J Sol-Gel Sci Technol (2009) 50:328336

DOI 10.1007/s10971-009-1958-6

ORIGINAL PAPER

Synthesis of silica nanoparticles by modified solgel process:

the effect of mixing modes of the reactants and drying techniques
M. Jafarzadeh I. A. Rahman C. S. Sipaut

Received: 8 August 2008 / Accepted: 20 March 2009 / Published online: 10 April 2009
Springer Science+Business Media, LLC 2009

Abstract A modified preparation of silica nanoparticles

via solgel process was described. The ability to control
the particle size and distribution was found highly dependent on mixing modes of the reactants and drying
techniques. The mixture of tetraethoxysilane and ethanol
followed by addition of water (Mode-A) produced monodispersed powder with an average particle size of
10.6 1.40 nm with a narrow size distribution. The freeze
drying technique (FD) further improved the quality of
powder. In addition, the freeze dried samples have shown
unique TGA decomposition steps which might be related to
the well-defined structure of silica nanoparticles as compared to the heat dried samples. DSC analysis showed that
FD preserved the silica surface with low shrinkage and
generated remarkably well-order, narrow and bigger pore
size and pore volume and also large endothermic enthalpies
(DHFD = -688 J g-1 vs. DHHD = -617 J g-1) that lead
to easy escape of physically adsorbed water from the pore
at lower temperature.
Keywords

Silica nanoparticles
Solgel
Freeze drying

1 Introduction
Synthesis of silica nanoparticles have drawn great interest
of research owing to their potential application in industries
I. A. Rahman (&)
School of Dental Sciences, Health Campus, Universiti Sains
Malaysia, 16150 Kubang Kerian, Kelantan, Malaysia
e-mail: arismail@usm.my
M. Jafarzadeh
C. S. Sipaut
School of Chemical Sciences, Universiti Sains Malaysia,
11800 Minden, Penang, Malaysia

123

(electronic devices, insulators, catalysis, etc.) and pharmaceuticals (enzyme encapsulation, drug delivery and cell
markers) [1, 2]. Solgel process has become an attractive
research area, in which extensive studies have been made
on the synthesis of silica nanoparticles [35].
In general, solgel process is very sensitive towards the
experimental conditions that affect the rate of hydrolysis
and condensation reactions, e.g., the type and concentration
of starting materials (alkoxides), H2O/alkoxide ratio, catalysts nature and concentration/pH, nature of solvent,
temperature, time of reaction, aging and drying method [1,
2, 69]. The Stober method was firstly introduced using
ammonia catalyzed hydrolysis and condensation of ethoxysilanes in low molecular-weight alcohols as solvent to
produce uniform silica particles [10]. Various methods
have been reported for the preparation of silica nanoparticles [5, 1120]. Bogush and Zukoski [5] successfully
prepared monodispersed silica particles in the range of
40 nm to few micrometers using modified Stober method.
The authors believed that concentration of TEOS, concentration of ammonia, concentration of water, as well as
types of solvent (alcohol) and reaction temperature were
the main parameters, which governed the particle size and
its distribution. By optimizing these parameters, Park et al.
[17] conveniently prepared ultrafine silica particles within
the range of 13.7 4.5 nm. Kim et al. [21] were able to
reduce the particle size up to 17.5 nm with 3.33 mL min-1
feed rate through addition of small amount of NaI as an
electrolyte additive during the synthesis. Rahman et al. [22]
reported that monodispersed silica of average size
20.5 3.5 nm under 0.1 mL min-1 feed rate can be synthesized in the presence of small quantity of NH4Br. Most
recently, Rahman et al. [23], have reported a solgel
route for the synthesis of silica nanoparticles in the primary
size range by optimizing various parameters such as

J Sol-Gel Sci Technol (2009) 50:328336

329

concentration of the reactants, ammonia feed rate, temperature under ultrasonic mixing.
There are several drawbacks in solgel process such as
the difficulties in controlling the particle size, aggregation
and agglomeration, and longer reaction time. In this work,
we have synthesized silica nanoparticles via modified sol
gel process by emphasizing the reactants mixing mode and
drying techniques that are not reported in earlier studies
[17, 2224]. The effect of mixing mode of reactant and
drying techniques on particle sizes and distribution of the
powders is highlighted.

