Fluoroalkoxides as Molecular Precursors of Fluoride Materials by the Sol-Gel Process

Numerous works have reported the preparation of pure oxide materials using the sol-gel process. The purpose of this paper is to show that it is possible to obtain pure fluoride homometallic or heterometallic materials at room temperature by the hydrolysis of tailored molecular precursors.The work is focussed on alkaline-earth and lanthanide fluoroalkoxides ([M(OR)n]n where OR = fluoroalkoxo group) and the characterization of the final products of their hydrolysis. The molecular precursors were characterized by FT-Raman and the final powders by XRD and EDXRMA.The formation of these fluoride materials involves fluoride organic by-products. The reactivity of these organic compounds on various substrates in terms of surface modification has been studied.     

溶胶-凝胶法合成锂离子电池正极材料LiV3O8

锂钒氧化物;扩散系数;溶胶-凝胶法合成锂离子电池正极材料LiV3O8     

Synthesis and Characterization of Nanocrystalline Zinc Aluminum Spinel by a New Sol-Gel Method

Using Al(OⁱPr)₃ (aluminium-iso-propoxide) and Zn(NO₃)₂⋅ 6H₂O as starting materials, HNO₃ as catalyst, ZnAl₂O₄ spinel nanometer powders were prepared at lower sintering temperatures. The gels and sintered samples of ZnAl₂O₄ were characterized by means of thermogravimetry and differential scanning calorimetry (TG/DSC), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectra and transmission electron microscope (TEM). Pure ZnAl₂O₄ spinel nanometer powders were produced by calcining the gel above 450^∘C, with the crystallite size of 7–20 nm in the temperature range of 500–900^∘C.     

Studies of LiNi0.6Co0.4O2 Cathode Material Prepared by the Citric Acid-Assisted Sol-Gel Method for Lithium Batteries

The layered LiNi_0.6Co_0.4O₂ powders were synthesized at low temperature by a sol-gel method using citric acid as a chelating agent. Submicron-sized particles of the precursor were obtained at temperature below 400°C and microcrystalline powders were grown by thermal treatment at 700°C for 4 h in air. The carboxylic-based acid acted such as a fuel, decomposed the homogeneous precipitate of metal complexes at low temperature, and yielded the free impurity LiNi_0.6Co_0.4O₂ single-phase suitable for electrochemical application. The synthesized products have been characterized by structural (XRD, SEM), spectroscopic (FTIR, Raman) and thermal (DTA/TG) analyses. Raman and FTIR measurements provide information on the local environment of the cationic sublattice of LiNi_0.6Co_0.4O₂ solid solution. Electrochemical performance of the synthesized products in rechargeable Li cells were evaluated by employing as cathodes in non-aqueous organic electrolyte mixture of 1M LiPF₆ in EC + DMC. The electrochemical behaviour of synthesized LiNi_0.6Co_0.4O₂ is discussed in relation with its synthesis procedure.     

Preparation and Characterization of BaTiO3 Long Fibers by Sol-Gel Process Using Catechol-Complexed Alkoxide

BaTiO₃ ceramic fibers were prepared by the sol-gel method in which catechol-complexed titanium isopropoxide and barium acetate hydrate were used as starting materials. The green fibers of ca. 30 cm in length were obtained from the precursor sols. The BaTiO₃ ceramic fibers with the average length of ca. 20 cm were of the order of 3 to 10 m in diameter and elliptical shapes in cross section. The green fibers and those sintered at different temperatures were characterized by TGA/DSC, XRD, IR, SEM and TEM techniques.     

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.     

