Tailoring the structural,magnetic and dielectric properties of Ni-Zn-CdFe2O4 spinel ferrites by the substitution of lanthanum ions

In this paper, we have tailored the structural, magnetic and dielectric properties of Ni_0.5Zn_0.3Cd_0.2Fe_2-yLa_yO₄ (y?=?0.0–0.21) nano-structured spinel ferrites by the substitution of La³⁺ ions. The investigated samples were synthesized by Sol-gel auto-combustion method and were characterized using XRD, SEM, VSM, FTIR and dielectric measurements. Single phase nanostructure formation of synthesized material was confirmed by XRD analysis. The effect of La³⁺ ions on crystallite size, grain size, lattice constant and bulk densities was calculated and it was found that lattice constant first increased upto concentration y?=?0.105 then decreased with further substitution of dopant ions. FTIR results for all synthesized samples demonstrated two absorption bands at υ₁ =?540.8?cm^?1 and υ₂ =?490.8?cm^?1 corresponds to tetrahedral and octahedral sites of spinel structure respectively. With the increase in La³⁺ ions concentration, saturation magnetization and remanence both found to be decreased down to lowest M_s value of 34.1?emu/g which is not yet reported in the literature according to best of our knowledge. Dielectric results showed that by decreasing frequency, both dielectric loss and dielectric constant decreases. AC conductivity has two regions, at low frequency region ac conductivity increases while at high frequency region, it decreases with increasing frequency. The measured results for all synthesized nano-ferrites suggested that synthesized nanoferrites are recommended for high frequency and microwave absorbing applications.     

Effects of Co-substitution on the structural and magnetic properties of NiCoxFe2−xO4 ferrite nanoparticles

The sol–gel auto-combustion method was used to prepare nanocrystalline powders of Co-substituted nickel ferrite with the general formula NiCo_xFe_2−xO₄ (x=0.0, 0.1, 0.25, and 0.5). The effects of Co-doping on the structural, morphological, and magnetic properties of the samples were subsequently evaluated by X-ray diffraction (XRD), Fourier transform infrared (FTIR), field emission scanning electron microscopy (FE-SEM), and vibrating sample magnetometer (VSM). Using the MAUD program, the full pattern fitting of Rietveld method was employed to determine the exact coordinate of the atoms, unit cell dimensions, and ion occupancy. X-ray diffraction measurements by Rietveld refinement confirmed the crystalline structure and phase purity of all the ferrites prepared. FTIR results also confirmed the formation of a spinel phase and FE-SEM images showed that the particles were in the nanosize range. Moreover, Rietveld analysis and saturation magnetization (M_s) revealed that Co³⁺ replaced Fe³⁺ in the tetrahedral A-sites up to x=0.1. then, it replaced Fe³⁺ in both A- and B-sites for x≥0.25. Finally, VSM results demonstrated that while M_s remained nearly constant with increasing Co³⁺ substitution, coercivity (H_c) increased significantly. It may be suggested that the larger magneto-crystalline anisotropy of Co³⁺ ions is responsible for the increased H_c observed in the Co-doped Ni ferrite samples.     

Synthesis and structural,magnetic characterization of nanocrystalline Zn1-xCoxO diluted magnetic semiconductors (DMS) synthesized by combustion reaction

Nanocrystalline Co⁺² doped Zn_1?xCo_xO, where x = 0.02, 0.03, 0.07 and 0.1 mol of Co⁺² diluted magnetic semiconductors (DMS), were synthesized by combustion reaction for spintronic applications. The effects of Co⁺² ion doping on the structural, morphological and magnetic properties of ZnO ware investigated. The products of the reactions were characterized by X-ray diffraction (XRD), nitrogen adsorption (BET), transmission electron microscopy (TEM), and magnetic measurements (VSM). XRD spectra data revealed the formation of a ZnO phase (removed text), indicating that the synthesis was efficient in diluting the Co⁺² ions in the ZnO lattice. Increasing the Co²⁺ ion concentrations reduced the maximum reaction and ignition temperature and contributed to reduce crystallite and particle sizes. The samples showed the typical behavior of soft magnetic materials at all the Co²⁺ concentrations evaluated here. The Curie temperature (Tc) was higher than room temperature at all the Co²⁺ concentrations.     

