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 ^? .     

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.     

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.     

The reaction Pu(VI) + Fe(CN)<Stack><Subscript>6</Subscript><Superscript>3−</Superscript></Stack> ⇄ Pu(VII) + Fe(CN)<Stack><Subscript>6</Subscript><Superscript>4−</Superscript></Stack> in NaOH solutions

A spectrophotometric study showed that, in 5 M NaOH, Pu(VII) prepared by ozonation of Pu(VI) is reduced with excess K₄Fe(CN)₆. The Pu(VII) content can be estimated from the amount of the Fe(CN)₆³⁻ formed. In NaOH solutions of concentration exceeding 8 M, the Fe(CN)₆³⁻ ion oxidizes Pu(VI). In 10.3 M NaOH, the tenfold excess of K₃Fe(CN)₆ fully converts 1 mM Pu(VI) to the heptavalent state within 4 min (rate constant 1.3 l mol⁻¹ s⁻¹ at 20°C). With an increase in the NaOH concentration, the oxidation rate increases, and smaller excess of K₃Fe(CN)₆ is required. This oxidant is consumed not only for Pu(VI) oxidation but also in reactions with H₂O and OH⁻ ions. Pu(VII) is unstable and is slowly reduced with water and with products of decomposition of iron complexes.     

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.     

Disproportionation of nonoxygenated U(V) bound in the complex with heteropoly anions P<Subscript>2</Subscript>W<Subscript>17</Subscript>O<Stack><Subscript>61</Subscript><Superscript>10−</Superscript></Stack>

The effect of experimental conditions on U^VL₂ (1–2 mM) disproportionation was studied spectrophotometrically through the U^IVL₂ accumulation (L = P₂W₁₇O ₆₁ ^10? ). In 1 M NaNO₃ solution containing 0.01 M HAc and 0.01 M NaAc, the rate of U^VL₂ disappearance is described by the equation V = k ₁[U^VL₂]. The k ₁ value is almost constant with pH decreasing from 4.5 to 1.7, but increases with increasing acetate concentration; the presence of 1 mM U^IVL₂, U(VI), or L does not affect k ₁. In the solutions of 0.1–1.0 M HClO₄ (ionic strength 1), the reaction rate is described by the equation V = 2k ₂[H⁺]^2.5[U^VL₂]². Probable disproportionation mechanism is discussed. The first stage is substitution of L by water molecules in the U^IVL₂ complex and appearance of the reactive U(V) complex with mixed coordination sphere.     

Codes over <Emphasis Type="Bold">Σ</Emphasis><Subscript>2</Subscript><Subscript><Emphasis Type="Italic">m</Emphasis></Subscript> and Jacobi forms over the Quaternions

We introduce codes over the ring We relate self-dual codes over this ring to quaternionic unimodular lattices and to self-dual codes over via a gray map. We study a connection between the complete weight enumerators of codes over the quaternionic ring _2m and Jacobi forms over the half-space of quaternions. This motivates us to construct an algebra homomorphism from a certain invariant polynomial ring, where the complete weight enumerators belong, to the ring of Jacobi forms over the quaternions. Higher genus modular forms over the quaternions are also constructed using joint weight enumerators of codes.This research was partially supported by KOSEF R01-2003-00011596-0Some of the results of this paper were presented at the IEEE Information Theory Workshop, April, 2003     

Probe Mössbauer Spectroscopy of BiNi<Subscript>0.96</Subscript><Superscript>57</Superscript>Fe<Subscript>0.04</Subscript>O<Subscript>3</Subscript>

This paper presents results of a ⁵⁷Fe probe Mössbauer spectroscopy study of the BiNi_0.96⁵⁷Fe_0.04O₃ nickelate. The spectra measured above its TN demonstrate that Fe³⁺ cations heterovalently substitute for Ni²⁺ nickel (←Fe³⁺), being stabilized on four sites of the nickel sublattice in the structure of BiNiO₃. Calculations in an ionic model with allowance for monopole and dipole contributions to the electric field gradient indicate that the parameters of electric hyperfine interactions between ⁵⁷Fe probe atom nuclei reflect the specifics of the local environment of the nickel in the structure of the unsubstituted BiNiO₃ nickelate. Below T^N, Mössbauer spectra transform into a complex Zeeman structure, which is analyzed in terms of first-order perturbation theory with allowance for electric quadrupole interactions as a small perturbation of the Zeeman levels of the ⁵⁷Fe hyperfine structure, as well as for specific features of the magnetic ordering of the Ni²⁺ cations in the nickelate studied.     

