A11v28n1 PDF
A11v28n1 PDF
A11v28n1 PDF
(Submitted: April 20, 2010 ; Revised: September 23, 2010 ; Accepted: October 5, 2010)
Abstract - The experimental conditions were optimized for the synthesis of amorphous SiO2 particles by the
reaction of neutralization of sodium silicate solution with H2SO4 solution. Amorphous SiO2 particles were
characterized by XRD, FT-IR, FE-SEM, EDS and microelectrophoresis. The amorphous peak was located at
2θ = 21.8o in the XRD pattern. Primary SiO2 particles were ~ 15 to ~ 30 nm in size and they aggregated into
bigger particles. Amorphous SiO2 particles showed a specific surface area up to 130 m2g-1, dependent on the
parameters of the precipitation process. The EDS spectrum of amorphous SiO2 particles did not show
contamination with sulfate or other ions, which cannot be excluded in traces. pHzpc =1.7 was obtained by
microelectrophoresis.
Keywords: Precipitated SiO2; XRD; FT-IR; FE-SEM; EDS; Microelectrophoresis
Instrumentation
FlowSorb II 2300 surface area analyzer Figure 1: X-ray powder pattern of precipitated SiO2
(Micromeritics, Norcross, GA, USA). with a characteristic amorphous peak
Electrophoretic mobilities were measured using a
microelectrophoresis apparatus manufactured by Jesionowski and Krysztafkiewicz (1999)
Rank Brothers, Cambridge, U.K. precipitated SiO2 using the reaction of sodium
silicate with dilute HCl, H2SO4 or CO2 in alcohol- "structural" water and 2.36% of “free water”
containing media. Dispersibility and size of the SiO2 (moisture). For comparison, the EDS spectrum of
particles depended on the nature of the alcohol added. precipitated SiO2 crystallized at high temperature was
In the presence of isopropanol, SiO2 particles were recorded under the same instrumental conditions and a
525 nm in size, with a tendency to form aggregates fully stoichiometric ratio Si:O = 1:2 was obtained due to
1340 nm in size. The precipitation of SiO2 in the removal of H2O molecules and condensation of –SiOH
presence of ethylene glycol yielded particles 112 nm groups. The EDS spectrum did not show the presence of
in size, whereas in the presence of glycerine SiO2 sulfate, chloride or sodium ions, thus indicating that
particles 360 nm in size were formed. Pajonk et al. these ions were well removed in the mother liquour.
(1995) prepared SiO2 aerogels using Generally, sulfate ions can specifically adsorb on
polyethoxydisiloxanes obtained by the reaction of (hydrous) oxide surfaces, similar to phosphates or
tetraethoxysilane (TEOS) and water in the presence of chromates (Musić et al. 1986). Their adsorption
sulfuric acid. Sol-gel reactions were conducted under decreases with a pH-increase, which is opposite to metal
acidic, neutral or basic conditions in methanol, cation adsorption, i.e., the adsorption of metal cations
ethanol or acetone. Hyeon-Lee et al. (1997) applied increases with a pH-increase (Musić et al. 1988). A
the aero-sol-gel procedure to prepare SiO2 powder good removal of SO 24− and Cl- ions can also be due to a
with a very high specific surface area, ~ 400 m2g-1. An low pHzpc of the amorphous SiO2 particles. Fig. 4 shows
inverse microemulsion sol-gel procedure was used to the dependence of electrophoretic mobility on the pH of
prepare SiO2 particles of colloidal dimensions the SiO2 suspension. The zero point of charge is located
(Espiard et al. 1995). The sol-gel procedure was also at pH = 1.7. Above pHzpc = 1.7 the surface of the
used to prepare porous and spherical SiO2 particles amorphous SiO2 particles is negatively charged.
