Sol-gel derived nanoparticles of Zn substituted lithium ferrite (Li0.32Zn0.36Fe2.32O4): magnetic and Mössbauer effect measurements and their theoretical analysis

Nanoparticles of Zn substituted lithium ferrite (Li_0.32Zn_0.36Fe_2.32O₄) have been prepared by a sol-gel method where the ultra-sonication technique has been adopted to reduce the agglomeration effect among the nanoparticles. The samples were heat-treated at three different temperatures and the formation of the nanocrystalline phase was confirmed by X-ray diffractograms (XRD). The average particle size of each sample has been estimated from the (311) peak of the XRD pattern using the Debye-Scherrer formula and the average sizes are in the range of 10-21 nm. The average particle size, crystallographic phase, etc. of some selected samples obtained from the high-resolution transmission electron microscopy are in agreement with those estimated from the XRD patterns. Static magnetic measurements viz., hysteresis loops, field cooled and zero field cooled magnetization versus temperature curves of some samples carried out by SQUID in the temperature range of 300 to 5 K clearly indicate the presence of superparamagnetic (SPM) relaxation of the nanoparticles in the samples. The maximum magnetization of the SPM sample annealed at 500 °C is quite high (68 Am²/Kg) and the hysteresis loops are almost square shaped with very low value of coercive field at room temperature (827.8 A/m). The particle size, magneto-crystalline anisotropy, etc. have been estimated from the detailed theoretical analysis of the static magnetic data. The dynamic magnetic behavior of the samples was also investigated by observing the ac hysteresis loops and magnetization versus field curves with different time windows at room temperatures. The different soft magnetic quantities viz., coercive field, magnetization, remanance, hysteresis losses, etc. were extracted from dynamic measurements. Dynamic measurements confirmed that the samples are in their mixed state of SPM and ordered ferrimagnetic particles, which is in good agreement with the results of static magnetic measurements. Mössbauer spectra of the samples recorded at room temperature (300 K) and at different temperatures down to 20 K confirmed the presence of the SPM relaxation of the nanoparticles of the samples.     

Synthesis and magnetic characterization of nickel ferrite nanoparticles prepared by co-precipitation route

Magnetic nanoparticles of nickel ferrite (NiFe₂O₄) have been synthesized by co-precipitation route using stable ferric and nickel salts with sodium hydroxide as the precipitating agent and oleic acid as the surfactant. X-ray diffraction (XRD) and transmission electron microscope (TEM) analyses confirmed the formation of single-phase nickel ferrite nanoparticles in the range 8-28 nm depending upon the annealing temperature of the samples during the synthesis. The size of the particles (d) was observed to be increasing linearly with annealing temperature of the sample while the coercivity with particle size goes through a maximum, peaking at ∼11 nm and then decreases for larger particles. Typical blocking effects were observed below ∼225 K for all the prepared samples. The superparamagnetic blocking temperature (T_B) was found to be increasing with increasing particle size that has been attributed to the increased effective anisotropy energy of the nanoparticles. The saturation moment of all the samples was found much below the bulk value of nickel ferrite that has been attributed to the disordered surface spins or dead/inert layer in these nanoparticles.     

Enhancement of magnetic anisotropy in mechanically attrited Cr2O3 nanoparticles

Cr₂O₃ nanoparticles of sizes from 24 to 12 nm were synthesized by mechanical grinding. Magnetic hysteresis loops were observed in the temperature range 5-300 K. Zero-field magnetization measurements showed two peaks, at low temperature in the range 36-52 K and at high temperature in the range 255-290 K. They were found to shift to higher temperatures as the particle size was reduced. This was ascribed due to the enhancement of the effective anisotropy constant with a decrease in particle size. The exchange bias was found to increase as the particle size became smaller. This is believed to arise due to an increase in uncompensated spins as a result of large surface area created.     

