1122
ISSN 1027-4510, Journal of Surface Investigation: X-ray, Synchrotron and Neutron Techniques, 2019, Vol. 13, No. 6, pp. 1122–1125. © Pleiades Publishing, Ltd., 2019.
Russian Text © The Author(s), 2019, published in Poverkhnost’, 2019, No. 12, pp. 3–7.
Features of Colloidal Aggregation in Tetraethoxysilane-Water-
Ethanol Ternary Mixtures by Small-Angle Neutron Scattering
O. V. Tomchuk
a, b,
*, M. V. Avdeev
a, c,
**, O. I. Ivankov
a, d, e
, L. A. Bulavin
b, d
, and V. L. Aksenov
a, f
a
Joint Institute for Nuclear Research, Dubna, 141980 Russia
b
Taras Shevchenko National University of Kyiv, Kyiv, 01601 Ukraine
c
St. Petersburg University, St. Petersburg, 199034 Russia
d
Institute for Safety Problems of Nuclear Power Plants, Ukraine National Academy of Sciences, Chornobyl, 07270 Ukraine
e
Moscow Institute of Physics and Technology, Dolgoprudny, 141701 Russia
f
“Kurchatov Institute” National Research Center, Moscow, 123182 Russia
*e-mail: tomchuk@jinr.ru
**e-mail: avd@nf.jinr.ru
Received January 20, 2019; revised March 18, 2019; accepted April 2, 2019
Abstract—The influence of the concentration of components in a tetraethyl orthosilicate (TEOS)–water–
ethanol mixture on the growth of silicate aggregates in a basic environment is studied with small-angle neu-
tron scattering. There is a general increase in the size of aggregates with an increase in the amount of both
water and TEOS. At the same time, when the H
2
O : TEOS molar ratio is 2 : 1, the structure of the aggregates
repeats, regardless of the TEOS concentration in the system. The scattering length density of the aggregates
is found via hydrogen/deuterium isotopic substitution and contrast variation to analyze the possible inclusion
of residual ethyl and hydroxyl groups into their structure.
Keywords: small-angle neutron scattering, tetraethyl orthosilicate, sol-gel method, colloidal aggregation
DOI: 10.1134/S1027451019060545
INTRODUCTION
Tetraethyl orthosilicate Si(C
2
H
5
O)
4
(TEOS) is
widely used in the synthesis of various organic materi-
als, including catalysts, flavors, dyes, agrochemicals,
and medicines [1–3]. Due to its ability to form
branched silicon-containing polymers [4, 5], TEOS is
an integral part of promising technologies in the ther-
mocatalytic decomposition of methane for hydrogen
production [6, 7] and in the manufacture of acid-base
sensors [8, 9] and various membrane filters [10],
including to protect the environment [11].
Varying the conditions of hydrolysis synthesis
(acidity, temperature, and concentration of compo-
nents) allows various structures to be obtained, from
polymers with weak intermolecular bonds to dense
colloidal particles [1, 12, 13]. Such structures are
actively studied with a small-angle X-ray and neutron
scattering (SAXS and SANS) [14], which make it pos-
sible to obtain their structural characteristics (size,
polydispersity, surface type, etc.) at the nanoscale (1–
100 nm). Indeed, previous small-angle scattering
curves for silicate aggregates grown in TEOS water–
alcohol (ethanol) solutions under basic conditions
indicated that fractal structures consisting of silicate
aggregates with a diffuse surface were formed [12, 13,
15, 16]. When the influence of the water–TEOS molar
ratio (w) on the structure of aggregates was studied
with SANS, the critical behavior of their structural
parameters (w = 2) was found [15]. The surface prop-
erties are independent of w for w > 2, which indicates
a situation close to the complete saturation of Si–OH
bonds in TEOS at w = 2. The internal structure of
aggregates was studied with external and internal vari-
ation of the SANS neutron contrast via isotopic
hydrogen/deuterium substitution [16]. The authors
showed that most hydrolyzed Si–OH bonds are not
closed and participate in the condensation reaction to
form Si–O–Si bonds.
The aim of this work is to study the structure of
such clusters with SANS (including contrast variation)
depending on the total concentration of components
in the system. Considering that the proportion of
TEOS with those of other components is in certain
ratios, the concentration of TEOS in the solution is
chosen as the parameter determining the structure,
which varies in our experiments. Experiments are also
performed at earlier cluster growth stages in compari-
son with previous studies [15, 16] to test the hypothesis
about the inf luence of the amount of TEOS on a sol–
gel polymerization processes during the active forma-
tion of aggregates.