Effect of varying the acid to metal ion ratio R on the structural and magnetic properties of SiO2-doped Ni-Zn ferrite

A nitrate-citrate-silica gel was prepared from metallic nitrates, citric acid and tetraethoxysilane (TEOS) by sol-gel process with different citric acid to metal nitrates ratio R, and it was further used to synthesize Ni_0.5Zn_0.5Fe₂O₄/20 wt% SiO₂ nanocomposites by auto-combustion. The effect of varying the citric acid to metal nitrates ratio R on the structural and magnetic properties of the composites were studied by IR, ²⁹Si CP/MAS NMR, XRD, EPR and SQUID measurements. The nitrate-citrate-silica gels exhibited self-propagating combustion behavior, and it directly transformed into nanosized (14-22 nm) NiZn ferrite particles with spinel crystal structure after combustion. The R value in the starting solution affects the magnetic interaction between NiZn ferrite and silica, and then determines the particle size. Further, varying the R value has a direct effect on the EPR parameters (ΔH_PP, g factor, N_S and T₂) and SQUID parameters (M_s, M_r and H_c) of the as-synthesized powder.     

Pt/SiO2 catalysts obtained by the sol-gel method. Influence of the pH of gelation on the surface and catalytic properties

Pt/SiO₂ catalysts prepared by impregnation and sol-gel method from a platinum acetylacetonate precursor have been studied. The pH was varied in the range of 3–9. Important changes in the surface area and pore distribution were found. High metal dispersity was found in all the catalysts, being lower at pH 9.     

Multi-step sol-gel process and its effect on the morphology of polyethylene oxide (PEO)/SiO2 anion-exchange hybrid materials

Polyethylene oxide (PEO)/SiO₂ anion-exchange hybrid materials were prepared through the sol-gel process of alkoxysilane functionalized PEO-1000 (PEO-[Si(OCH₃)₃]₂) and N-[3-(trimethoxysilyl)propyl] ethylene diamine (A-1120). The influence of the multi-step sol-gel processing procedure, i.e. the pre-hydrolysis of either of the two precursors on the homogeneity of the hybrid materials was investigated. Results showed that the sol-gel reaction of A-1120 and PEO-[Si(OCH₃)₃]₂ from the same time would result in hybrid materials with the highest homogeneity, and pre-hydrolysis of A-1120 or PEO-[Si(OCH₃)₃]₂ could only decrease the materials’ compatibility.     

Effect of sol-gel derived Al2O3-ZrO2 and Al2O3-TiO2 oxides on the selectivity of NO reduction by CO under oxidizing conditions

The role of Al₂O₃-ZrO₂ and Al₂O₃-TiO₂ sol-gel prepared supports in the activity of platinum for the NO reduction by CO under oxidizing conditions has been studied. ²⁷Al MAS-NMR spectra have shown the formation of pentacoordinate Al^V in alumina-zirconia support. ZrO₂ or TiO₂ crystalline phases cannot be identified by XRD diffraction, suggesting the formation of nanosized structures supported on alumina. When the reaction was carried out in presence of oxygen, large amounts of NO₂ were observed on Pt/Al₂O₃-ZrO₂catalyst, while the formation of N₂O is more prononced on Pt/Al₂O₃-TiO₂ catalyst. The effect of water during NO reduction is discussed. This revised version was published online in June 2006 with corrections to the Cover Date.     

Local order structure and surface acidity properties of a Nb2O5/SiO2 mixed oxide prepared by the sol-gel processing method

The sol-gel processing method was used as an alternative route to obtain Nb₂O₅ phase homogenously dispersed in the SiO₂ matrix, improving the thermal stability of the Brønsted acid sites, Nb-OH and Nb-OH-Si groups. The local niobium structure and the influence of the amount of niobia on the surface of the Nb₂O₅/SiO₂ system were studied by XAS and XPS, respectively. For the samples calcined at 423 and 873 K, the 3d_5/2 BE values are at ca. 208.2 eV, indicating an ionic character for Nb(V) species in the SiO₂ matrix, probably associated to Si-O-Nb linkages. The features of Nb K-edge XANES spectra of samples show the absence of NbO species. The Nb K-edge EXAFS oscillations exhibit a shoulder at ca. 5.6 Å⁻¹, which probably arises from Nb-O-Si. This fact corroborates the EXAFS simulation data of the second coordination shell, whose best fitting is achieved with three distances, two Nb-Nb lengths and one Nb-Si.     

