View Article Online / Journal Homepage / Table of Contents for this issue

Dynamic Article Links

RSC Advances
Cite this: RSC Advances, 2012, 2, 22942301

PAPER

www.rsc.org/advances

Solgel TiO2 in self-organization process: growth, ripening and sintering

Hsueh-Shih Chen* and Ramachandran Vasant Kumar

Published on 19 January 2012. Downloaded on 11/09/2013 07:46:52.

Received 23rd September 2011, Accepted 1st December 2011

DOI: 10.1039/c2ra00782g
TiO2 nanoparticles were synthesised by a self-organization method using a continuous water vapour
hydrolysis system without mixing. Formation of TiO2 particles was based on pure colloidal
interactions of hydrolyzed alkoxide molecules generated at the interface between titanium alkoxide
solution and water vapour. The effect of ethanol was proved to increase aggregation and packing of
primary particles, leading to a significant size enlargement of secondary particles in a post annealing
process above 500 uC. A new model to describe solgel TiO2 growth has been proposed, which
considers the formation of secondary particles to be the result of nucleation of oversaturated primary
particles, while the primary particles are the result of irreversible oligomerization of Ti oxo molecules.

Introduction
The solgel process offers many advantages for preparing oxide
materials such as low cost, high purity and a wide variety of
morphologies. The synthetic process of solgel materials in
general involves a wet-chemical process to form a precursor sol
or gel solution, which can be deposited on a substrate, followed
by a post heat treatment to convert the amorphous precursor
into crystalline particles or thin films.1 Typical solgel processing
of TiO2 nanocrystals includes the hydrolysis of titanium alkoxide
by water, which can react with alkoxyl groups, generating fully
or partially hydrolyzed (OR)42nTi(OH)n molecules. The (partially) hydrolyzed molecules can react with each other or with
other alkoxides or hydroxides, forming an oxo bridge (O)
between Ti atoms (oxolation) together with an elimination of a
water molecule, as shown below. Briefly, the hydrolysis of Ti
alkoxides leads to hydroxyl groups, which is able to change
Ti(OR)4 to TiOTi via the condensation (i.e., olation or
oxolation process), and produces Ti-oxo-alkoxy or polyoxotitanate molecular clusters, for example, [Ti12O16](OPri)16,
[Ti11O13](OPri)18 and Ti16O16(OEt)32.2 The Tioxoalkoxy clusters can further grow to larger denser nanoparticles (NPs)
dispersing in a solution (i.e. sol). The sol particles can further
associate with each other via collisions after aging for a certain
period of time and thus form bigger isolate gel particles, gel
network, or porous films depending on experimental conditions.
For the hydrolysis of titanium alkoxides, it is known that the
amount of water strongly affects the morphology of final
products. According to the molar ratio of water to titanium
alkoxides (h), the solgel processing of TiO2 may be classified
into two regimes; low H2O/Ti molar ratio (h , 10) and high
H2O/Ti molar ratio (h . 10). At low h values, spherical
TiO2 particles with relatively uniform size about 0.51 mm are
Department of Materials Science and Metallurgy, University of
Cambridge, Pembroke Street, Cambridge, CB2 3QZ, U.K.
E-mail: sean.chen@cantab.net

2294 | RSC Adv., 2012, 2, 22942301

obtained.3 At high h values, large aggregates of TiO2 rapidly

precipitate because fast hydrolysis leads to unstable colloids. The
aggregates can be separated to nano-sized particles (,100 nm) at
moderately elevated temperature by the so-called chemical
peptization process using acids such as nitric acid.4
Alcohol is often served as a solvent to slow down the
hydrolysis reaction of Ti alkoxides.5 However, effect of alcohols
on the morphology and microstructure is still an argument. Park
et al. reported that n-propanol acted as a dispersant for TiO2
particles in the thermal hydrolysis of titanium tetrachloride in a
mixture of n-propanol and water.6 They found that without any
n-propanol TiO2 particles were small and agglomerated. With
addition of n-propanol (n-propanol/water = 3), TiO2 particles
became uniform in size and discrete. On the other hand,
Vorkapic et al. found that alcohols caused the aggregation of
TiO2 primary particles, which were synthesised via hydrolysis
condensation of alkoxides at a high h value.7 They found that
chemical factors relating to the hydrolysis and the condensation
(e.g. temperature, the length of alkoxyl of alkoxide) affected
the primary particle size rather than the final particle size. Also,
alcohols had a negative effect on the peptization. The smallest
secondary particles (about 20 nm) were obtained without any
alcohol modification. Thus, they suggested that formation of
TiO2 particles was controlled by the colloidal interactions
between primary particles. Moreover, it has been reported that
ethanol could cause the amorphization of TiO2 particles.8 Hague
et al. prepared TiO2 by hydrolyzing an isopropoxideethanol
mixture with a large excess of water (h = 165). Before
calcination, the samples were found to be the anatase. But the
samples became amorphous after they were rinsed twice by
ethanol. The authors suggested that this crystalline-toamorphous transformation was possibly due to the fact that
the hydrolysis reaction was slightly reversed by rinse of ethanol.
Although the solgel process is widely applied for preparing
TiO2, the growth mechanism of the solgel TiO2 is thought to be
complicated and experimental factors such as alcohol modifiers
This journal is The Royal Society of Chemistry 2012

Published on 19 January 2012. Downloaded on 11/09/2013 07:46:52.

