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Synthesis and Characterization of Ultra-Fine

Colloidal Silica Nanoparticles

Article · September 2014

DOI: 10.1166/asem.2014.1578

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 Article
Advanced Science,
Copyright © 2014 American Scientific Publishers
Engineering and Medicine
All rights reserved Vol. 6, 965–973, 2014
Printed in the United States of America www.aspbs.com/asem

Synthesis and Characterization of Ultra-Fine

Colloidal Silica Nanoparticles
Mohd Qasim1 , J. Ananthaiah2 , S. Dhara2 , P. Paik1 , and D. Das1
∗
1
School of Engineering Sciences and Technology, University of Hyderabad, Hyderabad 500046, India
2
School of Physics, University of Hyderabad, Hyderabad 500046, India

A facile synthesis of colloidal silica nanoparticles of various sizes, employing the hydrolysis and con-
densation of tetraethyl orthosilicate (TEOS) in absence of any surfactant, is reported. The surfactant-
free colloids of SiO2 nanoparticles with diameter ∼ 5–6 nm are stable upto 50 days after synthesis.
The effects of different reaction parameters (e.g., concentration of TEOS, water, alcohol and ammo-
nia) on particle sizes have been investigated. Particle sizes have been found to increase with
increasing TEOS and ammonia concentration but decrease with increasing water concentration.
Obtained products have been characterized through XRD, UV-Vis spectrophotometry, FTIR, HRTEM
and FE-SEM. The colloidal stability has been characterized by zeta potential and rheological
measurements.
Keywords: Colloidal Silica, Rheology, Optical Properties, Silica Nanoparticles.
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Copyright: American Scientific Publishers
1. INTRODUCTION catalyst, temperature, reaction time etc.10 SiO2 nanoparti-
The colloidal silica nanoparticle is a stable dispersion of cles of size less than 5 nm to several micrometers can be
solid SiO2 nanoparticles in liquid media. Monodisperse synthesized by microemulsion method,11 organometallic
SiO2 nanoparticles are one of the most attractive mate- sphere endotemplate method,12 surfactant template method
rials in colloidal science because of their unique prop- etc. These techniques can yield smaller size particles with
erties, such as surface structure and functionality (–OH), narrow size distribution compared to those obtained from
optical properties, biocompatibility etc.1 Surface function- Stober process, but large amount of surfactant and co-
alized SiO2 finds application in electronics, sensors, catal- stabilizers are used in these processes.13 Therefore, the par-
ysis, polishing, paints, fillers and pigments.2–5 Because of ticles require through purification before being employed
the biocompatible nature and ease of surface modification, for any specific application. Removing surfactant micelles
amorphous SiO2 nanoparticles are a potential tool in med- from SiO2 network structure is not an easy task since it
ical biotechnology and used in several applications includ- can entrap the micelles due to the electrostatic interactions.
ing target drug and gene delivery,6–8 molecular bioimaging, Surfactant free SiO2 nanoparticles, therefore, have a great
labeling of bio-marker of infected cancer and tumor cells promise in biological applications. Stober process gener-
etc.7
8 However, SiO2 nanoparticles play different roles in ally produces larger size silica particles (0.05 to 2 m).9
different applications and their response strongly depend A number of research groups modified Stober process to
on the size and distribution, shape and surface properties.2 achieve silica nanoparticles of size <10 nm,14–21 but to the
Among various methods reported for SiO2 nanoparticles best of our knowledge none of them have succeeded to
preparation Stober’s process is known to produce monodis- achieve surfactant/metal ions free colloidal SiO2 of size
perse particles.5
9 Stober process involves hydrolysis and below 10 nm. Here, in this work, an effort has been made
condensation of alkoxide of Si in aqueous alcohol solu- to synthesize colloidal SiO2 nanoparticles of different sizes
tion, where liquid ammonia is used as a morpholog- (5 to 30 nm) without the use of any surfactant or related
ical catalyst. The size of SiO2 nanoparticles strongly compounds. The colloidal SiO2 nanoparticles have been
depends on the reaction parameters such as, solvent, prepared only by varying the concentration of TEOS, H2 O,
NH3 using sonochemical synthesis followed by the Stober
∗
Author to whom correspondence should be addressed. process. In the modified process very less TEOS has been

