The Dielectric Constant of Ba6−3x(Sm1−yNdy)8+2xTi18O54 (x = 2/3) Ceramics for Microwave Communication by Linear Regression Analysis

The electronics related to the fifth generation mobile communication technology (5G) are projected to possess significant market potential. High dielectric constant microwave ceramics used as filters and resonators in 5G have thus attracted great attention. The Ba_6−3x(Sm_1−yNd_y)_8+2xTi₁₈O₅₄ (x = 2/3) ceramic system has aroused people’s interest due to its underlying excellent microwave dielectric properties. In this paper, the relationships between the dielectric constant, Nd-doped content, sintering temperature and the density of Ba_6−3x(Sm_1−yNd_y)_8+2xTi₁₈O₅₄ (x = 2/3) ceramics were studied. The linear regression equation was established by statistical product and service solution (SPSS) data analysis software, and the factors affecting the dielectric constant have been analyzed by using the enter and stepwise methods, respectively. It is found that the model established by the stepwise method is practically significant with Y = −71.168 + 6.946x₁ + 25.799x₃, where Y, x₁ and x₃ represent the dielectric constant, Nd content and the density, respectively. According to this model, the influence of density on the dielectric constant is greater than that of Nd doping concentration. We bring the linear regression analysis method into the research field of microwave dielectric ceramics, hoping to provide an instructive for the optimization of ceramic technology.     

Hf1−xSixO2 Nanocomposite Coatings Prepared by Ion-Assisted Co-Evaporation Process for Low-Loss and High-LIDT Optics

Hf_1−xSi_xO₂ nanocomposites with different SiO₂ doping ratios were synthesized using an ion-assisted co-evaporation process to achieve dense amorphous Hf_1−xSi_xO₂ coatings with low loss and a high laser-induced damage threshold (LIDT). The results showed that the Hf_1−xSi_xO₂ nanocomposites (x ≥ 0.20) exhibited excellent comprehensive performance with a wide band gap and a dense amorphous microstructure. High-temperature annealing was carried out to ensure better stoichiometry and lower absorption. Precipitation and regrowth of HfO₂ grains were observed from 400 °C to 600 °C during annealing of the Hf_0.80Si_0.20O₂ nanocomposites, resulting in excessive surface roughness. A phenomenological model was proposed to explain the phenomenon. The Hf_1−xSi_xO₂ nanocomposites (x = 0.3 and 0.4) maintained a dense amorphous structure with low absorption after annealing. Finally, a 1064-nm Hf_0.70Si_0.30O₂/SiO₂ high-performance reflector was prepared and achieved low optical loss (15.1 ppm) and a high LIDT (67 J/cm²).     

An A- and B-Site Substitutional Study of SrFeO3−δ Perovskites for Solar Thermochemical Air Separation

An A‑ and B‑site substitutional study of SrFeO_3−δ perovskites (A’_xA_1−xB’_yB_1−yO_3−δ, where A = Sr and B = Fe) was performed for a two‑step solar thermochemical air separation cycle. The cycle steps encompass (1) the thermal reduction of A’_xSr_1−xB’_yFe_1−yO_3−δ driven by concentrated solar irradiation and (2) the oxidation of A’_xSr_1−xB’_yFe_1−yO_3−δ in air to remove O₂, leaving N₂. The oxidized A’_xSr_1−xB’_yFe_1−yO_3−δ is recycled back to the first step to complete the cycle, resulting in the separation of N₂ from air and concentrated solar irradiation. A-site substitution fractions between 0 ≤ x ≤ 0.2 were examined for A’ = Ba, Ca, and La. B-site substitution fractions between 0 ≤ y ≤ 0.2 were examined for B’ = Cr, Cu, Co, and Mn. Samples were prepared with a modified Pechini method and characterized with X-ray diffractometry. The mass changes and deviations from stoichiometry were evaluated with thermogravimetry in three screenings with temperature- and O₂ pressure-swings between 573 and 1473 K and 20% O₂/Ar and 100% Ar at 1 bar, respectively. A’ = Ba or La and B’ = Co resulted in the most improved redox capacities amongst temperature- and O₂ pressure-swing experiments.     

