Investigations on structural and magnetic properties of cobalt ferrite/silica nanocomposites prepared by the coprecipitation method

Magnetic nanocomposites consisting of cobalt ferrite nanoparticles embedded in silica matrix were prepared by the coprecipitation method using metallic chlorides as precursors for ferrite. Subsequently composites were annealed at 100, 200 and 300 °C for 2 h. The samples were structurally characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM). The magnetic properties were measured in the temperature range of 10-300 K using vibrating sample magnetometer (VSM). The effects of thermal treatment on structural and magnetic properties of nanocomposites were investigated. When the samples were annealed, CoFe₂O₄ nanocrystallites were observed in the SiO₂ matrix, whose size increases with increase in annealing temperature. The coercivity and saturation magnetization of nanocomposite (annealed at 300 °C for 2 h) are much higher than that of bulk cobalt ferrite. The realization of adjustable particle sizes and controllable magnetic properties makes the applicability of the CoFe₂O₄ nanocomposite more versatile.     

Dependence of the magnetic and magnetoelastic properties of cobalt ferrite on processing parameters

The dependence of the magnetic and magnetoelastic properties of highly magnetostrictive cobalt ferrite on processing parameters has been investigated. The cobalt ferrite samples used in this study were prepared via conventional ceramic processing methods. The processing parameters of interest were sintering temperature, holding time at the sintering temperature and powder compaction pressure. It was observed that the crystal structure, composition and saturation magnetization of the samples studied did not vary with changes in processing parameters but coercive field decreased with increasing sintering temperature. The amplitude of peak to peak magnetostriction was dependent on the holding time and powder compaction pressure. The strain derivative on the other hand was found to depend on powder compaction pressure at any given sintering temperature or holding time. The results show how the magnetoelastic properties of cobalt ferrite can be varied by changing the processing parameters.     

Inverse magnetocaloric effect in sol–gel derived nanosized cobalt ferrite

The magnetocaloric properties of cobalt ferrite nanoparticles were investigated to evaluate the potential of these materials as magnetic refrigerants. Nanosized cobalt ferrites were synthesized by the method of sol–gel combustion. The nanoparticles were found to be spherical with an average crystallite size of 14 nm. The magnetic entropy change (ΔS _m) calculated indirectly from magnetization isotherms in the temperature region 170–320 K was found to be negative, signifying an inverse magnetocaloric effect in the nanoparticles. The magnitudes of the ΔS _m values were found to be larger when compared to the reported values in the literature for the corresponding ferrite materials in the nanoregime.     

Preparation and characterization of cobalt ferrite nanoparticles coated with fucan and oleic acid

Cobalt ferrite has attracted considerable attention in recent years due to its unique physical properties such as high Curie temperature, large magnetocrystalline anisotropy, moderate saturation magnetization, large magnetostrictive coefficient, excellent chemical stability and mechanical hardness. In this work we present the preparation, of fucan coated cobalt ferrite nanoparticles by a modified co-precipitation method and the study of their structural, microstructural and magnetic characteristics for their application as a solid support for enzymes immobilization and other biotechnology applications. Aqueous suspensions of magnetic particles were prepared by coprecipitation of Fe(III) and Co(II) in the presence of NaOH, acid oleic and fucan polymer. The X-ray diffraction indicates that the funtionalization does not degrade the core cobalt ferrite. The infrared (FTIR) bands, indicate the functional characteristics of the coating on the cobalt ferrite. Mössbauer spectra at room temperature indicate the presence of a broadened sextet plus a doublet which is typical of superparamagnetic relaxation. For the Co-ferrite uncoated and coated with fucan the doublets have areas of 36.1 % and 40.3 % respectively, indicating the presence of non-interacting particles and faster relaxation time. The Co-ferrite coated with oleic acid and oleic acid plus fucan have areas around 17.5 % and 17.1 % respectively which indicate a weak superparamagnetic relaxation due to a slow relaxation time. The magnetization measurements of the cobalt ferrite nanoparticles with and without coating confirm that they are superparamagnetic and this behavior is produced by the core nanoparticles rather than the coatings. The cobalt ferrite nanoparticles coated with oleic acid presented the highest magnetization than when coating with fucan.     

