A comparative study of the magnetic and microwave properties of Al3+ and In3+ substituted Mg–Mn ferrites

The effect of substitution of diamagnetic Al³⁺ and In³⁺ ions for partial Fe³⁺ ions in a spinel lattice on the magnetic and microwave properties of magnesium–manganese (Mg–Mn) ferrites has been studied. Three kinds of Mg–Mn based ferrites with compositions of Mg_0.9Mn_0.1Fe₂O₄, Mg_0.9Mn_0.1Al_0.1Fe_1.9O₄, and Mg_0.9Mn_0.1In_0.1Fe_1.9O₄ were prepared by the solid-state reaction route. Each mixture of high-purity starting materials (oxide powders) in stoichiometric amounts was calcined at 1100 °C for 4 h, and the debinded green compacts were sintered at 1350 °C for 4 h. XRD examination confirmed that the sintered ferrite samples had a single-phase cubic spinel structure. The incorporation of Al³⁺ or In³⁺ ions in place of Fe³⁺ ions in Mg–Mn ferrites increased the average particle size, decreased the Curie temperature, and resulted in a broader resonance linewidth as compared to un-substituted Mg–Mn ferrites in the X-band. In this study, the In³⁺ substituted Mg–Mn ferrites exhibited the highest saturation magnetization of 35.7 emu/g, the lowest coercivity of 4.1 Oe, and the highest Q×f value of 1050 GHz at a frequency of 6.5 GHz.     

Chromium substituted copper ferrites via gluconate precursor route

CuFe_2−xCr_xO₄ spinel (0≤x≤2) powders were synthesized by a soft chemistry method—the gluconate multimetallic complex precursor route. The complex precursors were characterized by elemental chemical analysis, infrared (IR) and ultraviolet–visible (UV–vis) spectroscopy, thermal analysis and Mössbauer spectroscopy. The oxide powders were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), IR, Raman and Mössbauer spectroscopy. It was shown that the structure, morphology and magnetic properties of the obtained spinel powders depend on the concentration of Cr³⁺ ion. The XRD of the chromium substituted copper ferrite powders calcined at 700 °C/1 h indicated the formation of a cubic spinel type structure for x=0.5, 1.0 and a tetragonal structure for x=0, 0.2, 2. The crystallite size ranged from 19 nm to 39 nm. The Mössbauer spectroscopy revealed the site occupancy of iron ions, relative abundance and internal hyperfine magnetic fields in both tetrahedral and cubic CuFe_2−xCr_xO₄ spinels.     

Microwave dielectric properties and cation distributions of Zn1-3xAl2+2xO4 ceramics with defect structures

The spinel-structured Zn_1-3xAl_2+2xO₄ (x = 0–0.2) ceramics having defective structures were synthesized using the molten salt method, and their microwave dielectric properties and cation distributions were assessed. The ²⁷Al solid-state nuclear magnetic resonance spectra of these ceramics demonstrate that they have an intermediate spinel structure in which the tetrahedral site occupancy increases from 0.03 to 0.64 as x increases. Moreover, crystal structure refinements suggest that cation vacancies are located at octahedral sites for x = 0.1 and 0.2. Based on these data, the introduction of cation vacancies at octahedral sites appears to enhance the preferential occupation of tetrahedral sites by Al³⁺. The ε_r of these ceramics slightly decreased from 8.5 to 8.2 with increasing x, while the Q·f value increased significantly, from 127,532 to 202,468 GHz, upon the introduction of cation vacancies. An intermediate spinel structure with preferential occupancy of tetrahedral sites by trivalent cations exhibits an enhanced Q·f value.     

