Atomic oxygen erosion resistance of sol–gel oxide films on Kapton

Silica, alumina and silica-alumina composite films were deposited on Kapton substrate via sol–gel method and their atomic oxygen (AO) erosion resistance was test in a ground-based AO simulator. The surface morphology and the structure of as-deposited films were investigated by scanning electronic microscope, X-ray photoelectron spectroscopy, and Fourier transformed infrared spectroscopy. After AO exposure, more cracks and micro-pores appear on the surface of silica and alumina films, respectively. For the silica-alumina composite films, their toughness and densification are good, and the stable interface is formed between the alumina and silica phases. Therefore, the silica-alumina composite-coated Kapton shows the best AO resistance and the erosion yield is two orders of magnitude less than that of pristine Katpon. Moreover, the composite-coated Kapton remains optically stable under AO exposure.     

Encapsulation of Tetraazaannulenato Compounds in Matrix by Sol-Gel Process

The hybrid organic-inorganic catalyst constituted by {5,7,12,14-tetramethyldibenzo[b,i]-1,4,8,11-tetraaza[14]annulenato} nickel (II), NiTMTAA, encapsulated in an alumina matrix has been prepared. NiTMTAA was synthesized by the reaction of nickel acetate with o-phenylenediamine in the presence of 2,4-pentanedione under argon atmosphere. The alumina hybrid material was obtained by a non hydrolytic sol-gel route, through the condensation of aluminum chloride with diisopropylether in the presence of NiTMTAA. The material has been prepared through precipitation from a gel. Characterization of the alumina hybrid material has been performed by ultra violet-visible spectroscopy, electron spectroscopic imaging, surface area, atomic absorption, infrared spectroscopy, and thermogravimetric analysis. The ultra violet-visible absorption spectrum of the hybrid material has bands characteristic of the NiTMTAA compound showing that the structure of NiTMTAA has been preserved in the hybrid material. The new material has a surface area of 300 m²/g. The electron image was that of a non-crystalline microstructure. Comparison between the leaching of NiTMTAA from NiTMTAA adsorbed on commercial neutral alumina confirm that in the non-hydrolytic materials the NiTMTAA is entrapped and not only adsorbed on the alumina surface. The use of conventional hydrolytic sol-gel process leads to the complete leaching of NiTMTAA from matrix, underlining the importance of the non-hydrolytic alumina gel process in the matrix preparation. The new catalysts prepared were tested for their ability to catalyze the epoxidation of (Z)-cyclooctene using iodosylbenzene as oxygen donor, giving moderate yields in the epoxidation (40%), while the homogeneous NiTMTAA is inactive due to NiTMTAA bleaching. These results emphasize the effect of the non-hydrolytic alumina matrix to prevent chemical degradation of NiTMTAA.     

SiO2凝胶中铕(铽)-间甲基苯甲酸-邻菲咯啉配合物的热稳定性及发光性能研究

采用溶胶 凝胶法 ,以掺杂方式制备了含有铕 (铽 ) 间甲基苯甲酸 邻菲咯啉配合物的SiO2凝胶复合发光体 ,研究了其热分解曲线、激发光谱和发射光谱 ,并与固体粉末进行了比较 ,讨论了将配合物引入该凝胶后对其热稳定性及发光的影响。     

Supramolecular Templating of Mesopores in Phase-Separating Silica Sol-Gels Incorporated with Cationic Surfactant

Silica gels with hierarchical macropores and mesopores have been prepared by inducing phase separation in the alkoxide-based sol-gel system with an addition of alkyltrimethylammonium salt. Narrowly distributed mesopores were observed in the heat-treated gel samples possibly as a result of supramolecular templating of silica oligomers in the reacting solution. The ionic attractive interaction and hydrophobicity of the attached alkyl group cooperatively determined the phase separation tendency. No indication of long-range order of the mesopores was obtained.     

