Suppression of the exaggerated growth of barium ferrite nanoparticles from solution using a partial substitution of Sc<Superscript>3+</Superscript> for Fe<Superscript>3+</Superscript>

The effect of the substitution of Sc³⁺ for Fe³⁺ in barium ferrite on the size of the resulting nanoparticles was studied. These nanoparticles, with the nominal compositions BaFe₁₂O₁₉ and BaFe_11.5Sc_0.5O₁₉, were synthesized hydrothermally at 90–240 °C or by coprecipitation under reflux at 140 °C. The precursors were obtained using (co)precipitation at room temperature. The sizes and morphologies of the precursors and nanoparticles were inspected with transmission electron microscopy, while their structures were confirmed with a combination of X-ray powder and electron diffraction. The samples’ compositions were analyzed with energy-dispersive X-ray spectroscopy. The evolution of the particle size and its distribution with the synthesis temperature and time were studied in pure and Sc-substituted barium ferrite and correlated with the evolution of the magnetic properties. The Sc substitution in the barium ferrite results in the formation of magnetic nanoparticles with applicable magnetic properties and in a significant reduction of the exaggerated particle growth. This was explained on the basis of the reaction kinetics.     

Microwave absorption properties of Al- and Cr-substituted M-type barium hexaferrite

Aluminum- and chromium-substituted barium ferrite particles with single magnetic domain were prepared using self-propagating combustion method. The crystalline structure, size, coercivity and microwave absorption property of the particles were investigated by means of X-ray diffraction, transmission electron microscopy, vibrating sample magnetometry and vector network analyzer. The results show that the crystalline structure of BaFe_12−xAl_xO₁₉ is still hexagonal. But when the chromium substitution amount y exceeds 0.6, the extra chromium ions cannot enter the lattice of BaFe_12−yCr_yO₁₉. After Fe³⁺ is partly substituted with Al³⁺ and Cr³⁺, the microwave absorption properties of barium ferrite are improved. The maximum absorption reaches 34.76 dB. The ferromagnetic resonance is an important channel of barium ferrite to absorb microwaves with high frequency. Aluminum and chromium substitutions change the ferromagnetic resonant frequency of barium ferrite. The multipeak phenomenon of the ferromagnetic resonance increases the microwave absorption capability of barium ferrite.     

Preparation and medical application of magnetic beads conjugated with bioactive molecules

Ferrite nanobeads were synthesized from an aqueous solution utilizing Fe²⁺ to Fe³⁺ oxidation for use as magnetic carriers in bioscreening, bio-molecular recognition and anti-cancer diagnosis and therapy. The beads had a crystal structure that was intermediate between Fe₃O₄ and γ-Fe₂O₃. Functional biomolecules were strongly conjugated onto the surfaces of the ferrite beads via COOH and SH groups. The addition of ferrite seed crystals (3-8 nm in size) together with a disaccharide enabled the synthesis of monodisperse, spherical ferrite beads with average diameters (d¯) between 50 and 150 nm and relative deviation Δd/d¯=9-16%. Hollow ferrite nano-spheres (d¯=150-450 nm, Δd/d¯≈10%) were prepared using silica spheres as templates, which were dissolved in NaOH solution. Ferrite beads 40 nm in size were encapsulated in polymer spheres of styrene and polymerized glycidyl methacrylate (poly-GMA), 184±9 nm in diameter. They were used for high throughput bioscreening system for affinity purification of target proteins which make specific bindings to anti-cancer drugs, porphyrins, environment hormones, etc.     

