Synthesis and characterization of Ni1−xZnxFe2O4 spinel ferrites from tailored layered double hydroxide precursors

In this paper, a series of pure Ni_1 − xZn_xFe₂O₄ (0 ≤ x ≤ 1) spinel ferrites have been synthesized successfully using a novel route through calcination of tailored hydrotalcite-like layered double hydroxide molecular precursors of the type [(Ni + Zn)_{1 − x − y}Fe_y²⁺Fe_x³⁺(OH)₂]^x+(SO₄²⁻)_x/2·mH₂O at 900 °C for 2 h, in which the molar ratio of (Ni²⁺ + Zn²⁺)/(Fe²⁺ + Fe³⁺) was adjusted to the same value as that in single spinel ferrite itself. The physico-chemical characteristics of the LDHs and their resulting calcined products were investigated by powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS) and Mössbauer spectroscopy. The results indicate that calcination of the as-synthesized LDH precursor affords a pure single Ni_1 − xZn_xFe₂O₄ (0 ≤ x ≤ 1) spinel ferrite phase. Moreover, formation of pure ferrites starting from LDHs precursors requires a much lower temperature and shorter time, leading to a lower chance of side-reactions occurring, because all metal cations on the brucite-like layers of LDHs can be uniformly distributed at an atomic level.     

Substitutional effect on structural and dielectric properties of Ni1−xAxFe2O4 (A = Mg,Zn) mixed spinel ferrites

The Ni_1−xA_xFe₂O₄ (A = Zn, Mg; x = 0.0, 0.5) ferrites synthesized by chemical co-precipitation method. X-ray diffraction and Raman spectroscopy reveals that all the ferrite samples are in single-phase cubic spinel structure with Fd3m space group. The lattice parameter enhances with Mg and Zn substitution. Raman spectroscopy identifies a doublet like nature of A_1g mode for all the three ferrites. A blue shift in Mg doped ferrite and a red shift in Zn doped ferrite has been observed as compared to parent NiFe₂O₄. Frequency dependent dielectric response confirms the dielectric polarization and electrical conduction mechanism. The minimum value of loss tangent (∼0.03) at 5 KHz suggests that Ni_1−xA_xFe₂O₄ is effective material for microwave application. The activation energy for NiFe₂O₄, Ni_0.5Mg_0.5Fe₂O₄ and Ni_0.5Zn_0.5Fe₂O₄ are found to be 0.28 eV, 0.29 eV and 0.31 eV, respectively.     

Synthesis and electromagnetic properties of microwave absorbing material: Cox(Cu0.5Zn0.5)1−xFe2O4 (0 < x < 1) nanoparticles

Spinel ferrite Co_x(Cu_0.5Zn_0.5)_1−xFe₂O₄ over a compositional range 0 < x < 1 was prepared using a simple hydrothermal method. Particle sizes could be varied from 14 to 25 nm by changing the x value. X-ray diffraction results confirmed that all the as-prepared nanoparticles revealed typical spinel structure and transmission electron microscopy images showed that the particle size of the samples increased with increasing x value. The magnetic properties of the as-prepared Co_x(Cu_0.5Zn_0.5)_1−xFe₂O₄ nanoparticles have been systematically examined. The maximum saturation magnetization existed at the highest Co content (x = 1). The electromagnetic properties of all the samples have been measured by an Agilent network analyzer and the results showed that Co_0.1(Cu_0.5Zn_0.5)_0.9Fe₂O₄ possessed the best microwave absorbing properties.     

Hydrothermal synthesis and magnetic properties of Co0.2Cu0.03Fe2.77O4 nanoparticles

Co_0.2Cu_0.03Fe_2.77O₄ nanoparticles with different morphologies have been synthesized directly via a simple hydrothermal method. The effects of pH value, precursor concentration, reaction temperature and surfactant on the particle size were discussed. X-ray diffraction analyses showed that the as-synthesized Co_0.2Cu_0.03Fe_2.77O₄ nanoparticles possessed typical spinel structure. Scanning electron microscope images showed different morphologies of the particles, including truncated octahedron and octahedron. It was indicated that well-dispersed Co_0.2Cu_0.03Fe_2.77O₄ nanoparticles can be synthesized at pH values ranging from 11 to 13, and reaction temperature of 160 °C. The particle size decreased from 18 to 10 nm after the addition of sodium dodecyl sulphate at the pH value of 9. The magnetic measurement showed that the as-prepared Co-Cu spinel ferrite nanoparticles possessed hard magnetic property.     

