Synthesis and properties of hybrid hydroxyapatite–ferrite (Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>) particles for hyperthermia applications

Hybrid ceramics consisting of hydroxyapatite Ca₁₀(PO₄)₆(OH)₂ and ferrite Fe₃O₄ were synthesized using a two-stage procedure. The first stage included the synthesis of Fe₃O₄ ferrite particles by co-precipitation and the synthesis of hydroxyapatite. In the second stage, the magnetic hybrid hydroxyapatite–ferrite bioceramics were synthesized by a thorough mixing of the obtained powders of carbonated hydroxyapatite and Fe₃O₄ ferrite taken in a certain proportion, pressing into tablets, and annealing in a carbon dioxide atmosphere for 30 min at a temperature of 1200°C. The properties of the components and hybrid particles were investigated using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and Mössbauer spectroscopy. The saturation magnetization of the hybrid ceramic composite containing 20 wt % Fe₃O₄ was found to be 12 emu/g. The hybrid hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂)–ferrite Fe₃O₄ ceramics, which are promising for the use in magnetotransport and hyperthermia treatment, were synthesized and investigated for the first time.     

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.     

Synthesis of iron oxide nanoparticles under oxidizing environment and their stabilization in aqueous and non-aqueous media

Synthesis of magnetite (Fe₃O₄) nanoparticles under oxidizing environment by precipitation from aqueous media is not straightforward because Fe²⁺ gets oxidized to Fe³⁺ and thus the ratio of Fe³⁺:Fe²⁺=2:1 is not maintained during the precipitation. A molar ratio of Fe³⁺:Fe²⁺ smaller than 2:1 has been used by many to compensate for the oxidation of Fe²⁺ during the preparation. In this work, we have prepared iron oxide nanoparticles in air environment by the precipitation technique using initial molar ratios Fe³⁺:Fe²⁺?2:1. The phases of the resulting powders have been determined by several techniques. It is found that the particles consist mainly of maghemite with little or no magnetite phase. The particles have been suspended in non-aqueous and aqueous media by coating the particles with a single layer and a bilayer of oleic acid, respectively. The particle sizes, morphology and the magnetic properties of the particles and the ferrofulids prepared from these particles are reported. The average particle sizes obtained from the TEM micrographs are 14, 10 and 9 nm for the water, kerosene and dodecane-based ferrofluids, respectively, indicating a better dispersion in the non-aqueous media. The specific saturation magnetization (σ_s) value of the oleic-acid-coated particles (∼53 emu/g) is found to be lower than that for the uncoated particles (∼63 emu/g). Magnetization σ_s of the dodecane-based ferrofluid is found to be 10.1 emu/g for a volume fraction of particles ?=0.019. Zero coercivity and zero remanance on the magnetization curves indicate that the particles are superparamagnetic (SPM) in nature.     

Improvement of the magnetic properties of barium hexaferrite nanopowders using modified co-precipitation method

Barium hexaferrite BaFe₁₂O₁₉ powders have been synthesized using the modified co-precipitation method. Modification was performed via the ultrasonication of the precipitated precursors at room temperature for 1 h and the additions of the 2% KNO₃, surface active agents and oxalic acid. The results revealed that single phase magnetic barium hexaferrite was formed at a low annealing temperature of 800 °C for 2 h with the Fe³⁺/Ba²⁺ molar ratio 8. The microstructure of the powders appeared as a homogeneous hexagonal platelet-like structure using 2% KNO₃ as the crystal modifier. A saturation magnetization (60.4 emu/g) was achieved for the BaFe₁₂O₁₉ phase formed at 1000 °C for 2 h with Fe³⁺/Ba²⁺ molar ratio 8 using 5 M NaOH solution at pH 10 in the presence of 2% KNO₃. Moreover, the saturation magnetization was 52.2 emu/g for the precipitated precursor at Fe³⁺/Ba²⁺ molar ratio 12 in was achieved for the precipitated precursor ultrasonicated for 1 h and then annealed at 1200 °C for 2 h. Coercivities from 956.9 to 4558 Oe were obtained at different synthesis conditions.     

