Digest Journal of Nanomaterials and Biostructures Vol. 11, No. 4, October-December 2016, p.

1155-1164

A FACILE SYNTHESIS OF AMORPHOUS SILICA NANOPARTICLES BY

SIMPLE THERMAL TREATMENT ROUTE

I. M. ALIBEa,c, K. A. MATORIa,b*, E. SAIONb, A. M. ALIBEd,e, M. H. M. ZAIDb,

E. A. A. GHAPUR ENGKUa
a
Institute of Advanced Technology, Universiti Putra Malaysia, 43400 UPM Serdang,
Selangor, Malaysia
b
Departments of Physics, Faculty of Science, Universiti Putra Malaysia, 43400 UPM
Serdang, Selangor, Malaysia
c
National Research Institute for Chemical Technology Zaria, Kaduna State Nigeria
d
Mechanical Engineering Departments, Federal Polytechnique Damaturu Yobe, State
Nigeria
e
Departments of Mechanical, Automotive and Manufacturing, Faculty of Engineering and
Computing, Coventry University, CV1 5FB, Coventry, United Kingdom

A facile thermal treatment route was for the first time used to successfully synthesize
amorphous silica nanoparticles. Various techniques were employed to study the structural,
phase and elemental composition of the material at different calcination temperature
between 500750oC. The XRD analysis confirms the formation silica to be in an
amorphous state and further revealed that the material remained in amorphous state even
when calcined at 750oC. The FTIR spectra shows that the calcination process has enable
the removal of organic source from PVP and formation of amorphous silica nanoparticles.
The average particle size of the material estimated from the TEM images shows that the
particle were <10nm. The optical absorbance exhibited in the UV region reveals
amorphous silica nanoparticles possess a wide band gap ranging from 3.8034.126 eV
calcined between 500 to 750 oC. The EDX analysis has confirmed the presence of Si and
O as the only elements in the material formed, which implies thermal treatment method is
effective for the synthesis of amorphous silica nanoparticles.

(Received May 1, 2016; Accepted October 29, 2016)

Keywords: Amorphous silica, Calcination, Optical

1. Introduction

Nanotechnology is multi-disciplinary specialization which cut across the conventional

boundaries between physics, chemistry, mathematics, biology and engineering [1]. With these
ideas, the technologist and engineer maneuver materials at nanoscale to create a product which
make use of remarkable properties. In nanomaterial research and development, synthesis and
characterization plays an important role. Top-down and bottom-up approach technique, are the two
major approaches for nanomaterials assembling. In top-down method, nanomaterials are
constructed from large size material without molecule level control [2]. While the bottom-up
approach, is where materials are constructed from a few molecule components by chemical self-
assembling in solution into functional superstructure. The development of ceramic nanomaterial
with improved structural and optical properties has been studied with much success in recent
years. Such as silica, alumina, titania, zirconia, silicon nitride and silicon carbide.
Amorphous silica nanoparticles (ASN) occupy a prominent position in scientific research,
because of their easy preparation and their wide uses in various industrial applications, such as
catalysis, pigments, pharmacy, electronic and thin film substrates, electronic and thermal
insulators, and humidity sensors [3, 4].

*
Corresponding author: khamirul@upm.edu.my
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Several procedures and methods have been reported on the synthesis of ASN with the aim of its
improving the chemical and physical features. Such methods include sol-gel technique [5], spray
pyrolysis [6], hydrothermal growth [7] and micro wave assisted method [8]. However, most of
these methods are difficult to apply on large scale production due to the complicated procedure,
high temperature involved, and longer period of reaction, toxic chemical reagent and harmful by
product release to the environment at the end of the experiments [9].
The present study synthesized ASN by simple thermal treatment method from an aqueous
solution containing silicon tetraacetate, PVP Poly (vinyl pyrrolidone) and deionizes water only [9,
10]. The influence of calcination temperature on the structural and optical property have been
studied and discussed in details.

