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Acta Materialia 57 (2009) 54545465

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Direct comparison between hot pressing and electric

eld-assisted sintering of submicron alumina
Jochen Langer a,*, Michael J. Homann b, Olivier Guillon a
a
Institute of Materials Science, Technische Universitat Darmstadt, Petersenstrasse 23, D-64287 Darmstadt, Germany
b
Institute of Ceramics in Mechanical Engineering, Universitat Karlsruhe (TH), Haid-und-Neu-Strasse 7, D-76131 Karlsruhe, Germany

Received 21 January 2009; received in revised form 23 July 2009; accepted 24 July 2009
Available online 26 August 2009

Abstract

This study compares hot pressing (HP) and the electric eld-assisted sintering technique (FAST) of two dierent electrically insulating
Al2O3 submicron powders with median particle sizes of 150 and 500 nm. Sample geometry, heating schedule, applied pressure and atmo-
sphere were identical for both sintering methods. The densication behavior and characterization of the microstructure revealed that
FAST sintered samples reached a higher density compared with HP, in particular for the ner powder. It was found that an increase
in dwell time was required to reach the same nal density by HP. However, analysis of the sintering curves showed that the densication
mechanism for both sintering methods was grain boundary diusion. Increasing the heating rate up to 150 K min1 did not modify the
densication mechanism. The sintering trajectory showed that the grain size was only dependent on density and was insensitive to the
sintering method, in addition to showing a lack of preferential grain orientation.
2009 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: Alumina; Electric eld-assisted sintering (FAST); Hot pressing (HP); Densication

1. Introduction ment of new materials, relatively few papers have been

The rst investigations and development of the spark
plasma sintering technique (SPS) started in the 1960s
and 1970s in Japan. Because plasma formation could
not be validated, other terms were used for this technique,
such as pulse electric current sintering or the eld-assisted
sintering technique (FAST) [1,2]. Due to the new possibil-
ities, interest in this method has increased over the last
10 years. High heating rates of up to 1000 K min1 and
direct heating of electrically conductive densifying speci-
mens have been the driving force for this expansion,
allowing shorter production cycles for materials typically
dicult to fully densify [1] with limited grain growth
[3,4]. Although many researchers have focused on the
advantages of FAST over free sintering and the develop-
*
Corresponding author. Tel.: +49 6151 16 6313. fax: +49 6151 16 6314.
E-mail address: langer@ceramics.tu-darmstadt.de (J. Langer).
published on the specic mechanisms involved during
FAST, either thermally, electrically or mechanically [5
10]. It is not surprising that materials processed by FAST
often show better properties than those sintered in con-
ventional furnaces, as the processing parameters are not
identical [11,12]. Neglecting all possible eects of electrical
eld and direct heating oered by FAST, there is still one
signicant dierence from the free sintering case: the
applied compressive stress, which signicantly enhances
densication [1315]. It is thus sensible to make a direct
comparison of FAST with its closest alternative, hot
pressing (HP). The required equipment is similar: powder
is uniaxially pressed between two graphite punches in a
graphite die and heated in a dened atmosphere (vacuum
or inert gases). The primary dierence is how thermal
energy is transferred to the powder pellet. In the case of
FAST an electrical current ows through the graphite
punches and die so that the pressing tool acts as the heat-
ing element by the Joule eect. In the case of specimens

