Magnetic Anomalies and Electronic Structure of Ce<Subscript>2</Subscript>Cu<Subscript>2</Subscript>Mg and Ce<Subscript>2</Subscript>Pd<Subscript>2</Subscript>Mg

The intermetallic compounds RE ₂Cu₂Mg and RE ₂Pd₂Mg (RE=La, Ce) were prepared and characterized by magnetic susceptibility and heat-capacity measurements. They crystallize with an ordered U₃Si₂ type structure (space group P4/mbm) and the cerium compounds contain stable trivalent cerium ions, which undergo antiferromagnetic ordering at ∼7.5 and ∼4 K, respectively. In high magnetic fields Ce₂Cu₂Mg exhibits spin reorientation with critical field strength of 40 kOe at 5 K. The data are compared to the non-magnetic isotypic compounds La₂ T ₂Mg (T=Cu, Ni, Pd) and to the already reported intermediate valent Ce₂Ni₂Mg.     

Structural investigations of V<Subscript>2</Subscript>O<Subscript>5</Subscript>–P<Subscript>2</Subscript>O<Subscript>5</Subscript>–CaO glass system by FT-IR and EPR spectroscopies

xV₂O₅·(100 − x)[0.7P₂O₅·0.3CaO] glass system was obtained for 0 ≤ x ≤ 35 mol% V₂O₅. In order to obtain information regarding their structure, several techniques such as X-Ray diffraction, FT-IR, and EPR spectroscopies were used. X-Ray diffraction patterns of investigated samples are characteristic of vitreous solids. FT-IR spectra of 0.7P₂O₅·0.3CaO glass matrix and its deconvolution show the presence in the glass structure of all structural units characteristic to P₂O₅. Their number are increasing for x ≤ 3 mol% V₂O₅ then, for higher content of vanadium ions, the number of phosphate structural units are decreasing leading to a depolymerization of the structure. The structural units characteristic to V₂O₅ were not evidenced but their contribution to the glass structure can be clearly observed. EPR revealed a well resolved hyperfine structure (hfs) typical for vanadyl ions in a C_4v symmetry for x ≤ 3 mol% V₂O₅. For 5 < x < 20 mol% V₂O₅ the spectra show a superposition of two EPR signals one due to a hfs structure and another consisting of a broad line typical for associated V⁴⁺–V⁴⁺ ions. For x ≥ 20 mol% V₂O₅ only the broad line can be observed. The composition dependence of the line-width suggests the presence of dipole–dipole interaction between vanadium ions up to x ≤ 5 mol% V₂O₅ and superexchange interactions between vanadium ions for x > 5 mol% V₂O₅.     

Catalytic combustion of methane over Pt and PdO-supported CeO<Subscript>2</Subscript>–ZrO<Subscript>2</Subscript>–Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts

Catalytic combustion of methane was investigated on Pt and PdO-supported CeO₂–ZrO₂–Bi₂O₃/γ-Al₂O₃ catalysts prepared by a wet impregnation method in the presence of polyvinylpyrrolidone. The catalysts were characterized by X-ray fluorescence analysis, X-ray powder diffraction, X-ray photoelectron spectra, transmission electron microscopy, and BET specific surface area measurements. The Pt/CeO₂–ZrO₂–Bi₂O₃/γ-Al₂O₃ and PdO/CeO₂–ZrO₂–Bi₂O₃/γ-Al₂O₃ catalysts were selective for the total oxidation of methane into carbon dioxide and steam, and no by-products such as HCHO, CO, and H₂ were obtained. The catalytic activities of the PdO/CeO₂–ZrO₂–Bi₂O₃/γ-Al₂O₃ catalysts were relatively higher than those of the Pt-supported catalysts, due to the facile re-oxidation of metallic Pd into PdO based on lattice oxygen supplied from the CeO₂–ZrO₂–Bi₂O₃ bulk. A decrease in the calcination temperature during the preparation process was found to be effective in enhancing the specific surface area of the catalysts, whereby particle agglomeration was inhibited. Optimization of the PdO amount and calcination temperature enabled complete oxidation of methane at temperatures as low as 320 °C on the 11.6 wt% PdO/CeO₂–ZrO₂–Bi₂O₃/γ-Al₂O₃ catalyst prepared at 400 °C.     

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.     