NiZnCo ferrite films by spin spray technique: morphology and magnetic properties

In the present study, highly crystallized spinel NiZnCo ferrite films were prepared by spin-spray ferrite plating, employing a reaction solution (containing Fe²⁺, Ni²⁺, Zn²⁺ and Co²⁺) and an oxidizing solution (KNO₂ + CH₃COOK). The solutions were sprayed independently onto a glass substrate maintained at 90 °C. Series of films with various Zn and Co compositions were prepared and their structural and magnetic properties were studied. The films had a columnar structure perpendicular to the substrate surface as confirmed by scanning electron microscopy (SEM) studies and showed no preferential orientation confirmed by X-ray diffraction (XRD). The films had a saturization magnetization M _s of 325–520 emu/cc and H _c of 5–12 Oe. At the optimized compositions, we obtained an initial permeability of around 190 (Ni_0.18Zn_0.6Co_0.02Fe_2.2O_4−δ ) and resonance frequency f _r of 300 MHz (Ni_0.16Zn_0.2Co_0.02Fe_2.62O_4−δ ). Such films with high permeability can be employed as trimming layers of inductors to increase the inductance and films with high resonance frequency can be used as electromagnetic noise suppressors at high frequency.     

The structural and electrical property of CuCr1 − xNixO2 delafossite compounds

A series of CuCr_1 − xNi_xO₂ (0 ≤ x ≤ 0.06) polycrystalline samples was prepared. The electrical conductivity was measured in the temperature range of 160–300 K. It was found that the electrical conductivity (σ) increases rapidly with the doping of Ni²⁺ ions. At room temperature, the σ is 0.047 S cm^− 1 for the sample with x = 0.06, which is two orders of magnitude larger than that of the CuCrO₂ sample (9.49E− 4 S cm^− 1). The Seebeck coefficients are positive for all samples, which indicate p-type conducting of the samples. The experimental results imply that it is possible to get higher electrical conductivity p-type transparent conducting oxides (TCO) from CuMO₂ by doping with divalent ions.     

Finite size effect on Ni doped nanocrystalline NixZn1 − xFe2O4 (0.1 ≤ x ≤ 0.5)

Nanocrystalline nickel ferrite with different concentration of Ni and Zn (Ni_xZn_1 − xFe₂O₄ where x = 0.1, 0.3, 0.5) were synthesized using chemical co-precipitation method. The effect of doping ion concentration on physical properties like crystalline phase, crystallite size, particle size, and saturation magnetization are investigated. The X-ray diffraction pattern confirms the synthesis of single crystalline Ni_xZn_1 − xFe₂O₄ nanoparticles. The lattice parameter decreases with increase Ni content resulting in reduction of lattice strain. HRTEM images revealed that the as-prepared nanoparticles were crystalline with particle size distribution in 10-30 nm range. The saturation magnetization show the superparamagnetic nature of sample for x = 0.1 and x = 0.3 whereas for x = 0.5, the material is ferromagnetic. The saturation magnetization value is 23.95 emu/gm for Ni_0.1Zn_0.9Fe₂O₄ sample and it increases with increase in Ni content.     

Studies on the structure and gas sensing properties of nickel–cobalt ferrite thin films prepared by spin coating

The influence of Co²⁺ ions content on structure and sensing properties of Ni_1−xCo_xFe₂O₄ (x = 0.25, 0.5, 0.75) thin films deposited on glass substrates by spin coating is presented. Structural characterization evidenced thin films with cubic spinel structures and morphologies dependent on cobalt content. Repartition of cations in spinel tetrahedral and octahedral sites was determined and was found that the presence of Co²⁺ ions in octahedral sites favor the formation of Fe²⁺ species. The sensitivity to some reducing vapor gases (acetone, liquefied petroleum gas LPG, ethyl alcohol and methyl alcohol) was investigated and was found that thin films with x = 0.75 exhibit high sensitivity to ethyl alcohol and thin films with x = 0.25 have high sensitivity to acetone. This sensitivity largely depends on the temperature and test gas concentration and was related to the Fe²⁺ species formed in octahedral sites.     

Soft magnetic and high-frequency properties of Ni-Zn ferrite film with FeMn underlayer

Ni_0.45Zn_0.55Fe₂O₄ (40 nm) single-layer and Fe₅₀Mn₅₀ (25 nm)/Ni_0.45Zn_0.55Fe₂O₄ (40 nm) bilayer films were prepared on Si(111) substrates by radio frequency magnetron sputtering at room temperature, and the influence of FeMn underlayer on the microstructure and magnetic property of Ni-Zn ferrite film has been investigated. It was found that the introduction of Fe₅₀Mn₅₀ underlayer resulted in a decrease from 7.1 to 3.1 kA/m in coercivity and increase from 0.22 to 0.60 in residual magnetization ratio of the ferrite film. The complex permeability μ = μ′ − iμ″ values of the films were measured at a frequency of up to 5 GHz. An obvious resonance peak at about 1.65 GHz of the bilayer film appeared in the permeability spectrum. The reason has been researched preliminarily and was ascribed to the change of the film's microstructure with FeMn underlayer.     

