Beckmann rearrangement of cyclohexanone oxime to ε-caprolactam using mesoporous molecular sieves ALSBA-15

Vapor-phase synthesis of ε-caprolactam (ε-C) from cyclohexanone-oxime (CHO) has been studied at 300-400^oC and atmospheric pressure using AlSBA-15(X) catalysts with different Si/Al mol ratios X in a fixed-bed, integral-flow reactor. The catalysts were characterized with ICP-AES, XRD, TEM, N₂ adsorption, ²⁷Al and ²⁹Si MAS-NMR, FT-IR and TPD of ammonia. A decrease of X value in AlSBA-15(X) diminishes both the BET surface area and the unit cell length but enhances the acid amount. The catalytic activity correlates with the catalyst acidity. AlSBA-15(10) exhibits excellent catalytic performance. This revised version was published online in June 2006 with corrections to the Cover Date.     

Electrical and Optical Properties of MgO Thin Film Prepared by Sol-Gel Technique

MgO thin films with either (111) or (200) preferential orientation have been prepared on (100) Si substrates by sol-gel method after a heat-treatment at 800°C. The obtained (111) preferentially oriented MgO film has a dielectric constant of 7.0 with a loss factor of 5% and a dielectric strength higher than 8 × 10⁵ V/cm. The optical refractive index, which depends on the film thickness, is 1.71 when the film thickness is 260 nm. The surface structure of the Si substrate is believed to affect the preferential orientation of the sol-gel derived MgO film. Specifically, the microstructures at the interface indicate an interdiffusion of Mg, O, and Si between the film and the substrate.     

Preparation and dielectric properties of highly preferred-(100) orientation (Pb,La)(Zr,Ti)O<Subscript>3</Subscript> antiferroelectric thick films by sol–gel processing

Pb_0.97La_0.02Zr_0.95Ti_0.05O₃ (PLZT) antiferroelectric thick films of highly preferred-(100) orientation with different thickness were successfully deposited on Pt(111)/Ti/SiO₂/Si(100) substrates depending on the sol–gel process technique. The effects of the PLZT thick films in the preparation and electric properties are investigated. The films show polycrystalline perovskite structure with a (100) preferred orientation by X-ray diffractometer analyses. The antiferroelectric nature of the thick films is demonstrated by P (polarization)–E (electric field). The temperature dependence of the dielectric constant and dielectric loss displays the similar behavior in both cases at 100 kHz while the values of polarization characteristic are decreased with the increase of the film thickness. The phase switching current are studied as a function of a gradually change dc electric field and the voltage dependent current density of the most highly (100)-oriented PLZT film is 1.49 × 10⁻⁸ A/cm² over electric field range from 0 to ±261 kV/cm. The film at 2,498 nm exhibits excellent dielectric properties and highly preferred-(100) orientation.     

Low-temperature processing of sol-gel derived Pb(Zr,Ti)O<Subscript>3</Subscript> thick films using CO<Subscript>2</Subscript> laser annealing

Fabrication of ferroelectric Pb(Zr_0.52Ti_0.48)O₃ (PZT) thick films on a Pt/Ti/SiO₂/Si substrate using powder-mixing sol-gel spin coating and continuous wave CO₂ laser annealing technique to treat the specimens with at a relatively low temperature was investigated in the present work. PZT fine powders were prepared by drying and pyrolysis of sol-gel solutions and calcined at temperatures from 400 to 750°C. After fine powder-containing sol-gel solutions were spin-coated on a substrate and pyrolyzed, CO₂ laser annealing was carried out to heat treat the specimens. The results show that laser annealing provides an extremely efficient way to crystallize the materials, but an amorphous phase may also form in the case of overheating. Thicker films absorb laser energy more effectively and therefore melt at shorter periods, implying a significant volume effect. A film with thickness of 1 μm shows cracks and rough surface morphology and it was difficult to obtain acceptable electrical properties, indicating importance of controlling interfacial stress and choosing appropriate size of the mixing powders. On the other hand, a thick film of 5 μm annealed at 100 W/cm² for 15 s exhibits excellent properties (P _r = 36.1 μC/cm², E _c = 19.66 kV/cm). Films of 10 μm form a melting zone at the surface and a non-crystallized bottom layer easily at an energy density of 100 W/cm², showing poor electrical properties. Besides, porosity and electrical properties of thick films can be controlled using appropriate processing parameters, suggesting that CO₂ laser annealing of modified sol-gel films is suitable for fabricating films of low dielectric constants and high crystallinity.     