Structural and magnetic properties of single-step electrochemically deposited nanocrystalline cobalt ferrite thin films

In this paper, we study the structural, surface morphological and magnetic properties of single-step electrochemically deposited cobalt ferrite thin films. The prepared films were nanocrystalline with cubic crystal structure. Scanning electron micrograph image showed that the cobalt ferrite thin film was uniformly distributed over the substrate in addition to some random overgrowth of porous particles. The saturation magnetization of 298 emu/c was confirmed when films were used in magnetic studies.     

Sol-gel preparation and characterization of CoFe2O4-SiO2 nanocomposites

Magnetic nanocomposites formed by cobalt ferrite particles dispersed in a silica matrix were prepared by a sol-gel process. The effects of the thermal treatment temperature and the salt concentration on the structural and magnetic properties of the composites were investigated. By controlling these parameters, CoFe₂O₄/SiO₂ nanocomposites with different crystallite size and magnetic properties were obtained. By increasing the annealing temperature and salt concentration, composites with a progressive increase in the coercive field and of the density of magnetization were produced. In particular, a nanocomposite, with a Fe/Si molar concentration of 21%, obtained by drying the gel at 150 °C and further annealing at 800 °C, has a coercivity of 2000 Oe, which is more than twice higher than the coercivity of bulk cobalt ferrite.     

Influence of annealing temperature on the formation, microstructure and magnetic properties of spinel nanocrystalline cobalt ferrites

Nanocrystalline cobalt ferrites were synthesized by a simple, general, one-step sol–gel auto-combustion method. An interpretation based on the measurement of the adiabatic flame temperature and the amounts of gas evolved during reaction had been proposed for the nature of combustion. The influence of annealing temperatures on the magnetic properties was investigated. The microstructure was characterized by means of X-ray diffractometer (XRD) and transmission electron microscopy (TEM). It was found that the particle size and magnetic properties of the as-prepared ferrite samples showed strong dependence on the annealing temperature. The coercivity initially increased and then decreased with increasing annealing temperature whereas the particle size and saturation magnetization continuously increased.     

应变对钴铁氧体电子结构和磁性能影响的第一性原理研究

尖晶石型钴铁氧体(CoFe₂O₄)因具有良好的电磁性质, 广泛应用于计算机技术、航空航天及医学生物等领域. 特别是钴铁氧体薄膜在磁电复合材料中具有良好的应用前景. 本文基于密度泛函理论的第一性原理平面波赝势法, 结合广义梯度近似, 通过采用更接近于实验上外延生长的二维应变模型, 研究了钴铁氧体薄膜的结构稳定性、电子结构和磁性能. 结果表明: 在二维应变作用下, 反尖晶石结构的钴铁氧体比正尖晶石结构的稳定, 但是与平衡基态相比, 两者能量差减小, 这表明在应变作用下, 八面体晶格中的Co²⁺离子与四面体晶格中的Fe³⁺离子更容易进行位置交换, 形成混合型结构的钴铁氧体; 同时随着应变的增大, 钴铁氧体的能带带隙减小, 晶格中的原子磁矩发生变化, 但总磁矩变化不明显. 关键词： 尖晶石型钴铁氧体 第一性原理 电子结构 磁性能     

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.     

Effects of cobalt doping on the microstructure and magnetic properties of Mn-Zn ferrites prepared by the co-precipitation method

Mn-Zn ferrite nanoparticles with various amounts of cobalt doping have been synthesized by the co-precipitation method. The structure and morphology of the nanoparticles have been characterized by X-ray diffraction and transmission electron microscopy. The effects of cobalt ions on the crystallization behavior, lattice parameters and magnetic properties of Mn-Zn ferrites have been investigated. All the Co-doped ferrite nanoparticles calcined at 1150 °C possess a simple spinel structure and have an approximately spherical shape. The lattice parameters increase almost linearly with increasing Co content. The studies of magnetic properties show that the saturation magnetization M_s strongly depends on the Co content, having a maximum M_s value of 73 emu/g at a Co content of 1.0 at%, and all the Co-doped ferrites, with the average crystallite sizes ranging from 24.5 to 27.0 nm, exhibit superparamagnetism at room temperature.     