Variation of Microenvironment around Auramine O Molecules Doped in Silica Prepared from Tetramethoxysilane

Silica gel doped with Auramine O (AuO), which is known as a microscopic viscosity probe through fluorescence spectra, was prepared by the sol-gel method using tetramethoxysilane (TMOS) as a starting alkoxide. Fluorescence spectra from the starting solution to the dry gel were measured to pursue the variation of microscopic viscosity around the AuO molecules during the sol-gel process. The fluorescence intensity of AuO did not change at the gelation point, indicating that the microscopic viscosity around AuO did not change during the sol-to-gel transformation. The intensity was, however, increased largely in the drying process; the internal motion of AuO molecules became largely restricted by the surrounded silica matrix during the drying process.     

Carbon black/alumina gel composite: Preparation by sol-gel process in the presence of polymer-grafted carbon black and its electric properties

The preparation of a novel carbon black/alumina gel composite by sol-gel reaction of aluminum isopropoxide (AIP) was investigated. When sol-gel reaction of AIP was carried out in the presence of untreated carbon black, a thin film of alumina gel was hardly obtained, because of the presence of aggregated carbon blacks. On the contrary, in the presence of poly(N-vinyl-2-pyrrolidone)-grafted, poly(2-methyl-2-oxazoline)-grafted, and poly(N,N-diethylacrylamide)-grafted carbon black, a deep-black, thin film of alumina gel, in which carbon blacks were uniformly incorporated, was obtained. Carbon black was incorporated into an alumina gel matrix by the hydrogen bond between carbonyl groups of the grafted polymer and the residual hydroxyl groups in the alumina gel. Electric resistance of the polymer-grafted carbon black/alumina gel composite was very sensitive to the vapor of solvents of the grafted polymer chains on carbon black surface: the electric resistance of the composite drastically decreased in humidity and N,N-dimethylformamide vapor, but not in n-hexane vapor. The logarithm of electric resistance of polymer-grafted carbon black/alumina gel composite linearly decreased in proportion to relative humidity. In addition, the electric resistance of poly(N,N-diethylacrylamide)-grafted carbon black/alumina gel composite under humidity decreased drastically at 32°C. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3591–3597, 1999     

Optimized cleanup methods of organic extracts for the determination of organic pollutants in biological samples

The analytical performances of various adsorbents used to clean up an organic extract of biological samples, particularly for the determination of polycyclic aromatic hydrocarbons (PAHs), polychlorobiphenyls (PCBs), both in mussel tissue and in krill samples, are critically compared. DDT and its degradation products, namely DDE and DDD, are also considered. Silica gel, alumina, aminopropyl-silica, cyanopropyl-silica, florisil, graphitized nonporous carbon and silica gel–alumina mixture (3:1) were used for column chromatography cleanup in combination with modified supercritical CO₂ as a mobile phase. Recovery and reproducibility were evaluated by analyzing standard solutions and standard reference materials containing various classes of pollutants. A silica gel–alumina mixture was found to be the most effective in the cleanup of organic extracts, allowing quantitative recoveries of all analytes to be obtained. Finally, the application of the optimized procedure to the determination of PCBs in Antarctic krill samples is presented.     

Effect of preparation conditions on the optical and physical properties of an epoxy-functional inorganic-organic hybrid material system

A hybrid material system consisting of (3-glycidyloxypropyl)trimethoxysilane, dimethyldimethoxysilane and zirconium(IV) n-propoxide was prepared. The influence of processing parameters including Zr content, UV irradiation and sol ageing on the properties of the resultant thin films was discussed. Refractive index, at 633 nm, and reflectance measurements were performed and near-field waveguide images of the samples were taken. Optical propagation loss measurements, at 633 nm, were studied. Film thickness and cross-sectional scanning electron microscopy images were obtained as a function of process conditions. FT-IR spectroscopy was used to monitor chemical reaction pathways in the system during processing. It was demonstrated that the crosslinking of epoxy groups in the structure, along with inorganic network formation as a result of sol-gel reactions, was the primary reason for the changes in the optical and physical properties of the system. As Zr containing species and/or UV irradiation may be employed to crosslink the epoxy groups in the structure, the optical and physical properties of the system can be tuned by optimal combination of these two crosslinking methods, as well as sol ageing process.     