Efficiency and purity control in the preparation of pure and/or aluminum-doped barium ferrites by hydrothermal methods using ferrous ions as reactants

The synthesis of hexagonal barium ferrite (BaFe₁₂O₁₉) was studied under hydrothermal conditions by a method in which a significant amount of ferrous chloride was introduced alongside ferric chloride among the starting materials. Though all of the Fe²⁺ ions in the starting material were converted to Fe³⁺ ions in the final product, Fe²⁺ was confirmed to participate differently from the Fe³⁺ used in the conventional method in the mechanism of forming barium ferrite. Indeed the efficiency of the synthesis and the quality of the product and the lack of impurities such as Fe₂O₃ and BaFe₂O₄ were improved when Fe²⁺ was included. However, the amount of ferrous ions that could be included to obtain the desired product was limited with an optimum ratio of 2:8 for FeCl₂/FeCl₃ when only 2 h of reaction time were needed. It was also found that the role of trivalent Fe³⁺ could be successfully replaced by Al³⁺. Up to 50% of the iron could be replaced by Al³⁺ in the reactants to produce Al-doped products. It was also found that the ratio of Fe²⁺/M³⁺ could be increased in the presence of Al³⁺ to produce high quality barium ferrite.     

BaCO3 mediated modifications in structural and magnetic properties of natural nanoferrites

Preparing M-type barium hexaferrite and improving the magnetic response of natural ferrites by incorporating barium carbonate (BaCO₃) is ever-demanding. Series of barium carbonate doped ferrites with composition (100−x)Fe₃O₄·xBaCO₃ (x=0, 10, 20, 30 wt%) are prepared through solid state reaction method and sintered gradually at temperatures of 800 and 1000 °C. Nanoparticles of natural ferrite and commercial BaCO₃ are used as raw materials. Impacts of BaCO3 on structural and magnetic properties of these synthesized ferrites are inspected. The obtained ferrites are characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD) and vibrating sample magnetometer (VSM) at room temperature. Uniform barium hexaferrite particles in terms of both morphology and size are not achieved. The average crystallite size of BaFe₁₂O₁₉ is observed to be within 30–600 nm. The sintering process results phase transformation from Fe₃O₄ (magnetite) to α-Fe₂O₃ (hematite) and the formation of hexagonal barium ferrite crystals. The occurrence of barium crystal is found to enhance with the increase of BaCO₃ concentrations up to 20 wt% and suddenly drop at 30 wt%. Saturation and remanent magnetization of the doped ferrites are significantly augmented up to 16.37 and 8.92 emu g⁻¹, respectively compared to their pure counterpart. Furthermore, the coercivity field is slightly decreased as BaCO₃ concentrations are increased. BaCO₃ mediated improvements in the magnetic response of natural ferrites are demonstrated.     

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.     

Determination of cation distribution in Ti4+ and Co2+ substituted barium ferrite by Mössbauer spectroscopy

In barium ferrite, BaFe₁₂O₁₉, the Fe³⁺ ions were gradually substituted by Ti⁴⁺ and Co²⁺. The cation distribution of the various lattice sites is determined as a function of the degree of replacement. The preferred site population is discussed by a substitution model.     

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.     

Er3+离子掺杂钡镓锗玻璃上转换发光机理研究

研究了Er³⁺离子掺杂钡镓锗玻璃的吸收光谱、拉曼光谱和上转换光谱.分析了Er³⁺离子在钡镓锗玻璃中的上转换发光机理.结果表明：玻璃的最大声子能量为828cm^-1，紫外截止波长为275nm.采用800nm和980nmLD激发玻璃样品，在室温下观察到强烈的上转换绿光和红光发射.随着Er³⁺离子浓度的增加，绿光发光强度先增加后减小，而红光发光强度呈单调递增趋势.能量分析表明：800nmLD激发产生的绿光主要源于Er³⁺离子4I_13/2能级的激发态吸收过程；红光发射主要源于Er³⁺离子4I_13/2能级与4I_11/2能级之间的能量转移过程.980nmLD激发产生的绿光主要源于Er³⁺离子4I_11/2能级之间的能量转移过程；而红光发射主要源于Er³⁺离子4I_13/2能级与4I_11/2能级之间的能量转移过程和4I_13/2能级的激发态吸收过程.通过量子效率分析，发现采用800nmLD激发Er³⁺离子掺杂浓度为1mol% 的样品时，上转换绿光发光效率最高. 关键词： 上转换发光机理 3+离子掺杂')" href="#">Er³⁺离子掺杂 钡镓锗玻璃     

