Synthesis of Cu-modified Co2Z hexaferrite with planar structure by a citrate precursor method

Co₂Z hexaferrite is a planar anisotropic iron oxide which can present high values of permeability at high frequency. In this paper, Cu-modified Co₂Z hexaferrites powders were synthesized at a low temperature using a citrate precursor method. The formation of Z-type phases was characterized by X-ray diffraction and magnetization measurements. It is found that phase formation temperature and sintering temperature were influenced directly by the content of copper. The effects of Cu-substitution on the microstructure and high frequency properties of the ceramics have been investigated.     

Improvement of the magnetic properties of barium hexaferrite nanopowders using modified co-precipitation method

Barium hexaferrite BaFe₁₂O₁₉ powders have been synthesized using the modified co-precipitation method. Modification was performed via the ultrasonication of the precipitated precursors at room temperature for 1 h and the additions of the 2% KNO₃, surface active agents and oxalic acid. The results revealed that single phase magnetic barium hexaferrite was formed at a low annealing temperature of 800 °C for 2 h with the Fe³⁺/Ba²⁺ molar ratio 8. The microstructure of the powders appeared as a homogeneous hexagonal platelet-like structure using 2% KNO₃ as the crystal modifier. A saturation magnetization (60.4 emu/g) was achieved for the BaFe₁₂O₁₉ phase formed at 1000 °C for 2 h with Fe³⁺/Ba²⁺ molar ratio 8 using 5 M NaOH solution at pH 10 in the presence of 2% KNO₃. Moreover, the saturation magnetization was 52.2 emu/g for the precipitated precursor at Fe³⁺/Ba²⁺ molar ratio 12 in was achieved for the precipitated precursor ultrasonicated for 1 h and then annealed at 1200 °C for 2 h. Coercivities from 956.9 to 4558 Oe were obtained at different synthesis conditions.     

On the thermal stability of Co2Z hexagonal ferrites for low-temperature ceramic cofiring technologies

Co₂Z hexaferrite Ba₃Co₂Fe₂₄O₄₁ was prepared by a mixed oxalate co-precipitation route and the standard ceramic technology. XRD studies show that at T<1300 °C different ferrite phases coexist with the M-type hexaferrite as majority phase between 1000 and 1100 °C and the Y-type ferrite at 1230 °C. The Z-type material has its stability interval between 1300 and 1350 °C. Both synthesis routes result in almost single-phase Z-type ferrites after calcination at 1330 °C, intermediate grinding and sintering at 1330 °C. The permeability of Co₂Z-type ferrite of about μ=20 is stable up to several 100 MHz, with maximum losses μ′′ around 700 MHz. Addition of 3 wt% Bi₂O₃ as sintering aid shifts the temperature of maximum shrinkage down to 950 °C and enables sintering of Z-type ferrite powders at 950 °C. However, the permeability is reduced to μ=3. It is shown here for the first time that Co₂Z ferrite is not stable under these conditions; partial thermal decomposition into other hexagonal ferrites is found by XRD studies. This is accompanied by a significant decrease of permeability. This shows that Co₂Z hexagonal ferrite is not suitable for the fabrication of multilayer inductors for high-frequency applications via the low-temperature ceramic cofiring technology since the material is not compatible with the typical process cofiring temperature of 950 °C.     

Magnetic properties of cobalt substituted M-type barium hexaferrite prepared by co-precipitation

The co-precipitation and solid state methods were used in the synthesis of barium hexaferrite (BaM). Phase pure BaM was obtained with 1, 2, 3, 5, 10, 15, 20 and 30 wt% cobalt oxide (Co₃O₄). The addition of Co^2+/3+ ions to the BaM increased the permeability and magnetic loss tangent to a value of 3.5 at 5% and reduced to 1 at 30% doping. With increased Co doping, M_s was reduced from 87-58 emu/g, M_r increased from 11 to 40 emu/g with 3–5 wt% Co and 9 emu/g for 30% doping. H_c sharply increased from 540 to 2200 Oe with a reduction to 280 Oe at 10 K with increasing temperature to 300 K. T_c increased from 740 to 750 K for 30% Co doping. DTA–TGA studies of green body showed decarboxilation to occur at around 825 °C and the transformation of residual Co₃O₄ to Co₂O₃ at around 577 °C. The XRD data confirmed the Co ions substituting into Fe sites until a 10–15% doping level where the structure altered to W-type hexaferrite. The densities of the compounds varied with doping to a maximum of 4.45 g/cm³.     

