Structural characteristics of silica sonogels prepared with different proportions of TEOS and TMOS

Sonohydrolysis of mixtures of tetraethoxysilane (TEOS) and tetramethoxysilane (TMOS) with different TMOS/(TMOS + TEOS) molar ratio R was carried out to obtain ∼2.0 × 10⁻³ mol SiO₂/cm³ and ∼86%-volume liquid phase wet gels. Aerogels were obtained by supercritical CO₂ extraction in autoclave. The samples were analyzed by small-angle X-ray scattering (SAXS) and nitrogen adsorption. The structure of the wet gels can be described as a mass fractal structure with fractal dimension D ∼ 2.2 and characteristic length ξ increasing from ∼4.6 nm for pure TEOS to ∼6.4 nm for pure TMOS. A fraction of the porosity is eliminated with the supercritical process. The fundamental role of the TMOS/(TMOS + TEOS) molar ratio on the structure of the aerogels is to increase the porosity and the pore mean size as R changes from pure TEOS to pure TMOS. The supercritical process increases the mass fractal dimension and shortens the fractality domain in the mesopore region. A secondary structure appearing in the micropore region of the aerogels can be described as a mass/surface fractal structure with correlated mass fractal dimension D_m ∼ 2.6 and surface fractal dimension D_s ∼ 2.3.     

Synthesis of Si-MCM-48 membrane by solvent extraction of the surfactant template

Mesoporous MCM-48 silica membranes have been synthesized on porous supports under hydrothermal conditions, using tetraethyl orthosilicate (TEOS) as silica source, cetyltrimethylammonium bromide (CTAB) as template surfactant. And then the templates were removed by solvent extraction instead of calcination. The results of the TG and FT-IR showed that the solvent of 1 M HCl/EtOH solution was feasible to extract the templates in the MCM-48 materials and over 90% of the templates were extracted at room temperature for 24 h. The results of XRD, SEM indicated that the MCM-48 membranes were prepared on the porous supports and extraction did not destroy the mesostructure of the MCM-48. The compactness of the extracted MCM-48 membrane was evaluated by the permeation of single gas (N₂ and H₂) with transmembrane pressure of 60-220 kPa. The permeance of N₂ was independent of the transmembrane pressure and the ideal separation factor was about 3.45. All the results demonstrate that the method, solvent extraction to remove surfactant template, is more effective to synthesize high quality MCM-48 membranes than calcination.     

Mass fractal characteristics of sonogels prepared from sonohydrolysis of tetraethoxysilane with additions of dimethylformamide

Wet silica gels with ∼1.4 × 10⁻³ mol SiO₂/cm³ and ∼90 vol.% liquid phase were prepared from the sonohydrolysis of tetraethoxysilane (TEOS) with different additions of dimethylformamide (DMF). Aerogels were obtained by CO₂ supercritical extraction. The samples were studied mainly by small-angle X-ray scattering (SAXS) and nitrogen adsorption. Wet gels exhibit a mass fractal structure with fractal dimension D increasing from 2.23 to 2.35 and characteristic length ξ decreasing from ∼9.4 nm to ∼5.1 nm, as the DMF/TEOS molar ratio is increased from 0 to 4. The supercritical process apparently eliminates some porosity, shortening the fractality domain in the mesopore region and developing an apparent surface/mass fractal (with correlated mass fractal dimension D_m ∼ 2.6 and surface fractal dimension D_s ∼ 2.3) in the micropore region. The fundamental role of the DMF addition on the structure of the aerogels is to diminish the porosity and the pore mean size, without, however, modify substantially the specific surface area and the average size of the silica particle of the solid network.     

Morphology control of MSU-1 silica particles

Mesoporous silica, MSU-1 with spherical morphology was prepared using TEOS (tetraethylorthosilicate) as a silica source in the presence of an alkyl polyethylene oxide surfactant via the novel two-step process proposed by Prouzet’s group: hydrolysis of TEOS conducted in highly acidic condition at room temperature followed by condensation promoted by fluoride salt addition at 35 °C. The particles produced were characterized by XRD, SEM, and N₂ adsorption/desorption isotherm. Static condensation period was found to be essential to have spherical morphology. Growth of spherical particles and evolution of porosity were studied as a function of time, temperature, NaF/TEOS, and TEOS/surfactant ratio. The MSU-1 particles prepared under different synthesis conditions were briefly tested for chromatographic separation of selected organic molecules, which demonstrates the governing influence of the pore size in MSU-1 on retention time.     