Electrical and dielectric properties of nano crystalline Ni–Co spinel ferrites

Nanocrystalline samples of Ni_xCo₁–_xFe₂O₄, where x = 1, 0.8, 0.6, 0.4, 0.2 and 0, were synthesized by chemical co-precipitation method. The spinel cubic phase formation of Ni–Co ferrite samples was confirmed by X-ray diffraction (XRD) data analysis. All the Bragg lines observed in XRD pattern belong to cubic spinel structure of ferrite. Scanning Electron Microscopy (SEM) technique was used to study the surface morphology of the Ni–Co ferrite samples. Nanocrystalline size of Ni–Co ferrite series was observed in SEM images. Pellets of Ni–Co ferrite were used to study the electrical and dielectric properties. The resistivity measurements were carried out on the samples in the temperature range 300–900 K. Ferrimagnetic to paramagnetic transition temperature (T_c) for all samples was noted from resistivity data. The activation energy below and above T_c was calculated. The dielectric constant (ɛ′) measurements with increasing temperature show two peaks in the temperature range of measurements for all samples under investigation. The peaks observed show frequency and compositional dependences as a function of temperature. Electrical and dielectric properties of nanocrystalline Ni_xCo₁–_xFe₂O₄ samples show unusual behavior in temperature range of 500–750 K. To our knowledge, nobody has discussed such anomalies for nanocrystalline Ni_xCo₁–_xFe₂O₄ at high temperature. Here, we discuss the mechanism responsible for electrical and dielectric behavior of nanocrystalline Ni_xCo₁–_xFe₂O₄ samples.     

Preparation and characterization of NiO, Fe2O3, Ni0.04Zn0.96O and Fe0.03Zn0.97O nanoparticles

Nickel oxide (NiO), iron (III) oxide (Fe₂O₃), and mixed oxide (Ni_0.04Zn_0.96O and Fe_0.03Zn_0.97O) nanoparticles were synthesized by modified sol–gel method. The nanoparticle structural and morphological properties were investigated by infrared spectroscopy (FTIR), X-ray powder diffractometry (XRD), scanning electron microscopy (SEM), and Mössbauer spectroscopy. The mixed oxides were characterized by energy-dispersive X-ray spectroscopy (EDX). The oxide precursor powders were analyzed by thermogravimetry (TG) and differential scanning calorimetry (DSC). The average sizes of the obtained NiO and Ni_0.04Zn_0.96O nanocrystallites were evaluated by X-ray line broadening using Scherrer's equation and were found to be 36 and 23 nm, respectively. Fe₂O₃ and Fe_0.03Zn_0.97O nanoparticles presented similar sizes, around 19 nm. EDX spectroscopy indicated that the calculated compositions of the mixed oxides were nearly consistent with their estimated molar ratios.     

Synthesis of layered Li1.2+x[Ni0.25Mn0.75]0.8−xO2 materials (0 ≤ x ≤ 4/55) via a new simple microwave heating method and their electrochemical properties

Li_1.2+x[Ni_0.25Mn_0.75]_0.8−xO₂ (0 ≤ x ≤ 4/55) was prepared by a new simple microwave heating method and the effect of extra Li⁺ content on electrochemistry of Li_1.2Ni_0.2Mn_0.6O₂ (x = 0) was firstly revealed. X-ray diffraction identified that they had layered α-NaFeO₂ structure (space group R-3m). Linear variation of lattice constant as a function of x value supported the formation of solid solution, that is, extra Li⁺ is possibly incorporated in structure of layered Li_1.2Ni_0.2Mn_0.6O₂ (x = 0), accompanying oxidization of Ni²⁺ to Ni³⁺ to form Li_1.2+x[Ni_0.25Mn_0.75]_0.8−xO₂ (0 ≤ x ≤ 4/55). This was confirmed by X-ray photoelectron spectroscopy that Ni³⁺ appeared and increased in content with increasing x value. Charge–discharge tests showed that Li_1.2+x[Ni_0.25Mn_0.75]_0.8−xO₂ (0 ≤ x ≤ 4/55) truly displayed different electrochemical properties (different initial charge–discharge plots, capacities and cycleability). Li_1.2Ni_0.2Mn_0.6O₂ (x = 0) in this work delivered the highest discharge capacity of 219 mAh g⁻¹ between 4.8 and 2.0 V. Increasing Li content (x value in Li_1.2+x[Ni_0.25Mn_0.75]_0.8−xO₂) reduced charge–discharge capacities, but significantly enhancing cycleability.     

