Glass additive influence on the sintering behavior, microstructure and microwave magnetic properties of Cu-Bi-Zn co-doped Co2Z ferrites

The Bi₂O₃-B₂O₃-ZnO-SiO₂ (BB35SZ) glass effects on the sintering behavior and microwave magnetic properties of Cu-Bi-Zn co-doped Co₂Z ferrites were investigated to develop low-temperature-fired ferrites. The glass wetting characteristics on the Co₂Z ferrite surface, X-ray diffractometer, scanning electron microscopy and a dilatometer were used to examine the BB35SZ glass effect on Co₂Z ferrite densification and the chemical reaction between the glass and Co₂Z ferrites. The results indicate that BB35SZ glass can be used as a sintering aid to reduce the densification temperature of Co₂Z ferrites from 1300 to 900 °C. 3(Ba_0.9Bi_0.1O)·2(Co_0.8Cu_0.2O)·12(Fe_1.975Zn_0.025O₃) ferrite with 2 wt% BB35SZ glass can be densified below 900 °C, exhibiting an initial permeability of 3.4. This process provides a promising candidate for multilayer chip magnetic devices for microwave applications.     

Preparation and investigation of low firing temperature NiCuZn ferrites with high relative initial permeability

The effects of CuO and V₂O₅ additions and the particle sizes of precursor materials on the microstructure and relative initial permeability of low firing temperature NiCuZn ferrites were investigated. It was found that additions of CuO and V₂O₅ contribute to the grain growth and densification of matrix in the sintering process, which were favorable for increase in relative initial permeability. The relative initial permeability was also strongly affected by the average particle size of precursor materials. Through using precursor materials of 0.8 μm average particle size and adding 10 mol% CuO and 0.20 mol% V₂O₅, for the low firing temperature NiCuZn ferrite, very high relative initial permeability of 1417 can be achieved at the frequency of 1 MHz.     

Zn- and Cu-substituted Co2Y hexagonal ferrites: Sintering behavior and permeability

Y-type polycrystalline hexagonal ferrites Ba₂Co_2−x−yZn_xCu_yFe₁₂O₂₂ with 0≤x≤2 and 0≤y≤0.8 were prepared by the mixed-oxide route. Single phase Y-type ferrite powders were obtained after calcinations at 1000 °C. Samples sintered at 1200 °C show a permeability that increases with the substitution of Zn for Co and display maximum permeability of μ′=35 at 1 MHz for x=1.6 and y=0.4. A resonance frequency f_r=500 MHz is observed for Zn-rich ferrites with y=0 and 0.4. The saturation magnetization increases with substitution of Zn for Co. Addition of Bi₂O₃ shifts the temperature of maximum shrinkage down to T≤950 °C. Moreover, an increase of the Cu-concentration further lowers the sintering temperature to T≤900 °C, enabling co-firing of the ferrites with Ag metallization for multilayer technologies. However, low-temperature firing reduces the permeability to μ′=10 and the resonance frequency is shifted to 1 GHz. Thus substituted hexagonal Y-type ferrites can be used as soft magnetic materials for multilayer inductors for high frequency applications.     

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.     

Microwave sintering of high-permeability (Ni0.20Zn0.60Cu0.20)Fe1.98O4 ferrite at low sintering temperatures

The (Ni_0.20Zn_0.60Cu_0.20)Fe_1.98O₄ ferrite was sintered using microwave sintering and conventional sintering technique, respectively. It was found that microwave sintering technique can effectively promote the forward diffusion of ions and thus accelerate the sintering process, resulting in the grain growth and the densification of matrix. At the low frequency of 100 kHz, the magnetizing contribution of domain wall motion is predominant, and compact and coarse matrixes are favorable for domain wall motion, giving rise to improvement of relative initial permeability and loss of ferrites. Using microwave sintering technique, for the (Ni_0.20Zn_0.60Cu_0.20)Fe_1.98O₄ ferrite, the relative initial permeability μ_i of about 2000 and the relative loss factor tanδ/μ_i of about 8.7×10⁻⁶ at 100 kHz were achieved at only 980 °C sintering temperature. In addition, the sintering time of ferrites was reduced from 5 to 0.5 h by using microwave sintering technique.     

