New LiCo0.5PrxFe2−xO4 nanoferrites: Prepared via low cost technique for high density storage application

Praseodymium substituted nano crystalline LiCo spinel ferrites with different concentrations were fabricated by micro-emulsion route. TGA, X-ray diffraction and magnetic properties was employed to study the effect of substitution of the Pr on the structure and magnetic parameters. XRD confirmed the formation of the single phase spinel ferrites with minor coexistence of orthophase. The particle size from XRD data was calculated in range from 53 nm to 106 nm. The VSM was employed for magnetic studies between ? 10,000 Oe and 10,000 Oe range. Considerable high value of ‘Hc’ coercivity (1581 Oe) and an enhanced value of ‘Ms’ saturation magnetization (51 emu/g) have been obtained as result of substitution. The value of Hc is high enough value but in soft ferrite range. Hence synthesized LiCo_0.5Pr_xFe_2?xO₄ ferrites are suitable for high density storage devices application.     

Defect chemistry and dielectric behavior of Sr0.99Ce0.01Ti1−xO3 ceramics with high permittivity

Sr_0.99Ce_0.01Ti_1-xO₃ (SCT, x?=?0, ±?0.0025, ±?0.0050, 0.0075) ceramics were prepared by solid state reaction methods and sintered in air atmosphere at different temperatures, with a soaking time of 2?h. The dielectric properties of all samples presented excellent temperature independence over a broad temperature range from 25 to 330?℃ and frequency independence between 10?kHz and 1?MHz. Sr_0.99Ce_0.01Ti_0.9925O₃ (SCT0.9925) ceramics sintered in air atmosphere exhibited a high permittivity (~5400) and a low dielectric loss (~0.01) measured at room temperature and 1?kHz. XPS and complex impedance spectroscopy analysis confirmed that the high permittivity and low dielectric loss were attributed to the fully ionized oxygen vacancies and giant defect-dipoles in Ti-deficient samples. However, a higher dielectric loss of Ti-rich samples is owing to the destruction of giant defect dipoles, in which highly localized electrons were transformed into hopping electrons.     

Low-temperature sintering of Ti1−xCux/3Nb2x/3O2 (x = 0.23) microwave dielectric ceramics with CuO and B2O3 addition

The influence of CuO and B₂O₃ addition on the sintering behavior, microstructure and microwave dielectric properties of Ti_1?xCu_x/3Nb_2x/3O₂ (TCN, x = 0.23) ceramic have been investigated. It was found that the addition of CuO and B₂O₃ successfully reduced the sintering temperature of TCN ceramics from 950 to 875 °C. X-ray diffraction studies showed that addition of CuO-B₂O₃ has no effect on the phase composition. The TCN ceramics with 0.5 wt% CuO-B₂O₃ addition showed a high dielectric constant of 95.63, τ_f value of + 329 ppm/°C and a good Q × f value of 8700 GHz after sintered at 875 °C for 5 h, cofirable with silver electrode.     

Sintering,crystallization and properties of 2(Mg1−xMnx)O·2Al2O3·5SiO2 ceramics

Mn-substituted cordierites, 2(Mg_1?xMn_x)O·2Al₂O₃·5SiO₂ (x?=?0–1), were prepared from natural components (talc, clay, alumina) and MnO_2. Sintering behavior, phase transformation, and microstructural features of the samples were investigated using X-ray diffraction (XRD), differential thermal analysis (DTA), dilatometric measurements and scanning electron microscopy (SEM) with energy dispersive analysis (EDS). The results of DTA and XRD analysis indicate that MnO₂ is successively reduced to Mn₂O₃ and MnO in the sintering process. Mn²⁺ ions incorporate into the crystal structure of α-cordierite substituting Mg²⁺ ions in octahedral sites and thus increasing the cordierite unit cell volume. Mn promotes the sintering process: the crystallization temperature, melting point, density and open porosity of Mn-substituted cordierites lowered, whereas the shrinkage and medium pore diameter enlarged with an increase in MnO₂ content in the mixture of raw materials. Surface enrichment with Mn with the formation of manganese oxide crystallites was found for the samples with high substitution degree.     

