Niobium Powders of Mesoporous Structure

The mesoporous structure of niobium powders of specific surface areas from 32 to 150 m²/g obtained through reduction of niobium-oxide compounds by magnesium vapors has been investigated. A doubling of the specific surface area of magnesium-thermic niobium powders in comparison to tantalum powders has been shown to be caused by the larger volume and smaller size of pores. For a powder with a specific surface area of 150 m²/g, 90% of the surface is governed by pores of sizes smaller than 5 nm. Although the X-ray pattern of the powder corresponds to the metal niobium, 96.5% of this powder weight consists of a natural surface-oxide film, according to the TGA data. The thickness of this oxide decreases in comparison with the surface oxide on the compact metal depending on the powder mesoporous structure.     

Preparation and characterization of CuO-CoO-MnO/SiO2 nanocomposite aerogels as catalyst carriers

CuO-CoO-MnO/SiO₂ nanocomposite aerogels were prepared by using tetraethyl orthosilicate (TEOS) as Si source, and aqueous solution of Cu, Co and Mn acetates as the precursors via sol-gel process and ethanol supercritical drying technique. The gelatination mechanism was investigated by nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS). The microstructure and composition of the CuO-CoO-MnO/SiO₂ nanocomposite aerogels were characterized by field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), electron dispersive spectroscopy (EDS) and XPS. The specific surface area, pore size and pore size distribution of the nanocomposite aerogels were determined by the Brunauer-Emmett-Teller (BET) method. The products were analyzed by gas chromatography (GC). The results show that the CuO-CoO-MnO/SiO₂ nanocomposite aerogels are porous, with a particle size distribution of 10–150 nm, a pore size distribution of 2–16 nm, an average pore size of 7.68 nm, and a specific surface area of 664.4–695.8 m²/g. The molar fraction of transition metals in the nanocomposite aerogels is 0.71%-13.77%. This kind of structure is favorable not only to increase the loading of catalysts, but also to make full use of the effect of transition metal oxides as cocatalysts; CuO-CoO-MnO/SiO₂ nanocomposite aerogels can be used as a novel catalyst carrier in the safer and environment-friendly synthesis of diphenyl carbonate and other fields of catalysis.     

Carbon aerogels for electric double-layer capacitors

In this study, carbon aerogels were derived via the pyrolysis of resorcinol-formaldehyde (RF) aerogels, which were cost-effectively manufactured from RF wet gels by an ambient drying technique instead of conventional supercritical drying. By varying the R/C ratio (molar ratio of resorcinol to catalyst), mesoporous carbon aerogels with high specific surface area were prepared successfully and further investigated as electrode materials for electric double-layer capacitors (EDLCs). The textural properties of carbon aerogels obtained were characterized by nitrogen adsorption/desorption analysis and SEM. The electrochemical performances of carbon aerogels were investigated by impedance spectroscopy, galvanostatic charge/discharge and cyclic voltammetry methods. The results show that BET surface area and specific capacitance increase with R/C ratio, the maximum values of 727 m2·g-1 and 132 F·g-1 are achieved at R/C ratio will of 300. Increasing R/C ratio increase the average pore size of carbon aerogel electrode, which has improved the rate capability. Furthermore, EDLC with carbon aerogel electrodes has an excellent stability at large discharge current and long cycle life.     

Adsorption of Nickel(II) and Copper(II) Ions by Modified Aluminosilicates

According to X-ray phase analysis, modification of natural aluminosilicates with hydrogen chloride is accompanied by the destruction of the main component—calcium heulandite—the content of which decreases from 64.3 to 42.9%. An increase in temperature during the modification process contributes to the packing of the cristobalite structure, which positively affects the adsorption properties of the materials. In the process of activation of aluminosilicates by hydrogen chloride, their texture characteristics change: the specific surface (from 33 to 75 m²/g) and the specific pore volume (from 0.015 to 0.036 cm³/g) increase more than double. The average pore size is reduced from 1.8 to 1.6 nm. The result of such changes is an increase in the adsorption capacity. Adsorption of nickel(II) and copper(II) ions on modified aluminosilicates is most adequately described by the Langmuir adsorption model.     