1359-6454/$36.00 2009 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.actamat.2009.07.043
 J. Langer et al. / Acta Materialia 57 (2009) 54545465
with higher electrical conductivity the electric current can
also contribute to direct heating of the sintering powder.
In contrast, graphite heating elements in HP surround
the pressing tool, transferring heat by radiation/
convection.
At the macroscopic scale several nite element method
simulations have been performed to model temperature
and current distributions in insulating and conductive
materials during FAST [1618], highlighting possible tem-
perature gradients for high heating rates. However, addi-
tional phenomena induced by the electric eld which
aect densication were not taken into account, except
recently in a constitutive model including electromigration
by Olevsky and Froyen [19]. It is, however, known that
FAST has an eect on the reactivity between Si and Mo,
as investigated by Munirs group [5,8]. Their results
showed a higher growth rate of the reacted layer in the
presence of current, without changing the reaction mecha-
nism. It seems that neither current direction nor pulsing
aects the diusion kinetics. Nonetheless, in insulating
materials like alumina no direct current ow through the
powder is expected [20].
Alumina is a well-known ceramic material and is usually
used as a model powder for solid-state sintering experi-
ments. The advantages of using a-Al2O3 powder are its
(i) availability at high purity in a wide range of particle
sizes and (ii) thermodynamic stability at high temperature.
However, under a critical size of about 100 nm metastable
transition phases may signicantly aect the sintering
behavior when transforming into the a-phase [21]. Zhou
et al. [4] and Shen et al. [22] investigated the evolution of
the microstructure of FAST sintered a-alumina as a func-
tion of heating rate. They found that a high heating rate
leads to a smaller grain size for a given density. Wang
et al. [23] focused on microstructure, highlighting how het-
erogeneities depend on the position within the sample.
More recently, Stanciu et al. [12] found that during the ini-
tial stage of sintering there was a greater rate of neck
growth below 900 C in comparison with microwave and
conventional sintered alumina.
In the present work FAST and HP experiments were run
under the same conditions: unaxial shrinkage was mea-
sured at temperatures in the range of 11001250 C with
a dwell time of 12 h, a xed heating rate of 10 K min1
and a macroscopic uniaxial pressure of between 15 and
50 MPa. Special care was taken to check the validity of
these experimental parameters in both cases, including tem-
perature measurement. This enabled the identication of
the densication mechanism involved in each process by
determining the activation energy, stress exponent and
grain growth exponent. The heating rate was varied up to
150 K min1 to highlight any possible changes in the den-
sication mechanism in FAST. Further, microstructure
analysis was carried out to determine any gradient or pref-
erential orientation of pores and grains, as well as to ratio-
nalize similarities and dierences between FAST and HP
specimens obtained from the macroscopic measurements.
5455
2. Experimental procedure
2.1. FAST and HP experiments
All experiments were made with HP (model HPW 150/
2002200-100-LA) and FAST (model FCT HP D 25/1)
equipment manufactured by the same company (FCT Sys-
teme, Germany). This allowed a better comparison
between the two methods, as FAST units have been derived
from pre-existing HP set-ups. Used materials were a-Al2O3
powders: (i) purity 99.99% and median particle size 150 nm
(TMDAR, Taimei Chemicals, Japan) [24] and (ii) purity
99.78% and median particle size 500 nm (CT 3000 SG,
Almatis, Germany). Raw powders were sieved through a
100 lm mesh, allowing better packing and reproducibility
of the green bodies. The FAST graphite tool, with a wall
thickness of 10 mm (graphite type R7710, q = 1.88 g cm3,
SGL Carbon GmbH, Germany) and an internal diameter
of 20 mm was lled with 7.5 g of the sieved powder and
mounted into the FAST equipment. To avoid shifting of
the mobile die at the beginning of the sintering process a
gauge was used. The interior of the die and the surfaces
of the punches were covered with a compressible graphite
foil (type N998, FCT Systeme) with a thickness of
0.37 mm. This maximized the contact area between the
rough powder compact surface and the punches. Further-
more, this graphite foil had a lubricating eect, reducing
the friction between the movable parts and signicantly
reducing temperature inhomogeneities [25,26]. In addition,
the exterior of the die was covered by graphite felt with a
nal thickness of 10 mm to reduce possible temperature
gradients. A similar procedure was used to ll the die in
the HP graphite tool (graphite type R7500, q =
1.78 g cm3, SGL Carbon GmbH, Germany).
The initial sample height was 11 mm, with a relative
