Vanadia-silica xerogels: optical and structural properties

Vanadium doped silica gels were prepared from tetraethyl orthosilicate and three different inorganic vanadium precursors with formal oxidation states of V³⁺, V⁴⁺ and V⁵⁺ respectively. Optical and EPR studies were carried out on the dried gels to understand the changes in the oxidation state and coordination of vanadium in the doped silica gel matrix. The observed optical and EPR results provide very strong evidence to establish that irrespective of the starting material, vanadium is stabilized as vanadyl ion in the gel monoliths. EPR studies on the powdered samples corroborate the optical data on the gel samples and confirmed that the stabilized vanadyl ion is situated in a distorted octahedral geometry in these silica gels.     

MOCVD of titanium dioxide on the basis of new precursors

Thin films with a considerably higher dielectric constant than silicon dioxide, for example titanium dioxide or titanium containing barium strontium titanate, can be used for dielectrics in ultralarge scale integration devices. TiO₂ shows, besides its high dielectric constant, a sufficiently low leakage current and high breakdown field strength. MOCVD is the most promising method for depositing those dielectrics because of its obvious advantages like homogeneity of films, good step coverage and ultrathin film deposition. In this work, three new precursor chemicals have been developed and tested in a low pressure horizontal cold wall-type furnace. For the synthesis of the novel precursors, commercial titaniumisopropylate is brought to an reaction with an alcoholic compound at 150 °C and distilled under vacuum. The motivation for the development of new Ti precursors lies in an improvement of the handling and deposition characteristics as for example the hydrolytic stability. For the three precursors the deposition parameters temperature, pressure, gas flow and activation energy is presented. The electrical properties dielectric constant and leakage current were compared to commercially available titaniumisopropylate.     

X-ray scattering studies of polymeric zirconium species in aqueous xerogels

X-ray scattering in the small angle range was used to investigate the structure and size of the polymeric species present in zirconium acetate (ZrAc)-based gel powders (GP) and thin films (TF). The formation of amorphous zirconia aggregates/linear polymers was studied by measuring their gyration radii and their correlation and hydrodynamic lengths via Guinier, `longrods', Zimm and Porod plots. Scattering data obtained in this investigation suggest that both amorphous ZrAc-based GP and TF contain `tetrameric' units, arranged in a cylindrical fashion, that polymerize upon thermal treatment. Housdorff fractal dimensionality, D, of amorphous zirconia GP (D∼2.25) and TF (D∼2.5) indicates a diffusion-limited aggregation mechanism. Tricyclic cluster aggregates (Porod D∼1.85) with a M_w∼12 000 were found within amorphous ZrAc-based GP. This structure is preserved over the entire curing range. In contrast, a linear polymeric chain (Porod D∼1.52), with a M_w∼20 000 below 165 °C and ∼13 000 at higher temperatures, was suggested for amorphous ZrAc-based TF.     

Study of the phase transition and the thermal nitridation of nanocrystalline sol-gel titania films

Nanocrystalline titania films were prepared by a complexing agent-assisted sol-gel method and converted to titanium nitride by a thermal nitridation process. The effect of acetylacetone (AcAc), diethanolamine (DEA) and acid catalysts (HCl and HNO₃) on the structure and morphology of the heat-treated titania films and on their nitridation products was examined by FTIR spectroscopy, X-ray diffraction (XRD) and atomic force microscopy (AFM). The carbothermal reduction of titania during the nitridation process with the formation of carboxynitrides has been considered. The results showed that the oxide to nitride transition strongly depends on the complexing agent used to prepare the titania films. The XRD results indicated the dependence of the lattice parameter of the nitridation product on the complexing agent or acid catalyst: AcAc and DEA lead to TiN_x with a lattice parameter α close to the theoretical value, while with HCl the lattice parameter was found sensibly lower showing the presence of an oxynitride. These results are accounted for by the effect of complexing agents and acid catalysts on the size of both TiO₂ and TiN grains and the different reactivity of the anatase and rutile phases. The possibility of tailoring the composition and morphology of TiN films by using complexing agents is envisaged.     