Kinetics of Thermal Transformation of Mg<Subscript>3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript> · 8H<Subscript>2</Subscript>O to Mg<Subscript>3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>

The kinetics of thermal dehydration of Mg₃(PO₄)₂ · 8H₂O was investigated using thermogravimetry at four different heating rates. The activation energies of the dehydration step of Mg₃(PO₄)₂ · 8H₂O were calculated through the isoconversional Ozawa and Kissinger-Akahira-Sunose (KAS) methods and iterative methods, which were found to be consistent and indicate a single mechanism. The possible conversion function of the dehydration reaction for Mg₃(PO₄)₂ · 8H₂O has been estimated through the Coats and Redfern integral equation, and a better kinetic model such as random nucleation of the “Avrami–Erofeev equation (A _3/2 model)” was found. The thermodynamic functions (ΔH*, ΔG*, and ΔS*) of the dehydration reaction are calculated by the activated complex theory and indicate that it is a non-spontaneous process when the introduction of heat is not connected.     

AC Losses in YBCO-Added Bi<Subscript>1.6</Subscript>Pb<Subscript>0.4</Subscript>Sr<Subscript>2</Subscript>Ca<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript><Emphasis Type="Italic">δ</Emphasis></Subscript> Superconductors

The effect of YBCO adding on the superconducting of BPSCCO system with nominal starting composition of (Bi_1.6Pb_0.4Sr₂Ca₂Cu₃O _δ )_1?x(YBCO) _x with x = 0.00?0.10 was studied. The preparation methods used to prepare the samples are the conventional solid-state techniques. From the XRD data, it is observed that the percentage of the Bi-2223 phase increases and Bi-2212 decreases for addition x = 0.02–0.04, respectively. The effect of YBCO addition on the BPSCCO system also has been investigated in term of AC susceptibility study. We have studied the various applied field dependence of the AC susceptibility in polycrystalline samples. The AC susceptibility measurements in the range 0.05 to 2.00 Oe show that as the applied fields increases, the intergranular AC loss peaks move to lower temperature, and also height decreases and width increases. The effect of YBCO addition for the intergranular critical current J _cm, and the presence of weak links that coupled the superconducting grains were defined.     

Thermodynamic properties of (TeO<Subscript>2</Subscript>)<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>(MoO<Subscript>3</Subscript>)<Subscript>1–<Emphasis Type="Italic">n</Emphasis></Subscript> glasses

The thermal behavior of (TeO₂) _n (MoO₃)_1–n (n = 0.75, 0.85, 0.90) tellurite glasses has been studied by differential scanning calorimetry in the range from T = 300 to T = 850 K and heat capacity has been measured in the temperature range. The thermodynamic characteristics of the devitrification process and glassy state have been determined. The experimental data obtained have been used to evaluate the standard thermodynamic functions of the system in glassy and supercooled liquid states: heat capacity C _p °(T), enthalpy H°(T)–H°(320), entropy S°(T)–S°(320), and Gibbs function G°(T)–G°(320) in the temperature range 320–630 K. The composition dependences of the glass transition temperature and thermodynamic functions for the glasses have been obtained. The thermal and thermodynamic properties of the tellurite glasses have been compared to those of previously studied (TeO₂) _n (WO₃)_1–n and (TeO₂) _n (ZnO)_1–n glasses.     