Nanocrystalline/nanosized manganese substituted nickel ferrites – Ni1−xMnxFe2O4 obtained by ceramic-mechanical milling route

Manganese substituted nickel ferrites, Ni_1−xMn_xFe₂O₄ (x=0, 0.3, 0.5 and 0.7) have been obtained by a combined method, heat treatment and subsequent mechanical milling. The samples were characterised by X-ray diffraction, differential scanning calorimetry and magnetic measurements. The increase of the Mn²⁺ cations amount into the spinel structure leads to a significant expansion of the cubic spinel structure lattice parameter. The crystallite size decreases with increasing milling time up to 120 min, more rapidly for the nickel–manganese ferrites with a large amount of Mn²⁺ cations (x=0.7). After only 15 min of milling the mean crystallites size is less than 25 nm for all synthesised ferrites. The Néel temperature decreases by increasing Mn²⁺ cation amount from 585 °C for x=0 up to 380 °C for x=0.7. The magnetisation of the ferrite increases by introducing more manganese cations into the spinel structure. The magnetisation of the milled samples decreases by increasing milling time for each ratio among Ni and Mn cations and tends to be difficult to saturate, a behaviour assigned to the spin canted effect.     

Structural and magnetic properties of nanocrystalline zinc-doped metal ferrites (metal=Ni; Mn; Cu) prepared by sol–gel combustion method

In this work, nanocrystalline M–Zn ferrites (M=Ni; Mn; Cu) with compositions of M_1?xZn_xFe₂O₄ (x=0.0, 0.2 and 0.4) were synthesized from metal nitrate precursors by rapid the sol–gel combustion method using diethanolamine (DEA) as the fuel. As-synthesized powders were calcined at 1000 °C for 4 h. The crystal structures and morphologies of these compounds were characterized by X-ray diffraction (XRD) and field-emission scanning electron microscopy (FE-SEM), respectively. The chemical interaction of ferrite powders was investigated by Fourier transform infrared spectroscopy (FTIR). The magnetic properties of after-calcined nanoparticles were measured at room temperature using a vibrating sample magnetometer (VSM). The single phase spinel cubic structure formation is confirmed by XRD and FTIR results. Meanwhile FE-SEM micrographs show the appearance of both undoped and Zn-doped ferrite ceramic samples. In addition, the VSM analyses indicate that the Zn content has a significant influence on the magnetic properties such as saturation magnetization (M_s) and coercivity (H_c).     

Preparation of Ni1−xMnxFe2O4 ferrites by sol–gel method and study of their cation distribution

The spinel ferrite nanoparticles of the system Ni_1?xMn_xFe₂O₄ with x=0.0, 0.1, 0.3, 0.5, 0.7 and 0.9 were prepared by sol–gel auto combustion technique using chlorides of Ni, Mn and Fe as a source with citric acid as chelating agent. The structure of the ferrite materials and the particle size were determined by XRD, it was observed that the structure was a single phase, face centered cubic with lattice parameter ranging from 8.365 Å to 8.394 Å and the particle size ranging from 23.86 Å to 38.30 Å. The lattice parameter showed a linear dependence on concentration in accordance with the Vegard's law. By analyzing XRD patterns, the cation distribution over A and B-sites was estimated through the R-Factor method. The magnetic moment for each sample was determined from cation distribution on the two sites. An enhancement in the net magnetic moment was observed with gradual increase in the Mn content.     

Microwave dielectric properties and crystal structures of spinel-structured MgAl2O4 ceramics synthesized by a molten-salt method

The microwave dielectric properties and crystal structures of MgAl₂O₄ ceramics synthesized using either molten-salt (MA-M) or solid-state reaction (MA-S) methods were characterized in this study. Raman and ²⁷Al solid-state nuclear magnetic resonance spectra indicated that Al³⁺ cations primarily occupied in tetrahedral sites of the MA-M ceramic. The degree of inversion x, i.e., degree of cation disorder in tetrahedral and octahedral sites, of the MA-M was higher than that of MA-S; such the preferential site occupation of Al³⁺ cations enhanced the covalency of the MO bonds in the MO₄ tetrahedra (M = Mg and Al), leading to a decrease in the lattice parameters. The Q·f of the MA-M fired at 1600 °C was 201,690 GHz, while the MA-S synthesized at 1600 °C exhibited a Q·f of just 85,100 GHz. Based on these results, an intermediate spinel structure with a greater x evidently has a higher Q·f, and therefore the cation distribution is closely related to the Q·f of the ceramic.     