Sonochemical assisted synthesis of SrFe12O19 nanoparticles

We present the synthesis of M-type strontium hexaferrite by sonochemistry and annealing. The effects of the sonication time and thermal energy on the crystal structure and magnetic properties of the obtained powders are presented. Strontium hexagonal ferrite (SrFe₁₂O₁₉) was successfully prepared by the ultrasonic cavitation (sonochemistry) of a complexed polyol solution of metallic acetates and diethylene glycol. The obtained materials were subsequently annealed at temperatures from 300 to 900 °C. X-ray diffraction analysis shows that the sonochemical process yields an amorphous phase containing Fe³⁺, Fe²⁺ and Sr²⁺ ions. This amorphous phase transforms into an intermediate phase of maghemite (γ-Fe₂O₃) at 300 °C. At 500 °C, the intermediate species is converted to hematite (α-Fe₂O₃) by a topotactic transition. The final product of strontium hexaferrite (SrFe₁₂O₁₉) is generated at 800 °C. The obtained strontium hexaferrite shows a magnetization of 62.3 emu/g, which is consistent with pure hexaferrite obtained by other methods, and a coercivity of 6.25 kOe, which is higher than expected for this hexaferrite. The powder morphology is composed of aggregates of rounded particles with an average particle size of 60 nm.     

Preparation and characterization of Li1.2Ni0.13Co0.13Mn0.54O2 cathode materials for lithium-ion battery

Lithium-rich cathode materials Li_1.2Ni_0.13Co_0.13Mn_0.54O₂ with (sample SF) and without (sample SP) formamide was synthesized by a spray-dry method. The crystalline structure and particle morphology of as-prepared materials were characterized by X-ray diffraction and scanning electron microscope. The specific surface area (SSA) of the Li_1.2Ni_0.13Co_0.13Mn_0.54O₂ prepared from different routes was determined by a five-point Brunauer–Emmett–Teller (BET) method using N₂ as absorbate gas. Being compared with the material synthesized without spray-drying process (sample CP), sample SP has much higher SSA. The additive formamide is helpful to form regular and solid precursor particles in spray-drying process, which results in a slightly aggregation of grains and reduction of SSA for sample SF. The electrochemical activities of the materials are closely related to their morphology and SSA. In the voltage range of 2–4.8 V at 25 °C, sample SP present a discharge capacity of 257 mAh g^?1 at 0.1 C rate and 170 mAh g^?1 at 1 C rate. The sample CP delivered only 136 mAh g^?1 when discharged at 1 C rate. The elevated specific capacity and rate capability are attributed to smaller primary particle and higher SSA. Both cycle performance and rate capability of Li_1.2Ni_0.13Co_0.13Mn_0.54O₂ were improved when formamide was used in spray-dry process. Discharge capacity of SF is 140.5 mAh g^?1 at 2 C rate, and that of SP is 132.3 mAh g^?1. Overlarge SSA of SP may provoke serious side reaction, so that its electrochemical performance was deteriorated.     