Fabrication and optical properties of core-shell structured spherical SiO2@GdVO4:Eu phosphors via sol-gel process

Europium-doped nanocrystalline GdVO₄ phosphor layers were coated on the surface of preformed submicron silica spheres by sol-gel method. The resulted SiO₂@Gd_0.95Eu_0.05VO₄ core-shell particles were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (FESEM), energy-dispersive X-ray spectra (EDS), transmission electron microscopy (TEM), photoluminescence (PL) spectra, low voltage cathodoluminescence (CL), time resolved PL spectra and kinetic decays. The XRD results demonstrate that the Gd_0.95Eu_0.05VO₄ layers begin to crystallize on the SiO₂ spheres after annealing at 600 ^°C and the crystallinity increases with raising the annealing temperature. The obtained core-shell phosphors have spherical shape, narrow size distribution (average size ca. 600 nm), non-agglomeration. The thickness of the Gd_0.95Eu_0.05VO₄ shells on the SiO₂ cores could be easily tailored by varying the number of deposition cycles (50 nm for four deposition cycles). PL and CL show that the emissions are dominated by ⁵D₀-⁷F₂ transition of Eu³⁺ (618 nm, red). The PL and CL intensities of Eu³⁺ increase with increasing the annealing temperature and the number of coating cycles. The optimum concentration for Eu³⁺ was determined to be 5 mol% of Gd³⁺ in GdVO₄ host.     

Fe-assisted formation of α-Al2O3, starting from sol-gel precursors

The role of Fe³⁺ ions in the transformations from boehmites and pseudoboehmite xerogels via transition aluminas to corundum was studied here. Especially, the active iron species responsible for the decrease of the temperature of transformation to corundum were looked for. To enable the formation of various Fe³⁺ and Fe²⁺ species, samples were subjected to thermal treatments in different atmospheres as well as mechanically activated. Thermal analysis and ESR spectroscopy served to follow the processes and to characterise the resulting products. It was found that (i) isolated Fe³⁺ ions can indicate local structural changes but have (almost) no influence on the temperature of corundum formation, (ii) the temperature of corundum formation decreases in the result of action of small α-Fe₂O₃ particles and (iii) during thermal treatments Fe³⁺ ions are distributed between different phases or precursors thereof: transition aluminas, corundum, Fe₂O₃, and a Fe³⁺ pool.     

Preparation, thermal properties, morphology, and microstructure of phosphorus-containing epoxy/SiO2 and polyimide/SiO2 nanocomposites

A phosphorus-containing tri-ethoxysilane (dopo-icteos) reacting from the nucleophilic addition reaction of 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (dopo) and 3-(trieoxysilyl) isocyanate (icteos) was synthesized. The structure of dopo-icteos was confirmed by ¹H, ¹³C, ³¹P NMR and IR spectra. A triethylamine catalyzed mechanism for the dopo-icteos synthesis was proposed and verified by NMR spectra. The phosphorus-containing epoxy/SiO₂ and polyimide/SiO₂ nanocomposites were prepared from the in-situ curing of diglycidyl ether of bisphenol A (DGEBA)/4,4-diaminodiphenylmethane(DDM)/dopo-icteos, and imidization of poly(amic acid) of pyromellitic dianhydride (PMDA)/4,4′-oxydianiline (ODA)/dopo-icteos, respectively. The microstructure and morphology were investigated by ²⁹Si NMR, scanning electron microscope (SEM), EDS (Si and P mapping) analysis and atomic force microscope (AFM). The thermal properties, flame retardancy and dielectric properties of the organic-inorganic hybrids were investigated by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), limiting oxygen index (LOI), thermal gravimetric analysis (TGA) and dielectric analyzer (DEA).     

Al2O3 @ TiO2—A simple sol-gel strategy to the synthesis of low temperature sintered alumina-aluminium titanate composites through a core-shell approach

A simple sol-gel based core-shell approach for the synthesis of alumina-aluminium titanate composite is reported. Alumina is the core and titania is the shell. The coating of titania has been performed in aqueous medium on alumina particle by means of heterocoagulation of titanyl chloride. Further heat treatment results in low temperature formation of aluminium titanate as well as low temperature sintering of alumina-aluminium titanate composites. The lowering of the reaction temperature can be attributed to the maximisation of the contact surface between the reactants due to the core-shell approach involving nanoparticles. The mechanism of formation of aluminium titanate and the observations on densification features in the present process are compared with that of mixture of oxides under identical conditions. The sintered alumina-aluminium titanate composite has an average grain size of 2 μm.     

Antireflective and Self-cleaning Properties of SiO2/TiO2 Double-Layer Films Prepared by Cost-E ective Sol-Gel Process

SiO₂/TiO₂ double-layer films with antireflective and self-cleaning properties were prepared by dip-coating glass substrate into cost-effective SiO₂ and TiO₂ sol successively and subse-quently being calcined at 500 oC. The optical and structural properties of films have been in-vestigated by UV-visible spectrophotometer and field emission scanning electron microscope, respectively. At the same time, self-cleaning property generated from superhydrophilicity and photocatalysis was obtained. The results indicated that the as-prepared SiO₂/TiO₂ double-layer films show maximum transmittance of 95% and self-cleaning property.     