离子型钴铁氧体磁流体的稀土改性与机理研究

采用化学共沉淀法以柠檬酸三钠为表面改性剂制备了离子型稀土复合钴铁氧体磁流体.利用X衍射仪和透射电镜对磁粒子的组成、结构及粒径进行了分析.利用古埃磁天平和分光光度计研究了稀土离子改性对磁流体饱和磁化强度和磁感应的影响,实验结果表明:合成过程中添加稀土离子能明显降低磁性纳米粒子的粒径,制得的磁粒子均呈球形,钴铁氧体磁粒子的粒径为12～15nm,稀土钴铁氧体磁粒子的粒径为6～8nm.利用稀土改性的微观模型解释了粒径的降低.添加Dy3+能提高饱和磁化强度和磁感应,添加Y3+则能提高磁感应,却降低了饱和磁化强度.并从理论上对其改性机理进行了详细的分析.     

Composition and magnetic properties of cobalt ferrite nano-particles prepared by the co-precipitation method

Cobalt ferrite nano-particles were prepared using the co-precipitation method followed by annealing treatment. The formation of nano-particles with different composition, microstructure and sizes were confirmed by X-ray diffraction, Raman, thermogravimetric-differential thermal analysis and transmission electron microscope. The magnetic hysteresis loops measured at room temperature revealed smaller effective magnetic anisotropy constant, coercivity and remanence ratio for the samples prepared by adding the NaOH solutions into the mixed solutions of Co²⁺ and Fe³⁺ ions due to the formation of Co³⁺ ions. A small saturation magnetization and an enhanced coercivity were observed for the nano-particles prepared by adding the mixed solutions of Co²⁺ and Fe³⁺ ions into the NaOH solutions, which was related to the formation of outer layers with poor crystallization on the surfaces of the cobalt ferrite nano-crystals. Furthermore, the existence of these outer layers induced the oxidation of Co²⁺ ions in cobalt ferrite nano-crystals at 200 and 300 °C, and led to a large change on the composition and magnetic properties.     

Effects of Nd:YAG laser irradiation on structural, morphological, cation distribution and magnetic properties of nanocrystalline CoFe2O4

The cobalt ferrite nanoparticles of 20 nm size were synthesized by sol-gel auto-combustion technique. The samples were irradiated with Nd:YAG laser to understand the effects of irradiation on structural, cation distribution and magnetic properties. The virgin and irradiated samples were characterized by X-ray diffraction technique. The X-ray diffraction studies at room temperature shows that defects were created in the lattice after irradiation which causes effects on structural, cation distribution and magnetic properties. The energy dispersive analysis of X-rays (EDAX) showed the chemical composition is as per the expected stichiometry. The lattice constant observed from XRD data for virgin and irradiated samples shows increasing trend after irradiation. Cation distribution was investigated by using X-ray diffraction method. We observe decrease in magnetization of the samples after irradiation. The observed reduction in the saturation magnetization after irradiation can be understood on the basis of the partial formation of paramagnetic centers and rearrangement of cations in the lattice.     

Magnetoresistance in silicon based ferrite magnetic tunnel junction

We report magnetoresistance for silicon based magnetic tunnel junction. We used cobalt ferrite & cobalt nickel ferrite as free layer and pinned layer. The magnetoresistance measured at room temperature through silicon by fabricating FM/Si/FM magnetic tunnel junction. Magnetoresistance shows a loop type behavior with 3.7%. We have successfully demonstrated spin tunneling through silicon with ferrite junction that opens the door for potential candidate for spintronics devices. The spin-filtering effect for this double spin-filter junction is also discussed.     

