System ZnO ⋅ B<Subscript>2</Subscript>O<Subscript>3</Subscript>-CuO ⋅ B<Subscript>2</Subscript>O<Subscript>3</Subscript>

Differential thermal analysis and x-ray diffraction data indicate that the ZnO B₂O₃-CuO B₂O₃ join of the ternary system CuO-B₂O₃-ZnO is pseudobinary, with eutectic phase relations and a liquid-liquid miscibility gap in the composition range 25–35 mol % CuO.Translated from Neorganicheskie Materialy, Vol. 41, No. 3, 2005, pp. 339–340.Original Russian Text Copyright © 2005 by Kasumova, Bananyarly.This revised version was published online in April 2005 with a corrected cover date.This revised version was published online in April 2005 with a corrected cover date.     

Crystal structure of compounds CsA<Superscript>V</Superscript>A′<Superscript>VI</Superscript>O<Subscript>6</Subscript> (A<Superscript>V</Superscript> = Sb,Ta; A′<Superscript>VI</Superscript> = W,U)

Compounds CsA^VA′^VIO₆ (A^V = Sb, Ta; A′^VI = W, U) were synthesized by high-temperature solidphase reactions. The crystal structures of the compounds were refined by the Rietveld method (space group Fd \(\bar 3\) m).     

Synthesis,electronic state,and particle size stabilization of nanoparticulate [Co(OH)<Subscript>2</Subscript>(H<Subscript>3</Subscript>O)<Stack><Subscript>δ</Subscript><Superscript>+</Superscript></Stack>]<Superscript>δ+</Superscript>

We have synthesized nanoparticulate cobalt(II) hydroxide containing Co²⁺ in tetrahedral oxygen coordination (Co _Td ²⁺ ), atypical of such systems: nano- [Co(OH)₂(H₃O) _δ ⁺ ]^δ+. The (Co _Td ²⁺ ) coordination in the hydroxide is inferred from its electronic diffuse reflectance spectrum, which shows a multiplet of strong absorption bands at 14500, 15000, and 16000 cm^?1 (⁴ A ₂(F)-⁴ T ₁(P) transition). Nanoparticulate cobalt(II) hydroxide forms in a weakly acidic medium under essentially nonequilibrium conditions due to supersaturation (by three to four orders of magnitude) with the starting reagents (CoCl₂ and LiOH) at the instant of the formation of the poorly soluble phase Co(OH)₂. Presumably, colloidal particles of nanoparticulate cobalt(II) hydroxide in a weakly acidic aqueous medium have a positive surface charge, compensated by a counter-ion (Cl^?) layer: nano-[Co(OH)₂(H₃O) _δ ⁺ ]^δ+ · δCl^?. The XRD patterns of pastes (gels) containing this hydroxide show three broad-ened lines with d = 5.31 (2θ = 16.7°), 2.77 (2θ = 32.3°), and 2.32 Å (2θ = 38.8°). According to small-angle X-ray scattering data, nano-[Co(OH)₂(H₃O) _δ ⁺ ]^δ+ has a narrow particle size distribution (1.0–2.0 nm). Synthesis and storage conditions are identified which ensure stabilization of the electronic state and particle size of nano-[Co(OH)₂(H₃O) _δ ⁺ ]^δ+ for a long time.     

Tunable luminescence and energy transfer properties in Ca<Subscript>2−x</Subscript>NaMg<Subscript>2</Subscript>V<Subscript>3</Subscript>O<Subscript>12</Subscript>:xEu<Superscript>3+</Superscript> phosphors

Novel broadband luminescence phosphors Ca_2?xNaMg₂V₃O₁₂:xEu³⁺ have been successfully prepared via the conventional high-temperature solid-state reaction. The effects of concentrations of doped Eu³⁺ and introducing Li⁺, K⁺ on the luminescent properties of phosphor were studied. X-ray diffraction, GSAS structural refinement and photoluminescence spectra were used to characterize the samples. The refinement data ensured where the doped Eu³⁺ ions occupied the lattice site in the host. Under 355 nm excitation, the emission peak of Ca₂NaMg₂V₃O₁₂:Eu³⁺ phosphors are located at 610 nm (red) ascribed to the electric dipole transition of Eu³⁺ from ⁵D₀ → ⁷F₂. In the range of 400–575 nm, Ca₂NaMg₂V₃O₁₂:Eu³⁺ phosphors have broad emission bands attributed to charge transfer of \({\text{VO}}_4^{3 - }\) group. Energy transfer mechanism, energy transfer efficiency and critical distance (R_c) of \({\text{VO}}_4^{3 - }\) → Eu³⁺ would be analyzed. The emitting color of Ca₂NaMg₂V₃O₁₂:Eu³⁺ could be tunable from blue-green to near white light.     

