Metal oxide fine particles can be used for many applications, such as catalysts, coatings,

reinforcing materials, ceramics, and electronic devices. Fine metal oxide particles used in these fields
are required to have a narrow particle size distribution, uniform shape, and uniform crystal
structure ( high crystallinity or morphous).
Various methods for their preparation have been devel oped, including chemical vapor deposition
(CVD), physical vapor deposition (PVD), liquid-phase precipitation, solid state transformation, and
rapid expansion of a supercritical solution. 1 The ultimate aim of these processes is the simultaneous
control of particle size, particle size distribution, morphology, and crystal structure, which has been
considered to be a difficult task.
Hydrothermal synthesis of metal oxide fine particles from acidified metal salt aqueous solution is
one method for producing metal (hydrous) oxide particles. Matijcvic et al. have intensively studied
the effects of temperature, pH, and additives on the crystal structure and the morphology of
resulting particles using an autoclave method at around 373 K and atmospheric pressure. Their
results suggest that the properties of the oxide particles may be controlled through hydrothermal
crystallization. However, the reaction rate is not sufficiently high and the products are not always
metal oxide because of a low reaction temperature.
It is not uncommon to have a refining process subsequent to the process of metal oxide
production. Hydrothermal treatment of metal (hydrous) oxide sols at elevated temperature and
pressure is widely employed for the dehydration of metal (hydrous) oxide and the recrystallization
or treatment of metal oxide. However, the aging time is generally longer than a few hours because
of the batch wise autoclave method and the slow surface reaction of the large particles that are
grown.
If a metal salt aqueous solution can be rapidly heated to the temperature of hydrothermal
treatment, both the hydrolysis and in situ refining of the generated small metal (hydrous) oxide
nuclei may take place in the same vessel. Thus high refiningrates, as well as fast hydrolysis rates,
are expected.
From her viewpoint, water whose temperature and pressure is above its critical point (T, = 647.3
K and P, = 22.11 M Pa) perhaps has some advantages for the control of hydrolysis and aging
atmospheres, because properties of supercritical water, such as density, viscosity, diffusivity, and
dielectric constant, can be widely changed by pressure and temperature. Controlling the reaction
atmosphere may lead to the simultaneous control of size, crystal structure, and morphology of the
particle. In the proposed process, the rapid heating of the solution was achieved by mixing with
pre heated water. Furthermore, this method enabled continuous production of metal oxide
particles.
The object ive of this study is to elucidate the specific features of the process for the rapid and
continuous production of metal oxide fine particles.
II. Experimental Procedure
Ten metal salts were used as the sample materials. The apparatus used is schematically shown in
Fig. 1. The reactor employed was a stainless-steel vertical tube reactor (9.5 mm ID and 400 mm
long). A water solution of a sample whose concentration ranged from 0.0066 to 0.16 mol/L wa fed
from the top of the reactor at a feed rate of 0.8 lo 2.2 mL/min. At the inlet of the reactor the
solution was mixed with distilled water (2.5 to 6.0 g/min) which had been heated at 723 to 763 K. At
this point the solution was rapidly heated to the reaction tempera ture (673 K) and hydrolysis
immediately took place.