Structural evolution up to 1100 °C of xerogels prepared from TEOS sonohydrolysis and liquid phase exchanged by acetone

Silica xerogels were prepared from sonohydrolysis of tetraethoxysilane and exchange of the liquid phase of the wet gel by acetone. Monolithic xerogels were obtained by slow evaporation of acetone. The structural characteristics of the xerogels were studied as a function of temperature up to 1100 °C by means of bulk and skeletal density measurements, linear shrinkage measurements and thermal analyses (DTA, TG and DL). The results were correlated with the evolution in the UV-Vis absorption. Particularly, the initial pore structure of the dried acetone-exchanged xerogel was studied by small-angle X-ray scattering and nitrogen adsorption. The acetone-exchanged xerogels exhibit greater porosity in the mesopore region presenting greater mean pore size (∼4 nm) when compared to non-exchanged xerogels. The porosity of the xerogels is practically stable in the temperature range between 200 °C and 800 °C. Evolution in the structure of the solid particles (silica network) is the predominant process upon heating up to about 400 °C and pore elimination is the predominant process above 900 °C. At 1000 °C the xerogels are still monolithic and retain about 5 vol.% pores. The xerogels exhibited foaming phenomenon after hold for 10 h at 1100 °C. This temperature is even higher than that found for foaming of non-exchanged xerogels.     

Ultralow density silica aerogels prepared with PEDS

This paper deals with the synthesis of ultralow density silica aerogels using polyethoxydisiloxanes (PEDS) as the precursor via sol-gel process followed by supercritical drying using ethanol solvent extraction. Ultralow density silica aerogels with 5 mg/cc of density were made for the molar ratio by this method. A remarkable reduction in the gelation time was observed by the effect of the catalyst NH₄OH at room temperature. The microstructure and morphology of the ultralow density silica aerogels were characterized by the specific surface area, S_BET, SEM, TEM and the pore size distribution techniques. The results show that the diameter of the silica particles is about 13 nm and the pore size of the silica aerogels is about several nm. The specific surface area of the silica aerogel is 339 m²/g and the specific surface area, pore volume and average pore diameter decrease with increasing density of the silica aerogel.     

Acidity-dependent mesostructure transformation of highly ordered mesoporous silica materials during a two-step synthesis

Highly ordered mesoporous silica materials have been synthesized under mildly acidic conditions by templating with a nonionic triblock copolymer (Pluronic P104) in a two-step process. It was found that a transformation from the SBA-15 type 2-dimensional (2D) hexagonal channel mesostructure (p6mm symmetry) to the MSU-X type 3-dimensional (3D) worm-like mesostructure could be induced by varying the pH whilst keeping all other conditions constant. The transformation between two types of mesoporous silica materials can be attributed to the effect of varying proton concentration on the interaction between organic micelles and inorganic species. Both types of mesoporous materials have high surface areas, large pore volumes, thick pore walls, large mean pore sizes, and narrow pore size distribution.     

Characterization of HF-catalyzed silica gels doped with Degussa P25 titanium dioxide

SiO₂/TiO₂ composites were synthesized by adding Degussa P25 TiO₂ to a liquid sol that was catalyzed by HNO₃ and HF acids. Various composites were synthesized by altering the mass loading of TiO₂ and concentration of HF added to the liquid sol before gelation. The resulting materials were characterized by SEM, nitrogen adsorption-desorption, streaming potential, XRD, diffuse reflectance and TiO₂ surface area analyses. Approximate characteristics include an isoelectric point of 3, TiO₂ particle size of 30 nm, and a band gap energy of 3.2 eV. Small variations in these properties were noted for the different composites. Physical characteristics were largely affected by HF concentration and TiO₂ loading. Nitrogen adsorption-desorption isotherms were type IV for all materials and exhibited trends of decreased pore volume with an increase in TiO₂ loading and an increase in pore diameter with increased HF concentration. Surface areas of the composites ranged from 167 to 630 m²/g. Available TiO₂ surface area of the composite was also dependent upon TiO₂ loading and increased as the mass composition of TiO₂ increased but was not largely affected by HF concentration.     