Structural and electrical properties of MgO-doped Mn1.4Ni1.2Co0.4−xMgxO4 (0 ≤ x ≤ 0.25) NTC thermistors

We have prepared polycrystalline Mn_1.4Ni_1.2Co_0.4−xMg_xO₄ (0 ≤ x ≤ 0.25) samples using a solid-state reaction process and investigated the MgO doping effect on the microstructure and the electrical properties. It was found that, as the amount of Mg content in the Mn_1.4Ni_1.2Co_0.4−xMg_xO₄ samples increased, both the grain size and density decreased. The as-sintered Mn_1.4Ni_1.2Co_0.4−xMg_xO₄ samples contained Mn- and Ni-rich phases with cubic spinel structure. The MgO-doped Mn_1.4Ni_1.2Co_0.4−xMg_xO₄ negative temperature coefficient (NTC) thermistors provided various electrical properties, depending on Mg content. The electrical resistivity, B_25/85 constant, and activation energy of the Mn_1.4Ni_1.2Co_0.4−xMg_xO₄ NTC thermistors increased with increasing Mg content. The values of ρ₂₅, B_25/85 constant, and activation energy of the NTC thermistors were 11,185–20,016 Ω cm, 3635–4032 K, and 0.313–0.348 eV, respectively.     

Blue-violet ceramic pigments based on Co and Mg Co2−xMgxP2O7 diphosphates

Solid solutions of Co and Mg diphosphates with compositions Co_2?xMg_xP₂O₇ (x = 0, 0.1, 0.2, 0.3, 0.5, 0.7, 1.0, 1.5 and 1.8) have been prepared and characterized for the first time as alternative low-toxicity blue ceramic pigments. The compositions were prepared through the conventional coprecipitation route and calcined up to 1000 °C/2 h. Samples were characterized by thermal analysis, XRD, SEM/EDX, UV–vis-NIR spectroscopy and colour measurements (CIE-L^*a^*b^*). Isostructural Co_2?xMg_xP₂O₇ diphosphate solid solutions (monoclinic system and P21/c spatial group) formed successfully within the studied range of compositions, accompanied only by a minor quantity of residual Co or Mg orthophosphates (M₃(PO₄)₂). Interestingly, the obtained solid solutions developed nice blue-violet colourations even with high Mg doping after enamelling within double-firing (x = 1.5–1.8) and single-firing (x = 1.0–1.5) ceramic glasses. These optimal compositions containing a minimized Co amount (measured values around 7–16 wt%) could be therefore less toxic alternatives to the conventional Co₃(PO₄)₂ blue ceramic pigment.     

Cation distribution and magnetic analysis of wideband microwave absorptive CoxNi1−xFe2O4 ferrites

Co_xNi_1−xFe₂O₄ ferrites (x=0, 0.2, 0.4, 0.4, 0.6, 0.8 and 1) were prepared by a sol-gel auto-combustion method. The samples were structurally characterized by X-ray diffractometry (XRD), field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray analysis (EDX), and Fourier transform infrared spectroscopy (FTIR). The XRD patterns confirmed single phase formation of spinel structure. Cation distribution estimated from XRD data suggested the mixed spinel structure of ferrite. The EDX analysis was in good agreement with the nominal composition. The results of FTIR analysis indicated that the functional groups of Co-Ni spinel ferrite were formed during the combustion process. According to FE-SEM micrographs, by addition of cobalt ion the average particle size of substituted nickel ferrite was gradually became smaller from 450 nm to 280 nm. Magnetic measurement using vibrating sample magnetometer (VSM) showed an increase in saturation magnetization and coercivity by Co²⁺ substitution in nickel ferrite. For Co_0.8Ni_0.2Fe₂O₄ sample, M_s and H_c reaches as high as 93 emu/g and 420 Oe, respectively. The reflection loss properties of the nanocomposites were investigated in the frequency range of 8–12 GHz, using vector network analyzer (VNA). Cobalt substitution could enhance reflection loss of NiFe₂O₄ ferrite. The maximum reflection loss value of the Co²⁺ substituted Ni ferrite was ~ −26 dB (i.e. over 99% absorption) at 9.7 GHz with bandwidth of 4 GHz (RL<– 10 dB) through the entire frequency range of X-band.     