Effect of water intercalation on the structure and electrophysical properties of YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>6.9</Subscript>

The influence of water vapors and plastic deformation on the structure and electrophysical properties of YBa₂Cu₃O_6.9 (123) has been studied. It has been established that, at T = 200°C, the introduction of water into the structure of YBa₂Cu₃O_6.9 leads to its transition into a defect tetragonal phase of the 124 type as a result of the formation of planar stacking faults. After annealing at T = 930°C, these defects are partially retained and are efficient centers of pinning in the magnetic fields applied perpendicularly to the c axis, which makes it possible to increase (by an order of magnitude) the critical current density in the high-textured ceramics at 77 K in the external magnetic field of 5–10 T. The plastic deformation of the hydrated ceramics favors the reverse transition of the arising 124 phase to the 123 phase at T = 930°C and is accompanied by a recrystallization of the material, which leads to the appearance of a texture and an increase the critical current density.     

Synthesis of biomorphic hierarchical CeO2 microtube with enhanced catalytic activity

A biomorphic CeO₂ microtube with multiple-pore structure was fabricated by using the cotton as biotemplate, through cerium nitrate solution infiltration and thermal decomposition. Field emission scanning electron microscope (FESEM), powder X-ray diffraction (XRD), transmission electron microscope (TEM), N₂ adsorption–desorption isotherms, temperature-programmed reduction (TPR) and CO oxidation were used to characterize the samples. The results indicated that the synthesized products were composed of crystallites with grain size about 9 nm and exhibited a fibrous morphology similar to the original template and possessed a specific surface area (BET) of 62.3 m²/g. Compared with the conventional CeO₂ particles, the synthesized materials showed a superior catalytic activity for CO oxidation. For the synthesized fibrous CeO₂, the CO conversion at 320 °C was above 90% and a 100% CO conversion was obtained at 410 °C.     

Effects of co-precipitation temperature on structure and properties of La and Y doped cerium zirconium mixed oxides

Due to the oxygen storage and release properties, cerium zirconium mixed oxides are recognized as the key material in automotive three-way catalysts. To reveal the effects of co-precipitation temperature on structure, physical and chemical properties of multi-doped cerium zirconium mixed oxides, a series of La and Y doped cerium zirconium mixed oxides (CZLYs) were synthesized via a co-precipitation method, and the physical and chemical properties of CZLYs were systemically characterized by XRD, N₂ adsorption–desorption, TEM, XPS, oxygen storage capacity (OSC) and hydrogen temperature programmed reduction (H₂-TPR). The results show that co-precipitation temperature is an important parameter to influence the crystal size, oxygen storage capacity and thermal stability of CZLYs. When the co-precipitation temperature was 60 °C, the best redox properties and thermal stability of CZLYs were obtained. After thermal treatment at 1100 °C for 10 h, the specific surface area and oxygen storage capacity of the corresponding aged sample were 15.42 m²/g and 497.7 μmol/g, respectively. In addition, a mechanism was proposed to reveal the effects of co-precipitation temperature on the structure and properties of CZLYs.     

TMOS硅源一步法制备SiO2气凝胶微结构与光散射率的关系研究

采用溶胶凝胶法,以正硅酸甲脂(tetramethyl orthosilicate,TMOS)为硅源、甲醇为溶剂,利用碱催化“一步法”,结合乙醇超临界干燥制备了密度分别是95、110、135和165mg/cm₃的SiO₂气凝胶。运用小角X射线散射(small-angle X-ray scattering,SAXS)分析SiO₂气凝胶的微结构,并测量各密度样品635nm波长的90°方向光散射率,针对不同密度样品分别研究了光散射率与微结构的关系。研究表明：随着初始溶剂用量的增加,密度(r)、质量分形维数(Dm)随之减少,而初级粒子(a)与次级粒子(d)尺寸在增大,这可能是在初始溶剂用量增加情况下,因为原料TMOS初始浓度降低,导致相分离方式由成核主导向生长主导转变;此外分别从初级粒子、次级粒子的角度考虑,对散射率进行分析得出635nm光与气凝胶的相互作用主要是与次级粒子结构的不相干Rayleigh散射,且光散射的数值与二级结构内的体分形维数、初级粒子尺寸,次级粒子尺寸均有关。     

