Structure and Texture of Nickel-Molybdenum Catalysts on Alumina Support Modified with Fluoride or Chloride Ions

The performed study involves measurements of a specific surface area via a BET method, of the pore volume, FT-IR, and a derivatographic study of a series of Al₂O_3-supported nickel-molybdenum catalysts modified with fluoride and chloride ions. It was found that fluoride ions lead to a decrease in the specific surface area of catalysts, whereas chloride ions have a small effect on this parameter. Modification does not change the type of pores of the catalysts, yet it affects their size and increases concentration of OH groups adsorbed on the surface of the catalysts relative to the carrier and the unmodified catalyst. Addition of fluoride ions decreases the thermal stability of the catalyst, whereas chloride ions does not cause any change.     

The effect of boron addition on texture and structure of NiMo/Al2O3 catalysts

The effect of support (Al₂O₃) modification with borate ions and the effect of their concentration on the texture and structure of nickel-molybdena catalysts were studied. The surface area and pore volume of the samples were determined using the BET method, whereas pores distribution – besides the BET method also by mercury porosimetry. FT-IR, derivatographic, and diffractometric studies were also performed. Modification with borate ions does not bring about any change in the type of the support pores, nor does it change its crystallic structure. However, a considerable decrease in the surface area of the support was observed. It was shown that modification with borate ions leads to a decrease in thermal stability of catalysts, yet increase in concentration of borate ions raises the thermal stability of the samples. It was found that on the catalyst surface borate ions form a well-dispersed monolayer structure.     

Texture and structure of nickel-molybdenum catalysts supported on alumina modified with sulfate and phosphate ions

A series of nickel-molibdenum catalysts supported on alumina modified with sulfate and phosphate ions was studied. The studies involved texture evaluation measurements through N₂ adsorption isotherms. Besides, IR spectroscopic and derivatographic studies were carried out. Results of the studies enable us to conclude that modification of the alumina support with the above ions leads to a significant decrease in its surface area and pore volume. Modification does not result in a change of the type of pores of the support, but in the change of their size dimention. The pores present on the surface of the catalyst have the shape of “ink-bottles”. Modification with phosphate ions improves the thermal stability of the catalyst, whereas sulfate ions present on the surface of the catalyst undergo decomposition upon heating of the sample. Phosphate ions inhibit formation of aluminum molybdate, and instead form polymeric layer structures of phosphate on the surface of catalysts. Sulfate ions occur in the form of surface aluminum sulfate.     

The Effect of Sequence Incorporation of Sodium Ions on Structural and Thermal Properties of CoMo/Al2O3

The alumina supported cobalt-molybdena catalysts containing sodium ions were subjected to X-ray diffraction studies, IR spctroscopy and thermal analysis. Sodium ions were introduced onto Al₂O₃ either simultaneously with the other components, or prior to them or after them. Di- and polymolybdates phases were found to be formed on the support in all samples. In samples obtained in a two-stage process the interaction of Na⁺ ions with the support ions was detected which did not occur in samples obtained in a single-stage process. Nitrate ions introduced simultaneously with the other components undergo a relatively strong thermal decomposition while in the samples synthesised in two stages they are strongly bounded. The greatest number of strongly bound nitrates was found in the sample into which sodium ions were introduced in the second stage of the preparation procedure.     

镁/钛离子注入对蓝宝石微结构和机械性能的影响

离子注入已被证明是改善蓝宝石光学和机械表面性能的一种可靠方法.本文选择不同能量和剂量的镁/钛离子注入蓝宝石.利用TRIM(Transport of Ion Matter)程序分析了镁/钛离子在蓝宝石晶体中的射程分布.利用拉曼光谱和掠入射X射线衍射分析了损伤层深度和微结构变化.离子注入结果显示,蓝宝石的纳米硬度、纳米划痕和红外性能等均呈现出可调节的特性.     