Synthesis of Mg0.48Cu0.12Zn0.40Fe2O4 ferrite and its aptness for multilayer chip component application

Here we reported the synthesis of MgCuZn ferrite (Mg_0.48Cu_0.12Zn_0.40Fe₂O₄) by ceramic and self-sustaining auto-combustion (sucrose) methods. Required oxides in powder form were processed (hand mill=3 h, pre-sinter=600 °C for 180 min and final sinter=910 °C for 9 h) to obtain the ferrite sample through the ceramic methods. Whereas, aqueous metal nitrates along with the sucrose as fuel were processed (at 200 °C, final sinter=600 °C for 180 min) to obtain ferrite product via the auto-combustion route. As-synthesized ferrite samples were then subjected to crystallographic, structural and magnetic investigations by techniques viz. X-ray diffraction, IR spectroscopy and B–H measurements. Purity and phase formation were confirmed by XRD examinations. Cation redistribution was also suggested by XRD analyses which supplement the variation of magnetic properties. IR absorption bands were found to be in the expected high frequency range (574.95 cm^?1 and 582.39 cm^?1) and low frequency range (≈431 cm^?1) which fortifies the spinel phase formation. Boost in magnetic performance of sucrose methods' yield was observed owing to reduced porosity and increased surface area. Thus, MgCuZn ferrite prepared via the self-sustaining auto-combustion route has superior magnetic properties at relatively low sintering temperature and can be employed in multi-layer chip application readily.     

Layered particle-based polymer composites for coatings: Part I. Evaluation of layered double hydroxides

Layered double hydroxides (LDH) suitable as fillers for the formulation of waterborne polyurethane (WPU) nanocomposites in coating applications are designed and characterized. Their elaboration follows a simple and reproducible process leading to samples without impurity. The attention is paid to the impact of the LDH nature (M_xAl/CO₃^2?, M = Mg and/or Zn, and x = 2, 3 and 4) on the structure characteristics, i.e. cell parameters and coherent domain dimensions. Focusing on two end-member phases M₂Al/CO₃^2?, M = Mg or Zn, the microstructural characterization performed from X-ray diffraction peak profile analyses permits to point out larger coherent domain sizes for Zn₂Al species than for Mg₂Al ones, and then to correlate with the “macroscopic” crystallinity of the samples. The evolution of LDH slurries over time is tentatively considered in a prediction interest. The stability of a chosen organic–inorganic hybrid, taken Mg₂Al as inorganic host structure with anions of the 4-aminobenzene sulfonic acid (4-ABSA), is studied as function of its carbonate contamination in time. Finally, the dispersion of LDH fillers in WPU is scrutinized in terms of WPU/LDH structure revealed by indirect and direct observations, XRD and TEM, respectively.     

Synthesis of nanocrystalline Mg0.6Cd0.4Fe2O4 ferrite by glycine-nitrate auto-combustion method and investigation of its microstructure and magnetic properties

Nanocrystalline Mg_0.6Cd_0.4Fe₂O₄ ferrite powders were produced by the glycine-nitrate auto-combustion method for the first time. The influence of the different molar ratios of glycine-to-nitrate G.N⁻¹) on the characteristics of the prepared powders was systematically investigated by X-ray diffraction (XRD), inductively coupled plasma optical emission spectroscopy (ICP-OES), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), field-emission scanning electron microscopy (FE-SEM) and vibrating sample magnetometry (VSM). Thermodynamic calculations revealed that the adiabatic flame temperature changes from 598.79 K to 1757.97 K by increasing the G.N⁻¹ ratios from 0.30 to 0.85. The results confirmed that under fuel-lean combustion (G.N⁻¹ = 0.30), Mg_0.6Cd_0.4Fe₂O₄ nanoparticles can be obtained at a significantly lower temperature and shorter synthesis time, compared to other preparation methods like standard ceramic and co-precipitation. The XRD and ICP results showed that the crystallite size of the powders changes in the range of 8–43 nm, and their Cd content notably decreases with increasing the G.N⁻¹ values. The FE-SEM results proved that the porosity and size of the as-prepared ferrite nanoparticles drastically change with variations in the G.N⁻¹ ratio. The evolution of phase, crystallite/particle size, and magnetic properties after annealing was discussed in detail. At the optimized annealing condition, the synthesized Mg_0.6Cd_0.4Fe₂O₄ ferrite offered a high saturation magnetization of 41.70 Am² kg⁻¹ and a coercivity of 1.92 kA m⁻¹, indicating noticeably better soft magnetic properties compared to the same ferrite produced by the other wet chemical methods.     