Ni–Zn–Sm nanopowder ferrites: Morphological aspects and magnetic properties

Ni–Zn ferrites have been widely used in components for high-frequency range applications due to their high electrical resistivity, mechanical strength and chemical stability. Ni–Zn ferrite nanopowders doped with samarium with a nominal composition of Ni_0.5Zn_0.5Fe_2−xSm_xO₄ (x=0.0, 0.05, and 0.1 mol) were obtained by combustion synthesis using nitrates and urea as fuel. The morphological aspects of Ni–Zn–Sm ferrite nanopowders were investigated by X-ray diffraction, nitrogen adsorption by BET, sedimentation, scanning electron microscopy and magnetic properties. The results indicated that the Ni–Zn–Sm ferrite nanopowders were composed of soft agglomerates of nanoparticles with a high surface area (55.8–64.8 m²/g), smaller particles (18–20 nm) and nanocrystallite size particles. The addition of samarium resulted in a reduction of all the magnetic parameters evaluated, namely saturation magnetization (24–40 emu/g), remanent magnetization (2.2–3.5 emu/g) and coercive force (99.3–83.3 Oe).     

Mixed-metal carbonates as precursors for the synthesis of nanocrystalline Mn-Zn ferrites

A mixed Mn-Zn-Fe carbonate was prepared by precipitation of metal ions with ammonium carbonate and control of pH=7. Nanocrystalline Mn-Zn ferrite powders were synthesized by thermal decomposition of the carbonate precursor at 500 °C in air. The mean crystallite size of the ferrite particles is 14 nm with a specific surface of 74 m²/g. The magnetization at 5 K of the Mn-Zn ferrite powders (66 emu/g) is smaller than the saturation magnetization of the bulk material. Hysteresis loop measurements indicate ferrimagnetic behavior at 5 and 298 K with a small coercivity at room temperature.     

Structure and magnetic properties of nanocrystalline cobalt ferrite powders synthesized using organic acid precursor method

Nanocrystalline octahedra of cobalt ferrite CoFe₂O₄ powders were synthesized using the organic acid precursor route. The effect of the calcination temperature, Fe³⁺/Co²⁺ molar ratio, calcination time and type of organic acid (oxalic, benzoic and tartaric acids) on the formation, crystallite size, microstructure and magnetic properties was studied systematically. The Fe³⁺/Co²⁺ molar ratio was varied from 2 to 1.739 while the annealing temperature was controlled from 400 to 1000 °C for various periods from 0.5 to 2 h. The resulting powders were investigated using X-ray diffraction (XRD) analysis, Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and vibrating sample magnetometer (VSM). XRD results indicate that a well crystallized, single spinel cobalt ferrite phase was formed for the precursors annealed at 600-800 °C for 2 h, using oxalic and tartaric acids as precursors for Fe³⁺/Co²⁺ molar ratio 1.818. The crystallite size of as-formed powders was in the range of 38.0-92.6 nm at different operating conditions. The calcination temperature and Fe³⁺/Co²⁺ molar ratio have a significant effect on the microstructure of the produced cobalt ferrite. The microstructure of the produced powders was found to be octahedra-shaped. The crystalline, pure cobalt ferrite powders with magnetic properties having a maximum saturation magnetization (76.1 emu/g) was achieved for the single phase at Fe³⁺/Co²⁺ molar ratio 1.818 and annealing temperature of 600 °C for 2 h using tartaric acid precursor.     

Ultrasonic cavitation induced water in vegetable oil emulsion droplets--a simple and easy technique to synthesize manganese zinc ferrite nanocrystals with improved magnetization

In the present investigation, synthesis of manganese zinc ferrite (Mn_0.5Zn_0.5Fe₂O₄) nanoparticles with narrow size distribution have been prepared using ultrasound assisted emulsion (consisting of rapeseed oil as an oil phase and aqueous solution of Mn²⁺, Zn²⁺ and Fe²⁺ acetates) and evaporation processes. The as-prepared ferrite was nanocrystalline. In order to remove the small amount of oil present on the surface of the ferrite, it was subjected to heat treatment at 300 °C for 3 h. Both the as-prepared and heat treated ferrites have been characterized by X-ray diffraction (XRD), infrared spectroscopy (IR), TGA/DTA, transmission electron microscopy (TEM) and energy dispersion X-ray spectroscopy (EDS) techniques. As-prepared ferrite is of 20 nm, whereas the heat treated ferrite shows the size of 33 nm. In addition, magnetic properties of the as-prepared as well as the heat treated ferrites have also been carried out and the results of which show that the spontaneous magnetization (σ_s) of the heat treated sample (24.1 emu/g) is significantly higher than that of the as-synthesized sample (1.81 emu/g). The key features of this method are avoiding (a) the cumbersome conditions that exist in the conventional methods; (b) usage of necessary additive components (stabilizers or surfactants, precipitants) and (c) calcination requirements. In addition, rapeseed oil as an oil phase has been used for the first time, replacing the toxic and troublesome organic nonpolar solvents. As a whole, this simple straightforward sonochemical approach results in more phase pure system with improved magnetization.     