Morphology evolution of ZrB2 nanoparticles synthesized by sol-gel method

Zirconium diboride (ZrB₂) nanoparticles were synthesized by sol-gel method using zirconium n-propoxide (Zr(OPr)₄), boric acid (H₃BO₃), sucrose (C₁₂H₂₂O₁₁), and acetic acid (AcOH). Clearly, it was a non-aqueous solution system at the very beginning of the reactions. Here, AcOH was used as both chemical modifier and solvent to control Zr(OPr)₄ hydrolysis. Actually, AcOH could dominate the hydrolysis by self-produced water of the chemical propulsion, rather than the help of outer water. C₁₂H₂₂O₁₁ was selected, since it can be completely decomposed to carbon. Thus, carbon might be accounted precisely for the carbothermal reduction reaction. Furthermore, we investigated the influence of the gelation temperature on the morphology of ZrB₂ particles. Increasing the gelation temperature, the particle shapes changed from sphere-like particles at 65 °C to a particle chain at 75 °C, and then form rod-like particles at 85 °C. An in-depth HRTEM observation revealed that the nanoparticles of ZrB₂ were gradually fused together to evolve into a particle chain, finally into a rod-like shape. These crystalline nature of ZrB₂ related to the gelation temperature obeyed the “oriented attachment mechanism” of crystallography.     

Promoting effect of sol-gel method and pre-treatment on the activity of SnO2/Al2O3 catalyst for NO reduction by propene

SnO₂/Al₂O₃ catalyst prepared by sol-gel method showed higher activity than those prepared by impregnation method, and their activity was significantly improved by pre-treatment in the reaction gas. The increased activity is closely related to the agglomeration of SnO₂ species and the re-exposure of Al₂O₃, which was previously covered by dispersed SnO₂ species. This revised version was published online in June 2006 with corrections to the Cover Date.     

Synthesis and characterization of poly(EMA-co-HEA)/SiO2 nanohybrids

A series of silica-based organic-inorganic nanocomposites, which attempt to mimic the properties of mineralized matrix tissues from natural bone or dentin, have been prepared and characterized as potential candidates for the synthetic matrix of scaffolds for bone or dentin regeneration. The synthesis procedure consisted in the copolymerization of ethyl methacrylate (EMA) and hydroxyethyl acrylate (HEA) during the simultaneous acid-catalyzed sol-gel polymerization of tetraethoxysilane (TEOS) as a silica precursor, giving rise to poly(EMA-co-HEA)/SiO₂ nanohybrids with silica contents in the range of 0-30 wt%. Different structures of silica within the organic polymeric matrix were inferred from infrared spectroscopy, energy dispersive X-ray spectroscopy, thermogravimetry, pyrolysis, density assessments, solvent uptake and transmission electron microscopy. TEOS was efficiently hydrolyzed and condensed to silica during the sol-gel process in all cases, and presented a homogeneous distribution in the polymeric matrix, in the form of nanodomains either interdispersed or continuously interpenetrated with the organic network, depending on the silica content. Silica contents above 10% produced co-continuous interpenetrated structures where the silica network reinforces mechanically the organic matrix and at the same time confers bioactivity to the surfaces.     

Mechanism and kinetics of crystallization of α-Fe in amorphous Fe81B13Si4C2 alloy

The non-isothermal crystallization of α-Fe from Fe₈₁B₁₃Si₄C₂ amorphous alloy was investigated. The kinetic parameters of crystallization process were determined by Kissinger and Kissinger–Akahira–Sunose (KAS) methods. It was established that the kinetic parameters of transformation do not change with the degree of crystallization in the range of 0.1–0.7. The kinetic model of the crystallization process was determined using the Malek's procedure. It was established that the primary crystallization α-Fe phase from amorphous alloy can be described by Šesták–Berggren autocatalytic model with kinetic triplet E_a = 349.4.0 kJ mol⁻¹, ln A = 50.76 and f(α) = α^0.72(1 − α)^1.02.     

Effect of sol-gel derived nano-silica and organic peroxide on the thermal and mechanical properties of low-density polyethylene/wood flour composites

The influence of nano-silica, synthesized and mixed with low-density polyethylene (LDPE) through a sol-gel process, on the thermal and mechanical properties of LDPE and LDPE/wood flour (WF) composites, prepared in the absence and presence of dicumyl peroxide, was investigated. Scanning electron microscopic (SEM) analyses show a uniform dispersion of silica nano-particles of size 10-50 nm in the matrix, and Fourier-transform infrared (FTIR) spectroscopic results indicated interaction between the nano-silica and the LDPE matrix, which seems to improve for samples prepared in the presence of dicumyl peroxide (DCP). WF and nano-silica, as well as the presence of DCP during sample preparation, substantially improve the thermal stability of the LDPE matrix. The tensile strength of the samples decreased with increasing wood flour content, while the tensile modulus substantially increased. The presence of nano-silica gave rise to lower values for both tensile strength and tensile modulus, while higher tensile strength (and an increase in tensile strength with WF content) is observed for samples prepared in the presence of DCP. The tensile modulus increases with increasing WF content, but is not substantially influenced by the presence of nano-silica or by sample preparation in the presence of DCP. The DMA results were in line with the tensile results.     

