Aminoguanidinium closo-Borates and Their Reactions with Copper(II) Salts in Aqueous Solutions

Aminoguanidinium hexa-, deca-, and dodecaborates of (AguH)₂B _n H _n · xH₂O (Agu = (CN₄H₆), n= 6, 10, 12; x= 1, 2) composition were synthesized and studied by elemental analysis, magnetic susceptibility, and IR spectroscopy methods. Their reactions with copper(II) salts in aqueous solutions were investigated. A cation–anion interaction was shown to occur in aminoguanidinium closo-borates and to increase in the series B₁₂< B₁₀< B₆. Depending on the closo-anion (B _n H^2– _n ), the reactions of aminoguanidinium closo-borates with copper(II) salts in aqueous solutions yield either complex compounds (n= 10, 12) or metallic copper (n= 6).     

Crystal Structure and Properties of Strontium Phosphate Apatite with Oxocuprate Ions in Hexagonal Channels

Strontium phosphate apatites containing different amounts of copper were prepared by a solid state reaction at 1100 °C or by arc melting above 1600 °C in air. The samples were characterized by X‐ray diffraction, ICP analysis, scanning electron microscopy, IR spectroscopy, MAS—¹H—NMR, diffuse reflectance spectroscopy, and SQUID magnetometry. X‐ray crystal structure determination was carried out for a single crystal obtained from the melt. The compound is formulated as Sr₅(PO₄)₃(CuO₂)_1/3 and has an apatite structure (space group P6₃/m, a = 9.7815(4)Å, c = 7.3018(4)Å, Z = 2) with linear CuO₂^3— ions occupying hexagonal channels. For solid state synthesized samples, Rietveld refinement of powder XRD patterns was performed. The samples obtained at 1100 °C acquire the composition Sr₅(PO₄)₃Cu_xOH_y, with x changing from 0.01 to 0.62 and y < 1—x. The copper content can be increased to x = 0.85 by annealing in argon at 950 °C. The compounds represent a hydroxyapatite in which part of the protons is substituted by Cu⁺ and Cu²⁺ ions. The ions form linear O—Cu—O units which are progressively condensed creating the Cu—O—Cu bridges on increasing copper content. IR and NMR data testify existence of OH groups, non‐disturbed and disturbed by neighboring Cu atoms. In the electron spectra, the samples exhibit absorption bands at 7800‐7900, 14200‐14500 and 17500‐17550 cm^—1, which were assigned to Cu²⁺ d‐electron transitions. By annealing the sample with x = 0.1 in oxygen at 800 °C copper is fully oxidized while retaining in channels in unusual for Cu²⁺ linear coordination.     

Sol-gel prepared copper doped SiO2 glasses

SiO₂ glasses doped with nano-sized copper particles were prepared through sol-gel method. Samples with nominal composition xCu–(1–x)SiO₂ (x=0.02, 0.05, 0.1, 0.2, 0.4) were prepared by hydrolyzing tetraethylorthosilicate with various amounts of Cu(NO₃)₂. The dried gels were heat treated at 400, 500, 600, 700°C for 10 hrs under flowing 5% H₂-95% N₂ mixture gas to reduce Cu⁺² ions to metallic copper. The amorphous nature of the SiO₂ matrix was confirmed by powder X-ray diffraction. The size of particulate copper metal, which was determined by transmission electron microscopy, increases with the temperature of heat treatment and the copper content. The local structure of SiO₂ matrix was probed by FTIR. The silica matrix has no major structural change for gels heat treated at different temperatures and with different copper contents.     

Phase equilibria and isomorphism in the LiVWO<Subscript>6</Subscript>-NaVWO<Subscript>6</Subscript> system

Compounds of composition Li _x Na_{1 − x} VWO₆ (0 ≤ x ≤ 1), which are synthetic analogues of brannerite-type minerals, were produced for the first time by solid-state synthesis at high temperatures. The structure of the compounds and their unlimited miscibility in the solid phase in the LiVWO₆-NaVWO₆ binary system were determined by X-ray diffraction. The phase equilibrium diagram was studied by differential thermal analysis together with thermodynamic modeling. It was found that the system under investigation is described by the regular solid solutions model.     