The role of Mg2+-V-dipoles: In the thermoluminescence of LiF2:Mg single crystal

The thermoluminescence and radiation or thermally induced changes of the concentration of magnesium dipoles have been studied in LiF:Mg²⁺ crystal grown in an inert atmosphere. The evolution of the TL spectrum with γ-radiation dose shows that the glow peaks observed at the beginning of irradiation decrease at high doses whereas new peaks, positioned at higher temperatures, appeare. Moreover, it has been found that the thermally induced recovery of the dopant dipoles, destroyed during the irradiation, strongly depends on the dose applied. The recovery curves obtained for a fixed irradiation dose dose not exhibit thermal annealing steps at temperatures, at which glow peaks occur. Further, the number of the recovered magnesium dipoles is not correlated with the quantity of light emitted during heating the irradiated crystal what is expected in respect to some of the previously proposed models. On the basis of results obtained it is proposed that the decay of the magnesium dipoles is mainly due to the dopant aggregation induced by the γ-radiation. The role of the magnesium ions in thermoluminescent processes is discussed.     

Characterization of Nickel and Tungsten species supported on alumina

The effect of thermal activation on NiW/Al₂O₃ catalyst in their oxide, reduced and sulfided forms has been studied by X-ray diffraction (XRD), differential thermal analysis (DTA), diffusion reflectance spectroscopy (DTS), infrared spectroscopy (IR), Raman spectroscopy (RS), electron paramagnetic resonance (EPR) and magnetic susceptibility measurements. Thermal activation in oxygen results in production of many species of the mono-, di-, and polymeric type. Upon activation in hydrogen they are partially reduced, whereas upon sulfiding number of oxide ions are replaced by sulfide ones. Among others, formation of dithiotungstenates was proved, yet neither the exchange of hydroxyl groups for the thiol ones nor the exchange of bridge oxide ions for sulphur ions was indicated. The simultanous reduction and sulfiding process do not affect the spinel subsurface structure. With respect to the surface species, the catalyst's support takes on a stabilizing function.     

Sodium borosilicate glasses prepared by the sol-gel process

A sodium borosilicate gel of composition 80SiO₂·15B₂O₃·5Na₂O (wt%) was prepared from tetraethyl orthosilicate, trimethyl borate, sodium methylate, H₂O, and HCl as the catalyst. Variation of specific surface area and porosity as a function of heating temperature indicated that closed pores were opened at temperatures lower than 400°C and collapsed above 450°C. From TG and DTA curves, about 19% Si and B atoms are evaluated to have −OH bonds. X-ray diffraction patterns indicated crystallization of low-cristobalite out of the gel when it was heated at 700°C for 5 h, showing a difference from a melt-quenched glass of the same composition.     

The coprecipitation of magnesium chromium hydroxide powders from aqueous solution: Precipitate compositions and coprecipitation mechanisms

Magnesium chromium (III) hydroxides were coprecipitated at ambient temperature from different mixed metal cation solutions — at C_Mtot = 0.1 M and Mg/Cr₂ ratios varying from 1 to 4 — with sodium hydroxide solution. The coprecipitations were monitored by potentiometric (pH) titration and the final precipitate compositions were examined by chemical analysis, i.r. spectrophotometry and thermal analysis. Generally, microcrystalline chromium(III) hydroxide was first precipitated at pH about 5; this material then redissolved on further addition of hydroxyl ion to form hydroxochromate(III) anion and magnesium chromium hydroxide coprecipitates were then formed continuously (at OH/Cr ratios from 4 to 10) at pHs from 9.5–10 to about 11. The coprecipitates from Mg/Cr₂ = 1 systems was predominately magnesium hydroxochromate hydrate. The coprecipitates from Mg/Cr₂ = 2 to 4 systems were mixture or solid solutions of magnesium hydroxochromate hydrate with increasing amounts of magnesium hydroxide. The ionic equilibria involved in different coprecipitations are discussed.     