The charge states’ conversion of the activator ions in CaF2:Eu nanophosphors

According to stationary X-ray-excited luminescence spectra and thermally stimulated luminescence spectra of CaF₂:Eu nanophosphors, it was found that Eu³⁺?→?Eu²⁺ conversion can occur during thermal annealing of fine-grained (d?=?25?nm) nanoparticles in the 200–800°C range, which is accompanied by an increase in their size within 40–189?nm. An important role of the exciton mechanism of Eu²⁺ luminescence excitation was revealed according to the temperature dependence of X-ray-excited luminescence spectra of CaF₂:Eu nanoparticles of 114?nm size. The maximum of the X-ray-excited luminescence light output of CaF₂:Eu nanophosphors in the Eu²⁺ ions’ emission band was traced out at 400–500°C annealing temperature and at the size of nanoparticles of 114–180?nm. The subsequent growth of the annealing temperatures, particularly in the 800–1000°C range, causes the reduction of X-ray-excited luminescence light output because of the increment of lattice defects’ concentration due to a sharp increase in the size of nanoparticles and their agglomeration.     

Magnetic properties of NiZr substituted barium ferrite

Single-domain fine particles of NiZr substituted barium ferrite has been synthesized by citrate gel route. The magnetization value obtained are comparable with those observed in Co–Ti substitution. This has been attributed to strong preference of Ni²⁺ for octahedral coordination, and no particular preference for Zr⁴⁺ ion. Phase formation at lower temperature permits easy control over the microstructure and hence, a large variation in coercivity (180–4500 Oe) has been possible as a function of x and heat treatment temperature.     

Effect of zinc substitution on magnetic and electrical properties of nanocrystalline nickel ferrite synthesized by refluxing method

Nanocrystalline Nickel ferrite (NiFe₂O₄) and Zn substituted nickel ferrite (NiZnFe₂O₄) have been synthesized by the refluxing method. These ferrites were characterized by XRD, TEM, Mossbauer spectroscopy and VSM in order to study the effect of zinc substitution in nickel ferrite. XRD diffraction results confirm the spinel structure for the prepared nanocrystalline ferrites with an average crystallite size of 14-16 nm. Lattice parameter was found to increase with the substitution of Zn²⁺ ions from 8.40 Å to 8.42 Å. TEM images confirmed average particle size of about 20 nm and indicates nanocrystalline nature of the compounds. A shift in isomeric deviation with the doublet was observed due to the influence of Zn substitution in the nickel ferrite. The Zn content has a significant influence on the magnetic behavior and electrical conductivity of NiFe₂O₄. Saturation magnetization drastically increased whereas room temperature electrical conductivity decreased due to the addition of Zn content in NiFe₂O₄, indicating super magnetic material with lesser coercivity.     

Mössbauer study of substituted barium ferrite BaFe11−x−y Co0.5Ti0.5Ni x ZnyO19−r

Substituted barium ferrite BaFe_11–x–y Co_0.5Ti_0.5Ni _x Zn_yO_19–r powders were prepared using a coprecipitation method and investigated by X-ray diffraction (XRD) and⁵⁷Fe Mössbauer spectroscopy. The results show that the as-prepared magnetic powders possess the typical hexagonal structure and demonstrate both a good dispersibility and a narrow particle size distribution. The hyperfine fields for all sites decrease slightly asx (ory) increases. The Ni²⁺ ions prefer to occupy the 2a and 12k sites, and Zn²⁺ ions occupy the 4f_IV site.     

Charge states of the activator and size effects in BaF2: Eu nanophosphors

ABSTRACT

According to the spectra of stationary X-ray excited luminescence (XEL) of BaF₂: Eu nanophosphors at 80 and 294 K, it was revealed that the thermal annealing of fine-grained nanoparticles (d?=?35?nm) in the range of 400–1000°C, which is accompanied by an increase of their sizes in the range of 58–120?nm, does not result in effective changes of the charge state of Eu^{3 +} → Eu^{2 +} activator, in contrast to CaF₂: Eu nanoparticles. The maximum light output of X-ray excited luminescence of BaF₂: Eu nanophosphors in the 590?nm emission band of Eu³⁺ ion was observed at an annealing temperature of 600°C with the average size of nanoparticles 67?nm. The subsequent growth of annealing temperatures, especially in the range of 800–1000°C, causes decrease in the light output of X-ray excited luminescence due to the increase of defect concentration in the lattice as a result of sharp increase of nanoparticle sizes and their agglomeration. In BaF₂: Eu nanoparticles of 58?nm size, according to the thermostimulated luminescence (TSL) spectrum, transformation of Eu³⁺ → Eu²⁺ under the influence of long-time X-ray irradiation was revealed for the peak of 151?K. Thus, X-ray excited luminescence spectra of BaF₂: Eu nanophosphors are formed predominantly due to the emission of Eu³⁺ ions, while emission of Eu²⁺ ions is observed in the TSL spectra.     