Temperature dependence of magnetic properties of NiFe2O4 nanoparticles embeded in SiO2 matrix

Spinel ferrite NiFe₂O₄ nanoparticles (?25 nm) in SiO₂ matrix were prepared by sol–gel method. The phase and average crystallite size of the samples were determined by X-ray diffraction method and the particle size distributions were studied by a transmission electron microscope. Magnetic properties of the samples were investigated with different ferrite particle sizes and at various temperatures down to 10 K. Superparamagnetic properties were observed at room temperature when the particle size is less than 10 nm.In superparamagnetic state, the field dependence of magnetization follows Langevin function which was originally developed for paramagnetism. The effective anisotropy constant K_eff is found to increase significantly with the decrease in particle volume and an order of magnitude higher than that of the bulk samples when the particle size is below 5 nm due to the dominance of surface anisotropy. In case of nanosized systems, the effect of size reduction on the law of approach to saturation has also been studied in detail.     

Synthesis and characterization of manganese ferrite nanoparticles by thermal treatment method

Cubic structured manganese ferrite nanoparticles were synthesized by a thermal treatment method followed by calcination at various temperatures from 723 to 873 K. In this investigation, we used polyvinyl pyrrolidon (PVP) as a capping agent to control the agglomeration of the nanoparticles. The characterization studies were conducted by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The average particle sizes of manganese ferrite nanoparticles were determined by TEM, which increased with the calcination temperature from 12 to 22 nm and they had good agreement with XRD results. Fourier transform infrared spectroscopy confirmed the presence of metal oxide bands at all temperatures and the absence of organic bands at 873 K. Magnetic properties were demonstrated by a vibrating sample magnetometer, which showed a super-paramagnetic behavior for all samples and also saturation magnetization (M_s) increases from 3.06 to 15.78 emu/g by increasing the calcination temperature. The magnetic properties were also confirmed by the use of electron paramagnetic resonance spectroscopy, which revealed the existence of unpaired electrons and also measured peak-to-peak line width, resonant magnetic field and the g-factor.     

Synthesis and magnetic characterization of Zn0.6Ni0.4Fe2O4 nanoparticles via a polyethylene glycol-assisted hydrothermal route

Zn-doped nickel ferrite nanoparticles (Zn_0.6Ni_0.4Fe₂O₄) have been prepared via a surfactant, polyethylene glycol assisted hydrothermal route. X-ray powder diffractometry (XRD), Fourier transform infrared spectroscopy, transmission electron microscopy (TEM), and vibrating scanning magnetometry (VSM) were used for the structural, morphological, and magnetic characterizations of the product, respectively. TEM analysis revealed that the nanoparticles have a narrow size distribution, with average particle size of 15±1 nm, which agrees well with the XRD based estimate of 14±2 nm. The absence of saturation and remanent magnetization, and coercivity in the high temperature region of the M-H curve and non-zero magnetic moments indicate superparamagnetism of the nanoparticles with a canted spin structure. The appearance of a peak on the temperature-dependent zero-field cooling magnetization curve at ∼190 K indicates the blocking temperature of the sample.     

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.     

Magnetic memory effect in chelated zero valent iron nanoparticles

We report the study of nonequilibrium magnetic behavior of air stable zero valent iron nanoparticles synthesized in presence of N-cetyl-N,N,N-trimethyl ammonium bromide chelating agent. X-ray photoelectron spectroscopy study has suggested the presence of iron oxides on nZVI surfaces. Zero-field-cooled and field-cooled magnetization measurements have been carried out at 20–300 K and 100 Oe. For field-cooled measurements with 1 h stops at 200, 100 and 50 K when compared with the warming cycle, we found the signature of magnetic memory effect. A study of magnetic relaxation at the same temperatures shows the existence of two relaxation times.     

