Magnetic study of nanostructured zinc ferrite irradiated with 100 MeV O-beam

Nanostructured zinc ferrite of particle size 10 nm was synthesized by using the nitrates of appropriate cations and citric acid. This system was irradiated by 100 MeV oxygen beam with the fluence of 5×10¹³ ions/cm². The particle size of the system remains almost same after the irradiation. We observe decrease in magnetization of the sample after irradiation at 300 and 10 K. The nature of the σ-H plot shows the presence of superparamgnetic domains at 300 K even after irradiation. The blocking temperature decreases from 276 to 63 K after irradiation. The Mössbauer spectroscopy supports the presence of superparamgnetic domains at 300 K in both the samples. The decrease in magnetization after irradiation is attributed to the decrease in cation inversion and increase in canting angle as observed from in-field Mössbauer spectroscopy.     

Structural,magnetic and Mössbauer spectral studies of nanosize aluminum substituted nickel zinc ferrites

Nanosize aluminum substituted nickel zinc ferrites were prepared through aerosol route and characterized using TEM, XRD, magnetic measurements and Mössbauer spectroscopy. The particle size of as obtained samples was found to be ∼10 nm which increases up to ∼85 nm upon annealing at 1200 °C. The unit cell parameter ‘a’ decreases linearly with concentration of aluminum due to the small ionic radius of aluminum. The saturation magnetization for all the samples after annealing at 1200 °C lies in the range 12.9–72.6 emu/g and decreases linearly with concentration of aluminum. Room temperature Mössbauer spectra of all as obtained samples of ferrite compositions exhibited a broad doublet suggesting super paramagnetic nature. This doublet is further resolved into two doublets and assigned to the surface region and internal region atoms of the particles. The samples annealed at 1200 °C show broad sextets, which were fitted with five sextets, indicating different local environment of both tetrahedrally and octahedrally coordinated Fe cation.     

VSM and Mössbauer study of nanostructured hematite

In the present work, we have synthesized nanostructured hematite samples using chemical precipitation method. The crystal structure and the grain size of the samples were studied using XRD. The zero field cooled and field cooled magnetization curves of the samples were recorded in the temperature range from 300 to 10 K. The variations of Morin transition temperature and blocking temperature with the grain size of the samples were investigated. The hysterics curves of the samples were recorded and the samples showed a superparamagnetic nature at room temperature whereas, at 10 K the samples showed open hysteresis curves. The sample with smaller grain size showed higher value of coercivity compared to samples with larger grain size. Mössbauer spectra of the samples were recorded and the grain size dependence on Mössbauer parameters was investigated.     

Synthesis, structural, magnetic and optical properties of nanocrystalline ZnFe2O4

Nanocrystalline zinc ferrite (ZnFe₂O₄) is synthesized by high-energy ball-milling after 12 h from a powders mixture of zinc oxide (ZnO) and hematite (α-Fe₂O₃) with balls to powders mass ratio of 20:1. X-ray diffraction, vibrating sample magnetometer (VSM), the Mössbauer spectrometry and photoluminescence (PL) are used to characterize the samples. Rietveld analysis and VSM measurements show that the powder has an average crystallites size of 10 nm and a ferrimagnetic behavior with a saturation magnetization of 30 emu/g. After annealing at 700 °C, the lattice parameter reduces from 8.448 to 8.427 Å and the sample transforms into a superparamagnetic behavior, which was confirmed as well by the room temperature Mössbauer spectrometry. Different mechanisms to explain the obtained results and the correlation between magnetism and structure are discussed. Finally, the broadband visible emission band is observed in the entire PL spectrum and the estimated energy band gap is about 2.13 eV.     

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.     

Nanostructured Fe50Ni50 alloy formed by chemical reduction

A high purity Fe₅₀Ni₅₀ nanometric alloy was synthesized by ultra rapid autocatalytic chemical reduction of the corresponding transition metal ions in an aqueous solution. The ratio of metal concentration in solution is preserved in the precipitated powder alloy and no metal segregation has been detected. The alloy was characterized as a nanostructured chemically disordered taenite phase by X-ray diffraction (XRD) and Mössbauer spectroscopy (MS). Transmission electron microscopy (TEM) showed that the as prepared alloy contained spherical particles with 96 nm mean diameter size. The particles are composed of crystallites (of ∼15 nm size) and a predominant disordered interfacial region. A thermal treatment of 673 K/2 h produced a structural relaxation with a significant narrowing in the XRD and Mössbauer lines with a exothermic flow in the DSC signal and an increase in the crystallite size to 30 nm.     

