Preparation of M-Ba-ferrite fine powders by sugar-nitrates process

In this paper, fine M-type barium hexaferrite (M-Ba-ferrite) particles were synthesized from sugar and nitrates by simple route, which revealed the feasibility of using sugar as chelating agent in forming solid precursors of BaFe₁₂O₁₉. The effects of factors, such as the molar ratio of Fe/Ba, calcination temperature and time, on the morphology, the phase component and the magnetic properties of M-type barium hexaferrite particles were studied by means of X-ray diffraction, infrared spectroscopy, transmission electron microscopy and physical property measurement system. The results showed that the molar ratio of Ba²⁺ to Fe³⁺ influenced significantly on the formation of the single phase barium ferrite. The hexagonal platelet barium ferrite particles with a specific saturation magnetization of 64.48 emu/g, remanence magnetization (Mr) of 33.84 emu/g, and coercive force (Hc) of 1848.85 Oe were obtained when the molar ratio of Fe/Ba was 11.5 and the calcination temperature was 1100 °C for 2 h.     

Catalytic activity and magnetic properties of barium hexaferrite prepared from barite ore

Barium hexaferrite (BaFe₁₂O₁₉) has traditionally been used in permanent magnets and more recently used for high density magnetic recording. The classical ceramic method for the preparation of barium hexaferrite consists of firing mixture of chemical grade iron oxide and barium carbonate at high temperature. In this paper a mixture of chemical grade hematite, barium oxide and predetermined mixtures of iron oxide ore and barite ore containing variable amounts of coke were used to prepare barium hexaferrite (BaFe₁₂O₁₉) as a permanent magnetic material. The mixtures were mixed in a ball mill and fired for 20 h in a tube furnace at different temperatures (1100, 1150, 1200 and 1250 °C). XRD, magnetic properties, porosity measurements and catalytic activity were used for characterization of the produced ferrite. The results of experiments showed that the optimum conditions for the preparation of barium hexaferrite are found at 1200 °C for the mixture of chemical grade hematite and barium oxide. It was also found that the barium hexaferrite can be prepared from the iron and barite ores at 1200 °C. The addition of coke enhanced the yield of barium hexaferrite and improved its physicochemical properties. Samples prepared from ores with coke% = 0 show the most acidic active sites, they show a higher catalytic activity towards H₂O₂ decomposition. With addition of coke the catalytic activity decreases due to the poisoning effect of carbon on the available active site.     

A novel approach for synthesis of M-type hexaferrites nanopowders via the co-precipitation method

M-type hexaferrites; barium hexaferrite BaFe₁₂O₁₉ and strontium hexaferrite SrFe₁₂O₁₉ powders have been successfully prepared via the co-precipitation method using 5 M sodium carbonate solution as alkali. Effects of the molar ratio and the annealing temperature on the crystal structure, crystallite size, microstructure and the magnetic properties of the produced powders were systematically studied. The results indicated that a single phase of barium hexaferrite was obtained at Fe³⁺/Ba²⁺ molar ratio 12 annealed at 800–1,200 °C for 2 h whereas the orthorhombic barium iron oxide BaFe₂O₄ phase was formed as a impurity phase with barium M-type ferrite at Fe³⁺/Ba²⁺ molar ratio 8. On the other hand, a single phase of strontium hexaferrite was produced with the Fe³⁺/Sr²⁺ molar ratio to 12 at the different annealing temperatures from 800 to 1,200 °C for 2 h whereas the orthorhombic strontium iron oxide Sr₄Fe₆O₁₃ phase was formed as a secondary phase with SrFe₁₂O₁₉ phase at Fe³⁺/Sr²⁺ molar ratio of 9.23. The crystallite sizes of the produced nanopowders were increased with increasing the annealing temperature and the molar ratios. The microstructure of the produced single phase M-type ferrites powders displayed as a hexagonal-platelet like structure. A saturation magnetization (53.8 emu/g) was achieved for the pure barium hexaferrite phase formed at low temperature 800 °C for 2 h. On the other hand, a higher saturation magnetization value (M _s = 85.4 emu/g) was obtained for the strontium hexaferrite powders from the precipitated precursors synthesized at Fe³⁺/Sr²⁺ molar ratio 12 and thermally treated at 1,000 °C for 2 h.     

