Fluorescence properties of a ruthenium complex in silane sols and gels at different pH

Silane gels containing ruthenium Ru(bpy)₃²⁺ complex were obtained by the sol-gel method. The gelation of sols at different pH values was monitored by fluorescence stationary and time-resolved measurements. In all tested sols a blue shift of fluorescence emission maximum of the fluorophore was observed during the gelation. Changes in λ_max on subsequent days of sol-gel transition depended on starting pH of the sol. An increase of the excited state of fluorophore lifetime in the gelation process was observed. When the gelation was finished the lifetime τ₁ was constant. A strict correlation between the blue shift of fluorophore emission maximum and changes in the lifetime of ruthenium complex in this system on subsequent days of the sol-gel transition was observed. On this basis, changes in the fluorophore microenvironment in the sol induced by different rates of competing hydrolysis and condensation reactions were discussed.All observed effects were attributed to the interaction of molecules of the ruthenium complex with hydroxyl groups in the gel net.     

Rheology of sols and fiber drawing

The investigations on the viscosity of the metal alkoxide solutions in the course of hydrolysis and condensation reactions leading to the gelation of sols have been reviewed. All the solutions which gel finally show a continuous increase in viscosity with time until they gel at a certain viscosity higher than about 100 P which is dependent on the composition of the starting solution. When a metal alkoxide solution is catalyzed with an acid and its water content is small at less than 4 or 5 in the water to alkoxide mol ratio, the solution exhibits spinnability at viscosities above about 10 P and becomes drawable into gel fibers, whereas no spinnability appears when a solution contains a large amount of water or is catalyzed with an alkali like ammonia.

The investigations on the relation between the reduced viscosity and the concentration or the relation between the intrinsic viscosity and the number-averaged molecular weight have made it clear that the spinnable silicon alkoxide solutions have long-shaped siloxane particles and non-spinnable solutions have round particles.

It has been established that spinnable solutions exhibit Newtonian flow behavior up to high viscosities, where fibers can be drawn, while non-spinnable solutions exhibit marked structural viscosity and, sometimes, thixotropy. Similar behavior is confirmed in the alumina solutions prepared from inorganic salts. It has been reported that the viscosity measurements provide information on the rate of the reaction leading to gelation. It is also known that the viscosity of the alkoxide solution controls the thickness of the thin coating film made by the dip-coating technique using an alkoxide solution.     

Rheological characterization of the gel point in sol–gel transition

The gelation of hydrolyzed alcoholic solutions of acetic acid modified titanium isopropoxide has been analyzed through rheological measurements. A new method is proposed for determining the chemical gel point of these systems that fail to obey the Chambon–Winter criterion. The suggested method is based on defining the gel point as the instant at which the variation of the viscoelastic function tan δ with frequency is minimum. The influence of the sol composition on the gel point has also been investigated. The correlation between the gelation time and the examined compositional parameters, i.e. the modification and hydrolysis molar ratios, is reported. It can be concluded that the initial sol composition has a strong effect on the kinetics of the gelation process, but it does not significantly affect the gelation mechanism.     

Physico-chemical control of sol-gel transition of titanium alkoxide-based materials studied by rheology

Viscoelastic characterization of titania-based sol-gel materials are investigated. Small amplitude oscillatory measurements are used to determine the gelation time t_g and the critical exponent of the frequency dependence of the loss and storage moduli. The scaling exponent is analyzed in order to estimate a fractal dimension at t_g. Hydrolysis molar ratio, titanium concentration and temperature parameters have an effect on the gelation time but not on the structure of the critical gel (gel at gelation time). However the acetylacetone concentration used as an inhibitor to control the reactivity of titanium seems to modify both the kinetic process and the gel structure.     

Spinnablity and structure characterization of mullite fibers via sol–gel-ceramic route

Viscosity and rheology behaviors of the mullite sols prepared from aqueous solution of aluminum nitrate, aluminum isopropoxide and tetraethylorthosilicate has been investigated. Rheological measurement suggested that mullite sols exhibited good spinniabilty when the evaporation of the solvent is allowed during sol–gel process. Spinnable sols showed shear-thinning flow behavior with high viscosity to the time of gelation. By adjusting temperature, the gelation degree and viscosity of the sol could be stabilized at a certain value and the sol–gel transition could be transferred to the spinning line of a laboratory dry-spinning apparatus. Continuous mullite fibers were obtained from such sols using sol gel dry-spinning method. The final ceramic fibers had smooth surfaces with an average diameter of 50 μm. Structure evolution of mullite ceramic fibers were characterized by MAS NMR and specific surface area analyses.     

