Low temperature sintering of sub-stoichiometric Ni-Cu-Zn ferrites: Shrinkage, microstructure and permeability

We have studied sub-stoichiometric Ni-Cu-Zn ferrites with iron deficiency (i.e., <50mol% Fe₂O₃) of composition Ni_0.20Cu_0.20Zn_0.60+zFe_2−zO_4−(z/2) with 0≤z≤0.06. The temperature of maximum shrinkage rate is shifted from T=1000 °C for z=0 towards lower temperatures down to T=900 °C for a sub-stoichiometric ferrite with z=0.02. Dense samples are obtained after firing at 900 °C for z>0 only. Sub-stoichiometric compositions (z>0) do not form single-phase spinel ferrites after sintering at 900 °C, but rather represent mixtures of CuO and a stoichiometric ferrite with slightly modified composition. The formation of small amounts of CuO at grain boundaries is demonstrated by XRD and SEM. The permeability is increased from μ=80 for stoichiometric ferrites (z=0) to μ=660 for z=0.02. The formation of CuO during sintering of sub-stoichiometric ferrites supports densification and is a prerequisite for low temperature firing of multilayer inductors. Addition of 1 wt% Bi₂O₃ as liquid phase sintering aid is required to provide sufficient densification of the stoichiometric ferrite (z=0) at 900 °C. Addition of 0.37 wt% Bi₂O₃ to a sub-stoichiometric ferrite (z=0.02) results in dense samples after firing at 900 °C; however, the microstructure formation is dominated by heterogeneous grain growth.     

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.     

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).     

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.     

Low-temperature-fired NiCuZn ferrites with BBSZ glass

Addition of BBSZ (27% Bi₂O₃, 35% H₃BO₃, 6% SiO₂, and 32% ZnO in mol%) glass has been used to enhance densification and improve the magnetic properties of low-temperature-fired NiCuZn ferrites. It was found that the BBSZ glass did not form a visible second phase in our testing range. However, the densification and microstructure of the ferrites were initially very sensitive to the BBSZ glass content. Even a slight increase in BBSZ glass content from 0.25 to 0.5 wt% was sufficient to change the ferrite samples from not being well sintered with a uniform microstructure and very small grain size to a typical bimodal, inhomogeneous microstructure. It proved to be better to add more BBSZ glass than the critical content to obtain the appropriate microstructure and magnetic properties. In this study, a ferrite sample with 0.75 wt% BBSZ glass gave the best performance in terms of densification, microstructure, permeability, and Q-factor characteristics.     

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.     

Synthesis of (Mg0.476Mn0.448Zn0.007)(Fe1.997Ti0.002)O4 powder and sintered ferrites by high energy ball-milling process

(Mg_0.476Mn_0.448Zn_0.007)(Fe_1.997Ti_0.002)O₄ nanocrystalline powder prepared by high energy ball-milling process were consolidated by microwave and conventional sintering processes. Phases, microstructure and magnetic properties of the ferrites prepared by different processes were investigated. The (Mg_0.476Mn_0.448Zn_0.007)(Fe_1.997Ti_0.002)O₄ nanocrystalline powder could be prepared by high energy ball-milling process of raw Fe₃O₄, MnO₂, ZnO, TiO₂ and MgO powders. Prefired and microwave sintered ferrites could achieve the maximum density (4.86 g/cm⁻³), the average grain size (15 μm) was larger than that (10 μm) prepared by prefired and conventionally sintered ferrites with pure ferrite phase, and the saturation magnetization (66.77 emu/g) was lower than that of prefired and conventionally sintered ferrites (88.25 emu/g), the remanent magnetization (0.7367 emu/g) was higher than that of prefired and conventionally sintered ferrites (0.0731 emu/g). Although the microwave sintering process could increase the density of ferrites, the saturation magnetization of ferrites was decreased and the remanent magnetization of ferrites was also increased.     

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.     

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.     

