L. Esquivias

Sonogels and derived materials

Nowadays the sol–gel process is used by an increasing number of researchers for the preparation of various products, including bulk materials, films, membranes or fibers. The application of ultrasound (sonocatalysis) to the precursors gives rise to materials with new properties, known as sonogels. The absence of additional solvent and, mainly, the effects of ultrasonic cavitation create a unique environment for sol–gel reactions leading to particular features in the resulting gels: high density, fine texture, homogeneous structure etc. These properties determine the evolution of sonogels on further processing and the final material structure. In this sense, the full exploitation of sonocatalysis requires a thorough understanding of the processes involved and their sensitivity to reaction parameters. For this purpose, we have used diverse techniques to investigate the microstructural evolution during different steps in the sonogel process. The results of these studies are reported here. Finally, we present an overview of some applications for which the mechanical, textural and optical characteristics of sonogels are quite useful. Copyright

Sol-gel synthesis of SiO2P2O5 glasses

The synthesis of P2O5SiO2 glasses from solutions has been studied through gelation kinetics, Raman and nuclear magnetic resonance (NMR) spectroscopies. Different preparation methods are compared. The effect of the phosphorus precursor has been investigated. Phosphoric acid esters are not hydrolyzed and they do not yield condensation with silica. Reaction of anhydrous H3PO4 with SiOR groups leads to the formation of SiOP bonds which are easily hydrolyzed. Only a few remain after addition of water and gelation. Therefore, PSi homogeneity is difficult to achieve after gelation and the following drying and heat-treatment procedures. This absence of homogeneity is observed by solid-state magic angle spinning (MAS)-NMR and X-ray diffraction studies performed on gel samples heated at 300, 500 and 800°C in the case of xerogels and 500, 950 and 1140°C for aerogels.

Stress During Drying of Two Stone Consolidants Applied in Monumental Conservation

The object of this paper is to evaluate behaviour during drying of two stone consolidants: Wacker OH and Tegovakon V, containing tetraethoxysilane. During drying, the gel network contracts due to capillary pressure generated by solvent evaporation. When the consolidant dries inside the stone porous structure, the shrinkage is constrained in all three dimensions. In these conditions, the dried gel suffers a high stress that could cause it to crack. When there is a free surface, as for a consolidant layer on the surface of a pore, the stress can relax in the direction normal to the surface. In this case, the stress is controlled by network rigidity.The rigidity of the gel network has been evaluated by mercury porosimetry, while pore size, which controls capillary pressure, has been determined by nitrogen adsorption. The shrinkage of gels under mercury pressure is characterised by high moduli. This fact suggests a high rigidity of the networks. The small pore radii found in the network (<3 nm) indicate that high capillary pressures are generated within the gel network.

Procedure to use phosphogypsum industrial waste for mineral CO2 sequestration.

Industrial wet phosphoric acid production in Huelva (SW Spain) has led to the controversial stockpiling of waste phosphogypsum by-products, resulting in the release of significant quantities of toxic impurities in salt marshes in the Tinto river estuary. In the framework of the fight against global climate change and the effort to reduce carbon dioxide emissions, a simple and efficient procedure for CO(2) mineral sequestration is presented in this work, using phosphogypsum waste as a calcium source. Our results demonstrate the high efficiency of portlandite precipitation by phosphogypsum dissolution using an alkaline soda solution. Carbonation experiments performed at ambient pressure and temperature resulted in total conversion of the portlandite into carbonate. The fate of trace elements present in the phosphogypsum waste was also investigated, and trace impurities were found to be completely transferred to the final calcite. We believe that the procedure proposed here should be considered not only as a solution for reducing old stockpiles of phosphogypsum wastes, but also for future phosphoric acid and other gypsum-producing industrial processes, resulting in more sustainable production.

Structural study of silica sonogels

Abstract Silica sonogels obtained by the hypercritical drying of gels from the hydrolysis of a tetraethoxysilane + water mixture submitted to the action of ultrasounds were studied using small-angle X-ray scattering (SAXS), BET and density measurements. The Guinier regions in SAXS curves are wider and gyration radii are smaller than those of aerogels prepared from alcoholic dilution. These sonogels do not present self-similarity in the accessible scale length of the SAXS measurements. Slopes greater than 4 in the high angle region reveal important electronic density fluctuations on the pore-matrix boundaries, due to their very fine porosity as a consequence of the sonocatalysis.

