Mat. Res. Bull., Vol. 27, p p . 1393-1405, 1992. Printed in the USA.

0025-5408/92 $5.00 + .00 C o p y r i g h t (c) 1992 Pergamon P r e s s Ltd.

MICROWAVE-HYDROTHERMAL SYNTHESIS OF CERAMIC POWDERS

Sridhar Komarneni*, Rustum Roy and Q. H. Li

Materials Research Laboratory,

The Pennsylvania State University,
University Park, PA 16802, USA

*Also with the Department of Agronomy

(Received September 3, 1992; Communicated b y W.B. White)

ABSTRACT

We report herein for the first time, the use of microwave-hydrothermal processing in
catalyzing the synthesis of crystalline unary oxides such as TiO2, ZrO2 and Fe203
and binary oxides, such as KNbO3 and BaTiO3. While the combination of
microwave and hydrothermal techniques has been used in the last few years to
dissolve all kinds of powders (e.g. aluminosilicate rocks) rapidly for chemical
analysis, we report here the use of this technique for synthesizing fine powders. A
new layered alumina phase, which can be intercalated with ethylene glycol has also
been synthesized. The effect of different parameters such as concentration of
chemical species, time and temperature on the crystallization kinetics of the above
phases has been investigated under microwave-hydrothermal conditions using
microwaves of 2.45GHz frequency.

MATER/ALSINDEX: titania, zirconia, hematite, potassium, niobates,

barium, t i t a n a t e s , l a y e r e d alumina

Introduction

The first comprehensive survey of mineral synthesis under hydrothermal conditions was
provided by Roy and Tuttle in 1956A At that time and for two decades thereafter, there was
intense activity in the geological sciences in instrumentation development, oxide powder synthesis
including hydrated phases such as clays, micas, zeolites and the systematic phase equilibrium
research in increasingly complex systems beginning in the 1920's principally of the Carnegie
Institute in Washington and later at Penn State. References to later work can be found interspersed
in the many papers presented at the conferences held on hydrothermal reactions in Tokyo, 2, 3
Penn State and Moscow. In this work there is embedded the data on synthesis of fine well
crystallized micrometer-sized powders of literally hundreds of all the most important ceramic
materials. From 1948 onwards when Roy and Osborn started to study the system A1203-SiO2-
H20, it became clear that the hydrothermal condition was the only process by which one could
1393
1394 S. KOMARNENI et al. Vol. 97, No. 19

make certain crystalline phases involving the tetra and pentavalent ions and, of course, the
hydroxylated ones. But also as Roy points out in a 1963 review 4 the hydrothermal method was
the only way by which one could get ordered oxide phases where AI-Si, Mg-AI, and various
vacancy-disordering could approach an equilibrium state. Very recently there has been a major
revival of interest in hydrothermal processing for making powders, synthesizing new phases
and, to a lesser extent, consolidation. 2, 3 The hydrothermal method is a low-temperature'process
(many effects being achieved below 250"C) and environmentally safe. For example, zircon
(ZrSiO4) which is extensively used in ceramic colors or L~igmentscan be prepared hydrothermally
at 150"C ~ compared to sol-gel or solid-state methods o, / which require temperatures in the range
of 1200-1400"C. The hydrothermal method is environmentally benign because the reactions are
carried out in a closed system and the contents can be recovered and reused after cooling to room
temperature.
The hydrothermal literature is based very largely in the geosciences, concentrating on
simulating conditions in the earth. From 1950-1970, Roy and co-workers 8-19 used the
hydrothermal process to synthesize systematically for the fast time the whole range of 7A, 10A
and 14A clay minerals and selected zeolite families with an enormous range of compositions. In
the last decade, Komarneni et al., 20-22 Stambaugh et al., 23-26 and Adair et al., 27 have been active
in synthesis of fine powders of simple anhydrous oxides. The U. S. literature on hydrothermal
research on chemical synthesis has grown relatively slowly in the last two or three decades.
Probably the best summaries are to be found in the Proceedings and Compendia edited by Somiya
4, 5. The hydrothermal method, however, is an established process, in use in the large tonnage
cement-block industry and higher-tech synthetic quartz crystal growth. In addition, hydrothermal
(or super critical steam) processes are now being considered for closed cycle destruction of hazards
such as PCB's and TCE's.
In this study, we intend to explore the potential application of microwaves during the
hydrothermal method for fine powder preparation and this novel variation can be designated as
microwave-hydrothermal method z~. The combination of microwave and hydrothermal techniques
has been used in the last fewyears to dissolve all kinds of powders (e.g. aluminosilicate rocks)
rapidly for chemical analysis 29-31. There is only one reference in the literature which deals with
the crystallization of porous crystalline metallosilicate zeolites using this technique 32. However,
the value of this technique in synthesizing fine ceramic oxide powders has not been demonstrated.

