Role of (La,Gd) co-doping on the enhanced dielectric and magnetic properties of BiFeO3 ceramics

The effect of the La³⁺ and Gd³⁺ co-doping on the structure, electric and magnetic properties of BiFeO₃ (BFO) ceramics are investigated. For the compositions (x=0 and 0≤y≤0.15) in the perovskite structured La_xGd_yBi_1−(x+y)FeO₃ system, a tiny residual phase of Bi₂Fe₄O₉ is noticed. Such a secondary phase is suppressed with the incorporation of ‘La’ content (x). The magnitude of dielectric constant (ε_r) increases progressively by increasing the ‘La’ content from x=0 to 0.15 with a remarkable decrease of dielectric loss. For x=0.15, the system La_xGd_yBi_1−(x+y)FeO₃ exhibits highest remanent magnetization (M_r) of 0.18 emu/g and coercive magnetic field (H_C) of ~1 T in the presence of external magnetic field of 9 T at 300 K. The origin of enhanced dielectric and magnetic properties of La_xGd_yBi_1−(x+y)FeO₃ and the role of doping elements, La³⁺, Gd³⁺ has been discussed.     

Defects characterization of Dy-doped BaTiO3 ceramics via electron paramagnetic resonance

The point defects and the structural and dielectric properties of Dy-doped BaTiO₃ ceramics prepared at 1400 °C were investigated. The solubility of Dy in the self-compensation mode was determined to be x = 0.07 for (Ba_1−xDy_x)(Ti_1−xDy_x)O₃, and no EPR signals associated with the Dy³⁺ Kramers ion or the Ba and Ti vacancies were detected using the electron paramagnetic resonance (EPR) technique. As x increases, the dielectric behavior changed from a first-order phase transition to a diffuse phase transition to a Y7R dielectric-temperature stability. A strong EPR signal at g = 1.974, which is rare among rare-earth-doped BaTiO₃ ceramics appeared unexpectedly in the single-phase (Ba_1−xDy_x)Ti_1−x/4O₃ ceramics with deliberately designed Ti vacancies. This signal was attributed to ionized Ba vacancy defects. A preference for the self-compensation mode of Dy³⁺ ions is responsible for the appearance of Ba vacancies. The real formula of the nominal (Ba_1−xDy_x)Ti_1−x/4O₃ is expressed as (Ba_1−xDy_3x/4)(Ti_1−x/4Dy_x/4)O₃. In addition, the defect chemistry is discussed.     

New vacancied and Dy3+-doped molybdates – Their structure,thermal stability,electrical and magnetic properties

Microcrystalline samples of new Cd_1–3xDy_2x⌷_xMoO₄ solid solution with limited homogeneity (0<x≤0.2222) and cationic vacancies (denoted as ⌷) were prepared by a high-temperature solid state reaction. The XRD data and SEM analysis showed that as-prepared ceramics crystallize in the tetragonal scheelite type symmetry (space group I4₁/a) with the crystallite size varying between ~2 and ~20 µm. A systematic change in lattice constants, a and c, as well as in lattice parameter ratio c/a with an increase of Dy content was observed. Dy-doped molybdates are paramagnets with the antiferromagnetic short-range interaction and spin-orbit coupling. Optical and electrical investigations proved Cd_1–3xDy_2x⌷_xMoO₄ solid solution to be in the insulating state of E_g>3 eV at room temperature and the thermally activated conduction of the Arrhenius-type above 350 K. Moreover, the I-V characteristics provided the evidence of symmetrical and non-linear behavior typical of charge carrier emission weakly induced by the temperature. Relative dielectric permittivity ε_r below 10 as well as loss tangent tanδ below 0.15 do not substantially depend both on the temperature in the range of 76–400 K and the frequency in the range of 5·10²–1·10⁶ Hz. These results are interpreted in the framework of the acceptor and donor vacancy centers.     

