Journal of Asian Ceramic Societies

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Synthesis and characterization of silica

nanoparticles from clay

Usama Zulfiqar, Tayyab Subhani & S. Wilayat Husain

To cite this article: Usama Zulfiqar, Tayyab Subhani & S. Wilayat Husain (2016) Synthesis and
characterization of silica nanoparticles from clay, Journal of Asian Ceramic Societies, 4:1, 91-96,
DOI: 10.1016/j.jascer.2015.12.001

To link to this article: https://doi.org/10.1016/j.jascer.2015.12.001

© 2016 The Ceramic Society of Japan and

the Korean Ceramic Society

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 Journal of Asian Ceramic Societies 4 (2016) 91–96

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Journal of Asian Ceramic Societies

journal homepage: www.elsevier.com/locate/jascer

Synthesis and characterization of silica nanoparticles from clay

Usama Zulfiqar ∗ , Tayyab Subhani, S. Wilayat Husain
Department of Materials Science and Engineering, Institute of Space Technology, Islamabad, Pakistan

a r t i c l e i n f o a b s t r a c t

Article history: We report a method to synthesize silica nanoparticles from bentonite clay. A series of thermal and acid
Received 6 November 2015 treatment processes was performed on bentonite clay to lower the alumina and increase the silica content.
Received in revised form The obtained silica rich clay was treated in two different concentrations (10 wt% and 40 wt%) with sodium
24 November 2015
hydroxide solution to form sodium silicate solutions (SSS). One type of SSS was hydrolyzed with three
Accepted 12 December 2015
different concentrations (5 M, 10 M and 15 M) of nitric acid in the presence of ethanol as cosolvent while
Available online 30 December 2015
the other SSS was hydrolyzed with nitric acid in the presence of three different quantities (10 ml, 20 ml and
30 ml) of ethanol as cosolvent. A range of silica particle sizes from nanometer to micrometer was obtained
Keywords:
Clays
by varying the contents of silica rich clay, HNO3 , and ethanol. It was observed that the concentration of
SiO2 silica rich clay and HNO3 had a direct effect on the particle size. The increase in the quantity of ethanol
Sol–gel processes from 10 ml to 20 ml produced bimodal particles of nanometer and micrometer size, which maintained at
Powders 30 ml. Inductively coupled plasma optical emission spectroscopy, atomic absorption spectroscopy, X-ray
Chemical preparation fluorescence, scanning electron microscopy and X-ray diffraction were utilized to characterize the clay,
Sodium silicate solution SSS and nanoparticles.
© 2015 The Ceramic Society of Japan and the Korean Ceramic Society. Production and hosting by
Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/
licenses/by-nc-nd/4.0/).

1. Introduction Bentonite clay is a potential source of silica, which contains

Silica nanoparticles have found applications in a variety of fields
including drug delivery systems, catalysis, biomedics, biological
imaging, chromatography, sensors, liquid armors and as filler in
composite materials [1–4]. A method for the production of spher-
ical and mono-dispersed silica nanoparticles by the hydrolysis of
tetraethyl orthosilicate (TEOS) in basic conditions was first reported
in 1968 [5]. Later, the effect of concentration of TEOS, water and
alkali was also studied to find a correlation with the produced sil-
ica particle size [6]. The shape and size of silica particles can also
be tailored by controlling the reaction parameters such as time,
temperature and solvent concentration [7].
In addition to TEOS, sodium silicate solution (SSS) is another
low cost precursor used for the synthesis of silica particles [8,9].
Rice husk, rice hull, bagasse ash and semi-burned rice straw ash are
some of the waste materials used for the synthesis of SSS [10–13].
Silica particles are precipitated from SSS by using acids such as
hydrochloric acid (HCl) [14] as precipitating agent; carbon dioxide
is also used [15].
∗ Corresponding author. Tel.: +92 3347064887.
E-mail address: usamazulfiqar@live.com (U. Zulfiqar).
Peer review under responsibility of The Ceramic Society of Japan and the Korean
Ceramic Society.
smectite as a main clay mineral. As alumina component is present
in clays along with silica, a range of acid and alkali hydrometal-
lurgical methods are employed to isolate them from each other
[16–19]. Usually acids are used for the processing of clay rather
than alkalis [20] and HCl is preferred over other acids due to the easy
separation of filtrate from the residue [21]. For effective removal of
alumina from clays, calcination is a critical step; solubility of alu-
mina increases after thermal treatment in the temperature range of
500–900 ◦ C [22,23]. Previously, kaoline clay was studied for the pro-
duction of aluminum sulfate and it was found that heating the clay
to 700 ◦ C for 1 h followed by acid leaching with sulfuric acid (H2 SO4 )
were the optimum conditions to extract alumina [18]. In another
work, removal of alumina component from kaoline to produce
pure alumina was studied and the recommended process involved
the calcination of clay at 600 ◦ C for 1 h followed by leaching with
HCl. However, the synthesis of silica particles from bentonite clay
has not been studied previously and demands investigation in this
field.
In the present study, silica particles were synthesized from
bentonite clay in nanometer and micrometer size range. Alumina
content in bentonite clay was lowered by a series of thermal and
acid treatments. SSS was derived from the clay and the solution
was hydrolyzed with HNO3 in the presence of ethanol. The effect
of concentrations of clay, acid and ethanol on the particle size and
morphology of silica was studied.