Structural,magnetic and elastic properties of Mn0.3−xMgxCu0.2Zn0.5Fe3O4 nanoparticles

In this paper, Mn_0.3?xMg_xCu_0.2Zn_0.5Fe₃O₄ (x?=?0.00, 0.05, 0.10, 0.15, 0.20, 0.25, 0.30) nanoparticles were prepared by the nitrate-citrate technique at low temperature. The structural, microstructural, magnetic and elastic properties of the samples were characterized by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy, Transmission electron microscopy, field emission-scanning electron microscopy and vibrating-sample magnetometer at room temperature. Rietveld refinement of the XRD patterns indicated the formation of the single phase cubic spinel structure (space group Fd-3m) without any detectable impurity phase in all the samples that also was confirmed by FTIR studies. The lattice parameter is found to increase non-monotonically with an increase in Mg ion concentration. Also, the bond lengths and bond angles (A and B sites) of the studied ferrites were calculated by the refining of the XRD data. The values of the crystallite size decrease with increasing micro-strain (and conversely) and both of them reach extremum at x?=?0.15. The low remanence and coercivity values confirmed the formation of the superparamagnetic ferrites nanoparticles. The saturation magnetization of the samples gradually grows with Mg substitution and reach extremum at x?=?0.15. Variation of saturation magnetization with Mg content can be mainly attributed to change of cation distribution, and Yafet-Kittel angle occurred between magnetic moments on B-site in the samples. The values of Young's modulus, Debye temperature, bulk modulus, rigidity modulus of the samples were determined by the values of elastic constant and wave velocities obtained from the force constants. The improvement of the elastic properties of sample x?=?0.05 could be explained regarding the smaller values of the lattice parameter (a), the bond length and angle and the smaller crystallite size.     

Crystal structure and enhanced microwave dielectric properties of the Ce2[Zr1−x(Al1/2Ta1/2)x]3(MoO4)9 ceramics at microwave frequency

Dense microwave dielectric ceramics of Ce₂[Zr_1−x(Al_1/2Ta_1/2)_x]₃(MoO₄)₉(CZMAT) (x = 0.02–0.10) were prepared by the conventional solid-state route. The effects of (Al1/2Ta1/2)⁴⁺ on their microstructures, sintering behaviors, and microwave dielectric properties were systematically investigated. On the basis of the X-ray diffraction (XRD) results, all the samples were matched well with Pr₂Zr₃(MoO₄)₉ structures, which belonged to the space group R3¯c. The lattice parameters were obtained using the Rietveld refinement method. The correlations between the chemical bond parameters and microwave dielectric properties were calculated and analyzed by using the Phillips—Van Vechten—Levine (P—V—L) theory. Excellent dielectric properties of Ce₂[Zr_0.94(Al_1/2Ta_1/2)_0.06]₃(MoO₄)₉ with a relative permittivity (ε_r) of 10.46, quality factor (Q × f) of 83,796 GHz, and temperature coefficient of resonant frequency (τ_f) of −11.50 ppm/℃ were achieved at 850 ℃.     

Variation in structures and photoluminescence spectra of BaxEu1−xAl2O4 powders

Barium europium(II) aluminate (Ba_xEu_1?xAl₂O₄) powders were prepared by a solid-state reaction among barium carbonate (BaCO₃), europium oxide (Eu₂O₃), and alumina (Al₂O₃) powders at 1400 °C for 3 h under a mixed gas flow of H₂ and N₂. The powders were characterized by powder X-ray diffraction (XRD), infrared and Raman spectroscopy, and photoluminescence (PL). With increasing Ba²⁺ content in Ba_xEu_1?xAl₂O₄, the structure of Ba_xEu_1?xAl₂O₄ changed from a monoclinic (P2₁) to hexagonal (P6₃) phase. The hexagonal (P6₃22) phase was also observed between the two phases. The XRD pattern of a single Ba_0.6Eu_0.4Al₂O₄ phase, which has not been reported in the literature, was refined by the Rietveld method and its structure was confirmed by selected-area electron diffraction. With increasing x value, the emission peak in the PL spectra of Ba_xEu_1?xAl₂O₄ became weaker (x = 0–0.4) and then more intense (x = 0.6–0.98), and its position showed a blue shift from 520 to 498 nm.     

Microwave absorption of M-type hexaferrite Ba1-xCaxFe12O19 (x ≤ 0.4) ceramics in 2.6–18 GHz

Ba_1-xCa_xFe₁₂O₁₉ (x?=?0.0, 0.1, 0.2, 0.3 and 0.4, BCFO) ceramics were prepared using high-temperature solid-state method and the effect of Ca²⁺ substitution was investigated. The grain size of BCFO ceramics sintered at 1250?°C for 2?h increases from 1?µm to 5?µm as Ca²⁺ added. The BCFO ceramics show a typical hard magnetic behavior with a maximum saturation magnetization (M_S) of 51.8?emu?g^?1 at x?=?0.2. The bandwidth of microwave reflection loss (RL) below ??10?dB (> 90.0% microwave absorption) is obtained in 7.60???9.8?GHz with the minimum RL ??30.8?dB at 8.5?GHz for x?=?0.2 (thickness 2.0?mm), which makes Ba_0.8Ca_0.2Fe₁₂O₁₉ ceramic a potential microwave absorption candidate.     