Multigram scale synthesis and characterization of low-density silica xerogels

The synthesis of silica with preserved porosity and tailored morphology by sol–gel process can be achieved by hybrid organic–inorganic synthesis: a modified alkoxide, viz. 3-(2-aminoethylamino)propyltrimethoxysilane (EDAS), is introduced during the base catalysed synthesis with TEOS as main silica precursor. Additives with methoxy groups induce a nucleation mechanism because of their higher reactivity compared to main reagents with ethoxy groups. The nucleation model presented in previous papers was refined by taking into account the porosity of the particles and calculating the number of additive molecules by nucleus for each value of the ratio of additive/main reagent. The extrapolation of the synthesis process to semi-industrial scale goes through the replacement of laboratory grade reagents by industrial grade reagents and the scaling up to the production of higher quantities. At each of these two steps, the morphology and porosity of the samples has been compared to those of laboratory grade samples. It was shown that the texture and particle size has quasi totally been preserved.     

Immobilization of 5-amino-1,3,4-thiadiazole-thiol onto silica gel surface by heterogeneous and homogeneous routes

The compound 5-amino-1,3,4-thiadiazole-thiol (ATT) was anchored onto silica gel surfaces by homogeneous and heterogeneous routes. Both silica modification methodologies resulted in similar products, named SiCTT and SiATT, respectively. These materials were characterized by infrared and Raman spectroscopies, superficial area and elemental analysis as well as ¹³C and ²⁹Si NMR spectroscopy. Elemental analysis proved that the material SiCTT presented a higher ATT immobilization than SiATT, with values of 0.73 and 0.65 mmol g⁻¹, respectively. NMR, Raman and infrared spectroscopy corroborate to confirm the immobilization of ATT on both surfaces. Raman spectroscopy showed that the reaction of the ATT with silylant agent or pre-modified silica occurred by the thiol group, resulting in a surface with two sulfur groups and one free amine group able to complex soft and hard acids.     

The coordination state and valence state of selected transition metal ions in SiO2-B2O3 xerogels

A series of SiO₂-B₂O₃ xerogels with changing SiO₂/B₂O₃ mol% and doped with selected transition metal ions was prepared. These mixed oxide materials contained copper, nickel, cobalt, manganese, chromium and vanadium ions coordinated to oxygen donor atoms in water and OH groups. Extensive studies of the transition metal complexes in the xerogels by such spectral techniques as diffuse reflectance (UV-vis), electron paramagnetic resonance and fluorescence spectroscopies show that there exist Cu(II) in the coordination environment of D_4h symmetry, Ni(II) in octahedral coordination sphere, Co(II) in both tetrahedral and octahedral environments, Mn(II) preferably in the O_h coordination and Mn(III) in pseudo-octahedral sphere; then octahedrally coordinated Cr(III) ions occur in coupled pairs or clusters and V(IV) as VO²⁺ ions exist in distorted (C_4v) octahedral surrounding.     

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

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 method of preparation on photophysical properties of Rh-B impregnated sol-gel hosts

Rhodamine-B (Rh-B) impregnated sol-gel samples have been prepared using two different methods - mentioned as the dope and dip methods. Two types of dye impregnated samples were prepared using the dope method and one type using the dip method. A comparative study of photophysical properties of the three types of samples were carried out with the lapse of time of preparation up to about an year. The two types of samples prepared by dope method showed degradation in absorption/fluorescence properties with the lapse of time whereas no such degradation was observed with those samples prepared by dip method. The change in the absorption/fluorescence properties of Rh-B in dope samples has been associated with the increasing acid environment during sol-gel-xerogel transitions resulting in conversion of molecular form from cation to weakly fluorescent higher protonated form of Rh-B. On the other hand, Rh-B in dip samples have very stable absorption/fluorescence properties with high fluorescence quantum yield value equal to 0.98(±0.1). On the basis of a comparative study of the three types of Rh-B impregnated samples, Rh-B dipped samples were found to have the best performance and may be useful as laser active materials in solid state dye lasers.     

