38 research outputs found
Structure of supercritically dried calcium silicate hydrates (C-S-H) and structural changes induced by weathering
The nanostructure of supercritically dried calcium silicate hydrates was researched. This particular drying procedure was used to avoid nanostructure modifications due to conventional drying processes. Thus, in this study, the as-precipitated cementitious C-S-H structure was obtained for the first time. A specific surface area 20 % larger than conventionally dried C-S-H was measured. Given the importance of this nanostructured phase for the properties of hydrated cements, especially when in contact with CO2-rich environments, the supercritically dried C-S-H was weathered for 2 weeks. The structural effects of this weathering process on the C-S-H were researched and calcium carbonate microcrystal precipitation or the presence of silica by-product are reported. Calcite and aragonite polymorphs were observed, as well as nanoporous silica forming globular arrangements. In addition, 2 weeks of weathering was not enough to carbonate the entire C-S-H sample.Junta de Andalucía TEP11
The cluster model: A simulation of the aerogel structure as a hierarchically-ordered arrangement of randomly packed spheres
A new structural model based on the premises widely used for describing the structure of aerogels has been introduced. These structures have been described as an assemblage of randomly-packed spheres in several hierarchically-ordered levels. A new algorithm has been developed for constructing our models from these premises using computer simulation. Subsequently, several applications have been simulated to characterize real systems, obtaining textural parameters such as the specific surface area, specific porous volume or the apparent density of the systems, based on the Monte Carlo technique and on geometrical considerations. The object of these is to test the ability of the models to explain the structure of some real aerogels. This Cluster Model has also been applied as an initial approach to the study of the mechanical properties of aerogels. Results support the general conclusion that these models are useful for explaining the structure of aerogels.Ministerio de Ciencia y Tecnología MAT2002-00859Junta de Andalucía TEP 011
Nanostructured sonogels
Acoustic cavitation effects in sol-gel liquid processing permits to obtain nanostructured materials, with size-dependent properties. The so-called "hot spots" produce very high temperatures and pressures which act as nanoreactors. Ultrasounds force the dissolution and the reaction stars. The products (alcohol, water and silanol) help to continue the dissolution, being catalyst content, temperature bath and alkyl group length dependent. Popular choices used in the preparation of silica-based gels are tetramethoxysilane (TMOS), Si(OCH3)4 and tetraethoxysilane (TEOS), Si(OC 2H5)4. The resultant "sonogels" are denser gels with finer and homogeneous porosity than those of classic ones. They have a high surface/volume ratio and are built by small particles (1 nm radius) and a high cross-linked network with low -OH surface coverage radicals. In this way a cluster model is presented based on randomly-packed spheres in several hierarchical levels that represent the real sonoaerogel. Organic modified silicates (ORMOSIL) were obtained by supercritical drying in ethanol of the corresponding alcogel producing a hybrid organic/inorganic aerogel. The new material takes the advantages of the organic polymers as flexibility, low density, toughness and formability whereas the inorganic part contributes with surface hardness, modulus strength, transparency and high refractive index. The sonocatalytic method has proven to be adequate to prepare silica matrices for fine and uniform dispersion of CdS and PbS quantum dots (QDs), which show exciton quantum confinement. We present results of characterization of these materials, such as nitrogen physisorption, small angle X-ray/neutrons scattering, electron microscopy, uniaxial compression and nanoindentation. Finally these materials find application as biomaterials for tissue engineering and for CO2 sequestration by means the carbonation reaction.Ministerio de Ciencia y Tecnología MAT2005-158
Diatomite releases silica during spirit filtration
The purpose of this study was to ascertain whether diatomite is an inert filter aid during spirit filtration. Surely, any compound with a negative effect on the spirit composition or the consumer’s health could be dissolved. In this study different diatomites were treated with 36% vol. ethanol/water mixtures and the amounts and structures of the extracted compounds were determined. Furthermore, Brandy de Jerez was diatomite- and membrane-filtered at different temperatures and the silicon content was analysed. It was found that up to 0.36% by weight of diatomite dissolved in the aqueous ethanol and amorphous silica, in the form of hollow spherical microparticles, was the most abundant component. Silicon concentrations in
Brandy de Jerez increased by up to 163.0% after contact with diatomite and these changes were more marked for calcined diatomite. In contrast, reductions of more than 30% in silicon concentrations were achieved after membrane filtration at low temperatures
Formation of siliceous sediments in brandy after diatomite filtration
Brandy is quite a stable spirit but sometimes light sediment appears. This sediment was separated and analysed by IR and SEM-EDX. It was revealed that the sediment is composed mostly of silica and residual organic matter. Silica was present as an amorphous phase and as microparticles. In an attempt to reproduce the formation of the sediment, a diatomite extract was prepared with an ethanol/water mixture (36% vol.) and a calcined diatomite similar to that used in brandy filtration. This extract was added to unfiltered brandy in different amounts. After 1 month, the Si concentration decreased in all samples and sediments with similar compositions and features to those found in the unstable brandy appeared.