Sol-Gel Synthesis Route for the Preparation of Y(Ba1−x Sr x )2Cu4O8 Superconducting Oxides

Superconducting oxide ceramics of composition Y(Ba_1–x Sr _x )₂Cu₄O₈ (x = 0.00, 0.10, and 0.20) have been prepared by a simple sol-gel method based on the complexation of metal ions in aqueous medium, by chelating acetate and tartarate ligands. Homogeneous sols were obtained by complexing copper ions with tartaric acid, which prevented the flocculation of copper acetate during the gelation process. Single-phase bulk samples were obtained after firing the mixed-metal polymeric acetate-tartarate precursor to 835°C for 70 h in flowing oxygen atmosphere. Thermal decomposition of the gels was studied by thermogravimetry. Effect of strontium substitution on the properties of the compounds was studied by X-ray powder diffraction, electron microscopy, X-ray photoemission spectroscopy and resistivity measurements. These data indicate that nearly monophasic Y(Ba_1–x Sr _x )₂Cu₄O₈ superconducting samples were obtained for x < 0.30. The Sr-doping in the YBa₂Cu₄O₈ (Y-124) phase shows a pronounced effect on the superconducting properties enhancing the critical temperature from 78 K (for the non-substituted sample) to 88 K (for Y(Ba_1–x Sr _x )₂Cu₄O₈).     

Nuclearity Control in Molecular Copper Phosphates Derived from a Bulky Arylphosphate: Synthesis,Structural and Magnetic Studies

Starting from sterically encumbered 2,6-di-tert-butylphenyl phosphate (dtbppH₂) and co-ligand 3,5-dimethyl pyrazole (dmpz), it is possible to isolate either mono-, di- or tetranuclear copper phosphates by varying the copper source and making attendant changes in the reaction conditions. For example, reaction of copper nitrate with dtbppH₂ and dmpz at 60 °C leads to the isolation of the mononuclear copper phosphate [Cu(dtbppH)₂(dmpz)(MeOH)₂] ( 1 ) as the only product. However, the use of copper acetate in place of copper nitrate and conducting the reaction at the room temperature leads to the formation of both dinuclear [Cu(dtbpp)(dmpz)₂]₂ ( 2 ) and tetranuclear [Cu₂(dtbpp)(dmpz)₂(OAc)(MeO)]₂ ( 3 ) from the same reaction mixture. Compounds 2 and 3 could be isolated in pure form through fractional crystallization. Copper phosphates 1 – 3 have been characterized by both analytical and spectroscopic methods including EPR and magnetic measurements. The molecular structures of all three compounds were established through single crystal diffraction studies. Dc magnetic measurements indicate antiferromagnetic interactions between the metal centres in all the compounds.     

Solid state reaction synthesis of filled skutterudite compounds (Ce or Y)yFexCo4-xSb12 and the effect of filling atoms Ce or Y on lattice thermal conductivity

The synthesis of filled skutterudite compounds (Ce or Y)yFexCo₄-xSb12, through a solid state reaction using chloride of Ce or Y, high purity powder of Co, Fe, and Sb as starting materials, was investigated. (Ce or Y)yFexCo₄-xSb12 (x = 0 1.0,y = 0 0.15) compounds were obtained at 850 1 123 K. The results of Rietveld analysis demonstrate that (Ce or Y)yFexCo₄-xSb12 synthesized by a solid state reaction possesses a filled skutterudite structure. The filling fraction of Ce or Y obtained by Rietveld analysis agrees well with the composition obtained by chemical analysis. The lattice constant of CeyFexCo₄-xSb12 increases with increasing substitution of Fe at Co sites, and with an increasing Ce filling fraction in the Sb-dodecahedron voids. The lattice thermal conductivity of (Ce or Y)yFexCo₄-xSb12 decreases significantly with an increasing Ce or Y filling fraction in the voids and with substitution of Fe at Co sites.     