http://dx.doi.org/10.1016/j.jascer.2015.12.001
2187-0764 © 2015 The Ceramic Society of Japan and the Korean Ceramic Society. Production and hosting by Elsevier B.V. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
92 U. Zulfiqar et al. / Journal of Asian Ceramic Societies 4 (2016) 91–96

Fig. 1. Flow chart representing the process to produce silica particles from bentonite clay.

2. Materials and methods Table 1

Details of experiments including clay concentration and experimental conditions
for the synthesis of silica particles.
2.1. Materials
Clay (wt%) Sodium silicate Nitric acid Ethanol Particle size
solution (ml) concentration (ml)
Bentonite clay of foundry grade was provided by a local foundry.
(M)
Ethanol (C2 H6 O) was acquired from Lab-Scan and 37% hydrochlo-
ric acid (HCl) was purchased from Fisher Scientific. 65% nitric acid 10 50 15 10 98 ± 20 nm
10 50 10 10 86 ± 11 nm
(HNO3 ) was provided by EMSURE® . Commercially available sodium
10 50 5 10 69 ± 8 nm
hydroxide (NaOH) was purchased from local market while locally 40 50 15 10 223 ± 68 nm
available distilled water was used during the entire process. 40 50 15 20 169 ± 53 nm
1.3 ± 0.2 ␮m
40 50 15 30 99 ± 23 nm
2.2. Methods 1.4 ± 0.3 ␮m

Bentonite clay was sieved through a mesh size of 100 ␮m. It was
then heated at a temperature of 680 ◦ C for 1 h in a muffle furnace.
Later 100 g of clay was added in 1000 ml 2.5 M HCl solution and left
for stirring at 90 ◦ C for 2 h and filtered to separate the silica rich ben-
tonite clay. It was then washed and filtered repeatedly until the pH
was neutralized. Two different SSS were prepared by dissolving two
different loadings (10 wt% and 40 wt%) of clay in 2 M NaOH solution
at 90 ◦ C for 2 h. The solution was filtered to separate residue and
unwanted impurities. The obtained SSS was neutralized with HNO3
at 50 ◦ C in the presence of ethanol as a cosolvent. The SSS prepared
by dissolving 10 wt% clay was treated with three different concen-
trations of HNO3 (15 M, 10 M and 5 M) while keeping the amount of
cosolvent constant. The SSS prepared by dissolving 40 wt% clay was
treated with three different amounts of ethanol (10 ml, 20 ml and
30 ml) while keeping the acid concentration constant; the details
are given in Table 1. The neutralized solutions were centrifuged and
the obtained silica particles were washed repeatedly to remove the
impurities including sodium. A graphical abstract of the process of
synthesizing silica particles from bentonite clay is given in graph-
ical abstract and the flow diagram of the process is represented in
Fig. 1.
2.3. Characterization
Compositional analysis of as-received bentonite clay and silica
rich clay was performed by X-ray fluorescence (XRF) (WD XRD
PANalytical). Elemental analysis of SSS obtained from silica rich
clay was performed by inductively coupled plasma optical emis-
sion spectroscopy (ICP-OES) (IRIS ICP-OES, Thermo Jarrel Ash).
Quantification of the sodium present in the SSS was performed
by using atomic absorption spectroscopy (AAS). X-ray diffraction
(XRD) of bentonite clay (before and after thermal treatment) and
silica nanoparticles was performed for the phase analysis (Broker
D8 Advance, CuK␣,  = 1.54184, Step size = 0.02045 and scan speed
is 190 steps per minute). Before XRD analysis, the samples of silica
particles were washed with 8 M HCl solution to remove the sodium
and other impurities. Morphological examination and size mea-
surement of silica particles was performed by using field emission
gun scanning electron microscope (FEG-SEM) (Mira 3 TESCAN). For
SEM, silica was dispersed in ethanol and then dropped on glass
slide followed by carbon coating. For the average particle size and
 U. Zulfiqar et al. / Journal of Asian Ceramic Societies 4 (2016) 91–96 93

Table 2
Composition of bentonite clay and silica rich clay analyzed by XRF.

