29Si MAS-NMR Study of Silica Gels and Xerogels: Influence of the Catalyst

Four silica gels were prepared by hydrolysis of tetraethoxysilane (TEOS) in ethanol, using different catalysts: HCl, NaOH, NH₃, and NBu₄F. Nitrogen adsorption-desorption isotherms indicated that the HCl-catalyzed xerogel was purely microporous, whereas the other samples exhibited a very broad distribution of mesopores and a variable amount of micropores. ²⁹Si MAS NMR spectroscopy of the wet gels (before drying) pointed to a low degree of condensation for the HCl-catalyzed gel, and to the presence of unhydrolyzed TEOS monomer in the NaOH-catalyzed gel. Comparison with the ²⁹Si MAS NMR spectra of the xerogels indicated a significant increase of the degree of condensation during the drying procedure (3 hrs at 120°C under vacuum) for the HCl-catalyzed gel.     

Sol-Gel Particulate Float Process to Make Vitreous Silica Bodies

Particulate sol-gel technology uses larger particles than that of alkoxide-derived gels and provides larger pore sizes in the gelled object. This allows relatively rapid drying and fabrication of large rods or tubular shapes. However, the formation of more complex or flat shapes, which require extensive surface contact with a mold, is more difficult. The shrinkage during drying, with the significantly greater stress of surface friction due to adhesion, frequently leads to cracking.We have demonstrated a solution to this problem by floating the gel on the surface of a dense liquid. Dry silica panels up to 28 × 40 × 0.7 cm³ were prepared in this way. The use of patterning molds allowed the fabrication of more sophisticated shapes. These bodies were sintered to transparent vitreous silica articles of near net dimensions.     

Effect of Pr3+ Doping on the OH Content of Silica Xerogels

Pr2O3-SiO2 xerogels doped with different Pr/Si concentrations were annealed at 900°C for 120 h and then investigated by FTIR, NIR absorption, Raman and luminescence spectroscopies. It is observed that the content of surface silanol groups is lower for higher Pr3+ concentrations. Luminescence measurements indicate that the amount of the residual OH plays an important role in the spectroscopic properties of the Pr3+ ion and in particular the quantum yield of the emission from the 3P0,1 and 1D2 states.     

Influence of Hydrolysis Water Content on the Microstructure of BaTiO3 Xerogels Prepared from High Concentration Metal Alkoxide Solutions

Optically clear and partially crystallized barium titanate (BaTiO₃) monolithic xerogels were prepared by hydrolyzing the high concentration precursor solutions (1.1 mol/L) of metal alkoxides with water vapor to have different hydrolysis water contents (H₂O/Ba-alkoxide mole ratio (r _w) = 2.5–7.0). The microstructural changes of the xerogels have been studied by TEM, XRD and nitrogen adsorption/desorption analysis. The crystallite size of the xerogels was found to increase consecutively with increasing r _w, while the average pore size showed no substantial increase until r _w = 5.0 and it grew rapidly for r _w > 5.0. The influence of r _w on the microstructural development of the xerogels with heat-treatment was also discussed.     

Interaction and Microstructure of Polyurethane/Silica Hybrid Films Prepared by Sol-Gel Process

The polyester/silica hybrid resins and their hybrid polyurethanes were prepared via in situ (IS) or blending (BL) method using different silica sols. The effects of preparation methods, silica type and content on the interaction and microstructure of polymer/silica hybrid materials were investigated by FTIR, viscosity measurement, TGA, DMA and SAXS, respectively. It was found that both IS and BL methods formed agglomerates of silica-rich phases and primary silica-rich phases in the hybrid films, but the former caused stronger interaction between silica and polymer than the latter, resulting in much bigger agglomerates and compacter structure. The ethoxy group at silica was favorable for enhancing the interaction between silica phase and polymer, even between silica phases as well. The interaction between silica phase and polymer caused increasing viscosity, modulus and Tg, while the interaction between silica phases themselves increased the extent of micro-phase separation, especially for the hybrid films prepared by IS method.     