Synthesis,structural, dielectric and magnetic properties of spinel structure of Ca2+ substitute in Cobalt ferrites (Co1−xCaxFe2O4)

Non magnetic material Ca²⁺ as a substitute in Cobalt ferrite (Co_1?xCa_xFe₂O₄x?=?0.00, 0.05, 0.10 & 0.15) is prepared by self auto combustion method. The synthesized samples were carried out for various characterizations such as X-ray diffraction, Field emission scanning electron microscope (FE-SEM), Dielectric measurement and Magnetic property. X-ray diffraction reveals the values of crystalline size, lattice parameter and x-ray density by using the standard formula. The saturation magnetization (M_s) decreases from 63.92 to 43.17 emu/g for x?=?0.00 to 0.15 and the coercivity (H_c) increases gradually from 819.85 to 1312.32?Oe with the increase in Ca²⁺ concentration. The dielectric properties of synthesized nano materials were carried out at room temperature. The dielectric parameters such as tangent loss, Cole–Cole plot (Impedance, Modulus), and AC Conductivity were determined for various Ca²⁺ concentration. The frequency dependent dielectric dispersion behaviour of all the samples can be explained by the Maxwell–Wagner two-layer model along with Koop's phenomenological theory. As a result, Ca²⁺ substituted Cobalt ferrite is enhanced with their dielectric and magnetic property which is suitable for a memory device, recording media application and high frequency device.     

Sol–gel synthesis,magnetic and magneto-optical properties of CoFe2−xTbxO4 nanocrystalline films

The nanocrystalline thin films of terbium-doped cobalt ferrite were fabricated by a sol–gel method, and the effects of crystallization conditions on the phase, morphology, magnetic and magneto-optical (MO) properties of products were investigated. Due to its large radius, the doping content, x, of Tb³⁺ ion inside cobalt spinel cannot exceed 0.2. The CoFe_2−xTb_xO₄ films consist of the grains with the average size smaller than 50 nm even annealed up to 800°C. Saturation magnetization, coercive force and MO rotation are strongly dependent on the annealing temperature.     

Structural,morphological, magnetic and dielectric characterization of nano-phased antimony doped manganese zinc ferrites

Nano-phased doped Mn–Zn ferrites, viz., Mn_0.5−x/2Zn_0.5−x/2Sb_XFe₂O₄ for x=0 to 0.3 (in steps of 0.05) prepared by hydrothermal method are characterized by X-ray diffraction, Infrared and scanning electron microscopy. XRD and SEM infer the growth of nano-crystalline cubic and hematite (α-Fe₂O₃) phase structures. IR reveals the ferrite phase abundance and metal ion replacement with dopant. Decreasing trend of lattice constant with dopant reflects the preferential replacement of Fe³⁺ions by Sb⁵⁺ion. Doping is found to cause for the decrease (i.e., 46–14 nm) of grain size. An overall trend of decreasing saturation magnetization is observed with doping. Low magnetization is attributed to the diamagnetic nature of dopant, abundance of hematite (α-Fe₂O₃) phase, non-stoichiometry and low temperature (800 °C) sintering conditions. Increasing Yafet–Kittel angle reflects surface spin canting to pronounce lower M_s. Lower coercivity is observed for x≤0.1, while a large H_c results for higher concentrations. High ac resistivity (~10⁶ ohm-cm) and low dielectric loss factor (tan δ~10⁻²–10⁻³) are witnessed. Resistivity is explained on the base of a transformation in the Metal Cation-to-Oxide anion bond configuration and blockade of conductivity path. Retarded hopping (between adjacent B-sites) of carriers across the grain boundaries is addressed. Relatively higher resistivity and low dielectric loss in Sbdoped Mn–Zn ferrite systems pronounce their utility in high frequency applications.     