Mössbauer and magnetic studies in nickel ferrite nanoparticles: Effect of size distribution

The magnetic properties of nickel ferrite nanoparticles in the form of powders, prepared by the sol-gel process and subjected to different annealing temperatures, were investigated using both static and dynamic measurements namely hysteresis, zero field cooled-field cooled magnetization (ZFC-FC) measurements and Mössbauer spectroscopy. The Transmission Electron Microscopy (TEM) studies reveal particle sizes for the as-prepared particles which increases upto 52 nm with annealing. A bimodal distribution, upto an annealing temperature of was observed. ZFC-FC measurements for the as-prepared samples reveal twin peaks, indicative of the bimodal size distribution. ZFC-FC measurements performed for fields varying from 100 Oe to 3 kOe show a superparamagnetic phase with blocking temperatures between 320 and . Numerical simulations for the ZFC-FC studies indicate that the signature of the bimodal size distribution can be seen only at very low fields. The variation of coercivity with particle size, as determined from the hysteresis measurements, shows a transition from a single domain to a multi domain state for particle sizes larger than 35 nm. Mössbauer measurements performed at room temperature for the as-prepared sample shows a six finger pattern for the samples with higher particle size and a doublet pattern for the samples with smaller particle size, which is indicative of their superparamagnetic nature.     

Magnetic size growth in nanocrystalline copper ferrite

When nanocrystalline copper ferrite (average grain size D≈6 nm) is subjected to high-energy-milling in air over different periods up to 12 h, we observe both a progressive enhancement of the ferrite's magnetic response and a shifting of its superparamagnetic limit. These are revealed by the shift to higher values of the Mössbauer blocking temperature, the maximum of the zero-field cooled magnetization and the start of the irreversibility between the zero-field and field-cooled magnetization curves, while the saturation magnetization and the mean magnetic moment per particle increase. The X-ray diffraction data show that the spinel improves its crystallinity with the milling, by increasing the grain size up to ≈13 nm and, also, reducing its micro-strain level. After 10 h of milling the copper ferrite stabilizes in its cubic metastable phase.     

The effect of solution temperature on crystallite size and magnetic properties of Zn substituted Co ferrite nanoparticles

In this work zinc substituted cobalt ferrite nanoparticles (Co_0.5Zn_0.5Fe₂O₄) have been synthesized by the coprecipitation method, using stable ferric, zinc and cobalt salts with sodium hydroxide, at different solution temperatures, from room temperature to 363 K. The cobalt-zinc ferrite crystalline phase, the particle size and the morphology of the resulting nanoparticles were studied by X-ray diffraction and transmission electron microscopy. The average crystallite size of each sample was calculated from the broadening of the most intense peak (3 1 1), using Scherrer's formula and the results show crystallite sizes increased from 6 to 8 nm by increasing the solution temperature from room temperature to 363 K respectively. Room temperature VSM measurements show that the prepared nanoparticles have superparamagnetic behavior and did not saturate at maximum field of 800 kA/m. The variation of AC-susceptibility of the samples with respect to temperature was measured and it was found that the blocking temperature increased from 198 to 270 K by increasing the solution temperature from room temperature to 363 K respectively. FTIR spectra of the samples have been analyzed in the frequency range 400-4000 cm⁻¹, which also confirms the results of XRD.     

Correlation between site preference and magnetic properties of substituted strontium ferrite thin films

SrFe_12−x(Sn_0.5Zn_0.5)_xO₁₉ thin films with x=0−5 were synthesized by a sol-gel method on thermally oxidized silicon wafer (Si/SiO₂). The site preference and magnetic properties of Zn-Sn substituted strontium ferrite thin films were studied using ⁵⁷Fe Mössbauer spectroscopy and magnetic measurements. Mössbauer spectra displayed that the Zn-Sn ions preferentially occupy the 2b and 4f₂ sites. The preference for these sites is responsible for the anomalous increase in the magnetization at high Zn-Sn substitutions. X-ray diffraction (XRD) patterns and field emission scanning electron microscope (FE-SEM) micrographs demonstrated that single phase c-axis hexagonal ferrite films with rather narrow grain size distribution were obtained. Vibrating sample magnetometer (VSM) was employed to probe magnetic properties of samples. The maximum saturation of magnetization and coercivity at perpendicular direction were 265 emu/g and 6.3 kOe, respectively. It was found that the complex susceptibility has linear variation with static magnetic field.     

