ELSEVIER Solid State Ionics 101-103 (1997) 1229-1233

Do microwaves increase the sinterability of ceramics?

Ph. Both”, N. Lequeux

Ecole Sup&ieure de Physique et de Chimie Industrielles, I5 rue Vauquelin, F- 75005 Par& France

Abstract

Microwaves are reputed to enhance the sintering of ceramics, but the uncertainty of temperature in a microwave oven can
account for part of the microwave effect. In the two cases presented here (reaction-sintering of alumina-based ceramics and
devitrification of LAS glass-ceramics), the microwave effect does not exceed 50°C (at N = 2.45 GHz and T= 1200°C).
Theories of microwave effect are still tentative.

Keywords: Microwaves; Ceramics; Sintering

Materials: AI,Si,O,,; AI,TiO,

1. Conventional and microwave sintering ment, (ii) porosity reduction, (iii) grain growth, and
(iv) chemical reactions.
Ceramics are usually processed by high-tempera- Microwave heating is reputed to enhance sintering
ture sintering of a powder compact. The driving by comparison with conventional heating. The
energy for sintering is the difference between the ‘microwave effect’ is quantified by the difference
energy of solid-vapour interfaces (xv) and that of between the temperatures of two treatments that lead
grain boundaries (YJ~). In general, ysv > xo, which to a similar microstructure (AT =
means a powdered system decreases its energy when T convenrional r~ntenng - Tm,c,owave s,nterlng). For exam&
changing from the powder state to the polycrystal Janney and Kimrey [l] reported that AT = 300-
and eventually from the polycrystal to the single 400°C for alumina sintered in a 28 GHz microwave
crystal. Atomic transport works through various oven, which corresponds to a decrease in apparent
mechanisms: (i) volume diffusion, (ii) grain-bound- activation energy for densification from 575
ary diffusion, (iii) surface diffusion, (iv) solution- kJ mol-’ (conventional) to 160 kJ mol-’ (micro-
reprecipitation, (v) evaporation-condensation, and wave). However, the reality of the microwave effect
(vi) viscous flow. In iono-covalent ceramics, the is sometimes questioned, in particular because the
diffusing species are anions and cations. Four effects uncertainty of temperature can be very large in a
overlap during the sintering stage: (i) neck develop- microwave oven, which suggests that AT may solely
be the underestimate of the specimen temperature.
The recent studies, which have paid more attention
*Corresponding author. Fax: + 33-l-40-79-47-50; e-mail: to the temperature accuracy than the early ones,
philippe.boch@espci.fr generally give values of AT that are well below

0167-2738/97/$17.00 0 1997 Elsevier Science B.V. All rights reserved

PI/ SOl67-2738(97)00210-5
1230 P. Both, N. Lequeux I Solid State Ionics 101-103
those given ten years ago (typically: 5 50°C instead
of 2 200°C). The present paper is a contribution to
the controversy about the reality of the microwave
effect. It only concerns insulating and low-permit-
tivity ceramics (in contrast with conductive or high-
permittivity dielectrics) treated at the industrial fre-
quency of 2.45 GHz.
2. ‘Intrinsic’ microwave effect and ‘thermal’
microwave effect
One has to answer the following questions:
1. Is the microwave effect a reality?
2. If yes, is the microwave effect ‘thermal’ or
‘intrinsic’?
3. If the microwave effect is intrinsic (or includes an
intrinsic part), what is its origin? In particular, is
it of thermodynamic or kinetic character?
The first and the second question focus on the
difficulty of measuring the temperature of a speci-
men heated in a microwave oven, for four reasons:
(i) Microwave heating is a volume process, which
leads to ‘inverse’ gradients: the core is at a higher
temperature than the surface, in contrast with con-
ventional heating.
(ii) Inverse gradients are reinforced by the fact
that, in most ceramics, the dielectric losses and,
therefore, the deposition of energy, increase with
temperature. There is a risk of ‘thermal runaway’,
leading to ‘hot spots’. For low-thermal conductivity
ceramics heated at fast heating rates, the difference
of temperature between the core and the surface can
be several hundred degrees.
(iii) When the specimen temperature is measured
by an optical pyrometer, only the surface tempera-
ture is known. Moreover, there is an uncertainty
about the material emissivity (because ceramics do
not behave as a black body), which may be a cause
of error, even if a sophisticated pyrometry is used.
When the specimen temperature is measured by a
thermocouple, only the zone close to the tip of the
couple tip is considered. Moreover, the couple must
be shielded to be protected against the intense
microwave field, which is cause for a systematic
error, the shield being a thermal barrier between the
(1997) 1229-1233
sample and the couple and a thermal bridge between
the sample and the exterior. As recalled by Rothman
[2]: ‘The evaluation of experiments has been carried
out under the assumption that the reported tempera-
tures are accurate. If they are not, the analyses are of
course not valid’.
(iv) Even when the temperature problems are
solved, the evaluation of microwave sintering experi-
ments is puzzling, due to uncertainties on which path
and which species are the limiting factors and which
coupling mechanisms exist between consolidation,
densification, and grain growth. The studies devoted
to phenomena more ‘basic’ than sintering (for in-
stance studies of microwave enhanced ionic con-
ductivity [3]) will allow us to progress. However,
these studies encounter the same problem as conven-
tional sintering has always encountered, i.e. that
diffusion data are not enough to foresee the sintering
behaviour of ceramics. As a compromise, our pro-
gram [4-61 was conducted with two prerequisites:
(i) to minimize the error of temperature and (ii) to
select experiments that are easily comprehensible.
3. The microwave oven
The laboratory-designed microwave oven (Fig. 1)
is composed of eight sub-systems, namely: (i) a
generator using a 2.45 GHz, 1200 W magnetron, (ii)
a circulator, which diverts the reflected power from
the applicator, (iii) a waveguide (WR-340 standard),
(iv) a rectangular coupling iris, (v) a TE,,, single
mode cavity, (vi) a crucible, (vii) a thermocouple,
and (viii) a system to control and record the incident
and reflected powers. The disk shaped specimen
(= 10 mm in diameter and 5 mm in height) is
,=&y-q&
1 ,~~~~
Fig. 1. The microwave oven.
 P. Both, N. Lequeux I Solid State Ionics 101-103 (1997) 1229-1233 1231