2. Experimental

2.1 Materials
Silicon tetraacetate reagent 𝑆𝑖(𝑂𝐶𝑂𝐶𝐻3 )4(Mw = 264.26 g/mol), was purchased from
sigma Aldrich and used as metallic precursors, poly(vinyl pyrrolidone) (PVP M w = 29000 g/mol)
was also purchased from sigma Aldrich which served as capping agent, hence reduce
agglomeration and stabilize the nanoparticles. Deionized water served as solvent. All chemicals
used were more than 99% purity and used without any further purification

2.2 Procedure
A solution of PVP was made by dissolving 3 g of PVP in 100 ml of deionized water and
continuously stirred using magnetic stirrer for 2h, until no precipitate formed. Later 0.2 mmol of
𝑆𝑖(𝑂𝐶𝑂𝐶𝐻3 )4was added and stirred continuously for another 2 h, little. The solution was
transferred into a clean petri dish and dried in an oven for 24 h at 80 oC. The resulting solid gel
was grinded in a sterilized mortal into powder form. The powder was placed into crucible boat and
calcinated in a box furnace at 500 oC, 550 oC, 600 oC, 650 oC, 700 oC, and 750 oC, with constant
holding time 3 h to decompose PVP and produce ASN.

2.3 Characterization
The synthesized ASN were characterized by several techniques such as, FT-IR, EDX,
XRD, TEM, FESEM and UV-vis. The precursor before calcination was characterized by TGA
analysis. The bond formation and functional group of ASN has been studied by infrared spectra
(FT-IR Perkin Elmer model 1650). The structural behaviour of the ASN was examine by X-ray
diffraction (XRD Shimadzu model 6000 using Cu kα (0.154 nm) as a radiation source to generate
diffraction patterns from the sample at ambient temperature in 2θ within the range of 20-80°. The
elemental composition was examined using Field electron scanning microscopy (FESEM) (JEOL
JSM-7600F) equipped with EDX. The particle size and distribution were examine by
Transmission electron microscopy (TEM) (JEOL TEM model 2010F UHR) with an accelerating
voltage of 200 kN. The optical properties were determined by UV-vis spectrometer (Shimadzu
model UV-3600) at room temperature in the range of 200-800 nm.

3. Results and Discussion

3.1 Thermogravimetric Analysis (TGA-DTG)

TGA analysis for the removal or decomposition of poly (vinyl pyrrolidone) (PVP) are both
shown in Figure 1. The graph was plotted for weight loss percentage as a function of temperature
of the dried sample prior to calcination process. The sample exhibited two different steps of
decomposition. The first one was weight loss due to the moisture already entrapped in sample at
temperature of 83 °C. In 2014, Al Hada et al. [9] reported that the moisture entrapped in the PVP
could be removed at 84 °C. The other stage of weight loss was observed at 437 °C which implies
that most of the PVP has given off. There was no considerable weight losses observed as the
 1157

temperature approached 486 °C. At that instance, there was complete decomposition of PVP, thus
leaving behind only a residue of SiO2.

Fig. 1: The thermogravimetry (TG) and thermogravimetry derivative (DTG) curves

for PVP used to determine the minimum calcination temperature
at heating rate of 10 °C /min.

3.2 Phase and Elemental Composition Analysis

The elemental analysis of SiO2 was tested by Energy-dispersive X-ray spectroscopy
(EDX). The basic principle is such that every particular element possesses a unique atomic
structure allowing particular set of peaks on its X-ray spectrum.
The purpose of carrying out the EDX analysis here was to enable confirm the elemental
composition of the constituent atoms and figure out if there are any foreign impurity atoms. Figure
2 shows the EDX spectrum of SiO2 calcined at 500°C. The corresponding peaks of Si, and O2 were
observed in the sample which confirms the formation of pure SiO2 and further confirmed the
results obtained from XRD analysis. In conclusion, the EDX analysis confirms the formation of
SiO2 and also proves that the thermal treatment technique is effective, as there were no loss of
element was observed in the process.

