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.     

XRD, HRTEM, magnetic and Mössbauer studies on chemically prepared Fe-doped nanoparticles of cerium oxide

Nanocrystalline samples of Fe-doped cerium oxide (Ce_0.90Fe_0.1O₂) are prepared by sol-gel method. The precursor materials used for the synthesis are ferric nitrate and cerium nitrate. The as-prepared samples is annealed at different temperatures to obtain the sample with different particle sizes. The crystallographic phases of the nanocrystalline materials have been confirmed by X-ray diffractograms (XRD). The sizes of the nanoparticles estimated from the peaks of the XRD patterns using Debye-Scherrer equation are in the range 6-58 nm. Results extracted from the high-resolution transmission electron microscopy (HRTEM) are in agreement with the findings obtained from XRD. The average magnetic susceptibilities of all the samples with different particle sizes are measured in the temperature range 300-14 K. The average susceptibilities of the samples annealed below ∼740 °C show paramagnetic behaviour. The susceptibilities of the samples annealed at and above ∼740 °C sharply decrease at ∼240 K and this sharp transition is quite likely due to the anti-parallel alignment of Fe³⁺ spins and is attributed to Morin transition of α-Fe₂O₃. Mössbauer spectra of the samples annealed at and above ∼740 °C give sextet patterns indicating the presence of exchange interaction among the Fe³⁺ ions of these samples and these sextets are also of typical nature of the α-Fe₂O₃ phase. The Mössbauer spectra of the samples annealed below ∼740 °C are doublets which may be attributed to either superparamagnetic and/or paramagnetic type nanoparticles.     

An enthalpy of solution of chromium in iron studied with Fe Mössbauer spectroscopy

The room temperature Mössbauer spectra of ⁵⁷Fe were measured for iron-based solid solutions Fe_1−xCr_x with x in the range 0.01≤x≤0.05. The obtained data were analysed in terms of the binding energy E_b between two chromium atoms in the studied materials using the extended Hrynkiewicz–Królas idea. It was found that the energy is positive or Cr atoms interact repulsively. The extrapolated value of E_b for x=0 was used for computation of an enthalpy of solution of Cr in Fe. The result was compared with corresponding data derived from calorimetric measurements and resulting from the cellular atomic model of alloys by Miedema as well as with the proper values given in the literature which were calculated on the basis of density functional theory (DFT). The comparison shows that our findings are in good agreement with the recent DFT computations for ferromagnetic Fe–Cr alloys.     

Magnetic and Mössbauer studies of Ni substituted Li-Zn ferrite

Li-Zn ferrites substituted with Ni having the compositional formula Li_0.4−0.5xZn_0.2Ni_xFe_2.4−0.5xO₄ where x=0.02?x?0.1 in steps of 0.02 were fabricated by the citrate precursor method. This method has been employed to get nanosized particles and good magnetic properties. The spinel phase structure of the prepared ferrites was confirmed by XRD analysis. The effect of Ni concentration on magnetic properties such as saturation magnetization and Curie temperature were investigated. A good knowledge of these magnetic properties is desirable from application point of view. The values observed are large and both quantities were found to decrease with substitution. The saturation magnetizations were found to vary from 78 to 94 emu/gm while the Curie temperature which limits the operating temperature of the system ranges between 563 and 584 °C. Mössbauer data were also recorded at room temperature and the hyperfine parameters like isomer shift, quadrupole splitting and internal magnetic field estimated. The results obtained and mechanisms involved are discussed.     