Adv. Sci. Eng. Med. 2014, Vol. 6, No. 9 2164-6627/2014/6/965/009 doi:10.1166/asem.2014.1578 965
Synthesis and Characterization of Ultra-Fine Colloidal Silica Nanoparticles Qasim et al.

used for all sets of experiments and has been added drop
wise after diluting with absolute ethanol. Liquid ammonia
has also been added drop wise in two steps to avoid sudden
increase in particles size in all the experiments. To the best
of our knowledge the present work is the first report on the
synthesis of SiO2 of particles sizes ∼ 5–6 nm in absence of
any surfactant. The stability of the SiO2 colloids has been
studied using zeta potential () and rheological property
measurements. The changes in viscosity have been studied
as a function of shear rate and temperatures. The rheolog-
ical behavior of all the colloidal silica nanoparticles has
been explained in terms of their morphology, zeta potential
and compositions and has been reported in the articles.
Figure 1. Photograph of colloidal SiO2 nanoparticles after eight week
of synthesis. All the samples are found to be stable with time.
2. EXPERIMENTAL DETAILS
2.1. Materials
Tetraethyl orthosilicate (TEOS,99.99%, Sigma Aldrich), Yield %
ammonia (25%, Qualigens), and ethanol (99.9%, = Observed weightg × 100/Theoretical weight (g)
Hangzhou) were used in these experiments without any
purification. Deionized water was used in all experiments. where the theoretical weight of the sample was calcu-
lated based on 100% conversion of TEOS into SiO2 .10
2.2. Synthesis of Colloidal Silica Nanoparticles The yield (%) for each experiment is found to be ∼ 95%.
Under Different Conditions
The experiments were performed using the precursor con- 2.3. Characterization Techniques
centrations mentioned in Table I. All concentrations were Particle sizes, shape and morphology were measured using
calculated based on the final concentration in the reac- Transmission electron microscopy (FEI Tecnai T20G2
tion mixture. First, solution containing Delivered by Publishing
appropriate quan- Technology
S TWIN TEM) to: unknown
and field emission scanning electron
IP: 117.215.217.75 On: Fri,microscopy
17 Oct 2014 05:08:56
(Carl Zeiss Ultra 55 FESEM). A drop of dilute
tities of absolute ethanol, ammonia and deionized water
Copyright: American Scientific Publishers
was sonicated in a 50 Hz TRANS-O-SONIC sonicator for and well sonicated colloidal silica solution was placed on a
10 minutes in 100 ml closed mouth beaker to ensure no carbon coated copper grid, the solvent was evaporated and
evaporation of the solvent and complete mixing. Appro- the grid was examined by TEM. For the FESEM, a drop of
priate amount of TEOS in absolute ethanol was added to sample was placed on carbon tape pasted on holder, solvent
the above solution drop wise (0.03 ml/min) and after son- was evaporated and the particles were coated with ∼ 10 Å
icating for 100 minutes again ammonia was added drop thin gold layers before examining in FESEM. The particle
wise (0.05 ml/min) to promote the condensation reaction. size was estimated using analysis image processing soft-
Continuous sonication for about 70 minutes led to the for- ware. The compositional analysis of the sample was carried
mation of white turbid suspension of silica nanoparticles. out by a Horiba Energy Dispersive X-ray Micro-analyzer
Photograph of the as prepared colloidal silica nanoparti- attached to a Hitachi S-3400N SEM. Crystal structure of
cles after eight weeks of synthesis have been shown in the samples was analyzed by SAED pattern obtained from
Figure 1. Powder of silica nanoparticles were obtained by TEM and from XRD data. The as-prepared and calcined sil-
evaporating the solvent initially at 50  C for 2 hours and ica particles were analyzed by a Bruker D8 Advance X-ray
then at 150  C for 2 hours in hot air oven. The conversion Diffractometer with –2 geometry, using Cu K radiation,
of the reactants into silica nanoparticles has been estimated in the 2 range 5–50 . The optical absorption behavior was
using the following formula, analyzed using a UV-Vis spectrophotometer (Perkin Elmer
Lambda 35). Fourier transformed infrared (FT-IR) analysis
Table I. Concentrations of the precursors used in different experiments. was conducted on pellet made by mixing 1 mg of SiO2 in
Name of sample Solvent TEOS (M) H2 O (M) NH3 (M) 100 mg KBr using Perkin-Elmer 2000 FT-IR spectrome-
ter. The Zeta potential and particle sizes of colloidal sil-
S1 Ethanol 0.044 5.55 0.441 ica were measured by Zetasizer Ver. 6.20 (Malvern Serial
S2 Ethanol 0.134 5.55 0.441
S3 Ethanol 0.268 5.55 0.441
Number: MAL1048519). Dynamic viscosity was measured
S4 Ethanol 0.134 2.77 0.441 using a standard rheometer (Anton Paar MCR 501) with
S5 Ethanol 0.134 8.33 0.441 controlled shear rate (CSR). The measuring system was a
S6 Ethanol 0.044 5.55 0.147 coaxial cylinder (CC-27). The temperature of the system
S7 Ethanol 0.044 5.55 0.735 was controlled using a Peltier device with an accuracy of
S8 Isopropanol 0.044 5.55 0.735
± 0.1  C.