New Multicolor Tungstate-Molybdate Microphosphors as an Alternative to LED Components

Due to the ongoing need to create phosphors with the appropriate emission color for the production of light emitting diodes, we decided to synthesize a series of multicolour microphosphors with tunable visible emissions, depending on the composition of dopant ions. In this work, we investigated the structure, morphology, and luminescent properties of new molybdate–tungstate phosphors co-doped with Tb³⁺ and Eu³⁺ ions. The conventional high temperature solid state method was used to prepare a series of CaMo_yW_1−yO₄:Eu³⁺_x/Tb³⁺_1−x materials. In order to obtain phosphors with the most promising luminescent properties, the experiment was planned by taking into account the different composition of the matrix and the concentration of the particular dopant ions (Eu³⁺_x/Tb³⁺_1−x, x = 0.001, 0.003, 0.005, 0.007, 0.009). As a result, luminescent materials were obtained with a pure tetragonal crystal structure, the space group of I4₁/a, confirmed by X-ray diffraction (XRD). The size and shape of the particles obtained from the materials were analyzed based on scanning electron microscopy images. Luminescence spectroscopy (excitation and emission spectra, decay lifetimes) was utilized to characterize the luminescence properties of the as-prepared phosphors. The color change of the emission from green-yellow to orange-red was confirmed using the 1931 Comission Internationale de l’Eclairage (CIE) chromaticity coordinates and color correlated temperature (CCT).     

Synthesis,Crystal Structure and Luminescent Property of Cd (II) Complex with N-Benzenesulphonyl-L-leucine

A new trinuclear Cd (II) complex [Cd₃(L)₆(2,2-bipyridine)₃] [L = N-phenylsulfonyl-L-leucinato] has been synthesized and characterized by elemental analysis, IR and X-ray single crystal diffraction analysis. The results show that the complex belongs to the orthorhombic, space group P2₁2₁2₁ with a = 16.877(3) Å, b = 22.875(5) Å, c = 29.495(6) Å, α = β = γ = 90°, V = 11387(4) ų, Z = 4, D_c= 1.416 μg·m⁻³, μ = 0.737 mm⁻¹, F (000) = 4992, and final R₁ = 0.0390, ωR₂ = 0.0989. The complex comprises two seven-coordinated Cd (II) atoms, with a N₂O₅ distorted pengonal bipyramidal coordination environment and a six-coordinated Cd (II) atom, with a N₂O₄ distorted octahedral coordination environment. The molecules form one dimensional chain structure by the interaction of bridged carboxylato groups, hydrogen bonds and π-π interaction of 2,2-bipyridine. The luminescent properties of the Cd (II) complex and N-Benzenesulphonyl-L-leucine in solid and in CH₃OH solution also have been investigated.     

Boost the Crystal Installation and Magnetic Features of Cobalt Ferrite/M-Type Strontium Ferrite Nanocomposites Double Substituted by La3+ and Sm3+ Ions (2CoFe2O4/SrFe12−2xSmxLaxO19)

Spinel cobalt ferrite/hexagonal strontium hexaferrite (2CoFe₂O₄/SrFe_12−2xSm_xLa_xO₁₉; x = 0.2, 0.5, 1.0, 1.5) nanocomposites were fabricated using the tartaric acid precursor pathway, and the effects of La³⁺–Sm³⁺ double substitution on the formation, structure, and magnetic properties of CoFe₂O₄/SrFe_12−2xSm_xLa_xO₁₉ nanocomposite at different annealing temperatures were assayed through X-ray diffraction, scanning electron microscopy, and vibrating sample magnetometry. A pure 2CoFe₂O₄/SrFe₁₂O₁₉ nanocomposite was obtained from the tartrate precursor complex annealed at 1100 °C for 2 h. The substitution of Fe³⁺ ion by Sm³–⁺La³⁺ions promoted the formation of pure 2CoFe₂O₄/SrFe₁₂O₁₉ nanocomposite at 1100 °C. The positions and intensities of the strongest peaks of hexagonal ferrite changed after Sm³⁺–La³⁺ substitution at ≤1100 °C. In addition, samples with an Sm³⁺–La³⁺ ratio of ≥1.0 annealed at 1200 °C for 2 h showed diffraction peaks for lanthanum cobalt oxide (La₃Co₃O₈; dominant phase) and samarium ferrite (SmFeO₃). The crystallite size range at all constituent phases was in the nanocrystalline range, from 39.4 nm to 122.4 nm. The average crystallite size of SrFe₁₂O₁₉ phase increased with the number of Sm³⁺–La³⁺ substitutions, whereas that of CoFe₂O₄ phase decreased with an x of up to 0.5. La–Sm co-doped ion substitution increased the saturation magnetization (Ms) value and the subrogated ratio to 0.2, and the Ms value decreased with the increasing number of double substitutions. A high saturation magnetization value (Ms = 69.6 emu/g) was obtained using a La³⁺–Sm³⁺ co-doped ratio of 0.2 at 1200 for 2 h, and a high coercive force value (Hc = 1192.0 Oe) was acquired using the same ratio at 1000 °C.     

