Structure and electrical conductivity of multicomponent metal oxides having scheelite structure

The investigated bismuth vanadate, BiVO₄, bismuth vanadomolybdate, Bi_0.85V_0.55Mo_0.45O₄, and pure bismuth molybdate, Bi₂Mo₃O₁₂, oxides prepared by novel spray drying technique having the scheelite structure were found to be monoclinic in the case of BiVO₄ and Bi₂Mo₃O₁₂, whereas Bi_0.85V_0.55Mo_0.45O₄ is body-centered tetragonal. The distribution of intergranular porosity across polycrystalline samples is inhomogeneous, being larger parallel to the flat compression of the powder samples. The high polarizability of Bi³⁺ cations with their lone-pair electrons influences stability of the disordered oxygen sublattice. All as-prepared systems undergo a slight structural change of the oxygen arrangement during the sample heating in the temperature region of 340–390°C, probably due to an order ⇆ disorder transition, resulting in a decrease of lattice oxygen ion mobility and decrease of electrical conductivity. The total bulk electrical conductivity of both vanadate systems is essentially ionic at low temperatures and high oxygen partial pressures. Diffusion of the lattice oxygen ions in the Bi_1−x/3V_1−x Mo _x O₄ scheelite structure is indirectly related to the introduction of cation vacancies. The highest conductivity was observed in the multicomponent oxide Bi_0.85V_0.55Mo_0.45O₄, both as-prepared and thermally treated. Above 350°C the conductivity of BiVO₄ and partially also Bi_0.85V_0.55Mo_0.45O₄ oxides is affected by the n-type electron contribution. Published in Russian in Elektrokhimiya, 2009, Vol. 45, No. 6, pp. 659–667. The article is published in the original. Published by report at IX Conference “Fundamental Problems of Solid State Ionics”, Chernogolovka, 2008.     

Dielectric properties of ion-exchange beads of sulfonic acid type dispersed in aqueous solutions — effect of fixed charge density

Ion-exchange beads with different densities of fixed charges were prepared by sulfoethylation of dextran gel beads. The relative permittivities and the electrical conductivities of the ion-exchange beads in a sodium form were evaluated by a dielectric technique consisting of the following two procedures proposed in a previous study (2): (a) Dielectric measurements for densely packed sediments of the ion-exchange beads; (b) Analysis of the observed dielectric relaxations by means of a theoretical equation of interfacial polarization for suspensions of spherical particles. The deduced permittivities of the ionexchange beads in equilibrium with water were about 60, which is lower than those of outer aqueous phases. The deduced conductirities were of the order of 1 to 10 mS cm^–1 and were increased reasonably with the fixed charge density. Closer consideration on these deduced values indicates that no specific interaction exists between the counter ions and the fixed charges irrespective of changes in fixed charge density and temperature.     

Polyazomethine with m-tolylazo side groups: thermal,dielectric and conductive behaviour

Using solution polycondensation, a new polyazomethine with m-tolylazo side groups (PAz) exhibiting thermotropic liquid crystalline phase was synthesised and its chemical structure was characterised with generally accepted methods. Its phase transition temperatures were detected with both polarising optical microscopy and differential scanning calorimetry. Using dielectric spectroscopy method, both real and imaginary parts of the permittivity were investigated in wide regions of temperature (from ?100°C to 170°C) and frequency (from 1 Hz to 1 MHz). Analysis of frequency dependent permittivity allowed finding three relaxations (α, β₁ and β₂) in PAz. β-relaxations were described with the Arrhenius equation, whereas α-relaxation was described with the Vogel–Fulcher–Tammann equation. The alternating current conductivity (ACC) of PAz was studied in the same regions of temperature and frequency. The frequency dependent ACC was described with an exponent power equation. Presentation of ACC as a function of inverse temperature allowed us to describe ACC with the Arrhenius equation.     

Electrical Properties of Chain Microstructure Magnetic Emulsions in Magnetic Field

The work deals with the experimental study of the emulsion whose dispersion medium is a magnetic fluid while the disperse phase is formed by a glycerin-water mixture. It is demonstrated that under effect of a magnetic field chain aggregates form from the disperse phase drops. Such emulsion microstructure change affects its macroscopic properties. The emulsion dielectric permeability and specific electrical conductivity have been measured. It is demonstrated that under the effect of relatively weak external magnetic fields (～1 kA/m) the emulsion electrical parameters may change several fold. The work theoretically analyzes the discovered regularities of the emulsion electrical properties.     