Fig. 2: EDX pattern of ASN for sample calcined at 500 °C

The FT-IR offers vital evidence on the vibrational frequencies of functional groups and
network structures of a certain material. A certain vibration frequency range can be ascribed to a
bond type, as specific frequencies are absorbed by the molecules of the materials which are
characteristic of their structure. Frequency of the absorbed radiation is attributed to the frequency
of the bond or group that vibrates. In this work, the ASN were examined for the interface between
the formation of the compound and the polymer (PVP) matrix at different calcination temperatures
by the FT-IR.
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The analysis of the precursor at room temperature before calcination was conducted, to
observe the organic and inorganic behaviour of the material prior to calcination, as well as after
calcination. The analysis was conducted within the range of 280-400 cm-1 as being shown by the
FTIR spectra in Figure 3, and Table 1 respectively.

Fig. 3: FT-IR spectra of ASN precursor before calcinations

The availability of peaks in the precursor before calcination shown in Figure 3, beyond
1000 cm-1 indicates the existence of organic source coming from the PVP. The C-N stretching
vibration peak was observed at 1269 cm-1. The peak appeared at 1431 cm-1 was attributed to C-H
bending vibrations originated from methylene group. The band at 1649 cm-1 was due to N-H
stretching vibration and the two different bands at 2951 cm-1 and 3457 cm-1 observed was assigned
to C-H stretching and N-H stretching vibration respectively. The peak 1045 cm-1 was observed to
be OH group Si-O bending vibration and Si-O bond vibration was observed at 564 and 689 cm-1
respectively.
The FT-IR spectra of reveals the removal PVP and the effect of the calcination
temperature on bond formation of ASN as shown in Figure 4. The Si-O-Si bending vibration was
observed at 445 cm-1 for the sample calcined at 500-700 °C and shifted to higher wave number of
457 cm-1 when calcine at 750 °C. There were no shifts of peak at 798 cm-1 due to Si-O-Si bond
observed in all the samples calcined. An asymmetric vibration mode of Si-O-Si was exhibited at
1062 cm-1 at all calcination temperature [3, 11]. Band due to water molecules and OH in H-bonded
water where observed respectively between 500-600 °C. The FT-IR analysis revealed the bonds
related to SiO2 and further confirm the formation of SiO2 as shown in the EDX result.

Fig. 4: FT-IR spectra of ASN calcined at various temperatures in the range of 280-4500 cm-1
 1159

3.3 The Structural Analysis

The phase and structure of the material was observed by analyzing the sample using X-ray
diffraction spectroscopy. The main precursor that contain silicon tetraacetate and PVP after being
dried at 80 °C shows no diffraction peaks indicating that the sample was amorphous at room
temperature before calcination as shown in Fig. 5

Fig. 5: XRD patterns for SiO2 precursor before calcination at room temperatures

Upon calcination of the sample between 500-700°C as shown in Figure 6, the samples
behave to be in amorphous state (ASN), as there were no significant peaks. In 2014, Rida and
Harb[12] reported to have produced ASN at the calcination temperature of 650 °C. In the same
vain, an amorphous cobalt doped SiO2 was synthesized between 300-500°C [13]. Nevertheless, in
2014, Musić et al. [14] could not produce crystal phase of SiO2 at 800 oC until the temperature was
elevated to 1000 °C. However, in this work, a peak was observed after calcination at 750 °C at a
position of 2θ=26.56°. The spectrum corresponds to Cristobalite beta high with ICDS collection
code 77401.

Fig. 6: XRD patterns for ASN calcined at temperatures 500, 550, 600, 650, 700 and 750°C.

