Nanosilica 1813

Mohammad Edrissi Research Article

Meysam Soleymani
Morteza Adinehnia Synthesis of Silica Nanoparticles by
Faculty of Chemical Ultrasound-Assisted Sol-Gel Method:
Engineering, Amirkabir
University of Technology, Optimized by Taguchi Robust Design
Tehran, Iran.

Silica nanoparticles were prepared by ultrasound-assisted and conventional sol-

gel method. The synthesis procedures were designed and optimized by the Tagu-
chi experimental design method. Molar concentrations of TEOS, H2O, NH4OH,
and reaction temperature were chosen as main factors. The results showed that
the molar concentration of ammonia is the main factor which affects the particle
size of the silica nanoparticles. The chemical structure, size, and morphology of
the product were investigated by X-ray diffraction, Fourier transform infrared
spectroscopy, laser light scattering, and scanning electron microscopy. By the op-
timum conditions of the ultrasound-assisted sol-gel method, silica nanoparticles
with an average particle size of 13 nm were prepared.

Keywords: Nanosilica, Taguchi design, Synthesis, Sol-gel

Received: April 14, 2011; revised: August 11, 2011; accepted: August 15, 2011
DOI: 10.1002/ceat.201100195

1 Introduction
Silica (SiO2) is one of the most abundant oxide materials in
the earth’s crust. It has been extensively used as electrical insu-
lator, thermal insulator, filters, binder, and additive in many
product formulations. Size and particle size distribution of sili-
ca particles highly affect the properties and quality of silica [1].
Nanosilica was successfully synthesized by various methods,
including the sol-gel method, vapor-phase reaction, and the
thermal decomposition method [2–5]. The sol-gel method
presents many processing merits, due to facility, consistency,
and cheapness, and obtained materials which have good purity
and homogeneity [6, 7]. In the synthesis process of nanosilica
by sol-gel method, the particle size, the mean pore size, and
the particle size distribution of the product can be controlled
by several parameters, such as the molar ratio of water to pre-
cursor, type of catalyst, and gelation and drying temperatures.
The sol-gel method has been used by many researchers for the
synthesis of nanosilica with spherical shape. Stober et al. [8]
synthesized monodispersed silica particles by hydrolysis and
polymerization of tetraalkoxysiliane (TEOS) in mixed solutions
of ammonia, alcohol, and water. The mechanisms are as follows:
Si(OC2H5)4 + 4 H2O → Si(OH)4 + 4 C2H5OH (1)
Si(OH)4 → SiO2 + 2 H2O (2)
– use of mathematical and statistical methods, was introduced in
Correspondence: Prof. M. Edrissi (Edrisi@aut.ac.ir), Faculty of
Chemical Engineering, Amirkabir University of Technology, Hafez
Ave., P. O. Box 15875-4413, Tehran, Iran.
Since the study by Stober et al., many researchers have been
studying the effects of various variables on Stober’s reaction,
such as concentrations of TEOS, ammonia, and water, and reac-
tion temperature. The effect of different molar ratios of reactants
on the structure and properties of silica nanoparticles have been
studied [9]. It had been shown that to synthesize silica with a
narrow particle size distribution, the molar ratio of ethanol
should be small [10]. Stober et al. studied the influence of differ-
ent solvents on the size of silica particles [8]. Bogush et al. stud-
ied the ranges of reagent concentrations which result in the pre-
cipitation of monodisperse silica particles from ethanol
solutions containing water, ammonia, and TEOS [5]. Park et al.
prepared monodispersed silica particles with sizes ranging from
10 to 350 nm by dissolving TEOS in ethanol in a semi-batch pro-
cess [10]. Janet et al. prepared silica gels with different porosity
and surface areas through the sol-gel method using TEOS and
polyacrylic acid (PAA) in acidic media [11]. Ryu has also ob-
tained amorphous silica through the oxidation of silicon [12].
Santos and Vasconcelos [13] prepared porous silica glass via sol-
gel process using tetramethylorthosilicate (TMOS), HNO3, and
HF as precursor and catalysts, respectively. It is clear that the var-
ious parameters can affect the properties of silica nanoparticles
prepared by sol-gel method. The comprehensive analysis of all
parameters and variables, and interaction between them using
conventional experimental method is time-consuming. Hence,
the Taguchi experimental design method [14–17], which makes
this study.
Ultrasound irradiation has recently been employed in the
synthesis process of nanomaterials which results in unusual