Micro Raman,Mossbauer and magnetic studies of manganese substituted zinc ferrite nanoparticles: Role of Mn

A series of Mn–Zn Ferrite nanoparticles (<15 nm) with formula Mn_xZn_1−xFe₂O₄ (where x=0.00, 0.35, 0.50, 0.65) were successfully prepared by citrate-gel method at low temperature (400 °C). X-ray diffraction analysis confirmed the formation of single cubic spinel phase in these nanoparticles. The FESEM and TEM micrographs revealed the nanoparticles to be nearly spherical in shape and of fairly uniform size. The fractions of Mn²⁺, Zn²⁺ and Fe³⁺ cations occupying tetrahedral sites along with Fe occupying octahedral sites within the unit cell of different ferrite samples are estimated by room temperature micro-Raman spectroscopy. Low temperature Mossbauer measurement on Mn_0.5Zn_0.5Fe₂O₄ has reconfirmed the mixed spinel phase of these nanoparticles. Room temperature magnetization studies (PPMS) of Mn substituted samples showed superparamagnetic behavior. Manganese substitution for Zn in the ferrite caused the magnetization to increase from 04 to18 emu/g and Lande's g factor (estimated from ferromagnetic resonance measurement) from 2.02 to 2.12 when x was increased up to 0.50. The FMR has shown that higher Mn cationic substitution leads to increase in dipolar interaction and decrease in super exchange interaction. Thermomagnetic (M–T) and magnetization (M–H) measurements have shown that the increase in Mn concentration (up to x=0.50) enhances the spin ordering temperature up to 150 K (blocking temperature). Magnetocrystalline anisotropy in the nanoparticles was established by Mossbauer, ferromagnetic resonance and thermomagnetic measurements. The optimized substitution of manganese for zinc improves the magnetic properties and makes these nanoparticles a potential candidate for their applications in microwave region and biomedical field.     

Structural and magnetic properties of MnxCo1−xFe2O4 ferrite nanoparticles

We report on the structural and magnetic properties of nanoparticles of Mn_xCo_1−xFe₂O₄ (x=0.1, 0.5) ferrites produced by the glycothermal reaction. From the analysis of XRD spectra and TEM micrographs, particle sizes of the samples have been found to be about 8 nm (for x=0.1) and 13 nm (for x=0.5). The samples were characterized by DC magnetization in the temperature range 5-380 K and in magnetic fields of up to 40 kOe using a SQUID magnetometer. Mössbauer spectroscopy results show that the sample with higher Mn content has enhanced hyperfine fields after thermal annealing at 700 °C. There is a corresponding small reduction in hyperfine fields for the sample with lower Mn content. The variations of saturation magnetization, remnant magnetization and coercive fields as functions of temperature are also presented. Our results show evidence of superparamagnetic behaviour associated with the nanosized particles. Particle sizes appear to be critical in explaining the observed properties.     

A.C. and D.C. conductivity of NiZn ferrite nanoparticles in wet and dry conditions

Promising future applications of ferrite nanoparticles in medicine, drug delivery, sensors and ferrofluids are expected to be in wet or humid environments. Therefore nanostructured powders of ferrites having the chemical compositions.Ni_xZn _(1−x)Fe₂O₄ with (x=0.0, 0.25, 0.5, 0.75, and 1) were pressed immediately after preparation - by the co-precipitation method - without any drying to simulate a humid environment. The nanoparticles were characterized by X-ray diffraction analysis (XRD) to be sure of the formation of the ferrite in nanoscale. The infrared (IR) spectroscopy of the samples ensures the existence of water as well as the characteristic absorption bands of ferrites. The ac and dc conductivity of the samples had been investigated immediately after preparation (the as-prepared samples). Then, the samples were dried at 200 °C for about 12 h and reinvestigated. The behavior of conductivity differs significantly in the two cases showing a noticeable effect due to humidity. Also, the magnetic induction of the as-prepared samples was investigated by using the vibrating sample magnetometer (VSM). The samples show superparamagnetic behavior.     

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.     

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.     

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.     

Effect of magnesium substitution on dielectric and magnetic properties of Ni-Zn ferrite

The dielectric and magnetic properties of Mg incorporated Ni-Zn spinel ferrites have been investigated. Ni_0.5−xZn_0.5Mg_xFe₂O₄ ferrites have been prepared by sol-gel auto-combustion technique. The as prepared ferrites were annealed at 673, 873 and 1073 K. The X-ray diffraction studies reveal the spinel structure of annealed ferrites. The TEM results are in agreement with XRD results. FTIR study has also been carried out to get insight into the structure of these ferrites. The dielectric measurements show that the dielectric constant (ε′), dielectric loss (tan δ) and conductivity (σ_ac) increase on incorporation of Mg in the Ni-Zn ferrite. ε′, tan δ and σ_ac also show dependence on temperature, frequency of external applied electric field and microstructure of the samples. The magnetic moment measurements reveal that the saturation magnetization (M_s) increases and coercivity (H_c) decreases with the increase in concentration of Mg²⁺ ions. M_s and H_c also show dependence on the annealing temperature.     