Preparation and characterization of Li<Subscript>2</Subscript>O–CaO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–P<Subscript>2</Subscript>O<Subscript>5</Subscript>–SiO<Subscript>2</Subscript> glasses as bioactive material

The aim of the present investigation was to study the role of Al₂O₃ in the Li₂O–CaO–P₂O₅–SiO₂ bioactive glass for improving the bioactivity and other physico-mechanical properties of glass. A comparative study on structural and physico-mechanical properties and bioactivity of glasses were reported. The structural properties of glasses were investigated by X-ray diffraction, Fourier transform infrared spectrometry, scanning electron microscopy and the bioactivity of the glasses was evaluated by in vitro test in simulated body fluid (SBF). Density, compressive strength, Vickers hardness and ultrasonic wave velocity of glass samples were measured to investigate physical and mechanical properties. Results indicated that partial molar replacement of Li₂O by Al₂O₃ resulted in a significant increase in mechanical properties of glasses. In vitro studies of samples in SBF had shown that the pH of the solution increased after immersion of samples during the initial stage and then after reaching maxima it decreased with the increase in the immersion time. In vitro test in SBF indicated that the addition of Al₂O₃ up to 1.5 mol% resulted in an increase in bioactivity where as further addition of Al₂O₃ caused a decrease in bioactivity of the samples. The biocompatibility of these bioactive glass samples was studied using human osteoblast (MG-63) cell lines. The results obtained suggested that Li₂O–CaO–Al₂O₃–P₂O₅–SiO₂-based bioactive glasses containing alumina would be potential materials for biomedical applications.     

Syntheses and proton conductivity of mesoporous Nd<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript> and NdOCl–SiO<Subscript>2</Subscript> composites

Two mesoporous oxide composites of Nd₂O₃–SiO₂ and NdOCl–SiO₂ were synthesized using SBA-15 as a template and neodymium nitrate or neodymium chloride as a precursor. The porous Nd₂O₃–SiO₂ with a SBA-15-like structure has amorphous walls and the porous NdOCl–SiO₂ with a replicated structure of SBA-15 has crystalline walls. These porous materials were characterized by X-ray diffraction, transmission electron microscopy and nitrogen adsorption/desorption. They exhibited significant proton conductivities in the presence of moisture at low temperatures and the highest conductivity observed was 4.55 × 10⁻⁴ S/cm at 47 °C in wet air (RH = 28.6%).     

Evaluation of CaO–SiO<Subscript>2</Subscript>–P<Subscript>2</Subscript>O<Subscript>5</Subscript>–Na<Subscript>2</Subscript>O–Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> bioglass-ceramics for hyperthermia application

Magnetic bioglass ceramics (MBC) are being considered for use as thermoseeds in hyperthermia treatment of cancer. While the bioactivity in MBCs is attributed to the formation of the bone minerals such as crystalline apatite, wollastonite, etc. in a physiological environment, the magnetic property arises from the magnetite [Fe₃O₄] present in these implant materials. A new set of bioglasses with compositions 41CaO · (52 ? x)SiO₂ · 4P₂O₅  · xFe₂O₃ · 3Na₂O (2 ≤ x ≤ 10 mol% Fe₂O₃) have been prepared by melt quenching method. The as-quenched glasses were then heat treated at 1050°C for 3 h to obtain the glass-ceramics. The structure and microstructure of the samples were characterized using X-ray diffraction and microscopy techniques. X-ray diffraction data revealed the presence of magnetite in the heat treated samples with x ≥ 2 mol% Fe₂O₃. Room temperature magnetic property of the heat treated samples was investigated using a Vibrating Sample Magnetometer. Field scans up to 20 kOe revealed that the glass ceramic samples had a high saturation magnetization and low coercivity. Room temperature hysteresis cycles were also recorded at 500 Oe to ascertain the magnetic properties at clinically amenable field strengths. The area under the magnetic hysteresis loop is a measure of the heat generated by the MBC. The coercivity of the samples is another important factor for hyperthermia applications. The area under the loop increases with an increase in Fe₂O₃ molar concentration and the. coercivity decreases with an increase in Fe₂O₃ molar concentration The evolution of magnetic properties in these MBCs as a function of Fe₂O₃ molar concentration is discussed and correlated with the amount of magnetite present in them.     

