Effect of holmium on the magnetic and electrical properties of barium based W-type hexagonal ferrites

A series of BaHo_xFe_16−xO₂₇ (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0) W-type hexagonal ferrites were prepared by co-precipitation technique at high annealing temperature of 1320 °C. XRD reveals single W-type hexagonal phase in these ferrites. The grain size is measured by SEM analysis using line intercept method. Saturation magnetization, retentivity and coercivity were measured from MH-loops taken on VSM. It was observed that magnetization increases with the increase of Ho content due to difference in ionic radii of Ho³⁺ (0.901 Å) and Fe³⁺ (0.67 Å) ions. Room temperature dc resistivity increases as a function of Ho³⁺ that may be due to separation between grains. The dc electrical resistivity decreases as a function of temperature which indicates the semi-conducting behavior of the samples.     

Stress evolution in CoxFe1−x (x = 0.33-0.87) electrodeposited films

Electrodeposition of 0.5 μm thick Co_xFe_1−x (x = 0.33-0.87) films was carried out from a sulfate/chloride plating solution containing saccharin as an organic additive at constant current density and a controlled pH 2.3. The increase of Fe²⁺ concentrations in plating solution resulted in an increase of Fe-content and tensile stress in Co_xFe_1−x films, which is accompanied by a decrease of plating rate. Several possible origins for generation of tensile stress include the following: interfacial stress between CoFe films and Cu-substrate, crystal texture and grain size, coalescence and stress evolution during film growth, and hydrogen adsorption/desorption. The adsorption/desorption mechanism of hydrogen seems to be the most likely dominant stress mechanism. The relationship between increase of the tensile stress and decrease of plating rate was discussed.     

Fe doping and magnetic properties of zincblende SiC ceramics

Fe-doped SiC bulk ceramics were fabricated by hot-pressing, and their magnetic and electronic properties were investigated. Si_1−xFe_xC (x ≤ 0.04) samples having a zincblende crystal structure exhibited ferromagnetic hysteresis at room temperature with the saturation magnetization increasing with x. X-ray diffraction measurements revealed the creation of a Fe₃Si phase in the samples with its density increasing with x. The samples were found to be p-type semiconductors with a hole concentration (electrical resistivity) of ∼10¹⁹ cm⁻³ (∼10⁰ Ω cm) at room temperature. The observed magnetic properties of the samples are mainly ascribed to the presence of ferromagnetic Fe₃Si crystallites. The high carrier concentration of the samples likely implies the existence of acceptors due to individual Fe³⁺ occupation of the Si sites in the lattice. The randomly distributed Fe³⁺ ions represent a minor contribution to the magnetization of the samples through the formation of magnetic polarons with the carriers.     

Structural, morphological, magnetic and optical properties of chromium substituted strontium ferrites, SrCrxFe12 − xO19 (x = 0.5, 1.0, 1.5, 2.0 and 2.5) annealed with potassium halides

Chromium substituted strontium ferrites SrCr_xFe_12 − xO₁₉ (x = 0.5, 1.0, 1.5, 2.0 and 2.5) have been synthesized via sol gel method and the dry gels obtained have been annealed with various inorganic template agents (KCl, KBr and KI). The powder X ray diffraction studies reveal a crystallite size of ~ 40-45 nm. The use of KCl as inorganic template agent leads to an increase in the crystallite size. This may be attributed to the fact that the coordination ability of Cl⁻ is maximum due to its larger charge to size ratio, which promotes crystal growth in one dimension leading to needle-like morphology. On the other hand, KI undergoes sublimation to form I₂ which gets entrapped in the strontium ferrite crystal leading to a bubble-like morphology. A systematic change in the lattice constants, a and c, is not observed because the radius of Cr³⁺ ion (0.63 Å) is similar to that of Fe³⁺ ion (0.64 Å). The saturation magnetization decreases with increase in the chromium concentration from 43.03 emu/g to 17.40 emu/g due to the substitution of Fe³⁺ ions by less magnetic Cr³⁺ ions in 2a and 12k sites of the lattice. The coercivity decreases with increase in the chromium concentration due to decrease in magnetocrystalline anisotropy. In the presence of KCl and KBr, both saturation magnetization and coercivity increase and the saturation magnetization has the maximum value in case of samples annealed with KBr. However, with KI, the values of both saturation magnetization and coercivity decrease sharply which may be due to lower crystallinity due to bubble-like morphology because of the decomposition of KI to I₂. The energy band gap for all the ferrite compositions is found to be ~ 2.2 eV and its value increases in the samples annealed with KI.     