Structure of manganese zinc ferrite spinel nanoparticles prepared with co-precipitation in reversed microemulsions

The structure of Mn_0.5Zn_0.5Fe₂O₄ spinel ferrite nanoparticles is studied as a function of their size and the experimental conditions of their synthesis using X-ray absorption spectroscopy. The nanoparticles of different sizes down to approximately 2 nm and with a narrow size distribution were synthesized using co-precipitation in reverse microemulsions. Simultaneous refinement of the X-ray absorption fine structure (EXAFS) of three constituting metals shows a migration of Mn and Zn ions to the octahedral site of the spinel lattice compensated by the corresponding migration of the Fe ions. To a smaller extent, Mn ions switch the occupation site already in bulk and in larger nanoparticles, while a sporadic migration of Zn is detected only in the nanoparticles with sizes below approximately 5 nm. X-ray absorption near edge structure (XANES) reveals considerable variations in the position of the Mn K edge, suggesting the average Mn valence in the nanoparticles to be higher than 3+. Annealing at 500 °C relaxes the structure of as-synthesized nanoparticles toward the structure of the ceramic bulk standard. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Mössbauer study of CoFeRhO4

CoFeRhO₄ has been studied by Mössbauer spectroscopy and X-ray diffraction. The crystal is found to have a cubic spinel structure with the lattice constant a₀=8.451±0.005 Å. The iron ions are in ferric states. The temperature dependence of the magnetic hyperfine field is analyzed by the Néel theory of ferrimagnetism. The intersublattice superexchange interaction is antiferromagnetic and strong with a strength of J_AB=−12.39k_B while the intrasublattice superexchange interactions are weak with strengths of J_AA=−4.96k_B and J_BB=6.20k_B. As the temperature increases toward the Néel temperature T_N, a systematic line broadening effect in the Mössbauer spectrum is observed and interpreted to originate from different temperature dependences of the magnetic hyperfine fields at various iron sites.     

The influence of 3d transition metal substitution on the magnetic properties of MnGaGe

A study has been made of the effect of 3d transition element substitution on the magnetic moment and Curie temperature of MnGaGe. Substitution of 3d elements with atomic number less than Mn (i.e. Ti, V, or Cr) cause relatively small changes in magnetic properties, whereas substitution of Fe, Co, Ni and Cu cause a large reduction in moment and Curie temperature, e.g. substitution of 5 at.% Fe for Mn causes the moment to decrease by 30 per cent. The moment and ferromagnetism of MnGaGe are described in terms of a band model involving both strongly correlated and intinerant 3d electrons. The effect of 3d element substitution may be qualitatively understood in terms of this model.     

Effect of Mg substitution on electromagnetic properties of (Ni0.25Cu0.20Zn0.55)Fe2O4 ferrite prepared by auto combustion method

The ferrite compositions of (Ni_0.25−xMg_xCu_0.2Zn_0.55)Fe₂O₄ with x=0.0$x=0.0$, 0.07, 0.13, 0.18, and 0.25 were synthesized through nitrate-citrate auto-combustion method. The as-burnt powders showed the presence of crystalline cubic spinel ferrite with about 19–22 nm crystallite sizes. The resultant powders were calcined at 700 °C/2 h and pressed ferrites were sintered at 950 °C/4 h. The initial permeability, magnetic loss and AC resistivity were measured in the frequency range 10 Hz–10 MHz. The permeability and AC resistivity were found to increase and the magnetic loss decreased with Mg substitution for Ni, up to x=0.18$x=0.18$. The very high permeability in the composition x=0.18$x=0.18$, was due to better densification, lower magnetostriction constant and inner stresses, etc. The AC resistivity of the composition was also highest. The composition would be better than NiCuZn-based material for more miniaturization of multi layer chip inductor.     

