Small-angle X-ray scattering study of the smart thermo-optical behavior of zirconyl aqueous colloids

The smart thermo-optical systems studied here are based on the unusual thermoreversible sol-gel transition of zirconyl chloride aqueous solution modified by sulfuric acid in the molar ratio Zr/SO4:3/1. The transparency to the visible light changes during heating due to light scattering. This feature is related to the aggregates growth that occurs during gelation. These reversible changes can be controlled by the amount of chloride ions in solution. The thermoreversible sol-gel transition temperature increases from 323 to 343 K by decreasing the molar ratio Cl/Zr from 7.0 to 1.3. In this work the effect of the concentration of chloride ions on the structural characteristics of the system has been analyzed by in situ SAXS measurements during the sol-gel transition carried out at 323 and 333 K. The experimental SAXS curves of sols exhibit three regions at small, medium and high scattering vectors characteristics of Guinier, fractal and Porod regimes, respectively. The radius of primary particles, obtained from the crossover between the fractal and Porod regimes, remains almost invariable with the chloride concentration, and the value (4 Angstrom) is consistent with the size of the molecular precursor. During the sol-gel transition the aggregates grow with a fractal structure and the fractal dimensionality decreases from 2.4 to 1.8. This last value is characteristic of a cluster-cluster aggregation controlled by a diffusion process. Furthermore, the time exponent of aggregate growth presents values of 0.33 and 1, typical of diffusional and hydrodynamic motions. A crossover between these two regimes is observed.

Structural study of composites of aerosil fumed silica and tetraethoxysilane-derived sonogels

Composites of aerosil fumed silica and tetraethoxysilane-derived sonogel were prepared by changing the aerosil content between 0 and 30wt% with respect to the silica content in the original tetraethoxysilane (TEOS). The structural characteristics were studied by density and Vickers microhardness measurements and analyzed by means of small-angle X-ray scattering (SAXS). The structure of the composite aerosil/TEOS-derived sonogel can be described as inclusions of the aerosil particles embedded in the matrix of the TEOS-derived sonogel, forming an aerosil/matrix interfacial surface inside the composite. The weakening of the bonding of aerosil/matrix interface, as suggested by the reported decrease in microhardness, increases the fracture toughness of the composite. The additive effect of the aerosil particles on the structure of the sonogel accounts for the increase of the bulk density and reduction of the specific surface of the composite. Some internal structure associated with the microclusters making up the sonogels is apparent from systematic deviations from Porod's law found in the system with small aerosil contents. (c) 2005 Elsevier B.V. All rights reserved.

Nanostructure and luminescent properties of sol-gel derived europium-doped amine functionalised hybrids

The effect of doping by europium triflate on the nanoscopic structure of organic-inorganic hybrid formed by a siliceous network containing pendant amine-terminated propyl chains, called aminosils, was investigated by Small-Angle X-ray Scattering (SAXS). It appears that the composites exhibit a two-level structure. The first level consists of well-condensed cubic-like siloxane octamers, with a radius of gyration around 2 angstrom. The second level is formed by the aggregation of these siloxane nanodomains to form larger structures, in which the nanodomains are spatially correlated and separated by the organic pendant chains. Europium doping inhibits the aggregation between siloxane octamers, leading to a less compact second-level structure. This can be explained by the Eu3+ stop coordination close to the external surface of the siloxane nanodomains, as detected by luminescence spectroscopy.

Small-angle X-ray and nuclear-magnetic resonance study of siloxane-PMMA hybrids prepared by the sol-gel process

Transparent siloxane-polymethylmethacrylate (PMMA) hybrids were synthesized by the sol-gel process through hydrolysis of methacryloxyproyltrimethoxysilane (TMSM), tetramethoxysilane (TMOS) and polymerization of methylmethacrylate (MMA) using benzol peroxide (BPO) as catalyst. These composites have a good chemical stability due to the presence of covalent bonds between the inorganic (siloxane) and organic (PMMA) phases. The effects of siloxane content, pH of the initial sol and BPO content on the structure of the dried gels were analyzed by small-angle X-ray scattering (SAXS). SAXS results revealed the presence of an interference (or correlation) peak at medium q-range for all compositions, suggesting that siloxane groups located at the ends of PMMA chains form isolated clusters that are spatially correlated. The average intercluster distance - estimated from the q-value corresponding to the maximum in SAXS spectra - decreases for samples prepared with increasing amount of TMSM-TMOS. This effect was assigned to the expected increase in the number density of siloxane groups for progressively higher siloxane content. The increase of BPO content promotes a more efficient polymerization of MMA monomers but has no noticeable effect on the average intercluster distance. High pH favors polycondensation reactions between silicon species of both TMOS and TMSM silicon alcoxides, leading to a structure in which all siloxane clusters are bonded to PMMA chains. This effect was confirmed by Si-29 nuclear-magnetic resonance (NMR) measurements.