Luminescent properties of single-phase Ba<Subscript>2</Subscript>P<Subscript>2</Subscript>O<Subscript>7</Subscript>:Tb<Superscript>3+</Superscript>, R (R = Eu<Superscript>2+</Superscript>, Ce<Superscript>3+</Superscript>) phosphors for white LED

The Ba₂P₂O₇:Tb³⁺, R (R?=?Eu²⁺, Ce³⁺) phosphors were synthesized by use of a co-precipitation method. Crystal phase, excitation and emission spectra of sample phosphors are analyzed by means of XRD and FL, respectively. The emission spectra of Ba₂P₂O₇:Ce³⁺, Tb³⁺ phosphors exhibit four linear peaks attributed to the ⁵D₄?→?⁷F_J (J?=?6–3) transition of Tb³⁺ while four broad emission bands are observed in the emission spectra of Ba₂P₂O₇:Eu²⁺, Tb³⁺ phosphors. The effects of Eu²⁺ concentration on the luminescent properties of Ba₂P₂O₇:Tb³⁺, R (R?=?Eu²⁺, Ce³⁺) are studied. Ce³⁺ affects the luminescent properties of Ba₂P₂O₇:Ce³⁺, Tb³⁺ phosphors just as the sensitizer. However, Eu²⁺ is considered both as the sensitizer and the activator in Ba₂P₂O₇:Eu²⁺, Tb³⁺ phosphors. The chromaticity coordinates of Eu²⁺ and Tb³⁺ co-doped phosphors gather around the white light field with the CCT approximate to 5000 K, indicating that the luminescent property of Ba₂P₂O₇:Eu²⁺, Tb³⁺ phosphors may approach to a desired level needed for white LED application.     

Formation-decomposition equilibrium of the NpO<Stack><Subscript>2</Subscript><Superscript>+</Superscript></Stack>·UO<Stack><Subscript>2</Subscript><Superscript>2+</Superscript></Stack> complex in chloride melts

The absorption spectra of the NpO ₂ ⁺ (5f ²) ion were examined in the region of the 3H ₅ ← ³ H ₄ magnetic dipole transition (1530–1760 nm) for series of melts with the UO ₂ ²⁺ concentration varied in the opposite directions: (1) NaCl-2CsCl eutectic melt with growing additions of the Cs₂UO₂Cl₄ complex salt and (2) Cs₂UO₂Cl₄ melt with growing additions of the NaCl-2CsCl mixture. Measurements of the integrated intensities of the bands belonging to the NpO ₂ ⁺ ·UO ₂ ²⁺ complex and unbound NpO ₂ ⁺ throughout the UO ₂ ²⁺ concentration range examined (up to 4.4 M in neat Cs₂UO₂Cl₄ melt) and processing of the data obtained in terms of the mass action law showed that the formation-decomposition reaction of the cation-cation complex can be described adequately only using the equation of reaction in the form NpO₂Cl ₄ ^3? + UO₂Cl ₄ ^2? ? {Cl₄ONpO?UO₂Cl₃}^4? = Cl^? (with the equilibrium constant of 1.3±0.1). Thus, the formation of the cationcation complex should be treated as replacement of chloride ion in the equatorial plane of uranyl(VI) by neptunyl(V), rather than as simple addition of UO ₂ ²⁺ to NpO ₂ ⁺ . The reverse reaction, decomposition of the cation-cation complex, consists essentially in replacement of neptunyl(V) by chloride ion.     

