Journal of Non-Crystalline Solids 272 (2000) 119±126

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Dense silica microspheres from organic and inorganic acid

hydrolysis of TEOS
Basudeb Karmakar, Goutam De *, Dibyendu Ganguli
Sol±Gel Division, Central Glass and Ceramic Research Institute, 196 Raja S.C. Mullick Road, Jadavpur, Calcutta 700 032, India
Received 15 November 1999; received in revised form 22 February 2000

Abstract
It has been observed that any acid±water mixture (irrespective of the type of acid organic and inorganic) in the pH
range 1.35±2.25 can produce silica microspheres from tetraethyl orthosilicate (TEOS) with only a restriction of the
water/TEOS molar ratio which varies in the ranges 1.0±1.5 for strong acids and 1.5±4.0 for weak acids. Microspheres
have been found to form in situ from an intermediate heavier liquid phase of polysilicic acid which has been segregated
and separated from the sol during the progress of the reaction. FTIR spectral analysis reveals that this intermediate
liquid predominantly consists of four-membered siloxane rings (Si4 O12 ) as identi®ed by their absorption frequencies in
the ranges 550±600 and 670±710 cmÿ1 . The segregated liquid phase has been transformed into glass-like non-porous
dense microspheres during stirring. FTIR analyses of these silica spheres are similar to that of fused silica. Density,
surface area and size of the dried (150°C) microspheres vary in the ranges 2.10±2.16 g cmÿ3 , 0.5±0.9 m2 /g and 10±60 lm,
respectively. Their high densities and FTIR spectral data indicate a similar structure to that of silica glass. Ó 2000
Elsevier Science B.V. All rights reserved.

1. Introduction More recently, an acidic medium has also been

Silica microspheres are important technical
materials since they are widely used in clinical,
pharmaceutical, electronic packaging and other
applications and also in the preparation of silica
glass, structural ceramics, chromatographic col-
umns, etc. [1±5]. These applications require high
purity powders. Hydrolysis of tetraethyl orthosi-
licate (TEOS) is a versatile technique to synthesize
such powders [6±10]. Early work [6] demonstrated
sphere formation in a strongly basic medium.
* TEOS was conducted in the presence of nine dif-
Corresponding author. Tel.: +91-33 483 8086; fax: +91-33
473 0957.
E-mail addresses: goutamde@cscgcri.ren.nic.in, gde41@hot-
mail.com (G. De).
0022-3093/00/$ - see front matter Ó 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 3 0 9 3 ( 0 0 ) 0 0 2 3 1 - 3
found to be suitable for the synthesis [7±9]. Thus,
Karmakar et al. [7] prepared silica microspheres by
hydrolysing TEOS with acetic acid and Izutsu
et al. [8] with tartaric acid (weak organic acids)
whereas Kawaguchi and Ono [9] demonstrated the
same using nitric acid (strong inorganic acid).
These ®ndings raised the question whether the
presence of a particular acid (acetic, tartaric or
nitric) is responsible for the generation of silica
microspheres from TEOS or any type of acid, ir-
respective of their classi®cation (i.e., weak/strong;
organic/inorganic), can serve the purpose.
To address the above question, hydrolysis of
ferent sources of weak, strong, organic and inor-
ganic acids and a generalized conclusion is drawn.
The structures of the intermediate and ®nal solid
120 B. Karmakar et al. / Journal of Non-Crystalline Solids 272 (2000) 119±126

silica products obtained in this way have been in-
vestigated by FTIR spectral analysis. The shape
and size of the particles have also been determined
using scanning electron (SEM) and transmission
electron microscopies (TEM).
2. Experimental
Silica microspheres were prepared by hydroly-
sing TEOS, Si(OC2 H5 )4 with doubly distilled
water in the presence of analar grade formic
(HCOOH), acetic (CH3 COOH), propanoic
(CH3 CH2 CH2 COOH), pentanoic (CH3 CH2 CH2
CH2 COOH), hydrochloric (HCl), nitric (HNO3 ),
sulphuric (H2 SO4 ) and ortho phosphoric (H3 PO4 )
acid.
