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Journal of the UniversityY.ofDimitriev,
ChemicalY.Technology
Metallurgy, 43, 2, 2008, 181-192
ABSTRACT
The objective of this review is to summarize some of the most significant research achievements in the sol-gel
science and technology. Comprehensive review papers have been made regularly in the past three decades by outstanding
scientists such as Mackenzie, Sakka, Zarzycki, Schmidt, Uhlmann, Livage, Ulrich, Dislich. The main sources for the
scientific information are the Journal of Sol-Gel Technology started in 1993 and the International Sol-Gel Workshops
periodically held from 1981 up to now. In the beginning the studies have been centered mainly on silica and silicate glasses
but they progressively have been extended to many other oxide and non-oxide ceramics and composites. It has been shown
that the sol-gel methods have great potential in producing important materials in forms of bulk, fibers, sheets, coating
films, and particles at relatively low temperatures. It is also possible to produce materials of new compositions with high
purity, high homogeneity, and to control particle size distributions in a nano-scale level. One of the most important
advances of sol-gel science is the preparation of inorganic-organic hybrids. They started with the development of ormocers
based on the formation of chemical bonds between the constituents and nanocomposites, containing organic molecules
incorporated into porous gel matrix. That is why the sol-gel method is a representative nanotechnology. Specific examples
are presented that have been carried out in leading universities and laboratories. Some our results in this field are also
discussed briefly. A classification was made of sol-gel derived materials according to their functions: optical (solar
collectors, fibers, waveguide), electronic (piezoelectric transducers, non-volatile memory, solid electrolytes), thermal
(refractorys and low expansion ceramics, aerogels), chemical (catalysts, membranes, corrosion protection), biomedical
(entrapment of enzyme and living tissue, implants). It was emphasized the crucial role of starting precursors and the
processing routes to the final structure and the impact on the technological functions.
Keywords: sol-gel technology, sol-gel materials, hydrolysis, condensation, precursors.
INTRODUCTION
The preparation of inorganic refractory materials follows well elaborated technological schemes which
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An important peculiarity of the sol gel technologies is the possibility to control the mechanism and kinetics of the proceeding chemical reactions. In other
words, controlling each step of the sol gel process one
may affect the final structure of the materials and the
modification of the processes. Some of these principal
processes are subjected to detailed analysis by Livage et
al. [35] and by Yoldas [36]. The structure and phase
changes accompanying the development of a definite
sol gel process can be followed by different physical
experimental techniques, which are constantly improving. Among them the spectral methods proved very appropriate due to the relatively easy processing of the
results and their explicit interpretation in the case of
both amorphous and crystal state of the gel products.
Combining several structural methods adequate information have been obtained for sol-gel materials in the
system TiO2-SiO2 [37].
During the 90s of the past century a series of
reviews [38-50] were dedicated to the synthesis of various materials by sol gel methods and most of them are
still attracting. Important information on the synthesis
of ferroelectric polycrystalline and amorphous coatings
of alkoxides with the participation of LiNbO3, KNbO3
and BaTiO3 and the possibility of their application as
condensers, waveguide, etc. was summarized [39]. At
the same time, the successful development of nonlinear
optical devices with the participation of gold particles
[51] and CdS in a silicate matrix [44] were reported.
The development of a method for preparing optical fibres [47] and the wide application of the sol-gel processes to optical telecommunication technologies at
present show a high degree of realization on an industrial level [50]. Kakihana [49] made an exclusively detailed analysis of the applicability of the different variants of sol gel technologies for the preparation of complex multicomponent materials such as ceramic superconductors using a wide range of precursors. Gugliemi
[41] and Mackenzi [45] analysed the advantages of the
sol-gel coatings for protecting the metals from oxidation, thermal and chemical corrosion and especially for
improving their strength. An important problem concerning the density of gel coatings was solved successfully by Scherer [42]. He showed that sintering of the
amorphous gel particles at high temperatures preceding
the crystallization processes and realized by suitable
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Fig. 1. The award of prof. S. Sakka by the academic council of UCTM, 2005.