Enhancement of the dielectric permittivity and magnetic properties of Dy substituted strontium titanate ceramics

Structural, dielectric and magnetic properties of dense Dy-substituted strontium titanate ceramics are investigated. In the Sr_1-1.5xDy_xTiO₃ system, incorporation of Dy onto the Sr site is confirmed by a linear decrease of the lattice parameter up to x = 0.05. Dielectric spectroscopy analysis of Sr_1-1.5xDy_xTiO₃ ceramics reveals four relaxations. Two relaxations observed below 55 K are attributed to dipoles formed by off-centre displacement of Dy³⁺ ions on the Sr sites. Other two dielectric relaxations found at higher temperatures are attributed to the oxygen vacancy related mechanisms. As result, very high dielectric permittivity of ～33500 at 28 K and of ～9600 around room temperature at moderate dissipation factor of ～0.02 are obtained for Sr_0.985Dy_0.01TiO₃ ceramics, making it a promising material for capacitor electronic applications. Paramagnetic behaviour observed for Sr_1-1.5xDy_xTiO₃ as well as for Sr_1-xDy_2xTi_1-xO₃ ceramics indicates impossibility to induce a magnetic order and hence magnetoelectric coupling in strontium titanate by Dy substitution.     

Effect of dysprosium substitution on crystal structure and physical properties of multiferroic BiFeO3 ceramics

The polycrystalline samples of multiferroic Bi_1−xDy_xFeO₃ (x = 0, 0.1, and 0.2) were prepared by a modified solid state reaction method and characterized by X-ray diffraction, scanning electron microscopy, differential thermal analysis, dielectric and magnetic measurements. It was shown that the introduction of the Dy³⁺ ions stabilizes the perovskite structure and improves phase purity. The coexistence of the rhombohedral and orthorhombic phases was found to exist within the investigated concentration range 0.1 ≤ x ≤ 0.2. The changes and anomalies observed in dielectric response over a wide frequency range were correlated with the structural evolution and the development in microstructure. The SQUID measurements of the field-dependent magnetization at different temperatures demonstrated Dy doping to be a very effective method for inducing a weakly ferromagnetic state in the ferroelectric R3c phase of BiFeO₃ in the absence of an external magnetic field.     

Preparation and ionic conduction of CaZr1−xScxO3−α ceramics

A series of CaZr_1−xSc_xO_3−α (x=0, 0.05, 0.10, 0.15) perovskite oxide ceramics were successfully fabricated at 1400 °C for 10 h and then further sintered at 1650 °C for 10 h via a solid-state reaction sintering process. Conductivities of the ceramics were measured under the atmosphere that contains 1% H₂/Ar and 5.63 kPa H₂O/Ar by the electrochemical impedance spectra technique. It was found that the conductivities of CaZr_1−xSc_xO_3−α (x=0, 0.05, 0.10, 0.15) ceramics increased with the increase of the measuring temperature, and the conductivity achieved its maximum value of 2.03×10⁻⁵–6.5×10⁻³ S cm⁻¹ when the doping amount of Sc (x) was 0.10. Additionally, element doping can increase the conductivities and decrease the conductivity activation energies of CaZr_1−xSc_xO_3−α ceramics. The results of transport number measurement indicated that the CaZr_0.9Sc_0.1O_3−α is almost a pure protonic conductor at 500–750 °C, while it is a mixed protonic-oxygen ionic-electronic conductor at 750–1300 °C.     

Dielectric and magnetic properties of Nickel ferrite ceramics using crystalline powders derived from DL alanine fuel in sol–gel auto-combustion

Dielectric and magnetic properties of NiFe₂O₄ ceramics prepared with powders using DL-alanine fuel in the sol–gel auto combustion technique are studied. DL-alanine fuel yields crystalline as-burnt powders, and when used for ceramic processing yields varying microstructure at different sintering temperatures. The dielectric properties are influenced by the resulting microstructure and the magnetic properties show slight change in saturation magnetization M_s (~44 – 46 emu/g). The coercive fields, dielectric losses and dispersion are reduced considerably at higher sintering temperatures (1200–1300 °C). The influence of changing microstructure is analyzed through dielectric response, complex impedance analysis and electrical modulus spectroscopy in the frequency range (10⁻²–10⁷ Hz) to understand the interactions from the grain and grain boundary phases. Sintering at 1200 °C, is found to be optimum, yields lower losses & reduced dielectric dispersion, and high resistivity (3.4×10⁸ Ω cm).     

