J. Am. Ceram. Sor.

, 75 141 1019-22 (1992)

Rapid and Continuous Hydrothermal Crystallization of Metal Oxide

Particles in Supercritical Water
Tadafumi Adschiri, Katsuhito Kanazawa, and Kunio Arai
Department of Biochemistry and Chemical Engineering, Tohoku University, Sendai 980, Japan
Hydrolysis of 10 metal salt aqueous solutions of 6 metal oxides was conducted in supercritical water. Continuous and
rapid production of metal oxide fine particles was achieved
by mixing a metal salt aqueous solution with preheated
water fed from another line. The reaction time required was
less than 2 min. Particle size, morphology, and crystal
structure of the obtained metal (hydrous) oxides were examined. Particle size (20 to 600 nm) was different among the
systems but the size range was relatively narrow in all the
cases. [Keywords: crystallization, hydrothermal process,
metal oxides, hydrolysis, water.]

I.

and in situ refining of the generated small mctal (hydrous)

oxide nuclei may take place in the same vessel. Thus high
refining rates, as well as fast hydrolysis rates, are expected.
From another viewpoint, water whose temperature and
pressure is above its critical point (Tc= 647.3 K and f" =
22.11 MPa) 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 preheated water. Furthermore, this method enabled continuous
production of metal oxide particles.
The objective of this study is to elucidate the specific features of the process for the rapid and continuous production
of metal oxide fine particles.

Introduction

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 particlesize distribution, uniform shape, and uniform crystal structure (high crystallinity or amorphous).
Various methods for their preparation have been developed, including chemical vapor deposition (CVD), physical
vapor deposition (PVD), liquid-phase precipitation, solidstate transformation, and rapid expansion of a supercritical
solution.' 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. Matijevic et ~ 1 . have
~ 3 ~
intensively studied the effects of temperature, pH, and additives on the crystal structure and the morphology of resulting
particles using a n 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 aye 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 batchwise 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
ETAL

11.

Ten metal salts (A1(N03)3,Fe(NO;);, F C ~ ( S O ~FeCI2,

)~,
Co(NO&, N i ( N 0 3 h ZrOC12, TISO,,
Fe(NH4)2H(C6H~07)2,
and TiCI4) were used as the sample materials. The apparatus
used is schematically shown in Fig. 1. T h e reactor employed
was a stainless-steel vertical-tube reactor (9.5 mm I D and
400 mm long). A water solution of a sample whose concentration ranged from 0.0066 to 0.16 mol/L was fed from the top of
the reactor at a feed rate of 0.8 to 2.2 mL/min. At the inlet of
the reactor the solution was mixed with distilled water (2.5 to

HEATER

T.C.

PRESSURE

h h

WATER

L. C. Klein-contributing

Experimental Procedure

editoi

Manuscript No. 196504. Received July 31, 1991; approved January 16,
1992.

SOLUTION

SAMPLER

IUI

Fig. 1. Experimental apparatus

1019

BACK PRESSURE
REGULATOR

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Communications of the American Ceramic Society

Table I.
Solution

Concentration
(mol/Ll

0.038
0.038

TiS0,
TiC1,

Vol. 75, No. 4

Summary of Conditions and Results

Reaction condition
Temperature
(TI

Products
Particle
sizc (nm)

Pressure
(MPal

Chemical
cornnosition

400-490

35

AlOOH

=600

400
400
400
400
400
400
400-490

35
35
35
35
35
35
30

=50
=SO
=50
=50
=loo
=200
=I0

400
400-450

35
30

(Y-Fc~OI
a-Fez03
a-Fe 0
Fc~OJ
coio4
NiO
Zr02
(cubic)
TiOz
Ti02
(anatase)

6.0 g/min) which had been heated at 723 to 763 K. At this

point the solution was rapidly heated to the reaction temperature (673 K) and hydrolysis immediately took place.
The temperatures at the mixing point and in the reactor
were measured by two thermocouples which wcre located at
the inlet of the reactor and at the lower part of it. T h e reactor
temperature (673 to 763 K) was controlled by an electric furnace. In most experiments the reactor tempcrature was kcpt
the same as the inlet temperature. In the other experiments,
the reactor temperature was raised above the inlet tcmperature. The pressure of the reactor (30 to 35 MPa) was controlled by a back-pressure regulator. At the reactors 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 most of the experiments.
Morphology of the obtained particles was observed by
using scanning electron microscopy (SEM) and transmission
electron microscopy (TEM) analyses. T h e particle size was
evaluated from the obtained SEM and T E M micrographs.
The crystal structure of the products was analyzed by XRD.