Effect of Zn substitution on the structural and magnetic properties of nanocrystalline NiFe2O4 ferrites

Nanocrystalline Ni_1?xZn_xFe₂O₄ (where, x = 0.0, 0.2, 0.4, 0.6, 0.8 & 1) samples were synthesized through solution combustion technique using oxylyl de-hydrazide (ODH) as a fuel and the effect of dopant and its concentration on the structural and magnetic properties was investigated. As-prepared samples were characterized using different characterization techniques such as, XRD, SEM-EDS, TEM and Raman spectroscopy for their phase-purity, crystallinity, surface morphology and elemental composition; also magnetic properties were investigated through EPR, Mossbauer spectroscopy and vibrating sample magnetometer (VSM). Rietveld fitted XRD and Raman studies confirm the formation of cubic spinel structured ferrites and substitution of Zn ion at Ni site without formation of impurity phases. No other structural changes were observed and the structure remains in cubic phase with increase of Zn concentration. SEM and TEM micrographs reveal that the particles are agglomerated and the particles size were found in the nano range. Also good stoichiometric composition was observed in all the compositions of Zn substituted Ni ferrite samples. Magnetic measurements (VSM) reveal that pure Ni ferrites exhibits soft magnetic behaviour. Further the ferromagnetic behaviour suppressed with the substitution of diamagnetic Zn ion and with increase of its concentration in Ni ferrites, which was further evidenced in the Mossbauer spectroscopic results. At room temperature, electronic paramagnetic resonance spectra exhibits a broad resonance signal with Lande's g factor varies from 2.23 to 1.95 with increase in Zn content, which is attributed to spin exchange interactions between Fe³⁺, Ni²⁺ and Zn²⁺ ions also asymmetric EPR spectra was observed. The investigated results show that, Zn substitution has greater impact on the magnetic properties of Ni ferrites due to the diamagnetic nature of Zn, which inturn alters the cationic distribution and the exchange interactions between Ni-Fe and Fe-Fe.     

Structural and magnetic properties of Co1−xZnxFe2O4 nanorods prepared by the solvothermal annealing method

Co_1−xZn_xFe₂O₄ (0.1≤x≤0.9) nanorods have been prepared by the thermal decomposition of the corresponding oxalate precursor, which was synthesized by the template-, surfactant-free solvothermal method. The as-prepared samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), fourier transform infrared spectroscopy (FTIR) and vibrating sample magnetometry (VSM). The obtained Co_1−xZn_xFe₂O₄ (0.1≤x≤0.9) nanorods were built by many nanoparticles with average sizes around 20 nm to form one-dimensional arrays. Vibrating sample magnetometry measurements show that the coercivity of the ferrite nanorods decreases with increasing Zn content, whereas the specific saturation magnetization initially increases and then decreases with the increase of Zn content. The maximum saturation magnetization value of the as-prepared sample (Co_0.5Zn_0.5Fe₂O₄) reaches 43.0 emu g⁻¹.     

Magneto-optical properties of rare earth metals substituted Co-Zn spinel nanoferrites