Sintering behavior and electromagnetic properties of Fe-deficient NiZn ferrites

Sintering behavior and electromagnetic properties of Ni_0.5Zn_0.5Fe_2−xO_4−3/2x ferrite (x = 0, 0.4, 0.8) by the sol–gel method are investigated. Fe deficiency in the composition enhances sintering and retards grain growth. The near fully dense Fe-deficient samples could be obtained at a sintering temperature as low as 1120 °C and the highest relative density appears in the x = 0.8 sample sintered at 1150 °C. Second phase zincite ZnO resulting from Fe deficiency plays an important role in spinel NiZn ferrites by acting as a grain growth inhibitor and the grain growth of NiZn ferrite is effectively suppressed. When the sintering temperature is above 1200 °C, extensive grain growth occurs due to the probability of serious volatilization of zinc at high temperatures. The ratio of Ni to Zn of NiZn ferrites increases with increasing Fe deficiency due to the separation of zinc from spinel lattice, which results in the decrease in initial permeability and the increase in Curie temperature and resonant frequency.     

Structure,magnetic and electrical transport properties of the perovskites Sm1−xCaxFe1−xMnxO3

The structure of series Sm_1−xCa_xFe_1−xMn_xO₃ (0.0 ≤ x ≤ 1.0) compounds was investigated. The lattice parameters increase with coupled substitution Sm³⁺ by Ca²⁺ and Mn⁴⁺ for Fe³⁺. The variation of parameter, c, is larger than that of a and b, respectivly. The detailed analysis of magnetic properties of series Sm_1−xCa_xFe_1−xMn_xO₃ (0.1 ≤ x ≤ 0.9) shows that local magnetic interaction between Fe³⁺ and Fe³⁺ and Mn⁴⁺ and Mn⁴⁺ at below magnetic transition temperature is antiferromagnetic. Above magnetic transition temperature the presence of large magnetic cluster is proposed and the sizes of magnetic clusters decrease with Mn⁴⁺. The electrical transport behaviors related with small polaron hopping and variable range hopping models.     

Effect of Bi-substitution on the microstructure and electromagnetic properties of YCaZrVIG with low sintering temperature

Bi substituted YCaZrVIG ferrites, Y_2.3−xBi_xCa_0.7Zr_0.3V_0.2Fe_4.42O₁₂ (x=0.1, 0.25, 0.4, 0.5, 0.75) ferrites were prepared by conventional oxide method. The addition of Bi₂O₃ promoted the sintering performance and lowered the sintering temperature from 1420–1230 °C. However, it also resulted in the formation of minor second phases and the decrease of grain size. With the increase of Bi concentration, the dielectric constant increases linearly and then remains unchanged. The dielectric loss decreased firstly and then increased. The saturation magnetization (4πM_s) almost retained unchanged as the Bi concentration increased except for the sample with 0.75. The coercivity (H_c) decreased firstly and reached the minimum of 1.32 Oe at 0.25, and then rose when x>0.25, which was related to the facility of magnetic domain wall motion and magnetic moment reverse. Moderate addition of Bi also can increase the remanence (B_r) by improving sintering process. Additionally, we got the optimum electromagnetic properties in the samples with x=0.25 at 1230 °C: RD>97%, ε_r=15.7, tan δ_e=2.48×10⁻⁴, H_c=1.32Oe, 4πM_S=1663 Gs, B_r=583.91 Gs.     