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 and magnetic characteristics of Co1−xNix/2Srx/2Fe2O4 nanoparticles

Co_1−xNi_x/2Sr_x/2Fe₂O₄ (x=0–0.5 in steps of 0.1) ferrite nanoparticles have been synthesized at room temperature, without calcination, using a reverse micelle process. The site preference was determined by Mössbauer spectroscopy at 300 K. The hyperfine parameters were obtained, for the whole series of solid solutions. For the X≤0.20 samples, the spectra were fitted with two discrete sextets and for the X>0.20 samples, a magnetic hyperfine field distribution and a doublet were also imposed in the fit procedure. Hysteresis loops were measured using a superconducting quantum interference device magnetometer at 2 K and 300 K. The results indicate that the relative decrease in saturation magnetization of nanoparticles compared to the submicron particles could be attributed to a surface spin termination and disorder. Magnetic dynamics of the nanoparticles was studied by the measurement of ac magnetic susceptibility versus temperature at different frequencies and it is found that the results are well described by the Vogel–Fulcher model.     

Magnetic resonance study of Ce and Gd doped NiFe2O4 nanoparticles

Present work is a study of temperature dependent electron paramagnetic resonance spectra of Ce and Gd doped nickel ferrite nanoparticles. The samples, synthesised by chemical route were characterised by X-ray diffractometer, electron paramagnetic resonance spectroscopy (EPR) and vibrating sample magnetometer (VSM). The average crystallite size of pure nickel ferrite is ∼64 nm and for Gd and Ce doped samples it is ∼20 nm and ∼14 nm, respectively. The EPR spectra were recorded from 120 to 300 K. Doping with Gd and Ce reduces the line width and g-value in comparison to that of pure nickel ferrite. Ce doped samples have the lowest values of both these parameters at room temperature. This indicates that Ce doped samples show lowest loss and is suitable for high frequency devices. EPR spin numbers are reduced while the spin relaxation time is increased after doping with rare earth ions. Gd doped samples have higher values of relaxation time and lower spin numbers in comparison to that of Ce doped samples. VSM results show that the magnetisation and coercivity are reduced after doping with both Ce and Gd rare earth ions.     

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.     

Mossbauer, Raman and X-ray diffraction studies of superparamagnetic NiFe2O4 nanoparticles prepared by sol-gel auto-combustion method

Superparamagnetic nickel ferrite single phase nanoparticles with the average crystallite size of ∼9 nm have been synthesized at a low temperature (220 °C) by the sol-gel auto-combustion method. In the present study the as prepared powder was further calcined at different temperatures for 4 h, resulting in nanoparticles of larger size. The nanoparticles exhibited superparamagnetic behavior and changes in cation distribution as revealed by the Mossbauer, Raman and X-ray diffraction studies. The Mossbauer spectra collected at 5 K and under 5 T applied magnetic field showed mixed spinel structure and canted spin order for the nanoparticles, whereas there is collinear spin order with inverse spinel structure for larger particles. The vibrational spectra of the nanoparticles showed a redshift and broadening in the Raman line shape due to confinement effects.     

Dielectric relaxation and magnetic field dependent alternating current conductivity of nanocrystalline cadmium-zinc ferrite below room temperature

The dielectric permittivity of nanocrystalline cadmium-zinc ferrite prepared by the ball milling method has been investigated within a temperature range 77≤T≤300 K in presence of a magnetic field up to 1 T and in the frequency range 20 Hz-1 MHz. The dielectric permittivity follows the power law ε^/(f)∝Tⁿ where the temperature exponent ‘n’ is found to be frequency dependent. The dielectric properties of the samples have been analyzed in terms of electric modulus vector. The dielectric relaxation has been explained by interfacial polarization. The variation of the relaxation time with temperature indicates the presence of two different activation energies. The ac magnetoconductivity is positive for the milled sample and becomes negative for the unmilled sample. This behavior can be explained in terms of grain and grain boundary contribution to impedance of the samples.     