Synthesis of Hydrophilic and Hydrophobic High Surface Area Xerogels at pHs Below Silica Iso-electric Point

The synthesis of hydrophilic and hydrophobic high surface area (up to 1087 m²/cc) silica xerogels at pHs below 2 is demonstrated in this work. High surface area xerogels exhibit extremely fine microstructural features and fast gelation times (less than one hour). Contrary to conventional generalization that xerogels synthesized at low pH are polymeric, it is demonstrated that particulate xerogels can also be synthesized at pHs below 2. These xerogels are synthesized by the addition of large amounts of NH₄OH and have relatively lower surface areas. The particulate nature of these xerogels is indicated by their opacity and from their coarse microstructural features as observed by TEM.     

In Situ Formation of Particulate Silica in Natural Rubber Matrix by the Sol-Gel Reaction

The sol-gel reaction of tetraethoxysilane was conducted in natural rubber (NR) matrix to obtain NR/in situ silica mixtures. In other words, in situ filling of silica onto NR was conducted. The mixtures were compounded with curing regents, and their viscosities were evaluated. The in situ silica with a coupling agent afforded the lowest viscosity compared not only with a conventional silica (VN-3) but also with a carbon black (HAF). The curing behaviors were most favorable for in situ silica compound. Physical properties of the vulcanizates were also evaluated, and again in situ silica stock gave the best result.     

Synthesis of Silica Aerogels: Influence of the Supercritical CO2 on the Sol-Gel Process

The synthesis of silica aerogels was modified by addition of supercritical CO₂ during the sol-gel process. It was shown, that CO₂ acts as a catalyst and accelerates the gelation significantly. This effect was studied under a multitude of experimental conditions. The influence of the precursor concentration, temperature and the nature of the catalysts and solvent on the gel formation in presence of CO₂ was studied. Several gels obtained by this method were dried and transparent silica aerogels were produced.     

表面活性物质对SiO2干凝胶中甲基橙变色反应的影响

掺杂;表面活性物质对SiO2干凝胶中甲基橙变色反应的影响     

Synthesis and Characterisation of Sulfated Zirconia Sol-Gel Systems

A set of sulfated zirconia xerogels were prepared using a one and two step hydrolysis method, in different vessels (open or closed) and varying the molar ratio R = [HNO₃]/[Zr(On-Pr)₄]. In order to verify the influence of these variables on the gel time and the final samples, physisorpion, quantitative analysis of the sulfate, DTA and DTG, X-ray diffraction at small (SAXS) and wide (WAXS) angles, and FTIR measurements, were employed. The main differences were found regarding samples with different values of R. For samples with R constant, the preparation method and the kind of container employed only slightly influenced the samples.     

Preparation of Transparent, Partially-Crystallized BaTiO3 Monolithic Xerogels by Sol-Gel Processing

Transparent, partially-crystallized nanostructured barium titanate (BaTiO3) monolithic xerogels (dried at 90°C) have been successfully synthesized via hydrolysis of Ba, Ti alkoxide precursor solutions in a concentration range of 1.0 mol/l with addition of water with a molar ratio of H2O/Ba 6.3. Transparent monolithic xerogels obtained from a precursor solution of 1.0 mol/l remained transparent even after firing at 500°C in oxygen, although the degree of their transparency was considerably decreased. Firing at temperatures above 500°C yielded translucent ceramics of BaTiO3, and ultimately, firing above 600°C resulted in normal opaque ceramic bodies. Those obtained from a more concentrated precursor solution of 1.2 mol/l were, on the other hand, still transparent after firing at 600°C in oxygen, and turned opaque at 700°C. The results demonstrate that the materials retained their transparency even after pyrolysis of organic compounds involving exothermic oxidation at temperatures in the range of 200 to 400°C. The densification behavior of transparent BaTiO3 monolithic xerogels obtained was found to be excellent; for example, those derived from a 1.0 mol/l precursor solution could be sintered to form monolithic BaTiO3 ceramics with a relative sintered density of about 94% and an average grain size of 1 m by firing at 1100°C for 2 h in oxygen.     