Structural, electrical and dielectric properties of Bi1.5Zn0.92Nb1.5−xTaxO6.92 pyrochlore ceramics

The micro-structural, compositional, temperature dependent dielectric and electrical properties of the Bi_1.5Zn_0.92Nb_1.5−xTa_xO_6.92 solid solution has been investigated. The increasing Ta content from 0.2 to 1.5 caused; single phase formation, a pronounced grain size reduction from ∼7.0 to 2.5 μm, sharp decrease in the dielectric constant from 198 to 88 and an increase in the electrical conductivity from 3.16 × 10⁻¹⁰ to 5.0 × 10⁻⁹ (Ω cm)⁻¹, respectively. The temperature dependent dielectric constant which is found to be frequency invariant in the frequency range of (0.0-2.0 MHz) exhibited a sharp change in the temperature coefficient of dielectric constant at a (doping independent) critical temperature of 395 K. The analysis of the measured data reflects a promising future for this type of pyrochlore to be used in high voltage passive device applications.     

Preparation, characterization and electrical conductivity studies of NdYb1−xGdxZr2O7 (0 ≤ x ≤ 1.0) ceramics

Several compositions of NdYb_1−xGd_xZr₂O₇ (0 ≤ x ≤ 1.0) ceramics were prepared by pressureless-sintering method at 1973 K for 10 h in air. The relative density, microstructure and electrical conductivity of NdYb_1−xGd_xZr₂O₇ ceramics were analyzed by the Archimedes method, X-ray diffraction, scanning electron microscopy and impedance plots measurements. NdYb_1−xGd_xZr₂O₇ (0 ≤ x ≤ 0.3) ceramics have a single phase of defect fluorite-type structure, and NdYb_1−xGd_xZr₂O₇ (0.7 ≤ x ≤ 1.0) ceramics exhibit a single phase of pyrochlore-type structure; however, the NdYb_0.5Gd_0.5Zr₂O₇ composition shows mixed phases of both defect fluorite-type and pyrochlore-type structures. The measured values of the grain conductivity obey the Arrhenius relation. The grain conductivity of each composition in NdYb_1−xGd_xZr₂O₇ ceramics gradually increases with increasing temperature from 673 to 1173 K. NdYb_1−xGd_xZr₂O₇ ceramics are oxide-ion conductor in the oxygen partial pressure range of 1.0 × 10⁻⁴ to 1.0 atm at all test temperature levels. The highest grain conductivity value obtained in this work is 1.79 × 10⁻² S cm⁻¹ at 1173 K for NdYb_0.3Gd_0.7Zr₂O₇ composition.     

Properties of Ni1−xFex (0.1 < x < 0.9) and Invar (x = 0.64) alloys obtained by electrodeposition

Electrodeposition of Ni_1−xFe_x (x = 0.1-0.9) films was carried out from a chloride plating solution containing saccharin as an organic additive at a constant current density (5 mA/cm²) and a controlled pH of 2.5. X-ray diffraction studies revealed the existence of an fcc, or γ phase, in the range of 10-58 wt.% Fe, a mixed fcc/bcc phase in the range of 59-60 wt.% Fe, and a bcc, or α phase in the range of 64-90 wt.% Fe. The saturation magnetization, B_s, of electrodeposited Ni_1−xFe_x alloys at the room temperature was found to increase with the increase of Fe-content and follows the Slater-Pauling curve, but deviates from as-cast bulk NiFe alloys. The coefficient of thermal expansion, CTE, of electrodeposited alloys at room temperature also deviates from as-cast bulk NiFe alloys. Annealing of α-Ni₃₆Fe₆₄ alloy results in a martensitic α → γ phase transformation, which takes place between 300 and 400 °C. It was demonstrated that thermal treatment above 400 °C was necessary to obtain magnetic and mechanical properties similar to those to conventional Invar alloy. Annealing of α-Ni₃₆Fe₆₄ alloy at 700 °C brings about a decrease of B_s from 1.75 to 0.45 T. By controlling the annealing conditions of α → γ martensitic transformation, it is possible to adjust the CTE of Ni₃₆Fe₆₄ alloy over the broad limits from 2.7 to 8.7 × 10⁻⁶/°C.     