Crystallization and microstructural evolution of MgO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript>–TiO<Subscript>2</Subscript>–La<Subscript>2</Subscript>O<Subscript>3</Subscript> glass-ceramics

Crystallization and microstructure of glasses with the molar compositions 1MgO·1.2Al₂O₃·2.8SiO₂·1.2TiO₂·xLa₂O₃ (x = 0.1 and 0.4) were thermally treated at different temperatures in the range from 950 to 1250 °C and then analyzed by X-ray diffraction and scanning electron microscopy, in combination with energy-dispersive X-ray spectroscopy and electron backscatter diffraction. It was found that the microstructure is first homogeneous with the precipitation of randomly distributed crystals and then indialite domains with embedded perrierite and rutile crystals are formed. For higher temperatures or prolonged times, more domains appear and expand into the bulk of the sample. Finally, the entire sample consists of the indialite domains and the boundaries that are enriched in rutile, perrierite, and magnesium aluminotitanate. Nevertheless, very distinct differences are observed between the samples with different La₂O₃ concentrations. For the sample with x = 0.4, the domains were detected at lower temperatures, while the quantity and size of the domains increase faster due to the promoted precipitation of indialite. For the sample with x = 0.1, in addition to the domain boundaries, secondary boundaries between the “regions” (assemblages of the domains) are observed in a larger length scale. The average size of the crystalline phases found between the “regions” is larger than that typically observed at the domain boundaries. The sizes of the crystals at the boundaries decrease with higher concentrations of La₂O₃, and the crystals (especially perrierite) within the domains become larger, resulting in a more homogeneous microstructure. This results in better dielectric properties, i.e., much higher quality factor for the sample with x = 0.4 in comparison to that with x = 0.1 after heat-treatment at 1150 or 1250 °C.     

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.     

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.     

Thermodynamic and structural properties of PrBaCo<Subscript>2</Subscript>O<Subscript>5 + δ</Subscript>

The oxygen content of the double cobaltite PrBaCo₂O_{5 + δ} was determined by coulometric titration in broad temperature and oxygen pressure ranges, and the partial thermodynamic functions of oxygen were evaluated. The results on the nonstoichiometry and structural properties of PrBaCo₂O_{5 + δ} demonstrate that, at 5 + δ < 5.3, this cobaltite has a high-temperature phase with lattice parameters a = 11.774 Å, b = 11.932 Å, and c = 7.609 Å. The composition dependences of \(\Delta \bar H(O)\) and \(\Delta \bar S(O)\) indicate that the 3a_p × 3a_p × 2a_p orthorhombic structure persists in the range 5.15 ≤ 5 + δ ≤ 5.30. Some of the Co³⁺ ions are shown to disproportionate according to the scheme 2Co³⁺=Co²⁺+Co⁴⁺.     

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.     

Superconducting Bands Stabilizing Superconductivity in YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>7</Subscript> and MgB<Subscript>2</Subscript>

It is shown that the ceramic superconductor YBa₂Cu₃O₇ as well as the superconducting intermetallic compound MgB₂ possesses a narrow, partly filled “superconducting band” with Wannier functions of special symmetry in their band structures. This result corroborates previous observations about the band structures of numerous superconductors and non-superconductors showing that evidently superconductivity is always connected with such superconducting bands. These findings are interpreted in the framework of a nonadiabatic extension of the Heisenberg model. Within this new group-theoretical model of correlated systems, Cooper pairs are stabilized by a nonadiabatic mechanism of constraining forces effective in narrow superconducting bands. The formation of Cooper pairs in a superconducting band is mediated by the energetically lowest boson excitations in the considered material that carry the crystal-spin angular momentum 1⋅ℏ. These crystal-spin-1 bosons are proposed to determine whether the material is a conventional low-T _c or a high-T _c superconductor. This interpretation provides the electron–phonon mechanism that enters the BCS theory in conventional superconductors.     

Synthesis and characterization of TiO<Subscript>2</Subscript>–NiO and TiO<Subscript>2</Subscript>–WO<Subscript>3</Subscript> nanocomposites

TiO₂–NiO and TiO₂–WO₃ nanocomposites were prepared by hydrothermal and surface modification methods. The samples were analyzed using X-ray diffraction, Scanning Electron Microscope images, Transmission Electron Microscope, Energy dispersive analysis, Zeta potential, Electrophoretic mobility and Photocatalysis activity measurement. XRD data sets of TiO₂–NiO, TiO₂–WO₃ powder nanocomposite have been studied for the inclusion of NiO, WO₃ on the anatase-rutile mixture phase of TiO₂ by Rietveld refinement. The cell parameters, phase fraction, the average grain size, strain and bond lengths between atoms of individual phases have been reported in the present work. Shifted positional co-ordinates of individual atoms in each phase have also been observed.     

