Preparation and physical properties of the layered niobate Cu0.5Nb3O8: Application to photocatalytic hydrogen evolution

The new layered niobate Cu_0.5Nb₃O₈ is synthesized by soft chemistry in aqueous electrolyte via Cu²⁺→H⁺ exchange between copper nitrate and HNb₃O₈·H₂O. The characterization of the exchanged product is made by means of thermal gravimetry, chemical analysis, X-ray diffraction and IR spectroscopy. Thermal analysis shows a conversion to anhydrous compound above 500 °C. The oxide displays a semiconductor like behavior; the thermal variation of the conductivity shows that d electrons are strongly localized and the conduction is thermally activated with activation energy of 0.13 eV. The temperature dependence of the thermopower is indicative of an extrinsic conductivity; the electrons are dominant carriers in conformity with an anodic photocurrent. Indeed, the Mott–Schottky plot confirms n-type conduction from which a flat band potential of −0.82 V_SCE, an electronic density of 8.72×10¹⁹ m⁻³ and a depletion width of 4.4 nm are determined. The upper valence band, located at ~5.8 eV below vacuum is made up predominantly of Cu²⁺: 3d with a small admixture of O²⁻: 2p orbitals whereas the conduction band consists of empty Nb⁵⁺: 5s level. The energy band diagram shows the feasibility of the oxide for the photocatalytic hydrogen production upon visible light (29 mW cm⁻²) with a rate evolution of 0.31 mL g⁻¹ min⁻¹.     

Oligo(ethylene oxide) side‐chain steric screening effects on conductimetric properties of grafted poly(4‐vinylpyridinium) salts in aqueous solutions

A set of poly[N‐oligo(ethylene oxide)yl 4‐vinylpyridinium tosylate] (P4VOEOOTs) has been prepared by spontaneous polymerization of 4‐vinylpyridine. This method gives a grafted polyelectrolyte having a positive charge on every backbone pyridinic moiety. The P4VP15Ts, P4VP164Ts, P4VP350Ts and P4VP750Ts aqueous solution conductivities were determined in the concentration range from 6 × 10^?4 to 10^?2 M at 25 °C. The variation of the conductivity versus concentration of the investigated system exhibits typical polyelectrolyte behaviour. The polyelectrolyte mobility was found to be dependent on the oligo(ethylene oxide) (OEO) side‐chain length. Manning's rod‐like model fails to describe these results. A simple steric effect is proposed to explain the influence of the OEO length. Copyright © 2003 Society of Chemical Industry     

The effect of ionic cross-links on the deformation behavior of homoblends made of poly(styrene-co-styrenesulfonic acid) and poly(styrene-co-4-vinylpyridine)

Deformation behavior of stoichiometric blends made from poly(styrene-co-styrenesulfonic acid) (SPS) and poly(styrene-co-4-vinylpyridine) (SVP) was investigated by TEM observation of strained thin films. An FTIR investigation revealed that ionic cross-links were formed between the component polymers upon blending due to intermolecular ion-ion interactions, which arose from proton transfer from sulfonic acid groups to pyridine groups. TEM observations indicate that the deformation mode of the blends changed from crazing only to crazing plus shear deformation, with the shear contribution becoming larger, as the ion content in the blends increased. Such changes in deformation mode can be understood as arising from an increase in the ‘effective’ strand density due to the formation of ionic cross-links upon blending. It was also found that the ionic cross-links via pyridinium cation/sulfonate anion ion pairs were more effective in inducing the transition of deformation mode than ionic cross-links via -SO₃⁻/Na⁺ or -SO₃⁻/Ca²⁺ ion pairs.     

非稳定井流模型的半解析解

为了提高非稳定渗流计算的计算精度 ,通过数学分析得到了水位传导系数随时间变化时 ,一类非稳定渗流井流模型的半解析解 ,并进行了计算比较     

Ionic transport in amorphous anodic titania stabilised by incorporation of silicon species

Incorporation of silicon species from an alloy substrate into anodic titania is shown to stabilise the structure of the film, facilitating investigation of the ionic transport processes in amorphous titania grown at high efficiency. Thus, an amorphous anodic film developed on a sputtering-deposited Ti-6 at.%Si alloy formed to 100 V in phosphoric acid electrolyte in contrast to a partially crystalline film developed on relatively pure titanium at <20 V. Silicon species, which are immobile and act as marker species in the growing film, are present in the inner 58% of the film thickness. Evidently, the film material forms simultaneously at the film/electrolyte and alloy/film interfaces by co-operative transport of cations and anions, as is usual in amorphous anodic oxides. The phosphate anions incorporated from the electrolyte migrate inward at 0.34 times the rate of O²⁻ ions and hence are present in the outer 62% of the film thickness.     

磁场对泡沫钻井液电导率的影响研究

磁处理技术是利用磁场对非铁磁性流体作用．使被作用物的性质产生某些期望的变化，从而改善生产效果和使用效益。磁处理对常规钻井液流变性能的影响研究结果表明，磁化能明显改善钻井液性能。通过研究磁化后泡沫钻井液的性质．测定与控制钻井液的电导率，以便从电测曲线上取得更好的地层特性评价。泡沫钻井液的电导率与密度基本呈线性关系，电导率随密度的升高而变大；磁处理后泡沫钻井液的性质发生明显改变．泡沫钻井液的电导率有不同程度的下降，在磁场强度为100mT、蜂数为2的磁场条件下泡沫钻井液的电导率变化率降低最大，电导率平均下降16％左右。     

Thermal-lens and photo-acoustic methods for the determination of SiC thermal properties

In this paper we report the use of photothermal techniques such as Thermal lens (TL) spectrometry, Photoacoustic and heat capacity, ρc_p, to determine the thermo-optical parameters, such as thermal conductivity (K), thermal diffusivity (D), specific heat (c_p) and the optical path dependence with temperature (ds/dT), of an undoped polycrystalline 3C-SiC. To our knowledge, this is the first time that Thermal lens technique is used for wide band-gap systems. Results obtained for the polycrystalline sample with TL technique indicates that ds/dT is negative at room temperature. Moreover, the obtained values of thermal diffusivity and thermal conductivity are in good agreement with that found in the literature, indicating that the phototermal techniques can be used to obtain the referred parameters in circumstances where other techniques cannot be used, for example, in harsh environments.     

Concurrent effect of microporosity and chemical structure on the equilibrium sorption properties of cellulose-based hydrogels

Polyelectrolite hydrogels are crosslinked polymers which display high sorption capacity in water and water solutions. They are widely used in the marked of personal hygiene products, as well as in other biomedical and industrial applications. In the most industrial application they are not biodegradable and prepared starting from acrylamide.In this work, the chemical-physical analysis of a novel class of natural polymers-based microporous superabsorbent hydrogels has been presented. The main focus is the definition of the relationship between material's chemical-physical structure and its equilibrium sorption properties.The effect of the variation of the degree of crosslinking, the polyelectrolyte nature of the backbone and the hydrogel microporosity on its swelling properties has been analysed, and a good agreement with the theoretical statements has been displayed.The effect of the ionic strength and the pH of the external solution in contact with the hydrogel on its equilibrium sorption properties has also been assessed, and an high sensitivity to these variations was detected for all the tested chemical compositions and physical structures.This work have to be considered part of the efforts towards the reduction of the environmental impact of the large scale consumption industrial polymer based products.