(Hirose et al. 1994). Spherical SiO2 particles showed a Fig. 5 shows the FT-IR spectrum of precipitated
tendency to increase in size with an increase of SiO2. The IR band at 3437 cm-1 is due to the stretching
ultrasonic energy during the synthesis of these vibration of H2O molecules. Correspondingly, the IR
particles (Enomoto et al. 1996). band at 1632 cm-1 is due to the bending vibration of
In the present work, a specific surface area of up H2O molecules. The shoulder at 3246 cm-1 could be
to 130 m2g-1 could be obtained. This is important, assigned to the stretching vibrations of Si-OH groups in
especially if we consider the relative simplicity of the structure of amorphous SiO2. The presence of the
the procedure for the production of amorphous SiO2 Si-OH group is proved as bonded water. The very
as applied in the present work. strong and broad IR band at 1111 cm-1 with a shoulder
Fig. 2 shows FE-SEM images of the amorphous at 1188 cm-1 is usually assigned to the TO and LO
SiO2 particles at different optical magnifications. The modes of the Si-O-Si asymmetric stretching vibrations.
majority of primary SiO2 particles were ~15 to ~ 30 nm The IR band at 956 cm-1 can be assigned to silanol
in size. These primary particles showed a tendency to groups. In the case of alkali silicate glasses, this band is
form bigger particles (aggregates). Fig. 3 shows the assigned to Si-O- stretching vibrations. The IR band at
EDS spectrum of amorphous SiO2 particles. This 800 cm-1 can be assigned to Si-O-Si symmetric
spectrum showed only the presence of silicon and stretching vibrations, whereas the IR band at 474 cm-1
oxygen. An excess of oxygen in relation to the is due to O-Si-O bending vibrations. Murphy and
stoichiometric ratio Si:O = 1:2 can be attributed to the Greytak (1979) assigned the IR band at 380 cm-1 to the
presence of water and –SiOH groups. The analysis of Si-OH wagging mode. In the present work, the IR band
precipitated SiO2 showed that it contained 7.63% of at 380 to 377 cm-1 is recorded as a shoulder at 378 cm-1.
a) 1 μm b) 100 nm
Figure 2: FE-SEM images of precipitated SiO2 at different optical magnifications (details a and b).
Brazilian Journal of Chemical Engineering Vol. 28, No. 01, pp. 89 - 94, January - March, 2011 Short Communication
92 S. Musić, N. Filipović-Vinceković and L. Sekovanić
Figure 4: Electrophoretic mobility of amorphous SiO2 particles as a function of the pH of the suspension.
Bock and Su (1970) recorded the IR spectrum of in the far-IR region. Vibrational spectra of silica
fused silica and compared it with the results of glasses have been studied (Philips, 1987; Tomozawa
vibrational calculations. For fused silica, the IR et al. 2005) and IR spectroscopy used to monitor
bands at 377, 465, 800, 950, 1100 and 1190 cm-1 changes in amorphous SiO2 during its heating up to
were recorded. These IR bands also appear in 1150°C (Chmel et al. 1990). Innocenzi (2003) used
crystalline silica (quartz, crystobalite and tridymite). IR spectroscopy to investigate different stages during
Of course, the crystalline silicas have more the sol-gel formation of silica. The FT-IR spectrum
pronounced IR bands with narrower line-widths. shown in Fig. 5 agrees well with the spectrum
Amorphous silica and crystalline silica can really obtained for amorphous SiO2 precipitated by the
only be distinguished on the basis of measurements carbonation method (Cai et al. 2009).
SiO2
Relative transmittance
956
570
1632 378
800
3246
3437
474
1188
1111
Brazilian Journal of Chemical Engineering Vol. 28, No. 01, pp. 89 - 94, January - March, 2011 Short Communication
94 S. Musić, N. Filipović-Vinceković and L. Sekovanić
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Winyall, M. E., "Silica Gels: Preparation and with silicon-hydroxy group and the quick synthesis
Properties”, in: Applied Industrial Catalysis, 3, p. of coesite under lower temperature. High Pressure
43, Academic Press, Inc. (1984). Res., 28, p. 641 (2008).