Influences of Fe-deficiency on electromagnetic properties of low-temperature-fired NiCuZn ferrites

Low-temperature-fired NiCuZn ferrites with the formula Ni_0.45Cu_0.2Zn_0.35Fe_2−xO_4−3/2x with x values ranging from 0.00 to 0.25 in steps of 0.05 and sintered at 900 °C have been investigated in the present work. It was found that the content of Fe-deficiency could obviously influence the microstructure, sintering behavior, saturation magnetization, permeability and permittivity spectra properties of the ferrites. The variations were much different from those of the high-temperature-fired NiZn ferrites. And the corresponding mechanisms involved were discussed in detail. All-around consideration, the NiCuZn ferrite with 0.10 Fe-deficiency in composition had the best performances on sintering behavior and electromagnetic properties.     

Effect of zinc concentration on the structural,electrical and magnetic properties of mixed Mn–Zn and Ni–Zn ferrites synthesized by the citrate precursor technique

Mixed manganese-zinc and nickel-zinc ferrites of composition Mn_0.2Ni_0.8−xZn_xFe₂O₄ where x=0.4$x=0.4$, 0.5 and 0.6 have been synthesized by the citrate precursor technique. Decomposition of the precursor at temperatures as low as 500 °C gives the ferrite powder. The ferrites have been investigated for their electrical and magnetic properties such as saturation magnetization, initial permeability, Curie temperature, AC-resistivity and dielectric constant as a function of sintering temperature and zinc content. Structural properties such as lattice parameter, grain size and density are also studied. The mixed compositions exhibited higher saturation magnetizations at sintering temperatures as low as 1200 °C. While the Curie temperature decreased with zinc content, the permeability was found to increase. The AC-resistivity ranged from 10⁵–10⁷ Ω cm and decreased with zinc content and sintering temperature. The dielectric constants were lower than those normally reported for the Mn–Zn ferrites. Samples sintered at 1400 °C densified to about 94% of the theoretical density and the grain size was of the order of about 1.5 μm for the samples sintered at 1200 °C and increased subsequently with sintering temperature.     

Effect of sintering temperature on structural and magnetic properties of NiCuZn and MgCuZn ferrites

The low temperature microwave sintered NiCuZn and MgCuZn ferrites with compositions Ni_0.35Cu_0.05Zn_0.60Fe₂O₄ and Mg_0.35Cu_0.05Zn_0.60Fe₂O₄ were synthesized by conventional mixed oxide method. NiCuZn and MgCuZn ferrite samples obtained showed better sintered densities at 950 and 900 °C, respectively. The scanning electron micrographs of both the ferrite samples appear to be very much similar. The magnitude of initial permeability of MgCuZn ferrite samples is found to be obviously higher than those of NiCuZn ferrite samples at all sintering temperatures. This is mainly due to the fact that MgCuZn ferrite has smaller magnetocrystalline anisotropy constant and magnetostrictive constant. NiCuZn ferrites have higher saturation magnetization than MgCuZn ferrites, which is due to the higher magnetic moment of NiCuZn ferrites. Our results indicate that the microwave sintering method seems to be a potential technique in the MLCI technology.     

Heat treatment effects on microstructure and magnetic properties of Mn-Zn ferrite powders

Mn-Zn ferrite powders (Mn_0.5Zn_0.5Fe₂O₄) were prepared by the nitrate-citrate auto-combustion method and subsequently annealed in air or argon. The effects of heat treatment temperature on crystalline phases formation, microstructure and magnetic properties of Mn-Zn ferrite were investigated by X-ray diffraction, thermogravimetric and differential thermal analysis, scanning electron microscopy and vibrating sample magnetometer. Ferrites decomposed to Fe₂O₃ and Mn₂O₃ after annealing above 550 °C in air, and had poor magnetic properties. However, Fe₂O₃ and Mn₂O₃ were dissolved after ferrites annealing above 1100 °C. Moreover, the 1200 °C annealed sample showed pure ferrite phase, larger saturation magnetization (M_s=48.15 emu g⁻¹) and lower coercivity (H_c=51 Oe) compared with the auto-combusted ferrite powder (M_s=44.32 emu g⁻¹, H_c=70 Oe). The 600 °C air annealed sample had the largest saturation magnetization (M_s=56.37 emu g⁻¹) and the lowest coercivity (H_c=32 Oe) due to the presence of pure ferrite spinel phase, its microstructure and crystalline size.     