Microwave Dielectric Relaxation of Bound Water to Silica, Alumina, and Silica-Alumina Gel Suspensions

By the use of a time domain reflectomery method, dielectric measurements were carried out on silica, alumina, and silica-alumina gel suspensions (five types with composition varying between 0.3 < Si/Al atomic ratio <0.8) in the frequency range of 100 kHz to 20 GHz. For all the gels, a relaxation peak due to bound water was observed. This peak locates at around 1-10 MHz, indicating that the peak is a decade or 10 decades lower than those of biological polymers such as an aqueous DNA solution. The silica and alumina gels have a different bound water structure, judging from the fact that the peaks are different in their locations and shapes between the two gels. The silica-alumina gels exhibit two different peaks other than the peak of bulk water. The sum of the relaxation strength on the two peaks is proportional to the monolayer capacity obtained from water vapor isotherms. The shape of the one peak holds that of the silica gel, whereas the other retains that of alumina gel, and furthermore the ratio of the relaxation strength on the former peak to that on the latter depends on Si/Al atomic ratio. It is suggested that both peaks are caused by the orientation of bound water molecules. Copyright 1999 Academic Press.     

Differential Scanning Calorimetry Evaluates Relative Proportions and Strength of Acid-Sites in Catalytic Materials and Adsorbents Alumina and Amorphous Silica-Alumina

Abstract

Differential scanning calorimetry (DSC) is employed to evaluate the relative proportions and strength of acid-sites in gammaalumina and amorphous silica-alumina through presorption of tri-ethylamine (TEA) followed by its thermal desorption in the DSC equipment. From the data obtained, total acid-sites in silica-alumina is found to be 2.3 times as large as those present in gamma-alumina, and 5–5% of total acidity in alumina is of Bronsted type whereas in silica-alumina this type comprises 28.9%' The Bronsted acidity strength in alumina and silica-alumina is identical although greatly different in quantity. Lewis acidity in silica-alumina is significantly stronger than that in alumina.     

Effects of Ti Addition on Alumina/Titania Composite Aerogels Synthesized by Sol–Gel Process and Supercritical Ethanol Drying

Alumina/titania composite aerogels with different titania contents were synthesized by the sol–gel process and supercritical ethanol drying. The structures and morphologies of synthesized aerogels were analyzed by X‐ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetry, and N₂ adsorption–desorption tests. Supercritical ethanol drying induced the crystallization of titania, which prompted the transformation of the structure from pseudoboehmite to γ‐Al₂O₃ . Reversely, alumina retarded the anatase‐to‐rutile transformation of titania. The content of titania significantly affected the structure and morphology of alumina/titania composite aerogels. A high content of titania (≥40%) resulted in the phase separation of titania particles, which grew to form the anatase phase octahedral particles with well‐developed facets. When the titania content was low, titania particles could be homogeneously dispersed in alumina particles to form spherical clusters with the poor crystallinity. Titania particles were in the anatase phase, and no rutile phase was formed until the temperature rose to 1000°C. In addition, titania addition resulted in a decrease in the specific surface area (SSA) of alumina aerogels because the SSA of titania was lower than that of alumina aerogels.     

溶胶-凝胶法制备钯催化剂的织构与性能

采用溶胶-凝胶法制备了Pd/Al2O3催化剂，用LLS(激光光散射)、XRD和BET等技术考察了溶液pH值对所成胶体粒子流体力学半径、相应催化剂产品孔径分布及热稳定性的影响.研究发现，由pH=4.1的胶体制备的催化剂具有良好的热稳定性和CO、C3H6的氧化活性.氧化镧添加剂可抑制Al2O3载体在高温下由γ相向α相的转化，同时也促进了催化剂上Pd粒子的生长. La2O3可提高新鲜Pd催化剂的氧化活性，但对老化后催化剂活性的提高无促进作用.     

A new way to spinnable sols derived from modified aluminumalkoxides

The preparation of spinnable sols has been developed to obtain a new type of sol-gel derived pure alumina fiber. The starting material was aluminum sec-butoxide, which was modified in a first step with glycolether, e.g., isopropoxyethanol. This leads to a partial replacement of alkoxy groups via alcoholysis and a change of the precursor structure from a trimeric to a tetrameric one. In the second step, carboxylation, the transformation to six-coordinated aluminum could be observed. Due to the formation of a sol with Newtonian flow behavior after hydrolysis, gel fibers up to several kilometers long could be drawn directly from the clear colorless sol with spinning velocities up to 200 m/min. The addition of an organic filament-forming polymer is not necessary. The sol is spinnable for periods up to one year. The transformation of the gel fiber to -Al₂O₃ occurs at 1150° C.     