Atomistic structure and energetics of interface between Mn-doped γ-Ga<Subscript>2</Subscript>O<Subscript>3</Subscript> and MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript>

The interface between an Mn-doped γ-gallium oxide (Ga₂O₃) thin film and an MgAl₂O₄ (001) substrate has been investigated using high-resolution transmission electron microscopy (HRTEM), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), and first-principles calculations. A high-quality Mn-doped γ-Ga₂O₃ film with a defective spinel structure has been epitaxially grown by pulsed laser deposition. The γ-Ga₂O₃ crystal shows an uniform tetragonal distortion with a tetragonality of 1.05 throughout the film thickness of 75 nm. HRTEM and HAADF-STEM observations reveal that the γ-Ga₂O₃ and MgAl₂O₄ crystals form a coherent interface without any interfacial layers or precipitates. The atomistic structure and energies are theoretically evaluated for the interfaces with two types of termination plane, i.e., Mg- and Al₂O₄-termination of MgAl₂O₄. The cation sublattice is found to be continuous for both interfaces despite the defective spinel structure of Mn-doped γ-Ga₂O₃ with some vacant cation sites. The Al₂O₄-termination shows a lower interfacial energy than the Mg-termination under most conditions of the chemical potentials. This behavior is attributed to the energetic preference of the Mn–Al₂O₄ local configuration at the interface.     

Preparation and properties of Bi<Subscript>6</Subscript>Ti<Subscript>5</Subscript>WO<Subscript>22</Subscript>: a new phase in the Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>–TiO<Subscript>2</Subscript>–WO<Subscript>3</Subscript> system

In a recent report, the evaluation of the phase relations in the Bi₂O₃–TiO₂–WO₃ ternary system has shown the existence of a new phase with nominal composition close to Bi₆Ti₅WO₂₂. In the present contribution we attempt to prepare this single phase by using a solid state route. Although XRD analyses also show traces of two minority Aurivillius-type phases in the synthesized materials, the crystal structure of the Bi₆Ti₅WO₂₂ phase has been determined by Rietveld analyses revealing a complex structure similar to that of Bi₃(AlSb₂)O₁₁ and PbHoAl₃O₈ related compounds. The electrical response of this new phase was characterized as well. Three peaks are observed in its dielectric response: two of them positioned around 0 °C and can be assigned to this Bi₆Ti₅WO₂₂ structure. The third one rises up to 665 °C and confirms the presence of the Aurivillius-type phases.     

Thermodynamics and kinetics of MgH<Subscript>2</Subscript>–nfTa<Subscript>2</Subscript>O<Subscript>5</Subscript> composite for reversible hydrogen storage application

The thermodynamics and kinetics of hydrogen absorption–desorption of nfTa₂O₅–Mg–MgH₂—composite (nf stands for nano-flakes) have been studied. The nfTa₂O₅–Mg composite could absorb hydrogen at room temperature (17 °C). The hydrogen desorption of nfTa₂O₅–MgH₂ composite starts at 200 °C. The remarkably improved hydrogen absorption–desorption of catalyzed Mg–MgH₂ could be attributed to the nano-engineered surface by nfTa₂O₅. The enthalpies of hydrogen absorption–desorption were found to be 80 ± 2, and 76 ± 3 kJ/mol respectively. The activation energy of hydrogen absorption was evaluated as 49 ± 5 kJ/mol which is same as the energy barrier for diffusion of hydrogen in Mg matrix. The apparent activation of hydrogen desorption of nfTa₂O₅–MgH₂ was found to be 74 ± 7 kJ/mol. The nfTa₂O₅–MgH₂ composite has shown cyclic stability up to fifty hydrogen absorption–desorption without significant changes in the kinetics and hydrogen storage capacity.     

Fabrication of Yb<Subscript>2</Subscript>O<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–P<Subscript>2</Subscript>O<Subscript>5</Subscript>–SiO<Subscript>2</Subscript> Optical Fibers with a Perfect Step-Index Profile by the MCVD Process

An all-vapor phase MCVD process has been proposed for the fabrication of fiber preforms with a Yb₂O₃–Al₂O₃–P₂O₅–SiO₂ multicomponent glass core. We have investigated the tubular preform collapse into a rod and demonstrated approaches capable of preventing P₂O₅ losses in the central part of the core during the collapse process. Preforms with a flat, perfect step-index profile have been fabricated.     

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.     

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.