Influence of synthesis variables on the properties of barium hexaferrite nanoparticles

Barium hexaferrite (BaFe₁₂O₁₉) nanoparticles were synthesized by sol–gel auto-combustion route. Prepared samples were sintered at 950 and 1100 °C with Fe³⁺/Ba²⁺ = 12 and 20 mol ratio. The formation mechanism of barium hexaferrite was investigated by using X-ray diffraction (XRD) and differential scanning calorimetry (DSC) analyses. In addition, the effect of temperature and Fe³⁺/Ba²⁺ mole ratio on BaFe₁₂O₁₉ formation and magnetic properties, and the effect of increasing the Fe³⁺/Ba²⁺ upon gel ignition and subsequent phase development were investigated. Finally the magnetic behavior was monitored with VSM. DSC studies showed that pure barium hexaferrite phase was formed from maghemite (γ-Fe₂O₃), without the formation of hematite (α-Fe₂O₃). Also, XRD results confirmed the formation of barium hexaferrite phase in non stoichiometric Fe/Ba ratio. VSM results showed that the saturation magnetization was decreased and coercivity increased with decreasing the grain size.     

Barium hexaferrite magnet by topotactic reaction method

A new topotactic sintering method using Fe₂O₃ (obtained from FeO · OH) and BaCO₃ is developed for preparing cheaper grain oriented barium hexaferrite. Fe₂O₃ and BaCO₃ (precipitate grade) are wet mixed in a ball mill in stoichiometric proportion. The mixed slurry is then dried at 110° C for about 12h. The dried powder mixture containing moisture as a binder is uniaxially compacted at 5×10⁶–10×10⁶ kg m^–2 pressure. The green compacts are air sintered in the temperature range 1100–1300° C for 1 H. The best results of the sintered ferrite show maximum energy product (BH) _max in the range 7–10 kTAm^–1. The bulk of commercial requirements for toy magnets etc. may be met by this method of production which eliminates steps like calcination and cost intensive wet magnetic compaction.     

X-ray diffraction studies on aluminum-substituted barium hexaferrite

Effect of aluminum substitution in barium hexaferrite was studied following the hydrothermal precipitation–calcination techniques. It was attempted to prepare aluminum-substituted barium hexaferrites with compositions BaAl_xFe_12−xO₁₉ having x=2,4, 6, 8 and 10. The precursors were prepared by using stoichiometric amounts of Ba, Al and Fe³⁺ nitrate solutions with urea as the precipitating agent. The hydrothermally prepared precursors were calcined at temperatures in the range of 800–1200 °C. The detailed work carried out on identification of crystalline phases through XRD revealed that, after the hydrothermal treatment, the samples showed barium carbonate, hematite and boehmite as the crystalline phases (except that boehmite was not identified for Ba/Al/Fe ratio as 1:2:10). Irrespective of the Al content, none of the 1000 and 1200 °C calcined samples showed any crystalline phase of Al. The 1200 °C calcined samples showed that Al-substituted barium hexaferrite is formed only with the Ba/Al/Fe atomic ratio of 1:2:10. With increase in the Al content, formation of hexaferrite was not observed. BaCO₃ was found be present even at 1200 °C in all the samples except for the one having Fe/Al ratio 5. The normal decomposition temperature of BaCO₃ is between 950 and 1050 °C. It is difficult to explain the increased stability of BaCO₃, which is perhaps responsible for hindering the formation of aluminum-substituted barium ferrite having Fe/Al ratio ≤2. The Al substitution in barium hexaferrite was confirmed through magnetic measurements.     