Effect of Zr substitution on structural,magnetic, and optical properties of Bi0.9Dy0.1Fe1−xZrxO3 multiferroic ceramics prepared by rapid liquid phase sintering method

Zr substituted Bi_0.9Dy_0.1Fe_1−xZr_xO₃ (x=0.03, 0.06 and 0.10) multiferroic ceramics were synthesized by rapid liquid phase sintering technique to improve its multiferroic properties. Rietveld structural refinement of XRD patterns and Raman spectra revealed a partial structural phase transition from rhombohedral (R3c) to biphasic structure (R3c+P4mm) on codoping. The substitution of larger ionic radii and higher valence Zr⁴⁺ ions at Fe-site leads to decrease in the grain size as a result of charge compensation at Fe site. The weak ferromagnetic behavior were observed in all samples along with maximum M_r value of 0.159 emu/g for x=0.03 concentration, which is also endorsed by second order Raman modes. The distortion in FeO₆ octahedra due to Zr substitution leads to splitting of electronic bands of 3.2 eV into multiplets, which in turn reduced the optical band gap value in the range of 2.06–2.10 eV for all samples.     

Magneto-optical investigation and hyperfine interactions of copper substituted Fe3O4 nanoparticles

Copper substituted Fe₃O₄ nanoparticles (NPs) (Cu_xFe_1−xFe₂O₄ (0.0≤x≤1.0)) were synthesized by polyol method and the effect of Cu²⁺ substitution on structural, magnetic and optical properties of Fe₃O₄ was investigated. X-ray diffraction (XRD), Transmission electron microscopy (TEM), Scanning electron microscopy (SEM), UV–Visible spectroscopy and Vibrating sample magnetometer (VSM) were used to study the physical properties of the products. The room temperature (RT) magnetization (σ–H) curves revealed the superparamagnetic nature of the products. The extrapolated specific saturation magnetization (σ_s) decreases from 42.69 emu/g to 14.14 emu/g with increasing Cu content (x). The particle size dependent Langevin fit studies were applied to determine the magnetic particle dimensions (D_mag). The average magnetic particle diameter is about 9.89 nm. The observed magnetic moments of NPs are in range of (0.61–1.77) µ_B and rather less than 4 µ_B of bulk Fe₃O₄ and 1 µ_B of bulk CuFe₂O₄. Magnetic anisotropy was assigned as uniaxial and calculated effective anisotropy constants (K_eff) are between 10.89×10⁴ Erg/g and 26.95×10⁴ Erg/g. The average value of magnetically inactive layer for Cu_xFe_1−xFe₂O₄ NPs was calculated as 1.23 nm. The percent diffuse reflectance spectroscopy (DR%) and Kubelka–Munk theory were applied to determine the energy band gap (E_g) of NPs. The extrapolated optical E_g values from Tauc plots are between minimum 1.98 eV to 2.31 eV. From 57Fe Mössbauer spectroscopy data, the variation in line width, isomer splitting, quadrupole splitting and hyperfine magnetic field values on Cu⁺² ion substitution have been determined. Although, the Mössbauer spectra for the sample x=0.2 and 0.8 are composed of paramagnetic doublets, ferromagnetic sextets were also formed for other products.     

Structural,dielectric, vibrational and magnetic properties of Sm doped BiFeO3 multiferroic ceramics prepared by a rapid liquid phase sintering method

Rare earth Sm substituted Bi_1−xSm_xFeO₃ with x=0, 0.025, 0.05, 0.075 and 0.10 polycrystalline ceramics were synthesized by a rapid liquid phase sintering method. The effect of varying composition of Sm substitution on the structural, dielectric, vibrational, optical and magnetic properties of doped BiFeO₃ (BFO) ceramics have been investigated. X-ray diffraction patterns of the synthesized rare earth substituted multiferroic ceramics showed the pure phase formation with distorted rhombohedral structure with space group R3c. Good agreement between the observed and calculated diffraction patterns of Sm doped BFO ceramics in Rietveld refinement analysis of the X-ray diffraction patterns and Raman spectroscopy also confirmed the distorted rhombohedral perovskite structure with R3c symmetry. Dielectric measurements showed improved dielectric properties and magnetoelectric coupling around Néel temperature in all the doped samples. FTIR analysis establishes O–Fe–O and Fe–O stretching vibrations in BiFeO₃ and Sm-doped BiFeO₃. Photoluminescence (PL) spectra showed visible range emissions in modified BiFeO₃ ceramics. The magnetic hysteresis measurements at room temperature and 5 K showed the increase in the magnetization with the increase in doping concentration of Sm which is due to the structural distortion and partial destruction of spin cycloid caused by Sm doping in BFO ceramics.     

