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.     

Influence of vacuum sintering on microstructure and magnetic properties of magnetostrictive cobalt ferrite

Differences in the microstructure and magnetic properties of highly magnetostrictive cobalt ferrite resulting from the effects of different vacuum sintering temperatures and times have been investigated. A vacuum environment was chosen to allow direct comparison of results with air-sintered samples which are more often reported in the literature. It was found that vacuum sintering resulted in the development of a solid solution second phase with composition Co_1−xFe_xO₄ (x∼0.33). There was a decrease in magnetostriction as a result of the formation of the second phase. Furthermore, differences in sintering temperatures were found to have a greater effect on the magnetostriction than differences in sintering times. It was found that the first order cubic anisotropy coefficient initially increased with both sintering temperature and time, before peaking and decreasing to its lowest measured value. The lowest anisotropy was therefore achieved with samples sintered at higher temperatures and longer times.     

Effects of In-substitution on the structure and magnetic properties of multi-doped YIG ferrites with low saturation magnetizations

Multi-doped YIG ferrites {Y_1.7Gd_0.5Ca_0.8}[Fe_2−xIn_x](Fe_2.15V_0.4Mn_0.05Al_0.4)O₁₂ (x=0, 0.3, 0.6, 0.7, 0.8 and 0.9) with low saturation magnetizations (4πM_s=400-600 G at 298 K) were prepared by a conventional ceramic technology and the effects of In³⁺-substitution on their structures and magnetic properties were systematically investigated using XRD, SEM and VSM. It has been found that as-synthesized powders and sintered ferrites showed a single-phase of garnet structure with a cell parameter (a) that increased linearly with increase in In³⁺ concentration from x=0 up to 0.9. Apparent relative densities of sintered samples were all over 98%, but no remarkable influences of In³⁺-substitution were observed by SEM on the refinement of crystal grains and the enhancement of sintering of ferrites. In addition, the Curie temperature T_c decreased almost linearly as In³⁺concentration increased, while the corresponding saturation magnetization at room temperature presented a variation characterized by a gradual increase first and then a rapid plunge. On the basis of quantitative analysis of XRD data and the theory on super-exchange interactions, it has been established that the incorporated In³⁺ ions via doping were exclusively located at the sites with octahedral coordinations in the crystal structure and the aforementioned magnetic properties can be simply attributed to weakening super-exchange interactions between neighboring magnetic ions through oxygen ions due to the “dilution effect” of added non-magnetic In³⁺ ions.     

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.     

Microstructure and magnetic properties of low-temperature sintered CoTi-substituted barium ferrite for LTCC application

In this article, the influences of the BaCu(B₂O₅) (BCB) additive on sintering behavior, structure and magnetic properties of iron deficient M-type barium ferrite Ba(CoTi)_xFe_11.8−2xO₁₉ (BaM) have been investigated. It is found that the maximum sintered densities of BaM change from 86% to 94% as the BCB content varies from 1 to 4 wt%. Single-phase BaM can be detected by the XRD analysis in the sample with 3 wt% BCB sintered at 900 °C, and the microstructure is hexagonal platelets with few intragranular pores. This is attributed to the formation of the BCB liquid phase. Meanwhile, the experimental results illuminate that the CoTi ions prefer to occupy the 4f2 and 2b sites and the magnetic properties depend on the amount of CoTi-substitution. In addition, the chemical compatibility between BaM and silver paste is also investigated; it can be seen that BaM is co-fired well with the silver paste and no other second phase is observed. Especially, the 3 wt% BCB-added Ba(CoTi)_0.9Fe₁₁O₁₉ sintered at 900 °C has good properties with the sintered density of 4.9 g/cm³, saturation magnetization of 49.7 emu/g and coercivity of 656.6 Oe. These results indicate that it is cost effective in the production of Low Temperature Co-fired Ceramics (LTCC) multilayer devices.     