Preparation of Alumina Supported Palladium Catalysts by Sol-Gel Method

The chemical reactivity of the aluminium-sec-butoxide (ASB) and the palladium acetylacetonate Pd(acac)₂, used as precursors for the preparation of the alumina supported palladium catalysts by sol-gel method was investigated by the spectroscopic study of the precursor mixture during ageing, using FTIR, UV-VIS and ²⁷Al NMR. The obtaind results showed that acetylacetonate ligands were linked to aluminum when the mixture was aged at 40°C. This was proved by the bands observed at 1530 and 1600 cm^–1 in the FTIR spectra, the band obtained at 289 nm in the UV-VIS spectra and the ²⁷Al NMR sharp peak at 3 ppm. Furthermore, in order to avoid the Pd(acac)₂ reduction to metallic palladium by the SB occurring when the mixture is aged for 3 h, an optimum ageing time should be selected. The precursors modification and the preservation of the palladium oxidation state during ageing could be the required conditions to create a bond between palladium and aluminium during the gelation step. This should be the reason of the thermal stability improvement of the alumina supported palladium catalyst prepared by the sol-gel method.     

Modification of Thermo-Optic Characteristics of Sol-Gel Inorganic-Organic Hybrid Materials

The effect of the inorganic oxide network on the variation of thermo-optic characteristics (dn/dT) in inorganic-organic hybrid material prepared through the sol-gel process was investigated. The dn/dT values were negative for all samples, and decreased in magnitude with the increasing concentration of the inorganic oxide or heterometallic oxide network. The dn/dT also became less negative with the increase in the degree of inorganic condensation in sol-gel reaction. A negative dn/dT value is consistent with thermal expansion of the material, and it is believed that the value of the dn/dT in our inorganic-organic hybrid materials was principally sensitive to variations in expansion term.     

Preparation of Amorphous Silica-Alumina Using the Sol–Gel Method and its Reactivity for a Matrix in Catalytic Cracking

Amorphous silica-aluminas were prepared by the sol–gel method using organic templates such as carboxylic acid and the gel skeletal reinforcement method. Their reactivities as a matrix for the catalytic cracking were investigated. Malic acid (MA) was used as a catalyst for the sol–gel method, an organic template and a reagent for the dispersion of Al. When the ratio of MA/TEOS (tetraethoxysilane) increased from 0.22 to 1.22, surface area, pore volume and pore diameter increased and the mesopore was formed at 1.22. Their average BET pore diameters for 0.22 and 1.22 of MA/TEOS were 2.0 to 5.1 nm, respectively. Although conversions of n-dodecane were around 20% or less with single amorphous silica-aluminas, both single beta-zeolite and the mixed catalysts of zeolite and amorphous silica-aluminas showed much higher activity. Further, the mixed catalyst using silica-alumina with mesopore (MAT(MA122-5)) exhibited the higher ratio of multi-branched paraffin to single branched paraffin in the gasoline franction of products (C5–C11) than the mixed catalysts using silica-alumina with only micropore and silica with mesopore or single zeolite. In the gel skeletal reinforcement method, tetraethoxy orthosilicate (TEOS) was used as not only a precursor of silica but also an agent which reinforces the skeleton of silica-gel to prepare an aerogel and extremely large mesopores were formed for resultant silicas and silica-aluminas. When silica aerogel was reinforced by TEOS solution, the pore diameter and pore volume reached 30 nm and 3.1 cm³/g, respectively, in the N₂ adsorption measurement by the BJH method, indicating that most of pores for this silica consisted of mesopores. In catalytic clacking reaction of n-dodecane, the mixed catalyst prepared by beta-zeolite and silica-alumina with large mesopore exhibited not only the comparable activity to that for single zeolite but also the unique selectivity where large amounts of branched products were formed. When the catalyst beds of silica-alumina and zeolite were separated, the reference silica-alumina (ref.SA) → zeolite system exhibited the higher activity and the product selectivity close to those for MAT(ref.SA). It is likely that the primary cracking of n-dodecane on silica-alumina would occur to produce the primary cracked product which effectively reacted with zeolite and inhibited the coke formation by overcracking.     