Electromagnetic and microwave absorbing properties of Co2Z-type hexaferrites doped with La

Z-type ferrites doped with La³⁺, Ba_3−xLa_xCo₂Fe₂₄O₄₁ (x=0.00-0.30), were prepared by sol-gel method. The effect of the substitution La³⁺ rare-earth ions for Ba²⁺ ions on the microstructure, complex permeability, permittivity and microwave absorption of the samples was investigated. The results show that the major phase of the ferrites changed to Z-phase when sintering temperature was 1250 °C for 5 h. With the increase of the substitution ratio of La³⁺ ions from 0.0 to 0.3, the lattice parameters a and c increased gradually, which resulted in the change of the particle shape and size. The data of magnetism showed that the addition of La³⁺ ions make the ferrite a better soft magnetic material due to increase of magnetization (σ_s) and decrease of coercivity (H_c). The La³⁺ ions doped in the ferrite not only improved complex permeability and complex permittivity, but also microwave absorbency.     

Electromagnetic properties and microwave absorption of W-type hexagonal ferrites doped with La

W-type barium hexaferrites with compositions of Ba₁Co_0.9Zn_1.1Fe₁₆O₂₇ and Ba_0.8La_0.2Co_0.9Zn_1.1Fe₁₆O₂₇ were synthesized by the sol-gel method. The electromagnetic properties and microwave absorption behavior of these two ferrites were studied in the 2-18 GHz frequency range. The microstructure and morphology of the ferrites were characterized by X-ray diffraction (XRD), and scanning electron microscopy (SEM) techniques. The complex permittivity spectra, the complex permeability spectra and microwave reflection loss were measured by a microwave vector network analyzer. The XRD patterns show that the main phase of the Co₂W ferrite forms without other intermediate phases when calcined at 1200 °C. The SEM images indicate that flake-like hexagonal crystals distribute uniformly in the materials. Both the magnetic and dielectric losses are significantly enhanced by partial substitution of La³⁺ for Ba²⁺ in the W-type barium hexaferrites. The microwave absorption property of the La³⁺ doping W-type hexaferrite sample is enhanced with the bandwidth below −10 dB around 8 GHz and the peak value of reflection loss about −39.6 dB at the layer thickness of 2 mm.     

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.     

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.     

Synthesis and magnetic properties of hard magnetic (CoFe2O4)-soft magnetic (Fe3O4) nano-composite ceramics by SPS technology

CoFe₂O₄/Fe₃O₄ nano-composite ceramics were synthesized by Spark Plasma Sintering. The X-ray diffraction patterns show that all samples are composed of CoFe₂O₄ and Fe₃O₄ phases when the sintering temperature is below 900 °C. It is found that the magnetic properties strongly depend on the sintering temperature. The two-step hysteresis loops for samples sintered below 500 °C are observed, but when sintering temperature reaches 500 °C, the step disappears, which indicates that the CoFe₂O₄ and Fe₃O₄ are well exchange coupled. As the sintering temperature increases from 500 to 800 °C, the results of X-ray diffractometer indicate the constriction of crystalline regions due to the ion diffusion at the interfaces of CoFe₂O₄/Fe₃O₄ phases, which have great impact on the magnetic properties.     

Effects of different sintering temperature and Nb2O5 content on structural and magnetic properties of Z-type hexaferrites

Nb-doped Z-type hexaferrites (Ba₃(Co_0.4Zn_0.6)₂Fe₂₄O₄₁) with composition of Ba₃(Co_0.4Zn_0.6)₂Fe₂₄O₄₁+x Nb₂O₅ (where x=0.0, 0.1, 0.2, 0.4, 0.6, 0.8, 1.2, 1.6 and 2.0 wt%) were prepared by a solid-state reaction method. The effects of different sintering temperature (T_s) and Nb₂O₅ content on the sintering behaviors, phase composing, microstructure, and magnetic properties of the samples were investigated. The results from X-ray diffraction and scanning electron microscopy show that as the amount of Nb₂O₅ additive increases, the major phase changes to Z-phase, Simultaneously, M-phase and a small amount of niobate phase appear. The Nb₂O₅ additive promotes the grain growth as reaction center at lower sintering temperature (1220 °C), but at higher temperature (1260 °C), niobate phase separated out in grain boundaries as secondary phase will restrain abnormal grain growth, so closed pores in grains are not formed. The Nb₂O₅ additive can enhance densification, improve initial permeability of hexaferrites by increasing the grain growth of hexaferrite and the displacement of ions in the sintering process due to the aberration and activation of crystal lattice, which is accompanied by the solubility of Nb⁵⁺ in the hexaferrites. A relative density of 96%, maximum initial permeability (32–33), minimum coercivity (454–455 A/m) and resonance frequency above 400 MHz were obtained for the sample with 0.8 wt% Nb₂O₅ sintered at 1260 °C for 6 h.     