Microstructure and thermoelectric properties of La0.1Dy0.1SrxTiO3 ceramics

La_0.1Dy_0.1Sr_xTiO₃ (x=0.80, 0.78, 0.75, 0.70) powders were synthesized via a sol-gel method, followed by sintering at 1550 °C in a reducing atmosphere of 5 vol% hydrogen in nitrogen. The microstructure and thermoelectric properties of the Sr-deficient La and Dy co-doped SrTiO₃ were investigated. The result of XRD revealed that La_0.1Dy_0.1Sr_xTiO₃ consisted of SrTiO₃ with a cubic crystal structure as the main phase and of a small amount of Dy₂Ti₂O₇ as the second phase. All the Sr-deficient samples exhibited a step-like microstructure. As the nominal Sr deficient content increased, the electrical conductivity of the Sr-deficient La_0.1Dy_0.1Sr_xTiO₃ ceramics enhanced due to the increasing Sr and oxygen vacancies, the absolute value of the Seebeck coefficient increased a little, and the thermal conductivity decreased to ~3.0 W m⁻¹ K⁻¹, leading to a high ZT value of 0.19 for La_0.1Dy_0.1Sr_0.75TiO₃ at 500 °C.     

X-ray diffraction and infrared spectra studies of FexMn2.34−xNi0.66O4 (0 < x < 1) NTC ceramics

Series of Fe_xMn_2.34−xNi_0.66O₄ (0 < x < 1) NTC ceramics were prepared by the Pechini method. Resistivity, thermal constant (B) and aging values were measured. It was found that the resistivity increased with increasing iron content x. The B value however first decreased with increasing x in the range of x < 0.6 and then increased with further increase in x. Aging reached a maximum in the middle range (x = 0.4–0.6) of iron content. X-ray diffraction (XRD) and infrared analysis were used to determine the distribution of Fe³⁺ ions. The Fe³⁺ ions were found to occupy both A- and B-site when x < 0.6 and then go to B-site when x > 0.6. An redistribution of the Fe³⁺ ions between A- and B-site was related to the aging of the NTC thermistor.     

Effects of mechanical milling on preparation and properties of CuAl1−xFexO2 thermoelectric ceramics

CuAl_1?xFe_xO₂ (x = 0, 0.1, and 0.2) thermoelectric ceramics produced by a reaction-sintering process were investigated. Pure CuAlO₂ and CuAl_0.9Fe_0.1O₂ were obtained. Minor CuAl₂O₄ phase formed in CuAl_0.8Fe_0.2O₂. Addition of 10 mol% Fe lowered the sintering temperature obviously and enhanced the grain growth. At x = 0.1, electrical conductivity = 3.143 Ω^?1 cm^?1, Seebeck coefficient = 418 μV K^?1, and power factor = 5.49 × 10^?5 W m^?1 K^?2 at 600 °C were obtained. The reaction-sintering process is simple and effective in preparing CuAlO₂ and CuAl_0.9Fe_0.1O₂ thermoelectric ceramics for applications at high temperatures.     

Preparation and characterization of Co2+ substituted Li–Dy ferrite ceramics

Stoichiometric compositions of ferrites with the chemical formula Li_0.5?0.5xCo_xFe_2.4?0.5xDy_0.1O₄ with x=0, 0.25, 0.5, 0.75, 1.0 were prepared by the standard double sintering ceramic method. X-ray diffraction analysis confirmed the cubic spinel structure of the prepared samples. The structural, morphological and magnetic properties were studied by X-ray diffraction, infra-red spectroscopy (IR), scanning electron microscopy (SEM), vibrating sample magnetometry (VSM) and ac susceptibility measurements. Lattice constant, grain size and density increase whereas porosity decreases with the increase in Co²⁺ substitution. IR measurements show the characteristic ferrite bands. Spectral absorption bands were observed in IR spectroscopic analysis at ν₁=564?601 cm^?1, ν₂=486?519 cm^?1 and ν₃=551?578 cm^?1. The cation distribution estimated by the X-ray diffraction is supported by magnetization and susceptibility studies. The saturation magnetization decreases from 44.25 to 17.14 emu/g whereas coercivity remarkably increases from 240.69 to 812.14 emu/g with increasing Co²⁺ substitution. The mechanisms involved are discussed.     