Influence of the Native Oxide Layer on the Silicon Surface During Initial Stages of Nitridation

 Thin SiO₂ layers were produced by thermal oxidation of Si wafer material. To study the effect of nitridation on the oxide layers, the specimens were nitrided in a furnace at high temperature. Non-destructive ion beam analysis was performed to determine changes in the elemental concentrations and depth profiles of the major components. In particular, N and O concentrations were measured using the non-resonant nuclear reactions ¹⁴N(d, α)¹²C and ¹⁶O(d, p)¹⁷O, respectively. To obtain depth profiles of the as-prepared and nitrided specimens, the samples were measured with RBS and heavy ion elastic recoil detection analysis. The ion beam analyses revealed an increase in thickness of the SiO₂ layers with temperature. The specimens nitrided at 1200 °C were almost free of N. Surface topology investigations with scanning electron microscopy revealed concentric annular artificial patterns at the surfaces. In the centre of the pattern, only silicon was measured. Additionally, a band consisting of Si, O, and N surrounding the pattern was discovered. The findings are in agreement with specimens prepared at higher temperatures. Received June 19, 2000. Revision December 9, 2000.     

双功能改性的T型分子筛膜用于有机溶剂脱水

将3-氨丙基三乙氧基硅烷（APTES）引入到T型分子筛膜表面,用以修饰多晶膜合成过程中产生的缺陷。X射线衍射、场发射扫描电子显微镜、X射线光电子能谱和FT-IR等方法的表征结果显示,APTES通过“键合”的形式被成功地修饰到膜表面上。APTES层起到2个作用：一是提高膜的亲水性;二是减少膜层的缺陷。将修饰后的膜应用在348 K、90%的异丙醇水溶液的脱水时,该膜表现出比较高的分离因子和通量。该方法重复性良好,5个修饰后的膜样品的选择性平均增加了大约8倍（从359±23增加到2 934±183）,而渗透通量仅仅从（3.52±0.10） kg·m^-2·h^-1降低到（3.06±0.14） kg·m^-2·h^-1（减少13.07%）。在363 K下,修饰的膜经过100 h的连续测试,膜渗透测得的水含量均可达到99.50%以上,表明修饰后的膜性能较稳定。     

Surface-near analyses of ultra thin silicon nitride layers by NRA, channeling RBS, FT IR ellipsometry and AFM

Homogeneous ultra thin silicon nitride layers (SiN_x layers) close to the surface have been produced by 10 keV ¹⁵N ₂ ⁺ molecular ion implantation and an ion current density of 10 A/cm², into single crystal silicon at room temperature. Stoichiometric SiN_x layers with thicknesses of about 28 nm (analyzed by NRA) were obtained at fluences of 1.5×10¹⁷ at/cm². NRA analyses of samples annealed by EB-RTA at T=1150° C for 15 s indicated that the N/Si ratio and the layer thickness did not change drastically. FT IR ellipsometry analyses indicated the existence of Si₃N₄ bonds in as-implanted specimens. A disordered Si layer (d-Si, typically 15 nm thick) underneath the implantation region caused by the ion implantation was found by channeling RBS analyses. The d-Si layer partly recrystallized during EB-RTA showing a thickness of 6 nm afterwards. The SiN_x layers showed no decomposition and detachment after EB-RTA. Due to EB-RTA, however, the smooth surface of the as-implanted specimens changed into a surface with remaining whisker-like structures surrounded by circular recesses as shown by AFM analyses. A model for the growth of these whisker-liker structures caused by low energy ion implantation and EB-RTA is presented on the basis of the thickness of the SiN_x layer, the existence of the d-Si layer and the special annealing process.     