Synthesis and characterization of NiCoMnCuFe1.96O4 for circulator application

Modern accelerator design practice includes the use of high-quality ferrites for circulator applications with ever-increasing requirements on power handling ability. Modeling studies of new designs are of increasing economic importance, but are frequently hindered by lack of measured values of the ceramic loss factors. We have developed a nanocrystalline ferrite material with composition Ni_0.94Co_0.03Mn_0.04Cu_0.03Fe_1.96O₄. Nanocrystalline NiCoMnCu ferrite powders were synthesized using a microwave-hydrothermal method at 160 °C for 40 min. The ferrite formation conditions, such as pH, temperature and time, were optimized. The phase of the samples was identified by X-ray diffraction and was characterized by Fourier transformation infrared spectroscopy. The size of the nanocrystalline ferrite of as-synthesized powders was 10 nm. The powder was densified at different temperatures using a microwave sintering method. The complex permittivity and permeability of the sintered samples were measured over a frequency range from 10 kHz to 1.8 GHz at room temperature. The applicability of the samples for circulators was tested via the measurement of the ferromagnetic resonance linewidth and the results are presented.     

Influence of V2O5 on the magnetic properties of nickel–zinc–copper ferrites

Additions of V₂O₅ were used to decrease the sintering temperature and to enhance the densification of NiZnCu ferrite. With a small amount of V₂O₅ (0.6–1.2 wt%) as a sintering aid, densification at low sintering temperature was observed. EDS analyses showed the presence of vanadium inside the ferrite grains. Microstructure investigation revealed heterogeneous grain size. Magnetic properties were deteriorated when increasing the V₂O₅ content. As a consequence, the permeability decreased and the core losses increased, which can be explained by the pinning of the domain walls to the grain defects.     

Synthesis and ion conductivity of (Bi2O3)0.75(Dy2O3)0.25 ceramics with grain sizes from the nano to the micro scale

Using (Bi₂O₃)_0.75(Dy₂O₃)_0.25 nano-powder synthesized by reverse titration co-precipitation method as raw material, dense ceramics were sintered by both Spark Plasma Sintering (SPS) and pressureless sintering. According to the predominance area diagram of Bi-O binary system, the sintering conditions under SPS were optimized. (Bi₂O₃)_0.75(Dy₂O₃)_0.25 ceramics with relative density higher than 95% and an average grain size of 20 nm were sintered in only 10 min up to 500 °C. During the pressureless sintering process, the grain growth behavior of (Bi₂O₃)_0.75(Dy₂O₃)_0.25 followed a parabolic trend, expressed as D² − D₀² = Kt, and the apparent activation energy of grain growth was found to be 284 kJ mol^− 1. Dense (Bi₂O₃)_0.75(Dy₂O₃)_0.25 ceramics with different grain sizes were obtained, and the effect of grain size on ion conductivity was investigated by impedance spectroscopy. It was shown that the total ion conductivity was not affected by the grain size down to 100 nm, however lower conductivity was measured for the sample with the smallest grain size (20 nm). But, although only the δ phase was evidenced by X-ray diffraction for this sample, a closer inspection by Raman spectroscopy revealed traces of α-Bi₂O₃.     

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.     

Effect of nanocrystalline particles on the magnetic properties of Z-type hexaferrites

In order to improve the magnetic properties of Z-type hexaferrites such as high initial permeability and high-quality factor, the nanocrystalline hexaferrite particles (NHPs) with the same chemical composition were introduced. The influence of NHPs on the densification, microstructures and magnetic properties of the ceramics prepared by a combined method was investigated. The results show that these NHPs, which spread around the micron-sized hexaferrite particles (MHPs), enhance the densification by increasing the inter-diffusion of the particles due to the increase of contact area; simultaneously, the grain growth in the direction of c-plane is dominant. Due to the special microstructure, high sintering density, and no addition sintering aids with different chemical composition, relatively high initial permeability and Q-factor than those of the samples with 1.0 wt% Bi₂O₃ were obtained in the samples with proper nanocrystalline particles sintered at 900 °C.