located inside an alumina-fibre crucible, which en- been thoroughly investigated: mullite and aluminum
sures thermal insulation. The specimen is located in titanate:
the zone of the microwave cavity where the electric
3Al,O, + 2Si0, --+ Al,Si,O,, (mullite)
field is maximum. The core temperature is measured
by a shielded Nisil-Nicosil thermocouple, oriented and
perpendicular to the electric field lines, with its tip
Al,O, + TiO, + Al,TiO, (aluminum titanate)
located at the end of a hole drilled in the specimen.
Three sorts of temperature calibration tests were alumina was a-corundum, silica was a-cristobalite,
conducted: (i) comparing data given by either and titania was rutile. Purity was better than 99.5%.
pyrometers or thermocouples, (ii) comparing data The powder mixtures were ball-milled with disso-
given by thermocouples of various characteristics, in ciated ZrSiO, balls for 5 h in ethanol with defloccul-
particular of various diameters and, therefore, of ant (0.3 wt% of phosphate ester), down to a mean
various thermal conductivities, and (iii) determining particle size < 1 pm. A binder (3 wt% of poly-
the melting temperature (T,) of a eutectic com- vinylbutyral) was then added to improve the me-
position (49.4 wt% CaO + 50.6 wt% AJO,, T, = chanical strength of green material. Powders were
1360”(Y), assuming that eutectic melting is not granulated through a 200 pm sieve, then uniaxially
sensitive to any microwave effect. The calibration pressed (150 MPa) as pellets of 13 mm in diameter
plot gives the ‘true’ temperature vs. the measured and 3.5 mm in thickness.
temperature, which allows a genuine comparison The first stage of heat treatment was pyrolysis of
between conventional and microwave treatments. For organic binder and pre-sintering (2 h at lOOO”C,
instance, the temperature measured in the core of a electric furnace). The second stage was reaction
microwave heated alumina sample (heating rate = sintering in either a conventional electric furnace or
20°C min-‘) is underestimated by = 20-30°C at the microwave oven: heating at 20°C min- ’ from
I3OO”C. room temperature to the firing temperature (T,),
soaking for 1 h at T,, then cooling at 20°C min-’ to
room temperature.
4. Reaction sintering of mullite and aluminum Figs. 2 and 3, which plot reaction vs. temperature
titanate ceramics for mullite and aluminum titanate, show evidence of
a microwave effect of ==5O”C and 3O”C, respective-
Microwave sintering studies are generally con- ly. Densification plots (not shown here) lead to
ducted by measuring densification (p/p,) and/or similar conclusions as reaction plots but, as expected,
grain growth (@/@Jo). However, densification is are not so easy to interpret. SEM and XRD data (not
difficult to estimate at a local scale, which leads to presented here) are in agreement with reaction data.
difficulties for characterizing microwave sintered
specimens, which are heterogeneous (due to tempera-
ture gradients). Grain growth can bring local in-
formation, but puts forward the hard problem of
quantitative stereology. In contrast, reaction sintering
(where initial compounds A and B react during the
sintering stage to form a new compound C) allows
accurate, quantitative phase determination (using, for
instance, quantitative X-ray diffraction). Moreover,
reaction data can be usefully compared to densifica-
tion or grain growth data. Finally, reaction sintering
can be exploited by reference to the comprehensive
literature on phase diagrams.
01
1200 1300 1400 1500 1600 1700
Temperature (“C)
We used two reaction-sintering systems, chosen
because their conventional sintering behaviour has Fig. 2. Mullite formation.
1232 P. Both, N. Lequeux I Solid State Ionics 101-103 (1997) 1229-1233