2 Experimental

(Labconco, Freezon 12). The samples were calcined at

600 C for 2 h.
2.3 Synthesis of nanosilica at different mixing modes
of the reactants
Silica nanoparticles were prepared under similar conditions
as described in Sect. 2.2 with different mixing modes of the
reactants. Mode-A: TEOS ? EtOH (TEOS was first
dissolved in ethanol for 10 min, and then water was added
into the reaction medium). Mode-B: one-pot (TEOS,
EtOH and H2O were mixed simultaneously). Mode-C:
H2O ? EtOH (mixed for 10 min, then TEOS was added to
the mixture). The flow chart of the different mixing modes
is given in Fig. 1.

2.1 Reagents
2.4 Characterizations
Tetraethoxysilane (TEOS, 99%, Fluka), absolute ethanol
(EtOH, 99.5%, Systerm), ammonia (NH3 25%, A & M
Chemicals) and distilled water have been used in this work.
The chemicals were employed without any further
purification.
2.2 Standard procedure
Silica nanoparticles are synthesized by using a standard
procedure with experimental conditions provided in
Table 1. A quantity of 5 mL of TEOS was first dissolved in
30 mL of absolute ethanol under low frequency ultrasound
(Bransonic, Model 5510, 42 kHz) at room temperature for
10 min. Then, 1 mL of distilled water was dropped into the
reaction media with the feed rate of 0.2 mL min-1, to
facilitate hydrolysis of TEOS in the ultrasonic bath. After
1.5 h, 2 mL of ammonia (catalyst) was fed into the reaction
mixture at the feed rate of 0.01 mL min-1. Sonication was
continued for 3 h. Gelation was allowed for 1 h. The gel
was centrifuged and washed with ethanol and distilled
water (3 9 7 min, 6,000 rpm). Drying was carried out
using either a conventional oven at 70 C for 24 h or freeze
drying (FD) under vacuum for overnight in a freeze dryer

Table 1 Optimized experimental parameters for the preparation of

silica nanoparticles
Parameters

Optimal value

TEOS (mol L-1)

0.58

NH3 (mol L-1)

H2O/TEOS

0.6
28.8

Feed rate (mL min-1)

0.01

Temperature (C)

2550

Morphology of the samples was studied by using a transmission electron microscopy (TEM, Philips CM 12)
operated at an acceleration voltage of 80 kV. The particle
size and size distributions (PSD) were determined using
analysis Docu Version 3.2 image analysis software. Dilute
dispersion of powder of samples in ethanol were prepared
under ultrasonication for 10 min to obtain a homogeneous
suspension. One drop of suspension was evaporated on a
carbon-coated copper grid. Determination of the particle

Mode-A
Si(OEt)4 + EtOH

Mode-B
Si(OEt)4 + EtOH + H2O

(Sonication, 10 min)

H2 O

Ammonia (25%)

Mode-C
H2O + EtOH
(Sonication, 10) min)

Si(OEt)4

Reactants Mixture
(Sonication, 90 min)

COLLOIDAL SiO2
Sonication, 3 h

Gelation & Aging

1h

Heat Drying (HD) or Freeze Drying (FD)

Reaction time (h)

5.5

Sonication (kHz)

42

Calcination, 600 oC, 2 h

POWDERS

Fig. 1 Flow chart for nanosilica preparation by different mixing

modes

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J Sol-Gel Sci Technol (2009) 50:328336

size and statistical parameters were based on the measurement of more than 300 particles from the TEM micrograph.
Surface area and porosity of samples was measured by
adsorptiondesorption of nitrogen isotherm at 77 K on an
automatic physisorption analyzer (Micromeritics ASAP
2000). The samples were degassed overnight under vacuum at 105 C before measurement (10-3 mmHg).
Thermogravimetric analysis (TGA) was carried out on
TGA 7 instrument (PerkinElmer) with heating rate of
20 C min-1 under flowing nitrogen. TG-MS (ThermoStarTM, equipped with V8.10 Star software) was used to
recognize the species being released during the thermal
treatment at a heating rate of 10 C min-1 under flow of
N2. Differential scanning calorimetry (DSC) was used to
study the heat capacity using Pyris 1 DSC instrument
(PerkinElmer) at a heating rate of 10 C min-1 in the
range of -50 to 400 C.