Tetracycline and/or hydrocortisone incorporation and release by bioactive glasses compounds

The delivery of the tetracycline and hydrocortisone drugs that have been incorporated into bioactive glasses was studied in this work. The potentiality of these systems in direct pulp capping is also discussed. A bioactive glass with a composition of (SiO₂)_0.80(P₂O₅)_0.04(CaO)_0.16, was prepared by sol-gel. Sols were prepared with the addition of approximately 2 wt% of tetracycline or hydrocortisone separately for the delivery studies. A third set of samples of bioglass sols containing 2 wt% of each drug were prepared with the same purpose. The amounts of drugs delivered were monitored by ultraviolet spectrophotometry in the tetracycline and hydrocortisone wavelengths. The drug release behavior was strongly dependent on the system. The glass-tetracycline samples showed a rapid drug release kinetics, while glass-hydrocortisone samples show much slow release profiles. The different drug release behaviors have been explained by faster gel formation reaction between hydrocortisone and TEOS due to a stronger interaction between these reagents. On the samples with both drugs, the release was simultaneous and for each drug, the amounts delivered followed a profile similar to the samples with only this specific drug.     

Light scattering dynamic study of the gelation process

Light scattering is a choice method for studying the dynamic properties of fractal structures and growth processes. We present preliminary light scattering measurements to characterize the formation of small silica particles prepared in highly basic TMOS/methanol/water sols and the transformation of sol into gel employing digital clipped autocorrelation spectroscopy. The light scattering is due to gel clusters.     

Precursors for sol-gel preparations

Precursors used for the synthesis of oxide systems by the sol-gel method are reviewed and their role in the various stages of the process is discussed. Emphasis is given to alkoxide precursors and to their physical and chemical properties. In particular, the following topics are discussed: degree of oligomerization, volatility, viscosity, reactions with alcohol, molecular association between alkoxides, hydrolysis, stabilization against hydrolysis. Some information about preparation methods, commercial products and availability is also given. Among non-alkoxide precursors, nitrates, carboxylates, acetylacetonates, chlorides and other inorganics are described from the point of view of their use in sol-gel preparations. They are compared, when possible, with the corresponding alkoxides.     

Rheology of precursors for sol-gel derived YBa2Cu3O7−x superconductors

Aqueous-based precursors for high T_c superconductors are prepared by mixing solutions of copper acetate, barium acetate and yttrium hydroxide. The time-dependent dynamic moduli show the kinetics and extent of gelation of the precursor solution o be directly related to the age of yttrium hydroxide component; “age” being the length of time between the preparation of the yttrium component and its use in the precursor solution. The viscosity of the colloidal suspension of the yttrium hydroxide at low shear rates increases with the age of the material by an order of magnitude in two months. Dynamic oscillatory and controlled-stress experiments on the yttrium hydroxide suspension also reveal increases in moduli, and formation of network structure as this material ages. The particle size of the yttrium hydoxide, as measured by dynamic light scattering, almost doubles in two months of aging. Superconducting films made from different batches of precursors containing fresh and old yttrium components show differences in their morphology and electrical behavior. Fired films obtained from precursors containing aged yttrium hydroxide had a single phase perovskite and showed superconducting behavior whereas films made from fresh yttrium had an additional structural phase and never achieved zero resistance. A possible mechanism relating the changes in the yttrium hydroxide properties as it ages to the sol-gel kinetics of the precursor solution and the characteristics of the fired film is presented.     

Vegetal nanoclusters in hybrid silica films prepared by sol-gel spin coating technique

Hybrid sol-gel films containing Rosemary extract nanoclusters embedded into hybrid silica network have been successfully synthesized using the sol-gel procedure by exploiting the template route, in association with an adequate spin-coating method. Formation of film precursor sols and effect of selected amounts of octyl trimethoxysilane and ethyl oleate succinic anhydride into the starting acid sols on the sol-gel product size have been evaluated by dynamic light scattering technique. The spectral characteristics of hybrid organic-inorganic films have shown that the multiple functional groups from Rosemary extract associated with residual Si-OH groups can cause the increase in the degree of physical interaction. The effect of hybrid sols meaning the silica precursors molar ratio and template concentration on the fluorescence of hybrid films has been also investigated. The fluorescence properties of synthesized films were found to be dependent on template and natural extract concentration. A higher amount of template resulted in doubling the fluorescence intensity in the 400-480 nm domain. The microstructural characteristics of the hybrid films revealed by atomic force microscopy have shown a homogeneous surface morphology with cluster-like structure. Hybrid silica films exhibit a periodic structure with cluster size less than 150 nm.     