Diffusion layer thickness in a membrane system as determined from voltammetric and chronopotentiometric data

The thickness of the diffusion boundary layer (DBL) in solution near the surface of an ion-exchange membrane is compared at current densities (δ⁰) much less than the limiting value and at the limiting current density (δ_lim). The initial linear part of the current-voltage curve (CVC) of the membrane and the initial part of its chronopotentiogram are used to calculate δ⁰. Values of δ⁰ are found in a flow-through cell with an active membrane area of 2 × 2 cm² and 0.02 M NaCl solution for three membranes: AMX, Nafion-117, and MK-40. It is shown that δ⁰ is more than 20% less for Nafion-117 than for AMX and MK-40. Values of δ⁰ are close together for the latter two membranes and do not differ greatly from the value calculated from convective diffusion theory (the Leveque equation). In all cases, δ⁰ is significantly greater than δ_lim found from the value of the limiting current density by the method of intersecting tangents, which are drawn to the initial segment of the CVC and to the sloping plateau. The effects that determine the dependence of DBL thickness on not only hydrodynamic conditions, but also the state of the membrane surface, are discussed. The principal phenomenon responsible for the decrease in DBL thickness with increasing current is termed coupled convection, more likely, electroconvection. Among the significant properties of the surface are singled out its electrical heterogeneity and degree of hydrophobicity. The different rate of electroconvection near cation- and anion-exchange membranes is related to the Stokes radius of the counterions. The latter explains the well-known observation in the literature that the limiting current density in dilute NaCl solutions is approximately the same for cation- and anion-exchange membranes in spite of the fact that the mobility of Cl⁻ ions is approximately 1.5 times higher than that of Na⁺ ions.     

Dielectric properties and I-V characteristics of (Pb<Subscript>0.4</Subscript>Sr<Subscript>0.6</Subscript>)TiO<Subscript>3</Subscript> thin films improved by TiO<Subscript>2</Subscript> buffer layers

A TiO₂ thin buffer layer was introduced between the (Pb_0.4Sr_0.6)TiO₃ (PST) film and the Pt/Ti/SiO₂/Si substrate in an attempt to improve their electrical properties. Both TiO₂ and PST layers were prepared by a chemical solution deposition method. It was found that the TiO₂ buffer layer increased the (100)/(001) preferred orientation of PST and decreased the surface roughness of the films, leading to an enhancement in electrical properties including an increase in dielectric constant and in its tunability by DC voltage, as well as a decrease in dielectric loss and leakage current density. At an optimized thickness of the TiO₂ buffer layer deposited using 0.02 mol/l TiO₂ sol, the 330-nm-thick PST films had a dielectric constant, loss and tunability of 1126, 0.044 and 60.7% at 10 kHz, respectively, while the leakage current density was 1.95 × 10⁻⁶ A/cm² at 100 kV/cm.     

Silicone discs as disposable enrichment probes for gas chromatography-mass spectrometry determination of UV filters in water samples

This work describes an effective, low solvent consumption and affordable sample preparation approach for the determination of eight UV filters in surface and wastewater samples. It involves sorptive extraction of target analytes in a disposable, technical grade silicone disc (5 mm diameter × 0.6 mm thickness) followed by organic solvent desorption, large volume injection (LVI), and gas chromatography-mass spectrometry determination. Final working conditions involved overnight extraction of 100-mL samples, containing 10% of methanol, followed by analytes desorption with 0.2 mL of ethyl acetate. The method provides linear responses between the limits of quantification (from 0.003 to 0.040 ng mL⁻¹) and 10 ng mL⁻¹, an intra-day precision below 13%, and low matrix effects for surface, swimming pool, and treated sewage water samples. Moreover, the extraction yields provided by silicone discs were in excellent agreement with those achieved using polydimethylsiloxane-covered stir bars. Several UV filters were found in surface and sewage water samples, with the maximum concentrations corresponding to octocrylene.     