Inclusion of carbon nanotubes in a TiO2 sol-gel matrix

We report here the successful inclusion of carbon nanotubes (CNs) into a TiO₂ matrix prepared by a sol-gel method. The presence of CNs in the sol-gel matrix and the structure of the film were analyzed principally by transmission electron microscopy. Complementary information about the behavior of embedded carbon nanotubes versus heat treatment and ion irradiation were obtained by X-ray photoelectron spectroscopy. The elaboration of an inorganic matrix containing embedded carbon nanotubes leads to a new nanocomposite. The possible applications of this nanocomposite are discussed.     

FTIR and absorption edge studies on tungsten oxide based precursor materials synthesized by sol-gel technique

The sol-gel technique has been employed for synthesizing three precursor materials for the deposition of tungsten oxide based electrochromic films. The ion-exchange route yields tungstic acid precursor (ITA) which has a strong tendency to polymerize rapidly. Addition of hydrogen peroxide and/or acetic acid suppresses the gelation process and an ethanol soluble precursor material (AIPTA) possessing a low degree of polymerization and high chemical stability is obtained. Another precursor material APTA endowed with similar desirable characteristics is produced from direct reaction between tungsten metal powder and a mixture of hydrogen peroxide and acetic acid. These materials were characterized by FTIR and absorption edge studies and compared in terms of their degree of polymerization and modes of association of various functionalities with the tungsten metal ion.     

Luminescence of CaS and MnS nanocrystallites co-activated sol-gel derived silica xerogel

CaS and MnS nanocrystallites co-activated sol-gel derived silica xerogel has been prepared by sol-gel processing. Their photoluminescence characteristics have been evaluated and compared with those of the undoped silica xerogel. Two emission bands have been observed from the doped sample, one at 440 nm while the other at 580 nm. CaS and MnS nanocrystallites embedded in sol-gel derived silica xerogel show sharp emission band. The novel luminescence phenomenon is attributed to the luminescent centers of CaS and MnS in the silica xerogel.     

Fluorescent compacts prepared by the entrapment of benzoxazole type dyes into a silica matrix at high pressure

We have produced silica-gel compacts doped with 2,5-Bis(benzoxazol-2^′-yl)-4-methoxyphenol dye using high-pressure processing of powders synthesized by the sol-gel technique. The high-pressure compaction of powders with three different dye concentrations was done at 4.5 GPa and room temperature. We have measured optical and mechanical properties of the obtained compacts. They were very stable, transparent, crack free, hard (3.56 ± 0.07 GPa) and dense (1.95 ± 0.03 g/cm³), being resistant to polishing and leaching, which enables its use in optical applications. The Stokes shift observed was higher than 100 nm indicating that the intramolecular proton-transfer in the electronically excited state (ESIPT) of this dye is maintained, even in an OH rich environment like silica. A shift to higher wavelength in the fluorescence spectra of the compacts, attributed to the increasing in the conjugation of the π system, was observed.     

The effect of photo-irradiation in hydrolysis and condensation of silicon alkoxide

A silicon alkoxide-water-ethanol mixed solution was irradiated with ultraviolet rays, and the change of the silicon alkoxide molecular structure was evaluated by ²⁹Si nuclear magnetic resonance and Fourier transform infrared spectroscopies. Silicon alkoxide was hydrolyzed and the Si-OH bonds were produced by UV irradiation without any chemical catalyst for hydrolysis. The Si-O-Si bonds were also produced, and viscosity of the alkoxide solution became higher due to condensation of alkoxide.     

