Influence of iron ions on the structural properties of Zn-borosilicate glasses

The effects of iron on the structural properties of Zn-borosilicate glasses have been studied using X-ray diffraction, IR spectroscopy and⁵⁷Fe Mössbauer spectroscopy. Zn-borosilicate glasses were doped with α?Fe₂O₃. In the systems Na₂O?ZnO?B₂O₃?SiO₂?Fe₂O₃ the presence of only one crystalline phase, ZnFe₂O₄, was detected. X-ray diffraction showed that crystallization is more pronounced in the systems ZnO?B₂O₃?SiO₂?Fe₂O₃. In these systems the presence of different crystalline phases, such as ZnO, γ?Fe₂O₃, Fe₃O₄, ZnFe₂O₄ and Fe₃BO₅, was detected. The crystallization of α?Zn₂SiO₄ in the system ZnO?B₂O₃?SiO₂ was confirmed by X-ray diffraction and IR spectroscopy. The valence state and coordination of iron in Zn-borosilicate glasses were determined by⁵⁷Fe Mössbauer spectroscopy.     

Influence of iron ions on the structural properties of some inorganic glasses

The effects of iron on the structural properties of Zn-borosilicate glass and Pb-metaphosphate glass were studied using X-ray diffraction,⁵⁷Fe Mössbauer spectroscopy and IR spectroscopy. Zn-borosilicate glass was prepared with varying amounts of Fe₂O₃ (up to 30% wt.). It was found that the chemical form of added iron (-FeOOH, -Fe₂O₃ or Fe₃O₄) affects the Fe³⁺/Fe²⁺ ratio, as well as the distribution of iron ions at different coordination sites. At high concentration of iron the crystallization of zinc ferrite in the glass matrix takes place. X-ray diffraction and⁵⁷Fe Mössbauer spectroscopy showed that the amount of zinc ferrite in Zn-borosilicate glass decreases with the following order of addition: -FeOOH-Fe₂O₃Fe₃O₄. In Pb-metaphosphate glass doped with high concentration of -Fe₂O₃, the crystallization of Fe₃(PO₄)₂ is pronounced. The assignments of IR band positions and the corresponding interpretation are given. The importance of this study for the technology of vitrification of high-level radioactive wastes is emphasized.     

Influence of the oxide matrix on the electronic state of vanadium ions

ESCA spectra of V₂O₅, V₂O₅/TiO₂ and V₂O₅ dissolved in TiO₂ were recorded after oxidation and reduction. V⁴⁺ ions have the same effective charge in reduced V₂O₅ and in TiO₂, whereas the effective charge of V⁵⁺ ions in TiO₂ is higher than in V₂O₅, indicating enhanced electron acceptor properties.

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V₂O₅, V₂O₅ TiO₂ V₂O₅ TiO₂ . , V⁺⁴ V₂O₅ TiO₂ V⁺⁵ TiO₂ V₂O₅, .

     

Redox properties of vanadium ions in SBA-15-supported vanadium oxide: an FTIR spectroscopic study

The state of vanadium ions in VxOy/SBA-15 (2.7 wt % V) was studied with FTIR spectroscopy using CO and NO as probe molecules. Neither CO (at 85 K) nor NO (at RT) adsorb on the oxidized sample because of the coordinative saturation of V5+ ions and the covalent character of the V5+=O bond. After treatment of the sample in 50 kPa H2 at 673 K, the V5+ ions are reduced to two different types of V3+ sites, as manifested by carbonyl bands at 2189 and 2177 cm-1. In the presence of O2 at 85 K, thus formed V3+ ions are partly oxidized to V4+ sites showing carbonylic bands at 2202 and 2190 cm-1. When the reduced sample is exposed to O2 at room temperature, the V3+ ions are fully oxidized to V5+. The adsorption of NO on the reduced VxOy/SBA-15 shows that the V3+ and V4+ ions possess two effective coordinative vacancies and as a result can adsorb two NO molecules forming the respective V3+(NO)2 and V4+(NO)2 dinitrosyls. The introduction of O2 to the VxOy/SBA-15-NO system leads to reoxidation of the V3+ and V4+ ions to V5+ and formation of bridged (1639 cm-1) and bidentate (1573 cm-1) surface nitrates. After coadsorption of CO and NO on the reduced sample the formation of surface mixed carbonyl-nitrosyls (2108 and 1723 cm-1) was observed for the first time.     