Frequency, temperature and In dependent electrical conduction in NiFe2O4 powder

A series of polycrystalline spinel ferrites with the composition NiIn_xFe_2-xO₄ (0 ≤ x ≤ 0.3) were prepared by the solid state reaction to study the effect of In³⁺ ions substitution on their dc electrical resistivity and dielectric properties. The dc resistivity has been investigated as a function of temperature and composition. The indium ion increases the dc resistivity and activation energy of the system. A study of the dielectric properties of these mixed ferrites, as a function of composition, frequency and temperature, has been undertaken. The dielectric constant (ε′), dielectric loss (ε″) and dielectric loss tangent (tanδ) all decreases with frequency as well as with the composition. The dielectric constant (ε′) and dielectric loss tangent (tanδ) were increases with increasing temperature. AC conductivity increases with increase in applied frequency. The dielectric behavior of the present samples is attributed to the Maxwell-Wagner type interfacial polarization. The conduction mechanism in these ferrites is due to electron hopping between Fe²⁺ and Fe³⁺ ions on adjacent octahedral sites.     

Effect of zinc concentration on the microstructure and relaxation frequency of Mn–Zn ferrites synthesized by solid state reaction

Mn3Zn polycrystalline ferrites with Mn_1−xZn_xFe₂O₄ stoichiometry (x=0.59, 0.61, 0.65) were prepared by solid state reaction. These ferrites were heated at different temperatures. The cubic structure with space group Fd3m (O_h⁷) No. 227 was confirmed by the refinement of x-ray diffraction (XRD) powders through Rietveld´s method using fullprof. Scanning electron microscopy (SEM) results revealed for all compounds a non-homogeneous grain size and shape distribution, with a mean grain size of 9 μm. The Curie temperature T_c was found to decrease as the Zn concentration increases. The magnetic domain relaxation was investigated by inductance spectroscopy (IS). The relaxation frequency f_r shows an increase with the increase of the grain size while the initial permeability µ_i decreased. We propose an R_pL_p parallel arm equivalent circuit to model the IS results. The theoretical approximation is in agreement with the experimental results. We found that Mn–Zn ferrites with zinc concentration at x=0.59 and heated to 1300 °C during 6 h show a slight improvement of the homogeneous microstructure and a relatively higher relaxation frequency without the abrupt degradation of their permeability. This result suggests that ferrites treated in the manner presented in this paper are good candidates for high frequency applications.     

Effect of the Nb2O5 content on electrical properties of lead-free BaTiO3–Bi0.5Na0.5TiO3 ceramics

(1−x)BaTiO₃–xBi_0.5Na_0.5TiO₃ (BT–BNT) ceramics were prepared by the solid-state reaction method. With an increase of BNT content, both the Curie temperature and the room temperature resistivity increased. At 1 mol% BNT addition, the sample was not semiconducting, due to Bi₂O₃ volatilization resulting from the decomposition of pre-calcined BNT during sintering. Appropriate extra Nb₂O₅ doping in the raw materials could offset Bi₂O₃ volatilization and neutralize the redundant acceptor Na⁺ ions. When the extra Nb₂O₅ content was 0.6 mg, the sample room-temperature resistivity was 6.3×10³ Ω cm, with the Curie point about 135 °C and a high PTC effect of ∼3 orders of magnitude.     

Enhanced thermoelectric properties induced by chemical pressure in Ca3Co4O9

We report the investigation of boron substitution on structural, electrical, thermal, and thermoelectric properties of Ca_3−xB_xCo₄O₉ (x=0, 0.5, 0.75, and 1) in the temperature range between 300 K and 5 K. X-ray diffraction studies show that the Ca₃Co₄O₉ phase is successfully preserved as the majority phase in the x=0.5 sample despite the small size of boron ions. Electrical transport measurements confirm that B³⁺ substitution for Ca²⁺ causes an increase in resistivity due to the decrease in carrier concentration. x=0.5 sample is found to have a Seebeck coefficient of 181 μV/K at room temperature which is ~1.5 times higher than that of the pure Ca₃Co₄O₉. Our results indicate that the chemical pressure due to the large ionic radii difference between B³⁺ (0.27 Å) and Ca²⁺ (1 Å) enhances the thermoelectric properties as long as the unique crystal structure of Ca₃Co₄O₉ is preserved.     

