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.     

Microstructure and properties of the Ba<Subscript>0.75−x</Subscript>Ca<Subscript>x</Subscript>La<Subscript>0.25</Subscript>Fe<Subscript>11.6</Subscript>Co<Subscript>0.25</Subscript>Ti<Subscript>0.15</Subscript>O<Subscript>19</Subscript> hexaferrites

In the case of Ti⁴⁺ remain unchanged, the Ca²⁺ substituted Ba_0.75?xCa_xLa_0.25Fe_11.6Co_0.25Ti_0.15O₁₉ (0?≤?x?≤?0.05) were prepared by conventional solid-state reaction method at temperature of 1280 °C. A ball-to-power weight ratio of 10:1. Their crystal structure and magnetic properties were mainly investigated. The results show that the single magnetoplumbite phase structure transformed into the multiphase structure. Meanwhile, the small amount of α-Fe₂O₃ phase existed in M-type phase. The micrographs were observed by a field emission scanning electron microscopy (SEM). Vibrating sample magnetometer (VSM) was used to analyze the magnetic properties. The saturation magnetization (M _s ) first increases then decreases when x from 0 to 0.03. But, when x from 0.03 to 0.05, the saturation magnetization (M _s ) first increases then decreases too. The maximum value is at x?=?0.04 (M _s ?=?70.73 emu/g). The value of coercivity (H _c ) first increases then decreases when x from 0 to 0.04. But, the value increased when x from 0.04 to 0.05. The maximum value is at x?=?0.02 (H _c ?=?1691 Oe).     

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.     

Phase equilibria in the system “CaAl<Subscript>2</Subscript>Si<Subscript>3</Subscript>O<Subscript>10</Subscript>”-Na<Subscript>2</Subscript>Al<Subscript>2</Subscript>Si<Subscript>3</Subscript>O<Subscript>10</Subscript>-H<Subscript>2</Subscript>O

The phase equilibria in the “CaAl₂Si₃O₁₀”-Na₂Al₂Si₃O₁₀-H₂O system are analyzed using structural and thermal analysis data, and the ideal gonnardite structure is modeled. The results suggest that, to ensure a better correlation with the structures of the zeolites in this series, a new structural model of the gonnardite-based solid solution must be selected, with the structure rotated through 45° about the c axis in the ab plane.     

Phase equilibria in the Tl<Subscript>5</Subscript>Te<Subscript>3</Subscript>–Tl<Subscript>9</Subscript>BiTe<Subscript>6</Subscript>–Tl<Subscript>9</Subscript>TbTe<Subscript>6</Subscript> system

Phase equilibria in the Tl₅Te₃–Tl₉BiTe₆–Tl₉TbTe₆ system have been studied using differential thermal analysis, X-ray diffraction, and microhardness measurements. We have mapped out a number of vertical sections, the 760-K isothermal section of its phase diagram, and projections of its liquidus and solidus surfaces. The composition dependences of lattice parameters and microhardness have been obtained. The system has been shown to contain a continuous series of solid solutions, which crystallize in a tetragonal structure (Tl₅Te₃ type, sp. gr. I4/mcm).     

Enhanced microwave dielectric properties of Ba<Subscript>0.40</Subscript>Sr<Subscript>0.60</Subscript>TiO<Subscript>3</Subscript>–Zr<Subscript>0.80</Subscript>Sn<Subscript>0.20</Subscript>TiO<Subscript>4</Subscript> composite ceramics

The (1−x) Ba_0.40Sr_0.60TiO₃ (BST)−xZr_0.80Sn_0.20TiO₄ (ZST) composite ceramics with x = 10, 20, 30, and 40 wt% were fabricated by conventional solid-state reaction method. With increasing of ZST content, the dielectric constant of composite ceramics was decreased and dielectric loss increases. The effect of ZnO addition to 70 wt% BST–30 wt% ZST composition on the microstructure and dielectric properties was investigated. The improvements in dielectric constant, dielectric loss, and microwave dielectric properties of composite ceramics can be achieved by ZnO addition. The sample with 98 wt% (70 wt% BST–30 wt% ZST)–2 wt%ZnO composition exhibits promising dielectric properties, with dielectric constant, loss tangent and tunability at 4 kV/mm, of 125, 0.0016 and 12%, at 10 kHz and room temperature. At ~2 GHz, it possesses a dielectric constant of 101 and a Q factor of 187, which makes it a good candidate for tunable microwave device applications.     