green density of 52 2% (measured geometrically). To
facilitate comparison, the same heating rate of 10 K min1,
sintering temperatures of 1100, 1150 and 1200 C, dwell
times of up to 2 h and under vacuum (0.4 mbar) were cho-
sen for the sintering experiments. In the case of FAST a
pulse pattern of 25:5 was adopted for heating. The cooling
rate was 10 K min1 until a temperature 150C below the
maximum temperature was reached. The temperature con-
trol unit was shut o after this. To investigate densication
behavior assisted by mechanical stress loads ranging
between 4.5 and 15.7 kN were chosen (corresponding to
15 and 50 1.6 MPa, respectively). Axial shrinkage was
measured at a resolution of 10 lm for FAST and 5 lm
for HP. Thermal expansion of the machine was taken into
account through reference measurements obtained by plac-
ing a dense alumina sample in the pressing tool and sub-
tracting these measured values from the original sintering
curves. The eect of heating rate on the densication mech-
anism in FAST was also analyzed. Various heating rates
from 35 up to 150 K min1 were used, together with a sin-
tering temperature of 1200 C, a soak time of 10 min and a
stress of 50 MPa.
5456 J. Langer et al. / Acta Materialia 57 (2009) 54545465
The temperature was measured in two dierent ways: in
HP a thermocouple was used, while in FAST a pyrometer
was used. In both cases a hole was drilled in the surround-
ing graphite allowing temperature measurements approxi-
mately 5 mm from the sample. In the FAST set-up the
temperature was measured axially on the surface of the
punch [18]. The pyrometer was not able to measure temper-
atures under 450 C, limiting control to temperatures
above 450 C. The power input was set to 35% of the max-
imum nominal power. As a consequence, initial overheat-
ing up to 600 C could be observed. In HP the
temperature was measured with an S-type thermocouple
at the edge of the center plane perpendicular to the direc-
tion of loading of the powder compact. Additionally, ther-
mal homogeneity through the sample was critical. To this
end, 1 wt.% copper powder (mean diameter 0.751.5 lm,
Alfa Aesar) was mixed with the alumina powder in an inert
atmosphere and sintered. It was veried that this small
amount of copper metal well below the percolation
threshold did not alter the densication behavior of the
alumina powder. For both set-ups calibration experiments
were started at temperatures 20 C lower than the melting
point of copper (1084 C) and then increased in 5 C steps.
After each experiment a photograph of the sectioned spec-
imen was taken. Fig. 1a shows a HP sintered sample with a
dwell time of 60 s at 1085 C. Fig. 1b shows a schematic of
the behavior of the samples kept at constant temperature
for dwell times of 190 s. The outer area of the respective
ellipse indicates the area of molten copper, which increases
with time. These experiments showed that the HP and
FAST sintered samples needed 90 and 60 s at
1085 C, respectively, for the copper to become completely
molten. Temperature accuracy was better than 5 C,
because specimens heated at 1080 C did not show any
melting. The densities of all sintered specimens were mea-
sured by the Archimedes method in water at room
temperature.
2.2. Microstructural analysis
In order to obtain representative information over the
whole sample volume specimens of TMDAR alumina were
prepared as follows: a bar was cut out of the middle of the
sample (Fig. 2a), subsequently ground, nely polished and
then thermally etched for 20 min at a temperature 50 C
Fig. 1. (a) Photograph of polished copper/alumina sample (sintered at 1085 C for 60 s by HP). (b) Schematic of copper melting as a function of dwell time
at constant temperature (1085 C).
Fig. 2. (a) Sintered sample with the cutting direction. (b) Sample cut-out
showing four representative areas.
lower than the maximum temperature during the sintering
experiment. Micrographs were then taken at four dierent
positions on the sample (Fig. 2b) with a high resolution
scanning electron microscope (XL 30 FEG, Philips, The
Netherlands). The grain size was measured by the linear
intercept method using an image analysis program (Lince
v. 2.31, Ceramics Group, Technische Universitat Darms-
tadt, Germany), taking at least 2400 grains into account.
Finally, additional samples were sintered under 50 MPa
with a heating rate of 10 K min1 to a density between
55% and 65% by both methods. They were further charac-
terized at room temperature by means of intrusive mercury
porosimetry (Pore Sizer 9320, Micromeritics, USA) and the
laser ash method (ZAE Bayern, Wurzburg, Germany).
2.3. Macroscopic analysis of sintering
During HP and FAST a constant uniaxial mechanical
load was applied so that lateral shrinkage of the sample
remained negligible. Densication took place only along
the thickness direction. As large strains were observed,
the use of true strain ez was preferred:
 