Application of mercury porosimetry to the study of xerogels used as stone consolidants

Abstract Alkoxysilanes, low-viscosity monomers that polymerize into the porous network of stone by a sol–gel process, are widely used in the restoration of stone buildings. We have used the mercury porosimetry technique to characterize changes in microstructure of three granites following their consolidation with two popular commercial products (Wacker OH and Tegovakon V). The suitability of this technique is questioned because a surprising increase of stone porosity is observed. In order to investigate the feasibility of porosimetry, we analyze the behavior of xerogels prepared from the two commercial products, under mercury pressure. Gels are basically compacted and not intruded by mercury. Thus, the increase of stone porosity after consolidation can actually be associated with gel shrinkage. Mercury porosimetry, therefore, has been found unsuitable for characterizing the microstructure of consolidated rocks. However, it can be employed usefully to evaluate shrinkage of gels under mercury pressure, which permits the behavior of a consolidant during the process of drying in stone to be predicted. It is a key factor because many problems of consolidants are related to their drying process within the stone. Gels under study exhibit a high rigidity and an elastic behavior, as consequence of their microporous structure. Finally, the reduction in the porous volume of gels after the porosimetry test demonstrates that the shrinkage mechanism is based on pore collapse.

Effect of the method of preparation on the texture of TiO2SiO2 gels

Abstract The chemical reactivity of Ti(OBun)4 was modified through the addition of acetic acid to obtain sonogels of the TiO2SiO2 system by ultrasonic treatment of the alkoxide-water mixture. The characteristics of the resulting gels were compared with those of similar standard gels prepared in alcoholic solution. The influence of composition and method of preparation on the gels was studied. The results of density and BET measurements, thermal analysis and IR spectroscopy indicate that ultrasound drastically affects the texture.

Larnite powders and larnite/silica aerogel composites as effective agents for CO2 sequestration by carbonation

This paper presents the results of the carbonation reaction of two sample types: larnite (Ca(2)SiO(4)) powders and larnite/silica aerogel composites, the larnite acting as an active phase in a process of direct mineral carbonation. First, larnite powders were synthesized by the reaction of colloidal silica and calcium nitrate in the presence of ethylene glycol. Then, to synthesize the composites, the surface of the larnite powders was chemically modified with 3-aminopropyltriethoxysilane (APTES), and later this mixture was added to a silica sol previously prepared from tetraethylorthosilicate (TEOS). The resulting humid gel was dried in an autoclave under supercritical conditions for the ethanol. The textures and chemical compositions of the powders and composites were characterized.The carbonation reaction of both types of samples was evaluated by means of X-ray diffraction and thermogravimetric analysis. Both techniques confirm the high efficiency of the reaction at room temperature and atmospheric pressure. A complete transformation of the silicate into carbonate resulted after submitting the samples to a flow of pure CO(2) for 15 min. This indicates that for this reaction time, 1t of larnite could eliminate about 550 kg of CO(2). The grain size, porosity, and specific surface area are the factors controlling the reaction.

Fractionation and fluxes of metals and radionuclides during the recycling process of phosphogypsum wastes applied to mineral CO2 sequestration

The industry of phosphoric acid produces a calcium-rich by-product known as phosphogypsum, which is usually stored in large stacks of millions of tons. Up to now, no commercial application has been widely implemented for its reuse because of the significant presence of potentially toxic contaminants. This work confirmed that up to 96% of the calcium of phosphogypsum could be recycled for CO2 mineral sequestration by a simple two-step process: alkaline dissolution and aqueous carbonation, under ambient pressure and temperature. This CO2 sequestration process based on recycling phosphogypsum wastes would help to mitigate greenhouse gasses emissions. Yet this work goes beyond the validation of the sequestration procedure; it tracks the contaminants, such as trace metals or radionuclides, during the recycling process in the phosphogypsum. Thus, most of the contaminants were transferred from raw phosphogypsum to portlandite, obtained by dissolution of the phosphogypsum in soda, and from portlandite to calcite during aqueous carbonation. These findings provide valuable information for managing phosphogypsum wastes and designing potential technological applications of the by-products of this environmentally-friendly proposal.

Kinetic study of gelation of solventless alkoxide-water mixtures☆

Abstract A very high-speed rotatory blender was used to enhance the homogenization of TEOS + H 2 O mixtures. The effects of several reaction parameters on the gelation rate of these solutions and those submitted to ultrasonic treatment were studied. Comparison of the results points to differing accelerating mechanisms in each case.