Chem. Eng. Technol. 2011, 34, No. 11, 1813–1819 © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
1814 M. Edrissi et al.

properties of the product [18–23]. The ultrasound irradiation Table 1. Assigned factors and levels in this study.
improves solid-liquid mass transfer in the reaction solution by
continuous formation, growth, and implosive collapse of Parameter Levels
bubbles in the liquid. This phenomenon changes physico- Low (1) Medium (2) High (3)
chemical properties within the synthesis process. Due to the
A Molar concentration of TEOS 0.4 0.6 0.8
advantages associated with the use of ultrasound irradiation,
[mol L–1]
ultrasound irradiation in the sol-gel method (Stober method)
was applied in this study to improve the properties of obtained B Molar concentration of H2O 2.0 2.5 3.2
products. [mol L–1]
The aims of this study are: (1) comparison of the ultra- C Molar concentration of NH4OH 0.16 0.28 0.4
sound-assisted and conventional Stober method for the syn- [mol L–1]
thesis of silica nanoparticles, (2) optimization of synthesis
D Reaction temperature [°C] 25 45 60
methods employed to produce the silica nanoparticles with
lowest particle size, and (3) investigation of the effect of several
factors on the particle size of silica nanoparticles. the synthesis process is the mean particle size of silica in each
experiment.

2 Experimental
2.3 Synthesis
2.1 Materials and Instruments
Silica nanoparticles were synthesized according to the Stober
All chemicals were reagent grade, manufactured by MERCK. method. The reaction entails the hydrolysis and polymeriza-
Distilled deionized water was used in all experiments. The tion of tetraethyl orthosilicate in an aqueous solution of etha-
equipment used for the characterization of synthesized prod- nol, water, and ammonia. Reactants were divided into the two
ucts were X-ray powder diffraction (XRD) with a CuKa source initial solutions: (I) TEOS, methanol, and (II) NH4OH, H2O,
(Shimadzu XD3A, Japan), scanning electron microscope methanol.
(SEM), LEO model 1455VP Carl Zeiss SMT AG (Jena, Ger- The concentrations of reactants in both solutions were ad-
many), laser light scattering (LLS), SEMATECH WYATI QELS, justed according to the Taguchi experimental design method
Fourier transform infrared spectrometer (FTIR), Bruker model (Tab. 2). After mixing two solutions, the resultant solution was
Equinox 55 Ls 101, and Centrifuge KN 70 Kubato. treated separately with two different ways. In the first way, the
solution was immediately sonicated at different temperatures
(according to experimental design) for 30 min, using an ultra-
2.2 Experimental Design sonic generator with the output power set to 200 W with a fre-
quency of 20 kHz. After sonication, to complete the reaction,
In general, the Taguchi experimental design method employs the solution was maintained at the reaction temperature for
orthogonal arrays (OAs) to minimize the number of experi- 15 min.
ments in analyzing all effective variables on the response. It
utilizes a signal-to-noise (S/N) ratio to analyze the experimen-
tal data to obtain the optimum conditions for performing an
experiment. In the formation of silica nanoparticles by Stober Table 2. Average particle size and S/N ratio of silica nanoparti-
method, there are four main factors which affect the particle cles synthesized by two methods.
size of the product. These factors are the molar concentration Run A B C D Ultrasound-assisted Conventional method
of TEOS, H2O, NH4OH, and reaction temperature. The effects method
of the different solvents on the reaction rate and particle size
of silica in the Stober method have been investigated [8]. In Mean parti- S/N ratio Mean parti- S/N ratio
spite of that, before the experiments, four kinds of solvents cle size [nm] [dB] cle size [nm] [dB]
(methanol, ethanol, propanol, and acetone) were selected and 1 1 1 1 1 18.1 –25.15 23.2 –27.31
the effects of these solvents on the size of the silica particles
2 1 2 2 2 27.8 –28.88 42.2 –32.50
were examined. It was found that with increasing the polarity
of a solvent (methanol > ethanol > propanol > acetone), the 3 1 3 3 3 54.3 –34.70 72.3 –37.18
particle size of silica decreases. These results are consistent
4 2 1 2 3 21.2 –26.53 49.4 –33.87
with previous studies [8]. Therefore, methanol was chosen as
an effective solvent in all experiments. In this study, experi- 5 2 2 3 1 60.4 –35.62 85.3 –38.61
mental design was performed according to the L9 (34) Taguchi 6 2 3 1 2 30.0 –29.54 42.0 –32.46
orthogonal design [25] for optimizing the procedure to
synthesize nano silica particles with low particle size. The four 7 3 1 3 2 50.0 –33.98 56.9 –35.10
factors and their levels are summarized in Tab. 1. The numbers 8 3 2 1 3 27.5 –28.78 55.4 –34.87
1, 2, and 3 in Tab. 1 are related to the first, second, and third
9 3 3 2 1 75.6 –37.57 96.2 –39.66
levels of a factor, respectively. The interest output response of