Microstructure and Porosity of Silica Xerogel Monoliths Prepared by the Fast Sol-Gel Method

An adaptation of the fast sol-gel method to the synthesis of xerogel monoliths using tetramethoxysilane (TMOS) as the alkoxide precursor is described in this paper. The procedure involves running the reaction at 70–80°C in an open vessel, which accelerates hydrolysis and condensation and reduces the amount of liquid by expelling excess methanol through outdistillation. This procedure yields crack-free monoliths. The porosity and microstructure of these xerogel monoliths were studied by using N₂ adsorption and desorption and scanning electron microscopy (SEM). The SEM data show that the solid skeletal phase has a globular morphology with particles, 20–40 nm in diameter, arranged into agglomerates a few hundred nm in diameter. The microstructure of the acid-catalyzed xerogel is a consolidation of these agglomerates. The isotherm data show these xerogels to be microporous. In contrast, the base-catalyzed xerogel has a hierarchical morphology with the clusters of agglomerates organized into larger clusters approaching 1 m in diameter. An analysis of the isotherm data shows these xerogels to be less microporous with a narrow distribution of mesopores having an average diameter of 50 Å.     

A Sol-Gel Synthesis for Thermally Stable Aniline/Silica Material

Aniline/silica sol-gel material was obtained. The aniline was immobilized on the silica surface using chloropropyltrimethoxysilane as bridge reagent. The base activator NaH was used to produce a fast SN₂ reaction between the base and the alkylorganosilane. The resulting modified silica was characterized by elemental analysis and infrared spectroscopy using an oven cell. The organic coverage on the surface was proportional to the organic precursor concentration. The aniline/silica materials are thermally stable up to 300°C, in high vacuum.     

Fabrication of Chromophoric Xerogels by Synergistic Combination of Nucleophilic Aromatic Substitution and the Sol-Gel Process

The nucleophilic substitution of fluorine of aromatic compounds with n-aminoalkyl trialkoxysilanes and consecutive sol-gel process have been used for the fabrication of various chromophoric sol-gel materials. The displacement of the fluoro substituent of an activated aromatic molecule occurs by a primary or secondary amino group of (CH₃O)₃Si-(CH₂)₃-NHR [R- = H-; CH₃-, (CH₃O)₃Si-(CH₂)₃-] in tetraalkoxysilane or alcohol as solvent and the sol-gel process can be carried in the same vessel. The HF formed is trapped by a tertiary amine and simultaneously serves as the catalyst for the sol-gel process. Various aromatic compounds have been checked for this purpose: 1-(4-fluorophenyl)-2-nitroethylene, 1-(4-fluorophenyl)-2,2-dicyanoethylene, 4-fluorobenzonitrile, 4-fluoronitrobenzene, 4,4-difluorobenzophenone, 4,4-difluorobenzil, 7,7-difluorodibenzylideneacetone, tetrafluoro-p-benzoquinone, and 1,5-difluoro-2,4-dinitrobenzene. Mono and disubstitution has been studied by UV/Vis- and solid state NMR spectroscopy of the xerogels.     

Influence of Cd Content and Se Doping on the Formation of CdSe Nanocrystals in Silica Xerogels: A SAXS Study

Small-angle X-ray scattering (SAXS) experiments were carried out to characterize the structure of the composite formed by CdSe nanocrystals embedded in a popous silica matrix (silica xerogels containing Cd with formamide addition and ultrasound treatment). SAXS results from samples before Se diffusion indicate the presence of heterogeneities with a bimodal size distribution which was associated to the existence of mesopores (pores of several hundred Å) immersed in a nanoporous matrix (characteristic pore radii of 20–30 Å). The diffusion of Se induces the nucleation and growth of CdSe nanocrystals. The average size of the nanocrystals increases with Cd content. Higher Se doses promote the formation of larger nanocrystals (radius of gyration of ∼30 to 50 Å). Anomalous scattering results confirm the existence of Se aggregation associated with CdSe nanocrystal formation and suggest that only partial segregation of Cd and Se occurs.     

