: Nanostruct. Mater., 1997,
8, 637–643.