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 Nanosilica 1815

In the second way, the solution was mixed continuously by ating the quality of the product. In the case that the smaller
magnetic stirrer for 24 h at certain temperatures similar to characteristic is better, the S/N ratio is defined as [15, 16]:
those in the first way. In each two ways, depending on the dif- !
1X n
2
ferent concentration of the reactants, the condensation reac- S/N = –10 log Y (3)
n iˆ1 i
tion of the supersaturated silicic acid began after various times.
This reaction is visible by increasing the opalescence of the so- When the larger characteristic is better, the S/N is calculated
lution after the hydrolysis reaction. by Eq. (4):
!
1X n
1
S/N = –10 log (4)
3 Results and Discussions n iˆ1 Yi2
and, when the nominal characteristic is the best, the S/N is cal-
3.1 Determination of Optimum Conditions culated by Eq. (5):
 2
l
To identify the optimum conditions and most effective factors S/N = 10 log (5)
on the particle size of silica nanoparticles, the Taguchi experi- r2
mental design method was employed in this study. The struc- where:
ture of an orthogonal array of the Taguchi experimental design 1X n

method is shown in Tab. 2. The particle size distribution of l2 ˆ Y2 (6†

synthesized silica nanoparticles by two methods was measured
by LLS test. The results are shown in Figs. 1 and 2. The average
diameter of silica nanoparticles in each experiment was calcu-
lated from the size distribution curve using RTG correlator
software. Results are presented in Tab. 2 and Fig. 3. The lowest
average diameter belongs to sample 1 for the ultrasound-as-
sisted procedure (mean diameter 18.1 nm) and conventional
Stober method (mean diameter 23.2 nm). As can be seen in
Fig. 3, ultrasound irradiation decreases the particle size of na-
nosilica effectively.
Comparison of the size of silica nanoparticles obtained with
the two methods reveals that the ultrasound irradiation has an
important effect on the reduction of particle size (Tab. 2). In
the Taguchi method, the terms signal and noise represent the
desirable and undesirable values for the output characteristic,
respectively. The signal-to-noise ratio (S/N) is used for evalu-
n iˆ1 i
1 X
n
r2 ˆ Yi l †n (7†
n 1 iˆ1
In Eqs. (3)–(5), Yi is the measured value of each response
and n is the replication number of the experiment. The units
of S/N ratios are decibel (dB). To obtain optimum conditions,
Eq. (3) (smaller the better) was used for the preparation of
smaller particle size. Tab. 2 shows the S/N values for particle
size of silica obtained by two methods.
Since Taguchi uses an orthogonal array, it is possible to cal-
culate the effect of each factor at different levels. For example,
the mean S/N ratio for the TEOS molar concentration value at
levels 1, 2, and 3 can be calculated by averaging the S/N ratios
for the experiments 1–3, 4–6, and 7–9, respectively. The mean
S/N ratio for each level of the other parameters can be com-

Figure 1. Particle size distributions of synthesized samples by the conventional method.

Chem. Eng. Technol. 2011, 34, No. 11, 1813–1819 © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
1816 M. Edrissi et al.

