Dielectric and magnetoelectric properties of (x)Ni0.8Co0.1Cu0.1Fe2O4/(1 − x)PbZr0.8Ti0.2O3 composites

Ceramic composites of Ni_0.8Co_0.1Cu_0.1Fe₂O₄ and lead–zirconate–titanate (PZT) were prepared using conventional solid state reaction method. The presence of constituent phases in composites was confirmed by X-ray diffraction (XRD). The variation of dielectric constant with frequency (100 Hz–1 MHz) and temperature has been studied. The variation of loss tangent (tan δ) with temperature (at frequency 1 kHz) has also been studied. The magnetoelectric (ME) output was measured as a function of dc magnetic field. The maximum value of ME output (625 mV/cm) was observed for 25% ferrite + 75% ferroelectric phase. The maximum ME response can be explained in terms of the content of ferrite, permittivity of dielectric material and the intensity of magnetic field. The ME response of these composites was observed to be linear within low dc magnetic field. These composites may form the basis for the development of magnetic sensors and transducers for use in solid state microelectronics and microwave devices.     

Dielectric, electrical and magnetoelectric characterization of (x)Ni0.8Zn0.2Fe2O4 + (1 − x)Pb0.93La0.07(Zr0.60Ti0.40)O3 composites

The structural, electrical, dielectric, magnetic and magnetoelectric properties of (x)Ni_0.8Zn_0.2Fe₂O₄ + (1 − x)Pb_0.93La_0.07(Zr_0.60Ti_0.40)O₃ (x = 0, 0.15, 0.30, 0.45 and 1) have been studied by means of various experimental techniques. Polycrystalline samples of this series have been prepared by the double sintering ceramic method. X-ray diffraction data analysis revealed purity of the composites. Microstructural analysis using scanning electron microscopy mode depicts the presence of two phases in contact with each other. Dielectric properties were studied at and well above room temperature. Temperature dependent variation of the dielectric constant show diffused phase transition which can be well described by fitting the Lorentz-type relation, . Observation of well-saturated ferroelectric hysteresis loop and magnetic hysteresis loop for composites indicates that ferroelectric and magnetic ordering exist simultaneously at room temperature. The static value of magneto electric voltage coefficient (α_E) has been studied as a function of magnetic field at room temperature for all the composites. The maximum value of α_E is 7.53 mV/(cm Oe) for 85% PLZT-15% NZFO composites.     

Influence of Ca0.8Sr0.2TiO3 on the microstructures and microwave dielectric properties of Nd(Mg0.4Zn0.1Sn0.5)O3 ceramics

The influence of Ca_0.8Sr_0.2TiO₃ on the microstructures and microwave dielectric properties of Nd(Mg_0.4Zn_0.1Sn_0.5)O₃ ceramics were investigated by the conventional solid-state method. The X-ray diffraction peaks of (1 − x)Nd(Mg_0.4Zn_0.1Sn_0.5)O₃–xCa_0.8Sr_0.2TiO₃ ceramic system shifted to higher angles as x increased. The dielectric constant increased from 31.8 to 47.7, the quality factor (Q × f) decreased from 54,200 to 42,800 GHz, and the temperature coefficient of resonant frequency (τ _f ) increased from −43 to +41 ppm/°C as x increased from 0.5 to 0.7 when (1 − x)Nd(Mg_0.4Zn_0.1Sn_0.5)O₃–xCa_0.8Sr_0.2TiO₃ ceramic system sintered at 1,600 °C for 4 h.     

Magnetoelectric and electrical properties of WO3-doped (Ni0.8Zn0.1Cu0.1)Fe2O4/[Pb(Ni1/3Nb2/3)O3–Pb(Zn1/3Nb2/3)O3–PbTiO3] composites

A total of 5 mol% WO₃-doped (1−x)(Ni_0.8Zn_0.1Cu_0.1)Fe₂O₄/xPb(Ni_1/3Nb_2/3)O₃–Pb(Zn_1/3Nb_2/3)O₃–PbTiO₃ ((1−x)NZCF/xPNN-PZN-PT) magnetoelectric particulate ceramic composites were prepared by conventional solid-state reaction method via low-temperature sintering process. X-ray diffraction (XRD) measurement and scanning electron microscopy (SEM) observation indicate that piezoelectric phase and ferrite phase coexist in the sintered particulate ceramic composites. Dielectric property of the (1−x)NZCF/x0.53PNN–0.02PZN–0.05Pb(Ni_1/2W_1/2)O₃–0.40PT ((1−x)NZCF/xPNN-PZN-PNW-PT, nominal composition) composites is improved greatly as compared to that of the undoped (1−x)NZCF/xPNN-PZN-PT composites. The WO₃-doped (1−x)NZCF/xPNN-PZN-PT composites exhibit typical P–E hysteresis loops at room temperature accompanied by the decrease of saturation polarization (P _s) and remnant polarization (P _r). At the same time, piezoelectric property of the composites deteriorates greatly with the increase of ferrite content. The (1−x)NZCF/xPNN-PZN-PNW-PT composites can be electrically and magnetically poled and exhibit apparent magnetoelectric (ME) effect. A maximum ME voltage coefficient of 13.1 mV/(cm Oe) is obtained in the 0.1NZCF/0.9PNN-PZN-PNW-PT composite at 400 Oe d.c. magnetic bias field superimposed 1 kHz a.c. magnetic field with 5 Oe amplitude. The addition of WO₃ in the piezoelectric phase decreases sintering temperature greatly from 1180 °C to 950 °C and decreases dielectric loss sharply of the composites, thus the ME voltage coefficient increases. Such ceramic processing is valuable for the preparation of magnetoelectric particulate ceramic composites with excellent ME effect.     