Honnory plaque of UCTM for his outstanding contributions to the sol-gel science (Fig. 1). E. Zarzycky [108,
109] was an active participant in the work of the International School on Condensed Matter Physics in 1988
[108] and in the Conference on Glass and Ceramics in
1993 [109]. He read reviews on the fractal structure of
amorphous gels, peculiarities of preparation of monodisperse powders and the role of different precursors
with respect to the formation of gel materials (Fig. 2).
Dislich [110, 111] also contributed very much to the
Bulgarian scientists joining in this field by their participation in the conferences on Glass and Ceramics in
Varna in 1993 and 1996 (Fig. 3).
In an extensive report in 1996 Samuneva [112]
summarized the first investigations performed in our
country on the use of low-temperature sol-gel methods
for synthesis of glasses, glass-ceramic coatings, ceramic
powders, pigments and glazing. In this analysis it was
pointed out that the researchers of the Department were
interested in developing and applying new combinations
of precursors. In the middle of the 90s of the 20th century, several teams were formed at the Department, which
extended the investigations on new sol-gel products.
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The based on the data concerning the development of sol gel technologies, in summary one can say
that a very important moment is the choice of appropriate precursors. Most often these are alkoxides, soluble
metal salts, polymers, colloids, which, depending on
their nature, may be combined with suitable solvents,
and the aggregation processes stimulating solid phase
formation can be controlled. Fig. 4 shows schematically the most used variant of the sol-gel process. We
accepted a more general interpretation proposed by
Kachichana [49] according to which a chemical process
starting from solutions and leading to a solid phase without a precipitate is a sol-gel process even if the system
does not represent an infinite solid network. One of the
methods leading to colloid dispersions (sols) is based
on inorganic salts, water and occurrence of hydrolysis
processes at a definite pH. A classical example is the
formation of a gel of SiO2 whose detailed description is
given in the monograph of Iler [157]. This technique
was not a subject of the present review. The non-hydrolytic sol-gel method (without participation of water) is
also promising, especially with respect to transition metal
and pigments were obtained from precursors containing organic and inorganic components [120-126]. The
preparation of bioceramic materials is a permanently
topic for the researchers of the Department. The sol-gel
methods are used for investigating silicate and
phosphate systems containing fluoroappatite,
Hydrolysis and
condensation
tricalcium phosphate as well as gels with antiof metal alkoxides
bacterial effect [127-134]. A series of organoinorganic systems for immobilization of cells Colloidal dispersion
[135-138] can be attached among this group of
materials. Incorporation of rare-earth ions into
SolSol-gel processing
amorphous gel silicate matrices stable at high
temperatures without metastable phase separation, was achieved. Multicomponent ceramic
nanopowders containing rare-earth manganites Inorganic-organic
hybrids
were obtained [139-141]. Specific sol gel methPolymer pyrolisis
ods (peroxy method, ion exchange) were used
to obtain nanostructured transition metal oxides (V2O5, MoO3, WO3) [142-145]. Successful Fig. 4. Different routes of the sol-gel processing.
Non-hydrolytic
sol-gel reactions
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Optical and
photonic functions
Electronic functions
(ferrolectricity electronic and
ionic conduction)
Capacitor, piezoelectric
transfer;
Non-volatile memory,
transparent
semiconductors;
Solid electrolyte (battery,
fuel cell);
Chemical functions
Mechanical functions
Thermal function
Biomedical functions
-Entrapment of enzyme,
cell, coated implant,
medical test
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The sol-gel technology is very efficient in producing various functional materials in which particle
size, porosity, thin layer thickness, separation of particles with different compositions and structures may
be controlled and successful applications have been
achieved. Following the analysis of Sakka [106] they
may be summarized in a scheme (Fig. 5) where examples
of materials applied in electrotechnics, electronics, optics, photonics, high-temperature technologies, chemical technologies, biochemistry and medicine are given.
The history of the sol-gel technologies and the development of materials by using them is far from ending.
The possibility of varying both parameters and precursors
is endless. A typical example is the development of organic-inorganic hybrid and nanostructured materials on
which the attention of modern scientists is focused.
Acnowledgemens
This work was financially supported by the Nacional
Science Fund, Ministry of Education and Science of Bulgaria, contract No BY-TH 102 (No 806, UCTM, Sofia).
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