Structural peculiarities and electrical properties of multicomponent oxide crystals. Alkali ion conductors

Electrical and dielectric properties of anisotropic, “pure” and rare earth doped, K₅Bi(MoO₄)₄ (KBMO), β-BaB₂O₄ (BBO), and CsLiB₆O₁₀ (CLBO) single crystals are studied. Cationic conductivity by alkali ions is found in these crystals. Anisotropy of their electrical and dielectric properties is examined. Relations between the structure and transport mechanisms are discussed. Published in Russian in Elektrokhimiya, 2009, Vol. 45, No. 6, pp. 679–686. The article is published in the original. Published by report at IX Conference “Fundamental Problems of Solid State Ionics”, Chernogolovka, 2008.     

Dielectric and conductivity processes in poly(ethylene terephthalate) and poly(ethylene naphthalate) homopolymers and copolymers

Electrical relaxation and conductivity processes in amorphous and semicrystalline poly(ethylene terephthalate) (PET) and poly(ethylene naphthalate) (PEN) homopolymers and certain PET/PEN copolymers have been studied by means of dielectric spectroscopy. Homopolymers and copolymers able to crystallize were subjected to successive thermal runs to investigate the influence of the thermal history upon the morphology and the electrical behavior of the polymeric systems. The morphology of the untreated as well as the heat‐treated specimens was determined by means of Differential Scanning Calorimetry (DSC). All samples exhibit β‐relaxation process, due to local motions of the C?O polar side groups, and α‐relaxation process associated to the glass/rubber transition. In the PEN spectrum an additional, subglass, mode was recorded, most probably attributed to cooperative motions of the naphthalene groups. Finally, the dynamic nature of the crystallization process is expressed via the over glass transition mode and the temperature dependence of dc conductivity recorded in amorphous PET, PEN, and PET/PEN (85/15) (wt/wt) samples. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3078–3092, 2006     

Electrical relaxation in in situ dried acid-form nafion

Electrical relaxation studies have been carried out on dried, acid-form Nafion 117 (copolymer of tetrafluoroethylene and perfluoro 3,6-dioxa-4-methyl-7-octenesulfonic acid and which has an equivalent weight of 1100). Significant electrical conductivity is found and the data are found to be non-Arrhenius. The results are converted to the electrical modulus representation and a conductivity relaxation is observed. A stretched exponential is best-fit to the conductivity relaxation and again, non-Arrhenius behavior is observed for the peak position. Finally, at low temperatures, a new dielectric relaxation peak is found which has an activation enthalpy of about 0.57 eV (13 kcal/mol). This relaxation is analogous to the γ-relaxation observed in mechanical relaxation studies. © 1994 John Wiley & Sons, Inc.     

Practical Insights into the Impedance Response of Interdigitated Electrodes: Extraction of Relative Static Permittivity and Electrolytic Conductivity

This work aims to provide a detailed understanding of the challenges related to the computation of the relative static permittivity and electrolytic conductivity of a sample medium from its impedance response recorded with interdigitated electrode (IDE) geometries. Within the scope of the study, impedance data has been measured and evaluated for a total of nine sample media using two distinct IDE geometries. Particular emphasis is laid upon the compensation of parasitic influences affecting the impedance response. With the raw data supporting this study fully disclosed, the reader is offered the opportunity to comprehensively retrace the evaluation procedure proposed in the text.     

Dielectric spectroscopy of unsymmetrical liquid crystal dimers showing wide temperature range TGBA and TGBC* phases

The electrical properties of frustrated twist grain boundary (TGB) phase are a matter of curiosity. Some studies have indicated the existence of soft and Goldstone modes in TGBA and TGBC* phases respectively. However, the experimental results are still not very conclusive. In the present work, we report dielectric studies of wide temperature range TGBA and TGBC* phases of an optically active dimeric compound 4‐n‐decyloxy‐4′‐(cholesteryloxycarbonyl‐1‐butyloxy) chalcone in the frequency range of 1 Hz to 35 MHz for the planar and homeotropic anchoring of the molecules. Two different relaxation processes have been detected for the planar anchoring of molecules in the TGBA and TGBC^* phases. The soft mode like behaviour is obtained due to tilt fluctuation of molecules in the megahertz region for both TGBA and TGBC* phases. Goldstone mode like behaviour due to phase fluctuation of molecules has been detected for the TGBC* phase in the low frequency region (～200–300 Hz). Activation energies for DC conductivity have also been determined for various phases of the material.     