Phytoestrogen biomonitoring: an extractionless LC-MS/MS method for measuring urinary isoflavones and lignans by use of atmospheric pressure photoionization (APPI)

We present here a high-performance liquid chromatography−tandem mass spectrometry (LC-MS/MS) method for quantifying phytoestrogenic isoflavones (daidzein, equol, genistein, and O-desmethylangolensin) and lignans (enterodiol and enterolactone) in urine without the use of extraction or the preconcentration techniques inherent in existing methods. The development of this concept was made possible by use of atmospheric pressure photoionization (APPI); an ionization technique that we found to improve analyte sensitivity relative to electrospray ionization and atmospheric pressure chemical ionization for this particular group of compounds. The analytical performance of this method was equal to or exceeded that of comparable methods. Between-run coefficients of variation (CVs) across three quality control (QC) pool levels analyzed in duplicate over 20 days were 3.1–5.8% CV; within-run CVs were 2.3–6.0%. Accuracy, as determined by average spike recovery in QC pools, was generally within ±10% of being quantitative (100%). Relative limits of detection were 0.04–0.4 ng/mL urine, with absolute detection limits as low as 0.1 pg. This method was applied to the analysis of >2,500 urine specimens for the 2005–2006 Centers for Disease Control and Prevention’s National Health and Nutrition Examination Survey (NHANES). The method was capable of quantifying these compounds in 95–100% of study samples. This work is the first ever report of using APPI for the LC-MS/MS determination of these compounds in urine. It is also the first method of its kind to do so without any need for analyte extraction or preconcentration prior to analysis.     

Subnanometre depth resolution in sputter depth profiling of Si layers using grazing‐incident low‐energy O2+ and Ar+ ions

The sputter damage profiles of Si(100) by low‐energy O₂⁺ and Ar⁺ ion bombardment at various angles of incidence were measured using medium‐energy ion scattering spectroscopy. It was observed that the damaged Si surface layer can be minimized down to 0.5–0.6 nm with grazing‐incident 500 eV Ar⁺ and O₂⁺ ions at 80°. To illustrate how the damaged layer thickness can be decreased down to 0.5 nm, molecular dynamics simulations were used. The SIMS depth resolution estimated with trailing‐edge decay length for a Ga delta‐layer in Si with grazing‐incident 650 eV O₂⁺ was 0.9 nm, which is in good agreement with the measured damaged layer thickness. Copyright © 2004 John Wiley & Sons, Ltd.     

Sol–gel synthesis of Na<Subscript>2</Subscript>CaSiO<Subscript>4</Subscript> and its in vitro biological behaviors

In this work we prepared the hybrid material (SG) by the sol–gel method through the reaction between tetraethylortosilicate (TEOS) and acetylacetonatepropyltrimethoxysilane (ACACSIL). We also immobilized the acetylacetonate on silica surface (GR) by the grafting method through the reaction between a commercial silica and ACACSIL. Infrared thermal analysis showed that these materials were thermally stable until 200 °C. SG is a microporous material and has surface area of 500 m² g⁻¹, average porous volume of 0.09 cm³ g⁻¹ and organic content of 1 mmol g⁻¹. GR is a mesoporous material and has surface area of 300 m² g⁻¹, average porous volume of 0.7 cm³ g⁻¹ and organic content of 0.4 mmol g⁻¹. Iron(III) was coordinated to SG and GR resulting in the SG–Fe and GR–Fe silicas which were tested as catalysts on the aerobic epoxidation of cis-cyclooctene. SG–Fe yielded 100% of conversion and 94% of selectivity in epoxide whereas GR–Fe silica led to a maximum conversion of 50% and 100% of selectivity.     