3 Results and discussion

3.1 Effect of experimental parameters on the particle
size and morphology
Silica particles were prepared at the same conditions with
different feed rates of ammonia (0.01, 0.02,
0.03 mL min-1). Table 2 shows the effect of feed rates on
particle size of silica obtained via FD. The average particle
size was determined to be 10.6 1.4, 11.4 1.7 and
15.0 1.6 nm for feeding rates of 0.01, 0.02, and
0.03 mL min-1, respectively. Figure 2 shows the particle
size distribution (PSD) and TEM of nanoparticles prepared
in different ammonia feed rates. Results show that particle
size decreased with the decrease in the feed rate. At
0.01 mL min-1 feed rate, the smallest particle size and
narrowest particle distribution was obtained. TEM analyses
illustrate uniform and relatively aggregated particles prepared for 0.01 mL min-1 feed rate (Fig. 2b). Increase of
the feed rate enhanced the rate of hydrolysis, which
increased the concentration of hydrolyzed monomer that
lead to higher nucleation rate. Since the rate of nucleation
is equal to the rate of growth of particles [24], hence,
associated of hydrolyzed monomer under monomer
Table 2 Effect of feed rate on particle size of silica obtained via
freeze drying
Feed rate
(mL min-1)

Particle size
range (nm)

Average particle
size (nm)

0.01

7.113.6

10.6 1.4

0.02

7.016.3

11.4 1.7

0.03

10.519.8

15.0 1.6

123

addition model [3] produced larger particles for the higher

feed rates. Lower feed rate can control the nucleation and
growth of the primary particles and leads to smaller
nanoparticles.
3.2 Effect of mixing mode
Silica nanoparticles were prepared under similar condition
at different mixing mode of the reactants as illustrated in
Fig. 1. Table 3 shows the effect of mixing mode on the
particle size of silica obtained via FD. The average particle
size was found to be 10.6 1.4, 13.8 1.7 and
14.9 1.6 nm for Mode-A, B, and C, respectively. PSD
and TEM of the silica are given in Fig. 3. TEM images
reveal a narrow size and shape distribution in the morphology of the particles with roughly low aggregation and
agglomeration by using Mode-A (Fig. 3b).
TEOS is non-polar, immiscible in water, but dissolves
easily in ethanol. Thus the mixing mode greatly affects the
homogeneity of TEOS molecules in the reaction medium
(TEOS-ethanol) and interactions between TEOS and water
molecules. In Mode-C the presence of strong hydrogen
bonds between ethanol and water restricts the accessibility
(it means availability and proximity of reactants that lead
to higher probability of collision among them) of TEOS to
water molecules for the hydrolysis reactions. According to
natural structure of liquid water in which the molecules are
linked to some of neighbors by hydrogen bonding interaction [25], that can forms the different arrangement
[(H2O)n, n = 360] and shape such as dimmer, trimer
(cyclic), tetramer (cyclic), pentamer (cyclic), hexamer
(cyclic, cage or prism) and so on [26]. The same arrangement or cluster between water and ethanol might be
expected. It is clear that the interaction among polar molecules (waterethanol cluster) is stronger than polarnonpolar molecules (TEOS-ethanol). On the other hand,
low homogeneity of TEOS molecules in the mixture of
water and ethanol (waterethanol cluster) lead to microphase separation among them. In other words, hydrolysis
reaction performs when TEOS penetrate into the pore of
waterethanol cluster through homogeneous TEOS-ethanol
interface. Due to microphase separation phenomena,
accessibility between TEOS and water was restricted,
consequently, the growth of nanoparticles were increased
in competition with the nucleation in the cluster, leading to
relatively larger particles. For Mode-B due to moderate
homogeneity among the starting materials, the PSD shows
better results compared to Mode-C. The mixing of the
starting materials simultaneously provides the proximity
between the hydrolyzing agent (water) and target molecule
(TEOS), thus enhancing the hydrolysis reaction. On the
other hand, for Mode-A, there has been high homogeneity
among TEOS and ethanol compared to that in Mode-B