A microwave digestion system, MDS-2000 (CEM Corporation) was used throughout. The
system operates at a 2.45 GHz frequency and can operate at 0-100% of full power (630-~ 50
watts). The solutions and mixtures of solids and solutions were treated in lined digestion vessels
which are double walled vessels consisting of a Teflon PFA inner liner and cover surrounded by a
higher strength vessel shell of Ultem polyetherimide. The system is controlled by pressure and can
operate at a maximum of 200 psi. A variety of reactants involving, the principal ceramic unary
oxides and a few electroceramic binary compounds were treated under microwave-hydrothermal
conditions. The parameters which were varied include pressure (and thus, temperature) time,
concentration of metal solution, pH etc. A few conventional hydrothermal experiments were
conducted in teflon-lined Parr bombs for comparison with the microwave-hydrothermal
experiments. After the microwave-hydrothermal and conventional hydrothermal treatments, the
solid and solution phases were separated by centrifugation and the solid phases were dried in an
oven before characterization by powder x-ray diffraction (XRD) and scanning electron microscopy
(SEM). The XRD was done using a Scintag diffractometer with CuKo~radiation and the SEM was
performed using an ISI-DS 130 instrument.
Vol. 27, No. 12 CERAMIC POWDERS 1395

Results and Discussion

Titania Powders
Microwave-hydrothermal treatment of 0.5M TiCI4 in 1M HCI resulted in the formation of
pure rutile at - 164"C or 200 psi autogenous pressure within one-half hour (Table 1) whereas
conventional hydrothermal treatment did not lead to the crystallization of pure ruffle phase even
after treatment for 72 hours. This result clearly shows that the microwave-hydrotherrnal (M-H)
method leads to faster kinetics by one or two orders of magnitude compared to the conventional
hydrothermal processing. Figure 1 shows the scanning electron mierographs of ruffle prepared
from 0.5M TIC14 in three different HCI concentrations under M-H conditions. The M-H
conditions led to spherical agglomerated powders, each sphere having a finer structure. The size
of spheres increased with increasing HC1 concentration (Fig. 1) and the spheres appeared to fuse
(Figs. 1B and 1C) probably as a result of cavitation in an anologous manner to that of acoustic
wave stimulation or ultrasonication 33. The treatment of 0.5M TiChl in the absence of additional
HC1 resulted in much finer aggregates as can be seen from Fig. 2A. The presence of additional
acid promoted rutile formation. The anatase and ruffle powders made by the conventional-
hydrothcrmal method, however, do not form aggregates (Figs. 2B and 2C). A wide variety of M-
H conditions were used and the detailed experiments will be reported elsewhere 34

TABLE 1
XRD analyses of titania powders produced by microwave-hydrothermal and conventional
hydrothermal techniques

Conccnlration. M Tcmperaeure Duration ReacffonProducts in

(oc) (hrs) order of abundance as
TiCl4 HCI determined by X R D

Microwave-hvdrothermal
0.5 1 164" 0.5 Rutile
0.5 I 164* I Rulile
0.5 I 164" 2 Rutle

Convcntional-hvdrotbermal
0.5 1 164 2 Anatasc, small amount
of ruffle
0.5 1 164 24 Ruffle, small amount of
anatase
0.5 I 164 72 Ruffle, small amount of
anatase and
amorphous background

*Based on autogenous pressure of 200 psi.

1396 S. KOMARNENI et al. Vol. 27, No. 12

FIG. 1
Scanning electron micrographs of futile prepared at 164"C/1/2 hr from 0.5M TIC14 treated under
microwavc-hydrothcrmal conditions in different concentrations of acid: (A) 1M HC1, (B) 2M HC1
and (C) 3M HC1.
Vol. 27, No. 12 CERAMIC POWDERS 1397

Alllmm.P_my.d~s
When 0.5M aluminum nitrate solution was treated with or without 1 to 3 M HC1 under M-
H conditions, no alumina powder resulted (Table 2). However, when 0.1 to 1.0 M, NaOH was
used, precipitation of powders occurred as expected. These powders are platy in appearance (Fig.
3) and they have a layer structure as deduced from the formation of interlayer complexes with
ethylene glycol (Fig. 4). This appears to be a novel phase with a ~ 9.8A spacing which expands to
~ 12.4A upon forming a complex with about one layer of ethylene glycol. Solutions treated under
conventional hydrothermal conditions resulted in the formation of boehmite only (Table 2). Thus,
it appears, the M-H conditions led to a novel phase because of the presence of microwave field.
This is an extremely interesting development and this M-H method should be exploited in the
synthesis of new materials.