Interaction between colloidal particles in SiO2 and TiO2 sols

The effect of the interaction between colloidal particles in SiO₂ and TiO₂ sols on the viscosity of the sols has been examined. It was found that the interaction was significantly influenced by the zeta potential of electrical double layers and terminal bonds associated with particle surfaces. Water/alkoxide mole ratio and pH affect the zeta potential and the terminal bonds and, consequently, change the interaction between the particles and the viscosity of the sols. In addition, the relationship of viscosity with the volume fraction of the colloidal particles in SiO₂ sol has been described by a Dougherty-Kreiger equation when the viscosity reached a stable value with time.     

Applications of the rheo-dielectric technique

An apparatus for dynamical mechanic measurements was modified in order to allow broadband dielectric spectroscopy measurements (10 mHz to 10 MHz) on systems under shear stress. Shear oscillatory deformation was applied to different systems under conditions of controlled deformation amplitude, choosing different shear frequencies and amplitudes, including the range of the non-linear viscoelastic response. The plate–plate geometry was used, with the two metallic sample holders serving both as mechanical tools and as electrodes of a capacitor. The rheo-dielectric technique was used to study the effect of oscillatory shear on two classes of systems: nematic liquid crystals and polymeric melts.     

A novel sol-gel method for the synthesis of γ-aluminium oxide: development of the sol-gel transformation and characterization of the xerogel

A novel method for the synthesis of aluminium oxide gel has been developed, whereby the sol-gel transformation was investigated. Aluminium tri-sec-butoxide was used as precursor while acetone was chosen as solvent. The synthesis was carried out in a special reactor, which allowed the dosing of steam. ²⁷Al NMR spectroscopy showed that during the sol-gel process the signal at δ∼3 ppm increases strongly corresponding to the formation of hexacoordinated aluminium species. Beside hydrolysis and condensation reactions, the coordination of acetone to a strong Lewis acid aluminium site occurs, which was shown by FTIR and ²⁷Al NMR spectroscopy. Viscosimetric analysis showed that at the beginning of the sol-gel process short polymers are observed while before the gelation a three-dimensional polymer network is formed. After pyrolyzing the gel a high surface area γ-aluminium oxide xerogel was formed. The effect of heating on the morphology and structure was examined by nitrogen physisorption (BET and pore size distribution), XRD and ²⁷Al MAS NMR spectroscopy.     

溶胶-凝胶法制备Ca0.4Sr0.6Bi4Ti4O15细晶陶瓷

采用凝胶预碳化处理工艺制备了颗粒粒径较小,无硬团聚的Ca0.4Sr0.6Bi4Ti4O15纳米粉体,以Ca0.4Sr0.6Bi4Ti4O15非晶团簇粉体为陶瓷素坯的原料,同组分高浓度的Ca0.4Sr0.6Bi4Ti4O15溶胶为粘结剂,制备了Ca0.4Sr0.6Bi4Ti4O15细晶陶瓷,研究了Ca0.4Sr0.6Bi4Ti4O15粉体的相结构和微观形貌以及陶瓷的显微结构和铁电性能.实验结果表明:700 ℃焙烧粉体呈现为非晶团簇,800 ℃焙烧粉体形成了纯层状钙钛矿结构,粒径在100～150 nm之间,无硬团聚;950 ℃烧结的Ca0.4Sr0.6Bi4Ti4O15细晶陶瓷结构致密,晶粒尺寸在0.2～0.5 μm之间,其铁电性能优良,剩余极化Pr=12.5 μC/cm2,矫顽场强Ec=50 kV/cm.     

USAXS studies of monosaccharide gels. II. The common features of structural changes

The results of SAXS studies are compared for two groups of samples: (i) obtained by in situ process of gelation of α-galactose-based gel with benzene as solvent, (ii) gels of various concentrations prepared from glucofuranose-based gelator with toluene. The experimental conditions of sample preparation and SAXS measurements were very similar for both groups. The results include fractal analysis of aggregates, and – for aggregate envelopes – the radii of gyration, pair functions, and simulated models. For both groups only two aggregate types were found to be formed: the first – of simple, loose fractal structure and disk-like shape, and the second – smaller aggregates, of well-developed fractal structure and cylinder-like shape. The conditions of the change from the first type to the second one are discussed. In addition, it was verified by the SAXS method on the basis of kind of fractal analysis for the loose structure that the fractal aggregate is built of gelator molecules joined by hydrogen interaction.     