Polycrystalline YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>7−<Emphasis Type="Italic">δ</Emphasis></Subscript> with Nano-sized Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Inclusions

Series of (YBa₂Cu₃O_7−δ )_1−x (Al₂O₃) _x samples have been prepared using solid state reaction method. Various amount of nano-sized Al₂O₃ particles (∼50 nm) were added with (x=0, 0.005, 0.01, 0.02, and 0.05). The microstructure and the morphology of the polycrystalline samples have been characterized by X-ray diffraction (XRD) and atomic force microscopy (AFM). The magneto-transport properties of these samples were investigated using resistance–temperature (R–T) and current–voltage (I–V) characteristics. All samples showed an orthorhombic structure with a tendency to transformation to tetragonal phase at higher levels of nanoparticles addition. The morphology of the surface of pure samples reveals a considerable number of weak-links, randomly oriented and clean grain boundaries. While in samples with nano inclusions, grain boundaries were filled with nanosized particle and have less number of weak-links. Significant enhancement of the superconducting critical current density J _c in applied magnetic field was observed due to nano Al₂O₃ inclusions. However, further increase in the value of x decreases the transition temperature T _c and the critical current density J _c . These results were interpreted in terms of the flux pinning mechanisms in granular superconducting networks which leads to a better basic understanding of the performance of YBCO system in high applied magnetic fields.     

BaFe<Subscript>12</Subscript>O<Subscript>19</Subscript> films produced from BaFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> heterostructures

BaFe₁₂O₁₉ hexaferrite films have been produced on thermally oxidized single-crystal silicon (SiO₂/Si) substrates by sequential ion-beam sputtering of BaFe₂O₄ and α-Fe₂O₃ targets in an argon-oxygen atmosphere. Their crystal structure has been studied, and the origin of the impurity phases forming during heat treatment has been identified. The results show that heat treatment may lead to the formation of eutectic melts. As a result, the hexaferrite films may contain spherulites.     

Use of a nanostructured material for separation of <Superscript>238</Superscript>U and <Superscript>237</Superscript>U produced by the photonuclear reaction <Superscript>238</Superscript>U(γ, <Emphasis Type="Italic">n</Emphasis>)<Superscript>237</Superscript>U

²³⁷U was produced by the reaction ²³⁸U(γ, n) on an electron accelerator, MT-25 microtron, at the Flerov Laboratory of Nuclear Reactions. For the separation of ²³⁷U and [²³⁸U, the recoil nuclei were collected by a nanostructured material, hydrated manganese dioxide (of the cryptomelane type), in the solid-solid system. From fission products, ²³⁷U was separated by ion exchange. The specific activity of the resulting ²³⁷U was 4.5 × 10⁹ Bq (mg ²³⁸U)^-1, with the content of radioactive impurities of ≤10^-6 Bq Bq^-1. The chemical yield of ²³⁷U was 80%.     

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.     

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.     

Microwave dielectric properties of temperature-stable (Mg<Subscript>0.95</Subscript>Co<Subscript>0.05</Subscript>)<Subscript>2</Subscript>TiO<Subscript>4</Subscript>–Li<Subscript>2</Subscript>TiO<Subscript>3</Subscript> composite ceramics for LTCC applications

In this paper, the effects of Li₂O–B₂O₃–Bi₂O₃–SiO₂ (LBBS) glass on the phase formation, sintering characteristic, the microstructure and microwave dielectric properties of temperature-stable (Mg_0.95Co_0.05)₂TiO₄–Li₂TiO₃ ceramics were investigated. (Mg_0.95Co_0.05)₂TiO₄–Li₂TiO₃ powders were obtained by using the traditional solid-state process. A small amount of LBBS doping can effectively reduce sintering temperature and promote the densification of the ceramics. X-ray diffraction analysis revealed not only the primary phase (Mg·Co)₂TiO₄ associated with Li₂TiO₃ minor phase but also a third phase (Mg·Co)TiO₃. The dielectric constant and Qf values vary with the doping amount of LBBS and sintering temperatures. With the compensation of the positive temperature coefficient (τ _f ) of Li₂TiO₃ and the negative τ _f of (Mg_0.95Co_0.05)₂TiO₄, the τ _f of the specimens fluctuates around zero. The (Mg_0.95Co_0.05)₂TiO₄ ceramic with 2.5 wt% LBBS addition and sintering at 900?°C for 4 h exhibited excellent microwave dielectric properties: ? _r ?=?19.076, Qf?=?126100 GHz, and τ _f ?=?0.98 ppm/°C.     