Tuning of electromagnetic wave absorbing properties in Fe-deficient SrFe9.6-xCo1.2Ti1.2O19 hexaferrite-epoxy composites

We report the tunable electromagnetic (EM) wave absorption properties of Fe-deficient SrFe_9.6-xCo_1.2Ti_1.2O₁₉ hexaferrite–epoxy composites. SrFe_9.6-xCo_1.2Ti_1.2O₁₉ hexaferrite powders were prepared via solid-state reaction routes. It was observed that Sr–Ti-rich second phases were formed as x increased, i.e., the Fe content decreased. The ferromagnetic resonance (FMR) frequency of the composites gradually decreased from 8.8 GHz to 4.8 GHz with increasing x, and accordingly, the EM absorption frequency range also gradually changed. The gradual FMR frequency shift was attributed to the compositional shift in the mother phase. It is predicted that the Fe deficiency caused a decrease in the magnetocrystalline anisotropy, and in turn, it shifted the FMR frequency and modified the corresponding EM absorbing properties. All the samples demonstrated a high EM absorption performance with the lowest reflection loss of < −40 dB at the optimized frequency and thickness.     

Formation of nanostructured ω-Al 7 Cu 2 Fe crystalline phase by the ball milling technique

Crystalline ω-Al₇Cu₂Fe bulk samples were prepared by arc furnace and then by means of milling, the average grain size of these samples is reduced to the nanometer scale. The structural and magnetic properties of the nanostructured ω-Al₇Cu₂Fe phase have been studied by X-ray diffraction employing Rietveld method, Mössbauer spectroscopy and vibrating sample magnetometry. The results indicate that the average grain size of the synthesized sample (ω-phase) rapidly decreases from 79 to 12 nm after 5 h of milling. Furthermore, the hyperfine parameters of the nanostructured samples are higher than the values for the bulk ω-phase. Magnetic measurements show a weak ferromagnetic behavior with M _s ?=?0.46 emu.g^???1 for the bulk ω-phase. After the milling process this value increases to M _s ?=?1.50 emu.g^???1 due to the formation and growth of a magnetic interstitial region after reducing the average grain size of the sample.     

Permeability spectra of Co2Z hexaferrite compacts produced via a modified aqueous co-precipitation technique

Co₂Z hexaferrite materials possess intrinsically high permeability, zero field ferromagnetic resonance values (∼1 GHz), and have their magnetic orientation in the plane perpendicular to the c-axis. These characteristics make these materials practical for applications in low to mid ultra-high frequency and L-band microwave device designs. Due to the relatively large size of elements operating within these bands, it has become important to produce large amounts of Co₂Z type hexaferrite materials. A modified co-precipitation method has been proposed to produce scalable quantities of high quality Co₂Z hexaferrite particles, at ∼24 g/L. These particles have been thoroughly characterized by vibrating sample magnetometry (VSM) and X-ray diffraction (XRD) with regard to phase purity and magnetic properties. After formation and subsequent ball milling, to achieve single domain particles on the order of 0.5–2 um, particles were oriented and pressed into compacts inside a rotating field to ensure magnetization in plane. Samples then underwent VSM, XRD, and scanning electron microscopy to determine the orientation effect. In addition, the complex permittivity and permeability of these samples were measured as a function of applied field and processing conditions. The results show strong orientation in these compacts making them practical for a variety of device applications.     

Preparation and investigation of magnetic properties of MnNiTi-substituted strontium hexaferrite nanoparticles

A series of M-type strontium hexaferrite powders with substitution of Mn²⁺, Ni²⁺ and Ti⁴⁺ ions for Fe³⁺ ions according to the formula SrFe₉(Mn_0.5−xNi_xTi_0.5)₃O₁₉, where x ranges from 0 to 0.5 with a step of 0.1, has been prepared via the conventional ceramic method. In order to get nanoparticles, the obtained powders were milled in a high energy SPEX mill for 1 h. XRD investigations of the unmilled and milled powders show that the prepared samples are all single phase hexaferrite. Lattice parameters and mean crystallite sizes of the powders were determined from the XRD data and Scherrer’s formula. Transmission electron microscope (TEM) was used to analyze their structures. Room temperature magnetizations and coercivities of the samples in a magnetic field of 15 kOe have been determined from the hysteresis loops. It was found that magnetizations of the milled samples were smaller than the magnetization of the unmilled samples. This decrease, based on core-shell model, has been attributed to the presence of a magnetically dead layer on the particles’ surface of the milled powders. In addition, the magnetizations of the milled samples decrease with the increase in x value. This decrease has been discussed according to site occupation of the substituted cations on the sublattices. The discussion also supports the increase of lattice parameters and the decrease of Curie temperature as x increases.     