Investigation of solid solution of ZrP<Subscript>2</Subscript>O<Subscript>7</Subscript>–Sr<Subscript>2</Subscript>P<Subscript>2</Subscript>O<Subscript>7</Subscript>

In this study, ZrP₂O₇ was synthesized by the solid state reaction of ZrO₂ and NH₄H₂PO₄ at 900 °C. Then, in set 1; 10, 5, 1, 0.5, 0.1, 0.05, 0.03% previously prepared Sr₂P₂O₇ were doped into ZrP₂O₇, and Sr₂P₂O₇ slightly affect the unit cell parameter of cubic ZrP₂O₇ (a = 8.248(6)–8.233(8) Å). The reverse of this process was also applied to Sr₂P₂O₇ system (set 2). ZrP₂O₇ changes the unit cell parameters of orthorhombic Sr₂P₂O₇ in between a = 8.909(5)–8.877(5) Å, b = 13.163(3)–13.12(1) Å, and c = 5.403(2)–5.386(4) Å. Analysis of the vibrations of the P₂O ₇ ^4? ion and approximate band assignments for IR and Raman spectra are also reported in this work. Some coincidences in infrared and Raman spectra both sets were found and strong P–O–P bands were observed. Surface morphology, EDX analysis, and thermoluminescence properties of both sets were given the first time in this paper.     

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.     

Phase equilibria in the Tl<Subscript>2</Subscript>Te–Tl<Subscript>5</Subscript>Te<Subscript>3</Subscript>–Tl<Subscript>9</Subscript>TbTe<Subscript>6</Subscript> system

The Tl₂Te–Tl₅Te₃–Tl₉TbTe₆ system has been studied using differential thermal analysis, X-ray diffraction, and microhardness measurements. We have mapped out a number of vertical sections, the 680 K isothermal section of its phase diagram, and projections of its polythermal projections of its liquidus and solidus surfaces. The field of solid solutions with the Tl₅Te₃ structure (δ-phase) has been shown to account for more than 90% of the area of the composition triangle. Tl₂Te-based solid solutions (α-phase) exist in a narrow composition region.     

Dual relaxation behaviors and large electrostrictive properties of Bi<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>–Sr<Subscript>0.85</Subscript>Bi<Subscript>0.1</Subscript>TiO<Subscript>3</Subscript> ceramics

Lead-free ceramics (1???x)Bi_0.5Na_0.5TiO₃–xSr_0.85Bi_0.1TiO₃ (BNT–xSBT, x?=?0.4, 0.5, 0.6 and 0.7) were prepared by a solid-state reaction process. Coexistence of ferroelectric relaxation at low temperature and Maxwell–Wagner dielectric relaxation at high temperature was revealed for the first time in this system. Meanwhile, hysteresis-free P–E loops combined with a very high piezoelectric strain coefficient (d₃₃) of 1658 pC/N concurrently with large electrostrictive coefficient Q?=?0.287 m⁴C^?2 were achieved. The ferroelectric relaxor behavior and large electrostrictive strain might be linked to easy reorientation and reversal of ergodic PNRs and the combined effect of Bi off-center position and lone pair electrons.     

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.     