Dielectric properties of quaternary ammonium ion-exchange beads dispersed in aqueous phases

Dielectric measurements were carried out for dense sediments of quaternary ammonium type anion-exchange resin beads dispersed in deionized water over a frequency range of 30 Hz to 130 MHz. According to a method proposed in previous studies the relative permittivities and electrical conductivities of ion-exchange beads were evaluated from the relaxation data observed in a megahertz region on the basis of a theory of interfacial polarization. The permittivities of the ion-exchange beads were found to be unchanged irrespectively of the salt form and somewhat lower than that of a continuous medium, while the conductivities of the ion-exchange beads were characteristic of the salt form. The equivalent ionic conductances of different counter anions in the beads were estimated from the conductivities of the ion-exchange beads. These results indicate an ion-binding effect in the resin beads.     

Efficient Intermolecular Charge Transport in Self-Assembled Fibers of Mono- and Bithiophene Bisurea Compounds

Hydrogen bonds between urea units allow self-organization of π systems in mono- and bithiophenes into fibers as shown schematically. In these fibers there is a surprisingly high mobility of charge carriers as determined by pulse-radiolysis time-resolved microwave conductivity measurements.     

固固相反应合成牛磺酸水杨醛钾与锑、铋的配合物

合成了牛磺酸水杨醛钾,并采用室温固固相反应法合成了牛磺酸水杨醛钾与三氯化锑和三氯化铋的配合物,其组成为:K2MC18H20O8N2S2 (M = Sb, Bi)。两种配合物的晶体结构均属于单斜晶系,锑配合物的晶胞参数为:a = 1.2869 nm, b = 1.7636 nm, c = 1.9917 nm, β= 93.79埃活榕浜衔锏木О问篴 = 1.4770 nm, b = 2.0334 nm, c = 2.0149 nm, β= 94.05。红外光谱表明N、Cl原子参与了配位,中心离子的配位数为5。     

Structure of microemulsions of AOT and water in dodecane

The dielectric properties of the system water/AOT/dodecane are studied as a function of volume fraction of the dispersed phase and molar ration (water/surfactant). Data shows that the spherical model is valid only at lown values or low values. At high concentrations of dispersed phase, one has to consider micellar aggregation or deformation.     

砷、锑、铋类药物的应用历史和现状

近年来,由于对主族元素砷、锑、铋的生物功能研究的不断深入,人们已经从仅仅关注它们对人体的生物毒性到开始研究它们在化学药物领域的应用和潜力。本文简要的介绍了砷、锑、铋作为药物应用的历史,综述了近年来砷、锑、铋的化合物在抗癌、治疗白血病、抗寄生虫病和抗菌方面的一些应用,以及用于发现这些药物的靶分子和结合蛋白的现代生物技术。     

六亚甲基四胺锑(Ⅲ)、铋(Ⅲ)配合物的固相合成与表征

通过固相反应,合成了新的配合物六亚甲基四胺锑(Ⅲ)、铋(Ⅲ):SbCl3(C6H12N4)2·H2O(1)、BiCl3(C6H12N4)2·H2O(2).经元素分析、X 射线粉末衍射、远红外光谱和差热 热重分析进行表征,确定了配合物的组成和结构.对XRD谱指标化,确定其晶系和晶胞参数.SbCl3(C6H12N4)2·H2O(1):a=1.2490nm,b=1.4583nm,c=1.6870nm,β=91.78°,V=3.0706nm3;BiCl3(C6H12N4)2·H2O(2):a=1.3250nm,b=1.3889nm,c=1.7449nm,β=98.94°,V=3.1725nm3.     

