State of difficultly soluble uranosilicates MIHSiUO6 ? nH2O (M + = Li+, Na+, K+, Rb+, Cs+, NH4+) in saturated aqueous solutions

The solubility of uranosilicates M^IHSiUO₆ nH₂O (M^I = Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, NH ₄ ⁺ ) in aqueous solutions at 25°C was studied experimentally. The equilibrium constants of reactions that occur at dissolution of uranosilicates in acidic and neutral solutions were calculated. The composition of the equilibrium solutions was studied. The standard Gibbs energies of formation of the compounds were calculated from the solubility data. The behavior of the uranosilicates under various conditions was predicted on the basis of the previously suggested quantitative physicochemical model of the state of the heterogeneous system crystalline uranosilicate-aqueous solution.Translated from Radiokhimiya, Vol. 46, No. 5, 2004, pp. 418–422.Original Russian Text Copyright © 2004 by Chernorukov, Nipruk, Knyazev, Pegeeva.     

Synthesis, and study of magnetic properties, of Bi1?xCdxFeO3

Ceramic Bi_1−x Cd _x FeO₃ (x = 0.0, 0.05, and 0.1) samples were prepared by a citrate-gel method. The as-prepared compounds were calcined at 600 °C for 3 h to obtain nearly single-phase materials. The crystal structure, examined by X-ray powder diffraction (XRD) and Rietveld analysis, confirmed that the samples crystallize in a rhombohedral (space group, R-3c no. 161) structure. Magnetic measurements were carried out on the resultant powders from 300 to ~2.5 K. Magnetic hysteresis loops showed a significant increase in magnetization as a result of Cd doping in BiFeO₃.     

Structure,Performance, and Application of BiFeO3 Nanomaterials

Multiferroic nanomaterials have attracted great interest due to simultaneous two or more properties such as ferroelectricity,ferromagnetism,and ferroelasticity,which can promise a broad application in multifunctional,lowpower consumption,environmentally friendly devices.Bismuth ferrite(BiFeO3,BFO)exhibits both(anti)ferromagnetic and ferroelectric properties at room temperature.Thus,it has played an increasingly important role in multiferroic system.In this review,we systematically discussed the developments of BFO nanomaterials including morphology,structures,properties,and potential applications in multiferroic devices with novel functions.Even the opportunities and challenges were all analyzed and summarized.We hope this review can act as an updating and encourage more researchers to push on the development of BFO nanomaterials in the future.     

Preparation,magnetization, and microstructure of ionic ferrofluids based on γ-Fe2O3/Ni2O3 composite nanoparticles

Ionic ferrofluids based on γ-Fe₂O₃/Ni₂O₃ composite nanoparticles are a polydispersed system prepared by the Massart method. The magnetization and optical relaxation behaviors of these ferrofluids show that, in addition to the ring-free micelle aggregates, there are also chainlike aggregates in the ferrofluids. The chainlike aggregation is attributed to so-called “depletion force” in the polydispersed ferrofluids because magnetic interaction between the ferrofluid particles is so weak that these particles cannot form the aggregates just by the magnetic interaction. For the γ-Fe₂O₃/Ni₂O₃ ionic ferrofluids, the “depletion force” stimulates the larger ferrofluid particles, forming short chains in the absence of a magnetic field and their macroscopic properties, e.g., magnetization and optical relaxation, all result from the short chains. Ferrofluids having chainlike aggregates alone could have excellent magneto-optical effects.     

First-principles study on electronic structure, phase stability, and optical properties of In2X2O7 (X═C, Si, Ge or Sn)