LiMgxMn2−xO4 (x≤0.10) cathode materials with high rate performance prepared by molten-salt combustion at low temperature

LiMg_xMn_2−xO₄ (x≤0.10) cathode materials for lithium-ion batteries were prepared by molten-salt combustion and then structurally characterized by powder X-ray diffraction. All the cathode materials were identified as the spinel structure of LiMn₂O₄ and the lattice parameter decreased as the Mg content of LiMg_xMn_2−xO₄ increased. Scanning electron microscopy revealed that the average particle size and agglomeration decreased with increasing Mg content. Galvanostatic charge–discharge experiments showed that Mg doping could effectively enhance the cycling performance of the cathode materials. LiMg_0.05Mn_1.95O₄ demonstrated excellent electrochemical performance with an initial discharge specific capacity of 122.0 mA h g⁻¹ and capacity retention of 86.4% after 100 cycles at 0.5 C (1 C=148 mA g⁻¹). Rate performance, cyclic voltammetry and electrochemical impedance spectroscopy measurements showed that the Mg-doped spinels had high rate capability and reversible cycling performance.     

Frequency and temperature dependent electrical properties of Ni0.7Zn0.3CrxFe2−xO4 (0 ≤ x ≤ 0.5)

Series of the ferrite samples with a chemical formula Ni_0.7Zn_0.3Cr_xFe_2?xO₄ (x = 0.0–0.5) were prepared by a sol–gel auto-combustion method and annealed at 600 °C for 4 h. The prepared samples have the cubic spinel structure with no impurity phase. As the Cr³⁺ content x increases, the unit cell dimensions decrease with an increase in Cr³⁺ content x. The crystallite size is decreases from 37 nm to 21 nm as the Cr³⁺ content increases from x = 0.0 to 0.5. Resistivity increases whereas dielectric constant decreases with an increase in Cr³⁺ content x. Maxima in the dielectric loss tangent versus frequency appear when the frequency of the hopping charge carriers coincides with the frequency of the applied alternating field. Dielectric constant and dielectric loss tangent increases with increase in temperature. Saturation magnetization of sintered samples showed higher values as compared to as-prepared sample. Curie temperature deduced from AC susceptibility data decreases with increasing x.     

Microstructure and high-temperature thermoelectric properties of polycrystalline CuAl1−xMgxO2 ceramics

We investigated the effect of Mg-substitution on the microstructure and high-temperature thermoelectric properties of CuAl_1−xMg_xO₂ (0 ≤ x ≤ 0.2) fabricated by the tape casting method. The sintered CuAl_1−xMg_xO₂ bodies crystallized in CuAl_1−xMg_xO₂ solid solutions along with MgAl₂O₄ and Cu₂MgO₃ phases. Mg substitution up to x = 0.12 in the CuAl_1−xMg_xO₂ yielded a higher electrical conductivity and lower Seebeck coefficient mainly because of an enhanced carrier density. The highest value of the power factor (3.47 × 10⁻⁵ W m⁻¹ K⁻²) was attained for CuAl_0.88Mg_0.12O₂ at 800 °C. It is demonstrated that Mg substitution is highly effective for improving high-temperature thermoelectric properties.     