Composition Bentonite clay Silica rich clay

SiO2 58.10 65.05

Al2 O3 15.10 6.83
MgO 2.70 3.00
K2 O 1.83 3.55
CaO 0.36 1.25
TiO2 0.88 2.37

standard deviation, approximately 100 measurements were per-

formed using SEM images of each sample.

3. Results and discussion

The composition of bentonite clay was determined by XRF and

given in Table 2. The bentonite clay contains 58.1% SiO2 and 15.1%
Al2 O3 as major constituents. In a previous study, 36 samples of dif-
ferent types of bentonite clay were analyzed and up to a maximum Fig. 2. XRD patterns of bentonite clay before and after thermal treatment at 680 ◦ C
of 66.8% SiO2 and 21% Al2 O3 have been reported [24]. To produce for 1 h.
silica rich clay, the benonite clay was thermally treated at 680 ◦ C
for 1 h followed by acid leaching. An appreciable decrease in the
amount of alumina was observed in silica rich clay, i.e. 6.83%, while

Fig. 3. SEM images of silica particles synthesized from SSS after dissolving 10 wt% clay. (a and b) 15 M HNO3 , (c and d) 10 M HNO3 and (e and f) 5 M HNO3 .
94 U. Zulfiqar et al. / Journal of Asian Ceramic Societies 4 (2016) 91–96

Table 3
Composition of sodium silicate solution measured by ICP-OES.

Element Si Naa Al Zn Ti B

␮g/ml 2069 27,236 453.5 0.39 0.33 9.34S

a
Na was analyzed by AAS.

SiO2 content increased to 65.05%; SiO2 content increased 11.9%

while Al2 O3 decreased 45.2% (Table 2).
Fig. 2 shows the XRD patterns of pure bentonite clay and ben-
tonite clay after thermal treatment but before acid leaching. The
crystalline peaks of quartz can be clearly seen in both samples,
which are showing no effect of temperature, i.e. 680 ◦ C. Peaks of
kaoline and montmrillonite can also be seen in the pattern of
bentonite clay after thermal treatment. In bentonite clay after ther-
mal treatment, an amorphous phase was observed in the range of
11◦ –14◦ . In pure bentonite, peak of kaoline exists in this region,
which disappeared after the thermal treatment and substituted
Fig. 4. Graph showing a decrease in silica particle size with decreasing acid concen-
with an amorphous band, which indicates the transformation of tration. Particles were produced from SSS after dissolving 10 wt% silica rich clay.
kaoline to amorphous metakaolinite. Heating the bentonite clay
causes its dehydration, which completes at 650 ◦ C and further
increase in the temperature leads to its dehydroxylation [25]. The 2069 ␮g/ml whereas sodium is 27,236 ␮g/ml. Aluminum is also
transformation of kaoline to metakaolinite is associated with dehy- present as a major impurity element in the solution. This analy-
dration of clay and it increases the clay reactivity for easily alumina sis confirms the presence of silicon in the solution and formation of
extraction by acids or alkalis [22,26]. This argument is supported SSS. Other impurity elements present in SSS are zinc, titanium and
by XRF results as the amount of alumina was appreciably reduced boron.
by acid leaching the bentonite clay after heating (Table 2). Fig. 3 shows the morphology and size of silica particles synthe-
Table 3 shows the elemental analysis of SSS after dissolving sized from SSS prepared by dissolving 10 wt% clay in NaOH and
10 wt% silica rich clay in 2 M NaOH. Silicon in the solution is hydrolyzing the SSS with three different concentrations of HNO3 in