Structural and magnetic properties of Pr–Ni substituted Ca0.5Ba0.5Fe12O19 hexa-ferrite nanoparticles

Effect of Pr–Ni substitution on structural and magnetic properties of Ca_0.5Ba_0.5−xPr_xNi_yFe_12−yO₁₉ (x=0.00–0.10 and y=0.00–1.00) prepared by the sol–gel auto combustion method were investigated. The XRD analysis confirmed the single phase M-type hexa-ferrite structure. The lattice parameters were found to increase as Pr–Ni content increases, which is attributed to the ionic size of the implicated cations. The Pr–Ni seems to be completely soluble in the lattice. Transmission electron microscopy reveals that the grain size decreases with increase of Pr–Ni substitution. The coercivity and remanent magnetization ranges from 1511 to 1925 (Oe) and 21.4 to 26.5 (emu/g), respectively. The coercivity values of all the samples fall in the range of M-type hexa-ferrites.     

Magnetic and magnetotransport properties of La1−xSrxMn0.5Сo0.5O3 perovskites

La_1?xSr_xMn_0.5Сo_0.5O₃ (x ≤ 0.75) perovskites have been studied as a function of temperature by neutron powder diffraction (NPD), magnetization and magnetoresistance measurements. The NPD data show that x = 0.15 and 0.5 compounds are stoichiometric, so the Sr²⁺ doping transforms Co²⁺ ions into the Co³⁺ ones, whereas manganese ions remain in the 4+ oxidation state as in the parent ferromagnetic compound ${\mathrm{LaCo}}_{\mathrm{0.5}}^{\mathrm{2}+}{\mathrm{Mn}}_{\mathrm{0.5}}^{\mathrm{4}+}{\mathrm{O}}_{\mathrm{3}}$. The magnetization data show a decrease in the Curie temperature from 215 K for the compound with x = 0 down to 147 K for the compound with x = 0.05. The compounds with x > 0.15 show an increase in T_C up to 260 K (x = 0.75) in spite of a gradual decrease of the spontaneous magnetization. The stoichiometric compound x = 0.5 demonstrates a sharp ferromagnet-paramagnet transition with T_C = 250 K. However, there is no visible coherent magnetic contribution to the NPD patterns. All compounds are semiconductors and exhibit large magnetoresistance gradually increasing with decrease of temperature. The magnetic data have been interpreted assuming that the Co³⁺ ions are in high spin state, however, there is a fraction of cobalt ions in low spin state. It is suggested that the superexchange interaction between Co³⁺ ions in the high spin state and Mn⁴⁺ ions is ferromagnetic and that the ferromagnetism of the compounds with x > 0.5 and high T_C is associated with positive exchange interactions between Co³⁺ being in high spin state and Mn⁴⁺ ions distributed within the short range regions. Based on the NPD results and magnetization data the magnetic phase diagram has been constructed.     

Nb modified structural,magnetic and magnetocaloric properties of double perovskite Ba2FeMo1−xNbxO6

A systematic study focusing on the effect of Niobium (Nb) doping on the structural, magnetic and magnetocaloric properties of Ba₂FeMoO₆ samples is presented here. The samples of interest Ba₂FeMo_1?xNb_xO₆ (0 ≤ x ≤ 0.4) were prepared using the solid state reaction method and were confirmed to possess a cubic structure with Fm-3m space group using the X-ray diffraction analysis and Rietveld refinement. A second order of ferromagnetic phase transition was recorded in both the pure as well as the Nb doped samples using the temperature dependent magnetization and Arrott plots analysis. The pristine Ba₂FeMoO₆ (BFMO) sample indicated a spontaneous magnetization (34.6 emu/g at 100 K) with a relatively sharp magnetic transition at the Curie temperature (T_C) of 315 K as compared to the doped samples. A magnetic entropy change of 0.93 Jkg^?1K^?1 at an applied magnetic field of 2.5 T was measured for the pure BFMO sample. The doped BFMO samples with Mo partially substituted by Nb however, were observed to effectively modify the T_C accompanied by a decrease in magnetization. The results investigated in this work suggest that the magnetic and magnetocaloric properties of the BFMO can be tailored by controlled Nb doping which is of significant importance in order to realize the numerous potential applications of the material in the magnetic refrigeration technology.     