Li2+2xZn1-xSiO4水基溶胶-凝胶法合成及其离子导电性

用水基溶胶凝胶法制备了锂离子导体Li_2+2xZn_1-xSiO₄(0≤x≤0.5)。实验中对干凝胶的热稳定性进行了TG-DTG分析。XRD谱结果表明形成了与Li₃PO₄结构相关的固溶体Li_2+2xZn_1-xSiO₄。TEM结果则显示晶粒尺寸为50nm左右,并应用交流阻抗谱技术进行了样品烧结体的电性能测试。     

Preparation and Characterization of Compositions Based on PbO-MgO-Nb2O5 Using the Sol-Gel Method

Lead Magnesium Niobate, Pb(Mg_1/3Nb_2/3)O₃ (PMN), is an important relaxor ferroelectric material. A significant problem exists, however, in the preparation of this material: it is very difficult to prepare pure phase, without the presence of a pyrochlore impurity phase which degrades the dielectric properties. Depending on the processing conditions, the amount of pyrochlore phase varies.Considering the ternary diagram PbO-MgO-Nb₂O₅, different compositions have been prepared by a simple sol-gel method at room temperature using Pb(CH₃COO)₂, Mg(CH₃COO)₂, Nb(OC₂H₅)₅ as precursors. After the heat treatment, the samples obtained were analyzed by XRD and EPMA with the purpose of studying the compositions formed.From the analysis of these results, it seems to be that the appearance of pyrochlore can be related to the reactivity of the MgO and/or the presence of other phases of the binary system PbO-Nb₂O₅. An excess of Pb and Mg is necessary for compositions to be formed near the PMN. The control of the amount of these two elements is very important because an excess of MgO would lead to rich compositions in Mg as a secondary phase.     

A FT-IR Study of the Synthesis of Boron Ormosils by Means of the Sol-Gel Process

Borosilicon ormosil materials can be prepared by using the sol-gel method. The precursors used for the synthesis were TEOS (tetraethylorthosilicate), TEB (triethylborate) and PDMS (silanol terminated polydimethylsiloxane). Four samples containing different boron amounts were prepared and reactions were studied by FT-IR spectroscopy. The spectra were deconvoluted and the time evolution of the most important bands was analysed in order to know the role of the boron in the reaction process. Different plots show that boron affects the self-condensation process of the hydrolysed TEOS molecules but does not have much influence in the way of the co-polymerization.     

Preparation of Thick Films by Electrophoretic Deposition Using Surface Modified Silica Particles Derived from Sol-Gel Method

Thick films were prepared by the electrophoretic sol-gel deposition of organically modified, sub-micron silica particles. The silica particles were modified with 3-aminopropyltriethoxysilane (APS) and vinyltriethoxysilane (VTES). Smooth and crack-free films ca. 15 m thick were obtained when APS modified silica particles were used for the cathodic electrophoretic deposition. Thick films with decreased open spaces among particles were obtained when silica particles modified with VTES were co-deposited with an organic polymer, polyethylene maleate.     

Development of New Modifiers for Titanium Alkoxide-Based Sol-Gel Process

The effects of several hydroxyketones such as acetol, actoin, -ketobutanol themselves and their combinations with monoethanolamine (MEA) or ethylenediamine (ED) on the stabilization of titanium tetraisopropoxide (TTIP) in isopropanol solution are examined. Acetoin itself and the imine derivatives of acetol and acetoin were found to show extraordinarily strong stabilizing effect for the alkoxide. The properties including the crystal modifications and refractive index of TiO₂ films that were dip-coated using each stabilized solution are examined and discussed in comparison with those of the films obtained from the diethanolamine (DEA) systems. The effect of UV-light irradiation to the gel films on the crystallization of TiO₂ is also examined and discussed.     

Fractal Characterization of Silica Sol Prepared by the Sol-Gel Method: From the Sol Formation to the Flocculation Process

The fractal characterization of silica particles prepared by the sol-gel method was obtained; from the beginning of the sol-gel synthesis to the aggregation process of these particles by adding metal ions in solution, the fractal dimension was determined. At the beginning of the sol-gel process, unstable structures were formed due, essentially, to the auto-catalytic nature of the sol-gel condensation reactions; these particles are fractal structures with a fractal exponent corresponding to a reaction limited aggregation regime. As the time proceeds, the reactants are consumed approaching the system to equilibrium, stabilizing the size of the silica particles. The silica sol can be flocculated by adding metal ions in solution. The fractal exponent for the aggregation process was determined, obtaining a value corresponding to a diffusion limited aggregation regime.     