Microwave absorbing properties of rare-earth elements substituted W-type barium ferrite

W-type barium ferrites Ba(MnZn)_0.3Co_1.4R_0.01Fe_15.99O₂₇ with R=Dy, Nd and Pr were prepared by chemical coprecipitation method. Effects of rare-earth elements (RE) substitution on microstructural and electromagnetic properties were analyzed. The results show that a small amount of RE³⁺ ions can replace Fe³⁺ ions and adjust hyperfine parameters. An obvious increase in natural resonance frequency and high frequency relaxation, and a sharp decrease for complex permittivity have been observed. Furthermore, the matching thickness and the reflection loss (RL) of one-layer ferrite absorber were calculated. It reveals that thin and broad-band can be obtained by RE-substitution. But only when the magnetic moment of RE³⁺ is higher than that of Fe³⁺, can substitution be effective for higher RL. Dy-substituted ferrite composite has excellent microwave absorption properties. The frequency (with respect to −10 dB RL) begins from 9.9 GHz, and the bandwidth reaches far more than 8.16 GHz. The peak value is −51.92 dB at a matching thickness of 2.1 mm.     

A superior microwave absorption material: Ni2+-Zr4+ Co-Doped barium ferrite ceramics with large reflection loss and broad bandwidth

Large reflection loss and wide bandwidth are significant targets, determining the microwave absorption ability. However, it is still a challenge to simultaneously satisfy the two conditions. As a multifunctional material, BaFe₁₂O₁₉ possess excellent electromagnetic properties in the microwave frequency band. Due to the natural resonance phenomenon of the material, BaFe₁₂O₁₉ can produce a large magnetic loss which correlates with Fe³⁺ content, and the microwave absorption characteristics of barium ferrite can be modulated by ion doping. As a typical magnetic metal, Ni coupled with high-valence state Zr⁴⁺ doping helps to produce double resonance peaks. In this work, Ni²⁺-Zr⁴⁺ co-doping M-type barium ferrites (BaFe_12-2xNi_xZr_xO₁₉, BNZFO-x, x = 0–0.8) were prepared conveniently by solid-state reaction method. Several necessary measurements to characterize its microwave absorption property have been operated such as morphology, magnetic performance and electromagnetic parameters. The results show that reflection loss and bandwidth can be simply tuned by tailoring Ni²⁺-Zr⁴⁺ content. The reflection loss peak drifts from 18 GHz to 9.76 GHz, which involves a half of the studied frequency range. The maximum reflection loss achieves −60.6 dB and the corresponding bandwidth over −10 dB is 7.68 GHz for BNZFO-0.6 ceramic with only 2.1 mm thickness. Thus, the doping of Ni²⁺-Zr⁴⁺ ion pairs is beneficial to improve the absorbing properties of the material, and the superior microwave absorption property may originate from its inner double natural resonance in micro-scale. The excellent microwave absorption properties suggest that BNZFO-x is a promising candidate applied for designing electromagnetic shielding devices.     

Preparation of barium hexaferrite nanopowders by the sol-gel method, using goethite

A series of barium hexaferrite nanoparticles (BaO·nFe₂O₃) with different n values were prepared by the sol-gel method, using goethite and Ba carbonate as raw materials. Phase identification of the samples was investigated by X-ray diffraction (XRD). XRD investigations show that the samples with n=5 and calcined at temperatures higher than 875 °C are single-phase Ba ferrite. An average crystallite size of 22 nm was obtained for the single-phase sample with minimum calcining temperature of 875 °C, using the Scherrer's formula. The morphology of the samples was checked by transmission electron microscope (TEM) and magnetic properties were measured by a sensitive permeameter. The results show that the samples have nonzero coercivities, which shows the particle size are not less than the critical size of Ba ferrite and then are not superparamagnet.