Preparation of spinel-type ferrite thin films by the dip-coating process and their magnetic properties

Films of spinel-type ferrite, MFe₂O₄ (M=Ni, Co, Mg, Li_0.5Fe_0.5) have been prepared by a dip-coating method from the sol-gel process. Ferric nitrate, nickel nitrate, cobalt nitrate and lithium nitrate were used as raw materials, and glycerol and formamide were used as solvents. A film was prepared by dipping a silica glass plate. The spinel-type ferrite was obtained by heat-treatment at 700–900°C for 2 h in air. The film thickness was about 0.8 m. The saturation magnetization, _r, of the film and powder with composition 50NiO·50Fe₂O₃ was 196 emu cm^–3 and 29.1 emu g^–1, respectively, and the coercive force,H _c, was 140 and 95 Oe, respectively, after heat-treatment at 800°C for 2 h. In particular, the films were shown to have a much largerH _c than the powder. The grain growth of spinel ferrite may be subject to restriction because it is in progress above an amorphous base-plate. The crystals are therefore aligned with the base-plate and have uniaxial anisotropy.     

Preparation and magnetic properties of SrFe12O19/Ni0.5Zn0.5Fe2O4 nanocomposite ferrite microfibers via sol–gel process

SrFe₁₂O₁₉/Ni_0.5Zn_0.5Fe₂O₄ nanocomposite ferrite microfibers with diameters of 1–2 μm have been prepared by the sol–gel process. The SrFe₁₂O₁₉/Ni_0.5Zn_0.5Fe₂O₄ nanocomposite ferrites are formed after the precursor calcined at 850 °C for 2 h, fabricating from nanosized particles with a uniform phase distribution. The ferrite grain size increases with the calcination temperature. The magnetic properties for the nanocomposite ferrite microfibers are mainly influenced by the chemical composition and grain size. The nanocomposite ferrite microfibers obtained at 900 °C show the enhanced specific saturation magnetization (M_sh) of 64.8 Am² kg⁻¹, coercivity (H_c) of 146.5 kA m⁻¹ and remanence (M_r) of 33.6 Am² kg⁻¹ owing to the exchange–coupling interaction. This exchange–coupling interaction in the SrFe₁₂O₁₉/Ni_0.5Zn_0.5Fe₂O₄ nanocomposite ferrite microfibers has been discussed.     

Mössbauer Analysis and Cation Distribution of Zn Substituted BaFe<Subscript>12</Subscript>O<Subscript>19</Subscript> Hexaferrites

Barium hexaferrite is a well-known hard magnetic material. Doping using nonmagnetic cation such as Zn²⁺ were found to enhance magnetization owing to preferential tetrahedral site (4 f ₁) occupancy of the zinc. However, the distribution of cations in hexaferrites depends on many factors such as the method of preparation, nature of the cation, and chemical composition. Here, Zn-doped barium hexaferrites (Ba_1?xZn_xFe₁₂O₁₉) were synthesized by sol-gel method. In this study, we summarized the magnetic properties of Ba_1?xZn_xFe₁₂O₁₉ (x = 0, 0.1, 0.2, 0.3) BaM, investigated by Mössbauer spectroscopy. Moreover, cation distribution was also calculated for all the products. Mössbauer parameters were determined from 57Fe Mössbauer spectroscopy and according to it, the replacement of Ba-Zn affects all parameters such as isomer shift, the variation in line width, hyperfine magnetic field, and quadrupole splitting. Cation distribution revealed the relative area of undoped BaM, 12k, 2a, and 4 f ₂ positions which are close to theoretical values.     

Magnetic properties of Ni–Co doped barium strontium hexaferrite

A series of Ni–Co substituted barium strontium hexaferrite materials, Ba_0.5Sr_0.5Ni _x Co _x Fe_12–2x O₁₉ (x = 0.0, 0.2, 0.4, 0.6, 0.8 mol%) was synthesized by the sol–gel method. X-ray diffraction analysis has shown that the Ni–Co substitutions maintain in a single hexagonal magnetoplumbite phase. The room temperature magnetic properties and the cation site preferences of Ni–Co substituted ferrite were investigated by VSM. Substitutions led to decrease in coercivity while saturation magnetization remains the almost same. It indicates that the saturation magnetization (52.81–59.8 Am²/kg) and coercivity (69.83–804.97 Oe) of barium strontium hexaferrite samples can be varied over a very wide range by an appropriate amount of Ni–Co doping contents.     