Structural,electrical, dielectric and magnetic behavior of Gd1−xBixFe1−yZryO3 nanoparticles for advanced technological applications

Gd_1−xBi_xFe_1−yZr_yO₃ nanoparticles were synthesized via micro-emulsion route with different molar concentrations of Bi⁺³ (x) and Zr⁺⁴ (y). The values of x and y were kept in the range 0.00, 0.15, 0.30, 0.45 and 0.60. The characterizations were done by the thermo-gravimetric analysis (TGA), X-ray Diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The average particle size was ~50 nm. The effect of Bi³⁺ and Zr⁴⁺ contents on electrical, dielectric and magnetic parameters were studied. The DC resistivity measurements showed at certain Bi³⁺ and Zr⁴⁺ contents, more than two fold increase in electrical resistivity from 68×10⁸ Ω cm to 150×10⁸ Ω cm. The magnetic measurements showed the paramagnetic nature of Gd_1−xBi_xFe_1−yZr_yO₃ nanoparticles. The electrical and magnetic properties of these nanoparticles suggested that these materials are potential candidates for the fabrication of telecommunication and switching devices.     

High temperature properties of multiferroic BiFeO3–DyFeO3–BaTiO3 solid solutions

Dielectric and magnetic properties of the xBiFeO₃–yDyFeO₃–zBaTiO₃ solid solution ceramics at high temperature range of RT ∼600 °C have been characterized. For the more detailed understandings of the multiferroic property, the relation between the crystal structure transition, magnetic transition, dielectric transition with increasing temperature have been analyzed. Residual magnetization M_r under the low and high applied magnetic fields (H = 20 Oe, 8 kOe) and the dielectric properties, ɛ_r and tan δ, with varying measuring frequency and temperature have been characterized using the vibrating sample magnetometer and LCR meter, respectively. The neutron diffraction data has been collected at the temperature range of RT ∼800 °C. The low DyFeO₃ concentration samples (y = 0, 0.025) show the magnetic transitions at temperature range of 410–430 °C, while the high DyFeO₃ samples (y ≥ 0.05) show the additional transition at 250–290 °C. The magnetic transition at 410–430 °C corresponds to the crystal structural transition to the tetragonal P4mm from the rhombohedral R-3c, at which the BiFeO₃ and the DyFeO₃ samples lose their antiferromagnetic ordering.     

Structural,electrical, magnetic and magnetoelectric properties of Fe doped BaTiO3 ceramics

In the present work structural, electrical, magnetic and magnetodielectric properties of BaTi_1−xFe_xO₃ (0%≤x≤10%) ceramics have been investigated. X-ray diffraction (XRD) study reveals that the coexistence of tetragonal and hexagonal phases is strongly influenced by Fe doping concentration. The increase in Fe-doping content leads to the development of hexagonal phase along with an increase in average grain size. A reduction in the dielectric properties is also observed. All BaTi_1−xFe_xO₃ (BTFO) compositions exhibit ferroelectric behavior at room temperature. Remnant polarization (P_r) for pure BaTiO₃ (BTO) has been found to be 7.50 µC/cm² and further decreases with an increase in the Fe concentration. All Fe doped samples exhibit ferromagnetic ordering with saturation magnetization (M_s) being 26 memu/g for x=2.5%. Further, at x=5%, it decreases and thereafter again increases with Fe concentration. The magnetodielectric coefficient increases with Fe doping concentration and highest value found to be 2.80 at x=2.5%.     

Effect of Nd-doping on structural,thermal and electrochemical properties of LaFe0.5Cr0.5O3 perovskites