EPR and UV–Vis characterization of multicomponent germano-silicate glasses for photonics

Photosensitive, germanium-doped multicomponent silicate glasses with different amount of boron oxide and sodium oxide were prepared and investigated by means of electron paramagnetic resonance (EPR) and ultraviolet–visible (UV–Vis) spectroscopy in order to investigate the structural changes occurring in the glasses under UV laser irradiation at 248 nm (KrF excimer UV laser). Spectral data were recorded before and after UV laser irradiation: all the glasses showed EPR signals only after UV laser irradiation, independently from the presence of a UV–Vis absorption band on the as prepared glasses. The main results showed that the presence or the absence of boron and sodium and their amount play a role in the type and the number of defects, their time and thermal decay, under the same UV laser exposure conditions. A clear correlation between the EPR signal and the UV–Vis absorption is observed only for the 240 nm band. It is also demonstrated that the sodium ions decrease the number of paramagnetic defects in these glasses and deeply change the germano-silicate glass structure. The presence, the absence and the co-presence of sodium and boron ions has a role in the structure, the number, the nature and the stability of the paramagnetic defects. It is important to understand the role of sodium and boron in order to increase the photosensitivity of germano-silicate glasses, for their interest in the field of ion-exchangeable glasses for photonic waveguides and Bragg-grating based devices.     

反相微乳液法合成超细磷酸镁铵

利用反相微乳液法制备磷酸镁铵(MAP),并使用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、红外光谱仪(FT-IR)及热分析仪(TG-DSC)对其进行表征.结果表明,反相微乳液法制备出的MAP分布更窄,尺寸更小;不同方法得到了晶型不同的MAP;其中十六烷基三甲基溴化铵作为表面活性剂制备出的MAP粒径分布最窄;采用十二烷基苯磺酸钠作为表面活性剂制备出的MAP粒径最小,热稳定性最好.     

Europium environment and clustering in europium doped silica and sodium silicate glasses

The local environment and distribution of rare earth ions are important to the optical properties of rare earth doped oxide glasses. In this paper, we report studies of the structures of europium doped (around 1 mol% Eu₂O₃) silica and sodium silicate glasses using molecular dynamics simulations. By using effective partial charge potentials, systems with over 24,000 atoms were modeled in order to obtain better statistics of rare earth ion distribution. The simulated glass structures were validated by comparing the calculated neutron and X-ray structure factors with experimental data. It was found that europium ions have higher coordination number (5.9 versus 4.8) and more symmetric environments in sodium silicate glasses than in the silica glass. Rare earth ion clustering has been characterized in detail and it was found that the clustering probability of europium ions in sodium silicate glass is consistently less than that predicted from a random distribution, while the probability of clustering in pure silica glass is higher than that of random distribution at the 1 mol% doping level.     

The coprecipitation of magnesium hydroxide aluminium hydroxide powders from aqueous solution with sodium hydroxide: Precipitate compositions and coprecipitation mechanisms

Magnesium aluminium hydroxides were coprecipitated from different mixed metal cation solutions — at total C_M = 0.1 M and Mg/Al₂ ratios from 1 to 6 — with sodium hydroxide solution at ambient temperature, with different pre-ageing conditions for the aluminium hydroxide pre-precipitate. The coprecipitations were monitored by potentiometric (pH) titration and the final precipitate compositions were examined by chemical analysis, infrared spectrophotometry and thermal analysis. Magnesium hydroxide was coprecipitated onto completely recrystallised aluminium hydroxide as a simple mixture. Generally, with no to three days pre-ageing, microcrystalline aluminium hydroxide was first precipitated at pH about 4; this then partially redissolved on further addition of sodium hydroxide (to form hydroxoaluminate anion) and magnesium aluminium hydroxide coprecipitates were formed continuously at pHs from 8.0–8.7 to 12.0–12.5. Their compositions were similar to the magnesium hydroxoaluminate hydrates formed by direct precipitation from high pH sodium hydroxoaluminate solutions.      

Crystallization Kinetics of NaCl in Multicomponent Solutions

Experimental results of solubility and growth kinetics measurements of sodium chloride crystals in multicomponent systems at 303 K are given. The effect of several solutes in elevated concentrations on the growth and dissolution kinetics is analysed on volume diffusion and surface integration steps: While the diffusion of ions within the solution decreases by the presence of foreign ions, the integration resistance can increase (mobile or immobile adsorption of foreign ions) or may even be reduced in some cases (due to a decreased surface energy).     

Potassium surface enrichment in mixed alkali glass irradiated with electrons

Sodium-potassium-silicate glass was irradiated with electrons of energy of 1600 eV. The changes in the surface composition were analyzed by means of the angular-resolved X-ray induced photoelectron spectroscopy (ARXPS). Low electron dose irradiation enriched the uppermost glass surface with alkali ions, considerably more with potassium than with sodium ions.     