Comparison of the efficacy of sulfurization agents in decreasing the sheet resistance of polyamide and polyethylene with copper sulfide layers and influence of their compositions

The process of obtaining semiconductive and electrical conductive layers of copper sulfides by the sorption — diffusion method on polymers (polyamide 6 and low density polyethylene) using solutions of potassium pentathionate, K₂S₅O₆, and higher polythionic acids, H₂S _n O₆ (n = 21, 33), was investigated. The layers were characterized for compositional and electrical properties by X-ray diffraction (XRD) analysis and sheet resistance measurements. The thickness of copper sulfides layers on polyamide and polyethylene increased with increasing time of polymer sulfurization and varied from 10 to 43 μm. The variations of the sheet resistance of copper sulfides layers formed on the surface of polymers on sulfurization agent used, the conditions of sulfurization, chemical and phase composition of the obtained layers were established. Sheet resistance of copper sulfides layers decreases with increasing time of the duration of sulfurization and the number of sulfur atoms in the polythionate anion. The sheet resistance values for copper sulfide layers formed on the polyamide surface are much lower than those of Cu _x S formed on the polyethylene surface. XRD showed the predomination of Cu _x S phases with low x values.      

Synthesis and Structure Analysis of Aurivillius Phases Pb1‐xBi4‐+Ti1‐xMnxO15

Synthesis Pb_1‐xBi_4+xTi_4‐xMn_xO₁₅ compounds (0 ≤ × ≤ 1) were carried out by molten salts method using eutectic mixture of Na₂SO₄/K₂SO₄ salts (1:1 molar ratio) as the flux. The samples were characterized by X‐ray powder diffraction and refined by Le Bail method using Rietica program. The refinement results revealed that the compounds with the composition 0 ≤ x ≤ 0.6 formed Aurivillius phase with the space group A2₁am while the other composition (x ≥ 0.8) showed another phase beside A2₁am. The ratio b/a of the lattices constants for all the samples are larger than 1 indicating the direction of the orthorhombic along the b axis of their cells. The lattice parameters and volume of the unit cells decrease as the Mn content increasing from x = 0 to 0.6, for x ≥ 0.8 a second phase were observed. The morphologies of Pb_1‐xBi_4+xTi_4‐xMn_xO₁₅ samples were observed by SEM and show plate‐like aggregate crystals, typical of layered compounds belonging to the Aurivillius phase.     

Synthesis and complex investigation of potassium ammonium hexafluorozirconates: I. Synthesis and X-ray diffraction study of K2-x (NH4)xZrF6 (0 < x < 2) crystals

The synthesis and X-ray diffraction study of compounds K_2-x (NH₄)xZrF₆ (0 < x < 2) were carried out. In all crystals of mixed composition, potassium cations are isomorphously replaced by ammonium cations. The compounds with x < 0.5 are isostructural to K₂ZrF₆ and those with x > 1.5, to (NH₄)₂ZrF₆. At 0.5 < x < 1.5, the structures are built of linear polymeric chains formed by edge-sharing Zr dodecahedra. The distribution of potassium and ammonium cations over the cationic positions was considered.     

Thermochemical study of sorption of pyridine derivates by copper forms of synthetic and natural zeolites

Sorption of hazardous pyridine derivates by copper forms of synthetic zeolite ZSM5 and natural zeolite of the clinoptilolite type (CT) has been investigated. Sorption of 2-chloropyridine (clpy) and 2-ethylpyridine (ethylpy) from liquid and gas phase by copper forms of zeolites (Cu-ZSM5 and Cu-CT) has been studied by CHN analysis, thermal (TG, DTG and DTA) analysis, FTIR spectroscopy, X-ray powder diffractometry and determination of the surface areas and the pore volumes by low-temperature adsorption of nitrogen. The results of thermal analyses of Cu-ZSM5, Cu-(clpy) _x -ZSM5, Cu-(ethylpy) _x -ZSM5, Cu-CT, Cu-(clpy) _x -CT and Cu-(ethylpy) _x -CT zeolitic products with different composition (x depends on the experimental conditions of sorption of pyridine derivates) clearly confirmed their different thermal properties and the sorption of pyridine derivates. The main part of the decomposition process of zeolitic samples containing pyridine derivates occurs at considerably higher temperatures than the boiling point of pyridine derivates proving strong bond and irreversibility of clpy- and/or ethylpy–zeolite interaction. FTIR spectra showed well-resolved bands for pyridine derivates in the Cu-(clpy) _x -zeolite and Cu-(ethylpy) _x -zeolite. Surface area and pore volumes of the samples Cu-clpy-ZSM5, Cu-ethylpy-ZSM5, Cu-clpy-CT and Cu-ethylpy-CT in comparison with Cu-ZSM5 and Cu-CT decreased due to the adsorption of pyridine derivates.     