Kinetics of interaction of 3-aminopropyltriethoxysilane with silica gel using elemental analysis and 29Si NMR spectra

 Three silica gel sample systems, modified with 3-amino-propyltriethoxy silane (APTS), were prepared by sequentially sampling the reaction mixture at various time intervals. The concentrations of 3-aminopropylsilyl groups (APS) bound on the silica surface were determined by elemental analysis. For the same sample systems, ²⁹Si NMR intensities of an (–O)₄Si species belonging only to the silica gel particles and corrected by a cross-polarization correction factor were also measured. Both the APS-concentrations and the correc-ted ²⁹Si NMR intensities depended upon reaction time, reflecting the rate of the APTS–silica gel reaction. Kinetic analysis of these data was made by use of the Gauss–Newton method, and the overall reaction was found to consist of three reaction processes (an initial fast reaction, a slower second reaction and a much slower third reaction). In particular, the conversion of (–O)₃SiOH to (–O)₄Si is predominant in the second reaction process and the pore size of a silica gel particle affects the reaction mechanism. Received: 1 November 1996 Accepted: 24 January 1997     

Thermal and Chemical Properties of a Glass in the SiO2-CaO-F System for Dental Applications

The crystallization behaviour of a glass in the SiO₂-CaO-F system was analyzed using differential scanning calorimetry (DSC), X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). Three crystalline phases were detected according to ICDD patterns. The first phase formed at 583°C was identified as CaF₂. The morphology was spherulitic with a diameter of approximately 100 nm. The second phase was formed at 664°C. It was identified as calcium fluoride silicate ‘Ca₂SiO₂F₂’ (ICDD 35-0002). SEM investigation showed that the crystals were spherulitic with a diameter smaller than 100 nm. The crystals were precipitated in the volume of the glass and homogeneously distributed. As a third phase, cristobalite crystallized at 895°C. The simultaneous release of calcium and fluorine ions from the vitreous glass in lactate buffer solution at pH 4.0, simulating an acidic oral environment, was investigated using X-ray photoelectron spectroscopy (XPS). The release of calcium and fluorine ions is of special interest for dental applications. The atomic ratios of the components Si, Ca and F at the glass surface after different leaching periods were determined. In order to investigate the leaching process, concentration profiles were measured using ion beam sputtering with Ar⁺ -ions. The dependence of the atomic ratios of Si, Ca and F on the sputter time was determined in order to measure the depth of the leaching layers. Most probably, the release of calcium and fluoride was controlled by a surface layer rich in calcium and flourine ions which dissolved with increasing leaching time. After 2 min leaching, a fluoride-rich surface layer measuring approximately 10 nm was detected. The atomic ratios of Si, Ca and F were different from the bulk composition ratios in a surface reaction layer of 800 nm thickness. After 30 min leaching time, a calcium- and fluoride-rich surface layer approximately 50 nm thick was formed. The bulk composition was reached at a depth of approximately 500 nm. The main component in the surface layer, after 12 days leaching in acidic environment, was silicon. This revised version was published online in August 2006 with corrections to the Cover Date.     

Estimation of performance parameters of a frontal variant of optoacoustic determination with a model system

Using a model system, the applicability of the frontal configuration of optoacoustic spectroscopy in analytical practice is shown. An optoacoustic cell made using layered-prism geometry was designed and tested; it ensures operation with a layer thickness of 20–100 μm and sample volumes of 50–100 μl. Conditions are proposed for determining iron(II) in the form of tris(1,10-phenanthrolinate) with the detection limit of 3 × 10⁻⁷ M, which is less that the detection limit under similar induction conditions and for the same determination procedure using thermal-lens spectrometry (4 × 10⁻⁷ M). The determination has high reproducibility (relative standard deviation for 10⁻⁶ M is 0.005) and expressivity (1 min per sample detection).     

Facet-dependent lithium intercalation into Si crystals: Si(100) vs. Si(111)

Fast Li transport in battery electrodes is essential to meeting the demanding requirements for a high-rate capability anode. We studied the intercalation of a Li atom into the surface and subsurface layers of Si(100) and Si(111) using density functional calculations with a slab representation of the surfaces. We suggest that the Li atom migrates on the Si surfaces and is subsequently inserted into the inside for both Si(100) and Si(111). The rate-determining steps are the surface incorporation and subsurface diffusion in Si(100) and Si(111), respectively. Our diffusion rate calculations reveal that, once the Li atom is incorporated into the Si surface, Li diffuses faster by at least two orders of magnitude along the <100> direction than along the <111> direction. The importance of careful treatment of the slab thickness for the study of impurity insertion into subsurface layers is also stressed.     