Efficient oxidative desulfurization (ODS) of model fuel with H2O2 catalyzed by MoO3/γ-Al2O3 under mild and solvent free conditions

An efficient process to remove organic sulfur compounds from model fuel has been explored. Dibenzothiophene (DBT) and 4, 6-dimethyldibenzothiophene (4, 6-DMDBT) can be completely oxidized into their corresponding sulfones by H₂O₂ over 14 wt.% MoO₃/γ-Al₂O₃ catalyst under mild conditions in 15 min. The effects of solvent, initial sulfide concentration, loading of MoO₃ and amount of catalyst on oxidative removal of DBT were studied. The employments of solvents have decreased the reaction rate of DBT, which can be attributed to the competitive adsorption between the sulfide and solvent. The oxidative reactivity increases in the order of thiophene (Th) < benzothiophene (BT) < DBT < 4, 6-DMDBT. The catalyst can be regenerated by methanol washing at 333 K.     

Influence of LiBO2 addition on the microstructure and lithium-ion conductivity of Li1+xAlxTi2−x(PO4)3(x = 0.3) ceramic electrolyte

Concerning the safety problems of conventional Li-ion batteries with liquid electrolytes, it is crucial to develop reliable solid-state electrolytes with high ionic conductivity. Li_1+xAl_xTi_2?x(PO₄)₃ (LATP, x = 0.3) is regarded as one of the most promising solid electrolytes due to its high ionic conductivity and excellent chemical stability to humidity.Herein, a new strategy is proposed for improving the sintering behavior and enhancing the ionic conductivity of LATP by using LiBO₂ as the sintering aid via liquid phase sintering. The as-prepared sample LATP with homogeneous microstructure and high relative density of 97.1% was successfully synthesized, yielding high total ionic conductivity of 3.5 × 10^?4 S cm^?1 and low activation energy of 0.39 eV at room temperature. It was found that the addition of LiBO₂ could effectively enhance the densification and increase the ionic conductivity of LATP electrolyte, proving an effective way to synthesis LATP ceramics by a simple and reliable route.     

Glycol-citrate synthesis of fine-grained oxides La2−xGdxZr2O7 and preparation of corresponding ceramics using FAST/SPS process

Single-phase superfine refractory oxides of composition La_2?xGd_xZr₂O₇ (x = 0, 0.5, 1, 1.5, 2) have been synthesized using glycol-citrate route. Dependencies of degree of dispersion and phase composition on chemical composition for such oxides were determined. Fluorite-pyrochlore transition observed during thermal treatment of these oxides was examined. It was stated that this transition occurred in the temperature range 1000–1200?°C for all formulations with exception of gadolinium zirconate Gd₂Zr₂O₇ which kept the fluorite structure even after long-term exposure (4?h) at a temperature of 1400?°С. Samples of corresponding ceramics which density amount to 95–98% of the theoretical value were obtained using FAST/SPS process. Coefficients of linear thermal expansion (CLTE) of manufactured materials were measured. It was found that CLTE values for all samples except for gadolinium zirconate were independent of temperature in the range 400–1000?°C. It was shown that Gd₂Zr₂O₇ kept the fluorite structure under conditions of FAST/SPS process at a temperature of 1600?°C.     

Emission analysis of CdO–Bi2O3–B2O3 glasses doped with Eu and Tb

This article reports on the emission properties of cadmium bismuth borate (CdBiB) glasses as a function of doping concentrations of Eu³⁺ and Tb³⁺ ions. The functional groups present in the glasses have been identified by analyzing FT-IR spectra. The emission spectra of Eu³⁺ and Tb³⁺:CdBiB glasses have shown reddish green emissions at 616 nm (⁵D₀→⁷F₂) under the excitation at 465 nm and at 547 nm (⁵D₄→⁷F₅) under the excitation at 485 nm, respectively. The Judd–Ofelt (J–O) theory was applied to evaluate the J–O intensity parameters from the absorption and the emission spectra; by using the J–O intensity (Ω_λ) parameters, spontaneous emission transition probability (A), total radiative transition rate (A_T), radiative lifetime (τ_R) and branching ratios (β) of the various emission transitions have been computed for both Eu³⁺ and Tb³⁺:CdBiB glasses. The quenching behavior in the emission intensity with increased concentration of Eu³⁺ and Tb³⁺ was observed, which could be useful for optimizing the compositions toward practical applications.     