The amounts of sediment obtained were directly related to the decrease in Si concentration in solution. Consequently, it can be concluded that siliceous sediment in brandy originates from Si released during diatomite filtration
SANS study of hybrid silica aerogels under "in situ" uniaxial compression
We have modified the inorganic silica network of aerogels with polydimethylsiloxane (PDMS), a hydroxyl-terminated polymer, to obtain an organic modified silicate (ORMOSIL). Reactions were assisted by high-power ultrasounds. The resulting gels were dried under supercritical conditions of the solvent to obtain a monolithic sono-aerogel. The mechanical behaviour of these aerogels can be tuned from brittle to rubbery as a function of the organic polymer content. In order to determine the links between the mechanical behaviour and modifications made to the microstructure, SANS (small-angle neutron scattering) experiments were carried out. To measure the intensities under "in situ" uniaxial compression of the aerogel, a specific sample-holder was built. Under uniaxial compression the 2D-diagrams were significantly anisotropic (butterfly pattern), indicating the rearrangement of the polymer. The form factor of these aerogels is described well by two correlation lengths, small microporous silica clusters surrounded by entangled polymer chains of 6 nm average size (blobs), which form a larger secondary level of agglomerates governed by the "frozen-in" elastic constraints.Comisión Interministerial de Ciencia y Tecnología MAT2005-1583European Commission CT-2003-50592
Propiedades mecánicas de aerogeles híbridos de sílice
Se han obtenido aerogeles híbridos de sílice orgánico-inorgánico por aplicación de ultrasonidos de alta potencia en los precursores líquidos y posterior secado del gel húmedo en condiciones supercríticas en etanol. Las cadenas orgánicas no se degradan térmicamente y aceleran el proceso de contracción de la red por activación térmica. Los ultrasonidos inducen un entrecruzamiento de cadenas orgánicas que unen los cúmulos de sílice porosa y evitan su ciclidación. Los ensayos de ruptura en compresión uniaxial indicaron un aumento del módulo de ruptura, pasando de 8 MPa para el aerogel de sílice pura hasta 24 MPa para un aerogel de 50% en peso de contenido de polímero. Se observa asimismo una disminución continua en el módulo de Young con el contenido de polímero (de 100 a 56 MPa). Estos aerogeles híbridos se comportan como elastómeros con deformaciones de hasta el 50%, mostrando una disminución del módulo de relajación viscoelástica.Hybrids silica aerogels have been obtained by means the high power ultrasounds application in the precursor liquid and the drying of the wet gel under the supercritical condition of ethanol. The organic chains don't degrade thermally and accelerate the network shrinkage process by thermal activation. The ultrasounds induce an organic Chain crosslinking bonding to the porous silica clusters and avoid its cyclidation. The failure tests by uniaxial compression show an increase of the rupture modulus, passing from 8 MPa for a pure silica aerogel to 24 MPa for an aerogel with a 50 weight % of polymer content. It is also noted a continuous decrease of the Young's modulus with the polymer content (from 100 to 56 MPa). These hybrid aerogels behave as elastomers with up to a 50% strain, showing a decrease in the relaxation viscoelastic modulus.Ministerio de Ciencia y Tecnología MAT2002- 08
The cluster model: A hierarchically-ordered assemblage of random-packing spheres for modelling microstructure of porous materials
A new structural model based on the premises widely used for describing the structure of random materials, and especially aerogels, is introduced. Aerogels are described as an assemblage of randomly-packed spheres in several hierarchically-ordered levels. A new algorithm has been developed for constructing structural models from these premises using computer simulation. Subsequently, several techniques based both on the Monte Carlo technique and on geometrical considerations for characterizing real systems have been simulated, and textural parameters of the models have been obtained, including specific surface area, specific porous volume and the apparent density of the systems. This characterization process yields a set of parameters used for testing the capacity of the models to reproduce the structure of several real systems, like aerogels. Special attention has been paid to the pore size distribution calculations: the Monte Carlo integration and the triangulation algorithms have been compared.Comisión Interministerial de Ciencia y Tecnología MAT2005-158