TSDC spectroscopy of relaxational and interfacial phenomena

Applications of thermally stimulated depolarisation current (TSDC) technique to a variety of systems with different dispersion phases such as disperse and porous metal oxides, polymers, liquid crystals, amorphous and crystalline solids, composites, solid solutions, biomacromolecules, cells, tissues, etc. in gaseous or liquid dispersion media are analysed. The effects of dipolar, direct current (dc) and space charge relaxations are linked to the temperature dependent mobility of molecules, their fragments, protons, anions, and electrons and depend on thermal treatment, temperature and field intensity of polarisation, heating rate on depolarisation or cooling rate on polarisation. Features of the relaxation mechanisms are affected not only by the mentioned factors but also by morphological, structural and chemical characteristics of materials. The interfacial phenomena, especially the role of interfacial water, received significant attention on analysis of the TSDC data. Comparison of the data of TSDC and dielectric relaxation spectroscopy (DRS), differential scanning calorimetry (DSC), 1H NMR spectroscopy with layer-by-layer freezing-out of bulk and interfacial water, adsorption/desorption of nitrogen, water and dissolved organics demonstrates high sensitivity and information content of the TSDC technique, allowing a deeper understanding of interfacial phenomena.     

Electrical properties of polymeric composites based on nanocrystalline tin dioxide modified with copper iodide

Electrical properties of synthesized nanostructured materials based on nanocrystalline tin dioxide modified with copper iodide and polychlorotrifl uoroethylene were studied. It was shown that the complex dielectric permittivity in the microwave range and the low-frequency electrical conductivity of the polymeric composites depend on the copper iodide concentration on the surface of tin dioxide and reach the maximum values at a volume fraction of CuI of about 0.5. The percolation thresholds were determined for the three-component system. Their values increase from 0.04 to 0.05 vol. fraction as the content of copper iodide in the CuI/SnO₂ system is raised from 0.04 to 0.6 vol. fraction.     

Relationships between surface compositions and properties of surfaces of mixed fumed oxides

Fumed oxides SiO₂/Al₂O₃ (SA), SiO₂/TiO₂ (ST) and Al₂O₃/SiO₂/TiO₂ (AST) at different content of alumina and titania were investigated by one-pass temperature-programmed desorption (OPTPD) time-of-flight mass-spectrometry (TOFMS), Auger electron spectroscopy (AES), NMR, FTIR, thermally stimulated depolarization current (TSDC), microcalorimetry, adsorption of nitrogen, water, (dimethylamino)azobenzene (DMAAB) and metal ions (Pb(II) and Ni(II)). It was shown that all the studied adsorption/desorption and energetic properties of mixed fumed oxides depend strongly on the surface content of alumina (shown as a surface content of aluminum, ) in SA and AST and titania (shown as a surface content of titanium, ) in ST and AST. Many of these properties demonstrate clear correlations with the and values over the total range of alumina and titania content in the materials.     

Synthesis and properties of magnetite-poly(aminopropylsiloxane) composites

A method is developed for the synthesis of nanosized Fe₃O₄-(SiO₂) _x [NH₂(CH₂)₃SiO_3/2] _y magnetic composites with varied SiO₂: NH₂(CH₂)₃SiO_3/2, weight/weight, ratios. The structure, texture, morphology, and magnetic properties of the obtained materials are studied by several physicochemical methods. It is shown that the composites represent systems of magnetite nanoparticles coated with poly(aminopropylsiloxane). The specific surface areas, pore volumes, and saturation magnetizations of the composites are in the ranges of 21–27 m²/g, 0.03–0.04 cm³/g, and 59–62 G cm³/g, respectively.     

Surface electric and titration behaviour of fumed oxides

Adsorption of Pb(II), Sr(II), and Cs(I) on fumed silica, alumina, titania, silica/titania (ST), silica/alumina (SA), and alumina/silica/titania (AST) reveals that mixed oxides containing titania have a greater adsorptive capability in respect to metal cations than individual and SA oxides. Pyrocarbon deposits on fumed oxides enhance the adsorption of metal ions. Calculations of electrophoretic potential (ζ) with consideration for the porosity of aggregates of primary particles of AST show a significant influence of surface alumina (at pH<8) and titania and silica (at pH>8) on the ζ values. The effective diameter of particles (D_ef) of fumed oxides in aqueous media depends on pH for AST stronger than for ST (between isoelectric points (IEPs) of titania and alumina). A significant difference in the pH values of IEP and point of zero charge is observed for AST samples. A pyrocarbon influence on the ζ potential depends on the type of oxide matrix, since ζ increases for certain samples but for others it decreases. These changes depend nonlinearly on pH as well as the secondary particle size distributions (SPSDs) and D_ef.     