A kinetic study of the reactions of vanadium, iron, and cobalt with sulfur dioxide

A kinetic study of the reactions of ground state V, Fe, and Co with SO2 is reported. V, Fe, and Co were produced by the 248 nm photodissociation of VCl4, ferrocene, and Co(C5H5)(CO)2, respectively, and were detected by laser-induced fluorescence. V + SO2 proceeds by an abstraction reaction with rate constants given by k=(2.33 +/- 0.57)x 10(-10) exp[-(1.14 +/- 0.19) kcal mol(-1)/RT] cm3 molecule(-1) s(-1) over the temperature range 296-571 K. Fe + SO2 was studied in the N2 buffer range of 10-185 Torr between 294 and 498 K. The limiting, low-pressure third-order rate constants are given by k(0)=(3.45 +/- 1.19)x 10(-30) exp[-(2.81 +/- 0.24) kcal mol(-1)/RT] cm6 molecule(-2) s(-1). Co + SO2 was studied in the CO2 buffer range of 5-40 Torr between 294 and 498 K. This reaction is independent of temperature over the indicated range and has a third-order rate constant of k0=(5.23 +/- 0.28)x 10(-31) cm6 molecule(-2) s(-1). Results of this work are compared to previous work on the Sc, Ti, Cr, Mn, and Ni + SO2 systems. The reaction efficiencies for the abstraction reactions depend on the ionization energies of the transition metal atoms and on the reaction exothermicities, and the reaction efficiencies of the association reactions are strongly dependent on the energies needed to promote an electron from a 4s2 configuration to a 4s1 configuration.     

Influence of F‐ doping on the microstructure,surface morphology and electrochemical properties of the lead dioxide electrode

The lead dioxide electrode (PbO₂) with Ti substrate and SnO₂‐Sb₂O₅ intermediate layer was doped by F^‐ ion through the potentiostatic anode co‐deposition method. The content of F in the coating can be controlled by adjusting deposition potential. The effect of F^‐ doping on the composition, surface morphology and electrochemical properties of the PbO₂ electrode was characterized by X‐ray diffraction, scanning electron microscope, X‐ray photoelectron spectroscopy and electrochemical measurement methods. The results have confirmed that the content of β‐PbO₂ increases with increasing that of F, and the doping can make the β‐PbO₂ grains become fine and the electrode surface become smooth; the specific surface areas and conductivity increase, and the initial potential of oxygen evolution shifts toward positive direction compared with the free‐doped PbO₂ electrode; the oxygen evolution potential increases with the increasing of the F^‐content in the PbO₂ film electrode. The bulk electrolysis result demonstrated that the performances of the F‐PbO₂ electrode for anodic oxidation aniline have been improved to some extent. Copyright © 2012 John Wiley & Sons, Ltd.     