View Article Online

do not exhibit a similar effect on different synthetic systems. One

of the reasons is that hydrolysiscondensation of Ti alkoxide and
aggregation of monomers may occur simultaneously for a certain
period, which leads to different morphologies and sizes of TiO2
particles, and therefore affects the crystal growth of TiO2 in
the post annealing process. Some growth models have been
proposed to describe the growth of solgel TiO2. A general
growth mechanism is that TiO2 primary particles generate from
the nucleation of supersaturated monomers, which are produced
by the hydrolysis of Ti alkoxides in the induction period.3 The
TiO2 primary particles can continue the growth via additions of
monomers and aggregation. This model assumes that monomers
can accumulate and form embryos in a reversible process
before they form stable nuclei when the critical concentration
is reached. On the other hand, the growth mode of TiO2 particles
is affected by the amount of water. For example, Oskam et al.
obtained nanocrystalline TiO2 NPs from the hydrolysis of Ti
alkoxide at a high water/Ti ratio, followed by peptization at
85 uC.9 The average radius of primary particles increased linearly
with time, which was consistent with the predication made by the
LifshitzSlyozovWagner (LSW) theory. They observed secondary particles formed by epitaxial self-assembly of the primary
particles with a size range 1.58 nm.
In this report, we synthesised TiO2 by employing a water
vapour hydrolysis system, in order to investigate the growth of
solgel TiO2 NPs and the influence of the initial processing
parameters such as alcohol on the morphology and microstructure of TiO2 in the sintering process. In this design, no mixing is
applied and the complexity of growth modes is simplified. The
hydrolysis is caused by condensed water from vapour occuring at
the interface between the alkoxide and water vapour phase,
which has very low water/alkoxide ratio (y 1/700 for one second
vapour input). The sol particles form at the interface region and
self-organise to gel particles via pure colloidal interactions. This
design allows us to examine pure interactions between solgel
particles excluding the effect of external mixing. Instead of
considering that primary particles are from the nucleation of
hydrolyzed monomers, a plausible model considering that TiO2
secondary particles are from the nucleation of primary particles,
which are from irreversible coalescence of monomers, is
attempted to qualitatively describe to the growth of solgel TiO2.

Experimental

was carried out at 150 uC for 1 h, followed by 600 uC for 2 h with

a heating rate of 5 uC min21. White crystalline TiO2 powder were
obtained after the annealing process.
Synthesis of TiO2 by vapour hydrolysis
An experimental system deigned to synthesise TiO2 via slow
hydrolysis of TTIP by water vapour is shown in Fig. 1(a). The
water vapour was generated by heating water at 70 uC (reservoir
A) and carried by argon (99.9%) into reservoir B containing
TTIP kept at room temperature. The input rate of water vapour
was controlled by the flow rate of argon. The amount of water
input was estimated by the weight of water accumulated in
the reservoir C. Plastic pipes connecting each reservoir were
wrapped with aluminium foils to prevent water vapour from
condensation. In order to exclude the effects of stirring on the
formation and aggregation of particles, no stirring was applied
to the system throughout the process. As the TTIP was kept at
room temperature, the water vapour was expected to condense
to liquid as it contacted the TTIP surface. Thus, the hydrolysis
and the condensation would occur at the near surface region of
the TTIP. A typical input rate of water vapour was set at 5.21 6
1026 mol s21. The molar ratio of water/TTIP was about 1/700
for the vapour input lasting a second. The overall input time
(aging time) was eight hours. A white precipitate eventually
formed at the bottom of the reservoir. The product was then
milled to a powder for subsequent characterisation. Pure TTIP
and alcohol-modified TTIP were used as precursors. For
investigating the structure and morphology of samples in the
annealing process, pure TTIP or an ethanolTTIP mixture
(volume ratio = 0.1/1) was used. The overall reaction time was
8 h. Samples were placed into a furnace and taken out at a
desired temperature, as shown in Fig. 1(b).
Characterisation
The surface morphology of TiO2 was investigated by field
emission gun scanning electron microscopy (SEM). The average
size of particles was estimated according to SEM images for
more than 130 particles using computer software (ImageJ).
Powder X-ray diffraction (XRD) was employed to study the
crystallography of samples. The crystallite size of TiO2 is
estimated by FWHM according to Scherrers formula, D =
(0.9 l)/(b1/2 coshB), where D is the average grain size, l is the