To obtain silica particles, TEOS was added to a
mixture of acid and water under stirring (rate
550  20 rpm† at 25  1°C. Some typical molar
compositions of TEOS, water and acid are given in
Table 1. Fig. 1 shows the schematic diagram of
silica microsphere generation from the system
TEOS±water±acid. As marked in the ®gure, the
mixture of TEOS, water and acid is initially bi-
phasic. It transforms into monophasic liquid (sol)
on stirring. The stirring period for the transfor-
mation of biphasic to monophasic sol is di€erent
for di€erent acids. On further progress of stirring,
a biphasic liquid mixture containing a heavier
liquid phase (density > 1.5 g cmÿ3 ) of polysilicic
acid suspended (under stirring) in the mother sol is
again formed. This heavier liquid phase has been
found to transform into silica microspheres in all
the systems studied in this work, when further
stirred in the mother sol; it does not yield any
microsphere in absence of the mother sol. After
the appearance of particles, the suspension was
further stirred for 0.5 h. It was then quickly ®ltered
and washed successively with ethanol and acetone.
Finally, they were dried in an air oven 60  2°C).
The yield of silica powder (weight of 150°C dried
silica spheres X 100/total silica present in TEOS) in
all the cases varied 33  2%.
It may be noted here that in case of TEOS±
CH3 COOH±H2 O system, H2 O/TEOS molar ratio
<3 produces only the heavier liquid phase. H2 O/
TEOS molar ratios >3 but 6 4 do not show sep-
aration of any heavier liquid phase although the
®nal products obtained in these cases are similar to
those in the other cases.
The FTIR spectra of the intermediate species
were measured by placing the heavier liquid be-
tween two potassium bromide (KBr) windows
with a 0.05 mm thick te¯on spacer and those of
solid powder samples were taken following the
usual KBr pellet technique. All the spectra were
recorded averaging 32 scans at 4 cmÿ1 resolution
on a Nicolet 5 PC FTIR spectrometer. There was
normally no shift in peak position in repeated ex-

Table 1
Some typical compositions of reactants with reaction parameters and powder characteristics
Mole ratio Acid pH of Incubation Density of silica Shape of silica as
TEOS Water Acid acid±water period (min) powders observed under
mixture (g cmÿ3 ) optical microscope
1 4 4a Pentanoic 2.25 114  5 2:10  0:02 Spherical and
irregular powder
1 4 4a Butanoic 2.18 45  3 2:11  0:02 Spherical powder
(agglomerated)
1 4 4a Propanoic 2.01 24  1 2:14  0:02 Spherical powder
(less agglomerated)
1 4 4a Acetic 1.63 5  0:1 2:15  0:02 Spherical powder
1 1.5 1:2  10ÿ3 b Formic 1.35 17  1 2:13  0:02 Spherical powder
1 1.5 1:2  10ÿ3 b Nitric 1.35 17  1 2:16  0:02 Spherical powder
1 1.5 1:2  10ÿ3 b Hydrochloric 1.35 17  1 2:12  0:02 Spherical powder
1 1.5 1:2  10ÿ3 b Sulphuric 1.35 17  1 2:13  0:02 Spherical powder
1 1.5 1:2  10ÿ3 b Orthophosphoric 1.35 17  1 2:12  0:02 Spherical powder
a
Calculation based on added volume of acid.
b
Calculation based on pH value of acid±water mixture.
 B. Karmakar et al. / Journal of Non-Crystalline Solids 272 (2000) 119±126
Fig. 1. Schematic illustration of silica microsphere generation
from the system TEOS±water±acid.
periments; the maximum shift, if and when ob-
served, was not more than 1 cmÿ1 .
The shape and size of the silica particles were
measured with SEM. The heavy liquid silica phase
was dispersed in acetone and observed under
TEM. The density of the dried (150°C) powders
was measured with a pycnometer using water as a
liquid. The N2 adsorption/desorption experiments
were performed by the BET method.
3. Results
Some typical preparative compositions, `incu-
bation period' (time elapsed for ®rst appearance of
cloudiness i.e., separation of powders in the sol
from onset of reactions, as observed visually) and
121
powder characteristics have been given in Table 1.
