Materials Science and Engineering B 123 (2005) 194–202

One-step synthesis of titanium oxide nanoparticles by spray

pyrolysis of organic precursors
Wei-Ning Wang a , I. Wuled Lenggoro a , Yoshitake Terashi b , Tae Oh Kim c , Kikuo Okuyama a,∗
a Department of Chemical Engineering, Graduate School of Engineering, Hiroshima University, Kagamiyama 1-4-1, Higashi, Hiroshima 739-8527 Japan
b Kyocera Corporation R&D Center, 1-4 Yamashita-Cho, Kokubu, Kagoshima 899-4312, Japan
c School of Civil and Environmental Engineering, Kumoh National University of Technology, Kyungbuk 730-710, Korea

Received 15 June 2005; accepted 1 August 2005

Abstract
Titanium oxide (titania) nanoparticles (with a nominal size of about 10 nm) were synthesized directly from three organic precursors: titanium
tetraisopropoxide (TTIP), and water-soluble titanium sources TC-300® and TC-400® , by using a low-pressure spray pyrolysis (LPSP) method.
Effects of temperature, solvent, concentration and precursor type have been investigated systematically. We found that a higher temperature and
a higher concentration were beneficial for the formation of nanoparticles. Addition of ethanol as a co-solvent improved breakup of droplets, and
subsequently formation of nanoparticles. Water-soluble titanium sources showed great potentials for preparation of titania nanoparticles. The
nominal size of nanoparticles calculated from electron microscopical images agreed well with that estimated from corresponding X-ray diffraction
patterns, implying that nanoparticles were single crystals. The possible mechanism of particle formation in the LPSP process is also provided.
© 2005 Elsevier B.V. All rights reserved.

Keywords: Anatase; Aerosol; Surface tension; Low-pressure spray pyrolysis

1. Introduction reaction method (e.g. chemical vapor deposition, CVD) [9],

Titanium (IV) oxide (titania) nanoparticles are one of the
most interesting materials at the present time. Under ongoing
development, they attract increasing attention not only for their
unique properties [1], but also for their potential applications
in industries such as pigments [2], cosmetics [3], catalysts [4],
photocatalysts [5], etc.
Four crystal forms of titanium dioxide are naturally found:
rutile, anatase, brookite and TiO2 (B). Nanocrystalline anatase is
commonly obtained via aerosol (gas phase) routes. It is techni-
cally interesting for its semi-conducting and electrical properties
as well as its other properties [6]. Titania powders are commer-
cially prepared from TiCl4 using hydro-carbon assisted flame
synthesis, i.e., the so-called “chloride process”, where oxida-
tion of TiCl4 in the presence of oxygen gas takes place. Recently,
several other methods have also been developed to synthesize
nano-sized titania particles either using pyrolysis reactions or
hydrolysis methods, including spray pyrolysis [7,8], gas-phase
∗ Corresponding author. Tel.: +81 82 424 7716; fax: +81 82 424 7850/5494.
E-mail address: okuyama@hiroshima-u.ac.jp (K. Okuyama).
sol–gel method [10,11] and hydrolysis [12].
Among these methods, spray pyrolysis is of considerable
interest for the preparation of metals, metal oxides, non-oxides
and composite powders because this method can produce par-
ticles of controlled composition and morphology, good crys-
tallinity, and uniform size distribution, all of which can be readily
obtained in only one-step [13]. In a typical spray pyrolysis pro-
cess, the precursor solution is atomized into an aerosol reactor
where droplets undergo solvent evaporation and solute precipi-
tation within the droplets, which then undergo drying, followed
by thermolysis of precipitates at a higher temperature, and finally
sintering to form the final particles.
However, conventional spray pyrolysis (CSP) method, i.e.,
in the atmospheric environment results in limited product parti-
cle size in the range of submicrons to microns, due to difficult
generation of small droplets (sub-microns), based on the typical
mechanism of one droplet to one product particle. So far, no
study has reported preparation of titania nanoparticles using the
CSP method.
Recently, nickel and nickel oxide nanoparticles with a nomi-
nal size ranging from 10 to 30 nm, were successfully synthesized
using spray pyrolysis under low-pressure conditions, i.e., the