Materials
Titanium(IV) tetra-isopropoxide (TTIP, 97%) and absolute
ethanol (analytical reagent grade) were purchased form
Aldrich. All reagents were used without any further purification.
Doubly distilled water was used to initiate the hydrolysis and the
condensation process.
Synthesis of TiO2 by general approach
5 ml absolute ethanol was first used to modify TTIP (5 ml) using
magnetic stirring for 20 min in an argon atmosphere. Then, 5 ml
doubly distilled water was slowly added into the mixture of
ethanol and TTIP at room temperature to form a sol solution.
The molar ratio of water/TTIP is 15.4. Gel solution was obtained
by aging the sol for 18 h at room temperature. Annealing process
This journal is The Royal Society of Chemistry 2012

Fig. 1 (a) Experimental design of vapour hydrolysis. (b) Evolution of

the microstructure and the morphology of samples in the annealing
process. Red dots indicate that samples were taken out from a furnace at
100, 200, 300, 400, 500, 600, and 600 uC (15 h).

RSC Adv., 2012, 2, 22942301 | 2295

View Article Online

), b1/2 is the FWHM (full width

wavelength of Cu Ka (= 1.5405 A
at half maximum), and hB is the diffraction angle.

Results and discussion

Published on 19 January 2012. Downloaded on 11/09/2013 07:46:52.

TiO2 synthesised by general approach

As-prepared TiO2 sol was a white suspension. After aging, larger
white gel particles formed at the bottom of the vessel if no
stirring was applied. Dried TiO2 gel samples have no crystallinity, showing that highly crystalline TiO2 would not form at
room temperature without heat treatment, as shown in the XRD
data in Fig. 2 (curve a). The TiO2 crystalline phase is generated
after a heat treatment is carried out, shown in Fig. 2 (curve b).
The XRD data indicate that annealed TiO2 powders have an
anatase phase with average grain size of 30.1 nm. It also shows
that a small amount of anatase TiO2 transforms into the rutile
phase. SEM images (Fig. 3(a)) show that the morphology of
TiO2 particles is oval-shaped and coalesced and has a mean size
about 1.02 mm 36%. A high magnification image in Fig. 3(b)
shows that the TiO2 is made up of secondary particles composed
of primary nanoparticles with diameters of 33.2 nm 25%.
Note that the primary particle size is close to the average grain
size estimated from the XRD data, inferring the majority of the
primary particles are nearly single crystalline. The above SEM
and XRD results suggest that amorphous primary particles first
generate in the solgel process and then aggregate into secondary
particles. Since there is no existence of TiO2 crystalline phases
before the annealing process, the formation of the primary
particles in this case may not be mixed with the conventional
nucleation-growth process of crystalline materials.
The growth of TiO2 from the general solgel process is
schematically shown in Fig. 4(a). When water is introduced into
the TTIP solution, Ti-oxo (or Ti-oxo-alkoxy) molecular clusters
are generated through the hydrolysiscondensation reaction of
the alkoxides and form particulate sol particles. The primary
particles may be viewed as the coalesced Tioxo molecular
clusters generated from hydrolyzed Ti alkoxides. Thus, the size
of the primary particle should be dependent on the hydrolysis
condensation and chemistry of the solution. For the secondary
particles, their average size is related to the dimension of the gel
particles that is determined by the interaction between colloidal
particles.7

Fig. 2 XRD of TiO2 synthesised by a standard solgel method (volume

ratio TTIP/ethanol/water = 1/1/1). As-prepared sample (curves a) and
sample annealed at 600 uC for 2 h (curve b).

2296 | RSC Adv., 2012, 2, 22942301

Fig. 3 SEM images of TiO2 particles synthesised by a normal solgel

method (volume ratio TTIP/ethanol/water = 1/1/1) at pH = 7. (a) 30006.
(b) 70 0006.

TiO2 powders synthesised from the ordinary solgel process at

room temperature generally show a broad amorphous XRD
peak, which is actually contributed by numerous diffraction data
from Ti-oxo molecular clusters and domains in a microscopic
viewpoint. The Ti-oxo molecular clusters randomly connect with
each other and could not form periodic structures in a fast
hydrolysiscondenstation process. In some cases, crystalline
materials may be obtained by standing a solution of Tioxo
molecular clusters having a well-defined structure at room or

Fig. 4 (a) Normal solgel process of TiO2 particles. (b) TiO2 prepared
by solgel process in the vapour hydrolysis design.

This journal is The Royal Society of Chemistry 2012

View Article Online

elevated temperature for a longer time (e.g., couple of days). In

that case, stable Ti-oxo molecular clusters act as building blocks
being able to periodically assemble in a slow assembly process.
So the crystalline phase could be recorded by single crystal
XRD.2c,2d

Published on 19 January 2012. Downloaded on 11/09/2013 07:46:52.