Characterization of Fe and Fe50Ni50 ultrafine nanoparticles synthesized by inert gas-condensation method

Nanoparticles of Fe and Fe₅₀Ni₅₀ were synthesized by inert gas-condensation method under pure helium atmosphere. The prepared nanoparticles samples were examined by high-resolution transmission electron microscopy, X-ray diffraction and Mössbauer spectroscopy. The synthesized nanoparticles consisted of core-shell type structure nearly spherical shape with a size comprised within the range 4-70 nm and they occur as clusters or chains. The Mössbauer measurements as well as X-ray diffraction showed, in both cases, the presence of iron-oxide phases.     

Synthesis and characterization of the xZnO-(1−x)α-Fe2O3 nanoparticles system

The xZnO-(1−x)α-Fe₂O₃ nanoparticles system has been obtained by mechanochemical activation for x=0.1, 0.3 and 0.5 and for ball milling times ranging from 2 to 24 h. Structural and morphological characteristics of the zinc-doped hematite system were investigated by X-ray diffraction (XRD) and Mössbauer spectroscopy. The Rietveld structure of the XRD spectra yielded the dependence of the particle size and lattice constant on the amount x of Zn substitutions and as function of the ball milling time. The x=0.1 XRD spectra are consistent with line broadening as Zn substitutes Fe in the hematite structure and the appearance of the zinc ferrite phase at milling times longer than 4 h. Similar results were obtained for x=0.3, while for x=0.5 the zinc ferrite phase occurred at 2 h and entirely dominated the spectrum at 24 h milling time. The Mössbauer spectra corresponding to x=0.1 exhibit line broadening as the ball milling time increases, in agreement with the model of local atomic environment. Because of this reason, the Mössbauer spectrum for 12 h of milling had to be fitted with two sextets. For x=0.3 and 12 milling hours, the Mössbauer spectrum reveals the occurrence of a quadrupole-split doublet, with the hyperfine parameters characteristic to zinc ferrite, ZnFe₂O₄. This doublet clearly dominates the Mössbauer spectrum for x=0.5 and 24 h of milling, demonstrating that the entire system of nanoparticles consists finally of zinc ferrite. As ZnO is not soluble in hematite in the bulk form, the present study clearly demonstrates that the solubility limits of an immiscible system can be extended beyond the limits in the solid state by mechanochemical activation. Moreover, this synthesis route allowed us to reach nanometric particle dimensions, which would make the materials very important for gas sensing applications.     

Mössbauer,X-ray diffraction and AC susceptibility studies on nanoparticles of zinc substituted magnesium ferrite

Nanoparticles of zinc substituted Mg-ferrite with compositions Mg_(1-x)Zn _x Fe₂O₄ (x = 0.15, 0.30 and 0.50) having particle sizes in the range 6.4 nm to 21.4 nm prepared by the co-precipitation method were characterized by ⁵⁷Fe Mössbauer spectroscopy, X-ray diffratometry and AC magnetic susceptibility measurements. Mössbauer measurements at room temperature and down to 20 K clearly indicate presence of superparamagnetic particles in all the samples. AC magnetic susceptibility data show lowering of blocking temperature with decrease of particle size. Superparamagnetic relaxation was observed for larger particle size in samples with higher Zn content, which is attributed to the weakening of A-B exchange interaction in ferrite lattice due to replacement of Fe^{3 +} in tetrahedral site by Zn^{2 +} ions.Received: 16 April 2004, Published online: 23 July 2004PACS: 75.50.Tt Fine-particle systems; nanocrystalline materials - 76.80. + y Mössbauer effect; other gamma-ray spectroscopy - 75.30.Cr Saturation moments and magnetic susceptibilitiesS. Das: Present address: Department of Physics, Jadavpur University, Kolkata - 700032, India     

Effects of annealing temperature on structure and magnetic properties of CoAl0.2Fe1.8O4/SiO2 nanocomposites

CoAl_0.2Fe_1.8O₄/SiO₂ nanocomposites were prepared by sol–gel method. The effects of annealing temperature on the structure and magnetic properties of the samples were studied by X-ray diffraction, transmission electron microscopy, vibrating sample magnetometer and Mössbauer spectroscopy. The results show that the CoAl_0.2Fe_1.8O₄ in the samples exhibits a spinel structure after being annealed. As annealing temperature increases from 800 to 1200 °C, the average grain size of CoAl_0.2Fe_1.8O₄ in the nanocomposites increases from 5 to 41 nm while the lattice constant decreases from 0.8397 to 0.8391 nm, the saturation magnetization increases from 21.96 to 41.53 emu/g. Coercivity reaches a maximum of 1082 Oe for the sample annealed at 1100 °C, and thereafter decreases with further increasing annealing temperature. Mössbauer spectra show that the isomer shift decreases, hyperfine field increases and the samples transfer from mixed state of superparamagnetic and magnetic order to the completely magnetic order with annealing temperature increasing from 800 to 1200 °C.     