New extended magnetic systems based on oxalate and iron(III) ions

A series of oxalate-bridged iron(III) complexes have been synthesized by the reaction of FeCl 3 with oxalic acid (H 2ox) and XCl, where X is a substituted univalent ammonium or an alkaline cation. We have obtained basically two different types of compounds by varying the nature and the shape of the counterion, with the dimensionality of the resulting product being strongly influenced by the counterion. Three-dimensional (3D) networks of oxo- and oxalato-bridged iron(III) ions of the general formula {X 2[Fe 2O(ox) 2Cl 2]. pH 2O} n have been obtained for X = Li (+) ( 1), Na (+) ( 2), and K (+) ( 3) with p = 4 and X = MeNH 3 (+) ( 4), Me 2NH 2 (+) ( 5), and EtNH 3 (+) ( 6) with p = 2. Similar 3D hydroxo- and oxalato-bridged iron(III) networks of the formula {X[Fe 2(OH)(ox) 2Cl 2].2H 2O} n resulted for X = EtNH 3 (+) ( 7a) and PrNH 3 (+) ( 8). Compound 7a undergoes a solid-to-solid transformation, leading to a new species of the formula {(H 3O)(EtNH 3)[Fe 2O(ox) 2Cl 2].H 2O} n ( 7b). Chainlike compounds of the formula {X 2[Fe 2(ox) 2Cl 4]. pH 2O} n [X = Me 2NH 2 (+)( 9, p = 1), Me 3NH (+) ( 10, p = 2), and Me 4N (+) ( 11, p = 0)] have been obtained for the bulkier alkylammonium cations. Magnetic susceptibility measurements in the temperature range 1.9-295 K show the occurrence of weak ferromagnetic ordering due to spin canting in the 3D networks 1- 8, with the value of the critical temperature ( T c) varying with the cation in the range 26 K ( 2) to 70 K ( 8) without significant structural modifications. The last three one-dimensional compounds exhibit the typical behavior of antiferromagnetically coupled chains of interacting spin sextets [ J = -8.3 ( 9), -6.9 ( 10), and -8.4 ( 11) cm (-1) with H = - J summation operator i S i S i+1 ].     

Effects of iron,bismuth, and vanadium oxides on the properties of cordierite ceramics

The effects of iron oxide (10%), bismuth oxide (2.2%), and vanadium oxide (1.6%) admixtures on the physicochemical properties of cordierite ceramics are reported, including the phase composition, surface features, porous structure, and activity in ammonia oxidation. The formation of the cordierite phase is favored by introducing the oxide modifiers, by raising the heat treatment temperature, and by extending the heating time. The introduction of V₂O₅ affords well-crystallized cordierite with a small specific surface area and a large proportion of macropores. The oxide modifiers markedly enhance the ammonia oxidation activity and nitrogen oxide selectivity of the cordierite ceramics.     

Influence of DS of CMC on morphology and performance of magnetic microcapsules

In this paper, we present a reproducible method for the preparation of mixed colloidal nanoparticles, consisting of a magnetic Fe₃O₄ nanoparticle nucleus and a biocompatible self-assembly shell of substitution of sodium carboxy methyl cellulose and chitosan in different degree. The heterogeneous structure of the particles can confer them both the possibility of being used as drug delivery systems and the responsiveness to external magnetic fields, allowing a selective guidance of drug molecules to specific target tissues without a concurrent increase in its level in healthy tissues. The preparation method is based on a coordination and layers by layers self-assembly process. In order to specify that A complete physicochemical characterization of the composite particles is carried out, in order to use this preliminary investigation to show that the CMC/CS shell efficiently coating Fe₃O₄ nanoparticles, and leading to composite particles, the magnetic behavior of the core/shell particles is similar to that of bare magnetic Fe₃O₄ nanoparticles. It is observed that The magnetic microspheres with CMC DS 1.05 served as shell show the best dispersion, super paramagnetic, the range of magnetic field the particles can respond is an order of magnitude higher than others, and the specific saturation magnetization intensity is the highest. Thus we can indicate with the conclusion that if the DS of CMC becomes higher, the Fe₃O₄@CS/CMC would be more sensitive with the extant magnetic field. However, when the DS of CMC is higher than 1.1, the specific saturation magnetization intensity of magnetic microspheres would fall down again and the geometry becomes not well. Therefore, when the DS of CMC stay in 1.05, it would be a better material of magnetic microsphere.     

Influence of lignin on cellulose-NaOH-water mixtures properties and on Aerocellulose morphology

Microcrystalline cellulose and organosolv lignin, both dissolved in 8%NaOH-water, were mixed with the objective to study the influence of lignin on the properties of cellulose solutions and on the morphology of dry porous materials. Mixture viscosity and gelation were investigated. Cellulose-lignin gels were regenerated in aqueous acid baths and dried under supercritical CO₂ to obtain Aerocellulose, an aerogel-like material. The presence of lignin in the mixture speeded up gelation. During regeneration part of lignin was washed out. This created large pores and channels in the dry materials. The overall results obtained showed that cellulose and lignin are not compatible in the solvent used.     