X-Ray Diffraction and Cation Distribution Studies in Zinc-Substituted Nickel Ferrite Nanoparticles

Structural and cation distribution studies on Ni_1?x Zn _x Fe₂O₄ (with x=0.0, 0.2, 0.4, 0.6, 0.8, and 1.0) ferrite nanoparticles by using X-ray diffraction analysis are reported. In this work the Nickel–Zinc ferrites nanoparticles are synthesized by sol–gel auto combustion using respective metal nitrates and citric acid as fuel for the auto combustion reaction. Formation of ferrite nanoparticles having single-phase spinel structure is evident from the obtained X-ray diffraction patterns. Lattice constant values of the Ni_1?x Zn _x Fe₂O₄ ferrite system are found to increase with increase of zinc substitution x. Broad and intense XRD peaks in the patterns indicate the nanocrystalline nature of the produced ferrite samples. Average particle size calculated from most intense Bragg’s reflection (311) using Debye–Scherrer’s formula is found to be 30 nm. The particle size is found to decrease with increase in zinc substitution x. Observed X-ray density is found to decrease with increase in zinc substitution x. Bulk density, porosity, and unit cell volume are also calculated from the XRD data. Distribution of metal cations in the spinel structure estimated from X-ray diffraction data show that along with Ni²⁺ ions most of the Zn²⁺ ions also occupy the octahedral [B] sites, which are attributed to nanosize dimensions of the ferrite samples.     

Comparisons on the properties of (Zn1-xCox)2-W type barium hexaferrite thin films prepared on the Si (100) and (111) substrates

The (Zn_1-xCo_x)₂-W type barium hexaferrite thin films have been prepared by a radio frequency magnetron sputtering method on the Si (100) and the Si (111) substrates respectively. With increasing the annealing temperatures (800, 850, 900, 950, and 1000 °C), the Ba(CoZn)₂Fe₁₆O₂₇ phases emerge from the amorphous matrix. The hexaferrite thin films on Si (111) substrates have a larger saturation magnetic field (636.6 kA/m) than those on Si (100) substrates (159.1 kA/m). The magnetic hysteresis measurements show that they exhibit an isotropic behavior for thin films deposited on both substrates. Films on the Si (111) substrates are magnetically harder than those on the Si (100) substrates.     

Synthesis, characterization and magnetic properties of nanocrystalline Ni-Zn-Co ferrites

Nanocrystalline magnetic particles of Ni_0.7−xZn_0.3Co_xFe₂O₄ with x lying between 0.0 and 0.3 were synthesized by combustion method using metal nitrates, sucrose and polyvinyl alcohol (PVA). The synthesized powders where characterized by X-ray diffraction and Transmission electron microscopy (TEM). The average crystallite size determined from XRD data using Scherrer formula lie in the range of 20-30 nm. TEM micrographs show a well defined nano-crystallite state with an average particle size of around ~ 10 nm. The electron diffraction patterns confirm the spinel crystal structure of the ferrite. Magnetic properties measured at room temperature by vibrating sample magnetometer (VSM) reveal an increase in saturation magnetization with increase in cobalt concentration. Non-linear increase in saturation magnetization is related to surface effects and method of preparation.     

Magnetic and dielectric properties of Co–Zn ferrite

Nanocrystalline powders of Co substituted Zn ferrite with the chemical formula Co_xZn_1−xFe₂O₄ (x = 0, 0.2, 0.4, 0.6, 0.8, 1) were synthesized by sol–gel autocombustion method using tartaric acid as fuel agent. The samples were sintered in static air atmosphere for 7 h at 773 K, 7 h at 973 K and 10 h at 1173 K. The organic phase extinction and the spinel phase formation were monitored by means of Fourier transform infrared spectroscopy. The X-ray diffraction patterns analysis confirmed the spinel single phase accomplishment. Crystallite size, average grains size, lattice parameter and cation distribution were estimated. Magnetic behavior of the as-obtained samples by means of M-H hysteresis measurements was studied at room temperature. Permeability and dielectric permittivity at room temperature versus frequency was the subject of a comparative study for the Co_xZn_1−xFe₂O₄ series. In agreement with the proposed cation distribution the sample with Co_0.8Zn_0.2Fe₂O₄ formula exhibits the optimal magnetic and dielectric properties.     