Enhancement of structural stability of mesoporous silica via infiltration of SnCl4 vapor

Sn-infused MCM-41 was prepared using a pre-mixing method and two different vapor phase methods. The sample prepared by the pre-mixing method showed lower hydrothermal stability than pure silica MCM-41. MCM-41 prepared by vapor phase treatment with SnCl₄ before calcination showed higher structural stability in water and hexane at 423 K than the sample treated with SnCl₄ vapor after calcination. The pore size and pore volume of MCM-41 treated with SnCl₄ vapor before calcination were larger than those of pure silica MCM-41. With SnCl₄ vapor treatment after calcination, the SnCl₄ vapor must have reacted with silanol groups around the pore entrance and partly plugged the pore mouth of MCM-41. On the other hand, SnCl₄ also penetrated into the pore wall and uniformly dispersed into the silicate network. Thus, SnCl₄ vapor treatment before calcination was more effective in enhancing the structural stability in water and hexane.     

A low silica, barium borate glass-ceramic for use as seals in planar SOFCs

A low silica, barium borate glass-ceramic for use as seals in planar SOFCs containing 64 mol%BaO, 3 mol%Al₂O₃ and 3 mol%SiO₂ was studied. Coefficient of thermal expansion (CTE) between 275-550 °C, glass transition temperature (T_g), and dilatometric softening point (T_s) of the parent glass were 11.9 × 10⁻⁶ °C⁻¹, 552 °C, and 558 °C, respectively. Glass-ceramic was produced by devitrification heat treatment at 800 °C for 100 h. It was found that nucleation heat treatment, seeding by 3 wt%ZrO₂ as glass-composite and pulverization affected the amount, size and distribution of crystalline phases. SEM-EDS and XRD results revealed that crystalline phases presented in the devitrified glass-ceramic were barium aluminate (BaAl₂O₄), barium aluminosilicate (BaAl₂Si₂O₈) possibly with boron associated in its crystal structure, and barium zirconate (BaZrO₃). CTE of the devitrified glass-ceramic was in the range of (10.1-13.0) × 10⁻⁶ °C⁻¹. Good adhesion was obtained both in the cases of glass and devitrified glass-ceramic with YSZ and AISI430 stainless steel. Interfacial phenomena between these components were discussed.     

Microstructural and physical properties of the ambient pressure dried hydrophobic silica aerogels with various solvent mixtures

The experimental results on the microstructural and physical properties of the ambient pressure dried hydrophobic silica aerogels with various solvent mixtures have been reported. The aerogels were prepared with sodium silicate precursor, ammonium hydroxide catalyst, trimethylchlorosilane (TMCS) silylating agent, solvent mixture of methanol-isopropanol (MeOH/IPA) and various aprotic solvent mixtures namely, hexane and benzene (HB), hexane and toluene (HT), hexane and xylene (HX), heptane and benzene (HpB), heptane and toluene (HpT), heptane and xylene (HpX). The physical properties of the aerogels such as % of volume shrinkage, density, % of optical transmission, surface area, % of porosity, pore volume, thermal conductivity and heat capacities of the aerogels were studied. The hydrophobicity of the aerogels was studied by contact angle measurements. The HX and HpX aerogels have been found to be more hydrophobic (contact angle, θ > 155°) than the other aerogels. It has been observed that the % of weight increase is highest (1%) for the HT aerogels and lowest (0.25%) for HpX aerogels by keeping them at 70% humidity for 350 h. Further, the aerogels have been characterized by pore size distribution (PSD), Fourier transform infra red spectroscopy (FTIR) and thermogravimetric and differential thermal (TG-DGA) analysis and transmission electron microscopy (TEM) techniques. The results have been discussed by taking into account the surface tension, vapor pressure, molecular weight and chain length of the solvents. Low density (0.051 g/cc), hydrophobic (165°), transparent (85%), low thermal conductive (0.059 W/m K), low heat capacity (180 kJ/m³ K) and highly porous (97.38%) silica aerogels were obtained with HpX solvent mixture.     