Magneto-electric properties of xNi0.7Zn0.3Fe2O4 – (1-x)BaTiO3 multiferroic composites

Di-phase ceramic composites, with general formula xNi_0.7Zn_0.3Fe₂O₄ – (1-x)BaTiO₃(x = 0.9, 0.7, 0.5, 0.3, 0.1), were prepared by a mixing method. X-ray analysis, for powder and ceramics, indicated the formation of ferrite and barium titanate phases without the presence of the impurities. SEM analysis indicated that the composite morphology contained two types of grains, polygonal and rounded. Homogeneous microstructure and the smallest grain size were obtained in ceramics with 70% of barium titanate. The electrical properties of these materials were investigated using impedance spectroscopy, dielectric and ferroelectric measurements. The NZF-BT(30-70) composite has shown better electrical properties in comparison to other investigated ceramics, confirmed by dielectric and ferroelectric data analysis. Saturation magnetization and coercive field decreased with the increase of the content of ferroelectric phase.     

Interactions of MgO·Al2O3 spinel with Cu,Cu2O and copper matte at high temperature

Magnesia-chrome refractory has been used in the copper industry for decades, and the chromium in the used refractory has been proved to have the risk to harm the environment. A reliable chromium-free refractory is urged to replace the chromium-containing refractory in the future. In the present study, MgO·Al₂O₃ spinel was systematically tested with Cu, Cu₂O, and industrial matte respectively at 1300?°C. All samples were directly quenched into the water after the experiments and examined by electron probe X-ray microanalysis. The molten Cu and MgO·Al₂O₃ spinel did not react and showed a low wettability, while limited reactions between the spinel and matte were detected. However, severe reactions occurred between the spinel and Cu₂O at 1300?°C. The possible applications of the spinel in the copper-making industry are discussed based on the experimental results.     

Magnetic properties of hard (CoFe2O4)–soft (Fe3O4) composite ceramics

Composite ceramics of CoFe₂O₄/Fe₃O₄ with different weight ratios were synthesized by Spark Plasma Sintering (SPS) at a sintering temperature of 500 °C. The X-ray diffraction patterns demonstrate that all samples are composed of CoFe₂O₄ and Fe₃O₄ phases. The magnetization curves for all the composite ceramic are single-step loops indicating the existence of exchange spring effect. Due to the competition between the exchange interaction and the dipolar interaction, magnetic properties like coercivity (H_c) and remanence (M_r) are sensitive to the weight ratio of the soft phase.     

Low temperature sintering and microwave dielectric properties of Li2ZnTi3O8 ceramics doped with ZnO–La2O3–B2O3 glass

Li₂ZnTi₃O₈ ceramics doped with ZnO–La₂O₃–B₂O₃ glass were prepared by the conventional solid-state ceramic route. The effects of the ZnO–La₂O₃–B₂O₃ glass on the sintering temperature, phase composition, microstructure and microwave dielectric properties of Li₂ZnTi₃O₈ ceramics were investigated. The addition of ZLB glass can reduce the sintering temperature of Li₂ZnTi₃O₈ ceramic from 1075 °C to 925 °C without obvious degradation of the microwave dielectric properties. Only a single phase Li₂ZnTi₃O₈ with cubic spinel structure is formed in Li₂ZnTi₃O₈ ceramic with ZLB addition sintered at 925 °C. Typically, 1.0 wt% ZLB-doped Li₂ZnTi₃O₈ ceramic sintered at 925 °C can reach a maximum relative density of 95.8% and exhibits good microwave dielectric properties of ε_r=24.34, Q×f=41,360 GHz and τ_f=−13.4 ppm/°C. Moreover, this material is compatible with Ag electrode, which makes it a promising candidate for LTCC application.     

Crystal structure,Raman spectra and microwave dielectric properties of Li2Mg3Ti1-x(Mg1/3Nb2/3)xO6 (0 ≤x ≤ 0.25) ceramics

Li₂Mg₃Ti_1-X(Mg_1/3Nb_2/3)_XO₆ (0?≤x?≤?0.25) ceramics were prepared by a conventional solid-state reaction process. Their crystal structures, sintering characteristics, Raman spectra and microwave dielectric properties were then investigated. XRD patterns of the sintered samples indicated that all compositions showed a single phase and the rock-salt structure. As the (Mg_1/3Nb_2/3)⁴⁺ contents increase, the variations of ε_r values showed a downward trend, which could be explained by the changes of polarizabilities and the shift of Raman vibration modes. Q·f values initially increased to a maximum value and then decreased with increasing of x values. In addition, τ_f values decreased almost linearly with the x values, which significantly correlated with the thermal expansion coefficient. Excellent combined microwave dielectric properties with ε_r =?14.79, Q·f?=?204,900?GHz and τ_f =??18.43?ppm/°C were obtained for Li₂Mg₃Ti_.95(Mg_1/3Nb_2/3)_.05O₆ ceramic sintered at 1550?°C.