h
ez ln 1
h0
where h is the instantaneous sample height and h0 is the ini-
tial height of the green body.
Instantaneous density q can be computed from:
q q0 expez 2
where q0 is the initial sample density.
Densication was enhanced by the compressive loading
applied during HP and FAST. By limiting grain growth
both sintering techniques provided an eective method
for investigating densication behavior. When moderate
loads are applied and deformation is controlled by a
 J. Langer et al. / Acta Materialia 57 (2009) 54545465
diusional process (assumptions validated for alumina by
Coble [27]) the true strain rate can be described by the gen-
eral equation [15]:
dez 1 dq HD
_ez  m /pa n 3 1 dq
dt q dt G kT
where e_ z is the true strain rate (the inverse is equivalent to
the normalized densication rate), H is a numerical con-

stress /pa and temperature T are assumed to be constant,
stant, D D0 exp E RT
a
the diusion coecient of the
rate-controlling species, D0 a pre-exponential factor, Ea is
the activation energy, R is the gas constant, G the grain
size, k the Boltzmann constant, T the absolute temperature,
/ is the stress intensication factor, pa the uniaxial applied
stress and the so-called stress exponent n and grain size
exponent m depend on the mechanism of densication
and grain growth, respectively.
The stress intensication factor describes how the mac-
roscopic applied stress is magnied at the microscopic
scale. For a low density body the contact area between par-
ticles where stress is transmitted is small and stresses are
locally much higher than the macroscopic applied stress.
Recently, a numerical study by Montes et al. [28] showed
how critical is the choice of coecient on the eective
stress. By considering an ideal powder aggregate consisting
of spherical particles arranged in a simple cubic packing,
but avoiding the rigorous tensorial stressstrain relation-
ship at the particle contacts and neglecting friction and wall
constriction, they developed a simplied expression for uni-
axial compression:
  1
1q
/ 1 4 similar trend, in particular during the heating ramp, which
1  qM
where qM is the minimal equilibrium density without defor-
mation, which is assimilated in real packings to q0. As a
comparison, the formula proposed by Helle [29] for hot
isostatic pressing was also used:
1  q0
/ 5
q2 q q0
In order to properly apply Eq. (4) a uniaxial stress state
in the samples has to be ensured. After full densication the
specimen geometry was a at disc approximately 5.5 mm
thick. Although this nal geometry does not correspond
to the standard compression aspect ratio, previous work
has shown that a uniaxial stress with these boundary con-
ditions is developed. Wang et al. [26] indeed developed a
nite element model to investigate homogeneity of the tem-
perature distribution and stress eld components in alu-
mina and copper discs (20 mm diameter and 4 mm
height) during FAST. They highlighted the eect of ther-
mal expansion mismatch between the sample and the die/
punch materials on the stress state in the specimen. Because
alumina and graphite have similar coecients of thermal
expansion, all stress components, except the uniaxial
compressive stress, were negligible during changes in
temperature.
5457
Therefore, the following procedure was adopted to iden-
tify the exponents n and m. If negligible grain growth is
assumed and temperature is kept constant the stress expo-
nent n can be calculated using:
 
ln / n ln/pa G and T fixed 6
q dt
To calculate the grain size exponent m, the eective
giving:
 
1 dq
ln / m ln G T and /pa fixed 7
q dt
Finally, to calculate the activation energy of the diu-
sion coecient grain size has to be xed:
 
q_ T
ln / Ea =RT 8
q /pa n
3. Results
3.1. Characterization of the densication behavior
Fig. 3 shows the densication curves of TMDAR sam-
ples obtained during sintering in FAST and HP equipment
at two maximum temperatures with all parameters kept
identical above 450 C (same heating rate, applied stress
and dwell time). The densication curves were obtained
from Eq. (2) by calculating backwards from the nal den-
sity. The t to the initial geometrically measured density
was veried. Curves for each sintering method present a
shows good reproducibility.
First, dierences can be observed between the two pro-
cesses. Densication for FAST sintered samples occurred
at lower temperatures than those hot pressed (from
860 C, about 25 C lower than for HP). Final densities
reached with the FAST equipment were between 94%
and 99.5%, with a density of 93% already obtained upon
reaching the isothermal temperature of 1200 C. In con-
trast, hot pressed specimens showed a reduced densica-
tion: only limited densication had taken place at
1100 C, the isothermal temperature (70%, instead of
76% for FAST specimens). The nal density range for
HP samples lay between 88 and 97%, which illustrates
how signicant thermal activation is to densication. At
1200 C a longer dwell time would be required for HP to
achieve the same densities as obtained by FAST. As a ref-
erence, dry pressed specimens made of the same powder
and sintered freely in air have a nal density of 85% after
4 h at 1200 C [30].
In comparison, Fig. 4 shows strain curves for the coarser
alumina powder CT 3000 SG sintered by FAST and HP as
a function of time. The process parameters previously
described for the TMDAR powder were used. The sinter-
ing behavior was qualitatively similar to that of TMDAR.
Here initial densication and separation of the curves took
5458 J. Langer et al. / Acta Materialia 57 (2009) 54545465

Fig. 3. Relative density curves obtained for both methods (FAST and HP) at two dierent temperatures as a function of time (heating rate: 10 K min1,
applied stress: 50 MPa and dwell time: 1 h) for TMDAR alumina.