Effect of the temperature on the TMOS sono-hydrolysis and a study of the structure of the resulting aged sonogels

The effect of temperature on the oxalic acid catalyzed sono-hydrolysis of tetramethoxysilane (TMOS) was studied by means of a heat flux calorimetric method. The activation energy of the process was measured as (24.5 ± 0.8) kJ/mol in the temperature range between 10 and 50 °C. The structural characteristics of the resulting sonogels, after long period of aging in saturated conditions, were studied by means of small angle X-ray scattering. The structure can be described as formed by ∼2.7 nm mean size mass fractal-like aggregates (clusters) of primary silica particles of ∼0.3 nm mean size, all imbibed in a liquid phase. The average mass fractal dimension of the clusters was found to be 2.58. The primary particle density was estimated as 2.23 g/cm³, in good agreement with the value frequently quoted for fused silica. The volume fraction of the clusters in the saturated sonogels was estimated as about 28%. The moment in which the meniscus of the liquid phase penetrates into the clusters under rapid evaporation process has been detected by an inflection in the first derivative of the curve of weight loss in a simple thermogravimetric test.     

Cobalt ortho- and para-substituted tetraphenylporphyrins inserted in SiO2 gels

The sol-gel method, generally, allows the trapping of important organic and biological systems in inorganic networks. Free and metallic porphyrins feature a wide range of important electrical, optical, and catalytic properties. To fix them in gels it is necessary to substitute an appropriate reactive group in the periphery of the macrocycle, which thus becomes more soluble in water or alcohols. The substituents more frequently employed have been -SO₃⁻, -Na⁺, -COOH and pyridinium salts. We have tried to increase the number, type, and spatial position of such substituents, to evaluate their influence in the quality and properties of the final materials. In this work we report the results obtained with the Co(II) complexes of the meso-5,10,15,20-tetraphenylporphyrin macrocycle, in which the amino, -NH₂(basic) or hydroxyl, -OH (acid) groups have been placed in the ortho- and para-positions of the phenyl groups. The insertion of cobalt porphyrins was made possible by the addition of small quantities of pyridine, methanol or dimethylformamide (DMF). Maxima in the transparency and strength of the materials were obtained with the para-amino substituted porphyrin, when methanol and pyridine were employed as the solvent media. Our results reveals that methanol has no influence on the morphology of the silica network, but DMF changes it drastically. The procedure here described has been successfully extended to trap other free and metallic porphyrinic systems.     

Sol-gel preparation and optical properties of SiO2-Ta2O5 glass

Tantalum-doped silica glass was fabricated by the sol-gel process in order to obtain a glass with a high refractive index for optical use. A crack-free, clear glass rod was successfully prepared from a low-density gel and used as the core material for fabricating optical fibers. Transmission loss in the fabricated fibers was high, in the range of 10³-10⁴ dB/km, which may be caused by coloration due to the multivalency of tantalum; however, the loss was reduced by nearly one order of magnitude by heat treatment at 800 °C, that is, to 75 dB/km at a wavelength of 0.8 μm.     

A SAXS study of the nanostructural characteristics of TEOS-derived sonogels upon heat treatment up to 1100 °C

Xerogels obtained from the acid-catalyzed and ultrasound stimulated hydrolysis of TEOS were submitted to heat treatment at temperatures ranging from 60 to 1100 °C and studied by small-angle X-ray scattering (SAXS). The SAXS intensity as a function of the modulus of the scattering vector q was obtained in the range from q₀=0.19 to q_m=4.4 nm⁻¹. At 60 °C the xerogels exhibit an apparent surface fractal structure with a fractal dimension D_S∼2.5 in a length scale ranging from 1/q₁∼1 to 1/q_m∼0.22 nm. This structure becomes extremely rough at 120 °C (D_S∼3) and at 150 °C, it apparently converts to a mass fractal with a fractal dimension D∼2.4. This may mean an emptying of the pores with preservation of a share of the original mass fractal structure of the wet aged gel, for it had presented a mass fractal dimension D∼2.2. A well characterized porous structure formed by 2.0 nm mean size pores with smooth surface of about 380 m²/g is formed at 300 °C and remains stable until approximately 800 °C. At 900 °C the SAXS intensity vanishes indicating the disappearance of the pores in the probed length scale. The elimination of the nanopores occurs by a mechanism in which the number of pores diminishes keeping constant their mean size. The xerogels exhibit a foaming phenomenon above 900 °C and scatter following Porod's law as does a surface formed by a coarse structure.