水热反应条件对氢氧化镁晶体微观内应变的影响

用氯化镁和氢氧化钠反应合成氢氧化镁前驱体,通过水热反应制备出氢氧化镁阻燃剂粉体,采用X射线衍射进行表征,分析水热条件对氢氧化镁晶体(101)面微观内应变和晶体生长方向的影响.结果表明:在实验温度范围内,碱浓度和水热时间对氢氧化镁晶体在(101)面微观内应变的影响规律比较明显.碱浓度和水热温度是影响晶体生长方向的主要因素.     

Characterization of porous InP(001) layers by triple-crystal X-ray diffractometry

The structure of porous layers fabricated on the surface of an InP(001) semiconductor wafer by electrochemical oxidation has been studied by triple-crystal X-ray diffractometry. It is shown that, depending on the probe potential (current density), column-shaped pores of two types with different orientations with respect to the substrate are formed. It is established that, at a probe potential of ～6 V, pores are extended along the current lines (CLO pores) and directed normally to the sample surface. With a decrease in the potential to ～3 V, the longitudinal axes of pores are oriented at an angle of ζ = 52° ± 2° to the sample surface (CO pores). The average diameter and length of pores are determined (～80 and 300–900 nm, respectively) and the porosity of the samples is evaluated (P ～ 40–60%). The obtained data on the pore parameters are in satisfactory agreement with the scanning electron microscopy data.     

Influence of heat treatment on the colour of Au and Ag glasses produced by the sol-gel pathway

In this work, coloured glasses were produced based on the synthesis of gold and silver nanoparticles by the sol-gel process having in mind their application in art works. Gold and silver were used separately or as a mixture by varying the mole fractions in order to get a range of colours from yellow to red. The gold and silver nanoparticles were prepared by the reduction of tetrachloroauric acid and silver nitrate with sodium citrate in aqueous solutions which were further introduced in the sol-gel system. Attention was focused on the thermal treatment of the sol-gel samples. Different temperatures were used in order to determine their influence on the obtained colour. The glasses were characterized by UV-Vis absorption spectroscopy and the size of the nanoparticles was examined by transmission electron microscopy (TEM).The range of colours mentioned above is obtained either by preparing nanoparticles of each metal and mixing them or by preparing nanoparticles from solutions containing initially ions of both metals. In the former case, two surface plasmon resonance (SPR) bands were observed for temperatures below 200 °C while higher temperatures promote the formation of alloys between the Ag and Au nanoparticles. In the latter case, only one SPR band is observed and the nanoparticle size distribution is narrower. The results were explained by nanoparticle aggregation promoted by temperature. Glasses containing only Ag did not present the typical yellow colour above 300 °C but it was shown that the colour could be stabilized if Au was added in small amounts (Au/Ag molar ratio 0.1).     

ZrO_2纳米涂层修饰改性陶瓷微滤膜吸附机理研究

分别在MgCl2和NaCl稀溶液中,用AFM研究了四方相ZrO2纳米涂层的表面排斥力随作用距离的变化关系。当作用距离较远时,表现为长程排斥力,当作用距离较近时,为强烈的短程排斥力。Mg2+在ZrO2纳米涂层表面具有特征吸附,而Na+表现出惰性电解质的特征。随着MgCl2浓度的增大,渗透通量呈明显下降的趋势。随着NaCl浓度的增大,渗透通量呈稍有增大的趋势。     

A facile route to prepare boron nitride hollow particles at 450 °C

Hexagonal boron nitride (h-BN) particles including hollow spheres (with a proportion of ~30–40%) and nanotubes (10%) have been synthesized by using sodium fluoroborate and sodium azide at 450 °C for 20 h. X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) studies show that the as-obtained BN hollow particles are crystalline. The total specific surface area of the product calculated from Brunauer–Emmentt–Teller (BET) absorption measurement is 89.79 m²/g, indicating that it may be utilized as a promising candidate for hydrogen storage container or catalyst. Thermal gravimetric analysis (TGA) result reveals its excellent thermal stability below 800 °C. Its possible growth mechanism and the effects of reaction parameters were also briefly discussed.