Tailoring of structural, electrical and magnetic properties of BaCo2 W-type hexaferrites by doping with Zr-Mn binary mixtures for useful applications

Single-phase W-type hexaferrite, BaCo₂Fe_16−2x(ZrMn)_xO₂₇ (x=0.0-1.0), has been synthesized by the chemical co-precipitation technique. Mössbauer analysis indicates substitution of Zr ions on tetrahedral (4e and 4f_IV) sites and Mn ions on the octahedral ‘4f_VI site’ at low-doped concentration when the concentration is increased Mn ions but show preference for the octahedral ‘2b site’. The highest enhancement in the value of the room temperature resistivity of 2.82×10⁹ Ω cm has been obtained by doping with Zr-Mn content of x=0.6. The dissipation factor increases from 6.49×10³ to 9.97×10³ at 10 kHz with the addition of Zr-Mn dopants. Such materials are potentially suitable for electromagnetic attenuation purposes, for microwave absorption and as radar absorbing material. High values of saturation magnetization (67 emu/g) and remanent magnetization (34.7 emu/g) are obtained for substitution level of x=0.4 making them suitable for data processing devices.     

Synthesis and characterization of lithium ferrite by oxalate precursor route

Nanocrystalline lithium ferrite (LiFe₅O₈) powders have been synthesized by oxalate precursor route. The effects of Fe³⁺/Li⁺ mole ratio, and annealing temperature on the formation, crystalline size, morphology and magnetic properties were systematically studied. The Fe³⁺/Li⁺ mole ratio was controlled from 5 to 3.33 while the annealing temperature was controlled from 600 to 1100 °C. The resultant powders were investigated by differential thermal analyzer (DTA), X-ray diffractometer (XRD), scanning electron microscopy (SEM) and vibrating sample magnetometer (VSM). DTA results showed that LiFe₅O₈ phase started to form at around 520 °C. XRD indicated that LiFe₅O₈ phase always contained α-Fe₂O₃ impurity and the hematite phase formation increased by increasing the annealing temperature ?850 °C for different Fe³⁺/Li⁺ mole ratios 5, 4.55 and 3.85. Moreover, lithium ferrite phase was formed with high conversion percentage at critical annealing temperature 750–800 °C. Single well crystalline LiFe₅O₈ phase was obtained at Fe³⁺/Li⁺ mole ratio 3.33 and annealing temperatures from 800 to 1000 °C. Maximum saturation magnetization (68.7 emu/g) was achieved for the formed lithium ferrite phase at Fe³⁺/Li⁺ mole ratio 3.33 and annealing temperature 1000 °C.     

Effect of Fe/Sr mole ratios on the formation and magnetic properties of SrFe12O19 microtubules prepared by sol-gel method

The sol was obtained by sol-gel method. Then, the sol was dripped onto the absorbent cotton template. The gel was obtained after the evaporation of water. Strontium ferrite microtubules were prepared after carrying out calcination process at different temperatures. The phase, morphology and particle diameter and the magnetic properties of samples were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM) and vibrating sample magnetometer (VSM), respectively. The effects of Fe³⁺/Sr²⁺ mole ratio and calcination temperature on the crystal structure, morphology and magnetic properties of ferrite microtubules were studied. The external diameters of obtained SrFe₁₂O₁₉ microtubules were found to range between 8 and 13 μm; the wall thicknesses ranged between 1 and 2 μm. When the Fe³⁺/Sr²⁺ mole ratio and the calcination temperature were 11.5 and 850 °C, respectively, the coercivity, saturation magnetization and remanent magnetization for the samples were 7115.1 Oe, 70.1 and 42.4 emu/g, respectively. The mechanism of the formation and variation in magnetic properties of the microtubules were explained.     