常压制备低密度高比表面积SiO_2气凝胶的工艺研究

以正硅酸乙酯、乙醇、去离子水、盐酸和氨水为原料制备出SiO_2凝胶后,经老化、表面改性、溶剂置换工艺,再通过常压干燥制备出SiO_2气凝胶,研究了表面改性及溶剂置换工艺对SiO_2气凝胶性能的影响.结果表明,随着表面改性次数和改性剂浓度的增加,气凝胶的密度和比表面积降低;溶剂置换对气凝胶的密度和比表面积影响不大.通过优化的工艺制备出的SiO_2气凝胶具有疏水性,与水的接触角约为118°,密度为0.124 g/cm~3,孔隙率94.3%,平均孔径为23.3 nm,比表面积712 m~2/g.     

Modified aging process for silica aerogel

To increase the porosity and monolithic performance of silica aerogel, two methods were used to age the silica gels derived from tetraethoxysilane (TEOS) by two-step sol–gel process: aging in 100 °C-autoclave with TEOS/ethanol mixed solution and in pure ethanol at room temperature. The structural characteristics and physical properties of the resultant two kinds of aerogels after supercritical CO₂ drying were investigated and compared with the help of infrared spectra (IR), N₂ absorption, differential scanning calorimetry (DSC)/thermogravimetry (TG) and high-resolution ²⁹Si nuclear magnetic resonance (NMR) techniques. Aging in 100 °C-autoclave yields silica aerogel with high pore size and pore volume, twice of that aged in ethanol at room temperature. High aging temperature and pressure can promote the dissolution and reprecipitation process of silica and the esterification process of silanols, which will enhance the backbone strength of silica gel, and hence produce silica aerogel with low bulk density, good monolithic performance and hydrophobic features. While the latter aging method produces silica aerogel with high bulk density and cracking appearance.     

碳纳米管掺杂SiO2气凝胶隔热材料的制备与性能表征

以正硅酸乙酯（TEOS）和碳纳米管（CNTs）为原料，采用溶胶-凝胶法和常压干燥法制备不同碳纳米管（CNTs）含量的SiO2气凝胶隔热材料。采用DET、SEM、XRD等测试方法考察了添加CNTs对SiO2气凝胶比表面积、孔结构特征和密度的影响。结果表明：添加CNTs不仅能够增强SiO2气凝胶的强度，而且能够在很大程度上提高气凝胶的比表面积，使孔结构分布更加均匀。     

Redox abilities of rutile TiO2 ultrafine powder in aqueous solutions

Redox abilities of rutile TiO₂ powder with an acicular primary particle, having about a 200 m²/g BET surface area obtained by a homogeneous precipitation process in aqueous TiOCl₂ solution at 50°C for 4 hrs, were investigated using a photocatalytic reaction in aqueous 4-chlorophenol, Cu- and Pb-EDTA solutions. Its abilities were then compared with those of commercial P-25 powder, together with investigating those of anatase TiO₂ powder obtained from the aqueous TiOCl₂ solution, having a similar surface area and primary particle shape as those of the rutile powder. The powder was more effective than the anatase or P-25 powder, while the anatase powder unexpectedly showed the slowest decomposition rate and the smallest amount in the same experiments in spite of similar particle shapes and surface area. From the results, it is found that the excellent photo redox abilities of the powder is likely to be caused by the specific powder preparation method regardless of crystalline structures even when having similar particle shapes and values in the surface area. Also, many OH⁻ attached to the surface of the TiO₂ particle appeared to interfere with the adsorption of decomposing target materials to the TiO₂ surface in the solution during the photocatalytic reaction, resulting in a delay in the reaction.     