TABLE 2
XRD analyses of alumina powders produced by microwave-hydrothermal and conventional
hydrothermal techniques.

Concentration. M TemperattLre Duration Reaction products in

('C) (hrs) order of abundance as
AI(NO3)y9H20 NaOH HC1 determined by XRD

Microwave-hydrothermal
0.5 0 0 164 2 None
0.5* 0 1" 164 0.5 None
0.5 0.5 0 194 2 New layered phase with
10/~ spacing which
expands to 12.93/~ upon
exposure to ethylene glycol
0.5 1.0 0 194 2 Same as above

Conventional-hvdrothermal
0.5 0.5 0 195 24 Boehrnite
0.5 1.0 0 195 24 Boehmite

* The concentration of A1 nitrate varied between 0.5 to 2M and the HCI concentration varied
between 1 to 3 M. But no reaction products formed.

Poorly crystalline monoclinic zimonia was crystallized from 0.5 and 1M ZrOCI2 • 8H20 in
0.5 to 2 hours at 164" and 194"C. The crystaUinity increased with increasing temperature, as
expected.

Ima_O.zide,.t~a.w.d~s
Table 3 shows the crystallization behavior of FeCI3 solution under M-H conditions. No
crystalline products resulted when different concentrations of FeC13 were treated in the presence of
1 to 3M HC1 because of high acidity. However, when FeC13 solution was treated without acid,
very weU crystallized hematite powders resulted in the temper'anne range of 164" to 194"C. Poorly
crystalline hematite formed at ~ 115"C after treatment for 2 hours under M-H conditions. Fig. 5
shows the SEM micrographs of hematite crystallized at two different temperatures. The particles
are almost monodispersed and each particle appears to form by a process of aggregation of very
small particles.
1398 S. KOMARNENI et al. Vol. 27, No. 12

FIG. 2
Scanning electronmicrographs of titania:(A) rutilcprepared from 0.5M TiCI4 at 164"C/2 hours by
microwavc-hydrothermalprocess; (B) anatase prepared from 0.5M TiCI4 in 1M HCI at 164"CJ2
hours by conventional hydrothermalprocess and, (C) ruffle prepared from 0.5M TiCI4 at 164"C/72
hours by conventional hydrothermal process.
Vol. 27, No. 12 CERAMIC POWDERS 1399

FIG. 3
Scanning clcc~on micrograph of a novel layered phase synthesizedby microwavc-hydrothcrmal
process using 0.5M Al(NO3)3 in 0.5M NaOH at 194"C/2 hours.

o
A
7.57 4.04 2.79 2.15 1.76
I I I I I
@
12.582A

o
9.818A

.,.,l ,,..I,,,,I.,,,I,,,,I,,,
2 12 22 52 <.2 52
DEGREES TWO THETA (CuKa}

FIG. 4
Powder x-ray diffractogramsof new layeredphase: (A) as synthesizedand (B) afterintercalation
with ethylene glycol.
1400 S. KOMARNENI et al. Vol. 27, No. 12

TABLE 3
XRD analyses of zirconia powders produced by microwave-hydrothermal and conventional
hydrothermal techniques.
Concentration of Temperature Duration Reaction products in
ZrOC12 • 8H20 (°C) (hrs) order of abundance as
(M) determined by XRD

Microwave-hvdrothermal
0.5 164 0.5 Poorly crystalline mono-
clinicZr(~ (m-Zr02)
0.5 164 2.0 Same as above
1.0 164 2.0 Very poorly crystalline
m-TriO2
1.0 194 2.0 m-7_aO2
Conventional-h,cdrothermal
1.0 195 2.0

FIG. 5
Scanning electron micrographs of hematite synthesized by microwave-hydrothermal process at two
different temperatures: (A) 164"C/1 hour and (B) 194"C/1 hour.
V o l . 27, No. 12 C E R A M I C POWDERS 1401

TABLE 4
X R D analyses o f KNbO3 p o w d e r s p r o d u c e d by m i c r o w a v e - h y d r o t h e r m a l
and conventional hydrothermal techniques

Concentration (M) o f K c o m p o u n d * Temperature Duration Reaction products in

