J Sol-Gel Sci Technol (2010) 53:667–672
DOI 10.1007/s10971-010-2148-2
ORIGINAL PAPER
Silica nanoparticles obtained by microwave assisted sol–gel
process: multivariate analysis of the size and conversion
dependence
E. Mily • A. González • J. J. Iruin • L. Irusta •
M. J. Fernández-Berridi
Received: 14 September 2009 / Accepted: 1 January 2010 / Published online: 12 January 2010
Ó Springer Science+Business Media, LLC 2010
Abstract Silica nanoparticles were synthesized by the
sol–gel method in alcoholic solution under microwave
irradiation in the presence of an ammonium catalyst. The
effect of the reaction time, the reaction temperature, water
and ammonium concentrations on particle size and con-
version (measured by light scattering and FTIR respec-
tively) were analyzed using multivariate analysis. The
results showed that water and ammonium concentrations
are the main factors that control the particle size and the
conversion. Both properties increase with water and
ammonium concentration. Moreover, comparing with the
results obtained using traditional heating, the microwave
heating gave rise to higher reaction rate and narrower
dispersion of the particle size.
Keywords Silica
Microwave
Nanoparticles

Multivariate analysis
1 Introduction
Monodispersed spherical silica nanoparticles can be suc-
cessfully obtained by means of hydrolysis of alkoxysilanes
and subsequent condensation. In the method, originally
developed by Stöber et al. [1, 2], aqueous alcoholic solutions
of the silicon alkoxide at high pH are used. Since the publi-
cation of that work, the ‘‘Stöber’’ method has been exhaus-
tively explored by different authors [3–5]. In most cases the
E. Mily
A. González
J. J. Iruin
L. Irusta (&)

M. J. Fernández-Berridi
Department of Polymer Science and Technology and Institute
for Polymer Materials (POLYMAT), University of the Basque
Country, P.O. Box 1072, 20080 San Sebastian, Spain
e-mail: lourdes.irusta@ehu.es
silicon alkoxide used has been tetraethyl orthosilicate
(TEOS). The most important parameters in preparing silica
particles seem to be water and ammonia concentrations.
Thus, the silica particle size increases as the concentrations
of water and ammonia increase. Silica nanoparticles can also
be obtained under acidic conditions [6]. The rate of hydro-
lysis and condensation of TEOS is not the same under acidic
or alkaline conditions and therefore the formation mecha-
nism of these two species of silica materials is different.
The use of microwaves as an energy source for chemical
reactions and processes has been extensively investigated
during recent years [7–9]. Microwave-assisted synthesis is
generally much faster, cleaner and more economical than
the conventional methods. The exact nature of microwave
interaction with reactants during the synthesis of materials
is somewhat unclear and speculative. However, energy
transfer from the microwaves to the material is believed to
occur either through resonance or relaxation, which results
in rapid heating. Interestingly, microwave energy sources
that have been previously used for cooking have also been
used for research purposes. The control and setting of
reaction parameters of these ovens is problematic, since the
reaction control is only performed by energy input. In
recent years, specialized systems that are adapted to
chemical synthesis have extended the possibilities of
microwave-assisted reaction engineering.
Recently, some works have been published concerning
the production of spherical silica particles using the
microwave-assisted sol–gel methods [10–12]. These papers
have shown that under microwave radiation the reaction
time is extraordinarily short compared with conventional
methods. However, to the best of our knowledge, there has
been no report of the study of the different variables in the
conversion and particle size in the microwave-assisted
silica synthesis.
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In this work we studied the effect of 4 variables (ammonia
concentration, water concentration, reaction temperature
and reaction time) on the particle size and conversion
obtained in the microwave assisted silica synthesis. A full
factorial design with two levels of all the variables was used
and the analysis of variance (ANOVA) was used to interpret
the data. The mean diameter of the particles and the con-
version percentages were used as response dependent vari-
ables in this study. The obtained data were compared with
that obtained by using a conventional heating method.
2 Experimental
process was carried out by using the MARS5X (CEM
corporation) microwave system. The maximum power of
the microwave was selected to 800 W and the power was
automatically varied from 0 to 100% in order to reach the
desired temperature (Table 1) in 5 min. The microwave
frequency was 2.45 GHz. The reactions were carried out in
sealed Teflon vessels (GreenChem, CEM corporation)
under magnetic stirring. All the experiments were carried
out introducing 1 vessel separately in the microwave.
In order to compare the methods, the reaction in the
centre point (40 °C, 10 min, Table 1) was performed in a
single neck flask equipped with a reflux condenser heated
on a conventional thermostatic oil bath.