Fabrication of fluorine-doped silica glasses by the sol-gel method

Fluorine-doped silica glasses are produced by the sol-gel method for optical fiber preforms. In order to dope fluorine into silica glass, fluorinated silicon alkoxide, Si(OC₂H₅)₃F, is titrated into SiO₂ sol solutions. The fluorine content in silica glass depends on: the fluorine concentration in the gel, the specific surface area of SiO₂ particles and the heating rate in the sintering process. Fluorine-doped silica glass with a maximum relative refractive index difference of −0.93% is obtained. Using this technique, optical fibers with a triangular refractive index profile are fabricated with a minimum optical loss of 1.6 dB/km at 1.69 μm wavelength.     

Observation of the aggregation behavior of silica sols using laser speckle contrast measurements

We report on a new optical method to observe the onset of aggregation in alcoholic tetraethoxysilane (TEOS) sols using laser speckle contrast measurements. The contrast in a speckle image produced by coherent light provides information about the internal contrast of the medium being studied. For silica sols, changing the amount of acid or base catalyst was the most important factor in determining the aggregation behavior of the sol. We investigated this effect by varying the TEOS/base ratio by a factor of 6. This shifted the onset of aggregation as determined by speckle contrast from 46% of the gel time for the lowest amount of base to 74% for the highest. Conversely, varying TEOS/acid ratio by a factor of 3, shifted the onset of aggregation from 74% of the gel time for the lowest amount of acid to 64% for the highest. Measurements of this type provide information that can be used to test models of sol aggregation and gel formation.     

Investigation of inorganic network formation in photopatternable hybrid sol-gel films by Si liquid NMR

Liquid ²⁹Si NMR spectroscopy was used to investigate the sol-gel process of methacryloxypropyltrimethoxysilane. This hybrid precursor was involved in the realization of optical elements in laminated crack-free thick films (up to 100 μm), through spatially controlled photopolymerization. Understanding the formation of the inorganic network was of first importance to insure the creation of crack-free photopatterned thick films in a laminated configuration. Material preparation required evaporation of the volatile solvents released during the sol-gel process and limitation of the condensation degree. Both conditions were achieved by a drying process at room temperature. The structure and the composition of the sols were investigated and compared to non-dried sols. Evolution of inorganic species distribution was also studied under increasing aging time or storage temperature. NMR peak fitting of T1 species gave fruitful information on the sol structure evolution during the sol-gel process. It pointed out the presence of a large variety of oligomers in the sol. The study also allowed the identification of more constraint cyclic species in dried sols stored at room temperature. Their amount significantly decreased when increasing the storage temperature and was attributed to ring opening of cyclic species. Consequently, the structure of the dried sol will depend both of the aging time and of the storage temperature. All these results have to be taken into account when the degree of condensation has to be limited to achieved photopatternable hybrid layers for specific optical applications.     

Sol-gel preparation of wavelength-selective reflecting coatings in the system ZrO2SiO2

Multilayer, wavelength-selective reflecting coatings were prepared by alternate stackings of amorphous zirconia and silica by the sol-gel spinning technique; alkoxide-derived, polymeric sols were used. A detuned, i.e. non-λ/4 stacking system was applied. The spectrum showed a transmission minimum (∼ 4%) at a wavelength of 430 nm, with a bandwidth of 72.5 nm after deposition of the 17th layer.     

Silica glass tubes by new sol-gel method

Silica glass tubes were prepared by following a new sol-gel method. The pH of the sol containing hydrolyzed Si(OC₂H₅)₄ with HCl and colloidal silica was adjusted by adding ammonia solution. Sol was poured into a cylindrical tube and gelled while rotating cylinder at 1000 rpm to form a tube-shaped gel. Then the gel was dried carefully to be tube dry-gel and finally sintered to become a clear silica glass tube.

The effects were examined of the speed of rotation before and after gelation, to form the tubular gel, upon the shape and appearance of the derived tubes. The best speed of rotation was about 1000 rpm, and an adequate long period of rotation after gelation was necessary to maintain the tube shape. One of the large silica tubes had dimensions of 26 mm outside diameter, 13 mm internal diameter and 1000 mm length, and the ovality of the silica glass tube was 0.02%.

The derived tube can be applied in a silica glass tube for an optical fiber fabrication process or in a furnace tube for IC production.