Structure,electrical, and optical properties of ZnO-substituted PbO for the Er<Superscript>3+</Superscript>/Yb<Superscript>3+</Superscript> co-doped Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>–GeO<Subscript>2</Subscript>–Na<Subscript>2</Subscript>O glass system

Glasses of the 0.5Er³⁺/2.5Yb³⁺ co-doped (40Bi₂O₃–20GeO₂–(30 − x)PbO–xZnO–10Na₂O system where x = 0.0, 5, 10, 15, 20, 25, and 30 mol%) have been characterized by FT-IR spectroscopy measurements to obtain information about the influence of ZnO-substituted PbO on the local structure of the glass matrix. The density and the molar volume have been determined. The influences of the ZnO-substituted PbO on the structure of glasses have been discussed. The dc conductivity measured in the temperature range 475–700 K obeys Arrhenius law. The conductivity decreases while the activation energy for conduction increases with increase ZnO content. The optical transmittance and reflectance spectrum of the glasses have been recorded in the wavelength range 400–1100 nm. The values of the optical band gap E _opt for all types of electronic transitions and refractive index have been determined and discussed. The real and imaginary parts ε₁ and ε₂ of dielectric constant have been determined.     

Lewis and Brønsted acids in super-acid catalyst SO<Subscript>4</Subscript><Superscript>2−</Superscript>/ZrO<Subscript>2</Subscript>–SiO<Subscript>2</Subscript>

Super-acid catalyst, SO₄ ^2?/ZrO₂–SiO₂, with high zirconium loading was synthesized and the nature of the surface acid was investigated by FT-IR of pyridine adsorption. With the increasing ZrO₂ content, the Lewis and Brønsted acid sites increased and reached the maximum when Zr/Si (molar ratio) = 1.3. The sample with Zr/Si = 1.3 showed the strongest IR adsorption band in the S=O stretching region (1,300–1,400 cm^?1). Pyrosulfate and monosulfate species existed on the surface of the catalysts and the acidic strength could be enhanced by induction effect of their S=O groups. And there were two kinds of Brønsted acid sites on the surface of the catalysts.     

Structure and properties of CaF<Subscript>2</Subscript>–B<Subscript>2</Subscript>O<Subscript>3</Subscript> glasses

FTIR spectroscopy has been employed to investigate the structure of CaF₂–B₂O₃ glasses. It is proposed that CaF₂ partially modifies the borate network forming \textCa _{1 / 2} ²⁺ [\textBO _{3 / 2} \textF] ^- {\text{Ca}}_{ 1 / 2}^{ 2+ } [{\text{BO}}_{ 3 / 2} {\text{F]}}^{ - } units. The rest of CaF₂ is assumed to build an amorphous network formed of CaF₄ tetrahedra. Analysis of density and molar volume revealed that the volume of CaF₄ tetrahedron in the studied glasses is slightly greater than that in the crystalline form. Data of density, molar volume, and electric conductivity have been correlated with the glass structure. As far as the authors know, CaF₂–B₂O₃ glasses are investigated for the first time.     

Stability of actinide(III,IV) and lanthanide(III,IV) complexes with P<Subscript>2</Subscript>W<Subscript>17</Subscript>O<Stack><Subscript>61</Subscript><Superscript>10−</Superscript></Stack> heteropolyanions

The total stability constants of Th⁴⁺, U⁴⁺, Np⁴⁺, Pu⁴⁺, Am⁴⁺, Cm⁴⁺, Ce⁴⁺, Tb⁴⁺, Pr⁴⁺, Tb³⁺, and Pr³⁺ complexes with P₂W₁₇O ₆₁ ^10? heteropolyanion in 1 M sodium salt solutions at pH ≥ 5.5 (i.e., when the anion is not protonated; so-called “absolute” constants), were determined experimentally or calculated from published data. Plots of constants vs. ionic radius of the f element were considered for solutions with ionic strength 1 (1 M acid or sodium salt solutions at pH ≥ 5.5). The correlations found confirm that the interaction of counterions in the complex is predominantly electrostatic. At the same time, different contributions of the covalent interaction for actinides and lanthanides were suggested.     