J Sol-Gel Sci Technol (2009) 50:328336

(a)

140
0.01
0.02

120

0.03

100

No. of Particles

Fig. 2 PSD and TEM of silica

nanoparticles obtained via
freeze drying in different
ammonia feed a PSD, b 0.01
mL min-1, c 0.02 mL min-1
and d 0.03 mL min-1

331

80
60
40
20
0

0
-20

10

15

20

25

Particle Size (nm)

Table 3 Effect of mixing mode on particle size of silica obtained via

freeze drying

3.3 Effect of drying techniques

Mixing mode

The freshly synthesized silica nanoparticles (in gel form)

were dried under heat drying (HD) in oven for 24 h or FD
in deep vacuum for overnight. HD process cause the
decrease in gel volume due to the loss of liquid by evaporation through the silica pores. It is well-known that the
rapid removal of the water from the pores causes blistering,
shrinkage and shriveling of silica gel [27]. However, FD
(lyophilization) preserves the structure of materials without
shrinkage of the gel structure [28]. It appears to be one of
the most attractive methods to stabilize the colloidal
nanoparticles [29].
Particle size distribution of these two drying techniques
is illustrated in Fig. 4 showing no significant different.
However, FD technique revealed an interesting surface

Particle size
range (nm)
7.113.6

Average particle
size (nm)
10.6 1.4

9.018.3

13.8 1.7

10.320.7

14.9 1.6

and C. This leads to easy accessibility between TEOS and

water. Moreover, ethanol as an interface helps to establish
an effective contact between TEOS and water. In conclusion, the effective homogeneity of precursor in the solvent
at the initial stage ought to be very critical factor in solgel
process. Thus, Mode-A is a recommended procedure for
the preparation of monodispersed silica nanoparticles.

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J Sol-Gel Sci Technol (2009) 50:328336

Fig. 3 PSD and TEM of silica

nanoparticles obtained from
freeze drying in different
mixing modes a PSD,
b Mode-A, c Mode-B
and d Mode-C

(a)

160
a

140

c
b

No. of Particles

120
100
80
60
40
20
0

-20

10

15

20

25

Particle Size (nm)

(b)

(c)

(d)

120

FD-C
HD-C

No. of Particles

100
80
60
40
20
0
0
-20

10

12

14

16

Particle Size (nm)

Fig. 4 PSD of silica nanoparticles in different drying process: freeze

drying (FD-C) and heat drying (HD-C)

characteristic of the particles. The specific surface area,

micropore area, average pore diameter and micropore
volume of nanoparticles produced from FD are higher than

123

of HD drying techniques (Table 4). This may due to the

slow removal of water or other solvents through sublimation process under vacuum, reduce the capillary forces
(decrease the thermal tension), resulting in a minimal
shrinkage and preserve a high surface area and porosity of
the particles.
The adsorptiondesorption isotherm plot and pore size
distribution are shown in Fig. 5. The hysteresis loop shows
good agreement with typical pattern for mesoporous
materials based on Brunauers classification [30]. In addition, pore size diameters in Table 4 obviously support
the mesoporosity behavior in the silica according to the
IUPAC definition (250 nm in pore size) for mesoporosity
[31]. There are distinct differences in the shape and amount
of adsorbate that adsorbed on adsorbent in isotherm plot.
High volume of adsorbed gases reveals the larger volume
capacity in FD-C that shows a good consistent with
resulting pore volume in Table 4. The threshold capillary