0921-5107/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.mseb.2005.08.006
 W.-N. Wang et al. / Materials Science and Engineering B 123 (2005) 194–202
so-called low-pressure spray pyrolysis (LPSP) [14,15]. The pos-
sible mechanism for nanoparticle formation in this LPSP process
was suggested as being very different from that of the CSP
process. However, further investigations and detailed explana-
tions are still needed to describe this process more correctly and
clearly.
Organic precursors have not been trialed in LPSP until
now [14–18]. Metal alkoxide precursors, such as titanium (IV)
tetraisopropoxide (TTIP), as organic titanium sources, were
selected as precursors for titania particle synthesis mainly in
the sol–gel method and vapor phase reaction [9]. However, tita-
nium (IV) compounds are sensitive to moisture and water due
to rapid hydrolysis, and this causes some operation difficulties
in solution preparation. Hydrolysis could be avoided by using
ethanol as solvent in the preparation of TTIP solution [12]. In
the present study, in order to prepare titania particles in a simple
way, two kinds of water soluble organic titanium sources, were
selected as titanium sources.
This work aimed to synthesize titania nanoparticles from
organic titanium precursors via the LPSP route. Various oper-
ation parameters, such as reactor temperature, addition of co-
solvent, concentration and precursor type were investigated
systematically. The mechanisms involved were further demon-
strated based on experimental results.
2. Experimental
2.1. Set up and procedures
A schematic diagram of the LPSP setup was described in our
previous research [14]. The LPSP set up consists of an atom-
izer system, a glass filter, a quartz tubular reactor (I.D. = 35 mm,
L = 800 mm) with four independent outside heating zones, a par-
ticle collector and a vacuum system. The precursor solution is
atomized by a home-made two-fluid nozzle, and large droplets
(in the order of 100 mm) are poured onto the glass filter surface,
which has a nominal pore size of 5.5 mm (Shibata Scientific
Technology Ltd., Tokyo). After saturation of the glass filter pores
with the solution, continuous supply of excess solution is passed
through the glass porous filter with bubbles, aided by pressure
difference and the carrier gas. Meanwhile, downward of the glass
filter, droplets are formed in the low-pressure environment, and
are then delivered into the reactor and dried using heat from the
furnace. As the aerosol stream passes through the reactor, the
solvent evaporates and product particles are formed.
Due to limited direct measurement of droplets in the low-
pressure environment, droplet size was estimated indirectly
(around 2 mm) by measuring the size distributions of final par-
ticles [16], and was also confirmed using another material [19].
Droplet formation in this low-pressure system by using the glass
filter as the droplet generator was considered similar to that
obtained by virtual “multi” two-fluid nozzles, and has also been
illustrated in our previous research [19], though further investi-
gation is still needed.
Dry aerosol particles are collected in an electrostatic pre-
cipitator kept at around 150 ◦ C to avoid water condensation.
Residence time of droplets or particles along the furnace can be
195
Fig. 1. Temperature profiles along the axial direction in the furnace with air flow
rate of Qc = 2 l/min.
controlled by determining pressure difference of the filter, the
carrier gas flow rate applied and the temperature distribution.
Air was used as the carrier gas in this work, and the total
carrier gas flow rate (Qc ) to the glass filter was controlled at
2 l/min under 0.1 MPa and room temperature, unless otherwise
stated. Furnace temperature was maintained isothermally by K-
type thermocouples at 500, 700, and 900 ◦ C, respectively. The
corresponding temperature profiles along the axial direction in
the electrical furnace are shown in Fig. 1. Operating pressure
was kept at 40 Torr by using an Adaptive Pressure Controller
(ACX2200, Nihon Mykrolis, Tokyo).
2.2. Preparation of precursors
Three types of titanium sources were used in this work: tita-
nium isopropoxide (TTIP, 97% purity) from Kanto Chemicals
(Tokyo), and water soluble TC-300® and TC-400® from Mat-
sumoto Chemicals (Tokyo). Detailed physical properties of these
precursors are listed in Tables 1 and 2. TTIP solution was pre-
pared using diluted nitric acid and ethanol with different volume
percentages for solvents, respectively. Vigorous stirring with a
magnetic stirrer was applied during slow addition of TTIP into
the nitric acid solution at room temperature for about 1 h. The
transparent hydrolyzed titanium precursor solution with pH <1
was then obtained without any visible precipitates. Pure water
and ethanol were used as solvents in preparing TC-300® and TC-
400® solutions. Slightly yellowish clear solutions were obtained
after slow stirring for about 30 min. Fresh solutions were pre-
pared daily.
2.3. Particle and phase characterization
Morphology and size of the captured particles were exam-
ined by field emission scanning electron microscopy (FE-SEM,
S-5000, Hitachi Ltd., Tokyo). Crystalline phases were character-
ized using an X-ray diffractometer (XRD, Rint 2200 V, Rigaku,
Tokyo) with Cu Ka radiation (wavelength = 15.4 nm) operated
at 40 kV and 30 mA. Thermal analysis was carried out using ther-
mal gravimetric analysis (TG) and differential thermal analysis
196 W.-N. Wang et al. / Materials Science and Engineering B 123 (2005) 194–202