966 Adv. Sci. Eng. Med. 6, 965–973, 2014

Qasim et al. Synthesis and Characterization of Ultra-Fine Colloidal Silica Nanoparticles

3. RESULTS AND DISCUSSION 2 1/2 hours. XRD pattern shows that silica nanoparticles
The effects of TEOS, H2 O and NH3 with concentrations are amorphous upto the calcination temperature of 900  C.
on particle sizes and shape have been studied. The concen- It is also found that with increasing calcination tempera-
trations of reactants and their effects on particle sizes are ture the XRD peak intensity increases imploying crystal-
shown in Tables I and II respectively. It was observed from lization in silica phase. It is evident from the diffraction
TEM (Fig. 2) and FESEM (Fig. 3) that the particle sizes pattern that at 1000  C amorphous silica transformed into
of silica nanoparticles obtained from all the experiments crystalline (Cristobalite) silica.23 The diffraction spectra of
to be very small. The largest particle size observed in this the samples calcined at 1100 and 1200  C are almost simi-
investigation is 31 ± 137 nm for as prepared sample S8. lar in nature. The observed diffration peaks at 2 = 2188
Particle size of 54 ± 061 nm is obtained for sample S6. [101], 28.48 [111], 31.39 [102], and 36.193 [200] cor-
About 2–3 micrographs of each sample were considered relates well with the cristobalite tetragonal phase (Ref.
to obtain the mean particle sizes and ∼ 150 particles were JCPDF card number 89-3434). The crystallization temper-
measured for each sample. To the best of our knowledge ature of amorphous silica reported else where is 1300  C.24
this synthesis procedure with optimized condition (sample But, in this investigation the crystallization temperature is
S6) is the easiest way to produce ultrafine sized, highly observed at around 1000  C. The different synthesis route
pure and stable colloidal silica nanoparticles, without the or different experimental conditions used in this study
use of any surfactant, template based technique, and metal could lead to such difference in crystallization temperature.
salt catalyst, which cause contamination to the particles. The crystallite size of all samples, calcinated at different
Ultrafine silica nanoparticles are very prone to agglomera- temperatures, has been estimated from the XRD peak broa-
tion mainly due to the hydrogen bonding present between dining using Scherrer’s formula d = 09 / cos , where
the surface –OH groups and minimize the high surface d is the crystallite size, is the wavelength of X-ray radi-
energy. TEM and FESEM analysis of the 50 days aged ation (CuK,  is the Bragg angle and is the full width
colloidal silica show the same mean sizes of the particles at half maximum (FWHM) of the most intense diffraction
as those of the freshly prepared samples. peak.25 The crystallinity and crystallite size increases with
increase in calcination temperatures. Around 80% increase
3.1. Solid State Crystal Structure in crystallite sze is observed in increasing the calcina-
The solid state phase structure ofDelivered
all the SiO tion temperature
samples Technology
by 2Publishing from 1000  C to 1100C (16.3 nm at
to: unknown