J Sol-Gel Sci Technol (2009) 50:328336

333
1000

Table 4 The effect of drying process on specific surface area, pore

diameter, and particle size of the samples
Silica-FD

Silica-HD

BET surface area (m2 g-1)

226

170

Micropore area (m2 g-1)

19

11

Micropore volume (mL g-1)

0.00971

0.00556

Average pore diameter (nm)

24

22

Particle size range (nm)

7.113.6

7.814.8

Average particle size (nm)

10.6 1.4

11.0 1.4

800

Volume Adsorption (mL/g)

Properties

(a)

900

700
600
500
400
300
200

3.4 Thermal analysis

The TGA analysis showed two stage mass losses for HD
samples (Fig. 6a). The DTG reveals the initial loss at
below 100 C which is related to the physically adsorbed
water on the silica surface [31]. The second stage of mass
loss between 150 and 900 C represent the release of
trapped water within the pores, degradation of residual
starting materials and dehydroxylation of silanol groups
[31].
Significantly, there were four distinctive stages of
weight loss for FD sample (Fig. 6b). The m/e data was
extracted from TG equipped with mass spectrometer as
detector. At below 130 C, the weight loss related to the

FD-C

100

HD-C

0
0

0.2

0.4

0.6

0.8

1.2

Relative Pressure (P/P0)

35

(b)

30

Pore Area (m2/g)

25

20

15

10

FD-C
HD-C

0
0

50

100

150

200

Average Pore Diameter (nm)

0.5

(c)

0.45
0.4

Pore Volume (mL/g)

condensation leading to the sharp increase in adsorbed

volume commence at lower relative pressure (P/P0 = 0.57)
in HD-C than that in FD-C (P/P0 = 0.8). Also, the narrower
plot in FD-C may indicate the more similarity between the
adsorption and desorption behaviour compared to that in
HD-C. It might be proposed a wider pore size distribution
in HD-C.
Pore size distribution based on desorption isotherm was
calculated using the capillary condensation model assuming
cylindrical pores according to BJH (BarettJoyner
Halenda) method [32] (Fig. 5b, c). The results reveal uniform and narrower pore area as discussed earlier.
Concentration of hydroxyl groups (dOH) on the surface
of silica is the key parameter that influences the physical
interaction between coupling agents and matrices in the
preparation of nanocomposites. It is expected that high
number of hydroxyl group on the silica surface will
enhance the adhesion between inorganic filler and functional organic matrix. Nevertheless, determination of
silanol concentration of colloidal silica particles by
adapting the reported procedure (titration method) [33]
reveals different silanol concentration as 1.33 and
1.27 mmol g-1 for FD and HD, respectively. The finding
was very consistent with the result from BET; therefore, it
can be another evidence to highlight the difference between
freeze and HD process.

0.35
0.3
0.25
0.2
0.15
0.1
FD-C

0.05

HD-C

0
0

50

100

150

200

Average Pore Diameter (nm)

Fig. 5 Nitrogen sorption isotherm (a), pore area (b) and pore volume
(c) distribution (BJH method) of silica nanoparticles obtained via
freeze (FD-C) and heat (HD-C) drying

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water (m/e: 18 = H2O?, 17 = HO?), ammonia (m/e: 17 =