Structural,electrical, and magnetic properties of Zn substituted magnesium ferrite

Zinc substituted magnesium (Mg–Zn) ferrites with the general formula Mg_1−xZn_xFe₂O₄ (x=0.00, 0.25, 0.50, 0.75, and 1.00) were prepared using the solution combustion route. The dried powder after calcination (700 °C for 2 h) was compacted and sintered at 1050 °C for 3 h. The structural, morphological, dielectric and magnetic properties of the sintered ferrites were studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), impedance spectroscopy, and vibration sample magnetometry (VSM). The XRD analysis of sintered samples confirmed that the expected spinel cubic phase was formed for all samples. The crystallite sizes evaluated using Scherre's formula were found to be in the range of 47–80 nm. SEM analysis showed homogeneous grains with a polyhedral structure. The electrical conductivity increased with increasing frequency, which is normal dielectric behavior for such materials. The dielectric constant, dielectric loss tangent, and AC conductivity were found to be lowest for x=0.50. The VSM results showed that the zinc concentration had a significant influence on the saturation magnetization and coercivity.     

Catalytic properties in N2O decomposition of mixed cobalt–iron spinels

The effect of introduction of iron in the Co_3 − xFe_xO₄ on catalytic activity in N₂O decomposition was investigated. The spinel catalysts were characterized by XRD, SEM, RS, BET methods, work function measurements and Mössbauer spectroscopy. Introduction of iron in the Co_3 − xFe_xO₄ spinel catalysts at the level of x < 1 leads to preferential substitution of Fe³⁺ in tetrahedral sites, whereas for x > 1 also octahedral ones are substituted. A strong correlation between deN₂O activity (T_50%) and work function was observed showing that electronic factor controls the catalytic reactivity of Co–Fe spinels. The results revealed that the active centers for N₂O decomposition are cobalt ions and thus even a low level of their substitution by iron leads to substantial decrease of the deN₂O activity of the cobalt spinel.     

Sol-gel synthesis of MnxGa1−xFe2O4 nanoparticles as candidates for hyperthermia treatment

Sol-gel synthesis of novel Mn_xGa_1−xFe₂O₄ (x=0–1) magnetic nanoparticles (MNP's) was studied. An inverse spinel crystalline structure was identified for all samples. Magnetization saturation values (Ms) were in the range of 21.4–42.6 emu/g, while coercive field (Hc) was less than 27.4 Oe in all cases. Selected compositions of Mn_xGa_1−xFe₂O₄ (x=0.6, 0.8) showed nanoparticles with near-spherical morphology and average size of 15 nm. Magnetic induction curves indicate that a suspension concentration of MNP's equal or higher than 4.5 mg/mL was sufficient to reach the temperature required for hyperthermia treatment (>43 °C) in less than 10 min. The incorporation of Mn ions into the crystalline structure led to an increase of the magnetic response of the MNP's when an alternate magnetic field was applied, requiring a shorter time of exposition and a low dose of MNP's, which make these nanoparticles potential candidates for magnetic hyperthermia.     

Structural and optical characterization of Zn0.95−xMg0.05AlxO nanoparticles

The structural and optical properties of ZnO nanoparticles doped simultaneously with Mg and Al were investigated. XRD results revealed the hexagonal wurtzite crystalline structure of ZnO. The FE-SEM study confirmed the formation of nano-sized homogeneous grains whose sizes decreased monotonously with increasing doping concentrations of Mg and Al. The absorption spectra showed that band gap increased from 3.20 to 3.31 eV with Mg doping. As the Al concentration changed from x=0.01 to x=0.06 mol% at constant Mg concentration the band gap observed to be decreased. Particle sizes estimated from effective mass approximation using absorption data and these values are in good agreement with the crystallite sizes calculated from XRD data. Raman spectra of ZnO showed a characteristic peak at 436 cm⁻¹ correspond to a non-polar optical phonon E₂ (high). With increase of the Al doping concentrations, E₂ (high) phonon frequency shifted to 439 cm⁻¹ from to 436 cm⁻¹. The origin of E₂ (high) peak shift in ZnO nanoparticles is attributed to optical phonon confinement effects or the presence of intrinsic defects on the nanoparticles. PL spectra indicated that with increase of Al co-doping along with Mg into ZnO, intensity of the peak positioned at 395 nm was initially increased at x=0 and then decreased with increase of the Al concentrations from x=0.01 to x=0.06 mol%.