Combustion Synthesis and Photoluminescence Properties of Red-Emitting CaAlSiN3:Eu2+ Phosphor for White-LEDs

A combustion synthesis method has been developed for synthesis of Eu²⁺ doped CaAlSiN₃ phosphor and its photoluminescence properties were investigated. Ca, Al, Si, and Eu₂O₃ powders were used as the Ca, Al, Si and Eu sources. The addition of NaN₃, NH₄Cl and Si₃N₄ powders was found to increase significantly the product yield. These powders were mixed and pressed into a compact, which was then wrapped up with an igniting agent (i.e., Mg+Fe₃O₄). The compact was ignited by electrical heating under a N₂ pressure of ≤1.0 MPa. Effects of these experimental parameters on the product yield were investigated and a reaction mechanism was proposed. The synthesized CaAlSiN₃:Eu²⁺ phosphor absorbs light in the region of 200–600 nm and shows a broad band emission in the region of 500–800 nm due to the 4f⁶5d¹ → 4f⁷ transition of Eu²⁺. The sample doped with Eu²⁺ at the optimized molar ratio of 0.04 is efficiently excited by the blue light (460 nm) and generates emission peaking at ~650 nm with peak emission intensity ~106% of a commercially available phosphor, YAG:Ce³⁺(P46-Y3).The internal quantum efficiency of the synthesized phosphor was measured to be 71%, compared to 69% of the YAG:Ce³⁺ (P46-Y3).     

Nanorod Self-Assembly in High Jc YBa2Cu3O7?x Films with Ru-Based Double Perovskites

Many second phase additions to YBa₂Cu₃O_7−x (YBCO) films, in particular those that self-assemble into aligned nanorod and nanoparticle structures, enhance performance in self and applied fields. Of particular interest for additions are Ba-containing perovskites that are compatible with YBCO. In this report, we discuss the addition of Ba₂YRuO₆ to bulk and thick-film YBCO. Sub-micron, randomly oriented particles of this phase were found to form around grain boundaries and within YBCO grains in bulk sintered pellets. Within the limits of EDS, no Ru substitution into the YBCO was observed. Thick YBCO films were grown by pulsed laser deposition from a target consisting of YBa₂Cu₃O_y with 5 and 2.5 mole percent additions of Ba₂YRuO₆ and Y₂O₃, respectively. Films with enhanced in-field performance contained aligned, self-assembled Ba₂YRuO₆ nanorods and strained Y₂O₃ nanoparticle layers. A 0.9 µm thick film was found to have a self-field critical current density (J_c) of 5.1 MA/cm² with minimum J_c(Θ, H=1T) of 0.75 MA/cm². Conversely, J_c characteristics were similar to YBCO films without additions when these secondary phases formed as large, disordered phases within the film. A 2.3 µm thick film with such a distribution of secondary phases was found to have reduced self-field J_c values of 3.4 MA/cm² at 75.5 K and J_c(min, Θ, 1T) of 0.4 MA/cm².     

