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.
(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.