Study of electrochemical performances of multi-doped spinel Li1.1Mn1.85Co0.075Ni0.075O4 at 4.3 and 5 V

Li_1.1Mn_2???2x Co _x Ni _x O₄ (x?=?0, 0.075) spinel powders were successfully synthesized using a liquid stirred tank reactor method. The electrochemical performances of the undoped and doped spinels at 4.3 and 5 V were investigated by X-ray diffraction, field-emission scanning electron microscopy, and electrochemical impedance spectroscopy. The capacity of Li_1.1Mn_2???2x Co _x Ni _x O₄ could be divided into two parts, with 4.3 V as the dividing line in the 3–5 V charge–discharge range. Low capacity and good cyclic performance were obtained when cycled in the 3–4.3 V range for the multi-doped Li_1.1Mn_2???2x Co _x Ni _x O₄ spinel. In comparison with multi-doped spinel at 4.3 V, the results of the cyclic performance worsened at 5 V because the structure underwent further shrinkage, the charge transfer resistance rose and the electrolyte decomposed.     

Effect of pH value on the structural and magnetic properties of nanocrystalline strontium hexaferrite thin films

Strontium hexaferrite SrFe₁₂O₁₉ thin films have been synthesized at different pH, adjusted by NH₄OH, on the Si (1 0 0) substrate using a spin coating sol-gel process. Fourier transform infrared spectroscopy analysis and theoretical calculations were conducted for determination and controlling metal citrates in solution precursors. X-ray diffraction, scanning electron microscopy and vibrating sample magnetometer were applied to evaluate the composition, microstructure, crystallite size and magnetic properties of the SrFe₁₂O₁₉ thin films. Using the solution with pH 7, the approximately single phase strontium hexaferrite thin films with optimum physical properties can be obtained at calcination temperature of 800 °C. The SrFe₁₂O₁₉ thin films derived from the solution with pH 7 after calcination at 800 °C exhibited crystallite size of 42 nm and magnetic properties of M_s=267 emu/cm³ (at 10 kOe), M_r=134 emu/cm³ and H_c=4290 Oe.     

Synthesis and electrochemical performance of spherical LiNi<Subscript>0.8</Subscript>Co<Subscript>0.15</Subscript>Ti<Subscript>0.05</Subscript>O<Subscript>2</Subscript> cathode materials with high tap density

A series of spherical LiNi_0.8Co_0.15Ti_0.05O₂ cathode materials were synthesized through co-oxidation-controlled crystallization method followed by solid-state reaction at different calcination temperatures under oxygen flowing. The crystal structure and particles morphology of the as-prepared powders were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. All samples correspond to the layered α-NaFeO₂ structure with R-3m space group. The LiNi_0.8Co_0.15Ti_0.05O₂ prepared at 800 °C presents a better hexagonal ordering structure and better spherical particles and possesses a high tap density of 3.22 g cm^?3. Meanwhile, the NCT-2 sample exhibits an advanced electrochemical performance with an initial discharge capacity of 174.2 mAh g^?1 and capacity retention of 86.7 % after 30 cycles at 0.2 C.     

Structural and magnetic behaviour of aluminium doped barium hexaferrite nanoparticles synthesized by solution combustion technique