Fig. 5. SEM images of silica particles synthesized by using SSS after dissolving 40 wt% silica rich clay. (a–c) 10 ml ethanol, (d–f) 20 ml ethanol and (g–i) 30 ml ethanol.
 U. Zulfiqar et al. / Journal of Asian Ceramic Societies 4 (2016) 91–96
Fig. 6. Graph showing silica particles in nanometer and micrometer size range.
Ethanol in concentration of 20 ml and 30 ml produced bimodal particle distribution.
the presence of ethanol as cosolvent. When 15 M HNO3 was used to
hydrolyze SSS, spherical shaped silica nanoparticles with average
size of 98 ± 20 nm were produced, as shown in Fig. 3(a and b). The
size of silica nanoparticles reduced to 86 ± 11 nm when the SSS was
hydrolyzed with 10 M HNO3 . The size of the silica nanoparticles was
further decreased to 69 ± 8 nm when 5 M HNO3 was used, as shown
in Fig. 3(e and f). It can be inferred from the SEM images that particle
size reduced by decreasing the acid concentration. Moreover, par-
ticle size distribution also becomes narrow by decreasing the acid
concentration. Also, it can be clearly seen that the morphology of
the particles is spherical. The reduction in acid concentration means
the introduction of water in reaction system, which has resulted in
smaller size of silica particles. In our previous investigation, SSS
was diluted with water prior to the addition of acid and a decrease
in silica particle size was observed and it was concluded that the
addition of water leads toward production of more nuclei due to
enhanced solubility of intermediate species, and the solubility of
intermediates species is attributed to the high polarity of water
[27]. In the present study, water was added in acid instead of pre-
cursor and the amount of water was increased gradually in the form
of decreasing molarity of acid. It is evident from the present results
that amount of water in reaction system has direct relation with
particle size as shown graphically in Fig. 4.
Fig. 5 shows the SEM images of silica particles synthesized by
mixing 40 wt% clay in NaOH solution and hydrolyzing the SSS with
15 M HNO3 . Silica particles of 223 ± 68 nm were formed when 10 ml
ethanol was used as cosolvent, as shown in Fig. 5(a–c). When the
concentration of ethanol increased to 20 ml, bimodal particle size
distribution was produced: one size of particles was in microme-
ter, i.e. 1.3 ± 0.2 ␮m and the other size was in nanometer range,
i.e. 169 ± 53 nm (Fig. 5(d–f)). The presence of bimodal was also
observed when the amount of ethanol was increased to 30 ml
but with an increase in size of micrometer particles and decrease
in size of nanometer particles, i.e. 1.4 ± 0.3 ␮m and 99 ± 23 nm
(Fig. 5(g–i)). Fig. 6 graphically shows the variation in particle sizes
and modals with increasing amount of ethanol.
Bimodal distribution of silica particles was produced by increas-
ing the quantity of ethanol from 10 ml to 20 ml and it was observed
that the further rise in the quantity of ethanol (30 ml) did not dis-
turb bimodal distribution. It has been reported that ethanol has a
high miscibility with silica precursor solution and it increases the
formation of Si OH and Si O Si resulting in the formation
of large sized silica particles [28,29]. It was also observed that the
amount of silica rich clay in NaOH to prepare SSS had a direct effect
on silica particle size by keeping the quantity of ethanol (10 ml) and
95
Fig. 7. XRD patterns of silica nanoparticles produced by using 10 wt% silica rich clay
in NaOH to form SSS.
HNO3 (15 M) constant. For example, dissolving 10 wt% clay in SSS,
the particle size was 98 ± 20 nm, which increased to 223 ± 68 nm by
dissolving 40 wt% clay. The effect of concentration of silica source
in precursor solution on particle size was observed in our previous
study and it was observed that particle size and modal increases
with increasing amount of white rice husk in NaOH [27].
Fig. 7 shows the XRD patterns of silica nanoparticles produced
from SSS after dissolving 10 wt% silica rich clay. The pattern corre-
sponds to characteristic amorphous nature of silica. Silica particles
produced from SSS and rice hull show the amorphous nature
and similar XRD pattern, as observed in the present investigation
[30,31].
4. Conclusions
Silica particles were produced from bentonite clay in different
sizes from nanometer to micrometer range. Silica rich clay was
obtained from bentonite clay after a sequence of acid and ther-
mal processes which was later treated with sodium hydroxide
solution to prepare sodium silicate solution. Silica particles were
produced by hydrolyzing sodium silicate solution with nitric acid
in the presence of ethanol as a cosolvent. It was observed that the
concentration of silica rich clay and nitric acid has a different effect
on particle size, i.e. increased concentration produced particles of
larger diameter. It was also found that bimodal distribution of sil-
ica particles was produced by increasing the amount of cosolvent.
The silica particles were spherical in morphology and amorphous
in nature, as confirmed by SEM and XRD, respectively.
Acknowledgement
The authors are thankful to Dr. Sajjad and Mr. Tahir Mehmood
for their help in spectroscopic and microscopic analysis, respec-
tively.
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