Cathodic deposition of ternary In+As+Sb alloys and formation of InAsxSb1−x

In+As+Sb alloys have been deposited onto Ni and Ti cathodes from tartaric acid solutions at pH 2. Homogeneous deposits of composition suitable for achieving InAs_xSb_1−x can be obtained from this medium. The As-to-Sb ratio can be controlled by properly selecting solution composition and deposition potential.X-ray photoelectron spectroscopy and X-ray diffraction analyses show that formation of III–V compounds occurs at room temperature. In reacts preferentially with As rather than with Sb, but crystalline phases formed at room temperature are Sb-rich. After annealing the In+As+Sb alloys at 250°C, the composition calculated from cell parameters appears similar to that measured by energy-dispersive X-ray analysis, suggesting that the entire deposit has been converted into the InAs_xSb_1−x crystalline phase.     

Synthesis and characterization thesulphides type ZnS(1-x)MSx

ZnS_(1-x)MS_x(x=0.01 and M=Mn²⁺, Cu²⁺ and Eu²⁺) compounds have been obtained by precipitation from homogeneous solutions of zinc, copper, manganese and europium salts, with S^2- as the precipitating anion, formed by the decomposition of thioacetamide. The thermal study of the milled zinc acetate, thioacetamide, copper acetate, manganese acetate and europium nitrate, respectively, was studied for thermal analyis TG/DSC. XRD respect exhibits a zinc blend crystal structure. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thermal properties and stability of lithium titanophosphate glasses

DTA was used to study thermal properties and thermal stability of (50-x)Li₂O-xTiO₂-50P₂O₅ (x=0–10 mol%) and 45Li₂Ot-yTiO₂-(55-y)P₂O₅ (y=5–20 mol%) glasses. The addition of TiO₂ to lithium phosphate glasses results in a non-linear increase of glass transition temperature. All prepared glasses crystallize under heating within the temperature range of 400–540°C. The lowest tendency towards crystallization have the glasses with x=7.5 and y=10 mol% TiO₂. X-ray diffraction analysis showed that major compounds formed by annealing of the glasses were LiPO₃, Li₄ P₂O₇, TiP₂O₇ and NASICON-type LiTi₂(PO₄)₃. DTA results also indicated that the maximum of nucleation rate for 45Li₂O-5TiO₂-50P₂O₅ glass is close to the glass transition temperature.     

Electrophysical properties of materials based on BaGdCo2O5 + δ

The phase composition, linear thermal expansion coefficient, electroconductivity (in the temperature interval 600–900°C and partial pressures of oxygen 10⁻⁵–0.21 atm) of solid-oxide materials based on gadolinium-barium cobaltite doped with 3d-elements BaGdCo_{2 − x} Me _x O_{5 + δ}, Me = Cu, Fe; x = 0.0, 0.2, …, 2.0 were investigated. The homogeneity regions of samples were established by means of X-ray phase analysis. It was shown that the linear thermal expansion coefficient of cobaltite decreases with an increase in the copper or iron concentration. It was established that the electroconductivity of BaGdCo_{2 − x} Me _x O_{5 + δ} decreases with an increase in x. We concluded that upon a decrease in p(O₂), the electroconductivity of samples first decreases and then reaches a horizontal plateau.     

Excess molar enthalpies of binary mixtures for (tributyl phosphate+methanol/ethanol) at 298.15 K

Excess molar enthalpies of binary mixtures for tributyl phosphate (TBP)+methanol/ethanol were measured with a TAM air Isothermal calorimeter at 298.15 K and ambient. The results for xTBP+(1–x)CH₃OH are negative in the whole range of composition, while the values for xTBP+(1–x)C₂H₅OH change from positive values at low x to small negative values at high x. The experimental results have been correlated with the Redlich–Kister polynomial. IR spectra of the mixtures were measured to investigate the effect of hydrogen bonding in the mixture.     