Nanocrystalline M-type Al³⁺ substituted barium hexaferrite samples having generic formula BaFe_12−xAl_xO₁₉ (where x=0.00, 0.25, 0.50, 0.75, 1.00) were synthesized by the solution combustion technique. The precursors were prepared using stoichiometric amounts of Ba²⁺, Fe³⁺ and Al³⁺ nitrate solutions with citric acid as a chelating agent. The barium nitrate to citric acid ratio was taken as 1:2 and pH of the solution was kept at 8. The sintered samples were characterized by XRD, EDAX, SEM, TEM and VSM techniques. Pure barium hexaferrite shows only single phase hexagonal structure while samples at 0.25≤x≥1.00 show α-Fe₂O₃ peaks with M-phase of barium hexaferrite in the X-ray diffraction pattern. The lattice parameters (a and c) obtained from XRD data decreases with increase in aluminium content x. The particle size obtained from X-ray diffraction data is in the nanometer range. The magnetic behaviour of the samples was studied using vibrating sample magnetometer technique. The saturation magnetization (M_s) and magneton number (n_B) decrease from 38.567 to 21.732 emu/g and from 7.6752 to 4.2126μ_B, respectively, with increase in Al³⁺ substitution x from x=0.0 to 1.0.     

Structural and magnetic properties of Ga-substituted Co2−W hexaferrites

Precursor powders of BaCo₂Fe_16-xGa_xO₂₇ with 0.0 ≤ x ≤ 0.8 were prepared using high-energy ball milling, and the effects of chemical composition on the structural and magnetic properties of the powders sintered at 1300 °C were investigated using x-ray diffractometer (XRD), scanning electron microscopy (SEM), and vibrating sample magnetometry (VSM). XRD patterns of all samples indicated crystallization of pure BaCo₂−W (BaCo₂Fe₁₆O₂₇) hexaferrite phase. SEM measurements revealed large step-like formations with hexagonal crystallites. The magnetic data revealed small fluctuations of the saturation magnetization below the value 72.56 emu/g corresponding to the unsubstituted sample. The coercive field H_c of all samples ranged between 70 Oe and 130 Oe, indicating soft magnetic phase. Curie temperature determined from the thermomagnetic curves of the samples decreased from 485 °C at x = 0.0 down to 451 °C at x = 0.6. Also, the thermomagnetic curves revealed the presence of a minority magnetic phase with enhanced superexchange interaction, and the occurrence of complex magnetic phase transitions associated with spin reorientation transitions above room temperature.     

Structure and magnetic properties of nanocrystalline cobalt ferrite powders synthesized using organic acid precursor method

Nanocrystalline octahedra of cobalt ferrite CoFe₂O₄ powders were synthesized using the organic acid precursor route. The effect of the calcination temperature, Fe³⁺/Co²⁺ molar ratio, calcination time and type of organic acid (oxalic, benzoic and tartaric acids) on the formation, crystallite size, microstructure and magnetic properties was studied systematically. The Fe³⁺/Co²⁺ molar ratio was varied from 2 to 1.739 while the annealing temperature was controlled from 400 to 1000 °C for various periods from 0.5 to 2 h. The resulting powders were investigated using X-ray diffraction (XRD) analysis, Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and vibrating sample magnetometer (VSM). XRD results indicate that a well crystallized, single spinel cobalt ferrite phase was formed for the precursors annealed at 600-800 °C for 2 h, using oxalic and tartaric acids as precursors for Fe³⁺/Co²⁺ molar ratio 1.818. The crystallite size of as-formed powders was in the range of 38.0-92.6 nm at different operating conditions. The calcination temperature and Fe³⁺/Co²⁺ molar ratio have a significant effect on the microstructure of the produced cobalt ferrite. The microstructure of the produced powders was found to be octahedra-shaped. The crystalline, pure cobalt ferrite powders with magnetic properties having a maximum saturation magnetization (76.1 emu/g) was achieved for the single phase at Fe³⁺/Co²⁺ molar ratio 1.818 and annealing temperature of 600 °C for 2 h using tartaric acid precursor.     