The temperatures at the mixing point and in the reactor were measured by two thermocouples
which were located at the inlet of the reactor and at the lower part of it. The reactor temperature (673
to 763 K) was controlled by an electric furnace. In most experiments the reactor temperature was kept
the same as the inlet temperature. In the other experiments, the reactor temperat ure was raised above
the inlet temperature. The pressure of the reactor (30 to 35 MPa) was controlled by a back pressure
regulator. At the reactor's exit the reaction mixture was cooled and continuously recovered as a particle
water suspension through the back pressure regulator. The residence time of the solution in the reactor
was estimated as =2 min in mos of the experiments.
Morphology of the obtained particles was observed by using scanning electron microscopy
(SEM) and transmission electron microscopy (TEM) analyses. The particle size was evaluated
from the obtained SEM and TEM micrographs. The crystal structure of the products was analyzed
by XRD.
III. Results and Discussion
(1) Morphology
The ex perimental conditions and the results are summarized in Table I. Morphology of the metal
(hyd rous) oxide particles is shown in Figs. 2 t hrough 7, for Al( N03 h, Fe( N03 )J , Co( N03)z ,
Ni( N03h, ZrOCl 2 , and TiCl 4 . For FeClz , Fe2(S04h, and Fe(NH4)zH(C6H 501h, spherical fine
pa rticles similar to those in Fig. 3 (Fe( N03 h) were obtained. For TiS04 the particles obtained
were similar to those in Fig. 7. As shown in these micrographs, the particle size distribution was
relatively narrow. Although solution conversion was not evaluated in this experiment, the absence of
color in the recovered suspension suggests a high conversion despite the short react ion time (2
min).
(2) Hydrolysis and Dehydration
(A similar reaction scheme is available for other an ions.) The first step is the hydrolysis of a metal
salt to produce metal (hydrous) oxide, and the second step is dehydration of the hydrous oxide to
produce metal oxides. Since the dehydration proceeds from the outer surface of the hydrous oxide
particles, smaller hydrous oxide particles may have higher dehydration rates. In a conventional
two stage process (solgel format ion and its refining) or in a slow heat up hydrothermal method
(similar to an autoclave hydrothermal synthesis), the dehydration takes place after relatively large
hydrous oxide particles arc grown . Howeve, in this process dehydration may take place before
hydrolysis is completed and before the large hydrous particles grow. Therefore, a much higher reaction
rate is expected.
(3) Reaction Rate
To examine the effect of residence time on the reaction, the following experiment was
conducted . For the Fe( N03 ).i system , the reactor was removed from the system and the cooler was
placed just after the mixing point. The residence time of the solution was estimated to be shorter than 1
s. Even this case a-Fe2 03 particles were obtained, although the particle size (20 nm) was smaller
tha n in the case with the reactor (50 nm). Thus, the results demonstrate that the reaction rate is su
rprisingly high .
We think the high reaction rates obtained in this experiment are due to the elevated reaction
temperature , the high diffusivity of the reactants in supercritical water, and the fast dehydration
reaction of the fine hydrous oxide particles.
(4)

Crystallinity

According to the X RD analyses, in most cases, the products formed were metal oxides with a high
degree of crystallinity. For ZrOCl 2 and TiC14, when the reactor temperature was the same as the inlet
temperature (673 K), the products were amorphous hydrous oxide gel. However , when the reactor
temperature was raised above the inlet temperature , anatase (Ti02 ) and cubic zirconia (Zr02 )
were obtained . For the Al (N03H) system, the sharpness of the boehmite (AIOOH) peaks in the
XRD patterns increased with increased reactor temperature, although alumina particles could not be
obtained even at a reactor temperature of 763 K.
(5) Homogeneous Reduction
For the Fe( N H 4 )zH(C 6H501h system, Fc304 was obtained as a product. Thus FeH was
reduced to Fe2+ in this case. This may be due to the reduction of Fe3 + by CO which was
produced through the thermal decomposition of ammonium citrate. Since gas is miscible in
supercritical fluids to a considerable extent, a uniform reducing atmosphere might be realized
throughout the reactor in this experiment. Because of the miscibility of supercritical fluid with
gases, it may be possible to control oxidizing and reducin atmospheres by the introduction of
oxidizing (02, etc.) or reducing gases (H 2, CO, etc.).
IV. Conclusions
Some specific features of the continuous and rapid hydrothermal synthesis of metal oxide fine
particles in supercritical water (673 to 763 K and 30 to 35 M Pa) were elucidated. By mixing the
metal salt aqueous solution with preheated water fed from another line, rapid heating of the solution
to the reaction temperature (673 K) was achieved. In this system, dehydration of metal (hydrous)
oxide (intermediate species) took place before the hydrous oxide particles grew large. Therefore, a
high dehydration rate was obtained.
The reaction time required for this hydrothermal synthesis in supercritical water was less than 2 min,
especially for Fe203 production which was less than 1s. The high reaction rate can be attributed to the
high reaction temperature, high diffusivity in supercritical water, and fast dehydrogenation of fine
metal (hydrous) oxide particles. The particle size of the produced metal oxide ranged from 5 to 600 nm
and the particle size distribution was relatively narrow. The result obtained also suggests another
specific feature of hydrothermal synthesis in supercritical water, namely, a homogeneous reaction
atmosphere due to the miscibility of supercritical water with gases.