Table 1
Physical properties of precursors useda
Abbr. Chemical formula (main ingredient) Concentration (mol/l) Viscosity Surface tension
(cp, 25 ◦ C) (×102 N m−1 )

TTIP Ti(iso-OC3 H7 )4 0.05 (in HNO3 ) 1.37 5.97

0.05 (in EtOH) 1.27 2.54
TC-300® Ti(OH)2 (OCHCH3 COO− )2 NH4 + 0.05 (in water) 1.58 5.58
0.05 (in EtOH) 1.60 2.17
TC-400® Ti(OC3 H7 )2 (C6 H14 O3 N)2 0.05 (in water) 1.28 5.94
0.05 (in EtOH) 1.28 2.13
a Measured in lab under air at room temperature.

Table 2
Properties of solvents useda
Solvents Tboiling Vapor pressure Viscosity Surface tension
(◦ C) (Torr) (cp, 20 ◦ C) (×102 N m−1 )

Water 100 18 1 7.31

Ethanol (95%) 78.5 67.5 1.20 2.28
Nitric Acid (1 N) N/A N/A 1.31b 7.10b
a Cited from “CRC Handbook of Chemistry and Physics”, 69th, CRC press,

1989.
b Measured in Lab under air at room temperature.

(DTA) (TG-DTA 6200, Seiko Instruments Inc., Tokyo). During

TG-DTA measurements, about 18 mg sample was put into a Pt
crucible at a temperature range of 30–1030 ◦ C with a heating rate
of 10 ◦ C/min under flowing air (200 ml/min). Viscosity and sur-
face tension of additives used in this work were measured using a
programmable rheometer (DV-III Ultra, Brookfield Engineering
Labs, Middleboro, MA), and a surface tensiometer (CBVP-Z,
Kyowa Interface Science Co., Ltd., Tokyo), respectively.

3. Results and discussion

3.1. Thermal analysis of titanium sources

Before the spray experiment, thermal analysis was carried out

in order to correctly understand thermal properties of the precur-
sors, and to obtain some information for further investigations.
Fig. 2 shows TG-DTA curves of the three titanium precursors:
TTIP (Fig. 2a), TC-300® (Fig. 2b) and TC-400® (Fig. 2c).
TTIP began to decompose at 250 ◦ C according to the TG
curve, where the sharp decrease of weight loss ended (Fig. 2a).
The corresponding endothermic and exothermic peaks with
intensities of −13 and 44 mV, respectively, in the DTA curve
confirmed the pyrolysis reaction coupled with evolution of gases
and water vapor.

Ti(iso-OC3 H7 )4 → TiO2 + 4C3 H6 + 2H2 O (1)

Above this temperature, the TG curve became flat and smooth,

and the weight loss reached up to 70%, nearly the same as the
theoretical value, i.e., 71% in the case of 97% TTIP, which means
the formation of TiO2 . Around 350 ◦ C, there was another sharp
exothermic peak (52 mV) in the DTA curve of TTIP, indicat-
ing the phase transition from amorphous to anatase, which was Fig. 2. TG-DTA curves of three precursors (a) TTIP (b) TC-300® and (c) TC-
similar to that reported in sol–gel derived particles. 400® at the heating rate of 10 ◦ C/min under flowing air (200 ml/min).
 W.-N. Wang et al. / Materials Science and Engineering B 123 (2005) 194–202 197

One endothermic peak and several exothermic peaks were

also found in the DTA curve of the water-soluble TC-300®
(Fig. 2b), implying that there were more complicated reactions
compared with those with TTIP. Endothermic peak in this case
was assigned to the evaporation of the solvent including water
vapor and organic ingredients. The first three exothermic peaks
were attributed to burning of organic gases and decomposi-
tion/oxidation of TC-300® with continuous loss of weight in
the corresponding TG curve. Another peak at about 460 ◦ C was
believed to correspond to the phase transition from amorphous
to anatase, because there was no obvious weight loss in the
TG curve above this temperature. Thus, the possible pyroly-
sis/oxidation reaction of TC-300® under air atmosphere can be
summarized as follows.