O2/CO2气氛下O2浓度对燃煤PM2.5形成的影响

采用管式炉和荷电低压撞击器(electrical low pressure-impactor,ELPI)研究了徐州烟煤在O₂/CO₂条件下燃烧后生成的PM_2.5排放特性。结果表明,在O₂/CO₂气氛下,煤粉在不同O₂浓度燃烧所产生的PM_2.5质量浓度均呈双峰分布,峰值分别在0.1和2.0 mm左右;随着氧含量的增加,PM_2.5的质量浓度增加;S、K和Na在亚微米颗粒上明显富集,而Si和Ca未在亚微米颗粒上富集;通过对颗粒物的粒径分布、元素分析和形貌观察,认为亚微米颗粒主要是矿物质蒸发鄄凝结机制形成的,而超微米颗粒主要是煤焦与外部矿物质的破碎以及内在矿物质聚合形成的。     

Effect of milling and doping on decomposition of NH3BH3 complex

The thermal decomposition of borane-ammonia complex as well as of milled and doped samples was studied by volumetric titrations. The samples were heated at fixed temperature and the volume of the evolved gas recorded as a function of time. Milled and doped samples were prepared by mechanical and mechanochemical reactions, respectively. Samples containing 1 and 2 mol% hydrogen hexachloroplatinate hydrate were prepared. The materials were characterized by scanning electron microscopy (SEM) and X-ray diffractometry (XRD). Mechanical alloying was effective to modify the crystallinity of the complex and to change the material morphology enhancing the amount of gas evolved. Both the milled and the doped samples showed an increase of the pre-exponential factor in the Arrhenius equation. The activation energy decreased for the doped sample, and it increased for the milled sample. As a result it was found that the decomposition of 1 mol% doped sample could be provided by waste heat coming from polymer electrolyte membrane fuel cell.     

Low-temperature synthesis of SrAl2O4 by a modified sol-gel route: XRD and Raman characterization

Among other alkaline-earth aluminates, the monoclinic (M) polymorph of SrAl₂O₄ can be used as host material for Eu²⁺ luminescence based phosphors. With the aim of reducing the synthesis temperature of this polymorph, we have produced and characterized by XRD and Raman scattering solid solutions of the SrAl_2−xB_xO₄ system (x?0.3) obtained by two different methods, a ceramic route and a modified sol-gel synthesis. Though the addition of boron lowers the temperature of obtention of the M polymorph in both type of samples, lower B contents are needed to stabilize the M form as single phase for samples prepared by the sol-gel method than through the ceramic route. In the sol-gel method, the M polymorph can be obtained at temperatures as low as 1200 °C, with a Boron content of just 1%. Rietveld profile analysis allows us to conclude that coexistence of the monoclinic and hexagonal polymorphs of SrAl₂O₄ occurs for samples synthesized below an onset temperature of about 1000-1100 °C, that depends on the sample composition. Above those temperatures, only the monoclinic phase is formed.     

Influence of fluorine-modified SiO2-surfaces on the properties of V2O5/SiO2 catalysts

The preparation of vanadium catalysts is described using fluorine modified Aerosil as support. It is shown that modification with fluorine changes the concentration and topology of the surface silanol groups and, as a consequence, the catalytic properties.

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流化床O2/CO2气氛下添加石灰石对燃煤PM2.5的控制

采用小型流化床研究了在O₂/CO₂气氛下添加石灰石对PM_2.5(空气动力学直径小于2.5 μm的颗粒物)的控制.实验采用荷电低压撞击器(ELPI)采集和分析燃烧后的PM_2.5.结果表明,添加石灰石是燃烧过程中影响PM_2.5生成的重要因素.添加石灰石后,生成PM_1.0的数量浓度均降低,而PM_1.0~2.5的数量浓度均略有增加;PM_2.5质量粒径分布均呈双峰分布,峰值分别出现在0.2和2.0 μm左右.随着Ca/S物质的量比的增加,PM_2.5中Si、Na、K、S和Cu的含量呈减少的趋势;随着颗粒粒径的减小,S、Cu、K和Na的含量有增大的趋势,而Si的含量有减少的趋势.