Nitridation of Amorphous Silica with Ammonia

The reaction between amorphous silica and ammonia in the temperature range 200° to 1230°C has been investigated. The reaction process was monitored with respect to the nitrogen content of the reaction product, the specific surface area of the amorphous nitrided silica, and the decomposition of ammonia. A surface reaction was observed at temperatures between 300° and 500°C, but in agreement with other studies bulk reaction only occurred above 800°C, reaching its maximum rate at about 1000°C. It is suggested that the decomposition of ammonia, which also becomes important above 800°C, is essential for the bulk nitridation reaction. At temperatures above 1050°C the nitridation yield decreases, until gas-phase reaction between SiO( g ) and N₂ or NH₃ becomes dominant at 1230°C, leading to the formation of α-Si₃N₄.     

Nitridation of the Sol–Gel-Derived Titanium Oxide Films by Heating in Ammonia Gas

Dip-coated sol–gel-derived TiO₂ films on an alumina substrate were converted to nonstoichiometric titanium nitride (TiN _x ( x ≦ 1)) films by heating at approxmately 1000°C in NH₃ gas. TiO₂ films made from TiO₂ sols prepared from Ti(O– i -C₃H₇)₄ and stabilized by diethanolamine were more easily nitrided than those from sols containing HCl as a deflocculant reagent. This appears to be a result of the more porous structure of the former films.     

Fast and Almost Complete Nitridation of Mesoporous Silica MCM-41 with Ammonia in a Plug-Flow Reactor

The title reaction proceeded well to yield silicon (oxy)nitride at 973–1323 K using a plug-flow reactor. The degree of nitridation was studied as a function of temperature and time of nitridation, the sample weight, and the flow rate of ammonia. It was dependent on the reaction temperature and the amount of ammonia supplied per sample weight. The nitridation at 1273 K for 10–25 h yielded the oxynitride with 36–39 wt% nitrogen, which was very close to 40 wt% of Si₃N₄. Characterization with X-ray diffraction, field-emission scanning electron microscopy and transmission electron microscopy measurements, and nitrogen adsorption revealed the conversion of MCM-41 to the corresponding oxynitride without essential loss of the mesoporous structure, the decrements of the lattice constant and the pore diameter by 20–35%, and the increments of the wall thickness by ca. 45%. Solid-state ²⁹Si nuclear magnetic resonance spectra during the nitridation clearly showed fast decrease in SiO₄ species and slow in SiO₃(OH). Various intermediate species, SiO _x N _y (NH₂ or NH) _z , were observed to be formed and finally, ca. 70% SiN₄ species, ca. 20% SiN₃(NH₂ or NH), and ca. 10% SiON₂(NH₂ or NH) were produced, being consistent with the results of the above mentioned elemental analysis.     

Behavior of Microporous Nitroprussides in Presence of Ammonia

The behavior of microporous nitroprussides in the presence of ammonia, both in anhydrous and hydrated states, was studied using ammonia adsorption isotherms and IR, Mössbauer and XRD techniques. In their anhydrous state these materials behave as a zeolite for ammonia adsorption, however when structural water is present a decomposition process was observed. The crystallization or adsorbed water is used by ammonia to form NH⁺ ₄ and OH^–, creating basic conditions where the structural building unit [Fe(CN)₅NO] loses the NO group to form a pentacyano complex. This leads to the formation of mixed salts, M(NH₄)[Fe(CN)₅]·xH₂O. For ferrous nitroprusside the formed OH^– ion competes with the complex anion for the iron(2+) cation which is removed, then oxidized and finally observed as a ferric oxyhydroxide, FeOOH.     

Nitridation of Silica Characterized by High-Energy X-Ray Diffraction Technique

The structure of amorphous silicon oxynitride formed under nitridation conditions using ammonia gas, before the onset of silicon nitride crystallization, is determined employing high-energy X-ray diffraction (HEXRD) technique. The derived real-space function suggests that smaller ring structures, especially 3R and 4R (R: ring), which are the dominant rings in crystalline silicon nitride, are not major species in amorphous silicon oxynitride, and form in the latter part of the silicon nitride crystallization.     

Inkjet Printing of Microporous Silica Gas Separation Membranes

Inkjet printing was applied to manufacture silica‐based gas separation membranes, which were coated on a pore‐graduated alumina substrate with a mesoporous γ‐alumina interlayer. A silica sol diluted by 1‐propanol was used to print the membrane layer followed by thermal treatment in a rapid thermal processing furnace. The membrane thickness was varied between 30 and 110 nm by conducting one, two, and three coating steps. In the latter case, H₂ permeance in the range of 2.0 × 10^?8–3.3 × 10^?8 mol/s·m²·Pa combined with H₂/CO₂ selectivities in the range of 15–25 were achieved, proving the concept that inorganic gas separation membranes can be successfully processed by inkjet printing.     