The Mössbauer rotor experiment and the general theory of relativity

In the recent paper Yarman et al. (2015), the authors claim that our general relativistic analysis in Corda (2015), with the additional effect due to clock synchronization, cannot explain the extra energy shift in the Mössbauer rotor experiment. In their opinion, the extra energy shift due to the clock synchronization is of order 10⁻¹³ and cannot be detected by the detectors of γ$\gamma$-quanta which are completely insensitive to such a very low order of energy shifts. In addition, they claim to have shown that the extra energy shift can be explained in the framework of the so-called YARK gravitational theory. They indeed claim that such a theory should replace the general theory of relativity (GTR) as the correct theory of gravity.     

Thermodynamic properties of Fe-Ni solid solutions studied by Fe Mössbauer spectroscopy

The room temperature Mössbauer spectra of ⁵⁷Fe were measured for Ni_1−xFe_x solid solutions with x in the range 0.01≤x≤0.10. The obtained data were analysed in terms of short range order parameter (SRO) and the binding energy E_b between two iron atoms in the studied materials using the extended Hrynkiewicz-Królas idea. It was found that the binding energy is positive or Fe atoms interact repulsively. The extrapolated value of E_b for x=0 was used for computation of enthalpy of solution of Fe in Ni. Finally the values of enthalpies of solution were used to predict the mixing enthalpy curve for the Fe-Ni solid solutions. The results were compared with corresponding value given in the literature, which was calculated theoretically using DFT techniques, as well as with the value obtained from experimental calorimetric data and resulting from the cellular atomic model of alloys by Miedema.     

Mössbauer study of the re-entrant spin-glass behaviour in the mixed spinel ferrites Mg(0.9+x)Fe2(1−x)Ni0.1TixO4 (x=0.5 and 0.6)

Samples of the mixed spinel ferrite series Mg_(0.9+x)Fe_2(1−x)Ni_0.1Ti_xO₄ with x=0.5 and 0.6, prepared by solid state reaction of the appropriate oxides, have been investigated with ⁵⁷Fe Mössbauer spectroscopy. The as-prepared samples are found to be mainly superparamagnetic due to magnetic cluster formation. Samples after at least three times reheated exhibit spectra, which can be rather interpreted by a transversal relaxation of the spin above and spin-glass behaviour below the respective freezing temperatures T_f. External-field spectra reveal the canting to occur only on the octahedral sites. From the derived transition temperatures and thresholds together with data from earlier investigated sample with x=0.7 a compositional magnetic phase diagram for this spinel series is obtained.     

Structural studies of nanocrystalline SnO2 doped with antimony: XRD and Mössbauer spectroscopy

A series of Sb-doped SnO₂ samples, with doping levels 0, 3.1, 6.2, 11.9 and 14.0 at% Sb, has been hydrothermally prepared and characterized by X-ray powder diffraction. Diffraction lines were broadened, the line broadening being anisotropic. Both the line broadening and line anisotropy were dependent on the Sb doping level. The samples are tetragonal, space group P4₂/mnm and isostructural with TiO₂(rutile). Sb doping of SnO₂ causes the increase of unit-cell parameters. The structure of pure SnO₂ and of samples containing 6.2 and 11.9 at% Sb has been refined by the Rietveld method. Crystal structure indicated that both Sb³⁺ and Sb⁵⁺ are substituted for Sn⁴⁺ in the SnO₂ structure, Sb³⁺ being dominant for the investigated doped samples. The samples were also examined by ¹¹⁹Sn- and ¹²¹Sb-Mössbauer spectroscopy. Mössbauer spectroscopy confirmed the XRD results. Also, the values of the isomer shifts and quadrupole coupling constants indicated that the configuration around the Sb³⁺ site includes the presence of the stereochemically active lone pair electrons.