NH3) and small portion of residual solvent (m/e:
46 = EtO?H) in the pores. Stage 3 (320540 C) was due to
the dehydroxylation of the silanol group (m/e: 18 = H2O?,
17 = HO?) and the degradation of residual reactant
[m/e: 43 = C2H3O? (TEOS)]. Finally, stage 4 (540
900 C) was suggested to be due to the degradation of
residual TEOS (m/e: 43 = C2H3O?) and dehydroxylation of
silanol groups (m/e: 18 = H2O?, 17 = HO?).
Uniformity, cylindrically shaped pores (assumed cylindrical pores according to the BJH model), larger pore sizes
in the FD samples help to release the pore liquid at distinctive temperature ranges. However, in HD samples the
shrinkage caused deformity of cylindrical-shape pores. The
comparison between lost of physically adsorbed water via
freeze (0.88%) and heat (1.41%) drying obtained by TG
results had indicated the efficiently dehydration process for
FD. DSC results (Fig. 7) showed a large endothermic
enthalpy for FD (DHFD = -688 J g-1) as compared to HD
(DHHD = -617 J g-1). These results indicate that the ease
of evaporation of physically adsorbed water for FD that
occurred at lower temperature (Tonset = 10.82 C,
Tmax = 96.19 C) as compared to HD (Tonset = 28.78 C,
Tmax = 116.19 C). Also, it can be due to the uniformed
and well-ordered porous structure which makes the escape
of water molecules easy.
For the calcined silica only two steps of decomposition
were observed. The initial loss [30150 C (HD-C) or
30165 C (FD-C)] was due to the loss of adsorbed water
from the silica surface. Less volatile were released from
HD-C due to the increase in siloxane bonds and reduced
surface hydroxyl groups. The second decay [150900 C
(HD-C) or 165900 C (FD-C)] related to the dehydroxylation process (release of water molecules due to
?

Fig. 6 TGA and DTG thermograms of silica particles obtained a via

heat drying, before calcination (HD) and after calcination (HD-C)
b via freeze drying, before calcination (FD) and after calcination
(FD-C)

physically adsorbed water (m/e: 18 = H2O?, 17 = HO?)

and trapped residual ammonia (m/e: 17 = ?NH3). The
second stage (130320 C) indicated the escape of trapped
Fig. 7 DSC thermograms of
silica particles obtained via heat
drying (HD) and freeze drying
(FD)

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Table 5 The effect of drying
process on number of hydroxyl
content

Samples
SilicaHD

TGA method

Titration method

Silica-FD

335

Temperature
interval (C)

Mass loss
(wt%)

Absorbed water
(mmol g-1 SiO2)

OH groupsa
(mmol g-1 SiO2)

30150

0.1944

0.21

150900

1.8633

2.07

30165

0.9857

1.09

165900

2.5928

2.88

condensation of silanol groups and formation of siloxane

linkage). Ek et al. [34] elucidated an interesting method for
determination of the number of hydroxyl groups by thermogarvimetry (TG). The hydroxyl content was calculated
by using the following Eq. 1:
nOHSiO2

2%wtT0  %wtTf 
100 MH2 O

In which nOHSiO2 is the number of hydroxyl groups per

gram of silica. The weight loss is calculated in the interval
between initial (T0) and final (Tf) temperatures. MH2 O is the
molar mass of water.
The content of hydroxyl groups in FD-C samples was
found more than in HD-C samples due to higher surface
area of FD-C samples (Table 5). The large quantity of
physisorbed water in the FD-C samples was due to high
amount of hydroxyl groups present on its surface which
could bond more water molecules through hydrogen
bonding. The results (obtained from TG data) were found
consistent with the results obtained from titration method.
4 Conclusions
The ultrafine silica particles were synthesized by modified
solgel process under influence of different mixing mode of
the reactants and drying techniques. By decreasing the feed
rate of ammonia, smaller silica nanoparticles were obtained.
Mixing mode showed significant effect on the average particle size and PSD. Dehydration process exerted efficiently
via FD besides preservation of particle structure. FD provided high surface area and mesoporosity compared to
conventional drying process. The TG thermogram results
revealed four distinctive and defined weight loss steps for
the samples obtained via FD. A high amount of silanol
groups in silica nanoparticles can enhances interaction
between surface hydroxyl groups and functional groups of
organic moieties in an inorganicorganic hybrid. This
unique property has made the silica nanoparticles suitable
for preparation of silica-based polymeric nanocomposites.
Acknowledgment The authors appreciate Ministry of Higher Education for financial support of this research under Fundamental
Research Grant Scheme (FRGS, Grant No: 203/PKIMIA/671174). M.
Jafarzadeh would like to express his gratitude to Universiti Sains
Malaysia (USM) for USM-Fellowship.

OH groupsb
(mmol g-1 SiO2)

1.27
1.33

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