Reaction of Ammonia with Fumed Silica

The reaction between fumed silica and ammonia has been studied between 600° and 1200°C. Up to 24 wt% nitrogen can be introduced into vitreous silica by adjusting the partial pressure of ammonia, temperature, and reaction time. The experiments show that the amount of nitrogen incorporated into silica has a linear dependence on the partial pressure of ammonia and a square root dependence on the reaction time. The activation energy for the reaction was found to be 76.0 kJ/mol. The nitrided powders as well as several hotpressed samples were crystallized at 1550° to 1650°C. Silica glasses containing 0 to 1 wt% nitrogen crystallize to cristobalite. Glasses containing 2 to 10 wt% nitrogen are stable against devitrification in nitrogen, even at 1650°C. Glasses with 12 to 28 wt% nitrogen crystallize to fine-grained Si₂N₂O with residual glass.     

Porous Silicon Nitride Ceramics Prepared by Reduction–Nitridation of Silica

A new method for preparing porous silicon nitride ceramics with high porosity had been developed by carbothermal reduction of die-pressed green bodies composed of silicon dioxide, carbon, sintering additives, and seeds. The resultant porous silicon nitride ceramics showed fine microstructure and uniform pore structure. The influence of SiO₂ particle size and sintering process (sintering temperature and retaining time) on the microstructure of sintering bodies was analyzed. X-ray diffractometry demonstrated the formation of single-phase β-Si₃N₄ via the reaction between silicon dioxide and carbon at high temperature. SEM analysis showed that pores were formed by the banding up of rod-like β-Si₃N₄ grains. Porous Si₃N₄ ceramics with a porosity of 70–75%, and a strength of 5–8 MPa, were obtained.     

纳米二氧化硅填充PVDF聚合物微孔膜的研究

以丙酮及N,N-二甲基甲酰胺为混合溶剂、聚偏氟乙烯为成膜物质、纳米二氧化硅为填料,通过溶液共混法制备了聚偏氟乙烯/二氧化硅(PVDF/SiO2)复合微孔薄膜。研究发现,溶剂组分质量比对薄膜力学性能有重要影响,当m(丙酮)∶m(N,N-二甲基甲酰胺)=19∶1时,薄膜力学性能最佳,其拉伸强度为3.26 MPa;经纳米SiO2改性后,复合薄膜力学性能随SiO2质量分数的增大先提高后降低,在w(SiO2)=20%时,薄膜拉伸强度达最大值6.36 MPa;复合薄膜孔隙率随SiO2质量分数的升高而增大,当w(SiO2)=40%时,孔隙率达最大值113.9%。     

Sodium Coordination Environments in Silica Films

The local structure centered on sodium after diffusion in silica (Na-SiO₂ samples) has been determined by means of extended X-ray absorption fine structure (EXAFS) studies. The Na-SiO₂ samples are of particular interest because (i) their sodium content can be varied over a wide range of concentration and (ii) their local structure is representative of that of soda–silica glass. EXAFS analyses reveal the existence of a well-defined local structure involving oxygen, sodium, and silicon neighbors. The Na-O, Na-Na, and Na-Si bonds lengths, which amount to 0.23, 0.30, and 0.38 nm, respectively, do not depend on sodium concentration. This environment closely resembles that found in soda–silica glass. Moreover, it is compatible with the "target site" and "the site memory effect" suggested by recent theories of the ionic conductivity in oxide glasses.     

纳米TiO2/PVDF-HFP微孔膜的制备与性能

采用溶剂挥发法并以N,N二甲基甲酰胺为溶剂制备出聚偏氟乙烯-六氟丙烯（PVDF-HFP）/二氧化钛（TiO₂）聚合物微孔膜。通过对微孔膜的红外光谱、吸液率、力学性能及热重性能的测试分析,结果表明TiO₂含量为15%的微孔膜的吸液率为190%,拉力为46 N,断裂延伸率为130%,分解温度为250℃。可以满足锂离子电池的商业使用要求,具有广阔的应用前景。     

Highly Ordered N-Containing Mesoporous Silica from Carbothermal Reduction–Nitridation with the Nanocasting Procedure

Highly ordered N-containing mesoporous silica materials with high specific surface area were prepared by heat treatment of the as-synthesized mesoporous silica nanocasted with carbon in its channels in flowing N₂ at high temperatures. This is the first time N₂-assisted carbothermal reduction–nitridation with nanocasting procedure has been used to prepare ordered mesoporous materials.     