Enhancement of Y5−xPrxSb3−yMy (M = Sn,Pb) Electrodes for Lithium- and Sodium-Ion Batteries by Structure Disordering and CNTs Additives

The maximally disordered (MD) phases with the general formula Y_5−xPr_xSb_3−yM_y (M = Sn, Pb) are formed with partial substitution of Y by Pr and Sb by Sn or Pb in the binary Y₅Sb₃ compound. During the electrochemical lithiation and sodiation, the formation of Y_5-xPr_xSb_3-yM_yLi_z and Y_5−xPr_xSb_3−yM_yNa_z maximally disordered–high entropy intermetallic phases (MD-HEIP), as the result of insertion of Li/Na into octahedral voids, were observed. Carbon nanotubes (CNT) are an effective additive to improve the cycle stability of the Y_5−xPr_xSb_3−yM_y (M = Sn, Pb) anodes for lithium-ion (LIBs) and sodium-ion batteries (SIBs). Modification of Y_5−xPr_xSb_3−ySn_y alloys by carbon nanotubes allowed us to significantly increase the discharge capacity of both types of batteries, which reaches 280 mAh · g⁻¹ (for LIBs) and 160 mAh · g⁻¹ (for SIBs), respectively. For Y_5−xPrxSb_3−yPb_y alloys in which antimony is replaced by lead, these capacities are slightly smaller and are 270 mAh · g⁻¹ (for LIBs) and 155 mAh · g⁻¹ (for SIBs), respectively. Results show that structure disordering and CNT additives could increase the electrode capacities up to 30% for LIBs and up to 25% for SIBs.     

Thermal Evolutions to Glass-Ceramics Bearing Calcium Tungstate Crystals in Borate Glasses Doped with Photoluminescent Eu3+ Ions

Thermal evolutions of calcium-tungstate-borate glasses were investigated for the development of luminescent glass-ceramics by using Eu³⁺ dopant in a borate glass matrix with calcium tungstate, which was expected to have a combined character of glass and ceramics. This study revealed that single-phase precipitation of CaWO₄ crystals in borate glass matrix was possible by heat-treatment at a temperature higher than glass transition temperature T_g for (100−x) (33CaO-67B₂O₃)−xCa₃WO₆ (x = 8−15 mol%). Additionally, the crystallization of CaWO₄ was found by Raman spectroscopy due to the formation of W=O double bondings of WO₄ tetrahedra in the pristine glass despite starting with the higher calcium content of Ca₃WO₆. Eu³⁺ ions were excluded from the CaWO₄ crystals and positioned in the borate glass phase as a stable site for them, which provided local environments in higher symmetry around Eu³⁺ ions.     

Luminescent Afterglow Behavior in the M2Si5N8: Eu Family (M = Ca,Sr, Ba)

Persistent luminescent materials are able to emit light for hours after being excited. The majority of persistent phosphors emit in the blue or green region of the visible spectrum. Orange- or red-emitting phosphors, strongly desired for emergency signage and medical imaging, are scarce. We prepared the nitrido-silicates Ca₂Si₅N₈:Eu (orange), Sr₂Si₅N₈:Eu (reddish), Ba₂Si₅N₈:Eu (yellowish orange), and their rare-earth codoped variants (R = Nd, Dy, Sm, Tm) through a solid state reaction, and investigated their luminescence and afterglow properties. In this paper, we describe how the persistent luminescence is affected by the type of codopant and the choice and ratio of the starting products. All the materials exhibit some form of persistent luminescence, but for Sr₂Si₅N₈:Eu,R this is very weak. In Ba₂Si₅N₈:Eu the afterglow remains visible for about 400 s, and Ca₂Si₅N₈:Eu,Tm shows the brightest and longest afterglow, lasting about 2,500 s. For optimal persistent luminescence, the dopant and codopant should be added in their fluoride form, in concentrations below 1 mol%. A Ca₃N₂ deficiency of about 5% triples the afterglow intensity. Our results show that Ba₂Si₅N₈:Eu(,R) and Ca₂Si₅N₈:Eu(,R) are promising persistent phosphors for applications requiring orange or red light.     