(°C) (hrs) order o f abundance as
KOH KNO3 KC1 KI KBr determined by X R D

Microwave-hvdrothermal
10 - - 194 2 KNbO3
6 - - 194 2 KNbO3
6 - - 182 2 KNbO 3
4 - - 194 2 Layeredphase?
6 - - 164 2 KNbO3
6 - - 182 1 KNbO3
6 - - 164 1 KNbO3 + a m o r p h o u s
background
6 - - - 182 0.5 KNbO3
10 - - - 150 2 KNbO3
6 - - - 150 2 None
6 4 - - 150 2 KNbO3
4 6 - - 150 2 None
4 6 - - 194 2 KNbO3
2 8 - - 194 2 None
4 6 - - 182 2 KNbO3
4 6 - - 164 2 None
3 7 - - 194 2 KNbO3
2 8 - - 194 2 None
2.5 7.5 - - 194 2 None
3 7 - 194 2 None
3 3.5 3.5 - 194 2 KNbO3
4 3 - 194 2 KNbO3
3 3.5 3 194 2 KNbO3
3 3.5 3 194 2 KNbO3
3 3.5 1 1 194 2 KNbO3

Convenfional-hvdrothermal
3 3.5 1 1 194 48 None
3 3.5 3 194 48 None
3 3.5 3 194 48 KNbO3
3 3.5 3 194 48 KNbO3

* N b 2 0 5 was u s e d as the N b source in all cases.

1402 S. KOMARNENI et al. Vol. 27, No. 12

FIG. 6
Scanning electron micrographs of KNbO3 synthesized by rnicrowave-hydrothermal process at
194"C/2 hours using different KOH, KNO3 and KI concentrations: (A) 10M KOH, (B) 6M KOH
and (C) 3M KOH + 3.5M KNO3 + 3M KI.
Vol. 27, No. 12 CERAMIC POWDERS 1403

Powders
~ e KNbO3 of binary composition was successfullycrystallizedunder M - H conditions
(Table 4) using Nb205 and high concentrationsof K O H and mixtures of KOH, KCI, K N O 3 and
KI. The KNbO3 phase crystallizedonly above 6 M K O H concentration(Table 4). The temperature
of M - H treatmentcan be decreased with increasingK O H concentrationto crystallizeKNbO3
(Table 4). The particlesizecan be controlledby using differenttime,temperature and K
concentrationvariables(Fig.6). Large KNbO3 (1-5 ~tm) crystalsformed when 10M K O H was
used (Fig.6A) while small crystals(0.5-1~tm) resultedwhen 6 M K O H was used. Even smaller
crystals(0.2 to 0.4 ~tm) of KNbO3 resultedwhen 3 M K O H was used in combination with 3 M KI
and 3.5M KNO3. The use of KBr or KI with KOH appear to promote the M-H crystallization of
KNbO3 (Table 4). The formation of KNbO3 by M-H process is much faster than by the
conventional hydrothermal technique.

T!~xTL~Powders
F i n e (0.1 to 0.2 lain) powder (Fig. 7) of BaTiO3 was crystallized by the M-H method in 2
hours at 194"C using 0.5 M TiOCI2 in excess Ba(OH)2. However, a small amount of impurity
with d spacings at 4.576, 3.712, 2.945, 2.645, 2.587 and 2.144 also crystallized. Conventional
hydrothennal treatment for 1 day using the same starting Ti and Ba sources resulted in exactly the
same phases. When a commercial TiO2 powder was treated with Ba(OH)2 under M-H conditions,
the reaction was not complete at 194"C in 2 hours. BaTiO3, however, crystallized leaving some
residual TiO'2 behind. Further studies are needed to optimize the synthesis of BaTiO3 under the M-
H conditions.

FIG. 7
Scanning electron micrograph of BaTiO3 synthesized by microwave-hydrothermal process at
194"C/2 hours.

Conclusions
This preliminary study clearly demonsu'ates that microwave-hydrothermal synthesis
enhances the kinetics of crystallization of various ceramic oxides such as TiO2, ZrO2, Fe203,
KNbO3 and BaTiO3 by one or two orders of magnitude. In addition m catalyzing the reactions,
this novel processing may lead to novel phases as we have demons~'a~d here with a new layered
alumina phase. The crystal size, morphology and level of agglomeration of the different ceramic
oxides can be controlled by parmneters such as concentration of the chef, ileal species, pH, time and
temperature. Submicron powders of TiO2, ZrO2, Fe203, KNbO3 and BaTiO3 have been prepared
by optimizing the above parameters. It is suggested that microwave-hydrothermal processing may
prove to be a valuable process in the low temperature production of fine ceramic powders including
clays and zeolites.
1404 S. KOMARNENI et 81. Vol. 27, No. 19

Acknowledgements: Thisresearch was supported by the Materials Research Laboratory

consortium on chemically bonded ceramics.
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