Crystal growth,structural and electrical properties of rubidium and cesium vanadium oxide bronzes

Crystals of the following compounds were grown by cathodic reduction of CsV⁵⁺O or RbV⁵⁺O metls: Cs_0.3V₂O₅ (A), Cs₂V₅O₁₃ (B), CsV₂O₅ (C), Rb_0.4V₂O₅ (D), Rb_0.37V₂O_∼4.8 (E) (a new orthorhombic compound) and Rb_2−xV_3+2xO_8+2x (F). The crystal symmetry and cell parameters of the Rb compounds (which were known for F only) were determined, as well as those of Rb_0.3V₂O₅, which has the structure of A. Magnetic susceptibility and ESR measurements confirm the intermediate valence in E. A, C, and E are semiconductors with activation energies in the range 0.07–0.2 eV. Cs_0.3V₂O₅ (A), in which V⁴⁺ and V⁵⁺ do not occupy distinct crystallographic sites, has the highest electrical conductivity.     

Synthesis and magnetic properties of two-dimensional vanadium(IV) oxide nanostructures on silica surface

Vanadium(IV) oxide nanolayers on silica surface were prepared for the first time. Samples characterized by different degrees of surface coverage by vanadium(IV)-oxygen groups were studied. Samples containing only vanadium(IV) ions and both vanadium(IV) and vanadium(V) ions were obtained. The size effect on the phase transition parameters was determined by studying magnetic properties of vanadium(IV) oxide nanolayers. The phase transition temperature ranges from 140 to 220 K, depending on surface concentration of vanadium(IV) ions and their environment.     

Investigations on structural,electrical and magnetic properties of nickel substituted La-ferrites

Nanocrystalline nickel substituted La-ferrites, LaNi_xFe_1−xO₃ (where x = 0, 0.2, 0.4, 0.6 and 1.0) were synthesized by sol–gel autocombustion method. X-ray diffraction (XRD) technique was used to confirm the phase formation. The lattice parameter (a) decreases with increase of Ni content. The surface morphology and elemental analysis of the samples were studied by using scanning electron microscopy (SEM) and energy dispersive X-ray spectrometer (EDS). The electrical properties of the samples were measured by two-probe method. The hysteresis parameters viz. saturation magnetization (M_s), coercivity (H_C) and remanence (M_r) are reported as a function of nickel content. The substitution of nickel plays an important role in changing the structural, electrical and magnetic properties of La-ferrites.     

Synthesis, morphology, and magnetic characterization of iron oxide nanowires and nanotubes

We have explored the synthesis of iron oxide particles, tubes, and fibrils within the pores of nanoporous polycarbonate and alumina membranes. The membranes contain uniformly distributed cylindrical pores with monodispersed diameters (varying between 20 and 200 nm) and thicknesses of 6 and 60 microm, respectively. By hydrolysis and polymerization of iron salts, particles of different sizes and phases were formed in the pores, building iron oxide particle nanowires. Alternatively, by the sol-gel technique, using as reagents metalloorganic compounds, fibrils and tubes of different iron oxide phases were prepared. Structural and morphological investigations performed using scanning electron microscopy and transmission electron microscopy revealed ordered iron oxide particle wires, tubes, and fibrils formed inside the membrane nanopores. Magnetic characterization was accomplished with a vibrating sample magnetometer. Below the blocking temperature (T(B)), the magnetic behavior of the nanowires was governed by dipolar interaction between nearest-neighbor nanoparticles inside the pore, whereas the energy barrier, and therefore the T(B) value, was mainly governed by dipolar interaction between magnetic moments over larger (interpore) distances. As expected, crystalline iron oxide nanotubes exhibited magnetic perpendicular anisotropy due to their magnetocrystalline and shape anisotropy.     

The determination of cobalt,iron plus vanadium or manganese in soft magnetic alloys

A convenient ion exchange separation particularly designed for the separation of iron and vanadium or mangenese from cobalt has been developed for the determination of iron, cobalt and manganese or vanadium in soft magnetic alloys. After an anion exchange separation of their chloride complexes these elements are determined by a back titration of an excess of EDTA with a standard copper solution using calcein as an indicator under ultraviolet light.     