Variable—Range hopping in Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-K<Subscript>2</Subscript>B<Subscript>4</Subscript>O<Subscript>7</Subscript> glasses

The dc conductivity of the glasses in the Fe₂O₃-Bi₂O₃-K₂B₄O₇ system was studied at temperatures between 223 and 393 K. At temperatures from 300 to 223 K, T^–1/4 (T is temperature) dependence of the conductivity was found, however, both Mott variable-range hopping and Greaves intermediate range hopping models are found to be applicable. Mott and Greaves parameters analysis gave the density of states at Fermi level N (E_F) = 3.13 × 10²⁰–21.01 × 10²⁰ and 1.93 × 10²¹–16.39 × 10²¹ cm^–3eV^–1 at 240 K, respectively. The variable-range hopping conduction occurred in the temperature range T = 300–223 K, since W_D was found to be large (W_D = 0.08–0.14 eV for these glasses) and dominated the conduction at T < 300 K.     

Synthesis of thorn-like Ca<Subscript>2</Subscript>B<Subscript>2</Subscript>O<Subscript>5</Subscript>·H<Subscript>2</Subscript>O by hydrothermal method

Thorn-like polycrystalline Ca₂B₂O₅·H₂O microspheres with nano-sized slices were synthesized using boric acid and calcium hydroxide as reactants by a facile catalyst-free hydrothermal method at low temperature. The products were characterized by means of X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). The XRD pattern reveals that the Ca₂B₂O₅·H₂O is a monoclinic phase polycrystalline with cell parameters a = 0·6702, b = 0·5419 and c = 0·3558 nm. SEM also reveals that the monoclinic phase polycrystalline are thorn-like microspheres composed of many flakes with an average thickness of <100 nm. Possible reaction and growth mechanism were also discussed.     

Characterization of <Superscript>4</Superscript>I<Subscript>9/2</Subscript> ↔ <Superscript>4</Superscript>F<Subscript>3/2</Subscript> optical transitions in trivalent Nd<Superscript>3+</Superscript> ions in GaLaS glass

The positions of Stark levels have been determined, using a step-by-step procedure, in the ⁴I_9/2 and ⁴F_3/2 manifolds of Nd³⁺ ions from absorption and photoluminescence measurements in the 12–293 K temperature range. This data has been used to calculate the emission cross-section for which the maximum value turns out to be ～2.3 × 10^?20 cm². The radiative recombination time, calculated using Judd–Ofelt analysis, of the ⁴F_3/2 manifold is in close vicinity to the experimentally determined times that were measured by the conventional decay of PL after interruption of excitation and by QFRS. Moreover, the peak time defined by QFRS is independent of temperature. Therefore, the dominant relaxation mechanism from the ⁴F_3/2 excited manifold of Nd³⁺ ions in GaLaS glass is believed to be by radiative emission.     

Stability of the LaCl<Stack><Subscript>4</Subscript><Superscript>−</Superscript></Stack> and LuCl<Stack><Subscript>4</Subscript><Superscript>−</Superscript></Stack> Ions Studied by Mass Spectrometry

The enthalpy stability of the LaCl ₄ ^? and LuCl ₄ ^? ions is assessed using high-temperature mass spectrometry. The enthalpy of Cl^? detachment is determined to be Δ_rH⁰(298.15 K) = 332 ± 10 kJ/mol for LaCl ₄ ^? and 359 ± 10 kJ/mol for LuCl ₄ ^? .     

Synthesis and characterization of the M<Superscript>II</Superscript>U<Subscript>3</Subscript>O<Subscript>10</Subscript> · 6H<Subscript>2</Subscript>O (M<Superscript>II</Superscript> = Ni,Zn) triuranates

We have developed a process for the synthesis of Ni(II) and Zn(II) triuranates with the general formula M^IIU₃O₁₀ · 6H₂O through reaction of schoepite, UO₃ · 2.25H₂O, with aqueous solutions of nickel and zinc nitrates under hydrothermal conditions. Using chemical analysis, X-ray diffraction, IR spectroscopy, and thermal analysis, we have determined the composition and structure of the triuranates and investigated their dehydration and thermal decomposition.     