Cobalt–zinc ferrite nanoparticles (NPs) substituted with three different metals, Co_0.5Zn_0.5Re_xFe_2-xO₄ (RE = Ce, Dy, and Y; 0.00?≤?x?≤?0.05) were prepared hydrothermally. Fourier Transform-Infrared (FT-IR) Spectroscopy, X-ray powder diffraction (XRD), Field-Emission Scanning Electron Microscope (FESEM) coupled with energy-dispersive X-ray spectroscopy (EDX) and Vibrating Sample Magnetometry (VSM) analyzed the products. The formation of cubic phase of spinel Co-Zn ferrite NPs were confirmed through XRD, FT-IR and FE-SEM techniques. The structural investigation of NPs by XRD revealed that the lattice parameter "a" decreases with the introduction of the RE in the ferrite structure by the substitution of Fe³⁺ by RE ions. The different magnetic parameters of Co_0.5Zn_0.5Re_xFe_2-xO₄ (RE = Ce, Dy, and Y; 0.00?≤?x?≤?0.05) NPs such as the saturation magnetization, coercivity, remanence, and magnetic moment were calculated and discussed in relation to structure and microstructure properties. M (H) hysteresis curves indicated that the samples exhibit superparamagnetic nature at room temperature. A slight improvement in the magnetization was obtained especially for the Ce- and Y-substituted Co_0.5Zn_0.5Fe₂O₄ (CZF) NPs at a certain RE level. However, the case Dy-substituted CZF products showed a sharp decrease in the magnetization with x?>?0.01. The results are mostly ascribed to the substitution of smaller Fe³⁺ ions with larger RE³⁺ ions.     

High-performance inductive couplers based on novel Ce3+ and Co2+ ions co-doped Ni-Zn ferrites

High-performance inductive couplers require Ni-Zn ferrites of high saturation magnetization, Curie temperature, permeability and application frequency. However, for inductive couplers some of these properties run against each other in one ferrite. To balance these requirements, in this work, novel Ni-Zn ferrite ceramics co-doped by Ce³⁺ and Co²⁺ ions with chemical formula Ni_0.4Zn_0.5Co_0.1Ce_xFe_2-xO₄ (x = 0–0.06) were designed and fabricated by a molten salt method. For the acquired ferrites, both Ce³⁺ and Co²⁺ ions could come into the lattices. The initially doped Co²⁺ ions would cause a slightly decreased grain size and dramatically reduced the specimen densification, but the further added Ce³⁺ ions could effectively inhibit the density reduction, while the grain size continues to dwindle. The additional Ce³⁺ ions would generate a foreign CeO₂ phase in the acquired specimens. The sole doping of Co²⁺ ions would aggrandize the saturation magnetization of ferrites, but the introduction of Ce³⁺ ions would cause its decrease. However, with an appropriate doping level, the Ce³⁺ and Co²⁺ ions co-doped ferrites could preserve a relatively high saturation magnetization, while the Curie temperature and cut-off frequency of the ferrites are dramatically augmented, although the permeability would be somewhat reduced. The as-acquired ferrites were simulated to apply in inductive couplers, revealing that the devices manufactured by the Ni_0.4Zn_0.5Co_0.1Ce_xFe_2-xO₄ ferrites had significantly high maximum operating frequency, compared with that of the one manufactured by pure Ni_0.5Zn_0.5Fe₂O₄ ferrite.     

Phase Equilibria of the Zinc Oxide–Cobalt Oxide System in Air

Phase equilibria of the zinc oxide–cobalt oxide system were studied by a combination of X‐ray diffraction and in situ electrical conductivity and thermopower measurements of bulk ceramic specimens up to 1000°C in air. Rietveld refinement of X‐ray diffraction patterns demonstrated increasing solubility of Co in ZnO with increasing temperature, which is supported by the slight increase in wurtzite (Zn_1?xCo_xO) cell volume and lattice parameter a versus temperature determined for the phase boundary compositions. Similarly, the solubility of Zn in CoO increased with increasing temperature. In contrast, the spinel phase (Zn_zCo_3?zO₄) exhibited retrograde solubility for Zn. Electrical measurements showed that the eutectoid temperature for transformation of rocksalt Co_1?yZn_yO into wurtzite and spinel is 894 ± 3°C, and the upper temperature limit of the stability of the spinel phase is 894°C–898°C for the compositions Co/(Zn+Co) = 0.82–1. The resulting composition‐temperature phase diagram is presented and compared to the earlier (1955) diagram by Robin.     