Phase Formation Study of Alkaline Earth-doped Lanthanum Chromites

In this paper the influence of alkaline-earth admixtures on the synthesis of lanthanum chromites of La_1–xM_xCrO₃ (x=0; 0.3; M=Ca, Sr, Ca+Sr) type was studied. The formation mechanism as well as the phase composition evolution, under non-isothermal and isothermal conditions, were investigated by thermal analysis and X-ray diffraction. The structure of the compounds and of the solid solutions formed depends on the solute type by means of the structural distortion induced. The crystallinity of the chromites obtained is obviously influenced by both the temperature and the thermal treatment plateau. This revised version was published online in August 2006 with corrections to the Cover Date.     

Emf Measurements on Nanocrystalline Copper-Doped Ceria

Mixed oxide samples of nanostructured Cu_xCe_1−xO_2−yof various composition were generated by (i) chemical precipitation and ball milling and (ii) inert gas condensation. X-ray diffraction measurements suggested that copper oxide was dissolved in nanostructured cerium oxide up to concentrations ofx=0.15. Solid electrolyte cells of the typeA, Cu₂O/CuBr/Cu_xCe_1−xO_2−y(A=Cu or CuO) showed reversible cell voltages. The ratio of the formal chemical activities of CuO and Cu₂O dissolved in nanostructured cerium oxide were calculated from the cell voltages. The results are discussed in terms of an apparent macroscopic solubility, due to interfacial segregation of copper oxide on nanostructured cerium oxide.     

Synthesis and properties of colored copper-containing alkaline-earth phosphates with an apatite structure

Colored compounds A₅(PO₄)₃Cu_0.1OH _z , where A = Ba_1-x Sr _x (x=0,0.5,0.8), Sr_1-y Ca _y (y=0,0.2, 0.5, 1), and Ba_1/3Sr_1/3Ca_1/3 with an apatite structure containing copper ions in the hexagonal channels have been synthesized by the thermal treatment of the corresponding carbonates, oxides, and ammonium hydrophosphate at 1150°C. The use of the composition with A = Ba_0.5Ca_0.5 gives a multiphase product containing apatite (Ba_1-x Ca _x )₅(PO₄)₃Cu _y OH _z with x ∼ 0.2 as the major phase. The hexagonal lattice parameters of apatite depend linearly on the content of solid solution in the alkaline-earth metals. In the series of A = Ba, Ba-Sr, Sr, Sr-Ca, and Ca, the color of the samples changes smoothly from blue through violet to pink, whereas the samples with A = Ba_0.5Ca_0.5 and Ba_1-3Sr_1-3Ca_1-3 are light gray. The diffuse reflectance electronic spectra exhibit two absorption bands characteristic of the copper ions in the hexagonal channels. Their positions depend on the alkaline-earth metal content of the compound. The third characteristic band appears in the spectrum of calcium apatite. Its relative intensity increases when calcium is gradually replaced by strontium and especially by barium, which results in worsening and even loss of the sample color. These spectral changes are presumably due to the transition of some copper ions from the hexagonal channels to other positions of the crystal lattice.     

Structural Distortion in Perovskite Type KCaH3–xFx (0.54 ≤ x ≤ 3)

Representatives of the solid solution series KCaH_3–xF_x were synthesized by solid state reactions from binary metal hydrides and fluorides. Crystal structures were analyzed by Rietveld refinement based on X-ray powder diffraction. The degree of substitution was determined by refinement of site occupancy factors as well as elemental analysis for hydrogen. Three sections of x in KCaH_3–xF_x can be distinguished. For x < 0.54 no hydride fluoride exists, i.e. there is no hydride of the composition KCaH₃ and the solid solution starts only at x = 0.54. The tetragonal SrTiO₃ type structure with partial ordering of hydrogen and fluorine atoms is found for 0.54 ≤ x ≤ 1.7. Both anion positions show mixed occupation with some preference of hydrogen atoms for 8h and fluorine atoms for 4a sites (I4/mcm, SrTiO₃ type). For fluorine-rich compounds a solid solution with orthorhombic GdFeO₃ type structure (Pnma) and a perfectly statistical distribution of hydrogen and fluorine atoms is found (1.8 ≤ x ≤ 3). Interatomic distances resulting from the structure refinements are in the range of typical K–H, K–F, Ca–H, and Ca–F distances for mainly ionic compounds.