Effect of annealing temperature on the structural, photoluminescence and magnetic properties of sol-gel derived Magnetoplumbite-type (M-type) hexagonal strontium ferrite

Magnetoplumbite-type (M-type) hexagonal strontium ferrite particles were synthesized via sol-gel technique employing ethylene glycol as the gel precursor at two different calcination temperatures (800 and 1000 °C). Structural properties were systematically investigated via X-ray diffraction (XRD), field emission scanning electron microscopy, high resolution transmission electron microscopy (HRTEM), energy dispersive spectroscopy (EDS), thermogravimetric analysis (TGA), photoluminescence spectrophotometry and superconducting quantum interference device magnetometer. XRD results showed that the sample synthesized at 1000 °C was of single-phase with a space group of P6₃/mmc and lattice cell parameter values of a=5.882 Å and c=23.048 Å. EDS confirmed the composition of strontium ferrite calcined at 1000 °C being mainly of M-type SrFe₁₂O₁₉ with HRTEM micrographs confirming the ferrites exhibiting M-type long range ordering along the c-axis of the crystal structure. The photoluminescence (PL) property of strontium ferrite was examined at excitation wavelengths of 260 and 270 nm with significant PL emission peaks centered at 350 nm being detected. Strontium ferrite annealed at higher temperature (1000 °C) was found to have grown into larger particle size, having higher content of oxygen vacancies and exhibited 83-85% more intense PL. Both the as-prepared strontium ferrites exhibited significant oxygen vacancies defect structures, which were verified via TGA. Higher calcination temperature turned strontium ferrite into a softer ferrite.     

Effects of sintering temperature and Bi2O3 content on microstructure and magnetic properties of LiZn ferrites

The effects of sintering temperature and Bi₂O₃ content on the microstructure and magnetic properties of lithium–zinc (LiZn) ferrites prepared by a conventional ceramic method were investigated. The results show that the densification behavior and grain growth rate were greatly improved by the addition of Bi₂O₃, because a liquid phase sintering occurred during the sintering process at high temperature due to the low-melting point of Bi₂O₃ (825 °C). X-ray diffraction (XRD) patterns of the slightly doped samples did not reveal the appearance of any phase other than spinel LiZn ferrite. However, the secondary phase of perovskite BiFeO₃ was detected for Bi₂O₃ content of more than 0.25 wt%. The studies further show that Bi oxide was present at grain boundary, and promoted the grain growth as reaction center at lower temperature. A high saturation magnetization, squareness ratio, minimum ferromagnetic resonance linewidth and low coercive force were obtained for the sample with 1.00 wt% Bi₂O additive at lower sintering temperature (1100 °C).     

The effect of B2O3 addition to the microstructure and magnetic properties of Ni0.4Zn0.6Fe2O4 ferrite

The effects of 0.01 and 0.1 mol B₂O₃ addition to the microstructure and magnetic properties of a Ni–Zn ferrite composition expressed by a molecular formula of Ni_0.4Zn_0.6Fe₂O₄ were investigated. The toroid-shaped samples prepared by pressing the milled raw materials used in the preparation of the composition were sintered in the range of 1000–1300 °C. The addition of 0.01 mol B₂O₃ increased the grain growth and densification giving rise to reduced intergranular and intragranular porosity due to liquid-phase sintering. The sintered toroid sample at 1300 °C gave the optimum magnetic properties of B_r=170 mT, H_c=0.025 kA/m and a high initial permeability value of μ_i=4000. The increment of the B₂O₃ content to 0.1 mol resulted in a pronounced grain growth and also gave rise to large porosity due to the evaporation of B₂O₃ at higher sintering temperatures. Hence, it resulted in an air-gap effect in the hysteresis curves of these samples.     