常压干燥法制备CNTs掺杂TiO2气凝胶

以钛酸丁酯为原料,乙酸为有机配体,甲酰胺为干燥控制化学添加剂(DCCA),采用溶胶凝胶法制备碳纳米管(CNTs)掺杂TiO2复合醇凝胶,并结合常压干燥等后续工艺,制备了CNTs掺杂TiO2块体气凝胶。采用XRD、BET、TEM、SEM、EDS、DSC及FT-IR等对样品进行表征。结果表明:制备态CNTs掺杂TiO2气凝胶晶型为无定型,比表面积为601.7 m2/g;在氮气保护下,经950℃热处理后,比表面积为136.8 m2/g,TiO2以锐钛矿相存在,且均匀密集包覆在CNTs表面,对甲基橙光降解具有较高光催化活性。     

Influence of water vapor on the formation of pinning centers in YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> upon low-temperature annealing

The influence of the double heat treatment (T = 300 and 930°С) on the critical parameters of highly textured YBa₂Cu₃O_6.96 and YBa₂Cu₃O_6.8 ceramics has been investigated. It has been shown that, upon low-temperature annealing in humid air, planar stacking faults are formed in these ceramics. These defects are partly retained after reduction annealing (at T = 930°С) and are efficient pinning centers in magnetic fields applied parallel and perpendicular to the c axis. Due to the absorption of water, the oxygen content is increased in the ceramics, which is accompanied by an increase in the critical temperature of superconducting transition up to 94 K for YBa₂Cu₃O_6.96 and up to 90 K for YBa₂Cu₃O_6.8. Optimal conditions of the double annealing have been established, after which the critical-current density increased to j _c ≥ 10⁴ А/сm² in an external magnetic field of up to 6 T. The low-temperature treatment in the neutral atmosphere saturated by water vapors deteriorates the current-carrying capacity of the highly textured ceramics, which is connected with the disappearance of texture due to the copper reduction and the precipitation of impurity phases.     

Synthesis of porous nano/micro structured LiFePO4/C cathode materials for lithium-ion batteries by spray-drying method

In order to enhance electrochemical properties of LiFePO₄ (LFP) cathode materials, spherical porous nano/micro structured LFP/C cathode materials were synthesized by spray drying, followed by calcination. The results show that the spherical precursors with the sizes of 0.5–5 μm can be completely converted to LFP/C when the calcination temperature is higher than 500 °C. The LFP/C microspheres obtained at calcination temperature of 700 °C are composed of numerous particles with sizes of ～20 nm, and have well-developed interconnected pore structure and large specific surface area of 28.77 m²/g. The specific discharge capacities of the LFP/C obtained at 700 °C are 162.43, 154.35 and 144.03 mA·h/g at 0.5C, 1C and 2C, respectively. Meanwhile, the capacity retentions can reach up to 100% after 50 cycles. The improved electrochemical properties of the materials are ascribed to a small Li⁺ diffusion resistance and special structure of LFP/C microspheres.     

Evaluation of LaAlO3 as top coat material for thermal barrier coatings

Perovskite is a versatile group of oxide materials allowing their properties to be tailored by composition towards specific requirements. LaAlO₃ was prepared to study and report its properties in the context of its potential in thermal barrier coatings (TBCs) technology. A citric acid method was used for synthesis and the perovskite structure was confirmed using XRD and FT-IR. Viscosity of the solution precursor was checked as well as the particle size by laser particle size analysis. Densification behavior of the material was followed by conventional sintering and by spark plasma sintering. Apparent porosity by the Archimedes method, thermal conductivity and thermal expansion coefficient were studied. Mechanical and fracture properties were measured at elevated temperatures up to 1300 °C. For samples sintered at 1200?1400 °C, coefficient of thermal expansion ranged from 5.5×10^?6 to 6.5×10^?6 K^?1 and thermal conductivity ranged between 2.2 and 3.4 W/(m·K). Elastic modulus and ultimate stress were measured at 1000?1300 °C, while by micro-indentation, fracture toughness was found to be 3 MPa·m^1/2. As the sintering temperature increased from 1200 to 1500 °C, significant densification from 3.21 to 5.81 g/cm³ was found, indicating that material annealing should be made at least at 1400 °C. Under this condition, negligible dimensional change in phase transition temperature of LaAlO₃ from the rhombohedral (R3c) to the ideal cubic (Pm3m) is found. Data reported in this work can be useful for comparing the mechanical and fracture behaviours of different TBCs developed involving LaAlO₃ as well as input for numerical simulations.     