Fig. 4. Curves obtained for both methods (FAST and HP) at 1200 C as a function of time (heating rate 10 K min1, applied stress 50 MPa, dwell time
1 h) for CT 3000 SG.

place at 965 C. Final densities were 89% for FAST and
87% for HP. The higher temperature needed to initiate den-
sication is easily explained by the dierences in average
starting particle sizes (a ratio of about 3 between CT
3000 SG and TMDAR). However, it seems that FAST
induces a smaller positive eect on densication for the
coarser alumina. Further analysis can be made by plotting
in Fig. 5 the dierential relative density Dq = q(FAST)
q(HP) of the FAST and HP sintered powders as a function
of temperature (during the heating ramp) and time (during
the dwell time). Dq reaches a maximum at 1200 C and
decreases with dwell time, because signicant densication
takes place with HP. It can be seen that Dq is larger for the
ner alumina TMDAR (Dq = 0.076) than the coarser
(Dq = 0.027) CT 3000SG.
Further analysis was done on TMDAR specimens sin-
tered by FAST and HP at 1150 C for a maximum dwell
time of 90 min with densities lower than 95%. Fig. 6
displays the logarithm of the normalized densication rate
as a function of the logarithm of the eective stress (the
 J. Langer et al. / Acta Materialia 57 (2009) 54545465 5459

Fig. 5. Relative dierential density Dqrel between FAST and HP sintered alumina powders TMDAR and CT 3000 SG.

product of applied stress multiplied by intensication fac-
tor). It has been found that minimal grain growth occurs
up to 80% density for HP and 85% density for FAST. As
expected from the proportional relationship in Eq. (6), a
linear behavior was observed for all chosen densities. For
both FAST and HP processes a stress exponent of n  1
was calculated. No signicant dierences were observed
for the stress exponent values obtained using the models
of Montes et al. [28] and Helle et al. [29]. In the range of
applied stress and density investigated deviations in the
results lie within the error bars in Figs. 6 and 7. The aver-
age value of n using the simplied Eq. (4) was 1.04, whereas
with Eq. (5) it was 1.06. A value of 1 is associated with lat-
tice diusion, grain boundary diusion or viscous ow [15].
Due to the high purity of the investigated alumina, no
glassy phase formed during sintering, thus allowing us to
reject the third possibility. It has previously been observed
that submicron powder densies by grain boundary diu-
sion and not lattice diusion at temperatures up to
1400 C [31]. Validation of this assumption can be made
by computing the grain size exponent as well as the activa-
tion energy during sintering.

Fig. 6. Plot of the logarithm of the densication rate as a function of the eective pressure /pa at dierent relative densities.
5460 J. Langer et al. / Acta Materialia 57 (2009) 54545465
Fig. 7. Plot of the logarithm of the densication rate as a function of the
logarithm of the normalized grain size.
Fig. 7 shows the logarithm of the densication rate as a
function of the logarithm of the grain size normalized by
the grain size measured on samples with a relative density
of 65%. Temperature and eective stress were kept con-
stant (1100 C and 185 MPa). The complete sintering tra-
jectory (grain size as a function of density) is presented in
Fig. 12. As anticipated from the proportional correlation
in Eq. (7), a linear behavior can be observed and the grain
size exponent m can be calculated. For both FAST and HP
a grain size exponent of m  3 was obtained. This value is
characteristic of grain boundary diusion, whereas a value
of 2 would have indicated lattice diusion [15].
Fig. 8 shows the logarithm of the normalized densica-
tion rate as a function of the reciprocal of absolute temper-
ature (Arrhenius plot). Using Eq. (8), activation energies of
420 35 kJ mol1 for the FAST and 430 50 kJ mol1
Fig. 8. Arrhenius plot of FAST and HP sintered TMDAR alumina at 1100 C, 1150 C and 1200 C with a heating rate of 10 K min1 and a dwell time of 1 h.
for the HP sintered alumina were obtained. These values
correspond to the well-known value of 440 45 kJ mol1
for grain boundary diusion in alumina [31].
In addition, Fig. 9 shows a plot of the relative density as
a function of temperature for dierent heating rates
obtained for specimens sintered in the FAST equipment
(all other parameters were kept constant). It can be seen
that the starting temperature for densication was shifted
to higher temperatures with increasing heating rate. This
is most likely due to the dierence between the measured
temperature and the real temperature seen for the sample.
With increasing heating rate the temperature dierence
became larger, highlighted by nite element method tem-
perature gradient simulations [16,17]. Nevertheless, the
slopes of the densication curves in their linear regime
(Fig. 9) are similar, as shown in Table 1. The lowest values
in this series for the two largest heating rates can be attrib-
uted to the thermal bias. A constant slope is typically
observed for constant heating rate experiments [15] and
indicates that there is no change in the densication
mechanism, provided that the temperature bias does not
depend on temperature in the range considered. This
means that grain boundary diusion remains the primary
driving force for densication at higher heating rates (up
to 150 K min1). All of the samples showed a similar rela-
tive density of 99% after the sintering process and a dwell
time of 10 min.
3.2. Analysis of the microstructure and sintering trajectory
The local grain size was measured at dierent areas in
the sample, as shown in Figs. 2 and 10a and b shows typical
microstructures of FAST and HP sintered TMDAR alu-
mina under the same conditions, which are comparable
 J. Langer et al. / Acta Materialia 57 (2009) 54545465 5461

