Barriers to Transport and Mixing in Volume-Preserving Maps with Nonzero Flux

In this paper we identify the geometric structures that restrict transport and mixing in perturbations of integrable volume-preserving systems with nonzero net flux. Unlike KAM tori, these objects cannot be continued to the tori present in the integrable system but are generated by resonance and have a contractible direction. We introduce a remarkably simple algorithm to analyze the behavior of these maps and obtain quantitative properties of the tori. In particular, we present assertions regarding the distribution of the escape times of the unbounded orbits, the abundance of tori, and the size of the resonant regions

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

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

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

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

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

Bioactivity of wollastonite/aerogels composites obtained from a TEOS-MTES matrix

Organic-inorganic hybrid materials were synthesized by controlled hydrolysis of tetraethoxysilane (TEOS), methyltrimethoxysilane (MTES), synthetic wollastonite powders and polydimethylsiloxane (PDMS) in an ethanol solution. Aerogels were prepared from acid hydrolysis of TEOS and MTES with different volume ratio in ethanol, followed by addition of wollastonite powder and PDMS in order to obtain aerogels with 20 wt% of PDMS and 5 wt% of CaO of the total silica. Finally, when the wet gels were obtained, they were supercritically dried at 260°C and 90 bar, in ethanol. In order to obtain its bioactivity, one method for surface activation is based on a wet chemical alkaline treatment. The particular interest of this study is that we introduce hybrid aerogels, in a 1 M solution of NaOH, for 30 s at room temperature. We evaluate the bioactivity of TEOS-MTES aerogel when immersed in a static volume of simulated body fluid (SBF). An apatite layer of spherical-shaped particles of uniform size smaller than 5 microns is observed to form on the surface of the aerogels after 25 days soaking in SBF.Ministerio de Ciencia e Innovación MAT2005-01583Junta de Andalucía TEP 79

Simulating the effect of muscle weakness and contracture on neuromuscular control of normal gait in children

Altered neural control of movement and musculoskeletal deficiencies are common in children with spastic cerebral palsy (SCP), with muscle weakness and contracture commonly experienced. Both neural and musculoskeletal deficiencies are likely to contribute to abnormal gait, such as equinus gait (toe-walking), in children with SCP. However, it is not known whether the musculoskeletal deficiencies prevent normal gait or if neural control could be altered to achieve normal gait. This study examined the effect of simulated muscle weakness and contracture of the major plantarflexor/dorsiflexor muscles on the neuromuscular requirements for achieving normal walking gait in children. Initial muscle-driven simulations of walking with normal musculoskeletal properties by typically developing children were undertaken. Additional simulations with altered musculoskeletal properties were then undertaken; with muscle weakness and contracture simulated by reducing the maximum isometric force and tendon slack length, respectively, of selected muscles. Muscle activations and forces required across all simulations were then compared via waveform analysis. Maintenance of normal gait appeared robust to muscle weakness in isolation, with increased activation of weakened muscles the major compensatory strategy. With muscle contracture, reduced activation of the plantarflexors was required across the mid-portion of stance suggesting a greater contribution from passive forces. Increased activation and force during swing was also required from the tibialis anterior to counteract the increased passive forces from the simulated dorsiflexor muscle contracture. Improvements in plantarflexor and dorsiflexor motor function and muscle strength, concomitant with reductions in plantarflexor muscle stiffness may target the deficits associated with SCP that limit normal gait