Ti(OH)2 [OC2 H4 CO2 H][OC2 H4 CO2 NH4 ] + 6O2

→ TiO2 + 6CO2 + 6H2 O + NH3
Similarly, sharper and higher exothermic peaks, with intensi-
ties around 350 and 470 mV, respectively, were obtained in the
DTA curve (Fig. 2c) indicating that more violent reactions and
crystallization occurred in this case. Titania was formed around
550 ◦ C as seen from the corresponding TG/TDA curves. The
possible pyrolysis/oxidation reaction is suggested below.
Ti[OC3 H7 ]2 [NC6 H14 O3 ]2 + 15O2
→ TiO2 + 2C3 H6 + 2NH3 + 12CO2 + 12H2 O
Based on the thermal analysis results mentioned above, 500, 700
and 900 ◦ C were selected as operation temperatures for further
investigations, as will be discussed in the following section.
3.2. Effect of temperature
TTIP was selected as the model material to investigate tem-
perature effect, due to its relatively lower decomposition tem-
perature as discussed above. Fig. 3 shows FE-SEM images of
0.05 M TTIP HNO3 (1 N) solution pyrolyzed at different tem-
peratures at 40 Torr. Submicron, even micron sized spherical
particles with very smooth surfaces were obtained at 500 ◦ C
(Fig. 3c). No obvious crystals were observed. The correspond-
ing XRD patterns (Fig. 4c) showed only a very weak (1 0 1) peak
(2) Fig. 4. XRD patterns of TiO2 particles prepared from 0.05 M TTIP nitric acid
solution at 40 Torr, air 2 l/min and different temperatures (a) 900 ◦ C, (b) 700 ◦ C
and (c) 500 ◦ C.
of metastable titania phase (i.e., anatase, JCPDS 211272), which
indicated that particles prepared at this temperature were almost
amorphous due to insufficient heat transfer for crystallization
in very short residence time (0.48 s) inside the furnace. Sim-
ilar particle morphologies were observed at 700 ◦ C. However,
(3) some fragmented particles with smaller sizes were also obtained.
The insert picture in Fig. 3b shows detailed information of frag-
mented particles. No nanoparticle could be found in the center
of fragmented particles in this case. Relatively sharper anatase
peaks with higher intensity were obtained in the corresponding
XRD patterns (Fig. 4b). Even stronger anatase main peaks, such
as (1 0 1), (0 0 4), (2 0 0), (1 0 5) and (2 1 1), were obtained as seen
in Fig. 4a, at 900 ◦ C implying that crystallization improved with
increasing reaction temperature. The FE-SEM pictures (Fig. 3a)
show that particles at this temperature became irregular, and
many fragmented particles with nanoparticles inside could be
found as illustrated in the insert picture. Single crystalline size
could be calculated using the Scherrer’s equation:
Kλ
dcrystal = (4)
β cos θ