2.1 Materials 2.3 Infrared measurements

Tetraethyl orthosilicate (TEOS) GC grade and Ammonia
sol (28–30% NH3 basis) ACS reagent were purchased from
Sigma-Aldrich. Ethanol absolute was purchased from
Panreac. All products were used as received. Water was
doubly distilled and deionized (Milli-Q, 18 MXcm).
2.2 Synthesis of silica
Silica was synthesized by sol–gel method using TEOS in
ethanol under microwave irradiation in the presence of
water and ammonium catalyst.
A total of 3 mL of TEOS, 50 mL of ethanol and the
required amounts of water and ammonia (Table 1) were
introduced in the reaction vessel. The microwave heating
Infrared spectra of the obtained dispersions were carried
out using a liquid cell with KRS5 windows with a 0.1 mm
path length (Spectra Tech). The spectra were recorded
immediately after removing the reaction vessel from the
microwave in a Nicolet 6700 FTIR (Thermo-Fisher Cor-
poration) at a resolution of 2 cm-1. A minimum of 32
scans were signal averaged. Absorbance of the infrared
band was measured by means of a program included in the
spectrometer computer software.
2.4 Particle diameter measurements
Dynamic Light Scattering measurements (DLS) were used
to determine the diameters of the particles, D, using a

Table 1 Particle size and conversion of the experiments described

mol water mol ammonia
Experiment T (8C) Time (min) mol TEOS mol TEOS D (nm) rn-1 p rn-1

1 (- - - -) 30 2 7.9 1.19 27 10 0.06 0.05

2 (? - - -) 50 2 7.9 1.19 31 12 0.07 0.05
3 (- ? - -) 30 18 7.9 1.19 32 15 0.04 0.05
4 (? ? - -) 50 18 7.9 1.19 26 11 0.10 0.11
5 (- - ? -) 30 2 18.2 1.19 67 19 0.15 0.04
6 (? - ? -) 50 2 18.2 1.19 73 21 0.28 0.04
7 (- ? ? -) 30 18 18.2 1.19 62 14 0.28 0.07
8 (? ? ? -) 50 18 18.2 1.19 79 28 0.40 0.02
9 (- - - ?) 30 2 7.9 3.55 68 16 0.08 0.01
10 (? - - ?) 50 2 7.9 3.55 52 26 0.23 0.06
11 (- ? - ?) 30 18 7.9 3.55 56 16 0.17 0.06
12 (? ? - ?) 50 18 7.9 3.55 46 82 0.28 0.09
13 (- - ? ?) 30 2 18.2 3.55 223 31 0.31 0.12
14 (? - ? ?) 50 2 18.2 3.55 126 28 0.35 0.10
15 (- ? ? ?) 30 18 18.2 3.55 208 31 0.51 0.03
16 (? ? ? ?) 50 18 18.2 3.55 138 21 0.68 0.02
Centre (0 0 0 0) 40 10 13.0 2.37 63 14 0.32 0.06
* Particle size (D) was determined by DLS methods

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Coutier N4 Nanosizer at room temperature. The diameter
of the particles was measured 24 h after removing the
reaction vessel from the microwave. All the samples were
measured in ethanol 3 times and the final value was an
average of all of them. The samples were diluted before
measuring to avoid multiple light scattering.
2.5 Atomic force microscopy measurements
Atomic Force Microscopy (AFM, Digital Instruments
Nanoscope IV) was used to compare the morphology of the
particles obtained using microwave or conventional heat-
ing. AFM images were obtained in most of the samples
after a minimum of 24 h after removing the reaction vessel
from the microwave. The samples were prepared by casting
the dispersions over an aluminum dish. All the images were
obtained in air using a scan size of 5 lm.
2.6 Data analysis
The data analysis was performed using the software JMP
8.0.1 statistical discovery from SAS.
3 Results and discussion
According to literature reports on silica synthesis with
application of traditional heating [3], the reaction temper-
ature, the reaction time, and the water and ammonia con-
centrations were selected as the main variables. The higher
and lower levels were selected after some preliminary
experiments. Table 2 lists the variables chosen and the
values for the high and low levels and the centre points.
A full factorial design with two levels of the 4 selected
variables requires a total of 24 = 16 experiments and the
experiment of the centre point. All the experiments were
performed twice and the centre point experiment was
repeated four times. Table 1 summarizes the performed
experiments.
All the experiments were carried out using 3 mL of
TEOS and 50 mL of ethanol. It must be taken into account
that the water implied in variable X3 is the sum of the added
water and the water contained in the ammonia solution.
The diameter of the particles was measured 24 h after
removing the reaction vessel from the microwave oven.
The results obtained are shown in Table 1.
In order to check the stability of the dispersion, in some
of the samples the diameter was measured 48 h after
removing the vessels from the microwave and remained
constant. In addition no precipitation was observed for a
month. It must be pointed out that the diameter of the
particles measured after 24 h of removing the samples of
the microwave might not fit with the one that would be
obtained if the measurements had been done immediately
after removing the samples. Unfortunately, because of the
location of the DLS equipment it was not possible to
measure the diameter immediately after removing the
samples from the microwave.
The reaction conversion was calculated immediately after
removing the vessels from the microwave using infrared
spectroscopy [13–15]. Figure 1 shows the infrared spectra of
TEOS and ethanol. Absorptions related to the alkoxysilane
groups are &1167 cm-1 (Si–O–C rocking), &1100 cm-1
(ma(C–C ? C–O)), &960 cm-1 (d(CCH3)) and &790 cm-1
(m(Si–O ? C–O)). The bands at 1100 and 790 cm-1 over-
lap with the bands of ethanol (&1050 cm-1and 882 cm-1
(mC–O ? C–C)), especially if we consider that the spectra of
the suspensions have a high ethanol concentration.
When the Sol–Gel reaction takes place, the alkoxysilane
groups undergo hydrolysis and condensation reactions.
This process gives rise to a decrease in the intensity of the