Effect of Sintering Process on Ionic Conductivity of Li7-xLa3Zr2-xNbxO12 (x = 0, 0.2, 0.4, 0.6) Solid Electrolytes

Garnet-type Li₇La₃Zr₂O₁₂ (LLZO) is considered as a promising solid electrolyte. Nb-doped LLZO ceramics exhibit significantly improved ion conductivity. However, how to prepare the Nb-doped LLZO ceramics in a simple and economical way, meanwhile to investigate the relationship between process conditions and properties in Li_7-xLa₃Zr_2-xNb_xO₁₂ ceramics, is particularly important. In this study, Li_7-xLa₃Zr_2-xNb_xO₁₂ (LLZN_xO, x = 0, 0.2, 0.4, 0.6) ceramics were prepared by conventional solid-state reaction. The effect of sintering process on the structure, microstructure, and ionic conductivity of LLZN_xO (x = 0, 0.2, 0.4, 0.6) ceramics was investigated. Due to the more contractive Nb-O bonds in LLZN_xO ceramics, the cubic structures are much easier to form and stabilize, which could induce the decreased preparation time. High-performance garnet LLZN_xO ceramics can be obtained by optimizing the sintering process with lower calcining temperature and shorter holding time. The garnet samples with x = 0.4 calcined at 850 °C for 10 h and sintered at 1250 °C for 4 h exhibit the highest ionic conductivity of 3.86 × 10⁻⁴ S·cm⁻¹ at room temperature and an activation energy of 0.32 eV, which can be correlated to the highest relative density of 96.1%, and good crystallinity of the grains.     

Crystal and molecular structure of n,n'-diethyl-n,n'-diphenylurea

N,N′-diphenyl-N,N′-diethylurea (C₁₇H₂₀N₂O) crystallizes in the space group P2₁/c. The unit cell constants are: a = 10.42 ± 0.01 Å, b = 16.86 ± 0.02 Å, c = 10.66 ± 0.001 Å, β = 125°16′ ± 5′; Z = 4, D_x = 1.16 g·cm^-3, D_meas = 1.16 ± 0.01 g·cm^-3. Data for 1392 reflections were collected at room temperature on a Picker automated diffractometer. The crystal structure was solved by direct methods and refined by bloc-diagonalized matrix least-squares calculations. The molecule is characterized by a pseudo C₂ symmetry; both phenyl groups are trans with respect to the oxygen atom. The hybridization of the two nitrogen atoms is intermediate between trigonal and tetrahedral; the nonplanar distortion of the amide groups is about 30°. The amide C-N bond lengths are 1.37 Å.     

A First-Principles Study of the Cu-Containing β″ Precipitates in Al-Mg-Si-Cu Alloy

The nanostructured β″ precipitates are critical for the strength of Al-Mg-Si-(Cu) aluminum alloys. However, there are still controversial reports about the composition of Cu-containing β″ phases. In this work, first-principles calculations based on density functional theory were used to investigate the composition, mechanical properties, and electronic structure of Cu-containing β″ phases. The results predict that the Cu-containing β″ precipitates with a stoichiometry of Mg_4+xAl_2−xCuSi₄ (x = 0, 1) are energetically favorable. As the concentration of Cu atoms increases, Cu-containing β″ phases with different compositions will appear, such as Mg₄AlCu₂Si₄ and Mg₄Cu₃Si₄. The replacement order of Cu atoms in β″ phases can be summarized as one Si3/Al site → two Si3/Al sites → two Si3/Al sites and one Mg1 site. The calculated elastic constants of the considered β″ phases suggest that they are all mechanically stable, and all β″ phases are ductile. When Cu atoms replace Al atoms at Si3/Al sites in β″ phases, the values of bulk modulus (B), shear modulus (G), and Young’s modulus (E) all increase. The calculation of the phonon spectrum shows that Mg_4+xAl_2−xCuSi₄ (x = 0, 1) are also dynamically stable. The electronic structure analysis shows that the bond between the Si atom and the Cu atom has a covalent like property. The incorporation of the Cu atom enhances the electron interaction between the Mg2 and the Si3 atom so that the Mg2 atom also joins the Si network, which may be one of the reasons why Cu atoms increase the structure stability of the β″ phases.     