Thermoelectric properties of layered Ca3.95RE0.05Mn3O10 compounds (RE = Ce,Nd, Sm,Eu, Gd,Dy)

In this work, polycrystalline samples of the substituted n = 3 Ruddlesden-Popper Ca_4−xRE_xMn₃O₁₀ phase were prepared by solid-state reaction (RE, rare earth = Ce, Nd, Sm, Eu, Gd, Dy). Single phased samples were synthesized for sintering times larger than 150 h at 1350 °C. Complete thermoelectric characterizations were performed from 5 to 390 K, in terms of electrical resistivity (ρ), Seebeck coefficient (S) and thermal conductivity (κ). As expected, the substitution of Ca by different rare earth elements leads to a significant modification of the thermoelectric properties. With substitution level as low as 1.25 at.%, a remarkable decrease of the electrical resistivity is observed. The influence of this cationic substitution on the thermal conductivity (κ), Seebeck coefficient (S), and the figure of merit ZT is also discussed. In this study, the best one reaches 5.8 × 10⁻³ at 300 K for the Ca_3.95Eu_0.05Mn₃O₁₀ composition, a value 6 times higher than the ZT exhibited by the beginning Ca₄Mn₃O₁₀ sample.     

Effects of Sn4+ doping and oxygen vacancy on magnetic and electrical properties of yttrium iron garnet prepared by sol-gel method

Sn-substituted yttrium iron garnet samples, Y₃Fe_5-xSn_xO₁₂ (x = 0–0.1, step 0.02) were prepared using a citrate sol–gel method and followed by a sintering process. Synchrotron X-ray diffraction (SXRD), X-ray absorption near edge structure (XANES), scanning electron microscope (SEM) and Fourier infrared spectroscopy (FTIR) measurements were used to investigate the structure parameters, valence state of Fe, oxygen vacancies and lattice distortion in the samples. The magnetic properties of the samples were measured with the SQUID and VSM equipments. The Sn substitution and oxygen vacancies cause the transformation of Fe³⁺ to Fe²⁺ which leads to the decrease of Curie temperature and slight increase of saturation magnetization. Temperature dependence of the resistivity in the range of 300–573 K was investigated to elucidate the conduction mechanism in the samples. The resistivity of the sol-gel derived samples was found to be nine orders of magnitudes lower than the value for the bulk sample prepared by flux-grown method. The effects of Fe²⁺ centers, lattice dislocation, porosity and grain boundary on the resistivity are discussed. This study indicates that Sn-substituted yttrium iron garnets are good candidates for sensor elements which operate based on electrical signals.     

Synthesis and NTC properties of YCr1−xMnxO3 ceramics sintered under nitrogen atmosphere

YCr_1−xMn_xO₃ (0 ≤ x ≤ 0.8) negative temperature coefficient (NTC) compositions were synthesized by classical solid state reaction at 1200 °C, and sintered under nitrogen atmosphere at 1500 °C and 1600 °C. XRD patterns analysis has revealed that for x ≤ 0.6, the structure consists of a solid solution of an orthorhombic perovskite YCrO₃ phase with Mn substitute for Cr. For x ≥ 0.8, a second phase with a structure similar to the hexagonal YMnO₃ phase appears. SEM images and calculated open porosity have shown that the substitution of Mn for Cr results in a decrease in porosity. Whatever the sintering temperature, the electrical characterizations (between 25 and 900 °C) have shown that the increase in the manganese content involves the decrease in both resistivity and material constant B (parameter which characterizes the thermal sensitivity of material) when x ≤ 0.6. The magnitude order of the resistivity at 25 °C is of 10⁴-10⁸ Ω cm and activation energies vary from 0.28 to 0.99 eV at low and high temperatures, respectively.     