硅纳米粒子聚苯胺包覆改性及其嵌/脱锂电化学性能

利用直流电弧等离子体蒸发法合成硅纳米粒子（Si NPs）,粒径为20~30 nm。采用对氨基苯甲酸（ABA）处理Si NPs,并在ABA-Si NPs表面进行苯胺（ANi）原位化学氧化聚合,形成核/壳型聚苯胺包覆硅纳米复合粒子（PANi-Si NPs）。FTIR、DSC、XRD、TEM等分析结果表明,ABA与Si NPs之间形成了化学键,粒子表面引入了ANi基团,复合粒子中PANi质量含量约为62%。电化学性能测试表明,PANi包覆层的存在大幅度提高了Si NPs的循环稳定性能,在100 mA·g^-1的电流密度下循环100次后,电池容量保持率为92.5%,远高于未改性的Si NPs的性能。聚苯胺包覆改性Si NPs,改善其导电性能的同时,可以极大地缓冲充/放电过程中的体积变化,提高电极的循环稳定性能。     

硅纳米粒子聚苯胺包覆改性及其嵌/脱锂电化学性能

利用直流电弧等离子体蒸发法合成硅纳米粒子(SiNPs),粒径为20~30 nm。采用对氨基苯甲酸(ABA)处理SiNPs,并在ABA-SiNPs表面进行苯胺(ANi)原位化学氧化聚合,形成核/壳型聚苯胺包覆硅纳米复合粒子(PANi-SiNPs)。FTIR、DSC、XRD、TEM等分析结果表明,ABA与SiNPs之间形成了化学键,粒子表面引入了ANi基团,复合粒子中PANi质量含量约为62%。电化学性能测试表明,PANi包覆层的存在大幅度提高了SiNPs的循环稳定性能,在100 mA·g~(-1)的电流密度下循环100次后,电池容量保持率为92.5%,远高于未改性的SiNPs的性能。聚苯胺包覆改性SiNPs,改善其导电性能的同时,可以极大地缓冲充/放电过程中的体积变化,提高电极的循环稳定性能。     

An investigation of dielectric resonator antenna produced from silicon (100) enhanced by strontium doped-barium zirconate films

Dip-coated Ba_1−x Sr _x ZrO₃ thick films with different Ba/Sr ratios (x = 0.0, 0.1, 0.3, 0.5, 0.7 and 0.9) were fabricated on Si (100-orient) substrate at a low temperature of 800 °C via the sol gel method. The experimental results show that dielectric resonator (DR) properties of Ba_1−x Sr _x ZrO₃ films depend on the different Ba/Sr ratios. For structural characterization, the X-ray analysis revealed that phase transformation was affected by the increase in Sr concentrations for heat treatment at 800 °C. The films were crystalline and of single phase. The thickness of one BSZ film is around 1.259 μm when measured using the field emission scanning electron microscope. The BSZ film’s surface morphology as indicated by the atomic force microscopy showed the mean grain size to be in the range of 2.56 to 94.34 μm, and the surface roughness (RMS) was recorded to be between 2.35 to 19.64 nm. The dielectric resonator (DR) properties were measured using a network analyzer. By introducing Ba_1−x Sr _x ZrO₃ (BSZ) films on the high dielectric Si (100-orient) substrate, better frequency stability was achieved i.e. within the range of 8–10 GHz. Measured results show that Si (100-orient) DRA has a 10 dB impedance bandwidth of 4.11% at 9.34 GHz and the BSZ improved this to 11.34% with x = 0.7 at 9.15 GHz. The radiation pattern was observed to be stable throughout the operating frequency and holds good potential for DR applications.