‘intrinsic’ effects, with the assumption that ionic

diffusion is enhanced by microwaves. An early
explanation that the microwaves help the creation of
points defects is now abandoned, because the micro-
wave energy is much lower than the creation energy.
Resonance effects, relaxation effects [9], or non-
Boltzmann energy distribution effects [lo] have also
been mentioned, but they would require frequencies
or voltages much higher than those that are used in
microwave heating experiments. Such theories are
now more or less abandoned, in favour of two recent
i ioo 1200 so0 1400
models.
Temperature (“C)
(i) Comparing conventional and microwave plas-
Fig. 3. Aluminum titanate formation. ma sintering of alumina, Johnson [l l] found that
sintering was enhanced in the plasma, the sintering
rate being greater at lower pressure of oxygen. The
They bring the additional information that the core results may be explained in terms of creation of
had experienced a temperature superior to that of the excess aluminum interstitials in the material by the
surface by ~50°C. plasma, due to selective desorption of alumina
particle surfaces.
(ii) According to ref [3], the diffusive transport
5. Devitrification of LAS rate J of ions in ceramics can be written as:

J = - [DclkT][(kz-lc)Vc] - [DclkT][qW],
Glass in the system L&O-A120,-SiO, (LAS) can
devitrify to y-, then P-spodumene (Li,Al,Si,O,,). which is the product of a transport coefficient by a
We compared the devitrification and the y-to-l3 driving force.
transformation in conventional and microwave ther- Rybakov and Semenov [12] consider that the
mal analysis [6], using Matusita’s [7] treatments of effect of microwaves is not of increasing transport
Avrami’s method. The parameters that were mea- coefficient, which should manifest as a multiplicative
sured were the apparent activation energy (E,), increase of transport flux in the presence of a pre-
Avrami’s coefficient (n), and dimension parameter existing conventional driving force, but of intro-
(m), m being equal to 3 if the process is volume ducing an additional driving force, which should
controlled and equal to 1 if it is surface controlled. manifest as an additive increase of transport flux.
The main result is that the nucleation and growth The idea [3] is that a high frequency (HF) electric
process of spodumene seems to change from a field drives a HF flux of mobile species (vacancies/
volume-controlled mechanism (conventional) to a ions). In the bulk of the crystal, the fluxes are
surface-controlled mechanism (microwaves). spatially uniform. Near the surface, however, the
medium discontinuity results in a quasi-stationary
flux of charge carriers that does not cancel when
6. Theories of microwave effect averaged over a HF cycle. The model predicts: (i)
non-linearity (the effect is proportional to the square
(i) The microwave heating characteristics, in of the electric field), (ii) additive driving force rather
particular fast heating rates and large temperature than multiplicative enhancement of the transport
gradients [8], can justify (at least qualitatively), the coefficient, and (iii) effect that predominates near
microwave effect. However, it seems established that discontinuities, e.g. surfaces, grain boundaries, or
certain experimental results cannot be explained by vitreous-crystalline interfaces. The ‘ponderomotive
‘thermal’ effects only. force’ adds an extra pressure to the capillary pressure
(ii) ‘Non-conventional’ points of view advocate that acts during the sintering process, with enhance-
 P. Both, N. L.equeux I Solid State Ionics 101-103
ment of the sintering rate, similarly to what happens
during hot pressing when compared with natural
sintering. The study of Booske et al. [3] of ionic
conduction in NaCl and AgCl single crystals ir-
radiated by microwaves gave results in good agree-
ment with the theory.
Rybakov and Semenov’s theory may provide an
explanation for the change in the devitrification
process of LAS (volume-controlled+surface-con-
trolled mechanism), which is reported in the present
paper.
7. Conclusion
The results relative to reaction sintering of mullite
and aluminum titanate ceramics show a microwave
effect of AT 150°C (at T= 12OO”C), but they do not
allow us to discriminate between ‘thermal’ or ‘intrin-
sic’ effect. In contrast, the results relative to devitrifi-
cation of LAS may be considered as being in favour
of an intrinsic effect, associated with the presence of
interfaces, which may be considered as being in
support of Rybakov and Semenov’s theory.
It is doubtful whether the microwave enhancement
of sinterability of ceramics can have an industrial
interest per se. However, the use of microwave
(1997) 1229-1233 1233
heating for obtaining a specific thermal profile in a
specimen offers great potential for making parts with
specific properties, for instance parts with graded
properties.
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