Tuning the Charge Transport in Nickel Salicylaldimine Polymers by the Ligand Structure

The conductivity of the polymeric energy storage materials is the key factor limiting their performance. Conductivity of polymeric NiSalen materials, a prospective class of energy storage materials, was found to depend strongly on the length of the bridge between the nitrogen atoms of the ligand. Polymers obtained from the complexes containing C₃ alkyl and hydroxyalkyl bridges showed an electrical conductivity one order of magnitude lower than those derived from more common complexes with C₂ alkyl bridges. The observed difference was studied by means of cyclic voltammetry on interdigitated electrodes and operando spectroelectrochemistry, combined with density functional theory (DFT) calculations.     

Surface morphology and electrical properties of polyurethane nanofiber webs spray‐coated with carbon nanotubes

Multiwalled carbon nanotubes (MWNTs) were spray‐coated on electrospun polyurethane nanofiber webs for electrical conductive application. For the effective coating of MWNTs, hyperbranched polyurethane (HBPU) was used by blending with linear polyurethane, which was synthesized in the A₂ + B₃ approach using poly(ε‐caprolactone)diol, 4,4′‐methylene bis(phenylisocynate), and castor oil. SEM measurements showed that the MWNTs could be coated well along the surface of nanofibers when the HBPU was blended in the linear polyurethane nanofibers. Blending of HBPU in the nanofibers also affected the electrical conductivity of MWNT‐coated nanofiber webs. The low electrical resistance from 20 to 400 Ω/sq was obtained for MWNT‐coated nanofiber webs and their electrical resistance decreased with an increase of spraying frequency. As a potential application of MWNT‐coated nanofiber webs, the electrical heating effect because of applied voltage was demonstrated. Copyright © 2011 John Wiley & Sons, Ltd.     

Block copolymerization of methylmethacrylate via ATRP method using a macroinitiator produced by ring opening polymerization: Characterization,dielectric properties,and a kinetic investigation

Poly(2-(3-methyl-3-phenylcyclobutyloxirane-co-?-caprolactone) [P(PCBO-co-?-CL)] was synthesized by ring opening polymerization (ROP) of 2-(3-methyl-3-phenylcyclobutyloxirane and ?-caprolactone (?-CL) using benzyl alcohol as the initiator and Sn(Oc)₂ as the catalyst. To produce a macroinitiator from copolymer with hydroxyl end group was carried out reaction of acylation with choloroacetyl chloride. The molecular structures of copolymers were confirmed by FT-IR, ¹H-NMR spectroscopies and gel permeation chromatography (GPC). A kinetic series of methyl methacrylate (MMA) via ATRP method were studied in the presence of this macroinitiator and using CuBr/2,2′-bipyridine (bpy) as catalyst at 110°C. The kinetic study showed that the polymerization proceeded in a controlled way up to high conversions and the number-average molecular weight (M_n) increased depending on time. The thermal properties of copolymers were evaluated by TGA and DSC measurements. The temperature and frequency dependence of dielectric constant (?) and dielectric loss factor (?″) of P[(PCBO-co-?-CL)-b-PMMA] and that of doped with different concentration of EuCl₃ were investigated between the frequency of 100–2000 Hz and temperature range (300–430 K). Also, the ac conductivity has been measured to see the effect of frequency and temperature.     

Effect of Crystallization Kinetics on Microstructure and Charge Transport of Polythiophenes

We have examined the effects of crystallization kinetics of poly(3‐hexylthiophene) and poly[2,5‐bis(3‐hexadecylthiophen‐2‐yl)thieno(3,2‐b)thiophene] on microstructure and charge transport. Rapid crystallization increases the density of tie molecules in polythiophenes. As a consequence, ordered regions are better connected resulting in higher charge carrier mobilities. Our results suggest that controlling the crystallization kinetics might be an important factor for maximizing the charge mobility in semicrystalline polythiophene thin films.     

离子液介质中硫化铋单晶纳米棒制备与表征

采用硝酸铋和硫脲为先驱原料，以离子液为反应介质，合成了硫化铋单晶纳米棒。所得产物用X射线粉末衍射、X射线能量色散谱、透射电子显微镜、高分辨电子显微镜、选区电子衍射、扫描电子显微镜、紫外-可见吸收光谱进行了表征。结果表明，在含有乙基硫酸根离子的1-甲基3-乙基咪唑盐的离子液中，160 ℃下回流反应，可以得到结晶良好的硫化铋纳米棒，并对其形成机理进行了探讨。