Figure 2. Particle size distributions of synthesized samples by the ultrasound-assisted Stober method.

puted in a similar manner. The S/N responses for the particle must be in the stoichiometric value in the solution. On the
size of silica synthesized by ultrasound-assisted and conven- other hand, the ability of H2O in OH– ion generation is less
tional Stober method are summarized in Tabs. 3 and 4, respec-
tively. Table 3. S/N responses table for silica particle size obtained by
As can be seen in Tab. 3, the highest maximum-minimum the ultrasound-assisted method.
value belongs to the ammonia concentration. Therefore, it can
be concluded that ammonia concentration is the most impor- Effect Parameter Mean S/N ratio
tant factor which affects the particle size of silica nanoparticles. Level 1 Level 2 Level 3 Maximum-
Consequently, the particle size of silica nanoparticles was minimum
mainly affected by the concentrations of H2O and TEOS.
These results can be explained as follows: the mechanism of A Concentration of TEOS –29.57 –30.56 –33.44 3.87
[mol L–1]
hydrolysis and polycondensation are nucleophilic reactions
and the OH– ion in the solution is the nucleophilic reagent. B Concentration of H2O –28.55 –31.09 –33.93 5.38
Therefore, increasing the concentration of OH– ions due to in- [mol L–1]
creasing ammonia in the solution, increases the rate of reac- C Concentration of NH4OH –27.82 –30.99 –34.77 6.95
tion leading to a reduction of silica particles size. The effect of [mol L–1]
H2O in the synthesis reaction of nanosilica is the same as am-
monia, but H2O is the consumed reactant in the reaction and D Reaction temperature [°C] –32.78 –30.8 –30.0 2.78

Table 4. S/N responses table for silica particle size obtained by

the conventional method.

Effect Parameter Mean S/N ratio

Level 1 Level 2 Level 3 Maximum-
minimum

A Concentration of TEOS –32.33 –34.98 –36.54 4.21

[mol L–1]
B Concentration of H2O –32.09 –35.33 –36.43 4.34
[mol L–1]
C Concentration of NH4OH –31.55 –33.82 –36.89 5.34
[mol L–1]
Figure 3. Particle size reduction: Comparison of the ultrasound-
assisted with conventional Stober method. D Reaction temperature [°C] –35.19 –33.33 –35.30 1.97

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 Nanosilica 1817

than ammonia. Thus, the effect of H2O on the particle size of
silica is less than ammonia.
Also, the effect of TEOS concentration can be described as
follows: with increasing TEOS concentration, the rates of both
hydrolysis and condensation reactions increase [25]. As a re-
sult, the amount of intermediate [Si(OC2H5)4–X(OH)X] will
be rapidly increased due to the high hydrolysis reaction. When
the concentration of intermediate reaches the supersaturation
region, the consumption rate of it through the condensation
reaction is also relatively fast [26], which probably reduces the
period of nucleation. Thus, the total number of nuclei formed
will be fewer in number and the final particle size of synthetic
silica colloids will be relatively larger. Therefore, the low level
of TEOS concentration is suitable for producing smaller parti-
cle sizes of silica.
Figs. 4 and 5 show the S/N response graphs for particle size
obtained by ultrasound-assisted procedure and conventional
Stober method. Based on the S/N response graphs shown in
Figs. 4 and 5, in the ultrasound-assisted method, the optimum
level of each parameter is A1B1C1D3 (A, B, and C at level 1,
and D at level 3), whereas, in the conventional Stober method,
it is A1B1C1D2. As can be observed, in the conventional meth-
od, the medium temperature is desirable but, in the ultra-
sound-assisted method, the higher temperature is desirable
and, with increasing the reaction temperature, the rate of reac-
tion increases and silica particle size reduces.
After identification of the optimum level of each factor, the
lowest particle size of silica nanoparticles (improved character-
istic) can be predicted by the following equation [14]:
    X n     
S S S S
ˆ ‡ (8†
N predicted N m N i N m
iˆ1
where [S/N]m and [S/N]i are the total mean S/N ratio and the
mean S/N ratio at the optimum level, respectively; n is the
number of factors that influence the particle size of the silica.
The calculated value of [S/N]m for the ultrasound-assisted
method is –31.19. Also, the values of [S/N]i for A1, B1, C1,
and D3 are –29.57, –28.55, –27.82, and –30.0, respectively
(Tab. 3). With substitution of the values obtained for [S/N]m
and [S/N]i in Eq. (8), [S/N]predicted can be calculated as fol-
lows:
[S/N]predicted = –31.19 + [(–29.57 + 31.19) +
(–28.55 + 31.19) + (–27.82 + 31.19) + (–30.0 + 31.19)] (9)
To estimate the particle size of silica nanoparticles at opti-
mum conditions, the predicted S/N ratio obtained from
Eq. (9), i.e., –22.37, is substituted into Eq. (3). Therefore,
Eq. (3) can be written as –22.37 = –10 log (Y2). By solving
Eq. (3), the predicted particle size of silica nanoparticles under
optimum conditions was obtained as 13.13 nm. In a similar
manner, the silica particle size under optimum conditions for
the conventional Stober method was obtained as 18.77 nm.
Tab. 5 shows the comparison of the predicted particle size of
silica by the Taguchi experimental design with the experimen-
tal results obtained by LLS under optimum conditions. As can
be observed, the predicted values of particle sizes are in close
agreement with experimental data.