It has been observed in our previous work [7] that
the most suitable composition for the preparation
of silica microsphere using acetic acid is
TEOS:water:acid ˆ 1:4:4 (mol). The homologues
of acetic acid i.e., propanoic, butanoic and pen-
tanoic acid also yield silica microspheres with the
same molar ratio, whereas formic, nitric, hydro-
chloric, sulphuric and phosphoric acid under that
composition give only a clear sol. However, the
suitable molar composition to generate silica
microspheres using the latter strong acids is
TEOS:water:acid ˆ 1:1:5:1:2  10ÿ3 (Table 1). It is
also found that any acid±water mixture of the pH
range 1.35±2.25, irrespective of the acid source,
can produce silica microsphere from TEOS with
only restriction of molar ratio of water/TEOS
which varies in the ranges 1.0±1.5 for strong acids
and 1.5±4.0 for weak acids. In case of organic
homologous series, the incubation period is in-
creased from 5 min (acetic acid) to 114 min (pen-
tanoic acid).
It has already been mentioned that the heavier
liquid phase separated from the sol is the common
intermediate product of solid silica microspheres.
FTIR spectra of this intermediate liquid silica
product obtained by using di€erent acids and also
that of TEOS (for comparison) have been shown
in Fig. 2. The liquid phase clearly shows two
ranges of IR absorption frequencies due to silox-
ane rings at 500±600 and 670±710 cmÿ1 [18,20]
which are absent in the monomeric TEOS. On the
other hand the solid silica microspheres obtained
by using any type of acid shows the absorption
only at around 570 cmÿ1 (Fig. 3.).
This peak and the peak at around 940 cmÿ1 due
to Si±OH (silanol) stretching gradually weaken
during heat treatment and the spectrum of the
powder matches well with that of silica glass after
heat treatment at about 500°C for 1 h.
The pycnometric density of silica microspheres
varies in the range 2.10±2.16 g cmÿ3 (Table 1). The
density was measured after drying the samples at
150°C (16 h) to avoid contamination of trapped
water and solvents in the as prepared powders.
The corresponding surface area data obtained by
N2 adsorption showed very low value in the range
of 0.5±0.9 m2 /g. The N2 adsorption data of the
122 B. Karmakar et al. / Journal of Non-Crystalline Solids 272 (2000) 119±126
Fig. 2. FTIR spectra of (a) TEOS, and intermediate heavier
liquids obtained by using (b) acetic, (c) formic, (d) nitric,
(e) hydrochloric and (f) sulphuric acid.
powders dried at 150°C obtained from acetic acid
is also measured. In this case Type II isotherm re-
sults [11]. The dried powder samples do not con-
tain unhydrolyzed alkoxy groups and/or adsorbed
acids as supported by the absence of correspond-
ing IR peaks. Thermogravimetric (TG) analysis
(rate of heating 10°C/min) of 150°C dried samples
shows a weight loss of about 5% up to about
500°C and almost no weight loss is observed up to
1200°C. IR spectra (Fig. 3) indicate that this
weight loss is due to the removal of water formed
Fig. 3. FTIR spectra of silica microspheres dried or heated at:
(a) room temperature; (b) 150°C; (c) 350°C; (d) 500°C and
(e) silica glass.
by the condensation of silanols (IR peak at about
940 cmÿ1 ). This is further supported by the fact
that the above weight loss (due to escape of water)
also correlates well with their theoretical density.
Indeed, the silica microspheres, when heated at
500°C for 1 h, showed a density of 2.20 g cmÿ3 ,
similar to that of silica glass.
SEM micrographs of silica microspheres ob-
tained by using di€erent acids are similar excepting
the size of the microspheres varying in the range
10±60 lm. The particles are mostly agglomerate
free and having very smooth glass like surface.
Fig. 4 shows some representative examples of
particles obtained from acetic acid (weak acid) and
HCl (strong acid).
4. Discussion
It is found that the acetic acid generates silica
microspheres in a shorter incubation period com-
 B. Karmakar et al. / Journal of Non-Crystalline Solids 272 (2000) 119±126
pared to other organic as well as inorganic acids
(Table 1). In cases of organic acids, the increasing
pH values i.e. decreasing acid strength along the
homologues (going from acetic to pentanoic) re-
tards the hydrolysis time [12], resulting an increase
of the incubation period in this direction. It is also
noteworthy that the incubation period of acetic
acid is even lower than that of the inorganic acids
(Table 1). The formation of a highly hydrolyzable
intermediate, ¹Si±OOCCH3 by the reaction of
acetic acid and TEOS even in the presence of water
has been established by IR studies [7,13]. The
lowering of incubation period in case of acetic acid
suggests the fast hydrolysis of the intermediate
¹Si±OOCCH3 groups followed by growth com-
pared to the catalytic hydrolysis of TEOS in
presence of inorganic acids.