A crystallization conditions study of the Ti‐doped barium hexaferrite powders synthesized with the glass crystallization technique for microwave applications

For microwave applications Titanium doped M‐type hexagonal ferrites have been synthesized by means of glass crystallization technique varying the crystallization parameters and the melt doping concentrations. The chosen melt dopings were x = 5.4 and 7.2 mole‐% TiO₂ with the following basic composition (mole‐%): 40 BaO + 33 B₂O₃ + (27‐x) Fe₂O₃ + x TiO₂. We have studied the dependencies between the magnetic properties, the valence of the iron ions in the glasses and the powders, the formation of new dielectric phases and the microwave absorption. After the Ti⁴⁺ ions substitutions, the magnetocrystalline anisotropy changed, this effect was observed in the static magnetic properties (_JH_C and M_S) measured using a vibration sample magnetometer. Furthermore the Ti⁴⁺ ions preferably occupy mainly the 2a as well as slightly the 2b sites in the lattice of the barium hexaferrite, which are studied using Mössbauer spectroscopy. Besides, the X‐ray diffraction studies proved that the formation of the ferrimagnetic (BaFe_12‐xTi_xO₁₂) and dielectric (BaTi₆O₁₃) phases are dependent on the crystallization parameters. The controlled influencing of lattice sites occupation and of the Fe²⁺ content in the ferrimagnetic phase as well as the controlled formation of the dielectric phase rate during the annealing are possibilities to optimize the microwave absorption of Ti‐doped barium hexaferrite powders synthesized by glass crystallization technique.     

Liquid phase epitaxy of hexagonal ferrites

Single crystal films of the hexagonal ferrite Zn₂Y, having the chemical formula Ba₂Zn₂Fe₁₂O₂₂, were grown by the isothermal dipping method of liquid phase epitaxy using a PbOBaOB₂O₃ flux. The substrates were flux-grown M-type hexagonal ferrite crystals having the chemical formula BaFe₁₂O₁₉. The films and substrates were distinguishable by the differences in their crystallographic and magnetic properties.     

Synthesis of <Emphasis Type="Italic">c</Emphasis>-Axis Barium Hexaferrite Puck for Communication Application

Recent progress and needs by telecommunication industries require thick barium ferrite film with excellent magnetic properties for microwave monolithic integrated circuit applications. In the present work we show a novel barium hexaferrite (BaFe₁₂O₁₉, or BaM) composite material, BaFe₁₂O₁₉ nanopowder mixture with epoxy, as a low-cost solution to fabricate thick BaM films. The mix is used to fabricate thick puck of BaM within an alumina substrate. The resulting barium hexaferrite thick pucks have good magnetic properties with a magnetization saturation 4πMs between 2000 and 2500 Gauss, a perpendicular coercivity of 3800 to 4000 Oe and a close to 0.9 squareness. In addition, we have successfully fabricated and tested a self-biased microwave circulator by depositing and patterning copper contact lines on the alumina substrate and the BaM thick puck.     

Hydrothermal formation of Ni-Zn ferrite from heavy metal co-precipitates

The hydrothermal synthesis of Ni-Zn ferrite from simulated wastewater containing Ni²⁺ and Zn²⁺ ions has been studied. The influence of co-precipitation order, the existence of Na⁺ in suspension, the hydrothermal reaction time and temperature on the composition, morphology and saturation magnetization (_s) of the hydrothermal products is reported. Adding the simulated wastewater to the NaOH solution can prevent the formation of -Fe₂O₃ in the Ni-Zn ferrite. Increasing the hydrothermal reaction time improved the magnetization of the Ni-Zn ferrite, while the influence of temperature, stirring intensity and Na⁺ in suspension on the hydrothermal formation of ferrite were not obvious. Thermodynamic calculation indicated that under hydrothermal conditions (180–240°C), the order of chemical stability is as follows: NiFe₂O₄ > Fe₂O₃ > Na₂Fe₂O₄. The high Gibbs formation energy of Na₂Fe₂O₄ prevented the incorporation of Na⁺ into the ferrite lattice.     