The structural, thermal and electrochemical properties of the perovskite-type compound La_1−xNd_xFe_0.5Cr_0.5O₃ (x=0.10, 0.15, 0.20) are investigated by X-ray diffraction, thermal expansion, thermal diffusion, thermal conductivity and impedance spectroscopy measurements. Rietveld refinement shows that the compounds crystallize with orthorhombic symmetry in the space group Pbnm. The average thermal expansion coefficient decreases as the content of Nd increases. The average coefficient of thermal expansion in the temperature range of 30–850 °C is 10.12×10⁻⁶, 9.48×10⁻⁶ and 7.51×10⁻⁶ °C⁻¹ for samples with x=0.1, 0.15 and 0.2, respectively. Thermogravimetric analyses show small weight gain at high temperatures which correspond to filling up of oxygen vacancies as well as the valence change of the transition metals. The electrical conductivity measured by four-probe method shows that the conductivity increases with the content of Nd; the electrical conductivity at 520 °C is about 4.71×10⁻³, 6.59×10⁻³ and 9.62×10⁻³ S cm⁻¹ for samples with x=0.10, 0.15 and 0.20, respectively. The thermal diffusivity of the samples decreases monotonically as temperature increases. At 600 °C, the thermal diffusivity is 0.00425, 0.00455 and 0.00485 cm² s⁻¹ for samples with x=0.10, 0.15 and 0.20, respectively. Impedance measurements in symmetrical cell arrangement in air reveal that the polarization resistance decreases from 55 Ω cm⁻² to 22.5 Ω cm⁻² for increasing temperature from 800 °C to 900 °C, respectively.     

Properties of NiFe2O4 ceramics from powders obtained by auto-combustion synthesis with different fuels

Nickel ferrite (NiFe₂O₄) powders derived by auto-combustion synthesis using three different fuels (citric acid, glycine and dl-alanine) have been characterized. The sintering behavior of ceramics using these powders has been compared. Oxygen balance (OB) setting for the chemical reaction is found to regulate the combustion reaction rate. A rapid reaction rate and a high flame temperature are achieved with dl alanine fuel yielding single phase NiFe₂O₄ powder in the as-burnt stage, whereas powders derived with citric acid and glycine fuels show poor crystallinity and necessitate post-annealing. The powder particles are largely agglomerated with a non-uniform distribution in shape and size, and the average particle size is estimated in the range ~ 54–71 nm. Powders derived from dl-alanine fuel show better phase purity, smaller crystallite size, larger surface area and superior sintering behavior. Additional Raman modes discerned for dl-alanine derived powder support a 1:1 ordering of Ni²⁺ and Fe³⁺ at the octahedral sites relating to microscopic tetragonal P4₁22 symmetry expected theoretically for the formation of NiFe₂O₄ with inverse spinel structure. Microstructure of sintered ceramics depends on the precursor powders that are used and sintering at 1200 °C is found to be optimum. Citric acid and glycine derived powders yield high saturation magnetization (M_s~47–49 emu/g), but poor dielectric properties, whereas dl-alanine derived powders yield ceramics with high resistivity (~3.4×10⁸ Ω cm), low dielectric loss (tan δ~0.003 at 1 MHz) and high magnetization (46 emu/g). Dielectric dispersion and impedance analysis show good correlation with the changes in the ceramic microstructure.     

Magnetic,magnetostrictive, and AC impedance properties of manganese substituted cobalt ferrites

In this study, we investigated the effects of substituting Mn³⁺ for some Fe³⁺ in spinel lattice on the structure, magnetic properties, magnetostriction behavior, and AC impedance characteristics of cobalt ferrites. The manganese substituted cobalt ferrites (Co–Mn ferrites), CoMn_xFe_2−xO₄, with x varied from 0 to 0.3 in 0.1 increments, were prepared by solid-state reaction. XRD examination confirmed that all sintered Co-based ferrites had a single-phase spinel structure. The average grain size, obtained from SEM micrographs, increased from 8.2 μm to 12.5 μm as the Mn content (x) increased from 0 to 0.3. Both the Curie temperature and coercivity of Co-based ferrites decreased with greater amounts of Mn, while the maximum magnetization (at H=6 kOe) of Mn-substituted cobalt ferrites was larger than that of the pure Co-ferrite. Magnetostrictive properties revealed that the pure Co-ferrite had the largest saturation magnetostriction (λ_S), about −167 ppm, and the CoMn_0.2Fe_1.8O₄ sample exhibited the highest strain sensitivity (|dλ_⊥/dH|_m) of 2.23×10⁻⁹ A⁻¹m among all as-prepared Co-based ferrites. In addition, AC impedance spectra analysis revealed that the real part (Z′) of the complex impedance of Co–Mn ferrites was lower than that of pure Co-ferrite in the low frequency region, and the Co-based ferrites exhibited semiconductor-like behavior.