Structural and electrical properties of Dy3+ substituted NiFe2O4 ceramics prepared from powders derived by combustion method

Dysprosium (Dy) substituted nickel ferrite (NiDy_xFe_2-xO₄) powders with varying Dy content (x=0.0, 0.025, 0.05, 0.075, 0.1, 0.2) have been prepared by combustion method using DL-alanine fuel. Sintering characteristics of the powders and electrical properties of ceramics have been studied. Effective substitution of Dy³⁺ for Fe³⁺ is seen up to x=0.075 yielding improved properties, and a higher Dy content (x≥0.1) leads to partial substitution, disturbed stoichiometry, and diffusion of Dy to the grain boundaries and segregation as a secondary phase. Increasing Dy content reduces the crystallite size, powder particle size, and grain size in sintered ceramics, and the changing microstructural evolution is better resolved with back scattered electron imaging and compositional analysis. Raman spectroscopy confirms inverse spinel structure formation and substantiates the presence of secondary phase evidenced through X-ray diffraction and electron microscopy. A marginal increase in the electrical resistivity (ρ_dc) and magnetization are observed due to effectual substitution of Dy³⁺ for Fe³⁺ at the octahedral sites up to x=0.075. For x≥0.1, the increasing influence of highly resistive DyFeO₃ secondary phase at the inter-granular boundaries leads to a rapid increase in resistivity and reduction in dielectric losses, and the magnetization is reduced due to the anti-ferromagnetic nature of the secondary phase (DyFeO₃). Dense ceramics with high resistivity (~10⁹ Ω cm), low dielectric loss (tan δ ~0.002) at 1 MHz, and high magnetization (50.07 emu/g) are obtained for an optimum Dy content of x=0.075. Dielectric response, complex impedance, and electrical modulus spectroscopy in the frequency range (10⁻²–10⁶ Hz) reflect the changes in the microstructure, and suggests a non-Debye type relaxation.     

Electrical resistivity of silicon nitride-silicon carbide based ternary composites

New electrically conductive ternary composites were developed by adding 8 vol.% of ZrN or ZrB₂ to a Si₃N₄-SiC matrix. During hot pressing, ZrB₂ reacted with Si₃N₄ to form ZrSi₂, ZrN, Si and BN whereas added ZrN did not undergo any reactions in the Si₃N₄-SiC-ZrN composite. The composites modified by ZrN or ZrB₂ addition showed a lower resistivity (7 × 10³ Ω cm and 3 × 10⁻¹ Ω cm) compared to the matrix (3 × 10⁴ Ω cm). Further studies on the grain size distribution and the volume ratio of conducting and non-conducting phases excluded a percolation network of ZrN and ZrSi₂ grains. In fact, doping of SiC grains and modified grain boundaries as a consequence of the formation of liquid phases during sintering are suggested to be the reason for the significantly lower resistivity of materials containing ZrSi₂.A decrease in the composite resistivity due to a subsequent heat treatment was obtained for all hot-pressed composites.     

Synthesis and characterization of pure single phase Ni-Zn ferrite nanopowders by oxalate based precursor method

Series of single-phase Ni_1 − xZn_xFe₂O₄ (x = 0.20, 0.35, 0.50 and 0.60) nanopowders with average particle size of ∼ 35 nm have been synthesized by using oxalate based precursor method. Precursor powders were synthesized by reacting aqueous solutions of metal nitrates and oxalic acid by using different total metal ions: oxalic acid molar ratios and then evaporating them to dryness. Pure, single-phase Ni-Zn ferrite nanopowder was formed by calcining the precursor with total metal ion: oxalic acid ratio of 1:0.125 at a temperature of 850 °C. The synthesized nanopowders were characterized by using X-ray diffraction, Thermo-gravimetric and Differential Scanning Calorimetric analysis, Transmission Electron Microscope and Scanning Electron Microscope. Room temperature DC resistivity of the nanopowders was measured with respect to temperature by the two-probe method and was of the order of ∼ 10⁷ Ωcm. Room temperature saturation magnetization was measured by using Vibrating Sample Magnetometer and it varied between 34-49 emu/g depending on the composition. This aqueous solution based method provides a simple and cost-effective route to synthesize single phase, Ni-Zn ferrite nanopowders.