Magnetic properties and giant magnetoresistance in electrodeposited Co–Ag granular films

Small cobalt particles embedded in a silver matrix have been prepared using the electrodeposition technique. The size of the clusters is controlled by the deposition potential and the Co growth time. Structural, magnetic and magneto-transport properties of Co–Ag samples have been investigated as a function of the Co concentration between 2 and 40 at% cobalt. Superparamagnetic behavior is evidenced for the low contents of cobalt while long-range magnetic order appears at higher Co concentrations. The particles size has been determined from magnetic properties and from the X-ray diffraction technique, and varies between 3.5 and 9 nm. Magnetoresistance passes through a maximum as a function of the cobalt concentration. A maximum of ∼4% GMR is obtained at room temperature while GMR reaches a value of 14% at 10 K.     

Interaction effects in magnetic oxide nanoparticle systems

The interaction effects in magnetic nanoparticle system were studied through a Monte Carlo simulation. The results of simulations were compared with two different magnetic systems, namely, iron oxide polymer nanocomposites prepared by polymerization over core and nanocrystalline cobalt ferrite thin films prepared by sol-gel process. The size of the particles in the nanocomposites were estimated to be ∼15 nm with very little agglomeration. The low values of the coercivity obtained from the hysteresis measurements performed confirm that the system is superparamagnetic. SEM studies showed the cobalt ferrite films to have a nanocrystalline character, with particle sizes in the nanometer range. Hysteresis measurements performed on the thin films coated on silicon do not give evidence of the superparamagnetic transition up to room temperature and the coercivity is found to increase with decreasing film thickness. Comparison with simulations indicate that the nanocomposites behave like a strongly interacting array where exchange interactions lead to high blocking temperatures, whereas the films are representative of a semi-infinite array of magnetic clusters with weak interactions and thickness-dependent magnetic properties.     

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.     

Microstructure characterization and cation distribution of nanocrystalline cobalt ferrite

Nanocrystalline cobalt ferrite has been synthesized using two different methods: ceramic and co-precipitation techniques. The nanocrystalline ferrite phase has been formed after 3 h of sintering at 1000 °C. The structural and microstructural evolutions of the nanophase have been studied using X-ray powder diffraction and the Rietveld method. The refinement result showed that the type of the cationic distribution over the tetrahedral and octahedral sites in the nanocrystalline lattice is partially an inverse spinel. The transmission electronic microscope analysis confirmed the X-ray results. The magnetic properties of the samples were characterized using a vibrating sample magnetometer.     

Magnetic properties and local configurations of <Superscript>57</Superscript>Fe atoms in CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript> powders and CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/PVA nanocomposites

The composition and magnetic properties of the powders extracted from CoFe₂O₄ aqueous suspensions and the CoFe₂O₄/PVA (PVA is polyvinyl alcohol) nanocomposites with a cobalt ferrite content of 10–30 wt % have been investigated using Mössbauer spectroscopy, transmission electron microscopy, and vibration magnetometry. The cationic formulas of the cobalt ferrites synthesized have been determined. The differences between samples synthesized at temperatures of 72.5 and 82.5°C have been revealed. The specific features of the observed changes in the agglomeration of CoFe₂O₄ particles after introducing into the PVA matrix have been studied. It has been shown that the iron ion distribution determined by Mössbauer spectroscopy in octahedral and tetrahedral lattice sites correlates with vibration magnetometry data.     

稀土掺杂对钴铁氧体电子结构和磁性能影响的理论研究

尖晶石型铁氧体是十分重要的磁性材料之一, 具有独特的物理性质、化学特性、磁学特性和电子特性. 其中尖晶石型钴铁氧体具有较好的电磁性质而被广泛应用. 本文基于密度泛函理论(DFT) 的第一性原理平面波赝势法, 结合广义梯度近似(GGA+U), 研究了CoRE_0.125Fe_1.875O₄ (RE = Nd, Eu, Gd)体系的电子结构和磁性能. 结果表明随着稀土元素从Nd到Gd掺杂体系晶胞的晶格常数呈递减趋势. 磁性能依赖于稀土离子(RE³⁺)4f轨道未配对的电子数, 掺杂Eu和Gd能够提高钴铁氧体体系的磁矩, 主要因为它们3+价态离子具有较多未配对的4f电子, 因而对磁性能的影响较大. 然而Nd 的掺杂对体系磁性能的影响很小, 这是由于它的离子半径较大, 导致晶格发生畸变.