Preparation and Properties of Anti-Reflection/Anti-Static Thin Films for Cathode Ray Tubes Prepared by Sol-Gel Method Using Photoirradiation

A new technique for preparing anti-reflection/anti-static thin films for CRTs at low temperature has been developed. Double-layered films of SiO₂/SnO₂ were formed on a CRT panel surface by the sol-gel method using photoirradiation. The new method makes it possible to reduce heat treatment temperature (°C) by almost 50% and treatment time to approximately 33% of the conventional levels.     

Characterization of the Sol-Gel Process Using Raman Spectroscopy Organically Modified Silica Gels Prepared Via the Formic Acid-Alkoxide Route

For precursor mixtures containing tetraethoxysilane (TEOS) and phenyltriethoxysilane (PhTREOS), time of gelation can be reduced by up to two orders of magnitude depending on reaction conditions employed when reacting the silicon alkoxide mixture with formic acid instead of water. Results indicate that time of gelation depends on the amount of PhTREOS in the precursor mixture. Within the range of concentrations investigated, an exponential law describes best the dependence of reduced time of gelation on the molar fraction of PhTREOS. Therefore, we conclude that the phenyl ring acts as a steric hindrance to network formation. Raman spectroscopy is used to characterize the reaction between the alkoxide mixture and formic acid. During the acidolysis reaction, ethanol is formed as an intermediate. A preliminary reaction scheme is proposed to account for the time dependence of species involved. Furthermore, Raman spectroscopy is successfully employed to monitor the effects of post-gelation thermal treatment of the gel samples. The effects observed are interpreted with a model of a phenyl ring trapped in a siloxane cage.     

Preparation of Super-Water-Repellent Fluorinated Inorganic-Organic Coating Films on Nylon 66 by the Sol-Gel Method Using Microphase Separation

We have prepared super-water-repellent fluorinated inorganic-organic coating films on nylon 66 substrate from poly(methyl methacrylate) (PMMA), tetraethoxysilane (TEOS), and 2-perfluorooctylethyltriethoxysilane (17F) by the sol-gel method. The contact angle for water of the film was 149°. The fluorinated inorganic-organic film including PMMA particles exhibits the super-water-repellence on nylon 66 and the high ultrasonics-resistance in spite of the low 17F content of the molar ratio of 0.001 per mol of TEOS. The surfaces of the films were characterized by using XPS and SEM in combination with the surface roughness data. It was considered that the fluorinated component was segregated to form separated microphase regions, appropriate surface roughness being resulted to develop high water-repellence.     

Thermal Conversion of Gels Prepared by the Complex Sol-Gel Process (CSGP) from Li+-Me2+-CH3COO−-Ascorbic Acid (ASC)-NH4 +-OH−-H2O Systems to LiMn2O4 and LiNi x Co1 − x O2

The spinel LiMn₂O₄ and layered oxides LiNi _x Co_{1 – x} O₂ (x = 1; 0.75; 0) have been prepared by Complex Sol-gel Process (CSGP). The appropriate sol compositions were obtained from acetate aqueous solution of metals containing ascorbic acid by alkalizing it with aqueous ammonia. Gels were produced from the systems by evaporation of water and other volatilies at elevated temperatures. A very intense foaming was observed during the heating at the temperatures higher than 140°C. To avoid foaming in the course of the final thermal treatment, a very long (lasting several days) soaking step was found necessary. However pretreated materials exhibit self-ignition at temperature range 320–500°C dependent on socking conditions. The dependence of self-ignition temperature on carbon content in bed as well as on specific surface has not been proved. Final thermal transformation of gel to solid was studied by TG, DTA, XRD, and IR methods. It was observed that final compounds are formed faster from precursors which did not contain Ni (e.g. LiMn₂O₄ and LiCoO₂), while Li carbonate is not formed in these systems. In contrast, in Li-Ni(Co)-O the formation of Li(or Ni)CO₃ was always proved. In addition, during the thermal treatment Ni species are partially reduced even to metallic phase. This effect evidently restrains the formation of pure layered oxides phase. Electrochemical properties of carbonate free compounds are definitely better than of those containing CO₃.     