=20
=20

Shane

Hexagonal
or rhombic
or needle
Spherical
Spherical
Spherical
Spherical
Octahedral
Rodlike
Spherical
Prismatic
Prismatic

formation and its refining) or in a slow-heat-up hydrothermal

method (similar to an autoclave hydrothermal synthesis), the
dehydration takes place aftcr relatively large hydrous oxide
particles arc grown. However, in this process dehydration
may take place before hydrolysis is completed and before the
large hydrous particles grow. Thereforc, a much higher reaction rate is expected.
(3) Reaction Rate
To cxamine the effect of residence time on the reaction,
the following experiment was conducted. For the Fe(N03)?
system, the reactor was removed from the system and the
cooler was placed just aftcr the mixing point. The residence
time of the solution was estimated to be shorter than 1 s.
Even in this case a - F e 2 0 3particles were obtained, although
the particle size (20 nm) was smaller than in the case wirh the
reactor (50 nm). Thus, the results demonstrate that the reaction rate is surprisingly high.
We think the high reaction rates obtained in this cxperiment 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.

111. Results and Discussion

(1) Morphology

The experimental conditions and the results are summarized in Table I. Morphology of the metal (hydrous) oxide
particles is shown in Figs. 2 through 7, for A I ( N 0 3 ) ? ,
Fe(N03)3, Co(N03)*,Ni(N03)2, ZrOCI?, and TiCI,. For
FeCl 2, Fe2(S04)?,and Fe( N H 4)2H(ChHS07)2,
spherical fine
particles similar to those in Fig. 3 (Fe(NO&) were obtained.
For TiS0, 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 reaction time (2 min).
(2) Hydrolysis and Dehydration
The reaction taking place in the reactor is considered to bc
as follows:

Step 1. M(NO,),

+ xHzO = M(OH), + x H N 0 3

(1)

Step 2. M(OH), = MOXi2+ -2H 2 0

(2)

(A similar reaction scheme is available for other anions.) 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 (sol-gel

Fig. 2. Morphology of AIOOH p a r t i c l e s p r o d u c e d f r o m

0.05 mol/L AI(N03), at 673 K and 40 MPa.

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Communications of the American Ceramic Society

Morphology of F e 2 0 3particles produced from 0.016 mol/L

Fe(NO?), at 673 K and 35 MPa.

Fig. 3.

1021

Fig. 6. Morphology of ZrOz particles produced from 0.02 mol/L

ZrOC12 at 673 to 763 K and 30 MPa.

tase (TiOz) and cubic zirconia ( Z r 0 2 ) were obtained. For the

AI(NO& 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(NH4)2H(C6H507)2
system, Fe304was obtained
as a product. Thus Fe 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 reducing atmospheres by
the introduction of oxidizing (02,etc.) or reducing gases
( H 2 , CO, etc.).
M o r p h o l o gy of C o i O l p a r t i c l e s p r o d u c e d f r o m
0.0094 mol/L Co(N03)2 at 673 K and 35 MPa.
Fig. 4.

(4) Crystallinity
According to the XRD analyses, in most cases, the prod-

ucts formed were metal oxides with a high degree of crystallinity. For ZrOC12and TiC14, when the reactor temperature
was the same as the inlet temperature (673 K), the products
werc amorphous hydrous oxide gel. However, when the reactor temperature was raised above the inlet temperature, ana-

Morphology of NiO particles produced from 0.0066 mol/L

Ni(N02)2at 673 K and 30 MPa.
Fig. 5.

IV. Conclusions
Some specific features of the continuous and rapid hydrothermal synthesis of metal oxide fine particles in supercritical water (673 t o 763 K a n d 30 t o 35 MPa) 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.

Morphology of Ti02 particles produced from 0.038 mol/L

Tic14 at 673 to 723 K and 30 MPa.
Fig. 7.

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Communicationsof the American Ceramic Society

The reaction time required for this hydrothermal synthesis in

supercritical water was less than 2 min, especially for F ~
Droduction which was less than 1 s. T h e high reaction rate can
be attributed to the high reaction temperzure, 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 particlesize distribution was relativelv 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.

Vol. 75, No. 4

Acknowledgments:

The authors thank Nissan Chemical Industries,

Ltd.,
for the analyses of the products and Ms. Sima Miura for the SEM
o
~
analysis.

References
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i by the
l Rapid
~
Expansion
~
of Supercritical Solutions,J. Mater. Sci.,
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22, 1919-28 (1987).
E. Matiievic. A. D. Lindsav, S. Kratohvil, M. E. Jones, R. I. Larson. and
N.W. Cayei, Characterization and Stability of Chromium Hydroxide SOIS
of Narrow Size Distributions, J. Colloid Interface Sci., 36, 273-81 (1971).
E. Matijevic and P. Scheiner, Ferric Hydrous Oxide Sols: 111, Preparation of Uniform particles by Hydrolysis of Fe(II1)-Chloride, -Nitrate, and
-Perchlorate Solutiona, J Colloid Interface S C L , 63, 509-24 (1978).
0