TiO2 synthesised by vapour hydrolysis

Fig. 5 gives SEM images of a TiO2 sample prepared by
hydrolyzing pure TTIP in the vapour hydrolysis design. The
sample dried at room temperature contains secondary particles,
which are composed of primary particles. This result is similar to
those samples prepared by the standard solgel method. In the
experimental design of the vapour hydrolysis system, water
vapour is continuously transported into a vessel containing
TTIP. The vapour is condensed into liquid H2O at the interface
between the atmosphere and the TTIP surface. For a rate of
5.21 6 1026 mol s21, the molar ratio of water/TTIP is about
1/700 for a second of the water vapour input. The water would
not largely accumulate since reaction between water and TTIP is
very fast. The characteristic time of the hydrolysiscondensation
of TTIP precursor reported is in the range of tens of
milliseconds.10,11 So it is expected that reaction between water
and TTIP mainly occurs at the interface region, where Ti-oxoalkoxy molecular clusters generate and migrate into the solution
due to the Brownian interaction and gravity, as shown in region I
Fig. 4(b). The generated Ti-oxo-alkoxy clusters would only
contain single or few Ti atoms due to a limited water input. Some
stable clusters TinOm(OiPr)4n-2m-l(OH)l, with n = 3, 11, 12, and
17, have been found in the solutions containing TTTIP at low
hydrolysis ratio h = [Water]/[Ti] , 1.12 The smallest stable Tioxo-alkoxy cluster observed was Ti3-oxo clusters synthesised at
h y 0.05.13 Larger Ti-oxo clusters and nanoparticles were
obtained at higher h values (. 0.7).10

Fig. 5 SEM images of TiO2 dried at room temperature (a), 500 uC (b),
600 uC (c), and 600 uC for 15 h (d). Samples were prepared by vapourhydrolyzing pure TTIP.

This journal is The Royal Society of Chemistry 2012

In the vapour hydrolysis system, formations of sol and gel

particles are based on self-organisation since there is no mixing
applied in this system. So the collisions among the particles
instead dominate the growth. The Ti-oxo-alkoxy molecular
clusters are first generated at the TTIP surface where the
hydrolysis and condensation take place. Ti-oxo-alkoxy clusters
could grow into larger sol particles via collisions. This event then
produces a colloidal solution (i.e. sol process, region I). If the sol
particles link to each other, large gel particles are produced and
fall down from near the surface region due to gravity. The
formation of secondary particles is caused by the aggregation
of the primary particles shown in region III in Fig. 4(b).
Consequently, the sol and gel particles are assigned to the
primary and the secondary particles respectively. In addition, the
definition of the term sol particle is somewhat confusing since
its scale (several to tens of nm) overlaps with those of molecular
clusters and of nanoparticles. Basically, sol particles may be
viewed as large molecular clusters (e.g., polymers) with denser
structures and equivalent to nanoparticles with either amorphous or crystalline structures. Gel particles may be viewed as
larger coalesced sol particles in the micron scale.
Evolution of the morphology of TiO2 obtained by annealing
samples at various temperatures is given in SEM images in
Fig. 5. It shows that the TiO2 secondary particles have irregular
shapes and no significant change in the morphology takes place
below 500 uC. For samples annealed at 600 uC and 600 uC/15 h,
sintering of the particles is observed. The primary particles
coalesced and merged, as shown in Fig. 5 (images c and d). XRD
data show that there is no crystalline phase for an as-prepared
sample whereas the anatase appears at 100 uC (Fig. 6(a)). The
anatase is partly transformed into rutile after heating at 600 uC
for 15 h. The final product is a mixture of anatase and rutile, as
shown in Fig. 6(a). Variations of the crystallite size, the primary
particles, and the secondary particles, estimated from XRD data
and SEM images, are presented in Fig. 7 The as-prepared
primary and secondary particles at room temperature are 14 nm
14% and 1.3 mm 28% respectively. The size does not
significantly change for samples annealed at temperatures below

Fig. 6 XRD of TiO2 annealed at temperatures from room temperature

(R.T.) to 600 uC and 600 uC for 15 h. Samples were prepared by vapourhydrolyzing pure TTIP (a) and ethanolTTIP mixture (b).

RSC Adv., 2012, 2, 22942301 | 2297

View Article Online

Published on 19 January 2012. Downloaded on 11/09/2013 07:46:52.

Fig. 8 Nucleation and growth of TiO2 in the solgel process.

grain growth can continue via inter-particle coalescence caused

by sintering of primary particles.
Fig. 7 Size variations of TiO2 primary particles, secondary particles,
and crystallites prepared by vapour-hydrolyzing pure TTIP.