An anomalous behaviour in the phase stability of the system Fe2O3 and NiO

Iron-nickel mixed oxides containing up to 50 mol% of NiO were prepared by firing the corresponding co-precipitated hydrous oxides; characterization was performed by X-ray diffraction, infrared spectroscopy, magnetic susceptibility, electrical conductivity and thermoelectric power measurements. A non-stoichiometric ferrite phase was formed when a sample containing 20 mol% NiO was sintered at 1050°C. This phase had two- to three-fold higher conductivity than either Fe₂O₃ or the stoichiometric ferrite (NiFe₂O₄). The thermoelectric power of this phase indicated a sharp change of charge carriers from n- to p-type near 350°C. This non-stoichiometric ferrite phase was stable only in a small temperature range and dissociated into -Fe₂O₃ and stoichiometric ferrite above 1200°C. Samples containing 5 and 10 mol% NiO also had small fractions of this non-stoichiometric ferrite phase when sintered at 1050°C.     

Preparation of barium hexaferrite by a hydrothermal method: structure and magnetic properties

Barium hexaferrite, BaFe¹²O₁₉, was obtained in hydrothermal conditions from a water suspension of -FeOOH and Ba(OH)₂ · 8H₂O at a temperature about 315° C. X-ray and Mössbauer spectroscopy as well as electron microscopy investigations demonstrated the appearance of -Fe₂O₃ as an intermediate phase in the hydrothermal process. The magnetic characteristics of the obtained isotropic magnets are the following: coercive fieldH _c 159 kA m^–1, residual inductionB _r 0.26 T, maximum energy product (BH) _max12 kJ m^–3. The hydrothermal procedure for the preparation of barium hexaferrite in comparison with the conventional one is discussed.     

Synthesis of barium hexaferrite by the co-precipitation method using acetate precursor

Fine particles of barium hexaferrite were synthesised by a chemical co-precipitation method using acetate-nitrate (barium acetate + iron nitrate) precursors. The thermal properties, phase composition and morphology of hexaferrite powders were studied. Simultaneous DTA/TG results confirmed by those obtained from XRD and VSM, indicated that the formation of barium hexaferrite occurs at a relatively low temperature of 710°C. This temperature is affected by the Fe³⁺/Ba²⁺ molar ratio. The SEM investigations revealed that the mean particle size of barium hexaferrite increases with increasing calcination temperature. In this system the Fe³⁺/Ba²⁺ molar ratio of 12 (stoichiometric ratio) is favourable.     

Electrical and Dielectric Characterization of Bi–La Ion-Substituted Barium Hexaferrites

BaLa _x Bi _x Fe_12?2xO₁₉ (0.0 ≤ x ≤ 0.5) hexaferrites were produced by solid-state synthesis route, and the effect of Bi³⁺ and La³⁺ substitutions on electrical and dielectric properties of barium hexaferrite material were investigated. It is noticed that ac conductivity of barium (BaM) increases slightly with ionic substitutions of both La³⁺ and Bi³⁺ and then decreases. Ac conductivity is increased with increasing frequency at lower temperatures then remains constant for higher temperatures. This type of conductivity attitude could be originated from the indication of both electronics and polaron hopping mechanisms. The dielectric properties of BaLa _x Bi _x Fe_12?2xO₁₉ (0.0 ≤ x ≤ 0.5) hexaferrites represent a very interesting tunability as functions of frequency, temperature, and Bi³⁺ and La³⁺ ions.     

Mechanism of Ferrite Spinel Formation Revisited

Data on the volume changes of the starting reagents and reaction products were used to analyze the reactions taking place in the ferrite-forming systems MgO–Fe₂O₃, Mn_0.75Mg_0.25O–Fe₂O₃, and NiO–Fe₂O₃ in the temperature range 1255–1315°C. It was shown that, under these conditions, there is no oxygen transport through the gas phase. The possible formation of Fe²⁺ ions is attributed to partial electron compensation for the charge on the M²⁺ cations as a result of counterdiffusion. The presence of excess Fe in the spinel phase at the intermediate stages of ferrite formation is due to the transformation of -Fe₂O₃ into -Fe₂O₃ at a certain M²⁺ concentration.