In₂Ge₂O₇ and In₂Si₂O₇ are commonly used as scintillation materials. More studies on In₂X₂O₇ (X═C, Si, Ge, or Sn) are important to explore the possibility of using these materials for optoelectronic devices. This work presents results dealing with structural properties, electronic structure, chemical bonding, carrier effective masses, and optical spectra of polymorphs of In₂X₂O₇ obtained from first-principles calculations. The monoclinic phase of In₂Ge₂O₇, cubic and monoclinic phases of In₂Si₂O₇, as well as cubic phase of In₂Sn₂O₇ are known in scientific literature. From the total energy calculations at high pressure/strain we have found that the monoclinic phase of In₂Si₂O₇, In₂Ge₂O₇, and In₂Sn₂O₇ can be transformed into the cubic phase. The cubic phase of In₂Ge₂O₇ and In₂Sn₂O₇ is found to be more stable than the monoclinic phase. However, the monoclinic phase of In₂C₂O₇ and In₂Si₂O₇ is more stable than the cubic phase. The phase stability study suggests that In₂C₂O₇ is not stable, and that it might dissociate into corresponding binary oxides. Effective masses of electrons and holes have been estimated. Analysis of optical properties shows that in Si solar cells In₂Si₂O₇ and In₂Sn₂O₇ can be used as antireflection coating layer.     

Synthesis, composition, and structure of superconducting (Y, Ca)Sr, Ba)2Cu2GaO7?δ

The superconducting properties of Y_1–y Ca _y Sr₂Cu₂GaO_7– have been examined and related to the Ca content,y, and the use of annealing treatments at 350 bar oxygen. Superconductivity withT _c up to 41 K was found only for high-pressure-annealed samples, and the structural effects of Ca substitution and high-pressure treatment were examined using powder neutron diffraction. Small but significant changes in Cu-Cu and Cu-O distances were found and suggest that the Cu ions are more highly charged in superconducting samples. Partial substitution of Ba for Sr was found to be possible (up to 20%) to give samples which, after annealing in high-pressure oxygen, were superconducting at temperatures up to 68 K.     

IR Spectra of La1.85Sr0.15Cu1?xMxO4?δ(M = Zn, Ni, Mg)

Polycrystalline samples La_1.85Sr_0.15Cu_1–xZn_xO_4– (0 x 0.3), La_1.85Sr_0.15Cu_1–xNi_xO_4– (0 x 0.3), and La_1.85Sr_0.15Cu_1–xMg_xO_4– (0 x 0.3) were synthesized by the solid-state reaction method. The crystal structure and phonon vibration were investigated by means of X-ray diffraction (XRD) and infrared spectrum. Zn, Ni, and Mg doping results in the lattice parameter c decreasing and a (b) increasing. The change of the phonon modes around 504 cm^–1 and 681 cm^–1 can be satisfactorily interpreted in terms of the change of the crystal structure and the itinerant nature of charge carrier in CuO₂ sheet. The relation between the structure and phonon vibration is discussed.     

IR Spectra of La1.85Sr0.15Cu1?xMxO4?δ(M = Zn, Ni, Mg)

Polycrystalline samples La_1.85Sr_0.15Cu_1–xZn_xO_4– (0 x 0.3), La_1.85Sr_0.15Cu_1–xNi_xO_4– (0 x 0.3), and La_1.85Sr_0.15Cu_1–xMg_xO_4– (0 x 0.3) were synthesized by the solid-state reaction method. The crystal structure and phonon vibration were investigated by means of X-ray diffraction (XRD) and infrared spectrum. Zn, Ni, and Mg doping results in the lattice parameter c decreasing and a (b) increasing. The change of the phonon modes around 504 cm^–1 and 681 cm^–1 can be satisfactorily interpreted in terms of the change of the crystal structure and the itinerant nature of charge carrier in CuO₂ sheet. The relation between the structure and phonon vibration is discussed.     

Densification behavior, microstructure, and electrical properties of sol–gel-derived niobium-doped (Bi0.5Na0.5)0.94Ba0.06TiO3 ceramics

Superfine powders (~100 nm) with compositions of (1 − x)(Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ + xNb⁵⁺ (BNTBT6 + xNb) with x from 0 to 0.02 were synthesized by an improved citrate sol–gel method using Nb₂O₅ as Nb⁵⁺ source. The sintering behavior, microstructure, and various electrical properties of BNTBT6 + xNb ceramics were investigated. The results indicated that the addition of a small amount of Nb⁵⁺ has no remarkable effect on the crystal structure and grain morphology, but the electrical properties of the ceramics are obviously influenced. The BNTBT6 + 0.005Nb compositions exhibit enhanced densification behavior and improved electrical properties of a piezoelectric constant d ₃₃ ~ 205 pC/N and a planar electromechanical coupling factor k _p ~ 33%.     