Influence of metal ions on the structures of Keggin polyoxometalate-based solids: Hydrothermal syntheses, crystal structures and magnetic properties

Three new Keggin polyoxometalate (POM)-based compounds linked to 3d metal complexes have been synthesized under hydrothermal conditions: [Cu(phen)₂]₂{[Cu(phen)]₂ [SiMo₁₂O₄₀(VO)₂]} (1), {[Zn(phen)₂]₂[GeMo₁₂O₄₀(VO)₂]}{[Zn(phen)₂(H₂O)]₂ [GeMo₁₂O₄₀(VO)₂]}·3H₂O (2) and {[Co(phen)₂]₂[PMo₁₂O₄₀(VO)₂]}{[Co(phen)₂(OH)]₂ [PMo₁₂O₄₀(VO)₂]}·2.5H₂O (3) (phen=1,10-phenanthroline). These three compounds present, as building blocks, the bicapped Keggin anions [XMo₁₂O₄₀(VO)₂] (X=Si, Ge and P). Compound 1 consists of a bicapped Keggin anion [SiMo₁₂O₄₀(VO)₂]²⁻ linked to two [Cu(phen)]⁺ complexes with two [Cu(phen)₂]⁺ countercations. Compound 2 contains two bicapped Keggin anions [GeMo₁₂O₄₀(VO)₂]⁴⁻, one linked to two [Zn(phen)₂(H₂O)]²⁺ cations and the other one linked to two [Zn(phen)₂]²⁺ cations. Compound 3 is a two-dimensional POM-based square network formed by bicapped Keggin anions [PMo₁₂O₄₀(VO)₂]⁴⁻ connected by [Co(phen)₂]²⁺ cations. Discrete bicapped Keggin anions [PMo₁₂O₄₀(VO)₂] linked to two [Co(phen)₂(OH)]⁺ cations are located between the layers. The magnetic properties show the presence of antiferromagnetic interactions among the reduced Mo(V) atoms (in the three compounds) plus a paramagnetic contribution from the V(IV) atoms (in 1 and 2). Compound 3 shows, in addition, an antiferromagnetic interaction between the Co(II) and the V(IV) ions directly linked through an oxygen bridge. The low-temperature ESR spectra of compound 3 confirm the presence of the reduced Mo(V) ions and the antiferromagnetic coupling between the Co(II) and the V(IV) ions.     

The electrokinetic properties of colloidal magnetic iron oxides

A novel electrokinetic streaming potential technique has been used to determine the ζ potential behavior of three magnetic iron oxides, (Fe(3)O(4), γ-Fe(2)O(3), and CoFe(2)O(4)) as a function of pH and salt concentration. These colloidal materials, (nanosize in one dimension), are held in the form of a plug by means of external magnets. The streaming potential (E) is measured as a function of fluid flow induced by a pressure drop (ΔP) across the plug. The magnetically held plug is found to obey the requirements of the streaming potential technique; in each case an iso-electric point, (iep) independent of salt concentration is observed. However, if one uses the appropriate quantities in the standard formula, the calculated ζ potentials are very much lower than for oxides such as silica, alumina or goethite and other colloidal oxide, latex, etc. particulates in aqueous salt solutions. Furthermore, at a given pH, the measured ζ potentials anomalously increase in magnitude rather than decrease as observed conventionally as the salt concentration is increased. This apparent anomalous behavior could not be eliminated by incorporating surface conductance effects. However by including a conductance pathway, independent of pH or salt concentration, through the magnetic particle network itself, the anomaly was removed. Confirmation of the role of a conductance pathway through the magnetic particle network was obtained by using silica coated magnetic particles which displayed normal electrokinetic behavior. Finally, we have redesigned the plug-electrode assembly to allow measurement of streaming current, a technique know to eliminate contributions from plug network conductances of any kind. The resulting ζ potentials, derived from this streaming current technique are normal.