Phase Transition and Coefficients of Thermal Expansion in Al2−xInxW3O12 (0.2 ≤ x ≤ 1)

Materials from theA₂M₃O₁₂ family are known for their extensive chemical versatility while preserving the polyhedral-corner-shared orthorhombic crystal system, as well as for their consequent unusual thermal expansion, varying from negative and near-zero to slightly positive. The rarest are near-zero thermal expansion materials, which are of paramount importance in thermal shock resistance applications. Ceramic materials with chemistry Al_2−xIn_xW₃O₁₂ (x = 0.2–1.0) were synthesized using a modified reverse-strike co-precipitation method and prepared into solid specimens using traditional ceramic sintering. The resulting materials were characterized by X-ray powder diffraction (ambient and in situ high temperatures), differential scanning calorimetry and dilatometry to delineate thermal expansion, phase transitions and crystal structures. It was found that the x = 0.2 composition had the lowest thermal expansion, 1.88 × 10⁻⁶ K⁻¹, which was still higher than the end member Al₂W₃O₁₂ for the chemical series. Furthermore, the AlInW₃O₁₂ was monoclinic phase at room temperature and transformed to the orthorhombic form at ca. 200 °C, in contrast with previous reports. Interestingly, the x = 0.2, x = 0.4 and x = 0.7 materials did not exhibit the expected orthorhombic-to-monoclinic phase transition as observed for the other compositions, and hence did not follow the expected Vegard-like relationship associated with the electronegativity rule. Overall, compositions within the Al_2−xIn_xW₃O₁₂ family should not be considered candidates for high thermal shock applications that would require near-zero thermal expansion properties.     

Linking the Electrical Conductivity and Non-Stoichiometry of Thin Film Ce1−xZrxO2−δ by a Resonant Nanobalance Approach

Bulk ceria-zirconia solid solutions (Ce_1−xZr_xO_2−δ, CZO) are highly suited for application as oxygen storage materials in automotive three-way catalytic converters (TWC) due to the high levels of achievable oxygen non-stoichiometry δ. In thin film CZO, the oxygen storage properties are expected to be further enhanced. The present study addresses this aspect. CZO thin films with 0 ≤ x ≤ 1 were investigated. A unique nano-thermogravimetric method for thin films that is based on the resonant nanobalance approach for high-temperature characterization of oxygen non-stoichiometry in CZO was implemented. The high-temperature electrical conductivity and the non-stoichiometry δ of CZO were measured under oxygen partial pressures pO₂ in the range of 10⁻²⁴–0.2 bar. Markedly enhanced reducibility and electronic conductivity of CeO₂-ZrO₂ as compared to CeO_2−δ and ZrO₂ were observed. A comparison of temperature- and pO₂-dependences of the non-stoichiometry of thin films with literature data for bulk Ce_1−xZr_xO_2−δ shows enhanced reducibility in the former. The maximum conductivity was found for Ce_0.8Zr_0.2O_2−δ, whereas Ce_0.5Zr_0.5O_2-δ showed the highest non-stoichiometry, yielding δ = 0.16 at 900 °C and pO₂ of 10⁻¹⁴ bar. The defect interactions in Ce_1−xZr_xO_2−δ are analyzed in the framework of defect models for ceria and zirconia.     

Magnetic and Electrical Behaviors of the Homo- and Heterometallic 1D and 3D Coordination Polymers Based on the Partial Decomposition of the [Cr(C2O4)3]3− Building Block