Preparation, proton conduction, and application in ammonia synthesis at atmospheric pressure of La0.9Ba0.1Ga1– x Mg x O3–α

La_0.9Ba_0.1Ga_1–x Mg _x O_3–α (0 ≤ x ≤ 0.25) was prepared by the microemulsion method. A single phase of LaGaO₃ perovskite structure was formed when x was ≥0.15. Electrochemical hydrogen permeation (hydrogen pumping) proved that La_0.9Ba_0.1Ga_1–x Mg _x O_3–α had proton conduction, and the proton conduction was measured by AC impedance spectroscopy method from 400 to 800 °C in hydrogen atmospheres. Among these samples, La_0.9Ba_0.1Ga_0.8Mg_0.2O_3–α has the highest proton conductivity with the values of 9.51 × 10⁻⁴ to 4.68 × 10⁻² S cm⁻¹ at 400–800 °C. Ammonia was synthesized from nitrogen and hydrogen at atmospheric pressure in an electrolytic cell using La_0.9Ba_0.1Ga_0.8Mg_0.2O_3–α as electrolyte. The rate of NH₃ formation was 1.89 × 10⁻⁹ mol s⁻¹ cm⁻² at 520 °C upon imposing a current of 1 mA through the cell.     

Synthesis, crystal stability, and electrical behaviors of La0.7Sr0.3Cr0.4Mn0.6O3?δ–XCu0.75Ni0.25 for its possible application as SOFC anode

La_0.7Sr_0.3Cr_0.4Mn_0.6O_3−δ (perovskite-type) nanocomposites impregnated with XCu_0.75Ni_0.25 have been synthesized by sol–gel method. Crystal structure of LSCM–Cu_0.75Ni_0.25 composites were refined by the Rietveld method. Crystal symmetry of CuO and NiO nanoparticles have monoclinic and cubic symmetry, respectively, but after sintering at 1,200 °C and reducing the temperature to 600 °C, it’s transformed into a new Cu_0.75Ni_0.25 intermetallic solid solution without secondary phase. We have detected a cationic inter-diffusion in Cu ↔ Ni interphase crystals during this reduction process; however, when sintering time exceeds 2 h at 1,200 °C this reaction mechanism is interrupted by a sublimation phenomenon; which causes Cu₂O cubic structure segregation from monoclinic CuO structure. This leads to Cu precipitation from the Cu_1−x Ni _x solid solution. Cu_0.75Ni_0.25 inhibits the LSCM perovskite-type grain growth (t ≈ 220 nm). Electrical conductivity indicates the presence of semiconductor and metallic-type behaviors with a maximum electrical conductivity (800 °C) >4.5 (log σ, Sm cm⁻¹). When Cu_0.75Ni_0.25 concentration was 25 and 35 %, semiconductor behavior were dominated. Thermal expansion coefficients showed a linear dependence inversely proportional to Cu_0.75Ni_0.25 concentration. Electrical conductivity, Rietveld analysis, Porosity, TEC, and E _a behaviors lead to the conclusion that the anodes between 25 and 35 % (Cu_0.75Ni_0.25) are closer to applications at SOFC.     

Thermal conductivity of Ni, Co, and Fe-doped La5Ca9Cu24O41 thin films measured by the 3ω method

The effect of Ni-, Co- and Fe-substitution for Cu on the thermal conductivity of La₅Ca₉Cu₂₄O₄₁ thin films is investigated. Highly b-axis oriented polycrystalline films were grown onto MgO (100) substrates using the pulsed laser deposition technique. Thermal conductivity measurements were made between 90 K and 300 K using the dynamic 3ω method. The room-temperature thermal conductivity of 1% Ni:La₅Ca₉Cu₂₄O₄₁ and 1% Co:La₅Ca₉Cu₂₄O₄₁ is approximately 15% smaller than the thermal conductivity of pristine La₅Ca₉Cu₂₄O₄₁ thin films of similar thickness. On the other hand, the thermal conductivity of 1% Fe:La₅Ca₉Cu₂₄O₄₁ is approximately the same as the thermal conductivity of pristine La₅Ca₉Cu₂₄O₄₁ thin films of similar thickness. These results enable us to indirectly conclude that Ni²⁺ and Co²⁺ ions substitute Cu²⁺ ions in the crystal structure while Fe ions are not incorporated in the lattice.     