Vapor-phase methylation of pyridine with methanol to 3-picoline over Zn1−xCoxFe2O4 (x=0, 0.2, 0.5, 0.8 and 1.0)-type ternary spinels prepared via a low temperature method

The reaction of pyridine with methanol was carried out over Zn_1−xCo_xFe₂O₄ (x=0, 0.2, 0.5, 0.8 and 1.0)-type systems in a fixed-bed down-flow reactor. The influences of surface acidity, cation distribution in the spinel lattice and various reaction parameters are discussed. The activity and selectivity were shown to be strongly dependent on the surface acidity of the systems. Over all compositions of the systems, 3-picoline was formed as the major product, even though the activity and selectivity show a strong dependence on composition and reaction conditions. Generally, the systems possessing more acidic sites (x≥0.5) favor the production of 3-picolines and 3,5-lutidine. Pyridine conversion increased with the progressive substitution of Zn²⁺ ions by Co²⁺ ions. Cation distribution in the spinel lattice influences their acidic properties. These factors have been adequately considered as helpful to evaluate the activity of the systems.     

The effects of Mg2+ and Ba2+ dopants on the microstructure and magnetic properties of doubly-doped LaFeO3 perovskite catalytic nanocrystals

Using citrate sol-gel method, we prepared La_0.85Mg_0.15-xBa_xFeO₃(x?=?0.02–0.12) samples. X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and vibrating sample magnetometer (VSM) were used to investigate whether the microstructure, composition, and magnetic properties of LaFeO₃ were affected by the following parameters: calcination temperature, calcination time, and the doping concentration of Mg²⁺ ion and Ba²⁺ ions. The XRD spectra showed that a trace of impurity phase (MgFe₂O₄) is visible when the content of Mg²⁺ ions was higher; however, there was no change in the orthorhombic perovskite structure of LaFeO₃ even at higher doping concentrations. The space group was still Pnma. No other phase was generated in the sample subjected to low-temperature calcination. Furthermore, FT-IR spectra confirmed the presence of some functional groups in the sample. Then, SEM showed that the size distribution of the particles is uniform in the sample, and the grain boundary is also clear. Finally, VSM measurements proved that the significant changes were produced in the magnetic properties of samples when they were doubly doped with Mg²⁺ and Ba²⁺ ions. Moreover, calcination temperature has a great influence on the magnetic properties of the samples.     

Magnetic Properties of FeMn<Subscript>y</Subscript>Co<Subscript>y</Subscript>Fe<Subscript>2−2y</Subscript>O<Subscript>4</Subscript>@Oleylamine Nanocomposite with Cation Distribution

In this study, oleylamine (OAm) capped FeMn_yCo_yFe_2?2yO₄ (0.0?≤?y?≤?0.4) nanocomposites (NCs) were prepared via the polyol route and the impact of bimetallic Co³⁺ and Mn³⁺ ions on the structural and magnetic properties of Fe₃O₄ was investigated. The complete characterization of FeMn_yCo_yFe_2?2yO₄@OAm NCs were done by different techniques such as XRD, SEM, TGA, FT-IR, TEM, and VSM. XRD analyses proved the successful formation of mono-phase MnFe₂O₄ spinel cubic products free from any impurity. The average crystallite sizes were calculated in the range of 9.4–26.4 nm using Sherrer’s formula. Both SEM and TEM results confirmed that products are nanoparticles like structures having spherical morphology with small agglomeration. Ms continued to decrease up to Co³⁺ and Mn³⁺ content of y?=?0.4. Although Mössbauer analysis reveals that the nanocomposites consist three magnetic sextets and superparamagnetic particles are also formed for Fe₃O₄, Co_0.2Mn_0.2Fe_2.6O₄ and Co_0.4Mn_0.4Fe_2.2O₄. Cation distributions calculation was reported that Co³⁺ ions prefer to replace Fe²⁺ ions on tetrahedral side up to all the concentration while Mn³⁺ ions prefer to replace Fe³⁺ ions on the octahedral.     