Anionic structure and elasticity of Na2O-MgO-SiO2 glasses

The structure and elastic properties of a series of xNa₂O · MgO · 4SiO₂ glasses have been studied using both Raman and Brillouin spectroscopy. Relative to Na₂O-SiO₂ glasses, the maximum abundance for phyllosilicate structural units in the present glasses shows a lag of 0.5 units in the number of non-bridging oxygen per silicon atom (NBO/Si). This phenomenon has been attributed to the decrease in the average coordination number of modifying cations due to the presence of Mg²⁺. It has also been found that the decomposition of both metasilicate and disilicate (dimerized SiO₄) anionic structural units in Na₂O-SiO₂ glasses are enhanced by the addition of MgO. However, the presence of Mg²⁺ does not cause a considerable effect on the decomposition of phyllosilicate structural unit. The acoustic data have revealed that both shear and Young’s moduli of the present glasses decrease with increasing NBO/Si (the variation in bulk modulus is reversed, however). The resistance to shear deformation for the anionic structural units in silicate glasses has been found to decrease in the following order: tectosilicate > phyllosilicate > metasilicate > disilicate > orthosilicate. The relative contribution of the various anionic structural units to the bulk modulus of a glass remains to be determined. The ideal mixing model using Makishima-Mackenzie’s relationship for predicting Young’s modulus is not applicable to the present glasses.     

Fluorinated silica glass ablated with ArF excimer laser at low fluence

Amorphous SiO₂ (a-SiO₂) was formed by liquid-phase deposition (LPD) at room temperature. As a result of one shot of ArF excimer laser irradiation, LPD-formed a-SiO₂ shows a threshold fluence for ablation of below than 200 mJ/cm², which is much lower than the threshold fluence (∼1 J/cm²) of a-SiO₂ formed by thermal oxidation of silicon. Raman scattering spectroscopy revealed that two sharp lines at 495 cm⁻¹ and 606 cm⁻¹, respectively, labeled D₁ and D₂, had disappeared, and the main band at 430 cm⁻¹ was sharpened in LPD-formed a-SiO₂. It is presumed that the fluorine broke the silica network, relaxing the Si-O-Si bond angle and dramatically reducing the threshold energy for ablation of a-SiO₂.     

Electrical conductivity of NbN-SiO2 films obtained by ammonolysis of Nb2O5-SiO2 sol-gel derived coatings

The studies of electrical conductivity of NbN-SiO₂ films are reported. To obtain these films, sol-gel derived xNb₂O₅-(100 − x)SiO₂ (where x = 100, 90, 80, 70, 60, 50 mol%) coatings were nitrided at 1200 °C. The nitridation process leads to the formation of some disordered structures, with NbN metallic grains dispersed in insulating SiO₂ matrix. The structure of the samples was studied using X-ray diffraction (XRD) and atomic force microscopy (AFM). The electrical conductivity was measured with the conventional four-terminal method in the temperature range from 5 to 280 K. The superconducting transition was not observed even for the sample that does not contain silica. All the samples exhibit negative temperature coefficient of resistivity. The results of conductivity versus temperature may be described on the grounds of a model proposed for a weakly disordered system.     

The devitrification kinetics of silica powder heat-treated in different conditions

In the present paper, the devitrification kinetics of silica powder heat-treated in air and in nitrogen were investigated. The heat-treated powders were confirmed to partially crystallize into cristobalite by X-ray diffraction analysis. The devitrification kinetics data of silica powder fitted the Avrami equation very well. The measured value of n was ascertained to be 1.63 and 1.60 when the silica powder was heat-treated in air and in nitrogen, respectively, corresponding to activation energies of 408 kJ/mol and 529 kJ/mol, respectively. The effect of phenolic resin-derived carbon on crystallization of silica powder was also studied. By adding phenolic resin into silica powder, the devitrification of silica powder was fully restrained up to 1500 °C in flowing nitrogen. High concentrations of oxygen vacancies may retard the nucleation of cristobalite on the surface of silica powder. Phenolic resin-derived pyrolysis carbon restrained the nucleation of cristobalite, because it prevented the reactions of oxygen vacancies with H₂O and O₂ molecules.     

The glass transition temperature and infrared absorption spectra of: (70−x)TeO2 + 15B2O3 + 15P2O5 + xLi2O glasses

Glasses of the system: (70−x) TeO₂ + 15B₂O₃ + 15P₂O₅ + xLi₂O, where x = 5, 10, 15, 20, 25 and 30 mol% were prepared by melt quench technique. Dependencies of their glass transition temperatures (T_g) and infrared (IR) absorption spectra on composition were investigated. It is found that the gradual replacement of oxides, TeO₂ by Li₂O, decreases the glass transition temperature and increases the fragility of the glasses. Also, IR spectra revealed broad weak and strong absorption bands in the investigated range of wave numbers from 4000 to 400 cm⁻¹. These bands were assigned to their corresponding bond modes of vibration with relation to the glass structure.     