Morphology and surface properties of fumed silicas

Several series of fumed silicas and mixed fumed oxides produced and treated under different conditions were studied in gaseous and liquid media using nitrogen and water adsorption-desorption, mass spectrometry, FTIR, NMR, thermally stimulated depolarization current (TSDC), photon correlation spectroscopy (PCS), zeta potential, potentiometric titration, and Auger electron spectroscopy methods. Aggregation of primary particles and adsorption capacity (Vp) decrease and hysteresis loops of nitrogen adsorption-desorption isotherms becomes shorter with decreasing specific surface area (S(BET)). However, the shape of nitrogen adsorption-desorption isotherms can be assigned to the same type independent of S(BET) value. The main maximum of pore size distribution (gaps between primary nonporous particles in aggregates and agglomerates) shifts toward larger pore size and its intensity decreases with decreasing S(BET) value. The water adsorption increases with increasing S(BET) value; however, the opposite effect is observed for the content of surface hydroxyls (in mmol/m2). Associative desorption of water (2(SiOH)-->SiOSi+H2O) depends on both the morphology and synthesis conditions of fumed silica. The silica dissolution rate increases with increasing S(BET) and pH values. However, surface charge density and the modulus of zeta-potential increase with decreasing S(BET) value. The PCS, 1H NMR, and TSDC spectra demonstrate rearrangement of the fumed silica dispersion depending on the S(BET) value and the silica concentration (C(SiO2)) in the aqueous suspensions. A specific state of the dispersion is observed at the C(SiO2) values corresponding to the bulk density of the initial silica powder.     

Cryosynthesis of single-domain magnetite particles

The technique of low temperature synthesis of single-domain magnetite particles at the solid-liquid phase boundary was developed. Spherical magnetite particles 6–50 nm in size were obtained. The phase structure, elemental composition and morphology of the particles were studied using X-ray phase analysis, Auger spectroscopy, and scanning electron and atomic force microscopy.     

Thermal Behavior of Dispersed Vanadium Dioxide Particles in Polyethylene Glycol Matrix Containing Tetraethylammonium Bromide

A study has been made on samples of dispersed vanadium dioxide (VO₂) in a matrix of polyethylene glycol (PEG) doped with a quaternary ammonium salt (QAS), namely tetraethylammonium bromide. It has been established that under the influence of the dopant the heating of a sample up to the temperature of the metal-semiconductor phase transition (MSPT) results in a phase in homogeneity of the sample. On the basis of the results of this study it is possible to conclude that small concentrations of QAS in a PEG matrix can exert a strong effect on the electronic structure of dispersed VO₂ particles. This is accompanied by the appearance of phase heterogeneity of VO₂ which manifests itself in the fact that - with the onset of MSPT with increasing temperature - one portion of the substance passes into the metallic state, and the other remains in the semiconductive state. This revised version was published online in August 2006 with corrections to the Cover Date.     

Use of a fluorine-containing solvent in the synthesis of YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>7 − δ</Subscript> single crystals

A laboratory technological procedure has been developed for the synthesis of high-temperature superconducting YBa₂Cu₃O_{7 ? δ} single crystals (T _c ～ 90 K, ΔT _c ～ 1.0 K) up to 0.25 cm² in size from a nonstoichiometric fluorine-containing flux of (YO_1.5)(BaO)_{4 ? x}(BaF₂)_x(CuO)₁₀, where 2 ≥ x ≥ 0, using a combination of enhanced nucleation and directional crystallization by the Czochralski method. Studies using differential thermal analysis demonstrated that the addition of BaF₂ decreased the eutectic-crystallization temperature and increased the crystal-growth rate. The optimum concentration of BaF₂ in the starting melt composition was found (x = 0.2). The single-crystal surface was studied by atomic-force nanoscopy. The morphology of single crystals that have been synthesized from a melt of their own components differs substantially from that of crystals grown from a BaF₂-containing melt.