Study on magnetic properties of nanocrystalline La-, Nd-, or Gd-substituted Ni–Mn ferrite at low temperatures

The effects of rare-earth ions with different radii and magnetic moments on the magnetic properties of Ni–Mn ferrite are investigated. X-ray diffraction pattern has shown the presence of cubic structure of spinel ferrite for all samples. The values of M_s and H_c are decreasing with increasing of testing temperatures for all samples. The H_c value of Ni_0.7Mn_0.3La_0.1Fe_1.9O₄ reaches 1082 Oe at 2 K. Mössbauer spectra tested at 273 K indicate the presence of superparamagnetism for samples calcined at 873 K.     

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.     

Effects of SnO2 addition on the microstructure and magnetic properties of NiZn ferrites

The microstructure and magnetic properties of SnO₂-doped NiZn ferrites prepared by a solid-state reaction method have been investigated. Due to its low melting point (∼1127 °C), moderate SnO₂ enhanced mass transfer and sintering by forming liquid phase, which accelerated the grain growth. However, excessive SnO₂ producing much of liquid phase retarded mass transfer and sintering, leading to a decrease in grain size. The diffraction intensity of the samples doped with SnO₂ addition was stronger than that of the sample without addition. The lattice constant initially decreased up to a content of 0.10 wt% and showed an increase at higher content up to 0.50 wt%. The initial permeability (μ_i) initially increased up to a content of 0.15 wt% and showed a decrease at higher content up to 0.50 wt%; however, losses (P_L) measured at 50 kHz and 150 mT changed contrarily. Both saturation induction (B_S) and Curie temperature (T_C) decreased gradually with increasing SnO₂. Finally, the sample doped with 0.10–0.15 wt% SnO₂ showed the higher permeability and lower losses.     

Effects of Zr-substitution on microstructure and properties of YCaVIG ferrites

Y_2.6−xCa_0.4+xZr_xV_0.2Fe_4.8−xO₁₂ (Zr_x:YCaVIG) ferrite materials have been prepared by an oxide process. The phase formation and microstructure were analyzed by X-ray diffraction and scanning electron microscopy, respectively. The effects of Zr⁴⁺ substitution on phase compositions, sintering properties, microstructures and electromagnetic properties were investigated. The results indicate that all the sintered specimens with different Zr⁴⁺ contents show a single garnet structure. The addition of ZrO₂ can gradually increase the lattice constant, and lower the sintering temperature and the theoretical density. With the increase of Zr⁴⁺ content, the dielectric loss (tan δ_ε) and coercivity (H_c) decrease and then slightly increase, which is due to the variation of the microstructure. But the saturation magnetization (4πM_s) shows the opposite variation compared to the former two properties. However, the dielectric constant (ε_r) remains stable and remanence (B_r) monotonically declines. Finally, the specimen of Y_2.3Ca_0.7Zr_0.3V_0.2Fe_4.5O₁₂ sintered at 1350° possesses the optimum electromagnetic properties: ε_r=14.8, tan δ_ε=1.35×10⁻³, 4πM_s=1638 Gs, B_r=596 Gs, H_c=0.75 Oe and ΔH (ferromagnetic resonance linewidth)=66 Oe.     

The role of Mg substitution on the microstructure and magnetic properties of Ba Co Zn W-type hexagonal ferrites

A series of W-type hexagonal ferrites with the composition BaCoZn_1−xMg_xFe₁₆O₂₇ (0?x?0.6) were prepared by the conventional ceramic method to study their structural and magnetic properties as a function of temperature and composition. The characterization using X-ray diffraction indicated that a hexagonal W-type single-phase structure and the effect of composition on the unit cell parameters, density and porosity was studied. The variation of the magnetic susceptibility (χ_M) with temperature for all the investigated samples in the temperature range (300–800 K) shows three regions of behavior that was explained on the basis of the distribution of Zn²⁺ and Mg²⁺ ions in the lattice and leads to the anomalous behavior of the effective magnetic moment μ_eff. The Curie temperature indicated that the critical concentration is at x=0.5. Paramagnetic nature of the samples above the Curie temperature is observed. The Curie Weiss constant θ calculated from the plot of 1/χ_M vs. T (K) is in agreement with the expected value. The effective magnetic moment μ_eff decreases with increasing the intensity of magnetic field. The possible mechanisms contributing to these properties are discussed in the text.     