Sol-gel derived oxides and mixed oxides catalysts with narrow mesoporous distribution

A novel sol-gel process for preparing oxides and mixed oxides sols from precipitation and peptization process is reported in this article. Inorganic salts are used as raw materials in this study. It is found that the amount of acid has great influence on the stability and particle diameter distribution of the precursor sols. Ultrasonic treatment is used to prepare alumina sol at room temperature. The result of 27AI NMR shows that there exist AI_13~(7+) species in the sol. By controlling the sol particles with narrow particle diameter distribution, alumina, titania and silica-alumina (SA) materials with narrow mesoporous distribution are formed by regular packing of sol particles during gelation without using any templates. The results also show that the structure and particle diameter distribution of precursor sol determine the final materials' texture.     

Improvement of the Pd/Al2O3 Catalyst by the Control of the Sol-Gel Preparative Parameters

In this work, the metal dispersion of the Pd/Al₂O₃ catalyst prepared by sol-gel method is improved by an adequate optimisation of the preparative variables. First, the gelation temperature and the ageing time are selected, in order to avoid the reduction of the metal precursor (palladium acetylacetonate, Pd(acac)₂) by the solvent (sec-butanol, sB). The metal sintering effect on the catalysts treated in oxygen at 500°C is then minimized when the alumina pore size is controlled by the variation of the alumium alkoxide (AsB) concentration and the acetic acid amount ([AcA]/[AsB]). The appearance of new palladium particles on the alumina surface and the matching between the particle diameters and the pore sizes were also effective for the metallic surface area improvement on the samples treated in oxygen at 800°C. Compared to the reference catalysts, the higher metal dispersion obtained on the sol-gel ones was the determinant factor for their higher catalytic activity in methane combustion.     

Mullite Based Compositions Prepared by Sol-Gel Techniques

Ceramic powders and gels in the multi-alumina system with different compositions were prepared by sol-gel method. The preparation of gels was done in strong acidic conditions and also with the addition of ammonia. The powders were prepared by dropping the sols on a hot plate. The effect of water/alkoxide and ethanol/alkoxide ratios was studied together with the type of catalyst used (hydrochloric acid or ammonia). The thermal evolution of materials was followed by thermal analysis, X-ray diffraction, specific surface area measurements and electron microscopy. The morphology of powders was also studied. The characteristic exothermic peak attributed to a good mixing degree of the Al and Si species was observed at ∼980°C. The intensity of this exothermic peak was more pronounced in gels than in sol-gel derived powders. The crystalline phases formed are related with the preparation conditions and with the thermal treatment. The crystallisation of mullite and transient phases of alumina were observed in powder samples heat treated at 1000°C while in gel samples mullite was the only crystalline phase detected.     

Improvement of proteolytic efficiency towards low-level proteins by an antifouling surface of alumina gel in a microchannel

A microfluidic reactor has been developed for rapid enhancement of protein digestion by constructing an alumina network within a poly(ethylene terephthalate) (PET) microchannel. Trypsin is stably immobilized in a sol-gel network on the PET channel surface after pretreatment, which produces a protein-resistant interface to reduce memory effects, as characterized by X-ray fluorescence spectrometry and electroosmotic flow. The gel-derived network within a microchannel provides a large surface-to-volume ratio stationary phase for highly efficient proteolysis of proteins existing both at a low level and in complex extracts. The maximum reaction rate of the encapsulated trypsin reactor, measured by kinetic analysis, is much faster than in bulk solution. Due to the microscopic confinement effect, high levels of enzyme entrapment and the biocompatible microenvironment provided by the alumina gel network, the low-level proteins can be efficiently digested using such a microreactor within a very short residence time of a few seconds. The on-chip microreactor is further applied to the identification of a mixture of proteins extracted from normal mouse liver cytoplasm sample via integration with 2D-LC-ESI-MS/MS to show its potential application for large-scale protein identification.