3.4 Morphology and Particle Size Distribution

TEM analysis was used to examine the influence of the calcination temperature ranging
from 500-750 °C on the shape, size as well as particles distribution of the prepared ASN. The
TEM images were obtained using Model JOEL 2010F UHR version electron microscope at
accelerating voltage of 200 kV. The same procedures were followed in determining the
distribution of the particles and average size of the nanoparticles using image J software
1160

Fig. 7: TEM images of ASN calcined

at 500, 550, 600, 650, 700 and 750 oC.

Fig. 7: TEM images and particle size distribution of ASN calcined

at 500, 550, 600, 650, 700 and 750 oC.

In this work, the particles size of ASN ranges from 6.28 nm to 9.60 nm as the temperature
varies from 500 to 750 °C shown in Table 2 and Fig 7. The images seems to be <10 nm at the
entire calcination temperatures and obtained the smallest particle size at the temperature of 500 °C
and the particles size reluctantly increases with the increasing in temperature. This implies that
 1161

thermal treatment method was for the first time used to prepare amorphous silica nanoparticles
with less than 10 nm particle size.

3.5 Optical Properties

The absorbance behavior of ASN was studied using UV-visible spectrophotometer. The
samples were calcinated between 500-750°C as shown in Figure 8. The entire sample calcined
exhibits an optical absorbance in the UV region which implies that they possess a wide band gap
as reported in the literature [15, 16]. The peaks at 243 nm which appeared in all the sample was
famous in silica nanoparticles reported by some literatures to as singlet to singlet transition in
silicon related intrinsic defect [17, 18]. The peaks between 300-320 nm were attributed to various
defects due to non-bridging oxygen hole centre or neutral oxygen vacancies (ODCs) defects [17].

Fig. 8: Absorbance spectra of ASN calcine at various temperatures

3.6 Band gap energy of ASN

The influence of the calcination temperature was observed on the optical band gap of the
entire sample as shown in Figure 9 which was determined from the absorption coefficient value.
The energy gap (𝐸𝑔) is considered as reported assuming a direct transition between valence and
conduction bands [19]. The relation is given by the expression (1) below.

(∝ ℎ𝑣)2 = 𝐴(ℎ𝑣 − 𝐸𝑔) (1)

Where 𝐴 is a constant, the photon energy is denoted by ℎ𝑣 and 𝐸𝑔 is the optical energy band. As
shown in Figure 9 we have plotted the characteristics (∝ ℎ𝑣)2 versus ℎ𝑣 values, where the optical
band gap of the material was determined by simply extrapolating the linear region to where
(∝ ℎ𝑣)2 tends to zero.
1162

Fig. 9: Plot of the (∝ ℎ𝑣)2 as function of photon energy of ASN calcined at various temperatures

Table 2: The average particle size of ASN measured by TEM and comparison of the
band gap energy for samples calcined at various temperatures

Temperature (°C) DTEM (nm) Eg (eV)

500 6.28 3.803

550 6.51 3.965

600 6.80 4.000

650 7.06 4.096

700 9.26 4.126

750 9.60 4.352

The optical band gap was found to be 3.803, 3.965, 4.000, 4.096, 4.126 and 4.352 eV
respectively as the calcination temperature was increase from 500 to 750°C. Figure 10 gives the
relationship between the optical bandgap and the calcination temperature.
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Fig. 10: A graph showing the influence of calcination temperature on the

particles size and optical band gap ASN.

4. Conclusions

A simple thermal treatment method was successfully applied to synthesize ASN. The FT-
IR confirmed the bond formation after calcination which reveals the presence of SiO 2 bond and
also completes the disappearance of PVP in the sample. The XRD result reveals the sample to be
ASN at all calcination. A wide band gap energy observed in the material was attributed to the
absorption exhibited in the UV region.

Acknowledgments

The researchers gratefully acknowledge the financial support for this study from the
Malaysian Ministry of Higher Education (MOHE) and Universiti Putra Malaysia through the
Fundamental Research Grant Scheme (FRGS) and Inisiatif Putra Berkumpulan (IPB) research
grant.

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