High temperature tensile properties of hypereutectic Al-25Si based alloy

The high temperature tensile deformation of a hypereutectic Al-25Si based alloy fabricated by spray forming and subsequent hot extrusion was investigated. Tensile tests were conducted at various temperatures and strain rates. It was revealed that the ductility of the alloy is sensitive to both the test temperature and strain rate. At a given strain rate, the peak value of elongation was obtained at 500 °C. At 490 °C and above, the peak value of elongation was observed at a strain rate of 1.0 × 10^-2 s^-1, although the elongation increased with decreasing strain rate at 460 °C and below. The high elongation was exhibited when a high strain rate sensitivity index (m value) was attained and a liquid phase existed during deformation. The liquid phase appeared as a filament-like structure which is aligned with the tensile direction on the fracture surface of the tensile deformed specimen. A higher elongation (>35%) was obtained when the volume fraction of the liquid phase was 0.7%-1.7%. The maximum elongation of 75% was achieved when the volume fraction of the liquid phase was about 1%. The transition of the activation energy was observed at 430 °C when incipient melting occurred.     

环氧氯丙烷引发的氧化钽气凝胶表征(英文)

介绍了一种以环氧氯丙烷为凝胶促进剂,乙醇为溶剂的块状氧化钽气凝胶的合成工艺及气凝胶样品表征。氧化钽气凝胶的微观显微结构分别由场发射扫描电子显微镜(FESEM),高分辨透射电镜(HRTEM)给出,其孔结构及其分布由等温N2吸附实验给出。结果表明,气凝胶的骨架主要由粒径约1.5nm的初级颗粒构成,等温吸附结构表明,气凝胶主要是由微孔和中孔构成的BET比表面积为835m2/g气凝胶样品。     

Adsorption of NO synthase inhibitor on dehydroxylated silica

A series of thiazine derivatives with the NO inhibiting effect was synthesized. These derivatives can be used in the treatment of gastrointestinal diseases, as well as antihypotensive (antishock) drugs. The potentially prolonged effect of these substances was studied by the adsorption of 2-N-benzoyl-2-amino-5,6-dihydro-4H-1,3-thiazine hydrobromide (I) on silica (nonporous Polysorb MP with specific surface area S = 330 m²/g and narrow-porous KSS-3 silica gel with S = 600 m²/g). The dehydroxylation of a silica surface significantly increased the adsorption of I. The adsorption kinetic curves of I showed a peak due to the rehydroxylation and deactivation of the silica surface in aqueous solutions. The adsorption rate in physiological solution of I was shown to decrease at a lower concentration of I on the surface of dehydroxylated silica and larger silica particles.     

The effect of nanoporous silica aerogel on corrosion protection properties of epoxy coatings on carbon steel

In this paper, due to special properties of aerogels such as ultra-low density and hydrophobic nature of aerogels, this nanomaterial was used as anticorrosive pigments. Silica aerogel was dispersed in epoxy resin by using sonication method. The dispersion of nanoparticles were characterized by transmission electron microscopy. The anticorrosive properties of these coatings were investigated by salt-spray and electrochemical impedance spectroscopy methods in a 3.5 wt % NaCl solution. Impedance parameters showed a decrease in coating resistance over immersion time. Results indicated that epoxy coatings containing nano silica aerogel could significantly increase the corrosion resistance of composite coatings compared to those of pure epoxy and the highest value was obtained for 0.5% aerogel nanocomposite coatings after 160 days immersion. Pull off adhesion test showed the highest value of adhesion was related to coating containing 0.5% aerogel. According to salt-spray methods, it was found that the best results were obtained with coatings containing 0.5 and 1 wt % of silica aerogel.