Fig. 4. SEM micrographs of silica microspheres obtained by
using (a) acetic, and (b) hydrochloric acid.
123
It has been mentioned above that, in any acid of
Table 1, dense silica microspheres have been gen-
erated through the separation of a common in-
termediate heavier liquid phase which is insoluble
in the mother sol (Fig. 1) and this heavier liquid
phase is transformed into tiny droplets on stirring
which harden into solid microspheres. In fact, Fig.
5 shows that nucleation of spherical silica already
starts within the heavy phase. Kozuka and Sakka
[14] also found a similar sedimentary layer in the
system TMOS±H2 O±HCl. They suggested that
this layer is responsible for the creation of highly
interconnected round shaped silica.
Comparison of the FTIR spectra of the inter-
mediate liquid obtained by using various acids
with that of TEOS (Fig. 2) indicates that the in-
termediate liquid is constituted of polysilicic acids,
generated via complete hydrolysis of TEOS. Ab-
sence of characteristic IR peak of residual unhy-
drolyzed ethoxy groups also supports this
conclusion. The peak at around 620 cmÿ1 in
Fig. 2(b) is due to acetic acid [15].
Amorphous silica having no siloxane ring does
not show any IR absorption bands in the range
500±800 cmÿ1 [16]; it is reported that the ring
bands of amorphous and crystalline silicas appear
in this region [16±20]. A comparison of IR ab-
sorption frequencies in this region for the heavier
liquids (present work), amorphous sol±gel silica
[19], crystalline silica (coesite) [20] and silicate
Fig. 5. TEM micrograph of a typical intermediate heavy liquid
phase by using sulphuric acid, showing the existence of ®ne
spherical silica particles.
124 B. Karmakar et al. / Journal of Non-Crystalline Solids 272 (2000) 119±126
(neptunite) [20] containing four-membered rings
(Si4 O12 ) with those obtained by theoretical calcu-
lation [18] have been presented in Table 2. It is
seen that the four-membered rings of crystalline
silica and silicate minerals [20] strongly absorb in
two IR ranges, namely, at 550±600 and 680±690
cmÿ1 , whereas sol±gel derived amorphous silica
®lms show only one absorption band at 550±600
cmÿ1 as reported by Yoshino et al. [19]. The
heavier liquid phases obtained by using di€erent
acids absorb in the ranges 550±600 and 670±710
cmÿ1 (Fig. 2, Table 2). This comparison, therefore,
clearly indicates that the intermediate liquid phase
mainly consists of fourfold siloxane rings (cyclic
tetramers) and the generation of four-membered
siloxane rings in the intermediate product is inde-
pendent of the nature of acids, viz. organic, inor-
ganic, weak and strong. The IR spectrum of the
mother sol (after separation of silica spheres) in all
the cases shows absence of any band in the 670±
710 cmÿ1 region, apparently con®rming the ab-
sence of cyclic tetramers in the sol. This result
suggests that only the available hydrogen ion (H‡
or H3 O‡ ) is responsible for the segregation of a
cyclic siloxane tetramer which in turn transforms
into dense silica.
It has been already mentioned that the suitable
pH of microsphere formation varies in the range
1.35±2.25. This is very close to the isoelectric point
(IEP) or point of zero charge (PZC) of polymeric
silica which ranges in the pH 1.5±2.0 [21]. It is well
known that at IEP or PZC, the rate of polymer-
ization is very slow and the gelling time is very
Table 2
IR absorption frequencies (cmÿ1 ) related to the four-membered siloxane rings (Si4 O12 ) of the intermediate heavier liquids obtained by
using di€erent acids and those observed both by theoretical calculation and experimentation using amorphous and crystalline silica and
silicatea
Intermediate liquids obtained by Acetic acid
using Formic acid
Nitric acid
Hydrochloric acid
Sulphuric acid
Theoretical calculation [18]
Experimentation [20] using Sol±gel derived SiO2 (amorphous) [19]
Coesite, SiO2 (crystaline) [20]
Neptunite (crystaline) [20]
a
s ± strong, w ± weak.
high [21]. However, at this low pH, due to neutral
character of Si(OH)4 (generated via complete hy-
drolysis of TEOS), the most obvious reaction is
self-polymerization which results in dimers fol-
lowed by linear tetramers. In the linear tetramer,
ring closure is very rapid due to the proximity of
Si±OH end group and cyclic tetramer is mainly
formed since bond angles make ring closure of
linear tetramers favorable. Once cyclic species
predominates, monomers and dimers react with
these species increasing their molecular weight. At
the same time the adjacent Si±OH groups of the
resulting polymers condense internally leading to
more compact three dimensional particles [12,21].