500 uC. The stability of the particles size below 500 uC is

understandable; there is no significant sintering of TiO2 particles
below 500 uC observed (melting point of TiO2 y 1840 uC) so
they are able to keep their original size. But at 600 uC the
primary and the secondary particles readily enlarge since the
sintering causes grain growth. A slight decrease in size at 100 uC
is ascribed to the removal of organic compounds that lead to
some shrinkage and/or cleavage of the large particles.
The grain size of TiO2, on the other hand, does not correspond
to the size of the primary particles. Initially the grain size is
4.5 nm and increases to 7.5 nm at 500 uC. Note that 7.5 nm is still
smaller than the diameter of the primary particles. The grain
enlargement may be caused by the crystallisation in the primary
particles and/or sintering between the particles. In the present
case, the grain growth below 500 uC would be caused by the
crystallisation in the primary particles rather than the sintering
between the particles because the crystallisation of TiO2 is able to
take place below 500 uC, while the sintering requires a higher
temperature to overcome the inter-particle diffusion barrier. The
sintering event could be observed when the temperature is equal
to 600 uC, as shown in Fig. 7. Both of the primary particles and
the secondary particles enlarge, indicating inter-particle grain
growth via necking occurs. Moreover, the grain size is nearly the
same as the primary particle size, indicating that the primary
particles are nearly single crystalline at 600 uC. A further heat
treatment (600 uC for 15 h) for grain growth or coarsening
occurs via the sintering process between the primary particles, as
shown in Fig. 5(d). The primary particles disappear and larger
grains appear on the TiO2 secondary particles when heated at
600 uC for 15 h. It is noted that the sintering mainly occurs
among primary particles, which transform to a certain layered
growth mode. The necking between the secondary particles is
hardly seen in the present study. Based on the above results,
crystal growth of TiO2 in the heat treatment process may be
illustrated in Fig. 8. TiO2 crystallites nucleate in the matrix of the
primary particles and further develop to larger grains with
increasing temperature. When the annealing temperature is high
enough, the primary particles become single crystalline. Further
2298 | RSC Adv., 2012, 2, 22942301

Influence of ethanol on the morphology of TiO2

Although alcohols, e.g. ethanol, have been widely used to dilute
TTIP for reducing the hydrolysis rate, however, alcohols affect
the solution chemistry and thus alter the self-organisation
process of TiO2 particles. For the addition of ethanol to TTIP
solution, a certain degree of the substitution for propoxy groups
by ethoxy ones is expected. The substitution is reversible. For
partially hydrolyzed polyoxotitanates, e.g. [Ti11O13](OPri)18,
[Ti11O13](OPri)13(OEt)5 could exist after reacting with ethanol.2
On the other hand, it has been shown that alcohols destabilise
the colloidal solution and enhance the rate of re-aggregation
because alcohols decrease the dielectric constant of the solvent
that correlates with the zeta potential of TiO2.6,14 The degree of
aggregation of the primary particles was found to increases with
lengthening alkyl chain of alcohols when the TiO2 powders are
re-dispersed in various alcohols, for example, the degree of
aggregation: propanol . ethanol . methanol.
The effect of ethanol on the particle morphology in the vapour
hydrolysis system can be clearly examined. As shown in SEM
images in Fig. 9, the morphology of TiO2 particles is largely

Fig. 9 SEM images of TiO2 particles synthesised by pure TIP and

ethanolTTIP (volume ratio = 5/7). The samples were annealed at 150 uC
for an hour, followed by 400 uC for another hour with a heating rate of
10 uC min21.

This journal is The Royal Society of Chemistry 2012

Published on 19 January 2012. Downloaded on 11/09/2013 07:46:52.

View Article Online

changed by introducing ethanol to modify TTIP. Increasing the

volume ratio of ethanol (TTIP : ethanol from 5 : 0 to 5 : 7)
results in a denser packing for TiO2 secondary particles, implying
that ethanol is beneficial to the coalescence of the primary
particles. The secondary particles tend to be spherical in the
presence of ethanol. The ethanol increases the surface tension
of the secondary particles (if treating the primary particles as
atoms), and causes a reduction of the surface area of the
secondary particles. This inward force could be correlated to the
inter-particle interaction for the primary particles, which pull
inwards the secondary particles. The inter-particle interaction
may be related to the surface functional groups (e.g. hydroxyl
groups) and the zeta potential of TiO2 particles. Another
possibility is that ethanol stabilized the TTIP so that the
generation of the monomers and the primary particles are so
slow that the stacking of the particles is improved, which leads to
a dense structure.
The evolution of the crystallinity and morphology of the TiO2
crystallite, the primary particles, and the secondary particles
from the hydrolysis of the ethanol-modified TTIP with respect to
annealing temperature are shown by XRD (Fig. 6(b)) and in
SEM images (Fig. 10). Variations of size of the primary particles
and the crystallites are shown in Fig. 11(a). The change in size of
the secondary particles is shown in Fig. 11(b). As-prepared TiO2
from ethanolmodified TTIP is amorphous (curve R.T. in
Fig. 6(b)). The TiO2 crystallites form at 100 uC and have a size
of about 2.6 nm, which is much smaller than those from pure
TTIP (about 4.5 nm), as shown in Fig. 11(a). This result shows
that the ethanol has a negative effect on the crystallisation of
TiO2 in the heating process. The ethanol molecules could offer
coordinative and hydrogen bonding to the anatase TiO2
surface.15 This ethanol coordination to Ti would offer a chemical
stabilising effect on embryos and/or crystallites that delay the

Fig. 11 Evolution of sizes of the TiO2 crystallite, primary particle, and

secondary particle in the annealing process. (a) Variations of the
crystallite size and the primary particle size. (b) Variation of the
secondary particle size.