Influence of manganese substitution and annealing temperature on the formation,microstructure and magnetic properties of Mn–Zn ferrites

The effects of annealing temperature and manganese substitution on the formation, microstructure and magnetic properties of Mn_xZn_1−xFe₂O₄ (with x varying from 0.3 to 0.9) through a solid-state method have been investigated. The correlation of the microstructure and the grain size with the magnetic properties of Mn–Zn ferrite powders was also reported. X-ray diffraction (XRD), a scanning electron microscope (SEM) and a vibrating sample magnetometer (VSM) were utilized in order to study the effect of variation of manganese substitution and its impact on crystal structure, crystalline size, microstructure and magnetic properties of the ferrite powders formed. The XRD analysis showed that pure single phases of Mn–Zn ferrites were obtained by increasing the annealing temperature to 1200–1300 °C. Increasing the annealing temperature to ?1300 °C led to abnormal grain growth with inter-granular pores and this led to a decrease in the saturation magnetization. Moreover, an increase in the Mn²⁺ ion substitution up to x=0.8 increased the lattice parameter of the formed powders due to the high ionic radii of the Mn²⁺ ion. Mn–Zn ferrites phases were formed and the positions of peaks were shifted by substituting manganese. The average crystalline size was increased by increasing the annealing temperature and decreased by increasing the substitution by manganese up to 0.8. The average crystalline size was in the range 95–137.3 nm. The saturation magnetization of the Mn–Zn-substituted ferrite powders increased continuously with an increase in the Mn concentration up to 0.8 at annealing temperatures of 1200–1300 °C. Further increase of Mn substitution up to 0.9 led to a decrease of saturation magnetization. The saturation magnetization increased from 17.3 emu/g for the Mn_0.3Zn_0.7Fe₂O₄ phase particles produced to 59.08 emu/g for Mn_0.8Mn_0.2Fe₂O₄ particles.     

Preparation and magnetic properties of BaFe12O19/Ni0.8Zn0.2Fe2O4 nanocomposite ferrite

Nanocomposite of hard (BaFe₁₂O₁₉)/soft ferrite (Ni_0.8Zn_0.2Fe₂O₄) have been prepared by the sol–gel process. The nanocomposite ferrite are formed when the calcining temperature is above 800 °C. It is found that the magnetic properties strongly depend on the presintering treatment and calcining temperature. The “bee waist” type hysteresis loops for samples disappear when the presintering temperature is 400 °C and the calcination temperature reaches 1100 °C owing to the exchange-coupling interaction. The remanence of BaFe₁₂O₁₉/Ni_0.8Zn_0.2Fe₂O₄ nanocomposite ferrite with the mass ratio of 5:1 is higher than a single phase ferrite. The specific saturation magnetization, remanence magnetization and coercivity are 63 emu/g, 36 emu/g and 2750 G, respectively. The exchange-coupling interaction in the BaFe₁₂O₁₉/Ni_0.8Zn_0.2Fe₂O₄ nanocomposite ferrite is discussed.     

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.     

Superparamagnetic silica nanoparticles with immobilized metal affinity ligands for protein adsorption

Superparamagnetic silica-coated magnetite (Fe₃O₄) nanoparticles with immobilized metal affinity ligands were prepared for protein adsorption. First, magnetite nanoparticles were synthesized by co-precipitating Fe²⁺ and Fe³⁺ in an ammonia solution. Then silica was coated on the Fe₃O₄ nanoparticles using a sol–gel method to obtain magnetic silica nanoparticles. The condensation product of 3-Glycidoxypropyltrimethoxysilane (GLYMO) and iminodiacetic acid (IDA) was immobilized on them and after charged with Cu²⁺, the magnetic silica nanoparticles with immobilized Cu²⁺ were applied for the adsorption of bovine serum albumin (BSA). Scanning electron micrograph showed that the magnetic silica nanoparticles with an average size of 190 nm were well dispersed without aggregation. X-ray diffraction showed the spinel structure for the magnetite particles coated with silica. Magnetic measurement revealed the magnetic silica nanoparticles were superparamagnetic and the saturation magnetization was about 15.0 emu/g. Protein adsorption results showed that the nanoparticles had high adsorption capacity for BSA (73 mg/g) and low nonspecific adsorption. The regeneration of these nanoparticles was also studied.     

Magnetic properties of prussian blue modified Fe3O4 nanocubes

Size controlled cubic Fe₃O₄ nanoparticles in the size range 90–10 nm were synthesized by varying the ferric ion concentration using the oxidation method. A bimodal size distribution was found without ferric ion concentration and the monodispersity increased with higher concentration. The saturation magnetization decreased from 90 to 62 emu/g when the particle size is reduced to 10 nm. The Fe₃O₄ nanoparticles with average particle sizes 10 and 90 nm were surface modified with prussian blue. The attachment of prussian blue with Fe₃O₄ was found to depend on the concentration of HCl and the particle size. The saturation magnetization of prussian blue modified Fe₃O₄ varied from 10 to 80 emu/g depending on the particle size. The increased tendency for the attachment of prussian blue with smaller particle size was explained based on the surface charge. The prussian blue modified magnetite nanoparticles could be used as a radiotoxin remover in detoxification applications.     