Study of the changes in the structure and optical properties of MgxCo1-xCr2-yAlyO4 spinel caused by A/B site ion substitution

In this work, nanosubmicron blue-green pigment powder based on the composition of Mg_xCo_1-xCr_2-yAl_yO₄（0 = x ≤ 1, 0 = y ≤ 2）was prepared by a gel casting method. X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Rietveld refinement with GSAS (General Structure Analysis System), and UV–Vis absorption spectroscopy were used to study the phase composition, grain size, morphology, cation distribution in the crystal structure and spectral absorption of the samples. Colour parameters were also studied by using a colour measurement spectrophotometer. The studies demonstrate that the distribution of cations in the crystal structure is disordered and that divalent and trivalent cations are mixed to occupy tetrahedral and octahedral sites. Furthermore, the substitution of ions at the A/B site leads to a change in the cation distribution ratio at the tetrahedral and octahedral sites. With increasing Mg²⁺ doping concentration, the inversion parameter of the spinel increases, while with increasing Al³⁺ doping concentration, the inversion parameter of the spinel decreases. In addition, changes in the calcining atmosphere lead to a change in the oxygen vacancy content in the structure. Under the condition of a reductive atmosphere, the oxygen vacancy content significantly increases, and the inversion parameter also increases. The colour difference for the synthesized Mg_xCo_1-xCr_2-yAl_yO₄ spinel powder is related to the proportion of chromophore ions occupying tetrahedral and octahedral sites and the number of oxygen vacancies.     

Enhanced thermoelectric properties induced by chemical pressure in Ca3Co4O9

We report the investigation of boron substitution on structural, electrical, thermal, and thermoelectric properties of Ca_3−xB_xCo₄O₉ (x=0, 0.5, 0.75, and 1) in the temperature range between 300 K and 5 K. X-ray diffraction studies show that the Ca₃Co₄O₉ phase is successfully preserved as the majority phase in the x=0.5 sample despite the small size of boron ions. Electrical transport measurements confirm that B³⁺ substitution for Ca²⁺ causes an increase in resistivity due to the decrease in carrier concentration. x=0.5 sample is found to have a Seebeck coefficient of 181 μV/K at room temperature which is ~1.5 times higher than that of the pure Ca₃Co₄O₉. Our results indicate that the chemical pressure due to the large ionic radii difference between B³⁺ (0.27 Å) and Ca²⁺ (1 Å) enhances the thermoelectric properties as long as the unique crystal structure of Ca₃Co₄O₉ is preserved.     

Structural and magnetic evaluation of substituted NiZnFe2O4 particles synthesized by conventional sol–gel method

The aim of this study is to evaluate the structural and magnetic properties of Ni–Zn doped ferrite with trivalent Al³⁺ and Cr³⁺ cations substitution in Ni_0.6Zn_0.4Fe_2−xCr_x/2Al_x/2O₄ (x=0, 0.1, 0.2, 0.3, 0.4 and 0.5) synthesized by employing conventional sol–gel method. X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, field emission scanning electron microscopy (FE-SEM), Mössbauer spectroscopy (MS) and vibrating sample magnetometer (VSM) analysis were carried out in order to characterize the structural and magnetic properties of particles. The XRD results confirmed the formation of single phase of spinel ferrite particles for a whole series of samples. The results of FTIR analysis indicated that the functional groups of Ni–Zn spinel ferrite were formed during the sol–gel process. Furthermore, FE-SEM micrographs revealed that the distribution of particles size is narrow. According to Mössbauer spectra,the doped cations are replaced in iron site occupancy of octahedral sites. It was found that with an increase in substitution contents magnetization decreased due to occupation of Al and Cr cations at low level substitutions in octahedral sites.     