Table 2 The experimental variables and their levels

Variable Level Centre point
- ?

Temperature (8C) (X1) 30 50 40

Time (min) (X2) 2 18 10
Mol water/mol TEOS (X3) 7.9 18.2 13.05
Mol ammonia/mol TEOS (X4) 1.19 3.55 2.37
Fig. 1 Infrared spectra of TEOS and ethanol

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bands corresponding to the alkoxysilane and an increase in
the intensity of the bands of ethanol and silica
(&1066 cm-1 ma (Si–O–Si) and &950 (m Si–OH)). The
intensity of the band assigned to silanol stretching is low if
we consider that under alkaline conditions the condensa-
tion rate is high [16].
Bearing in mind all these considerations, we selected the
band at 960 cm-1 to monitor the advance of the Sol–Gel
reaction. Figure 2 shows the scale expanded infrared
spectra obtained using a fixed path length liquid cell for the
dispersion obtained in experiments 6, 16 and for a refer-
ence mixture (3 mL TEOS ? 50 mL of ethanol).
As a constant path length cell was used, and we ana-
lyzed only one absorption, the intensity changes can be
directly related to the alkoxysilane concentration. Thus, the
reference sample showed the highest absorption because in
this sample the alkoxysilane groups did not react. In the
two dispersions, the intensity decreased as a consequence
of the Sol–Gel reaction. The conversion of the reaction can
be estimated using expression (1)
As
p¼1
Ar
where As and Ar are the area of the 960 cm-1 band in the
sample and in the reference respectively. This calculation
yields values of 0.28 and 0.68 for experiments 6 and 16.
Using the infrared spectra of all the dispersions and
expression 1, the conversion of all the experiments was
calculated. The results obtained are shown in Table 1.
Fig. 2 Scale expanded infrared spectra for the dispersion obtained in
experiment 6 and 16 and for a reference mixture (3 mL
TEOS ? 50 mL of ethanol)
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As it was shown, using the described experimental
conditions particle size between 26–223 nm and conver-
sions between 0.04–0.68 were obtained.
3.1 Conversion analysis
Figure 3 shows the measured conversion by predicted
conversion values with a regression line (full line) and 95%
confidence curves (dashed curves). The regression line and
the 95% confidence curves cross the sample mean (the
horizontal line), which shows that the whole factorial
model explains a significant proportion of the variation in
conversion.
Table 3 displays the regression coefficients (Estimate),
the standard error of the parameter, t Ratio (parameter
estimate divided by standard error) and Prob [ jtj (the
probability of a greater absolute t-value occurring by
chance alone if the parameter has no effect in the model)
for all terms in the regression model. The effects are sorted
by the absolute value of the t-ratio, showing the most
significant effects at the top.
ð1Þ The terms with t ratio higher than 2 (indicated with * in
Table 3) are statistically significant, so the variables X3
(molwater/molTEOS), X4 (molammonia/mol TEOS) and
the interaction X2 X3 (time*molwater/molTEOS) will
govern the obtained conversion. Thus, the largest conver-
sion is obtained when the water and ammonia concentra-
tions are high. An increased water concentration combined
with a growing time tends also to enhance the conversion.
Fig. 3 Measured vs. predicted conversion. The full line is the fitted
multivariate regression curve
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Table 3 Regression coefficients (estimate), standard error of the Table 4 Regression coefficients (estimate), standard error of the
parameter, t ratio and Prob [ jtj for all terms in the conversion parameter, t ratio and Prob [ jtj for all terms in the particle diameter
regression model regression model
Term Estimate Std error t ratio Prob [ |t| Term Estimate Std error t ratio Prob [ |t|