Effect of P2O5 content in two series of soda lime phosphosilicate glasses on structure and properties - Part I: NMR

The effect of the variation in phosphate (P₂O₅) content on the structure of two series of bioactive glasses in the quaternary system SiO₂-Na₂O-CaO-P₂O₅ was studied. The first series (I) was a simple substitution of P₂O₅ for SiO₂ keeping the Na₂O:CaO ratio fixed (1.00:0.87). The second series was designed to ensure charge neutrality in the orthophosphate , therefore as P₂O₅ was added the Na₂O and CaO content was varied to provide sufficient Na⁺ and Ca²⁺ cations to charge balance the orthophosphate present. The glass network connectivity (NC) was calculated for each glass and a modification for the presence of a separate P₂O₅ phase was included (NC′). ³¹P and ²⁹Si magic-angle-spinning nuclear magnetic resonance (MAS-NMR) spectroscopy was performed on glass series I and II to determine the structural units present and their relation to glass properties. ³¹P MAS-NMR spectra of series I resulted in a broad resonance around 9 ppm corresponding to orthophosphate in an amorphous environment. The 9.25 mol% P₂O₅ glass shown to be partially crystalline by X-ray diffraction was heat treated, and the ³¹P MAS-NMR spectrum showed a sharp peak around 3 ppm corresponding to calcium orthophosphate or sodium pyrophosphate and overlapping broader peaks at 8.5, 10.5 and 14 ppm possibly corresponding to two mixed calcium-sodium orthophosphate phases and amorphous sodium orthophosphate respectively. ³¹P MAS-NMR spectra of series II resulted in a broad resonance around 10.5 ppm corresponding to orthophosphate in an amorphous environment. ²⁹Si MAS-NMR spectra of glasses from series I showed a shift in the resonance peak from around −78 to −86 ppm indicating an increase in Q³ species in the glass and a reduction in Q² with phosphate addition confirming the presence of orthophosphate. The heat treated sample showed a sharp ²⁹Si-NMR resonance at −88 ppm, indicating a crystalline Q² six-membered combeite (Na₂O · 2CaO · 3SiO₂) silicate-type phase, which was confirmed by powder X-ray diffraction. ²⁹Si MAS-NMR spectra of glasses from series II showed no shift in the resonance at around −78 ppm across the series, confirming an orthophosphate environment.     

Fluorescent porphyrins covalently bound to silica xerogel matrices

We study the influence of the nature and ring positioning of amino, hydroxy, and carboxy substituent groups on the fluorescence and some other physicochemical properties of free (H₂TPP) and metalled tetraphenylporphyrins (MTPP). Furthermore, we have studied the feasibility of covalently bonding TPP species on the surface of the pores of a silica matrix prepared by the sol-gel method through the bridging action of either one of the following functionalized alkoxides: 3-isocyanatopropyltriethoxysilane, (IPTES) or 3-aminopropyltriethoxysilane (APTES). Importantly, the red fluorescence observed in free porphyrin solutions is preserved even after the macrocyclic species is covalently bound to the silica matrix. The formation of a chemical union between the porphyrin substituting groups and the organic groups of the IPTES or APTES alkoxides render the H₂P-f precursory species has been proved successful by FTIR spectroscopy; likewise, the bond between Si-OH groups on the silica surface and the H₂P-f has been made evident. The best results, in terms of fluorescence preservation, are obtained by using a TPP substituted with -NH₂ groups in the ortho position of the phenyl rings, i.e. H₂T(o-NH₂)PP. A comparative fluorescence study of xerogels physically grafted or covalently bound with the latter TPP species confirm that, in the first case, the interaction of the molecule with the silanol groups of the silica surface of the gel inhibits fluorescence; while in the second case fluorescence is preserved.     

Structure of Ni/SiO2 films prepared by sol-gel dip coating

The sol-gel dip coating technique has been used to deposit composite oxide films (NiO)_x(SiO₂)_1−x with x = 0.1 on silicon wafers. Single and multilayer coatings allowed a variation of the film thickness from 70 to 400 nm. Film morphology, atomic structure and atomic composition have been investigated by transmission electron microscopy (TEM) and Rutherford backscattering spectrometry (RBS). The local environment of the Ni atoms was characterized by extended X-ray absorption fine structure (EXAFS). The samples were studied in the as-prepared state and after annealing in H₂ at 600 °C for 1 h. The structural and chemical state evolution of clusters present inside the silica matrix is discussed in terms of out-of-equilibrium reaction processes specific to low-dimensional objects and superficial effects.