Fig. 3. FE-SEM images of TiO2 particles prepared from 0.05 M TTIP nitric acid solution at 40 Torr, air 2 l/min and different temperatures (a) 900 ◦ C, (b) 700 ◦ C and
(c) 500 ◦ C.
198 W.-N. Wang et al. / Materials Science and Engineering B 123 (2005) 194–202
where dcrystal represents the single crystalline size, K is the spher-
ical factor (=0.9), λ is the X-ray wavelength, β is the full width at
half maximum (FWHM) in radians, and θ is the glancing angle.
Calculated single crystalline sizes were 9.3, 5.9 and 1.5 nm at
900, 700 and 500 ◦ C, respectively, clearly reflecting effects of
temperature on crystallization.
The transition temperature of anatase to rutile (thermal stable
phase) was reported to be between 400 and 1100 ◦ C depend-
ing on various conditions [6,20]. No trace of rutile phase was
detected even in 900 ◦ C in the present work, possibly due to the
very short residence time, rapid drying rate and heat transfer, i.e.,
thermal energy adsorbed from the heated furnace was not suffi-
cient for the required activation energy for phase transformation.
As discussed in our previous research [15], crystalline growth
could be accelerated with very fast solvent evaporation rate in a
low-pressure environment. Drying kinetics, such as drying rate,
is considered as another important factor for evolution of mor-
phology and crystallization. The drying rate, for example, was
as fast as 3.7 × 103 K/s, calculated from the corresponding resi-
dence time of 0.32 s at 900 ◦ C and 40 Torr, with a carrier gas flow
rate of 2 l/min. As indicated by Messing et al. [13], fragmenta-
tion of particles will occur when drying rates are high enough
due to some stresses formed between solids and the liquid, which
is similar to that proposed for sol–gel systems [21]. Broken par-
ticles at high temperatures, such as 700 and 900 ◦ C in this work
possibly resulted from mechanisms as discussed above. Results
and discussion on temperature effects in the present work were
also confirmed by our previous studies [14,15], that is, higher
reaction temperature is favorable for the formation of nanoparti-
cles in the LPSP process. Thus, 900 ◦ C was selected as reaction
temperature in all subsequent experiments.
3.3. Effects of solvent
For TTIP solution preparation with spray pyrolysis, many
groups [22–24] directly added TTIP into diluted nitric acid to
make the desired solution through vigorous stirring, and this has
been described in details in the experimental section. However,
other groups [12,25] suggested that because of very intensive
hydrolysis, TTIP nitric acid solution is in fact a transparent
“sol” with a colloidal size of about several nanometers to submi-
crons depending on the water-to-titanium ratio (r = [H2 O]:[Ti]).
At higher r values (>10), particles formed due to hydroly-
sis are smaller than 100 nm, usually several nanometers when
pH <2 [26]. Taking 0.05 M TTIP HNO3 (1 N) solution (in the
present work) as an example, the r value was calculated as 1043,
much larger than 10, which means that colloidal nanoparticles
are of several nanometers resulting into a transparent sol solu-
tion. Obviously, it is difficult to use this “sol” as a precursor
to get distinct nanoparticles. Some additives should be used to
moderate/prevent hydrolysis, which was previously extensively
studied in the sol–gel process [27]. For this reason, ethanol was
selected as the additive and co-solvent to make titanium pre-
cursor solutions, in the present work. Figs. 5 and 6 show XRD
patterns and FE-SEM images of titania particles prepared at
900 ◦ C and 40 Torr, by adding ethanol as additive/solvent with
different volume percentages, i.e., 0, 10, 70 and 100 vol%.
Fig. 5. XRD patterns of TiO2 particles prepared from 0.05 M TTIP solution with
different volume percentages ethanol addition at 900 ◦ C, 40 Torr and air 2 l/min
(a) 0 vol%, (b) 10 vol%, (c) 70 vol% and (d) 100 vol%.
Anatase as the main titania phase was detected in all cases
in the corresponding XRD patterns (Fig. 5), which has been
explained in the above section. Stronger and clearer peaks of
anatase, such as (1 0 3), and (1 1 2) at 36.944 and 38.573◦ , respec-
tively, were found in cases of ethanol addition, except in the case
of 100 vol% ethanol as the solvent. Corresponding Scherrer’s
sizes were calculated as 9.3 nm (0 vol%), 14.4 nm (10 vol%),
16.3 nm (70 vol%) and 6.3 nm (100 vol%), respectively, which
indicated that addition of ethanol improved crystal growth of
titania. Titania prepared from TTIP ethanol solution (Fig. 5d)
was an exception, possibly because of the precursor physical
properties (real solution), which were very different from those
of the transparent sol (in the case of 0, 10, and 70 vol% ethanol
addition).
From Fig. 6a and b, it is clear that particle size decreases
after addition of ethanol. The corresponding nominal sizes and
the geometric standard derivations (GSD) were calculated as
706.5 nm, 1.817 and 390.01 nm, 1.497, respectively, as seen in
Fig. 7. With the addition of 70 vol% ethanol, many broken and
irregular particles were observed (Fig. 6c). Nanoparticles with
a nominal size of about 10 nm (sputter particles) were obtained
with 0.05 M TTIP ethanol solution (Fig. 6d). The corresponding
single crystal sizes calculated from Scherrer’s equation were
6.3 nm, which indicated that nanoparticles in this case were all
single crystals.
This is possibly due to addition of ethanol that
improved breakage of droplet/particles and nanoparticles. From
Tables 1 and 2, we can clearly see that surface tensions of ethanol
and its solutions are smaller than those of water and nitric acid
solutions, though viscosities are nearly the same. From the the-
ory of droplet formation [28], it is clear that surface tension
and viscosity are important factors in controlling droplet size
and morphology. Decrease of surface tension following addi-
tion of ethanol may be one of the reasons for generation of
smaller droplets and fragmentation of droplets. The lower boil-
ing point and higher vapor pressure of ethanol as listed in Table 2
may be considered as other reasons for droplet breakup. Obten-
 W.-N. Wang et al. / Materials Science and Engineering B 123 (2005) 194–202
Fig. 6. FE-SEM images of TiO2 particles prepared from 0.05 M TTIP solution with different volume percentages ethanol addition at 900 ◦ C, 40 Torr and air 2 l/min
(a) 0 vol%, (b) 10 vol%, (c) 70 vol% and (d) 100 vol%.
tion of smaller product particles in the case of ethanol addition
confirmed this hypothesis. Similar investigations using ethanol
addition in spray pyrolysis were also investigated by Kato et al.
[29] and Otsuka et al. [30] They claimed that droplet breakup
came from burning of ethanol which was used as the liquid
fuel. It should be noted that generation of smaller droplets due
to addition of ethanol as discussed above may be another, but
not the main reason for generation of smaller particles, since
Fig. 7. Logarithmic normal size distribution of particles prepared from 0.05 M
TTIP nitric solution with (a) 0 vol% and (b) 10 vol% ethanol addition at 900 ◦ C,
40 Torr and air 2 l/min.
199
the calculation of final particle size dose not obey the one-
droplet to one-particle mechanism in the case of nanoparticle
formation.
Ongoing investigations on concentration effects of the TTIP
ethanol solution are still carried on, as described in the following
section.
3.4. Effects of concentration
Figs. 8 and 6d show FE-SEM images of titania particles pre-
pared with different concentrations of TTIP ethanol solutions
at 900 ◦ C and 40 Torr, i.e., 0.01 M (Fig. 8a), 0.05 M (Fig. 6d)
and 0.1 M (Fig. 8b). At very low concentrations, only submi-
cron sized spherical particles could be obtained. This might
be explained as follows. Solvent concentration on the surface
of droplets, which were obtained in a much lower concen-
tration, hardly reached supersaturation compared with that in
precursors with higher concentrations. Thus, submicron or soft
agglomerates formed more easily as opposed to nanoparti-
cles. Similar results were obtained in our previous study in
the preparation of nickel and nickel oxide [14,15]. Nanopar-
ticles were obtained in both cases, with concentrations of 0.05
and 0.1 M, respectively. Slightly larger particles were observed
with 0.1 M compared with 0.05 M as shown from correspond-
ing FE-SEM pictures. We suggest that a higher concentration
is beneficial for the production of nanoparticles in the LPSP
process, which shows large potentials for industrial applica-
tions.
200 W.-N. Wang et al. / Materials Science and Engineering B 123 (2005) 194–202