Fig. 10 SEM images of TiO2 synthesised by vapour-hydrolyzing

ethanolTTIP mixture (TTIP/ethanol = 1/0.1) annealed at room
temperature (a), 500 uC (b), 600 uC (c), and 600 uC for 15 h (d).

This journal is The Royal Society of Chemistry 2012

crystallisation and crystal growth and thus the crystallite size

reduces. We have found that alcohols with longer alkyl groups
significantly suppressed the crystallization of TiO2 (results will
be published elsewhere).
The crystallite enlarges with increasing temperature from 2.6,
4.6, 6.0, 6.4, and 9.0 nm for samples annealed at 100, 200, 300,
400, and 500 uC, respectively, compared with those prepared
without ethanol (4.4, 4.8, 6.0, 6.3, and 8.1 nm for 100, 200, 300,
400, and 500 uC respectively), implying that the ethanol effect is
reduced at around 200 uC. For the primary particles prepared
from ethanol-modified TTIP, similar to those from pure TTIP,
they become nearly single crystalline at around 600 uC and
RSC Adv., 2012, 2, 22942301 | 2299

View Article Online

enlarge readily after dwelling for 15 h. For the secondary

particles, their average size has no significant change at lower
annealing temperatures (100500 uC), but largely increases as the
annealing temperature is above 500 uC. This event is similar to
those from pure TTIP; size of the secondary particles increases
due to the sintering of the primary particle. As the secondary
particles from ethanol-stabilised TTIP have densely packed
primary particles, the densification is more feasible and thus the
secondary particles enlarge faster than those from pure TTIP.

Published on 19 January 2012. Downloaded on 11/09/2013 07:46:52.

Growth model of TiO2 secondary nanoparticles

The general growth model of solgel TiO2 considers that primary
particles are the result of nucleation of supersaturated hydrolyzed monomers from hydrolysis of Ti alkoxides. In the
induction period, monomers (e.g., Ti-oxo-alkoxy) generate due
to the hydrolysis of alkoxides that increases the monomer
concentration.16 When the monomer concentration reaches a
critical level, nucleation occurs. The induction time is defined by
the visual turbidity of reaction liquid and reflects the rate at
which critical supersaturation is achieved.3 However, it was
found that nanoparticles already generate and grow during the
induction period in a dynamic light scattering study.17 So the
induction time may not precisely reflect the formation of
particles in the nanoscopic scale. On the other hand, accumulation of monomers in the induction period is not considered in
some studies. As the Ti-O-Ti oxo bonds are very strong and
condensation of hydrolyzed clusters is irreversible, Ti-oxo
clusters enlarge through the reactions or additions with other
Ti-oxo clusters.18 In the present case, Ti-oxo-alkoxy clusters
generated at the TTIP surface are thought to connect with each
other via the condensation reaction between metalOH groups
and/or metalOR groups. The coalescence of Ti-oxo-alkoxy
clusters towards denser/bigger primary particles is considered an
irreversible process. Then, the primary particles drop down to
the lower pure TTIP area due to their increasing weight. The
surface of the primary particles could be deactivated because the
hydroxyl groups on the primary particles could be converted to
non-reactive alkyl chains by reacting with TTIP molecules. In
this pure TTIP region, there is no external water molecules
provided so the irreversible condensation between the primary
particles surfaces could be effectively suppressed. Instead, the
reversible coalescence process becomes dominant in the aggregation of the primary particles. The stability of coalesced primary
particles is determined by the GibbsThompson relationship, Cr
= C0exp[(2cv)/(rkT)]. As there is no stirring in the present system,
the primary particles randomly collide with each other in the
solution due to Brownian motion and can result in a local
concentration fluctuation. In this situation, some primary
particles could coalesce to a meta-stable particle aggregate,
which could either grow larger (forward process), or dissociate
into individual primary particles (inverse process). Therefore, the
aggregate of the primary particles would have the critical size at
which the aggregate is stable. The process is somewhat like the
conventional homogeneous nucleation process of crystals, where
the number of the nuclei containing n monomers is given by the
Boltzmanns distribution, Nn = N(n)exp[2DGn/(kT)], where N(n)
is a function of n, k is Boltzmanns coefficient, T is temperature,
and DGn is the activation energy, which is a function of the
2300 | RSC Adv., 2012, 2, 22942301