Low temperature fired Ni-Cu-Zn ferrite with Bi4Ti3O12

The Ni-Cu-Zn ferrites with different contents of Bi₄Ti₃O₁₂ ceramics (1-8 wt%) as sintering additives were prepared by the usual ceramic technology and sintered at 900 °C to adapt to the low temperature co-fired ceramic (LTCC) technology. The magnetic and dielectric properties of the ferrite can be effectively improved with the effect of an appropriate amount of Bi₄Ti₃O₁₂. For all samples, the ferrite sintered with 2 wt% Bi₄Ti₃O₁₂ has relatively high density (98.8%) and permeability, while the ferrite with 8 wt% Bi₄Ti₃O₁₂ has relatively good dielectric properties in a wide frequency range. The influences of Bi₄Ti₃O₁₂ addition on microstructure, magnetic and dielectric properties of the ferrite have been discussed.     

Sintering characteristics of LiZn ferrites fabricated by a sol-gel process

Ultra-fine powders of LiZn ferrites with composition of Li_0.4Zn_0.2Fe_2.4O₄ were synthesized by a sol-gel process. X-ray diffraction pattern reflected that the synthesized powders were single spinel structure, with crystallite size of about 35 nm. Then the powders were granulated, pressed and sintered at different temperatures. The sintered samples were investigated by means of characterizing microstructures and magnetic properties by scanning electron microscope and B-H analyzer, respectively. The results indicate that when compared with a traditional ceramic process, the sol-gel process could slightly bring down the sintering temperature of LiZn ferrite whereas the microstructures are not homogeneous in the sintered samples. The sintering mechanisms of LiZn ferrites sintered at 1360 °C were studied, which reveal that during sintering, solid mass transfer is dominant in the LiZn ferrites fabricated by a traditional ceramic process while in the gel-derived ferrites, gas mass transfer is dominant.     

Synthesis and characterizations of microwave sintered ferrite powders and their composite films for practical applications

Phase pure single phase ferrite powders of (Ni_xR_1−x)_0.5Zn_0.5Fe₂O₄ (R=Mn, Co, Cu; x=0, 0.5) were manufactured using microwave sintering at 930 °C for 10 min in air atmosphere. The powders were characterized for their structure, microstructure, thermal, and magnetic properties. Selected powders were used as fillers to prepare their composite films using polymethyl methacrylate polymers as matrix. The composite films were prepared using the melt blending approach and were tested for their microstructure, thermal, and magnetic hysteresis loop as well as 3D magnetic field space mappings using an electromagnetic compatibility scanner. Among the studied ferrites, cobalt doped ferrites and their composites showed the best electromagnetic interference (EMI) shielding effectiveness value and have potential for practical EMI shielding applications.     

Surface study of fine MgFe2O4 ferrite powder prepared by chemical methods

To study surface behaviors, MgFe₂O₄ ferrite materials having different grain sizes were synthesized by two different chemical methods, i.e., a polymerization method and a reverse coprecipitation method. The single phase of the cubic MgFe₂O₄ was confirmed by the X-ray diffraction method for both the precursors decomposed at 600-1000 °C except for a very small peak of Fe₂O₃ was detected for the samples calcined at 600 and 700 °C by the polymerization method. The crystal size and particle size increased with an increase in the sintering temperature using both methods. The conductance of the MgFe₂O₄ decreased when the atmosphere was changed from ambient air to air containing 10.0 ppm NO₂. The conductance change, C = G(air)/G(10 ppm NO₂), was reduced with an increase in the operating temperature. For the polymerization method, the maximum C-value was ca. 40 at 300 °C for the samples sintered at 900 °C. However, the samples sintered at 1000 °C showed a low conductance change in the 10 ppm NO₂ gas, because the ratio of the O₂ gas adsorption sites on the particle surface is smaller than those of the samples having a high C-value. The low Mg content on the surface affects the low ratio of the gas adsorption sites. For the reverse coprecipitation method, the particle size was smaller than that of the polymerization method. Although a stable conductance was obtained for the sample sintered at 900 and 1000 °C, its conductance change was less than that of the polymerization method.     