was checked by XRD with a CuK IP: 117.215.217.75
radiation (CuKOn:= Fri,1000
17 Oct C to
2014 nm at 1100  C). Further increase in cal-
29.205:08:56
1540598 Å) at room temperature. Figure Copyright: American
4(a) shows the Scientific Publishers caused less effect on crystallite size.
cination temperature
X-ray diffraction pattern of as prepared S1, S2, S3, S5, The crystallite size of the sample calcined at 1200  C is
and S8 samples. XRD results show that all the SiO2 sam- ∼ 31.1 nm.
ples are amorphous in nature as expected and reported
by others.22 The broad diffraction peak at 2 = 23 and 3.2. FTIR Analysis
absence of any diffraction peak from impurities confirmed To confirm the chemical structure related to the functional
the formation of pure amorphous silica nanoparticles. groups and purity of the prepared samples FT-IR analy-
Same has also been confirmed from the SAED patterns sis was performed. The FTIR spectra of silica nanopar-
(inset of TEM, Fig. 2). ticles (S8) is shown in Figure 5. The intense and broad
The effect of calcination temperatures on the phase band appearing at ∼ 1079–1167 cm−1 is assigned to the
structure has also been studied. The XRD patterns of asymmetric stretching vibrations of Si O Si bond.7 The
the representative sample S8, calcined at different tem- absorption band at ∼ 1079 cm−1 is arising from asymmet-
 
peratures varying from 150 C to 1200 C, are shown ric vibration of Si O bond. The bands at ∼ 960 cm−1 and
in Figure 4(b). All samples have been calcined for ∼ 801 cm−1 can be assigned to the asymmetric vibration of

Table II. Physical properties of colloidal silica nanoparticles, S1–S8.

Mean particle Mean particle Zeta Observed SiO2 Theoretical

Sample size (nm) size (nm) by potential concentration SiO2 conc.
name by TEM SD (nm) FESEM SD (nm) (mV) pH (mg/ml) (mg/ml) Yield (%)

S1 94 0.65 113 2.25 −20.1 945 257 27 95.1

S2 129 0.78 137 1.42 −21.9 954 74 81 91.5
S3 122 0.84 129 1.77 −21.7 948 150 161 93.1
S4 149 0.91 15 1.41 −32.4 954 75 81 92.8
S5 102 0.80 102 1.22 −25.4 989 72 81 89.1
S6 54 0.61 6 1.25 −36.9 996 25 27 92.5
S7 209 2.41 264 1.92 −32.7 1023 26 27 96.3
S8 31 1.37 375 7.00 −30.9 1021 247 27 91.4

Adv. Sci. Eng. Med. 6, 965–973, 2014 967

Synthesis and Characterization of Ultra-Fine Colloidal Silica Nanoparticles Qasim et al.

Figure 2. TEM images and SAED pattern (inset) of all (S1–S8) SiO2 nanoparticles. The scale bar is 50 nm.
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Si OH bond,18 and symmetric vibration of Si O bond concentration of primary particles at the induction period,
respectively. The band at ∼ 468 cm−1 corresponds to the i.e., [primary particles]  [TEOS]. Induction period is the
bending mode of Si O Si bond. An intense characteris- time period when generation of nuclei takes place from
tic absorption band around 3300–3500 cm−1 arises due to the supersaturated solution and induces formation of pri-
the O H stretching vibration mode of Si(OSi)n (OH)4−n mary particles. Therefore, TEOS concentration determines
(n = 2–4) linkage of the solid state network structure of sil- the concentration of primary particles, but at the same
ica or due to the unbounded absorbed water.26–28 The band time the concentration of these primary particles deter-
at ∼ 1631 cm−1 is due to scissor bending vibration of mines the subsequent growth of these particles. TEOS was
molecular water.29 diluted with ethanol and was added to the reaction sys-
tem drop wise very slowly in order to promote the for-
3.3. Effect of TEOS Concentration mation of smaller particles. Figure 6 shows the effects of
on the Size of Particles TEOS concentration on size of silica nanoparticles. The
The effect of TEOS concentration on the size of SiO2 particle size increases with increasing TEOS concentra-
nanoparticles is controversial in some literature it is found tion up to 0.134 M and after that it does not change
that there is no significant effect of TEOS concentra- much. The particle size is seen to vary from 94 ± 06 to
9
tion on particle sizes but, Bogush et al. and a group of 129 ±07 nm, measured by TEM, and 113 ±22 to 137 ±
researchers 3
4
10
15
reported that increasing particles sizes 14 nm, measured by FESEM. Both the TEM and FESEM
with increasing TEOS concentration. Helden et al.30 how- analysis show that the particles are almost monodispersed.
ever reported that high TEOS concentration can decrease The particles sizes for all the samples are mentioned in
the particle sizes also. In the present study, increased Table II.
size of the silica nanoparticles was observed with increas-
ing TEOS concentration (0.044–0.268 M), with 5.55 M 3.4. Effect of Water Concentration on
water, and 0.441 M ammonia concentration (samples: Size of Particles
S1, S2, S3). Being the source of monomer, concentra- In the present study, decrease in size of the silica nanopar-
tion of TEOS will determine the concentration of the ticles was observed with increasing water concentration
nuclei/primary particles present in the system.4 Hence, the in the range 2.77–8.33 M, with 0.441 M ammonia,
increase in particle size is attributed to the increase in and 0.134 M TEOS concentration (sample S4, S2, S5).