Fig. 8. FE-SEM images of TiO2 particles prepared at 900 ◦ C, 40 Torr and air 2 l/min from TTIP ethanol solution with different concentrations (a) 0.01 M and (b)
0.10 M.

In order to correctly understand the mechanisms of parti-
cle formation, another two precursors were selected for further
investigations as discussed below.
3.5. Effects of precursor type
New types of water soluble titanium sources, i.e., TC-300®
and TC-400® , were chosen in the present study in an attempt to
avoid the influence of the hydrolysis reaction. These precursors
were real solutions compared to the transparent sol. Fig. 9a and
b show FE-SEM images of particles prepared with 0.05 M TC-
300® and 0.05 M TC-400® aqueous solutions, respectively at
900 ◦ C and 40 Torr. Submicron and even micron sized spherical
particles were observed in the case of TC-300® (Fig. 9a). How-
ever, nanoparticles with a few submicron particles were obtained
in the case of TC-400® (Fig. 9b). Anatase was identified as the
main product in XRD patterns (Fig. 10) in all cases. A possi-
ble reason for the very different particle morphologies obtained
with these two precursors lies in their physical/chemical prop-
erties. As shown in Table 1, chemical formulas of these two
materials are very different from each other. In the case of TC-
300® , two hydroxyl groups are found near each other resulting in