Gelation and drying of weakly bonded silica-PPO nanocomposites

Silica-poly(oxypropylene) (PPO) nanocomposites containing PPO with weak physical bonds between the organic (PPO) and inorganic (silica) phases were obtained by the sol-gel procedure. Three precursor sols containing silica and PPO with molecular weights of 1000, 2000 and 4000g/mol were prepared. The structure changes during the whole sol-gel process, i.e. sol formation, sol-gel transition and gel aging and drying were investigated in situ by small angle X-ray scattering (SAXS). The experimental SAXS curves corresponding to sols and wet gels containing PPO of molecular weight 1000g/mol indicate that the aggregates formed during the studied process are fractal objects. Close to the sol-gel transition and during gel aging the fractal dimension is D=2.5. A clearly different structure evolution occurs in samples prepared with PPO with molecular weights 2000 and 4000 g/mol. Our SAXS results indicate the presence of two coexisting and well-defined structure levels, one of them corresponding to small silica clusters and the other to large silica aggregates. These two levels remain along the whole transformation. The SAXS curves of all dry samples are similar to those of the corresponding wet gels suggesting that no significant changes at nanoscopic scale occur during the drying process.

Photopatternable di-ureasil-zirconium oxocluster organic-inorganic hybrids as cost effective integrated optical substrates

Organic-inorganic hybrids containing methacrylic acid (McOH, CH(2)= C(CH(3))COOH)) modified zirconium tetrapropoxide, Zr(OPr(n))(4), classed as di-ureasil-zirconium oxo-cluster hybrids, have been prepared and structurally characterized by X-ray diffraction (XRD), small-angle X-ray scattering (SAXS), Fourier transform infrared (FT-IR) and Raman (FT-Raman) spectroscopies, Si and C nuclear magnetic resonance (NMR), and atomic force microscopy (AFM). XRD and SAXS results have pointed out the presence of Si- and Zr-based nanobuilding blocks (NBBs) dispersed into the organic phase. Inter-NBBs correlation distances have been estimated for the pure di-ureasil and a model compound obtained. by hydrolysis/condensation of Zr(OPr(n))(4):McOH (molar ratio 1: 1): d(Si) approximate to 26 +/- 1 angstrom and d(Zr) approximate to 16 +/- 1 angstrom, respectively. In the case of the di-ureasil-zirconium oxo-cluster hybrids, these distances depend on the Zr relative molar percentage (rel. mol. Zr %) (d(Si) ranges from 18 to 25 angstrom and d(Zr) from 14 to 23 angstrom, as the rel. mol. Zr % increases from 5 to 75), suggesting that the Si- and Zr-based clusters are interconstrained. Complementary data from FT-IR, FT-Raman, (29)Si and (13)C NMR, and AFM support to a structural model where McOH-modified Zr-based NBBs (Zr-OMc) are present over the whole range of composition. At low Zr-OMc contents (rel. mol. Zr % <30) the clusters are well-dispersed within the di-ureasil host, whereas segregation occurs at the 0.1 mu m scale at high Zr-OMc concentration (rel. mol. Zr % = 50). No Zr-O-Si heterocondensation has been discerned. Monomode waveguides, diffractions gratings, and Fabry-Perot cavities have been written through the exposure of the hybrid monoliths to UV light. FT-Raman has shown that the chemical process that takes place under illumination is the polymerization of the methacrylate groups of the Zr-OMc NBBs. The guidance region in patterned channels is a Gaussian section located below the exposed surface with typical dimensions of 320 mu m wide and 88 mu m deep. The effective refractive index is 1.5162 (maximum index contrast on the order of 1 x 10(-4)) and the reflection coeficient of the Fabry-Perot cavity (formed by a grating patterned into a 0.278 cm channel) is 0.042 with a free spectral range value of 35.6 GHz.