968 Adv. Sci. Eng. Med. 6, 965–973, 2014

Qasim et al. Synthesis and Characterization of Ultra-Fine Colloidal Silica Nanoparticles

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Figure 3. IP: 117.215.217.75
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(S1–S8).
Copyright: American Scientific Publishers

The obtained result is in good agreement with the results 3.5. Effect of Ammonia Concentration
reported by Rahman et al.4 Figure 6 illustrates the trend on the Size of Particles
in particle sizes with increasing water concentrations. Normally acid catalyzed hydrolysis is a very slow process
It is observed that as the R value (water/TEOS ratio) compared to the basic one and hence base catalyzed pro-
increases the particles size also decreases. The R val- cess is preferable to synthesize ultra-fine monodispersed
ues for samples S4, S2 and S5 are 20.67, 41.41 and SiO2 nanoparticles. In this work NH3 is used as a catalyst
62.16, respectively. Generally, water promotes hydrolysis for hydrolysis and condensation of TEOS in ethanol. It is
and condensation reaction resulting in increase in par- worth mentioning that the higher NH3 and water content
ticle sizes. At higher H2 O concentration the oligomers in the reaction mixture increase the rate of hydrolysis.7 It
in reaction solution get diluted, resulting in the forma- has been found in earlier work that slow drop wise addi-
tion of smaller particles. In the present investigation, the tion of NH3 for a longer period controls the growth and
decrease in size of the silica nanoparticles with increasing limits the size of particles, whereas faster rate of addition
water concentration may be associated with the dilution reverse the effect and produce bigger size particles.9 On
of silicate concentration which slows down the hydroly- addition of NH3 the pH of the solution increases and leads
sis and condensation reaction, resulting in restricted par- to the formation of large number of SiO2 nuclei, which
ticle growth. Matsoukas and Gulari31 have also reported subsequently grow into silica particles. From Figure 6,
that the increase in water concentration yields smaller par- it is clearly observed that as the NH3 is increased from
ticles. The estimated particle size is seen to vary from 0.147 M to 5.55 M the particle size increased from
149 ± 09–102 ± 08 nm. The particle size data obtained 6 nm to ∼ 26.4 nm in presence of 0. 0.044 M TEOS
from TEM (Fig. 2) correlates well with those obtained and 5.55M H2 O in the fixed volume of EtOH. (Samples
from FESEM (Fig. 3). Although the average particle size S6, S1, S7). The probable reason for this is that as the
is seen to decrease with increasing water concentration NH3 increases the rate of hydrolysis of TEOS increases
and their tendency to form a chain like structure (by join- to form [Si(OC2 H5 4−X (OH)X ], which subsequently con-
ing many single particles) increases with increasing water denses to produce large number of oligomers leading to
concentration. the formation of larger sized particles.2
4 At very low

Adv. Sci. Eng. Med. 6, 965–973, 2014 969

Synthesis and Characterization of Ultra-Fine Colloidal Silica Nanoparticles Qasim et al.

(a)

(b) Figure 6. Effect of precursors (TEOS, H2 O and NH3 ) concentration on

size of SiO2 nanoparticles. The filled squares represent estimated size
from TEM data and filled circles that from FESEM data.