Fig. 9. FE-SEM images of TiO2 particles prepared at 900 ◦ C, 40 Torr and air 2 l/min from different precursors with concentration of 0.05 M (a) TC-300® aqueous
solution, (b) TC-400® aqueous solution, (c) TC-300® ethanol solution and (d) TC-400® ethanol solution.
 W.-N. Wang et al. / Materials Science and Engineering B 123 (2005) 194–202
Fig. 10. XRD patterns of TiO2 particles prepared at 900 ◦ C, 40 Torr and air
2 l/min from different precursors with concentration of 0.05 M (a) TC-300®
aqueous solution, (b) TC-400® aqueous solution, (c) TC-300® ethanol solution
and (d) TC-400® ethanol solution.
stronger hydrogen bonding between molecules, and thus result-
ing in higher viscosity. On the contrary, TC-400® molecules do
not have OH groups. Droplet sizes are thus considered larger
and harder to be broken in the case of TC-300® compared with
those of TC-400® .
Ethanol solutions of TC-300® and TC-400® were also inves-
tigated for comparison. Particle size dramatically decreased in
the case of TC-300® ethanol solution compared with that in
its water solution, which further confirmed the generation of
smaller droplets/droplet breakups after ethanol addition. Possi-
ble reasons for that are similar to those explained with TTIP.
Nanoparticles with a nominal size of about 8 nm were obtained
in the case of TC-400® ethanol solution. Single crystal size
(5.3 nm) was obtained using Scherrer’s equation, which again
implied that nanoparticles produced in a low-pressure environ-
ment, are all single crystals.
We proposed that these nanoparticles formed possibly
because of breakup of larger particles. Drying kinetics is one
explanation for fragmentation as discussed in the above Section
3.2. Another reason for nanoparticle formation may come from
pyrolysis of TC-400® as already explained in thermal analy-
sis. Violent reaction coupled with evolution of many gases and
water vapor may easily destroy the network of dried particles,
and nanoparticles are formed subsequently. Higher vapor pres-
sure of ethanol solutions may be considered as the third reason
for fragmentation of dried particles into nanoparticles, with sin-
gle crystals.
Thus we can suggest the following possible mechanism of
nanoparticle formation in the LPSP process. Upon entering into a
low-pressure chamber, droplets will undergo rapid evaporation.
Nucleation and crystal growth will be accelerated by fast evap-
oration rate of the solvent. Droplets may breakup depending on
properties of the precursor itself and the additive/solvent as well.
Furthermore, because of rapid drying rate at high temperatures,
final particles could be fragmented into multiple nanoparticles,
which really were single primary crystals. Low-pressure is con-
201
sidered as a driving force for the formation of nanoparticles.
Submicron even micron particles formed in this case, possibly
due to physical properties of the precursor, which indicated that
the mechanism of particle formation in the LPSP process is obvi-
ously complex including process parameters such as pressure,
carrier gas flow rate, temperature, but also the physical proper-
ties of the precursor.
4. Conclusions
Titania nanoparticles (anatase) were directly prepared using
spray pyrolysis of organic titanium sources at a low-pressure.
Effects of temperature, solvents, concentrations and precur-
sor types were investigated systematically. Results showed that
ethanol as solvent, dramatically improved the preparation of
nanoparticles, possibly due to its lower surface tension and boil-
ing point compared with those of water/nitric acid solutions.
Results also showed that a higher temperature, concentration
and the real solution, instead of a transparent sol are beneficial
for the synthesis of nanoparticles. Nominal sizes of nanoparticles
calculated from FE-SEM images agreed well with the Scherrer’s
size estimated from corresponding XRD patterns, implying that
all nanoparticles prepared using the LPSP process were primary
crystals. Nanoparticles may come from droplet breakup, fast
crystal growth and fragmentation of dried particles. The LPSP
method is a powerful tool for the direct-synthesis of nanoparti-
cles and shows promising perspectives.
Acknowledgements
The authors wish to thank Mr. K. Sasakawa (Hiroshima
University), Dr. Yucong Wang (Kyocera Corporation) for their
assistance in the experiments and Prof. S.B. Park and Dr. Y.C.
Kang (KAIST) for introducing the glass filter type atomizer.
Matsumoto Chemicals (Tokyo, Japan) is acknowledged for sup-
plying water-soluble organic titanium sources. Grant-in-Aid
sponsored by Ministry of Education, Culture, Sports, Science
and Technology of Japan and the Japan Society for the Pro-
motion of Science are greatly acknowledged. This work is also
supported partially by the NEDO’s “Nanotechnology Particle
Project” based on the funds provided by the Ministry of Econ-
omy, Trade, and Industry (METI), Japan.
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