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).     

Structural characterization and magnetic properties of superparamagnetic zinc ferrite nanoparticles synthesized by the coprecipitation method

Single phase zinc ferrite (ZnFe₂O₄) nanoparticles have been prepared by the coprecipitation method without any subsequent calcination. The effects of precipitation temperature in the range 20–80 °C on the structural and the magnetic properties of zinc ferrite nanoparticles were investigated. The crystallite size, microstructure and magnetic properties of the prepared nanoparticles were studied using X-ray diffraction (XRD), Fourier transmission infrared spectrum, transmission electron microscope (TEM), energy dispersive X-ray spectrometer and vibrating sample magnetometer. The XRD results showed that the coprecipitated nanoparticles were single phase zinc ferrite with mixture of normal and inverse spinel structures. Furthermore, ZnFe₂O₄ nanoparticles have the crystallite size in the range 5–10 nm, as confirmed by TEM. The magnetic measurements exhibited that the zinc ferrite nanoparticles synthesized at 40 °C were superparamagnetic with the maximum magnetization of 7.3 emu/g at 10 kOe.     

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.     

Synthesis of cobalt ferrite nano-particles and their magnetic characterization

Cobalt ferrite nano-particles (CoFe₂O₄) were synthesized by the co-precipitation method with ammonium hydroxide as an alkaline solution. The reactions were carried out at different temperatures between 20 and 80 °C. The nano-particles have been investigated by magnetic measurements, X-ray powder diffraction and transmission electron microscopy. The average crystallite size of the synthesized samples was between 11 and 45 nm, which was found to be dependent on both pH value of the reaction and annealing temperatures. However, lattice parameters, interplane spacing and grain size were controlled by varying the annealing temperature. Magnetic characterization of the nano-samples were carried out using a vibrating sample magnetometer at room temperature. The saturation magnetization was computed and found to lie between 5 and 67 emu/g depending on the particle size of the studied sample. The coercivity was found to exhibit non-monotonic behavior with the particle size. Such behavior can be accounted for by the combination between surface anisotropy and thermal energies. The ratio of remanence magnetization to saturation magnetization was found to exhibit almost linear dependence on the particle size.     

Room temperature single-step electrosynthesized copper ferrite thin films and study of their magnetic properties

A single-step electrosynthesis of copper ferrite thin films from aqueous bath (which avoids anodization step for an incorporation of oxygen species into deposit) has been carried out at room temperature. Observed tetrahedral structured nanocrystalline copper ferrite thin films showed smooth, uniform and compact surface morphology. After annealing, increase in dielectric constant and reduced dielectric loss were observed. The saturation magnetization for annealed films was 292 emu/cm³ comparable to that of other reported ferrites.     

Preparation, and magnetic and electromagnetic properties of La-doped strontium ferrite films

SrLa_xFe_12−xO₁₉ films (x=0-1.0) with large magneto-crystalline anisotropy were synthesized on SiO₂ substrate by sol-gel and self-propagating high-temperature synthesis technique. The films were characterized by various experimental techniques including X-ray diffraction analysis, Field Emission Scanning Electron Microscope, Atomic Force Microscopy, Vibrating Sample Magnetometry and vector network analyzer. The results show that La ions completely enter into strontium ferrite lattice without changing the ferrite appearance; its grain size is approximately 40-80 nm, its length is 100 nm; the magnetoplumbite structure is proved through testing a concertina form of the crystal grain; the maximum coercivity is 5986 Oe at x=0.2; La-doped films possess a wider microwave absorption frequency range with better gross loss angle tangent (tan δ>0.1), from 9 to 10.5 GHz at x=0.2, where the maximum value of tan δ reaches 0.2709. The La-doped films reach smaller nanometer size, better magnetic properties and microwave absorption properties with the doping of lanthanum.     