Magnetic softness and interparticle exchange interactions of (Fe65Co35)1 − x(Al2O3)x (x = 0-0.50) nanogranular films

The effect of Al₂O₃ content on the structure, electrical properties, magnetic properties, and interparticle exchange interactions of (Fe₆₅Co₃₅)_1 − x(Al₂O₃)_x films with Al₂O₃ volume fractions x ranging from 0 to 0.50 was systematically investigated. Among the films with x between 0 and 0.25, the lowest coercivity of 0.56 kA/m was achieved in the (Fe₆₅Co₃₅)_0.82(Al₂O₃)_0.18 film. This is ascribed to the strongest exchange interactions between the Fe₆₅Co₃₅ nanoparticles in this film. Combined with the microstructure analysis of the (Fe₆₅Co₃₅)_1 − x(Al₂O₃)_x films, the modified Herzer's model was extended to interpret the variation of the coercivity with x and analyze the effect of the exchange interactions between the Fe₆₅Co₃₅ nanoparticles on the magnetic softness. The remanence curves confirm the existence of the exchange interactions and reveal the evolution of the exchange interaction strength with Al₂O₃ content.     

Low temperature synthesis of nanosized Mn<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Zn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Fe<Subscript>2</Subscript>O<Subscript>4</Subscript> ferrites and their characterizations

Nanosized Mn_1−x Zn _x Fe₂O₄ (x = 0, 0·1, 0·3, 0·5, 0·6, 0·7, 0·9) mixed ferrite samples of particle size < 12 nm were prepared using the co-precipitation technique by doping the Zn²⁺ ion impurities. Autoclave was employed to maintain constant temperature of 80°C and a constant pressure. The X-ray analysis and the IR spectrum analysis were carried out to confirm the spinel phase formation as well as to ascertain the cation distribution in the ferrite samples. This clearly points to the fact that the Zn²⁺ ion’s presence is not restricted to A-site alone for some of the Mn-Zn ferrite series. The real part of a.c. susceptibility measurements clearly indicated the superparamagnetic behaviour of the ferrite samples. There is a systematic decrease in the particle size, Curie temperature and magnetization with the increase in the Zn²⁺ ion doping, measured using magneto thermal gravimetric analysis (MTGA) and vibrating sample magnetometer (VSM), respectively. The lattice constant is found to be constantly decreasing till x = 0·6 and beyond this an unusual slight increase in the lattice constant is found.     

Synthesis of nanocrystalline Ni0.5Zn0.5Fe2O4 ferrite and study of its magnetic behavior at different temperatures

Ni_0.5Zn_0.5Fe₂O₄ ferrite nanocrystals with average diameter in the range of 1–2 nm have been synthesized by reverse microemulsion. X-ray diffraction (XRD), transmission electron microscopy (TEM) and vibrating sample magnetometer (VSM) are used to characterize the structural, morphological and magnetic properties. X-ray analysis showed that the nanocrystals possess cubic spinel structure. The absence of hysteresis, negligible remanence and coercivity at 300 K indicate the superparamagnetic character and single domain in the nanocrystalline Ni_0.5Zn_0.5Fe₂O₄ ferrite materials. The nanocrystalline Ni_0.5Zn_0.5Fe₂O₄ ferrite were annealed at 600 °C. As a result of heat treatment the average particle size increases from 2 nm to 5 nm and the corresponding magnetization values have increased to 21.69 emu/g at 300 K. However, at low temperature of 100 K, the annealed samples show hysteresis loop which is the characteristic of a superparamagnetic to ferromagnetic transition. In addition, a comparative study of the magnetic properties of Ni_0.5Zn_0.5Fe₂O₄ ferrite nanocrystals obtained from reverse microemulsion has been carried out with those obtained from the general chemical co-precipitation route.     

Microstructure and magnetic properties of BaTiO3-(Ni,Zn)Fe2O4 multiferroics

The microstructures of composite xBaTiO₃-(1−x)(Ni_0.5Zn_0.5)Fe₂O₄ (BT-NZF) multiferroics with various mixing ratios (x = 0.50, 0.60 and 0.70) are investigated by means of electron backscatter diffraction (EBSD) and magnetic force microscopy (MFM). The EBSD measurements reveal a change in the texture of the ferrite and the BaTiO₃ grains upon increasing the ferrite content in the sample. The sample with x = 0.70 exhibits the best ferrite texture, where only some directions are present. Furthermore, the resulting grain sizes vary from several µm (x = 0.50) to about 100 nm in the sample with x = 0.70. The MFM images reveal the presence of magnetic domains being extended over several adjacent grains, which according to the EBSD data may comprise different crystallographic orientations. In this way, we can explain the differences in the magnetic contrast obtained.