surface energy and the volume free energy. If the number of

monomers (n) is much more than embryos, N(n) can be assumed
a constant (N0), Nn = N0 exp[2DGn/(kT)]. The VolmerWeber
theory predicts the nucleation rate of oversaturated vapour
condensing to liquid.19 The nucleation rate is proportional to
number of the embryos at the critical size and the condensation
rate. The condensation rate of vapour is proportional to the
surface area of an embryo (Ac) and the probability of a vapour
atom liquidized on the embryo per unit area and time (P). I =
AcPNn = AcPN0 exp[2DGn/(kT)]. The VolmerWeber theory
assumes the process to be a quasi-steady state where the atoms
are constantly introduced to the condensation system. The model
also assumes that once the nuclei forms the particle will continue
to enlarge. The predication made by the theory has been found
to be consistent with the experimental results if the atoms are
much more than the nuclei. According to the theory, the
nucleation rate increases with increasing concentration of the
vapour atoms. In a colloidal system, the monomer concentration
strongly determines the nucleation and growth. Higher monomer
concentration allows generation of the smaller nuclei generated
according to the GibbsThompson relationship. Variation of
monomer concentration also affects the size and size distribution
of crystals.20 Higher monomer concentration prevents smaller
particles from dissolution in the solution and diminishes the size
broadening process (i.e. Ostwald ripening).
Fig. 12 shows that the secondary particle size decreases with
increasing vapour input rate. The average sizes of the secondary
particles are 0.83 mm and 0.42 mm for vapour rates of 3.47 6
1026, and 8.68 6 1026 mol s21, respectively. The particle size
distribution of the samples also decreases from 73.9 to 42.3%
with increasing vapour input rate. Considering the smallest
stable aggregate of the primary particles to be the nuclei of the
secondary particles, the concentration of the primary particles
can alter the size of the secondary particles according the above
model. In the water vapour hydrolysis system, the vapour input
leads to the hydrolysis of TTIP at the interface that continuously
supplies the hydrolyzed molecules and the primary particles into
the TTIP solution, where the quasi-steady state is able to
establish if the generation and consumption of the primary
particles reach a dynamic equilibrium situation. This process
resembles the model of crystallisation. The addition of the
primary particles onto the secondary particles may be based on

Fig. 12 SEM images of TiO2 secondary particles produced by hydrolyzing pure TTIP with vapour input rates of 3.47 6 1026 mol s21 (a) and
8.68 6 1026 mol s21 (b).

This journal is The Royal Society of Chemistry 2012

View Article Online

the reductions of the surface energy of the secondary particles.

The secondary particle size therefore decreases with increasing
the water vapour input rate.

Published on 19 January 2012. Downloaded on 11/09/2013 07:46:52.

Coalescence of secondary particles

Since the generation of the TiO2 secondary particles from the
primary particles is similar to the material crystallization process,
it is worth to check if there is a process similar to Ostwald
ripening occurring in the crystallization process. Fig. 13 shows
SEM images of the secondary particles (vapour rate = 5.21 6
1026 mol s21, TTIP/ethanol = 5/1) dried at 400 uC for 1 h, at
which no sintering event occurs, proved in the above data.
The secondary particles appear to combine with each other
(Fig. 13(a)). The junction between the particles clearly shows
that the combination is not caused by the sintering (necking)
between the secondary particles (Fig. 13(b)) and appears to be
the coalescence of the secondary particles. The coalescence
would not be caused by the evaporation of solvents in the
separation process of products because the products formed in
the system were a solid precipitate in the bottom of the reaction
vessel rather than a colloidal solution. Presumably, the
combination of the secondary particles is caused by the
coalescence between secondary particles in the solution. This
event is similar to Ostwald ripening based on the difference in the
solubility of larger and smaller crystals. The driving force of
combination of the secondary particles in the present system
would be relating to the surface functional groups and the zetapotential of the secondary particles, which is under investigation.

Fig. 13 Association of the secondary particles (Ostwald ripening)

before the coarsening of grains takes place. (a) A secondary particle
merged with two other smaller secondary particles. (b) The cross section
of the junction of a merged secondary particle.

This journal is The Royal Society of Chemistry 2012

Conclusion
TiO2 was prepared in a self-organization process with an ultraslow
hydrolysis rate via a vapour hydrolysis system without mixing and
in a normal solgel process for reference. Experimental results
from both methods suggest that solgel TiO2 were secondary
particles composed of primary particles, which were amorphous
before an annealing process was performed. The crystalline
anatase primary particles were generated at 100 uC and became
single crystalline at around 600 uC. The ethanol effect on solgel
TiO2 was proved to aid aggregation and packing of TiO2 primary
particles. This phenomenon leads to a size enlargement of the
secondary particles when the post annealing temperature is above
500 uC. A plausible model considering that TiO2 secondary
particles are the result of the nucleation of the primary particles is
attempted to qualitatively describe to the growth of solgel TiO2.
Experimental results show that the secondary particles size
reduces with increasing vapour input rate, which is consistent
with the prediction of the growth model.