Electrical properties of B site substituted (K<Subscript>0.48</Subscript>Na<Subscript>0.52</Subscript>)(W<Subscript>2/3</Subscript>Bi<Subscript>1/3</Subscript>)<Subscript>x</Subscript>Nb<Subscript>1−x</Subscript>O<Subscript>3</Subscript> piezoceramics

Lead-free (K_0.48Na_0.52)(W_2/3Bi_1/3)_xNb_1−xO₃ (KNN-WBi) piezoceramics with x ranging from 0.004 to 0.010 were synthesized by conventional ceramic processing. The sintered KNN-WBi ceramics showed perovskite structure without detectable secondary phase containing W and Bi. With increasing x, the orthorhombic-tetragonal phase transition temperature (T _O-T) decreased from 200 to 184 °C whereas, the tetragonal-cubic phase transition temperature (T _C) decreased slightly. With the doping of (W_2/3Bi_1/3), the piezoelectric properties were greatly improved and the piezoelectric constants d ₃₃, k _p, Q _m exhibited maximum values of 136 pC/N, 43.3% and 175, respectively at x = 0.008. The KNN-WBi ceramics also exhibited good ferroelectric properties with remnant polarizations P _r higher than 25 μC/cm² and coercive fields E _c lower than 1,000 V/mm. The results strongly suggest that the B site doping of constructed quinquevalent element is an effective method for the investigation of potassium sodium niobate system.     

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.     

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.     

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.     

Microwave dielectric properties of Sr<Subscript>0.7</Subscript>Ce<Subscript>0.2</Subscript>TiO<Subscript>3</Subscript>–Sr(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript> ceramics

xSr_0.7Ce_0.2TiO₃–(1???x)Sr(Mg_1/3Nb_2/3)O₃ ceramics, referred to xSCT–(1???x)SMN, were successfully produced by conventional solid-state sintered technology. The compounds, belonging to perovskites with a secondary phase of CeO₂, can be detected even with x down to 0.1 of SCT composition. The overall trend for grain growth illustrates the increase with increasing SCT doping level. The Raman peak at 825 cm^?1 splits into two peaks and causes red shift phenomenon. XPS spectra indicate that Ti and Nb ions exist respectively in tetravalence and pentavalence, and Ce ions exist in trivalence and tetravalence. Dielectrics constant (ε _r ) of SCT–SMN ceramics gradually increases with increasing theoretical dielectric polarizabilities. A wider width of the 825 cm^?1 for FWHM of A_1g mode Raman peaks suggests to a lower Q?×?f value. The increasing tolerance factor in agreement with temperature coefficient of resonant frequency (τ _f ), denotes that the rise of perovskite symmetry. The 0.1SCT–0.9SMN ceramic sintered at 1450?°C for 4 h illustrates excellent microwave dielectric properties with ε _r ?~?35.4, Q?×?f?~?11282 GHz and τ _f ?~?1.7 ppm/°C. Activation energies of 0.1SCT–0.9SMN ceramic at 100, 300 and 500 V, are ~0.436, 0.427 and 0.331 eV, respectively, indicative of a decreased trend with external electric field.     

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.     

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.     

A physicochemical study of the Sb<Subscript>2</Subscript>Se<Subscript>3</Subscript>–Nd<Subscript>2</Subscript>Se<Subscript>3</Subscript> system

We have studied phase relations in the Sb₂Se₃–Nd₂Se₃ system and mapped out its T–x phase diagram using differential thermal analysis, X-ray diffraction, microstructural analysis, microhardness tests, and density measurements. The system contains one compound, with the composition NdSbSe₃, which melts incongruently at 865 K and crystallizes in orthorhombic symmetry with the following lattice parameters: а = 12.77(1) Å, b = 14.08(1) Å, and c = 5.82(5) Å (Z = 8, ρ_meas = 6.20 g/cm³, ρ_x = 6.38 g/cm³). At room temperature, the Nd₂Se₃ solubility in Sb₂Se₃ is 5 mol % and the Sb₂Se₃ solubility in Nd₂Se₃ is 2.5 mol %. The Sb₂Se₃–Nd₂Se₃ system has a eutectic located at 15 mol % Nd₂Se₃, with a melting point at 755 K. The electrical conductivity and thermoelectric power of the (Sb₂Se₃)_1–x (Nd₂Se₃) _x solid solutions have been measured as functions of temperature.     

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.