At higher temperature (resulting from the exo-
thermic hydrolysis reaction), growth continues to
larger sizes.
Iler [21] pointed out the existence of cyclic tri-
and tetramer as fully condensed species in poly-
silicic acid. However, he mentioned that these
fractions are small and have never been isolated
from polymerizing solutions. In the present case
about 1/3 of total silica (yield of silica spheres is
33  2%; see Section 2) is separated from the
mother sol as cyclic tetramer species, known to be
hydrolysis resistant [12] and of high skeletal den-
sity [22]. Kelts and Armstrong [23] also showed the
formation of an adequate amount of cyclic trimer
and tetramer during the hydrolysis of TEOS by
29
Si NMR.
The non-porous and dense character of the sil-
ica powders have been con®rmed by their high
density value (2:13  0:03 g cmÿ3 ) which is close to
587 s 710 w
600 s 700 w
598 s 700 s
540 s 672 s
572 s 670 s
564±567 684
550±600 )
557±600 683
530±560, 684±690, 590±655
 B. Karmakar et al. / Journal of Non-Crystalline Solids 272 (2000) 119±126
the theoretical density of silica glass. The corre-
sponding BET surface area value (0.5±0.9 m2 /g)
also supports this. The non-porous nature of the
silica powders (dried at 150°C) obtained by acetic
acid has been further con®rmed by the N2 -
adsorption isotherm data. In this case, typical
Type II adsorption isotherm data suggests non-
porous character of the material [11,24].
IR peaks at around 570 and 940 cmÿ1 shown by
the 60°C dried silica microspheres have been found
to be heat sensitive (Fig. 3). The peak at 570 cmÿ1
has been assigned to fourfold siloxane ring by
Yoshino et al. [19]. The peak at 940 cmÿ1 is at-
tributed to silanol [25,26]. These two peaks grad-
ually decrease in intensity and ®nally disappear
with increase in heat-treatment temperature of the
microspheres. The spectrum after heating the
samples at about 500°C closely matches that of
silica glass (Fig. 3). At this temperature the density
also increases to 2.20 g cmÿ3 . It may be noted here
that high temperature, i.e., 1000°C is needed to
densify TEOS derived silica gels [27]. The forma-
tion of such dense silica spheres (density
2:13  0:03 g cmÿ3 after drying at 150°C and
2.20 g cmÿ3 at 500°C) in solution clearly indicates
the genesis of these particles from relatively com-
pact silica rings (here four-membered) as their
presence would increase the network density [22]
and as a consequence glass like density is achiev-
able at such a low temperature. In case of the dried
silica spheres no IR band was found at around 700
cmÿ1 (one of the bands assigned here to cyclic
tetramers; Fig. 2); this may be explained to be due
to the transformation of the four-membered rings
into more open structures i.e., ®vefold and larger
rings in a continuous random network present in
fused silica.
5. Conclusions
(a) The synthesis of high purity and silica glass
like dense silica microspheres from TEOS has
been demonstrated using a variety of acid±wa-
ter mixture of the pH range 1.35±2.25 with the
only restriction of the molar ratio of water/
TEOS which varies in the ranges 1.0±1.5 for
strong acids and 1.5±4.0 for weak acids.
125
(b) Silica microspheres have been generated in
situ from an intermediate heavy liquid phase
of polysilicic acid, which has been separated
from the sol during progress of the reactions
and predominantly consists of fourfold siloxane
rings. Microspheres and siloxane ring formation
processes have been found to be independent of
the origin of H‡ ion.
(c) The presence of fourfold siloxane rings in
the heavy phase has been identi®ed with the
IR absorption bands in the ranges 550±600
and 670±710 cmÿ1 by reference both to theoret-
ical data, and crystalline silica and silicate
spectra.
Acknowledgements
Thanks are due to our colleagues of Electron
Microscope Division for their help in SEM and Dr
D. Kundu for helpful suggestions.
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