From TEM analysis it is observed that the size of SiO2 par-

ticles increases from 21 nm, obtained in EtOH, to 31 nm
obtained in isopropanol. Similar results have also been
reported by Wang et al.3 where it was observed that as
the chain length of the alkyl group increases the dielectric
constant of the solvent decreases, which led to the increase
in particle sizes. It is worth mentioning that the dielectric
constants of ethanol and isopropanol are ∼ 24.3 and 19.9,
respectively. The dominance of van der Waals attractive
Delivered
Figure 4. (a) X-ray diffraction patterns of as preparedby
S1,Publishing
S2, S3, S5, Technology to: unknown
forces or static repulsive forces between the nuclei or pri-
IP: of
and S8 SiO2 nanoparticles; (b) XRD patterns 117.215.217.75 On: Fri, 17 Oct 2014 05:08:56
SiO2 nanoparticles (S8)
calcined at different temperatures. mary particles
Copyright: American Scientific depends on the dielectric constant of the
Publishers
solvent. In a solvent with low dielectric constant the attrac-
tive force between the nuclei dominates over the static
NH3 concentration ultrafine silica nanoparticles of dimen- repulsive forces and hence promotes the reaction kinetics
sions 5–6 nm are obtained. This finding will help other with subsequent particle growth.319
researchers to prepare ultra fine silica nanoparticles with-
out using any surfactant.
3.7. Zeta Potential
Zeta potential measurement was carried out to check the
3.6. Effect of Other Alcohols on the Size of Particles
stability of colloidal silica nanoparticles and is seen to
To observe the effect of solvent on the particle sizes, two vary from −20.1 to −36.9 mV depending of the parti-
different types of alcohols, such as ethanol (sample S7), cle size and morphology and is mentioned in Table II.
and isopropanol (sample S8), were chosen keeping all
the other experimental conditions constant (see Table I).

Figure 7. Variation of zeta potential of all colloidal SiO2 with reactant

Figure 5. FT-IR spectra of as prepared SiO2 nanoparticles (S8). concentrations (TEOS, H2 O and NH3 ) for colloidal SiO2 nanoparticles.

970 Adv. Sci. Eng. Med. 6, 965–973, 2014

Qasim et al. Synthesis and Characterization of Ultra-Fine Colloidal Silica Nanoparticles

The zeta potential values of the samples suggest that SiO2 a coaxial cylinder (CC-27). The temperature of the system
nanoparticles are moderately stable in suspension. Sam- was controlled using a Peltier device with an accuracy of
ples S1, S2, S3, and S5 have lower zeta potentials than ± 0.1  C. In Figure 8(a) the variation of dynamic viscosity
samples S4, S6, S7, and S8. It is observed (in Tables I is shown as a function of shear rate. In the low shear
and II) that a changes in particles sizes (9–12 nm) and rate range (< 200 s−1 ) the dynamic viscosity varies from
zeta potentials (Fig. 7) are weakly dependent on changes 1.4 to 2 mPa s depending on the sample and does not
in TEOS concentration. Change in water concentration change with shear rate. Thus, in the low shear rate range
from 2.77 M (S4) to 5.55 M (S2) changes the zeta poten- all the samples show behavior of a typical Newtonian fluid.
tial value from −32.4 to −21.9 mV. Further increase in It is observed that S5 and S3 exhibit larger viscosity than
water concentration does not affect the zeta potential of other samples. This is because of higher concentration of
colloidal SiO2 (S5). With increasing ammonia concentra- silica (S3) and water (S5) in these samples as both lead to
tion, zeta potential decreases at beginning (−36.9 mV for extensive networking or formation of chain like structure
S6 to −20.1 mv for S1) followed by a rapid increase to as discussed later. It was observed that the samples S4,
−32.7 mV for S7 with further increase in the ammonia S2, and S5, because of their increasing water contents,
concentration. NH4 OH produces hydroxyl ions, which get show increasing trend in viscosity. Sample S5 shows larger
adhered to the silica particle surfaces and helps in stabi- viscosity than S4 and S2. It was confirmed by TEM that as
lizing the colloids by static repulsion force against van the amount of water content increases the particles tend to
der Waals forces of attraction. However, the change in form longer chain or networks by joining with each other.
zeta potential depends on the particle sizes and the surface This is due to increasing tendency of hydrogen bonding
charge density, which is strongly associated with the pH between particles and formation of chain like structure that
of the solution. gives rise to larger viscosity. Sample S1, S6, and S7 show
almost similar viscosity because they have same amount
3.8. Rheological Measurements of water and silica content.
Dynamic viscosity of the colloidal silica was measured In the high shear rate range i.e., beyond 200 s−1 , the
using a standard rheometer (Anton Paar MCR 501) with viscosity abruptly changes slope and increases with the
controlled shear stress (CSS). The measuring system was increasing shear rate showing shear thickening behav-
ior. Similarto:
Delivered by Publishing Technology type of shear thickening behavior is reported
unknown
(a) IP: 117.215.217.75 On: Fri,on17colloidal
Oct 2014 05:08:56of silica nanoparticles.32
33 It was
dispersion
Copyright: American Scientific
suggestedPublishers
that in polar liquid silica nanoparticles could
interact via hydrogen bonding and hence they have strong
tendency to form microstructures. In the present samples
the solvent contains ethanol and water and both of them
are polar liquids. Hence there is a strong tendency to form
nanostructures or nanoclusters due to hydrogen bonding
as discussed earlier. In the low shear rate range the equi-
librium nanostructure remains undisturbed and the sam-
ples behave as a stable non-flocculated sol with constant
viscosity. As the shear rate is increased the short-range
hydrodynamic lubrication forces can bring the nanoclus-
(b)
ters closer and facilitate the microstructure formation and
hence can form a gel like structure. This can lead to
higher rates of energy dissipation and abrupt increase in
the dynamic viscosity. Further investigation is needed to
shed more light on the shear thickening behavior of the
samples. Since the viscosity of colloids strongly depends
on temperature, temperature dependence of viscosity has
been measured for two samples, namely S1 and S4 and
a typical variation is shown in Figure 8(b). The viscosity
decreases for both the sample rapidly with the increasing
temperature and shows an Arrhenius type of behavior i.e.,
= o exp [E/RT] where E is the activation energy and
o is the pre-exponential factor. The logarithm of the vis-
Figure 8. (a) Variation of shear viscosity of colloidal SiO2 nanoparti-