Effect of iron doping concentration on magnetic properties of ZnO nanoparticles

The ZnO:Fe nanoparticles of mean size 3-10 nm were synthesized at room temperature by simple co-precipitation method. The crystallite structure, morphology and size estimation were performed by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM). The wurtzite structure of ZnO gradually degrades with the increasing Fe doping concentration. The magnetic behavior of the nanoparticles of ZnO with varying Fe doping concentration was investigated using a vibrating sample magnetometer (VSM). Initially these nanoparticles showed strong ferromagnetic behavior, however at higher doping percentage of Fe, the ferromagnetic behavior was suppressed and paramagnetic nature was observed. The enhanced antiferromagnetic interaction between neighboring Fe-Fe ions suppressed the ferromagnetism at higher doping concentrations of Fe. Room-temperature Mössbauer spectroscopy investigation showed Fe³⁺ nature of the iron atom in ZnO matrix.     

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.     

Sol–gel synthesis of 8 nm magnetite (Fe3O4) nanoparticles and their magnetic properties

Magnetite (Fe₃O₄) nanoparticles were successfully synthesized by a sol–gel method. The obtained nanoparticles were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy dispersive analysis by X-ray (EDAX), transmission electron microscopy (TEM), superconducting quantum interference device (SQUID) and Mössbauer spectrometry. XRD and Mössbauer measurements indicate that the obtained nanoparticles are single phase. TEM analysis shows the presence of spherical nanoparticles with homogeneous size distribution of about 8 nm. Room temperature ferromagnetics behavior was confirmed by SQUID measurements. The mechanism of nanoparticles formation and the comparison with recent results are discussed. Finally, the synthesized nanoparticles present a potential candidate for hyperthermia application given their saturation magnetization.     

Mössbauer spectroscopy and magnetic properties in thin films of FexNi100−x electroplated on silicon (1 0 0)

Fe_xNi_100−x thin films were produced by galvanostatic electrodeposition on Si (1 0 0), nominal thickness 2800 nm, and x ranging 7-20. The crystalline structure of the sample was determined by X-ray diffraction (XRD). The magnetic properties were investigated by vibration sample magnetometry (VSM) and room temperature ⁵⁷Fe Mössbauer spectroscopy. Conversion Electron Mössbauer spectroscopy (CEMS) in both film surfaces for the thick self-supported films showed that the magnetic moment direction is in the plane and conventional transmission (MS) that the directions are out of the plane films. The results were interpreted assuming a three-layer model where the external layer has in-plane magnetization and the internal one, out of plane magnetization.     

Inversion degree and saturation magnetization of different nanocrystalline cobalt ferrites

The inversion degree of a series of nanocrystalline samples of CoFe₂O₄ ferrites has been evaluated by a combined study, which exploits the saturation magnetization at 4.2 K and ⁵⁷Fe Mössbauer spectroscopy. The samples, prepared by sol-gel autocombustion, have different thermal history and particle size. The differences observed in the saturation magnetization of these samples are explained in terms of different inversion degrees, as confirmed by the analysis of the components in the Mössbauer spectra. It is notable that the inversion degrees of the samples investigated are set among the highest values reported in the literature.     

Mössbauer study of cobalt ferrite nanocrystals substituted with rare-earth Y ions

Mössbauer spectroscopy is used to characterize the crystallite size and structure of CoFe_2−xY_xO₄ (x=0, 0.1, 0.3, 0.5) ferrite nanocrystallites synthesized by the sol-gel auto-combustion method. The effect of the substitution of Fe³⁺ ions by Y³⁺ ions on the structure of cobalt ferrite nanocrystallites is investigated. The Mössbauer spectra showed two sets of six-line hyperfine patterns for all the samples, indicating the presence of Fe in both A and B-sites. On increasing the concentration of doped Y, the hyperfine field strength and the isomer shift first increase and then decrease, whereas the quadrupole splitting continuously increases. The superparamagnetism was observed for all the samples and the change of ratio of the superparamagnetism component reflects the size of crystal grain.