Fig. 9. Comparison of dierent heating rates of FAST sintered TMDAR with a maximum temperature 1200 C, a stress of 50 MPa and a dwell time of
10 min.

the reference grain size (at 65% density). This result was
Table 1
expected, as it has been shown that the temperature distri-
Slopes of the densication curves in the linear regime obtained from
Fig. 9. bution in the sample was homogeneous and a low heating
rate was used. High heating rates (several hundreds of
Heating rate (K min1) Slope (103 K1)
degrees per minute) could lead to thermal gradients and
10 1.7 0.2
subsequently gradients in microstructure, as previously
35 1.6 0.2
50 1.7 0.2 observed [23].
100 1.5 0.2 The average grain size aspect ratio Gy/Gx was 1, which
150 1.4 0.3 shows no marked grain anisometry and preferential grain
orientation, as can be seen in Fig. 10. This low degree of
anisotropy had already been observed in hot pressed alu-
with those obtained by other researchers [4,32]. No local mina at similar stress levels with a sintering temperature
variation in density was observed. of 1450 C, as long as signicant grain growth did not
As highlighted in Fig. 11, samples of a given density had occur (grain size smaller than 2 lm) [33].
a constant grain size. It was found that grain size did not Fig. 12 shows the sintering trajectory of FAST and HP
depend on the measurement position. The measured grain sintered alumina, with normalized grain size plotted as a
size was homogeneous throughout the sample for the range function of relative density. No dierences can be found
of densities investigated by both FAST and HP. There was between FAST and HP samples. The grain size remained
a limited amount of grain growth, as the maximal nal constant up to 90% relative density. A steep increase was
grain size (at 99% density) was no larger than 2.5 times then observed starting from 95%, explaining the dierences

Fig. 10. High resolution SEM pictures of polished and thermal etched (a) FAST and (b) HP sintered alumina at 1200 C, with a stress of 50 MPa, a
heating rate of 10 K min1 and a dwell time of 1 h.
5462 J. Langer et al. / Acta Materialia 57 (2009) 54545465

Fig. 11. Grain size as a function of the position in the sample (TMDAR).

between the micrographs presented in Fig. 10. As a com- 4. Discussion

parison, the sintering trajectory of specimens sintered freely
[30] reveals that grain growth started earlier: this can be
rationalized by the additional driving force for densica-
tion provided by the applied mechanical pressure. The
microstructure of specimens sintered at dierent heating
rates was not analyzed. Because the grain size is dependent
on the real local temperature it is dicult to compare spec-
imens with increasing heating rate due to the increase in
thermal bias between the sample and measured tempera-
tures. If the dwell time is too short the sample may not even
be exposed to the maximum temperature [22,34].
Direct comparison of hot pressing and eld-assisted sin-
tering for electrically insulating alumina has shown that
densication is mainly controlled in both processes by
grain boundary diusion. The stress and grain size expo-
nents (n = 1 and m = 3), as well as the activation energy
(430 kJ mol1) determined from the macroscopic behavior,
agree remarkably well. This is further conrmed by grain
size measurements done at the microscopic scale, which
show similar sintering trajectories for HP and FAST.
Therefore, the hypothesis of possible accelerated diusion