Thermo-Reversible Sol-Gel Transition of Surface Modified Titanium Poly Oxo Building Blocks

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Structure and properties of conducting bacterial cellulose-polyaniline nanocomposites

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Thermo-reversible sol-gel transition of TiO2 nanoparticles with surface modified by p-toluene sulfonic acid

In this paper an unprecedent thermo-reversible sol-gel transition for titania nanoparticles dispersed in a solution of p-toluene sulfonic acid (PTSH) in isopropanol is reported. The sol formed by the thermo-hydrolysis at 60 degrees C of titanium tetraisopropoxide (Ti((OPr)-Pr-i)(4)) reversibly changes into a turbid gel upon cooling to room temperature. Turbidimetric measurements performed for samples containing different nominal acidity ratios (A = [PTSH]/[Ti]) have evidenced that the gel transformation temperature increases from 20 to 35 degrees C as the [PTSH]/[Ti] ratio increases from 0.2 to 2.0. SAXS results indicate that the thermo-reversible gelation is associated to a reversible aggregation of a monodisperse set of titania nanoparticles with average gyration radius of approximate to 2 nm. From the different PTSH species evidenced by Raman spectroscopy and TG/DTA of dried gels we proposed that the then-no-reversible gelation in this systems is induced by the formation of a supramolecular network, in which the protonated surface of nanoparticles is interconnected through cooperative hydrogen bonds between -SO3 groups of p-toluene sulfonic acid. (C) 2009 Elsevier Ltd. All rights reserved.

Effects of Synthesis Conditions on the Nanostructure of Hybrid Sols Produced by the Hydrolytic Condensation of (3-Methacryloxypropyl)trimethoxysilane

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Modulation of the Pharmacological Activities of Secretory Phospholipase A2 from Crotalus durissus cascavella Induced by Naringin

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Small angle X-ray scattering study of structural changes in silica gel modified with organofunctional groups

Silica gel surfaces, organofunctionalized with 2-mercaptobenzimidazole, iminosalicylaldehyde and imidazole groups were examined using the small angle X-ray scattering technique (SAXS). From the scattering intensity data it was concluded that particles have a uniform size after the coupling reaction. The chemical treatment of the silica gel leads to an attachment of the organofunctional groups on the solid-pore interface of the silica with an increase of the mean size of the solid phase and some coalescence of the pores. © 1989.

Pore structure characterization of kaolin, metakaolin, and their acid-treated products using small-angle X-ray scattering

Pore structure of dealuminated kaolin and metakaolin was studied by small-angle X-ray scattering (SAXS). Both parent kaolin and metakaolin have about 10% of the total pore volume provided by globular pores with 105 Å mean pore size. Their surface area is about 14 m2/g. Acid dealumination of kaolin causes an increase of its globular pore volume without an appreciable change in the mean pore size, its surface area increasing up to about 90 m2/g. Acid dealumination of metakaolin enhances the globular pore volume, although there is generation of slit-shaped pores with a narrow thickness distribution whose mean value is 14 Å. This interlayer spacing causes an increase in surface area of about 190 m2/g by SAXS. © 1994.

Time evolution of the structure function and dynamical scaling in porous SnO2 dry gels

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Formation of colloidal particles of hydrous iron oxide by forced hydrolysis

The mechanism of formation and growth of hydrous iron oxide (FeOOH) during the initial stages of forced hydrolyses of ferric chloride aqueous solution was studied by small angle X-ray scattering (SAXS). The effect of the hydrolysis temperature (60°C, 70°C and 80°C) and of the addition of urea on the formation of colloidal particles under isothermal conditions were investigated. Based on the experimental scattering functions in the Guinier range, we suggest the presence of elongated colloidal particles. The particle diameter and length, and their variation with time, were determined by fitting the form factor of prolate ellipsoids to the experimental scattering functions. We have assumed that our solutions are in a dilute state and that all colloidal particles are approximately of the same size. The colloidal particles have geometrical shapes similar to those of the subcrystals that build up the superstructure of β-FeOOH crystals, indicating that the formation of this hydrous iron oxide is governed by an aggregation process. Otherwise, the addition of urea hinders the growth and yields smaller particles, with a reduction in size greater than 50%. © 2000 Elsevier Science B.V. All rights reserved.