Table 5. Results of confirmation experiments for the particle size

of silica nanoparticles by the LLS method.

Ultrasound-assisted method Conventional method

Level Particle S/N Level Particle S/N
size ratio size ratio
Figure 4. The mean effects plot for the signal-to-noise ratio for [nm] [dB] [nm] [dB]
silica particle size obtained by the ultrasound-assisted method.
Prediction A1B1C1D3 13.13 –22.37 A1B1C1D2 18.77 –25.47
Experiment A1B1C1D3 13.3 –22.47 A1B1C1D2 19.1 –25.62

3.2 Characterization of Silica Nanoparticles

The powder X-ray diffraction pattern of nanosilica obtained

Figure 5. The mean effects plot for the signal-to-noise ratio for
silica particle size obtained by the conventional method.
by ultrasound-assisted Stober method according to optimum
conditions is shown in Fig. 6. The XRD pattern of nanosilica
with a strong broad peak centered at an angle, 2h, of 23° con-
firms the amorphous nature of silica. Using Scherrer’s formula
[28], the particle size of nanosilica is found to be 13.1 nm,
which is comparable with previous results. The SEM image
and particle size distribution of the silica nanoparticles pre-
pared under optimum conditions using the ultrasound-
assisted method are shown in Figs. 7a) and 7b), respectively.

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1818
Figure 6. XRD pattern for the silica nanoparticles obtained by
the ultrasound-assisted method.
Figure 7. a) SEM photograph and b) particle size distribution of
the silica nanoparticles obtained under optimum conditions,
using the ultrasound-assisted Stober method.
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M. Edrissi et al.
Fig. 7 shows that silica nanoparticles with an average particle
size of about 13 nm and narrow particle size distribution are
synthesized through the optimized ultrasound-assisted Stober
method. Also, the obtained particles are almost spherical in
shape with good dispersibility.
Fourier transform infrared spectroscopy (FTIR) was used to
identify vibration modes of different functional groups in the
functionalized silica and the result is shown in Fig. 8. As can
be observed, the three main absorption peaks appear at 466.25,
801.39, and 1095.90 cm–1, which are related to rocking vibra-
tions of the O-Si-O band [27], bending vibrations of the Si-O
band, and antisymmetric stretching vibrations of the Si-O-Si
band, respectively [29]. Also, the absorption peak at
3460.20 cm–1 is due to the absorption of water and the peak at
1629.78 cm–1 belongs to the OH bending vibration.
4 Conclusion
The Taguchi experimental design method was used to optimize
the synthesis procedure of silica nanoparticles using the ultra-
sound-assisted and conventional sol-gel method. Molar con-
centrations of TEOS, H2O, NH4OH, and reaction temperature
were selected as effective factors on the particle size of silica. It
was found that the molar concentration of ammonia is the
most effective factor on the size of silica nanoparticles. The
chemical structure, particle size, and morphology of the prod-
uct were investigated by XRD, FTIR, LLS, and SEM analyses.
Also, the results showed that the use of ultrasound irradiation
in the synthesis process can reduce the particle size of silica. By
optimum conditions of the ultrasound-assisted sol-gel meth-
od, silica nanoparticles with an average particle size of about
13 nm with narrow particle size distribution were prepared
and these results were in good agreement with estimated data
obtained by the Taguchi experimental design method.
The authors have declared no conflict of interest.
Figure 8. The FT-IR spectrum for the silica nanoparti-
cles obtained by the ultrasound-assisted Stober meth-
od.
Chem. Eng. Technol. 2011, 34, No. 11, 1813–1819

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