Magnetic Properties of Nanoparticles Useful for SQUID Relaxometry in Biomedical Applications

We use dynamic susceptometry measurements to extract semiempirical temperature-dependent, 255-400 K, magnetic parameters that determine the behavior of single-core nanoparticles useful for SQUID relaxometry in biomedical applications. Volume susceptibility measurements were made in 5 K degree steps at nine frequencies in the 0.1-1000 Hz range, with a 0.2 mT amplitude probe field. The saturation magnetization (M_s) and anisotropy energy density (K) derived from the fitting of theoretical susceptibility to the measurements both increase with decreasing temperature; good agreement between the parameter values derived separately from the real and imaginary components is obtained. Characterization of the Néel relaxation time indicates that the conventional prefactor, 0.1 ns, is an upper limit, strongly correlated with the anisotropy energy density. This prefactor decreases substantially for lower temperatures as K increases. We find, using the values of the parameters determined from the real part of the susceptibility measurements at 300 K, that SQUID relaxometry measurements of relaxation and excitation curves on the same sample are well described.     

Thermal and magnetic properties of DyB62 at low temperatures

Temperature dependences of heat capacity C_P(T) and magnetization M(T) of an icosahedral dysprosium boride (DyB₆₂) single crystal have been experimentally investigated in the temperature range of 2-300 K. The magnetic susceptibility χ(T) of DyB₆₂ follows Curie-Weiss law with a paramagnetic Curie temperature of −3.7 K, which implies that the antiferromagnetic interactions are dominant in this material and suggests the possibility of magnetic ordering at low temperatures. This conjecture is supported by the temperature dependence of heat capacity C_P(T), which decreases upon heating from 2 to 7 K. The heat capacity of DyB₆₂ at 2 K is analyzed as a sum of magnetic, Debye, two-level system and soft atomic potential components.     

Electrical- and magneto-resistance control for magnetite nanoparticle sinter by regulation of heat treatment temperature

We investigated electrical- and magneto-resistance control in magnetite (Fe₃O₄) nanoparticle sinter (MNPS) by the regulation of heat treatment (HT) temperature. MNPS was produced from hematite (α-Fe₂O₃) nanoparticles (HNP’s) using a deoxidization reaction. The average size of HNP was 30 nm, and HT was carried out between 400 and 800 °C. X-ray diffraction, magnetization, electrical resistivity (ER), and magneto-resistivity (MR) measurements were performed at temperatures ranging from 5 to 300 K. The ER and MR behaviors were considerably different at HT temperatures above and below ∼600 °C. After HT below ∼600 °C, ER followed the Mott-type variable-range-hopping conduction, and MR showed large values over a wide temperature range. After HT above ∼600 °C, ER indicated a Verwey transition near 110 K and MR showed small values, except in the vicinity of the Verwey transition temperature. Changing the HT temperature altered the coupling between adjacent magnetite nanoparticles (MNPs) and affected the crystallinity of MNPS. Below ∼600 °C, ER and MR were dominated by grain-boundary conduction, while above ∼600 °C they were determined by inter-grain conduction. The application of a magnetic field to the grain-boundary region, which had random localized spins, caused a large enhancement in MR.     

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.     

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.     

Controlling the crystal structure of Ni nanoparticles by the use of alkylamines

Ni nanoparticles were prepared via thermal decomposition of nickel acetate tetrahydrate in the presence of long-chain amines, which acted as both solvents and reducing agents. By tuning the reaction temperature, Ni nanostructures with either hcp or fcc crystal structure were obtained. In principle, higher temperatures favored the formation of hcp nanoparticles. The employment of additional surfactants such as 1-adamantanecarboxylic acid and trioctylphosphine-oxide facilitated the tuning of the particles’ growth limit. The size of the particles varied between 5 and 120 nm. The magnetic features of fcc-Ni nanoparticles were quite similar to the corresponding ‘bulk’ ones. On the other hand, the hcp-Ni particles showed weak magnetic features, reflected by low magnetization values, the absence of saturation magnetization and by blocking temperatures far below room temperature.