Structural,magnetic, and electrical evaluations of rare earth Gd3+ doped in mixed Co–Mn spinel ferrite nanoparticles

The controlled and stable crystal structure, reduction in Curie temperature and semiconducting nature of oxide materials are the key factors for magnetoelectrical applications. Therefore, Co_0.6Mn_0.4Gd_xFe_2-xO₄ where x = 0, 0.033, 0.066 and 0.10 were synthesized to analyse the structural, morphological, magnetic, and electrical properties using a sol-gel autocombustion approach. The X-ray diffraction pattern reveals that the cubic crystallite size decreases with increasing smaller content of Gd³⁺ oxides without any secondary phase. Field emission scanning electron microscopy (FE-SEM) and high-resolution transmission electron microscopy (HR-TEM) study explain the complete morphology, agglomeration and dense structure of rare earth-doped Gd oxide in the mixed Co–Mn spinel ferrite nanoparticles. Fourier transform infrared spectra confirms the formation of a spinel structure with absorption bands below 1000 cm^?1. The magnetic analysis shows that the saturation magnetization (59.20 emu/g - 49.71 emu/g) and coercivity (985.21 Oe – 254.11 Oe) of the synthesized samples decreased with increasing content of Gd³⁺ ions. The increase in DC conductivity with increasing temperature verifies the semiconducting nature of the synthesized samples, and a higher DC conductivity of the Co_0.6Mn_0.4Gd_0.10Fe_1.90O₄(CMGF3) samples was observed at approximately 0.0362 S/cm at 973 K temperature.     

Structural,magnetic and dielectric behavior of Mg1−xCaxNiyFe2−yO4 nano-ferrites synthesized by the micro-emulsion method

Ca–Ni co-substituted samples of nanocrystalline spinel ferrites with chemical formula Mg_1−xCa_xNi_yFe_2−y O₄ (x=0.0–0.6, y=0.0–1.2) were synthesized by the micro-emulsion method and were annealed at 700 °C for 7 h. The synthesized samples were characterized by x-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, vibrating sample magnetometry (VSM) and dielectric measurements. The XRD and FTIR analysis reveals that single phase samples can be achieved by substituting Ca and Ni ions at Mg and Fe sites respectively in cubic spinel nano-ferrites. The crystallite size of the synthesized samples was found in the range 29–45 nm. The saturation magnetization (M_s) increases from 9.84 to 24.99 emu/g up to x=0.2, y=0.4 and then decreases, while the coercivity (H_c) increases continuously from 94 to 153 Oe with the increase in dopants concentration. The dielectric properties of these nano materials were also studied at room temperature in the frequency range 100 MHz to 3 GHz. The dielectric parameters were found to decrease with the increased Ca–Ni concentration. Further the peaking behavior was observed beyond 1.5 GHz. The frequency dependent dielectric properties of all the samples have been explained qualitatively on the basis of the Maxwell–Wagner two-layer model according to Koop's phenomenological theory. The enhanced magnetic parameters and reduced dielectric properties make the synthesized materials suitable for switching and high frequency applications, respectively.     

Cobalt and nickel aluminate spinels: Blue and cyan pigments

M²⁺-doped aluminate spinels (M=Co or Ni) were prepared by a polymeric route leading to pure phases for synthesis temperatures equal to 800 or 1200 °C and characterized by UV–vis–NIR spectroscopy, ²⁷Al NMR and XRD refinements. Coloration of the synthesized pigments is clearly sensitive to the distribution of doping ions in the aluminate spinel lattice. As the synthesis temperature increased, a color shift from green to blue has been observed for Zn_1−xCo_xAl₂O₄ compound while coloration of Zn_1−xNi_xAl₂O₄ compound remains greenish-gray. Hence, to improve pigment coloration and/or synthesis cost, two different strategies have been proposed: (i) the synthesis of aluminum over-stoichiometric spinel with Zn_0.9Co_0.1Al_2.2O_4+δ formal composition in order to force Co²⁺ to be located in tetrahedral sites and (ii) changing from ZnAl₂O₄ to MgAl₂O₄ as host lattices for Ni²⁺ doping ions in order to force Ni²⁺ to be located in octahedral sites.     