References
1 P. Periyat, F. Laffir, S. A. M. Tofail and E. Magner, RSC Adv., 2011, 1, 1794.
2 (a) V. W. Day, T. A. Eberspacher, W. G. Klemperer and C. W. Park, J.
Am. Chem. Soc., 1993, 115, 8469; (b) G. Fornasieri, L. Rozes, S. L.
Calve, B. Alonso, D. Massiot, M. N. Rager, M. Evain, K. Boubekeur
and C. Sanchez, J. Am. Chem. Soc., 2005, 127, 4869; (c) A. Senouci, M.
Yaakoub, C. Huguenard and M. Henry, J. Mater. Chem., 2004, 14,
3215; (d) J. V. Barkley, J. C. Cannadine, I. Hannaford, M. M. Harding,
A. Steiner, J. Tallon and R. Whyman, Chem. Commun., 1997, 1653.
3 (a) E. A. Barringer and H. K. Bowen, Langmuir, 1985, 1, 414; (b)
E. A. Barringer and H. K. Bowen, Langmuir, 1985, 1, 420; (c) J. H.
Jean and T. A. Ring, Langmuir, 1986, 2, 251; (d) J. L. Look and C. F.
Zukoski, J. Am. Ceram. Soc., 1992, 75, 1587; (e) J. L. Look and C. F.
Zukoski, J. Am. Ceram. Soc., 1995, 78, 21.
4 Q. Xu, M. J. Gieselmann and M. A. Anderson, Polym. Mater. Sci.
Eng., 1989, 61, 889.
5 (a) H. S. Chen, R. V. Kumar and B. A. Glowacki, Mater. Chem.
Phys., 2010, 122, 305; (b) H. S. Chen, R. V. Kumar and B. A.
Glowacki, J. Sol-Gel Sci. Technol., 2009, 51, 102.
6 H. K. Park, D. K. Kim and C. H. Kim, J. Am. Ceram. Soc., 1997, 80, 743.
7 D. Vorkapic and T. Matsoukas, J. Am. Ceram. Soc., 1998, 81, 2815.
8 D. C. Hague and M. J. Mayo, Nanostruct. Mater., 1993, 3, 61.
9 G. Oskam, Z. Hu, R. L. Penn, N. Pesika and P. C. Searson, Phys.
Rev. E, 2002, 66, 011403.
10 R. Azouani, A. Soloviev, M. Benmami, K. Chhor, J. F. Bocquet and
A. Kanaev, J. Phys. Chem. C, 2007, 111, 16243.
11 J. Livage, M. Henry and C. Sanchez, Prog. Solid State Chem., 1988, 18, 259.
12 (a) L. Rozes, N. Steunou, G. Fornasieri and C. Sanchez, Monatsh.
Chem., 2006, 137, 501; (b) L. Rozes and C. Sanchez, Chem. Soc. Rev.,
2011, 40, 1006.
13 J. Blanchard, F. Ribot, C. Sanchez, P. Bellot and A. Trokiner, J.
Non-Cryst. Solids, 2000, 265, 83.
14 Y. T. Moon, H. K. Park, D. K. Kim and C. H. Kim, J. Am. Ceram.
Soc., 1995, 78, 2690.
15 (a) M. L. Shepotko and A. A. Davydov, Theor. Exp. Chem., 1991, 27,
210; (b) S. Pilkenton, S. J. Hwang and D. Raftery, J. Phys. Chem. B,
1999, 103, 11152.
16 S. Tieng, R. Azouani, K. Chhor and A. Kanaev, J. Phys. Chem.C,
2011, 115, 5244.
17 A. Soloviev, D. Ivanov, R. Tufeu and A. V. Kanaev, J. Mater. Sci.
Lett., 2001, 20, 905.
18 M. Kallala, C. Sanchez and B. Cabane, Phys. Rev. E, 1993, 48, 3642.
19 M. Volmer and A. Z. Weber, Phys. Chem., 1926, 119, 227.
20 (a) X. Peng, J. Wickham and A. P. Alivisatos, J. Am. Chem. Soc.,
1998, 120, 10937; (b) Y. Chen, E. Johnson and X. Peng, J. Am. Chem.
Soc., 2007, 129, 10937; (c) H. S. Chen and R. V. Kumar, Cryst.
Growth Des., 2009, 9, 5343; (d) H. S. Chen and R. V. Kumar, J. Phys.
Chem. C, 2009, 113, 31; (e) H. S. Chen and R. V. Kumar, J. Phys.
Chem. C, 2009, 113, 12236.

RSC Adv., 2012, 2, 22942301 | 2301