二氧化硅介孔膜材料的研究进展及应用前景

重点介绍了国内外近年来在二氧化硅介孔膜的制备与应用方面的最新进展,并对其制备与应用研究前景进行了展望。     

Preparation of ZSM-5 Zeolite Honeycomb Monoliths Using Microporous Silica Obtained from Metakaolinite

Zeolite honeycomb monoliths were prepared from ZSM-5 powders synthesized under hydrothermal conditions using microporous silica obtained by selective leaching of metakaolinite. This honeycomb material was compared with those prepared using alkoxides (TEOS) as the silica source. The honeycomb monoliths were formed by extrusion of paste made from the synthesized powders through a multi-channel honeycomb die. The morphology and porous properties of these materials were studied using XRD, FTIR, SEM and N₂/Ar adsorption. ZSM-5 grains in the monoliths prepared from metakaolinite showed platy morphology with preferred orientation of the crystals in the extruded surface, and displayed an absence of secondary growth. The twinned morphology of ZSM-5 crystals was observed in the monoliths prepared using TEOS and this contributed to an increase in the external surface area even though the total surface area was identical to that of samples prepared from metakaolinite. The physical properties, thermal stability and mechanical strength of the monoliths was compared with zeolite-coated honeycombs. The results show that microporous silica prepared by acid leaching of metakaolinite is a cost-effective raw material for preparing ZSM-5 honeycomb monoliths with controlled morphology and tunable SiO₂/Al₂O₃ ratios.     

共聚物为模板制备草莓状二氧化硅空心球

成功地通过三嵌段共聚物聚乙二醇-聚丙二醇-聚乙二醇(PEG-PPG-PEG)为模板,正辛烷为壳材料来制备介孔外壳的草莓状二氧化硅空心球。其中正硅酸乙酯(TEOS)作为二氧化硅的前驱体。通过改变反应参数,我们发现当将反应最终溶液先室温下静置24h然后加热到较高温度12h可以获得草莓状结构。产物的表面形貌通过扫描电子显微镜(SEM)来分析;透射电子显微镜(TEM)表明空心球的平均直径为800nm,外壳为20nm;多孔性分析通过氮气吸附-解附法来测量,同时用Brunauer-Emmett-Tell-er(BET)的方法来测孔径大小。另外我们提出了二氧化硅的形成机理。     

Synthesis and Characterization of Low-Dielectric Silica Aerogel Films

Thin films of silica aerogel on a silicon wafer have been synthesized via supercritical drying of wet gel films that were obtained by spin coating the polymeric silica sol, followed by aging in an isopropanol (IPA) or tetraethoxysilane/isopropanol (TEOS/IPA) solution. The viscosity of the sol and the spin rate required to form uniform coating layers were optimized. The film thickness and microstructures could be controlled by adjusting the concentration of the sol, the spin rate, and the aging conditions. The porosities and the dielectric constants of the thin films were in the range of 76%–90% (densities of 0.59–0.22 g/cm³) and 2.0–1.5, respectively. The degree of planarization in the aerogel thin film was ∼100%, and the gap-filling capability on a 0.2 μm tungsten patterning wafer was excellent. In particular, aging the wet gel film in the TEOS/IPA solution was very effective in improving the properties of the aerogel films.     

中孔二氧化硅薄膜的仿生制备技术

以薄膜的形式仿生制备二氧化硅中孔材料于1996年首次报道，最后，在其制备方法得以改进、分析和表征技术得以提高的基础上，所制备出的中孔薄膜不但具有很好的几何孔型，而且孔道有序排列的方向及膜的厚度均可在合成过程中进行调控，通过仿生制膜技术裁剪无机中孔膜的各种特性，可使它们广泛应用于对中相形态控制要求严格的催化及微电子领域。     

129Xe NMR Investigations for the Textural Characterization of Sol-Gel Derived Amorphous Microporous Silica

The aim of this work was to evaluate the potentialities of 129Xe NMR as an innovative technique for the textural characterization of microporous amorphous materials. We applied this technique to a series of sol-gel derived meso- and microporous silica materials with relatively narrow pore size distributions. The study of the Xe chemical shifts (Xe) as a function of the Xe pressure (PXe) is classically used to extrapolate Xe to zero xenon loading. This parameter can be related to the mean sample pore size using models which cannot however be considered as generally applicable for every type of material. In this study, several original results related to the NMR line shapes and to the slopes, sXe, of the lines Xe = f(PXe) have been obtained. NMR data have been interpreted on the basis of the sample textural characteristics determined by N2 adsorption. Extension of the results to other microporous materials such as zeolites has also been considered. The results showed that sXe is a useful parameter which can be related to the pore hydraulic radius of the different amorphous and zeolitic microporous materials investigated.     

多孔SiO2增透膜改性研究

本文通过在SiO2溶胶中掺入聚乙二醇(PEG)或同时掺入PEG和聚硅氧烷,研究了改性后SiO2增透膜的性能.结果表明掺入PEG仅提高了薄膜的激光损伤阈值,而同时掺入PEG和聚硅烷不仅提高了薄膜的激光损伤阈值,还极大地提高了膜层的抗机械损伤能力,延长了薄膜的使用寿命,达到了改善薄膜性能的目的.     

Synthesis of Low-Dielectric Silica Aerogel Films by Ambient Drying

A new ambient drying process that is simple, effective, and reproducible has been developed to synthesize low- k SiO₂ aerogel thin films for intermetal dielectric (IMD) materials. The SiO₂ aerogel films having a thickness of 9500 Å, a high porosity of 79.5%, and a low dielectric constant of 2.0 were obtained by a new ambient drying process using n -heptane as a drying solvent.