Magnetic and rheological properties of monodisperse Fe3O4 nanoparticle/organic hybrid

Fe₃O₄ nanoparticle/organic hybrids were synthesized via hydrolysis using iron (III) acetylacetonate at ∼80 °C. The synthesis of Fe₃O₄ was confirmed by X-ray diffraction, selected-area diffraction, and X-ray photoelectron spectroscopy. Fe₃O₄ nanoparticles in the organic matrix had diameters ranging from 7 to 13 nm depending on the conditions of hydrolysis. The saturation magnetization of the hybrid increased with an increase in the particle size. When the hybrid contained Fe₃O₄ particles with a size of less than 10 nm, it exhibited superparamagnetic behavior. The blocking temperature of the hybrid containing Fe₃O₄ particles with a size of 7.3 nm was 200 K, and it increased to 310 K as the particle size increased to 9.1 nm. A hybrid containing Fe₃O₄ particles of size greater than 10 nm was ferrimagnetic, and underwent Verwey transition at 130 K. Under a magnetic field, a suspension of the hybrid in silicone oil revealed the magnetorheological effect. The yield stress of the fluid was dependent on the saturation magnetization of Fe₃O₄ nanoparticles in the hybrid, the strength of the magnetic field, and the amount of the hybrid.     

Microwave anneal effect on magnetic properties of Ni0.6Zn0.4Fe2O4 nano-particles prepared by conventional hydrothermal method

Ni_0.6Zn_0.4Fe₂O₄ ferrite nano-particles with a crystallite size of about 20 nm were prepared by the conventional hydrothermal method, followed by annealing in a microwave oven for 7.5-15 min. The microstructure and magnetic properties of the samples were characterized by scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy and vibrating sample magnetometry. The microwave annealing process has slight effect on the morphology and size of Ni_0.6Zn_0.4Fe₂O₄ ferrite nano-particles. However it reduces the lattice parameter and enhances the densification of the particles, and then greatly increases the saturation magnetization (50-56 emu/g) and coercive force of the samples as compared to the non-annealing condition. The microwave annealing process is an effective way to rapidly synthesize high performance ferrite nano-particle.     

Magnetic properties of barium ferrite synthesized using a microemulsion mediated process

Ultrafine barium ferrite particles have been synthesized using a microemulsion mediated process. The aqueous cores (typically 10–25 nm in size) of water-in-oil microemulsions were used as constrained microreactors for the precipitation of precursor carbonates of Ba²⁺ and Fe³⁺. These precursors (5–15 nm in size) when heated at 950°C, transformed to the hexagonal ferrite BaFe₁₂O₁₉ as confirmed by X-ray diffraction. This barium ferrite powder had an intrinsic coercivity of 5089 Oe and a saturation magnetization of 60.1 emu/g.     

Magnetic properties of nanosized γ-Fe2O3 and α-(Fe2/3Cr1/3)2O3, prepared by thermal decomposition of heterometallic single-molecular precursor

Thermal decomposition of the trinuclear complex [Fe₂CrO(CH₃COO)₆(H₂O)₃]NO₃ at 300, 400 and 500 °C gave γ-Fe₂O₃ nanoparticles along with amorphous chromium oxide, while decomposition of the same starting compound at 600 and 700 °C led to the formation of α-(Fe_2/3Cr_1/3)₂O₃ nanoparticles. Size of γ-Fe₂O₃ nanoparticles, determined by X-ray diffraction, was in the range from 9 to 11 nm and increased with formation temperature growth. Average size of α-(Fe_2/3Cr_1/3)₂O₃ nanoparticles was about 40 nm and almost did not depend on the temperature of its formation. γ-Fe₂O₃ nanoparticles possessed superparamagnetic behavior with blocking temperature 180-250 K, saturation magnetization 29-35 emu/g at 5 K, 44-49 emu/g at 300 K and coercivity 400-600 Oe at 5 K. α-(Fe_2/3Cr_1/3)₂O₃ nanoparticles were characterized by low magnetization values (2.7 emu/g at 70 kOe). Such magnetic properties can be caused by non-compensated spins and defects present on the surface of these nanoparticles. The increase of α-(Fe_2/3Cr_1/3)₂O₃ formation temperature led to decrease of magnetization (being compared for the same fields), which may be caused by decrease of the quantity of defects or non-compensated spins (due to decrease of particles' surface).