Structural and magnetic properties of Li-Cu mixed spinel ferrites

Li_0.5−x/2Cu_xFe_2.5−x/2O₄ (where x=0.0-1.0) ferrites have been prepared by solid-state reaction. X-ray diffraction was used to study the structure of the above investigated ferrites at various sintering temperatures. Samples were sintered at 1000, 1100 and 1200 °C for 3 h in the atmosphere. For the sintering temperature of 1000 °C, Li_0.5−x/2Cu_xFe_2.5−x/2O₄ undergoes cubic to tetragonal transformation for higher Cu content. However, for the sintering temperature of 1100 and 1200 °C, X-ray diffraction patterns are mainly characterized by fcc structure, though presence of tetragonal distortion was found by other temperature dependence of initial permeability curves. The lattice parameter, X-ray density and bulk density were calculated for different compositions. Curie temperature was measured from the temperature dependence of initial permeability curves. Curie temperatures of Li-Cu mixed ferrites were found to decrease with the increase in Cu²⁺ content due to the reduction of A-B interaction. As mentioned earlier, temperature dependence of initial permeability curves was characterized by tetragonal deformation for the samples containing higher at% of Cu. The complex initial permeability has been studied for different samples. The B-H loops were measured at constant frequency, f=1200 Hz, at room temperature (298 K). Coercivity and hysteresis loss were estimated for different Cu contents.     

Effects of V2O5 addition on NiZn ferrite synthesized using two-step sintering process

The combined influence of a two-step sintering (TSS) process and addition of V₂O₅ on the microstructure and magnetic properties of NiZn ferrite was investigated. As comparison, samples prepared by the conventional single-step sintering (SSS) procedure were also studied. It was found that with 0.3 wt% V₂O₅ additive, the sample sintered by the two-step sintering process at a high temperature of 1250 °C for 30 min and a lower temperature of 1180 °C for 3 h exhibited more homogeneous microstructure and higher permeability with a high Q-factor. The results showed that the TSS method with suitable additive brought positive improvement of the microstructure and magnetic properties of NiZn ferrite.     

Influence of rare earth Ce on structural, electrical and magnetic properties of Sr based W-type hexagonal ferrites

A series of single phase W-type Sr_3−xCe_xFe₁₆O₂₇ (x=0, 0.02, 0.04, 0.06, 0.08, 0.10) hexagonal ferrites prepared by the Sol-Gel method was sintered at 1050 °C for 5 h. The X-ray diffraction analysis reveals that all the samples belong to the family of W-type hexagonal ferrites. The c/a ratio falls in the range of W-type hexagonal ferrites. The grain size was measured by SEM varies from 0.7684 to 0.4366 μm which shows that the Ce³⁺ substituted samples have smaller grain size than pure ferrite Sr₃Fe₁₆O₂₇ which results from the difference in ionic radii of Ce³⁺ (1.034 Å) and Sr²⁺ (1.12 Å). The room temperature resistivity of the present samples varies from 6.5×10⁸ to 272×10⁸ Ω-cm. The coercivity increases from 1370 to 1993 Oe which is consistent with the decrease in grain size. The coercivity values indicate that the present samples fall in the range of hard ferrites. The large value of H_c may be due to domain wall pinning at the grain boundaries.     

Effects of calcining temperature and heating rate on properties of high-permeability NiCuZn ferrites

The effects of calcining temperature and heating rate during sintering on densification and magnetic properties of high-permeability NiCuZn ferrites were investigated. It was confirmed that increasing calcining temperature lead to increase of the molding density (the pressed density of samples that have not been sintered), both molding density and activity of the calcined powders determined the sintering density (the density of samples after sintering) of the samples. With the calcining temperature of 1060 °C, the sintering density reached a peak. The initial permeability also peaked with the calcining temperature of 1060 °C, which could be attributed to the highest sintering density and relatively big grain size. Quality factor peaked with the calcining temperature of 1020 °C, which could be attributed to the biggest grain size. Calcining temperature had no distinct connection with Curie temperature, and it had a slight effect on the saturation magnetism (B_s) due to varieties of the sintering density. Further studies showed that heating rate had a pronounced effect on initial permeability and quality factor, which could be attributed to a variety in the grain size. The critical heating rate value was 2 °C/min in order to obtain high-performance NiCuZn ferrites with both high initial permeability and high quality factor.