Highly Oxygen-Permeable NiV<Subscript>2</Subscript>O<Subscript>6</Subscript>–25 wt % V<Subscript>2</Subscript>O<Subscript>5</Subscript> Molten-Oxide Membrane Material

A NiV₂O₆–25 wt % V₂O₅ molten-oxide material has been prepared and characterized, and its transport properties (electrical conductivity, oxygen ion transport number, and oxygen permeability) have been studied in the temperature range 680–700°C. The results demonstrate that the molten-oxide membrane material obtained possesses high selective oxygen permeability (KO₂ = (2.5–5.6) × 10^–10 mol/(cm s) in the range 680–740°C and \(\frac{{{j_{{O_2}}}}}{{{j_{{N_2}}}}}\) ~ 1500) and can be used in separators for the preparation of extrapure oxygen from air.     

Estimating the effect of C<Stack><Subscript>2</Subscript><Superscript>−</Superscript></Stack> and C<Stack><Subscript>3</Subscript><Superscript>+</Superscript></Stack> radicals and neutral clusters on the fullerene formation

The mass spectrum of the products of arc discharge in helium between graphite electrodes has been studied for various values of the gas flow rate. As the gas flow rate increases, the intensity of C₆₀^±, C₇₀^±, C₈₄^± and C₉₀^± fullerene peaks increases and that of the C₂⁻ and C₃⁺ cluster radicals decreases, but the total decay in radicals amounts to only 21% of the total growth of fullerenes. From this it follows that a contribution to the formation of fullerenes from the neutral clusters (which are taken into account for the first time) significantly exceeds the contribution due to small radical species.     

Effect of Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> on the dynamics of Li<Superscript>+</Superscript> ions in Li<Subscript>2</Subscript>O·P<Subscript>2</Subscript>O<Subscript>5</Subscript> glasses

Lithium ion transport has been studied in bismuth lithium phosphate glasses in the frequency range 20 Hz–1 MHz and in the temperature range 423–573 K using impedance spectroscopy. The addition of Bi₂O₃ in Li₂O·P₂O₅ glass is related to the modification of the glass structure and facilitates the Li⁺ ions migration. The ac and dc conductivities, activation energy of the dc conductivity and relaxation frequency are extracted from the impedance spectra. Conductivity of the present glass system is found to be ionic in nature. The electrical response of the glasses has been studied using both conductivity and electric modulus formalisms. A single ‘master curve’ for normalized plots of all the modulus isotherms observed for a given composition indicates the temperature independence of the dynamic processes for ions in these glasses. Nearly identical values of activation energy for dc conduction and for conductivity relaxation time indicate that the ions overcome same energy barrier while conducting and relaxing.     

Spectroscopic characterisation of local structure in Y<Subscript>2</Subscript>O<Subscript>3</Subscript>–B<Subscript>2</Subscript>O<Subscript>3</Subscript>–Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> glasses doped with gadolinium

Gadolinium doped bismuth borate glasses containing up to 30 mol% Y₂O₃ were prepared by fast melt quenching method. The effect of yttrium on the local order in 3B₂O₃ · Bi₂O₃ and B₂O₃ · Bi₂O₃ glass matrices, particularly on the bismuth sites, was investigated by infrared (IR) spectroscopy and electron paramagnetic resonance (EPR) of Gd³⁺ ions. The IR results show that the local structure is more ordered in the glass system with higher bismuth content and the progressive addition of yttrium increases the local disorder in both bismuth–borate glass matrices. The EPR results indicate that Gd³⁺ ions occupy both bismuth and yttrium sites and reflect the same structural disorder like that suggested by IR results.     

Structural investigation of V<Subscript>2</Subscript>O<Subscript>5</Subscript>–P<Subscript>2</Subscript>O<Subscript>5</Subscript>–K<Subscript>2</Subscript>O glass system with antibacterial potential

The xV₂O(1?x)[0.8 P₂O₅ ? 0.2 K₂O] glass system with 0 ≤ x ≤ 50 mol% was prepared and the structural changes induced in these glasses by increasing the vanadium oxide content were investigated by IR and ESR spectroscopies. The dual behaviour role of V₂O₅ oxide, as network modifier (for x ≤ 10 mol%) and the network former (x ≥ 20 mol%), as a consequence of phosphate network depolymerization and P–O–V and V–O–V linkages appearance was also highlighted. The antibacterial effect of the glasses with x ≤ 20 mol% V₂O₅ content was tested by optical density (OD) measurements. A linear correlation between the amount of vanadium and the antibacterial effect was evidenced.