Effects of impurity Na ions on the structural and magnetic properties of Ni-Zn-Cu ferrite powders: An improvement for chemical coprecipitation method

Ni-Zn-Cu ferrite powders with nominal composition Ni_0.4−xZn_0.6Cu_xFe₂O₄ (x=0.00-0.20) were prepared via chemical coprecipitation method. X-ray diffractometer, vibrating sample magnetometer, scanning electron microscopy, inductively coupled plasma-atomic emission spectrometry and energy dispersive spectrum were used to study the effects of impurity Na⁺ ions on the structural and magnetic properties. As a result, it was found that the impurity Na⁺ ions affect the crystalline structures and magnetic properties greatly. Moreover, the heterogeneous distribution of impurity Na⁺ ions and the formation of Na compounds retard the phase formation and the grain growth of specimens. Our study also reveals that for the chemical coprecipitation method, a second washing process introduced after drying can eliminate the impurity Na⁺ ions effectually and thus helps in the formation of single-phase structure and the growth of grains, which is very important for the improvement of magnetic properties and the preparation of ferrites via chemical coprecipitation method.     

Effects of Ta2O5 addition on the microstructure and temperature dependence of magnetic properties of MnZn ferrites

MnZn ferrites with the chemical formula Mn_0.68Zn_0.25Fe_2.07O₄ have been prepared by the conventional ceramic technique. Toroidal cores were sintered at 1350 °C for 4 h in N₂/O₂ atmosphere with 4% oxygen. Then the influence of Ta₂O₅ addition on the microstructure and temperature dependence of magnetic properties of MnZn ferrites was investigated by characterizing the fracture surface micrograph and measuring the magnetic properties over a temperature ranging from 25 to 120 °C. The results show that, when the Ta₂O₅ concentration is not more than 0.04wt%, the grain size has a slight increase with the increase of Ta₂O₅ concentration, the temperature of secondary maximum peak in the curve of initial permeability versus temperature and the lowest power loss shift to lower temperature. However, excessive Ta₂O₅ concentration (>0.04wt%) results in the exaggerated grain growth and porosity increase, which make the initial permeability and saturation magnetic flux density decrease and the power loss increase at room temperature. Furthermore, the temperature of secondary maximum peak in the curve of initial permeability versus temperature and the lowest power loss shift to about 100 °C.     

Effects of excessive grain growth on the magnetic and mechanical properties of hot-deformed NdFeB magnets

The magnetic and mechanical properties of rare-earth magnets hot-deformed at temperature range 750-950 °C have been investigated. The grains tended to grow excessively from dozens of nanometers to several microns at the temperatures above 850 °C. The alignment of grains was disrupted by the hot deformation at the high temperatures. The Nd-rich phase was extruded at the temperatures which are higher than 850 °C. The Nd-rich phase extrusion resulted in the reduction of density by 1% and the reduction of remanence from 1.42 to 0.72 T. The reduction of grain boundaries caused by flat platelet-shaped grains changing to spherical grains and the weak binding strength among large grains of Nd₂Fe₁₄B phase may be the main reasons for the low mechanical strength of hot-deformed magnets.     

Changes of microstructure and magnetic properties of Nd-Fe-B sintered magnets by doping Al-Cu

The microstructural and magnetic properties of Al_100−xCu_x (15at%≤x≤45 at%) doped Nd-Fe-B magnets were studied. The distribution and alloying effects of Cu or Al on the intergranular microstructure were investigated by thermodynamic analysis, differential scanning calorimetery and microscopy techniques. It was observed that when the Cu content of Al_100xCu_x exceeds to 25 at%, the (Pr, Nd)Cu and CuAl₂ phases form in these magnets. The formation of (Pr, Nd)Cu phase depends on the negative formation enthalpy of (Pr, Nd)Cu and the exclusive distribution of Cu in the intergranular regions. The eutectic reaction between (Pr, Nd)Cu phase and (Pr, Nd) occurs at 480 °C, which forms the liquid phase that dissolves the (Pr, Nd)₂Fe₁₄B surface irregularities and thus increases the quantities of (Pr, Nd)-rich phase at the grain boundaries. These changes benefit the grain boundary microstructure, especially the distribution of (Pr, Nd)-rich phase, which effectively improves the intrinsic coercivity _iH_c due to the decreases of exchange coupling between the (Pr, Nd)₂Fe₁₄B grains.