Ni0.5Zn0.5Fe2O4 nanoparticles and their magnetic properties and adsorption of bovine serum albumin

Ni_0.5Zn_0.5Fe₂O₄ nanoparticles were synthesized by the facile citrate-gel process and the preliminary measurement for adsorption of bovine serum albumin (BSA) protein on these nanoparticles was carried out. The gel precursor and resultant nanoparticles were characterized by TG-DSC, FTIR, XRD, TEM and VSM techniques and the BSA adsorption on the nanoparticles was analyzed by UV spectrophotometer at room temperature. The results show that the single phase of spinel Ni_0.5Zn_0.5Fe₂O₄ is formed at 400 °C. With increasing calcination temperature from 400 to 700 °C, the average grain size increases from about 14 to 45 nm and consequently, the specific saturation magnetization of Ni_0.5Zn_0.5Fe₂O₄ nanoparticles increases from about 46 to 68 Am²/kg. The coercivity initially increases and then decreases with increasing calcination temperature, with a maximum value 9.2 kA/m at 500 °C. The as-prepared Ni_0.5Zn_0.5Fe₂O₄ nanoparticles exhibit a good adsorbing ability for BSA and the optimized adsorption is achieved for the Ni_0.5Zn_0.5Fe₂O₄ nanoparticles calcined at 500 °C with grain size about 24 nm.     

Structural,electrical and magnetic properties of Co0.5Zn0.5AlxFe2−xO4 (x = 0, 0.2, 0.4, 0.6, 0.8 and 1.0) prepared via sol–gel route

Nanoparticles of Co_0.5Zn_0.5Al_xFe_2?xO₄ (x = 0, 0.2, 0.4, 0.6, 0.8 and 1.0) were synthesized by sol–gel method and the influence of Al³⁺ doping on the properties of Co_0.5Zn_0.5Fe₂O₄ was studied. X-ray diffraction studies revealed the formation of single phase spinel type cubical structure having space group Fd-3m. A decreasing trend of the lattice parameter was observed with increasing Al³⁺ concentration due to the smaller ionic radii of Al³⁺ ion as compared to Fe³⁺ ion. TEM was used to characterize the microstructure of the samples and particle size determination, which exhibited the formation of spherical nanoparticles. The particle size was found to be increases up to ～45 nm after annealing the sample at 1000 °C. Electrical resistivity was found to increase with Al³⁺ doping, attributed to the decrease in the number of Fe²⁺–Fe³⁺ hopping. The activation energy decreased with increasing Al³⁺ ion concentration, indicating the blocking of conduction mechanism between Fe³⁺–Fe²⁺ ions. The value of saturation magnetization decreased, when Fe³⁺ ions were doped with Al³⁺ ions in Co_0.5Zn_0.5Fe₂O₄; however, the coercivity values increased with increasing Al³⁺ ion content.     

Microwave dielectric properties,microstructure, and bond energy of Zn3-xCoxB2O6 low temperature fired ceramics

Low temperature co-fired ceramics (LTCCs) technology plays an important role in modern wireless communication. Zn_3-xCo_xB₂O₆ (x = 0–0.25) low temperature fired ceramics were synthesized via traditional solid-state reaction method. Influences of Co²⁺ substitution on crystal phase composition, grain size, grain morphology, microwave dielectric properties, bond energy, and bond valence were investigated in detail. X-ray diffraction analysis indicated that the major phase of the ceramics was monoclinic Zn₃(BO₃)₂. Solid solution was formed with Co²⁺ substituted for Zn²⁺ because no individual phase that contained Co was observed. An increase in the amount of Co²⁺ substitution changed average grain sizes, and regrowth of grains were observed with Co²⁺ substitution. Appropriate amount of Co²⁺ substitution improved densification. With changes in Co²⁺ substitution, bond energy of major phase and average bond valence of B–O were positively correlated to temperature coefficient of resonant frequency. The Zn_2.927Co_0.075B₂O₆ ceramic sintered at 875 °C for 4 h exhibited excellent microwave properties with ε_r = 6.79, Q × f = 140,402 GHz, and τ_f = −87.42 ppm/°C. This ceramic is regarded as candidate for LTCC applications.