Heterogeneous equilibria in aqueous solutions of uranophosphates MII(PUO6)2·nH2O (MII = Mg2+, Ca2+, Sr2+, Ba2+)

The stability of uranophosphates M^II(PUO₆)₂·nH₂O (M^II = Mg, Ca, Sr, Ba) in aqueous solutions at pH from 0 to 14 was studied. These compounds preserve their composition and structure in the interval of pH 1–11 and congruently pass into the solution within the limits of their solubility. In strongly acidic media (pH < 1), alkaline-earth metal uranophosphates transform into uranophosphoric acid HPUO₆·4H₂O. In alkaline solutions at pH > 11, the uranophosphates MII(PUO₆)₂·nH₂O irreversibly transform into diuranates. Using the methods of equilibrium thermodynamics, the solubility products and Gibbs functions of formation of alkalineearth metal uranophosphates were calculated, the solubility curves were calculated and experimentally confirmed, and the speciation diagrams of U(VI) and P(V) in solutions and in equilibrium solid phases were constructed.     

Effect of Nb?+?Ti coating on the wetting behavior, interfacial microstructure, and mechanical properties of Al/Al2O3 joints

The subject of the work was to study the effect of Nb + Ti thin film deposited by PVD method on alumina substrates on the wetting behavior, bond strength properties, and structure of interface in the Al/Al₂O₃ joints. Applying the sessile drop method, the wetting behavior of molten Al (99,999%) on coated alumina substrates was studied in the temperature range between 953 and 1373 K under a vacuum of 0.2 mPa for 30 min of contact. The sessile drop samples were used to examine the interface structure, shear strength, and interfacial fracture toughness under the concentrated load. The introduction of the thin Nb + Ti film layer of 900 nm thickness: (1) greatly improves the wettability of alumina by molten Al at above 1223 K and the shear strength of Al/Al₂O₃ joints produced at 1223 K, (2) has positive effect on structure transformation in the interface and leads to fabrication of reliable metal–ceramic joints. Microstructural investigations of the interface indicated that the precipitates of Nb and Ti-rich intermetallic phases were formed at the Al/Al₂O₃ interface, which influenced strengthening of these joints. Hence a conclusion can be drawn that the interface structure influences the durability increase in Al/Al₂O₃ joints.     

Optical Properties, Electronic Structure and Magnetism of α′-NaxV2O5

The optical properties of sodium-deficient -Na _x V₂O₅ (0.85 x 1.00) single crystals are analyzed using ellipsometry, and infrared reflectivity techniques. In sodium deficient samples, the optical absorption peak associated to the fundamental electronic gap develops in the middle of the pure -NaV₂O₅ gap at 0.44 eV, and the material remains insulating up to the maximal achieved hole concentration of about 15%. Nonmetallic behavior under hole doping provoked reinterpretation of the -NaV₂O₅ optical spectra. We argue that the absorption peak at about 0.9 eV corresponds to the photoionization energy of a large polaron.     

The effect of Sm substitution on properties of Bi1.6Pb0.4Sr2Ca2? x Sm x Cu3O y superconductors

The effect of the partial substitution of Ca by Sm in the Bi-2223 superconducting samples have been investigated in terms of X-ray diffraction (XRD), EDXRF (Energy Dispersive X-ray Fluorescent), magnetoresistivity, critical temperature, transport critical current density, and ac susceptibility measurements. The samples were prepared by the conventional solid-state reaction method. XRD patterns are used to calculate lattice parameters and phase ratio of the Bi-2223 samples. The volume fraction was determined from the intensities of Bi-2223 and Bi-2212 peaks. The room temperature XRD patterns of the samples showed the presence of Bi-2223 phase decreases with increasing the Sm content. We estimated the transition temperature of the samples from the resistivity versus temperature measurements in dc magnetic fields up to 0.6 T. We observed that transition temperature, T _c , and transport critical current density, , depend on the Sm substitution. They both decrease with increasing the Sm substitution. We extracted the peak temperature, T _p , and the pinning force density from our previous ac susceptibility measurements. The pinning force density decreased with increasing the Sm content. The possible reasons for the observed decreases in critical temperature and critical current density due to Sm substitution were discussed.     