Structure and Superconductivity of (MgB<Subscript>2−<Emphasis Type="Italic">x</Emphasis></Subscript>C<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>)<Subscript>0.97</Subscript>Cu<Subscript>0.03</Subscript>

A series of samples of (MgB_2−x C _x )_0.97Cu_0.03 (x=0.00, 0.05, 0.10, 0.15, 0.20, 0.25) and MgB₂ were synthesized by a solid state reaction method. The structure, superconducting transition temperature and transport properties of the samples were studied by means of X-ray diffraction (XRD) and resistivity measurements. It is found that the c-axis of the lattice remains unchanged with increasing C doping, while the a-axis shows a small decrease. The T _c of the samples steadily decreases with increasing C doping. It is suggested that the chemical pressure effect plays a more important role influencing the normal state transport and T _c than the change of carrier concentration.     

Synthesis and Magnetic Properties of Bi<Subscript>1.7</Subscript>Pb<Subscript>0.3</Subscript>Sr<Subscript>2</Subscript>Ca<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>10+<Emphasis Type="Italic">δ</Emphasis></Subscript> Added with Nano Y

Bi₁₇Pb_0.3Sr₂Ca₂Cu₃O_10+δ superconductor samples were synthesized by the conventional solid-state reaction method. To study the effects of the addition of yttrium nanoparticles to the superconducting system, nano Y₂O₃ was introduced by small weight percentages (0.2, 0.4, 0.6, 0.8, and 1.0 wt%) in the first step of the synthesis process. Phase identification and microstructural characterization of the samples were investigated using X-ray diffraction and scanning electronic microscopy (SEM). Energydispersive X-ray spectroscopy (EDX) analysis was utilized to confirm the presence of the desired elements in the chemical composition of the samples. Moreover, DC electrical resistivity as a function of the temperature, critical current density (J _c), AC magnetic susceptibility, and DC magnetization measurements were carried to evaluate the relative performance of samples. XRD analysis showed that both (Bi,Pb)-2223 and Bi-2212 phases coexist in the samples having an orthorhombic crystal structure. Both the onset critical temperatures (T _c) (onset) and zero electrical resistivity critical temperatures (T _c) (R = 0) of the samples were determined from the DC electrical resistivity measurements. An improvement of the superconducting transition temperature of 3.0 % was obtained with increasing Y₂O₃ nanoparticles to x = 1.0 wt%, while the critical current density is improved by 200 %. AC magnetic susceptibility measurement showed that the diamagnetic fraction and intergranular coupling of the x = 1.0 wt% sample are greater than those of the others. The variation of magnetization with temperature (M–T curve) of the samples was measured by cooling the sample in zero fields (ZFC) and an applied field of 10 Oe (FC). The results of AC magnetic susceptibility and DC magnetization measurements were in good agreement with DC electrical resistivity measurement.     

Increased Solubility of Mg at Ca Site in Cu<Subscript>0.5</Subscript>Tl<Subscript>0.5</Subscript>Ba<Subscript>2</Subscript>Ca<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>10−<Emphasis Type="Italic">δ</Emphasis></Subscript> Superconductor

The Cu_0.5Tl_0.5Ba₂Ca_2?y Mg _y Cu₃O_10?δ (y=0, 0.05, 0.1, 0.2, 0.4, 0.6, 0.8, 1.0, 1.5, 2.0) superconductor has been synthesized at the atmospheric pressure by the solid-state reaction method. The zero resistivity critical temperature is found to increase to 98 K with Mg concentration of y=0.6, but saturates to 97 K with further enhancement of Mg to y=0.8, 1.0, and 1.5. The Mg doped material grows in tetragonal structure and follows P4/mmm symmetry with a &; c-axes lengths of 3.894 Å &; 15.091 Å for y=1.5. The axes lengths were decreased with the increase of Mg content in the unit cell, which shows that anisotropy of the material decreases. The critical current density and the quantity of diamagnetism in the samples with Mg contents are higher than in the samples without Mg. In order to realize the effects of decreased axes lengths on the phonon modes of Cu_0.5Tl_0.5Ba₂Ca_2?y Mg _y Cu₃O_10?δ , we have carried out FTIR absorption measurements.