X3 0.1305845 0.027329 4.78 0.0014* X4 17.207362 2.931188 5.87 0.0004*

X4 0.0384653 0.009239 4.16 0.0032* X3X4 8.0219809 2.931188 2.74 0.0256*
X2X3 0.0545625 0.018959 2.88 0.0206* X3 19.997193 8.670654 2.31 0.0500*
X2X4 0.0157455 0.009239 1.70 0.1267 X1X4 -5.134799 2.931188 -1.75 0.1179
X1 0.0385956 0.027329 1.41 0.1956 X1X3 -10.2375 6.015307 -1.70 0.1272
X1X4 0.009959 0.009239 1.08 0.3125 X1X2 5.0125 6.015307 0.83 0.4289
X2 0.0218927 0.027329 0.80 0.4462 X1 2.9518538 8.670654 0.34 0.7423
X1X3 0.0101875 0.018959 0.54 0.6057 X2X3 -1.9375 6.015307 -0.32 0.7556
X3X4 0.0005177 0.009239 0.06 0.9567 X2X4 0.7004767 2.931188 0.24 0.8171
X1X2 -0.001063 0.018959 -0.06 0.9567 X2 0.1451801 8.670654 0.02 0.9871

3.2 Particle diameter analysis
Figure 4 shows the regression curve of multiple regression
analysis based on particle diameter and Table 4 displays
the regression coefficients for all term in the regression
model.
According to the results, the variables X4 (molammo-
nia/molTEOS), X3 (molwater/molTEOS), and the interac-
tion X3 X4 increase the obtained particle size. In this case,
the reaction temperature and the reaction time do not have
significant influence on the particle size in the studied
interval. Comparing the results of this work with literature
data [3] obtained with conventional heating the same trends
are observed, so the microwave irradiation does not change
the general tendency of the parameters.
Keeping the variables in the limits used in our work it is
not possible to obtain low diameters at high conversions.
More work should be done in order to maximize the con-
version. However, the results suggest that in order to obtain
low particle size, variables X4 (mol ammonia/mol TEOS)
and X3 (mol water/mol TEOS) should be at their lowest
values. Comparing the values of the conversion obtained in
experiments 1–4, where X3 and X4 are at their lowest
values the results suggest that the conversion increases
when the reaction time and temperature increase. Accord-
ing to this observation, using low ammonia and water
concentration but increasing the reaction time and tem-
perature out of the limits used in our work, low diameter
particles could be obtained at high conversion, and the
proposed procedure could be recommended for the prepa-
ration of silica from TEOS.

3.3 Comparison between microwave and traditional

heating

The reaction in the centre point was also performed using

Fig. 4 Measured vs. predicted particle diameter. The full line is the
fitted multivariate regression curve
conventional heating. Compared with the values obtained
using microwave irradiation, the obtained conversion using
conventional heating was lower (ptraditional heating = 0.14,
pmicrowave = 0.32). This result confirms literature [10–12]
data and therefore, under microwave radiation the reaction
time is shorter compared with conventional methods.
The morphology of the particles obtained in the centre
point using microwave and conventional heating was
analyzed by atomic force microscopy. The obtained images
for the experiment in the centre point are shown in Fig. 5.
As can be observed in Fig. 5, in both cases AFM images
show a spherical particle shape. In addition, AFM images
of the particles obtained under microwave heating show
diameters around 50 nm, very close to the data obtained by
DLS (Table 1, 63 nm). However, the mean particle size is

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Fig. 5 AFM images of silica
particles synthesized in the
centre point (0000) (T = 40 °C,
t = 10 min, X3 = 13,
X4 = 2.37) using traditional
(left) and microwave (right)
heating
higher using traditional heating. Moreover, under micro-
wave irradiation the particle size distribution is very nar-
row while under traditional heating various shapes and
different sizes of the particles are observed.
4 Conclusions
Submicrometer spheres were prepared by the microwave
irradiated sol–gel reaction of TEOS in basic media. Using
multivariate analysis it has been concluded that water and
ammonia concentrations are the main factors that govern
particle size as well as the obtained conversion. The mul-
tivariable approach allows the detection of interactions
between variables and this is not possible using a con-
ventional experiment design, changing one variable and
maintaining all the other variables constant. Compared
with traditional heating, the microwave technology allows
us to obtain particles with narrower particle size distribu-
tion in a shorter reaction time. However, in most experi-
ments relatively low conversion degrees (0.06–0.68) were
obtained, depending on reaction conditions. Thus, low
molecular weight silicates, bearing non-reacted Si–OH and
Si–OEt functional groups might be side products of silica
synthesis.
Acknowledgement The authors would like to thank the financial
support of the Ministerio de Educación y Ciencia (INTERHYBRID
project, n8 MAT2005-08033-C02-01).
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