Influence of CdS Nanoparticles on the Photoluminescence of Silica Xerogel

The optical properties of CdS‐doped silica xerogels were studied. The results suggested that doping of CdS nanocrystals enhanced the photoluminescence of the silica xerogels. The X‐ray diffraction and spectra analysis confirmed the formation of CdS nanoparticles in the silica matrix.     

Ethanol Washing Effect on Textural Properties of the Sodium Silicate-Derived Silica Xerogel

This study deals with the use of ethanol as washing solvent in the preparation of the silica gels from sodium silicate in order to enhance the textural properties, especially surface area. We here examined the effect of ethanol-washing on surface area, micro- and mesopore volume, and average pore size. The silica xerogels prepared from sodium silicate solution exhibited an extremely high surface area of 1139 m2/g by washing their hydrogels with ethanol. Compared to water-washed xerogels, ethanol-washed xerogels showed higher surface areas, total pore volumes, and larger average pore sizes. Unlike the surface area of water-washed xerogel, that of the ethanol-washed xerogel was not affected by the silica concentration of initial solution. This study indicates that the textural properties of sodium silicate-derived xerogels are further enhanced by using ethanol as washing solvent.     

SiO2纳米粒子对溶胶凝胶涂层性能的影响

在高强钢表面制备了防护性溶胶凝胶涂层,并研究了不同浓度二氧化硅纳米粒子的加入对于涂层形貌、耐蚀性和硬度的影响。采用扫描电子显微镜(SEM)和电子能谱(EDS)观察了涂层的微观结构和成分;采用显微硬度计测试了涂层的硬度;采用电化学方法研究了二氧化硅纳米粒子的浓度对于涂层耐蚀性能的影响;采用傅里叶红外光谱研究涂层的化学结构,进而探讨了二氧化硅纳米粒子对于涂层的强化机理。结果显示涂层加入二氧化硅纳米粒子的最佳浓度为500 mg.L-1,此条件下的涂层表面均匀致密,有较高的硬度并且在3.5%NaCl溶液中体现出较好的耐蚀作用。纳米粒子在溶胶中反应形成活性羟基基团并与硅烷发生反应生成空间网状结构,从而强化涂层。     

Surface Energy Changes of Heat Treated TEOS Derived Silica Xerogels

The surface energy of monolithic silica xerogels was examined by measuring the interaction of organic probes with xerogels heated at temperatures close to the gel-to-glass transition temperature. Values of the dispersive component of the surface energy, , between 60 and 80 mJ m^-2 have been observed using n-alkanes for silica xerogels heated at 700, 800 and 900°C. At 1000°C, decreases to 8.37 mJ · m^-2. Also the differential heat of adsorption, variation of standard free energy and entropy of adsorption decrease when the silica xerogel is heated at 1000°C, showing a lower interaction potential of the organic probes with the silica surface. For the silica xerogels heated between 700 and 900°C, the acid character varies in accordance with the variation of the chemical nature of the silica. Upon heating at 1000°C, both acid and base characters are very close in accordance with a neutral surface. Within the experimental conditions used in this work, the surface of the obtained monolithic silica xerogels behaves as a glass surface when the treating temperature is 1000°C.     

Atomistic Modeling of Silica Based Sol-Gel Processes

Density Functional Theory is used to study water, methanol, ethanol, TMOS, and TEOS molecules and the most important silica clusters participating in sol-gel processes. Calculated bond lengths, bond angles and electric dipole moments compare well with experimental data. The energy of these molecules is reported and used to discuss the energetics of the hydrolysis and condensation reactions. Molecular Dynamics is employed to simulate liquid water, methanol, ethanol, TMOS, TEOS and experimental sol-gel solutions. Calculated densities and enthalpies of vaporisation compare well with experimental data. Preliminary results are presented for MD simulations of sol-gel solutions.