Fig. 12. Normalized grain size as a function of relative density measured on FAST, HP and conventionally sintered TMDAR alumina (heating rate
10 K min1, stress 50 MPa and dwell time between 1 and 2 h).
 J. Langer et al. / Acta Materialia 57 (2009) 54545465
processes due to the application of an electrical eld or pro-
motion of another densication mechanism, such as diu-
sion through a melted surface or plastic deformation,
during FAST as proposed by other researchers [79] do
not seem to hold for the present experiments. It must be
noted that the sintering parameters utilized here were all
identical except for the heating rate under 450 C, which
was, as previously mentioned, uncontrolled for FAST.
All FAST sintered samples began to densify at lower
temperatures and, therefore, had a higher nal density than
HP (corresponding to a temperature shift of 25 C for the
TMDAR powder). Similar results were also observed by
Oh et al. [35] with a coarser alumina (mean particle size
0.2 lm) and a heating rate of 30 K min1. In order to
explain this moderate decrease in the initiation of densica-
tion temperature two possibilities may be considered: (i)
temperature is locally higher than the macroscopic mea-
sured temperature and (ii) smaller inter-particle necks are
present.
The rst point has already been addressed and is dicult
to assess experimentally. In low permittivity materials such
as alumina, electrical discharges occurring in pores under a
high electric eld is not thought to increase the local tem-
perature more than a few degrees centigrade [36], although
this may be sucient to substantially aect mass transfer
through thermal gradients. The possible role of the powder
has been described by Chaim [37], who proposed that for
insulating dielectric materials the particle size and mor-
phology have an eect on densication under an applied
electric eld. It may be possible that as the surface to bulk
conductivity ratio increases as the inverse of particle size
accumulation of electrical charges at the surface induces
surface breakdown (especially when particles are contami-
nated with adsorbed water and a low oxygen partial pres-
sure is maintained, such as in this study). A discharge
breakdown through particles is not possible in our opinion,
because the global voltage applied to the compact sample
was divided among all particles. Even at temperatures of
several hundreds of degrees centigrade and a porosity
above 30%, where the electrical strength of compact alu-
mina may be under 100 MV m1 (0.1 V nm1), the elec-
trical potential dierence seen for a 100 nm particle
aligned in a 10 mm thick specimen loaded under 15 V is
1.5  104 V. Under the prevailing sintering conditions a
maximum voltage of 5 V was applied by the FAST set-
up. In addition, a large local elevation of temperature
induced by such phenomena could not be seen in copper
particles observed under scanning electron microscopy
(SEM) in the present specimens. In support of these con-
clusions, recent work done by Hulbert et al. [38] proved
the absence of sparking events by atomic emission spec-
troscopy and ultrafast in situ voltage measurements on
electrically conducting or insulating materials (including
alumina).
Therefore, a plausible explanation for the dierences
observed between the FAST and HP densication curves
could be the previously mentioned transient overheating
5463
of 110130 C at the beginning of the FAST sintering pro-
cess. This phenomenon could inuence neck building and
neck growth at the beginning of the heating cycle and the
subsequent nal densities, even though the densication
mechanisms are identical to those observed in this study.
The eect of this transient temperature excess seems to be
larger for smaller particles than for coarser ones, as the dif-
fusion processes start at lower temperatures for ner pow-
ders. As a consequence, attention has to be focused on the
rst stage of sintering, prior to massive densication.
Microscopic models describing the normal stress distribu-
tion along a grain boundary between two particles show
that the intensity of the sintering stress decreases with neck
growth, leading to a decrease in the densication driving
force and, consequently, the plating rate at the particle
scale and the densication rate at the macroscopic scale
[15]. Fast ring schedules are justied by this fact, promot-
ing densifying mechanisms at the expense of the neck
coarsening phenomenon. Therefore, in order to explain
the earlier densication onset with FAST we propose that
overheating in the present FAST experiments did not lead
to a simple growth of the inter-particle contacts, but more
likely to an increase of the number of inter-particle necks,
which had a benecial eect on densication rate. Better
mechanical properties such as bending strength [35,39]
measured for FAST alumina specimens are in agreement
with this hypothesis.
Unfortunately, direct observation of the evolution of
selected inter-particle contacts cannot be done in situ by
transmission electronic microscopy and quantitative char-
acterization through SEM micrograph analysis is dicult
and sensitive to artifacts. Therefore, measurements were
carried out by mercury porosimetry on TMDAR speci-
mens with relative densities of 55% and 60% heated under
the same conditions until the required density was reached
during the heating ramp. Fig. 13 shows the measured mer-
cury volume as a function of the mean pore diameter on a
logarithmic scale for FAST and HP sintered samples. For a