cles as function of shear rate at 27 C. (b) Temperature variation of shear
cosity with inverse of the temperature for the two samples
viscosity for two colloidal SiO2 samples namely S1, S4 at shear rate 5 is shown in Figure 8(b) (inset). The activation energies for
s−1 and inset shows the Arrhenius behavior of viscosity. the two samples, S1 and S4 are 4031 and 3776 cal/mol

Adv. Sci. Eng. Med. 6, 965–973, 2014 971

Synthesis and Characterization of Ultra-Fine Colloidal Silica Nanoparticles Qasim et al.

4. CONCLUSIONS
Ultra-fine colloidal silica nanoparticles of different sizes
and morphology have successfully been synthesized by a
modified Stober process using a low frequency ultrasonic
bath. Obtained sizes varied from 5–31 nm. Colloidal silica
nanoparticles with such tight distribution in sizes, which
conveniently fall into primary size range, have been pre-
pared without the use of any surfactant or metal salt as cat-
alyst. The effect of reactants concentration (TEOS, water,
ammonia and alcohol) on particle sizes has been investi-
gated. The particle sizes are seen to increase with increas-
ing TEOS and ammonia concentration but decrease with
increasing water concentration. Alcohol of larger molecu-
lar weight enhances the particle growth. The maximum in
UV-Vis absorption spectra is seen to shift at higher wave-
Figure 9. UV-vis absorption spectra of colloidal SiO2 nanoparticles lengths with decreasing size of the silica nanoparticles.
sample S1, S3, S4 and S6 and variation of max with particles size (inset). At low shear rate (<200 s−1 ), a typical Newtonian behav-
ior is observed for all the colloidal silica nanoparticles, but
at high shear rate (>200 s−1 ), a shear thickening behavior
respectively. These values are comparable to the activation
is observed.
energy reported in the binary mixture of pure water and
ethanol with similar concentration.34
Acknowledgment: Mohd Qasim greatly acknowledges
the financial support obtained from UGC in the form of
3.9. UV-Vis Spectroscopy MANF fellowship in carrying out this research work. The
In silica nanoparticles the optical phenomena is related to technical support received from the Centre of Excellence
the presence of different defects due to incomplete for- in Materials Science (Nanomaterials) Aligarh Muslim Uni-
mation of Si O Si tetrahedral network at the silica sur- versity, School of Engineering Sciences and technology
face, such as oxygen and siliconDelivered by
vacancies. 35 Publishing Technology to: unknown
To study
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ior, UV-Vis spectra of powder samples S6 (5.4 nm), S1
(9.4 nm), S3 (12 nm), S4 (15 nm) have been taken after
dispersing in water. UV-vis absorption spectra of differ- References and Notes
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Received: 26 March 2014. Accepted: 29 April 2014.

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