Study of the electron structure of Mn, Sr, La, Ce, and Sm cations in Ln1 ? x Sr x MnO3 (Ln = La, Ce, Sm) manganites by the X-ray line shift method

The X-RayK _α line shifts of all cations in Ln_{1 − x} Sr _x MnO₃ (Ln = La, Ce, Sm) manganites have been measured using crystal diffraction spectrometers. The Mn K _αline shifts have been found in the Sm_{1 − x} Sr _x MnO₃ system correspond to an increase in the valence from Mn³⁺ to Mn⁴⁺. In the Ce_{1 − x} Sr _x MnO₃ system, in addition to this, the valence of cerium have been found also increases to almost 4. It is shown that the dependence of the valence of manganese on the content of strontium does not correspond to a simple model of the local mixture of Mn³⁺ and Mn⁴⁺ ions, which is usually applied to these systems. It is also demonstrated that the bonds of Sr, La, and Sm in the manganites studied exhibit a significant covalent character. In cation-deficient Sm_{1 − y} Mn_{1 − z} O₃, an increase in the valence of Mn is found accompanied by a decrease in the covalence of Sm.     

High-pressure/high-temperature synthesis, crystal structure, and electrical properties of CaCu3 ? xFexV4O12

A perovskite-like compound of composition CaCu_{3 − x} Fe _x V₄O₁₂ (x = 0.7−1.0) has been synthesized at high pressures (p = 5.0−8.0 GPa) and temperatures (t = 1000−1300°C). Its crystal structure has been determined by X-ray diffraction (sp. gr. Im[`3]Im\bar 3, Z = 2, a = 7.3051(5) angles have been evaluated. The electrical conductivity of the high-pressure phase CaCu₂FeV₄O₁₂ exhibits metallic behavior.     

Improvement of the Irreversibility Line of the 1212 Compound Tl0.5Pb0.5Sr2CaCu2O7?δ

The superconducting properties and the irreversibility line of the Tl_0.5Pb_0.5Sr₂CaCu₂O_7– were studied by ac susceptibility on both ceramic and powder samples prepared in sealed quartz tube at 960°C. In parallel, carefull investigations by DTA/Tg, X rays diffraction and plasma emission spectroscopy were performed on each sample after each thermal treatment. It is shown that the superconducting properties are strongly dependent on further heat treatments and that the irreversibility line may be optimized. Nevertheless, the results obtained suggest that further improvement of the irreversibility line might be expected.     

Effect of Dissipation on Quantum Tunneling of Vortices in Tl2Ba2Ca2Cu3O10+δSuperconductors

The temperature and magnetic field dependence of the magnetic relaxation rate has been investigated at low temperatures (1.8 < T < 10 K) on two Tl₂Ba₂Ca₂Cu₃O₁₀₊ samples (epitaxial thin film and sintered pellet). The temperature dependence gives evidence of a crossover in the mechanism of vortex motion, from classical thermal activation to quantum tunneling as temperature decreases. The field dependence of the relaxation rate indicates a crossover in the dimensionality of vortices, from three-dimensional flux lines to two-dimensional pancake vortices as field increases. For the thin film, the temperature dependence of the rate has been fitted to the theoretically predicted expressions for finite-temperature enhancement of the quantum rate in different regimes of dissipation. In spite of the similarity of the fits, the estimate of the ratio of Hall to viscous drag terms in the equation of motion indicates that quantum tunneling in this system occurs in an intermediate dissipative regime, where both terms contribute to the motion of vortices.