better comparison, pieces of same mass (0.45 g) were cut
out of the specimens. These curves conrm that the pore
size and accumulated pore volume decrease as density
increases from 55% to 60%. For both processes a monomo-
dal pore size distribution is observed, with a homogeneous
pore size under 80 nm. More interestingly, there is a slight
dierence between both types of specimens for the two den-
sities investigated: the mode of the pore size distribution is
larger for the samples produced by HP by about 5% than
for the FAST alumina. Of course, computation of the pore
equivalent size requires that we assume that pores are like
capillary tubes of constant and circular cross-section. In
reality pores are more ink bottle shaped. Therefore, mer-
cury porosimetry gives a measure of the pore smallest sec-
tion. This, unfortunately, does not give a direct indication
of the neck area.
Additional information was obtained by means of the
laser ash method [12,40]. Samples heated under the same
conditions with densities varying from 54% to 65% were
5464 J. Langer et al. / Acta Materialia 57 (2009) 54545465
Fig. 13. Mercury intrusion as a function of the mean diameter of the pores of FAST and HP sintered samples (TMDAR, heating rate 10 K min1, stress
50 MPa, dwell time 10 s, 750 C to reach 55% density for FAST and HP, 925 C for FAST and 950 C for HP to reach 60% density).
characterized by cutting out 10 mm radius discs from
FAST and HP sintered TMDAR and grinding them down
to a thickness of 0.5 mm. Fig. 14 shows that the measured
thermal diusivity increases as a function of the relative
density. This is due to the microstructural changes that
occur on the formation of sintering necks during the rst
stage of sintering, before massive densication takes place.
According to simple isotropic models the thermal diusiv-
ity is roughly proportional to the neck radius [12,40] for a
given unit cell with a constant number of inter-particle con-
tacts. In addition, thermal diusivity is higher at lower den-
sities for FAST sintered samples in comparison with the
HP ones (about 30% for a density of 54%). This dierence
reduces as density increases, so that values are similar for a
density of 65%. This means that at the beginning of the sin-
Fig. 14. Thermal diusivity as a function of the relative density for FAST
and HP sintered samples (TMDAR, heating rate 10 K min1, stress
50 MPa, dwell time 10 s, 750 C to reach 54% density for FAST and HP,
900 C to reach 57% density for FAST, 950 C to reach 60% density for
HP, 1030 C for FAST and 1060 C for HP to reach 65% density).
tering process (temperatures below 800 C) the total neck
area for FAST sintered samples is higher than for HP spec-
imens. In the absence of proof of electric eld/current
assisted mechanisms this fact may be explained by the tem-
perature overshoot in FAST when the pressing tool and the
powder are heated from room temperature to 450 C. At
this stage of the sintering process the FAST sintered sam-
ples experienced dierent heat treatment in comparison
with the HP samples, due to a rapid transient overheating.
Enhanced by the non-spherical, elongated and distorted
shape of the TMDAR alumina particles [24], we could
envisage a larger number of contacts per particle without
a signicant increase in density. This could be a benet
of the FAST process in this situation.
5. Conclusion/summary
Processing of submicron pure alumina by hot pressing
and eld-assisted sintering with the same parameters (heat-
ing rate, mechanical load, temperature and atmosphere)
has shown that densication is enhanced by FAST from
the beginning of the temperature cycle. However, analysis
of sintering curves reveals that densication for both meth-
ods is controlled by grain boundary diusion. A heating
rate increase up to 150 K min1 does not change the densi-
cation mechanism. Furthermore, the microstructure and
average grain size as a function of density are similar at
higher relative densities. To reach the same density as the
FAST sintered samples in the hot press the dwell time must
be increased by a few minutes. FAST specimens begin to
densify at a lower temperature, which may be due to rapid
transient overheating in the initial stage, which increases
the global inter-particle area but not the average contact
size. These results apply to both investigated alumina pow-
ders, the coarser one showing a less marked benecial eect
 J. Langer et al. / Acta Materialia 57 (2009) 54545465
of FAST, probably due to a lower sensitivity to overheat-
ing. An improvement in the FAST measurements would
be to accurately control the heating rate from room tem-
perature up to 450 C. Moreover, a specimen could be sin-
tered rst in the FAST equipment up to 55% density and
subsequently transferred to the hot press and densied fur-
ther. We could expect a better densication compared with
a specimen sintered only in the HP set-up. Unfortunately,
all partially sintered samples cracked when the minimal
mechanical load (5 kN) inherent to the hydraulic system
was applied. Little is known about the sintering mecha-
nisms of other oxide powders under FAST conditions.
Thus, a similar thorough analysis has yet to be performed,
for example, on ionic conductive and semi-conductive
materials showing temperature-dependent electrical con-
ductivity.
Acknowledgement
This work was nancially supported by the Deutsche Fors-
chungsgemeinschaft (Emmy Noether Program GU993-1/1).
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