非钛醇盐溶胶-凝胶法制备高光活性纳米晶TiO2气凝胶

 以TiCl4为前驱体,采用环氧丙烷快速成胶法合成了具有高光催化活性的纳米晶TiO2气凝胶,利用X射线衍射、N2物理吸附和透射电镜等手段考察了H2O/TiCl4摩尔比和热处理等制备参数对TiO2气凝胶织构性质的影响,并以苯酚的光催化降解为模型反应评价了样品的光催化活性. 结果表明, H2O/TiCl4摩尔比为3时体系的成胶过程较为缓慢,制备的纳米晶TiO2气凝胶样品具有最小的晶粒尺寸及最大的比表面积和孔容,并且具有最佳的光催化活性.     

Preparation of Porous Titania Film by Modified Sol-Gel Method and its Application to Photocatalyst

Sol-Gel derived mesoporous titania films with controlled pore sizes were prepared by surfactant templating. The coating sol was obtained by hydrolysis of Ti(OC₄H₉)₄ in ethanol/HCl solution. The gel films, prepared by spin coating on glass substrate, were dried after immersion in surfactant solutions under an atmospheric pressure. The porous films of anatase with columnar and rectangular structure were obtained after annealing at 500°C. The annealed films are transparent and 80–140 nm in thickness. Refractive indices of the films with surfactant immersion were 10–20% lower than those of the films without immersion. The spacing between the columns or rectangular grains and the grain shape were found to depend on the surfactant species. The pohoto-catalytic activity of the films for the oxidation of NO _x was improved by the surfactant modification.     

Synthesis of Inorganic Compounds (Metal, Oxide and Hydroxide) in Polyol Medium: A Versatile Route Related to the Sol-Gel Process

A new route for the preparation of powdery metal, oxide and hydroxide materials is presented as a chimie douce alternative to the sol-gel method. It consists in the reduction or the hydrolysis of a metal salt dissolved and heated in a polyol medium. It appears through zinc and cobalt examples that the use of acetate precursors contrarily to chloride or sulfate ones leads to the precipitation of a solid (metal, oxide, hydroxide) whose nature depends on two main factors: the hydrolysis ratio, defined by the water to metal molar ratio, and the reaction temperature. As in the sol-gel method, acetate leads to the formation of intermediate alkoxyacetate complex. The absence of water favors metal formation while its presence favors oxide or hydroxyacetate formation.     

Low Temperature Synthesis of Nano-Sized Lithium Manganese Oxide Powder by the Sol-Gel Process Using PVA

Lithium manganese oxide (LiMn₂O₄) powder with spinel structure has been synthesized by a sol-gel method using an aqueous solution of metal nitrates containing polyvinyl alcohol (PVA). The role of PVA and the calcination conditions for the formation of LiMn₂O₄ have been studied. Homogeneity and reactivity of the precursor powder are enhanced with an increase in the amount of PVA in the starting solution. When the amount of PVA is low, an impurity phase-Mn₂O₃ is formed at low temperature. On the other hand, when the vinyl alcohol monomer unit of PVA to metal ion ratio is 2 : 1 in the starting solution, only spinel phase is formed at 180°C and organic-free LiMn₂O₄ powder is obtained at as low as 400°C. Nanosized LiMn₂O₄ particles with a narrow size distribution have been successfully prepared by this technique. This method with proper amount of PVA results in much lower calcination temperature and shorter calcination time for producing the single spinel phase in comparison with the conventional solid state reaction and other solution techniques.