One-dimensional (1D) oxalate-bridged homometallic {[Mn(bpy)(C₂O₄)]·1.5H₂O}_n (1) (bpy = 2,2’-bipyridine) and heterodimetallic {[CrCu₃(bpy)₃(CH₃OH)(H₂O)(C₂O₄)₄][Cu(bpy)Cr(C₂O₄)₃]·CH₂Cl₂·CH₃OH·H₂O}_n (2) coordination polymers, as well as the three-dimensional (3D) heterotrimetallic {[CaCr₂Cu₂(phen)₄(C₂O₄)₆]·4CH₃CN·2H₂O}_n (3) (1,10-phenanthroline) network, have been synthesized by a building block approach using a layering technique, and characterized by single-crystal X-ray diffraction, infrared (IR) and impedance spectroscopies and magnetization measurements. During the crystallization process partial decomposition of the tris(oxalato)chromate(III) happened and 1D polymers 1 and 2 were formed. The antiferromagnetic interactions between the manganese(II) ions were mediated by oxalate ligands in the chain [Mn(bpy)(C₂O₄)]_n of 1, with intra-chain super-exchange interaction 𝐽 = (−3.134 ± 0.004) K; magnetic interaction between neighbouring chains is negligible making this system closer than other known Mn-chains to the ideal 1D Heisenberg antiferromagnet. Compound 2 comprises a 1D coordination anion [Cu(bpy)Cr(C₂O₄)₃]_nⁿ⁻ (Cr2–Cu4) with alternating [Cr(C₂O₄)₃]³⁻ and [Cu(bpy)]²⁺ units mutually bridged through the oxalate group. Another chain (Cr1–Cu3) is similar, but involves a homodinuclear unit [Cu(bpy)(H₂O)(µ-C₂O₄)Cu(bpy)(CH₃OH)]²⁺ (Cu1–Cu2) coordinated as a pendant group to a terminal oxalate oxygen. Magnetic measurements showed that the Cu1−Cu2 cationic unit is a strongly coupled antiferromagnetic dimer, independent from the other magnetic ions within ferromagnetic chains Cr1–Cu3 and Cr2–Cu4. A 3D polymer {[CaCr₂Cu₂(phen)₄(C₂O₄)₆]·4CH₃CN·2H₂O}_n (3) comprising three different metal centers (Ca²⁺, Cr³⁺ and Cu²⁺) oxalate-bridged, contains Ca²⁺ atoms as nodes connected with four Cr³⁺ atoms through oxalate ligands. The network thus formed can be reduced to an underlying graph of diamondoid (dia) or (6⁶) topology. Magnetization of 3 shows the ferromagnetic oxalate-bridged dimers [Cu^IICr^III], whose mutual interaction could possibly originate through the spin polarization of Ca²⁺ orbitals. Compounds 1 and 3 exhibit lower electrical conductivity at room temperature (RT) in comparison to compound 2.     

Local convergence theorems for adaptive stochastic approximation schemes

For the regression model y = M(x) + ε, adaptive stochastic approximation schemes of the form x_n+1 = x_n — y_n/(nb_n) for choosing the levels x₁,x₂,... at which y₁,y₂,... are observed converge with probability 1 to the unknown root θ of the regression function M(x). Certain local convergence theorems that relate the convergence rate of x_n — θ to the limiting behavior of the random variables b_n are established.     

Insertion Compounds of 2H-TaS(2).NH(3)

A new method of intercalating metals into layer compounds has been developed using electrolytic generation from the salt solution in ammonia. The results suggest that metals that are soluble in ammonia will form a homogeneous metal-ammonia intercalate layer, NH₃·M_x, when x is less than the limiting solubility of M in NH₃. The superconducting transition temperature (T_c) was found to increase as the c-axis expansion [2δ = c(TaS₂·NH₃·M_x) - c(2H-TaS₂)] decreased when M = lithium, sodium, and potassium. Of all the alkali metals, potassium gave the most stable compounds and the highest T_c, 4.7°K.     

New O3-Type Layer-Structured Na0.80[Fe0.40Co0.40Ti0.20]O2 Cathode Material for Rechargeable Sodium-Ion Batteries

Herein, we formulated a new O3-type layered Na_0.80[Fe_0.40Co_0.40Ti_0.20]O₂ (NFCTO) cathode material for sodium-ion batteries (SIBs) using a double-substitution concept of Co in the parent NaFe_0.5Co_0.5O₂, having the general formula Na_1-x[Fe_0.5–x/2Co_0.5–x/2M⁴⁺_x]O₂ (M⁴⁺ = tetravalent ions). The NFCTO electrode delivers a first discharge capacity of 108 mAhg⁻¹ with 80% discharge capacity retention after 50 cycles. Notably, the first charge–discharge profile shows asymmetric yet reversible redox reactions. Such asymmetric redox reactions and electrochemical properties of the NFCTO electrode were correlated with the phase transition behavior and charge compensation reaction using synchrotron-based in situ XRD and ex situ X-ray absorption spectroscopy. This study provides an exciting opportunity to explore the interplay between the rich chemistry of Na_1–x[Fe_0.5–x/2Co_0.5–x/2M⁴⁺_x]O₂ and sodium storage properties, which may lead to the development of new cathode materials for SIBs.