Influence of synthesis conditions on structural,optical and magnetic properties of iron oxide nanoparticles prepared by hydrothermal method

The iron oxide nanoparticles were synthesized by a simple hydrothermal method at different heating temperatures and pH conditions. The synthesized materials were characterized by X-ray diffractometer, Fourier transform infrared spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, UV–visible spectrometer and vibrating sample magnetometer. With increment in pH of the synthesized materials were resulted in orthorhombic (goethite) and cubic (magnetite) structures at pH 6 and 12, respectively. The banding nature of synthesized materials was analyzed by infrared spectra. The synthesized powders at 130?°C showed higher percent of nanorods (length = 90–120 nm) in addition to lower percentage of nanoparticles. The material at pH 12 consisted of maximum nanoparticles with size = 10–60 nm with small agglomerations. Band gap energy of synthesized materials was 2.2–2.8 eV. Herein, the reaction conditions tuned the saturation magnetization (M_S). The maximum M_S (59.38 emu/g) was obtained at pH 12 and lower M_S (0.65 emu/g) was observed at pH 6 due to intrinsic property of goethite phase.     

Influence of Gd3+ and Dy3+ co-doping and sintering regime on enhancement of electrical conductivity of ceria-based solid electrolyte

In order to improve the conductivity of ceria-based solid electrolytes, effect of co-doped Gd³⁺ and Dy³⁺ was evaluated. For this purpose, nano-crystalline Gd_0.2???x Dy _x Ce_0.8O_1.9 powders with various composition ranges (x?=?0.05, 0.1, 0.15, 0.2) were initially synthesized by high-energy milling method. The effect of micro-structural evolution and co-doping on electrical properties of the dense sintered samples fabricated by two-step sintering and conventional sintering of the synthesized powders were investigated. Electrical conductivity of the samples was discussed based on the results obtained by AC impedance spectroscopy at temperatures in the range of 300–700 °C. The co-doping and sintering regime were found to significantly influence the conductivity of the electrolytes. The electrical conductivity of the co-doped samples depends on Dy³⁺ content and the maximum conductivity obtained by 0.15 mol% Dy and 0.05 mol% Gd. The conductivity of Gd_0.2???x Dy _x Ce_0.8O_1.9 (x?=?0.15) was 0.03 S/cm at 700 °C. A thorough discussion was made, based on the present experimental data.     

Hydrothermal impregnation synthesis of cobalt pentlandite as anode material of H<Subscript>2</Subscript>S SOFC

In the present work, cobalt pentlandite (Co₉S₈) is studied as a solid oxide fuel cells (SOFC) anode material which is stable in H₂S-containing fuels and is promising in coal-based SOFCs. Co₉S₈ is synthesized via a simple hydrothermal method. Uniform and fine Co₉S₈ particles are deposited on to the YSZ skeleton directly by using hydrothermal impregnation method and adhered to the skeleton closely after heat treating in N₂. The symmetrical cells are measured in the presence of 50 ppm H₂S–H₂ to determine the electrochemical performance at intermediate temperatures. The polarization resistance is only 0.3385 Ω cm² at 650 °C. It is concluded that Co₉S₈ exhibits a combination of good electronic conductivity and catalytic activity and has the potential to be used as a sulfur-tolerant anode material of SOFCs.     

Causes of the Metamagnetism in a Disordered EuMn<Subscript>0.5</Subscript>Co<Subscript>0.5</Subscript>O<Subscript>3</Subscript> Perovskite

The magnetic properties of the EuMn_0.5Co_0.5O₃ perovskite synthesized under various conditions are studied in fields up to 140 kOe. The sample synthesized at T = 1500°C is shown to exhibit a metamagnetic phase transition, which is irreversible below T = 40 K, and the sample synthesized at T = 1200°C demonstrates the field dependence of magnetization that is typical of a ferromagnet. Both samples have T_C = 123 K and approximately the same magnetization in high magnetic fields. The metamagnetism is assumed to be related to a transition from a noncollinear ferromagnetic phase to a collinear phase, and the presence of clusters with ordered Co²⁺ and Mn⁴⁺ ions leads to ferromagnetism. The noncollinear phase is formed due to the competition between positive Co²⁺–Mn⁴⁺ and negative Mn⁴⁺–Mn⁴⁺ and Co²⁺–Co²⁺ interactions, which make almost the same contributions, and to the existence of a high magnetic anisotropy.