Microstructure, domain structures and ferroelectric properties in (Pb0.8,La0.1,Ca0.1)TiO3/Pb(Zr0.2,Ti0.8)O3 bilayered thin film

Ferroelectric (Pb_0.8,La_0.1,Ca_0.1)TiO₃/Pb(Zr_0.2,Ti_0.8)O₃ (PLCT/PZT) bilayered thin film was prepared on Pt(111)/Ti/SiO₂/Si(100) substrate by RF magnetron sputtering technique. Pure perovskite crystalline phase, determined by X-ray diffraction, was formed in the PLCT/PZT bilayer. The bilayered film exhibited a very dense and smooth surface morphology with a uniform grain size distribution. The ferroelectric domain structures were investigated by a combination of vertical and lateral piezoresponse force microscopy (VPFM and LPFM, respectively). It is demonstrated by both VPFM and LPFM observations that out-of-plane and in-plane lamellar ferroelectric domains coexist in the bilayered thin film. The PLCT/PZT bilayered film possesses good ferroelectric properties with relatively high spontaneous polarization (2P_s = 82 µC/cm²) and remnant polarization (2P_r = 26.2 µC/cm²).     

Composition dependent phase connectivity, dielectric and magnetoelectric properties of magnetoelectric composites with Pb(Mg1/3Nb2/3)0.67Ti0.33O3 as piezoelectric phase

Ferrite (Ni_0.6Co_0.4Fe₂O₄) phase, ferroelectric (Pb(Mg_1/3Nb_2/3)_0.67Ti_0.33O₃) phase and magnetoelectric composites of (x)Ni_0.6Co_0.4Fe₂O₄ + (1 − x)Pb(Mg_1/3Nb_2/3)_0.67Ti_0.33O₃ with x = 0.15, 0.30 and 0.45 were prepared using solid-state reaction technique. Presence of Ni_0.6Co_0.4Fe₂O₄ and Pb(Mg_1/3Nb_2/3)_0.67Ti_0.33O₃ was confirmed using X-ray diffraction technique. The scanning electron microscopic images were used to study the microstructure of the composites. Connectivity scheme present in the magnetoelectric (ME) composites are discussed from the microscopic images. Variation of dielectric constant and dielectric loss with temperature for all the composites was studied. Here we report the effect of Ni_0.6Co_0.4Fe₂O₄ mole fraction on connectivity schemes between Ni_0.6Co_0.4Fe₂O₄ and Pb(Mg_1/3Nb_2/3)_0.67Ti_0.33O₃ composite. The variation of magnetoelectric voltage coefficient with dc magnetic field shows peak behaviour. The maximum value of magnetoelectric voltage coefficient of 9.47 mV/cm Oe was obtained for 0.15Ni_0.6Co_0.4Fe₂O₄ + 0.85Pb(Mg_1/3Nb_2/3)_0.67Ti_0.33O₃ composites. Finally we have co-related the effect of Ni_0.6Co_0.4Fe₂O₄ content and dielectric properties on magnetoelectric voltage coefficient.     

Studies on electrical properties of ( x ) BaTiO3?+?(1? x ) Ni0.92Co0.03Mn0.05Fe2O4 ME composites

The (1−x) Ni_0.92Co_0.03Mn_0.05Fe₂O₄ + (x) BaTiO₃ magnetoelectric (ME) composite have been prepared using conventional double sintering ceramic process where x varies as 1.00, 0.85, 0.70, 0.55 and 0.00. The presence of both phases has been confirmed by X-ray diffraction and the microstructure study will be carried out by SEM technique. The dc resistivity and thermo-emf of the samples have been studied with variation in temperature. The variation of dielectric constant (έ) and loss tangent (tan δ) will be measured in the frequency range 100 Hz–1 MHz. The ac conductivity has been derived from dielectric constant (έ) and loss tangent (tan δ). The static value of magnetoelectric conversion factor dc (ME)_H has been studied as a function of intensity of magnetic field.     

Dielectric and magnetoelectric properties of (Ni,Cu)Fe2O4 + [(Ba,Pb)(Ti,Zr)]O3 composites

The observation of magnetoelectric coupling is reported in (x) Ni_0.8Cu_0.2Fe₂O₄ + (1 − x) Ba_0.5Pb_0.5Ti_0.5Zr_0.5O₃ composites synthesized by normal solid state reaction method. The phase formation was confirmed by X-ray diffraction technique and no intermediate or impurity phase is present in all the composites. The dielectric constant (ε′) and dielectric loss (tan δ) were measured as a function of frequency and temperature. The dielectric constant was found to be enhanced with increase in ferrite content in the composite. It was also revealed that magnetoelectric output decreases with increase in ferrite content in the composite due to leakage current. The maximum voltage coefficient of 0.411 mV/cm/Oe was observed in 15% Ni_0.8Cu_0.2Fe₂O₄ + 85% Ba_0.5Pb_0.5Ti_0.5Zr_0.5O₃ composite.     

Synthesis and structural characterization of (Bi2O3)1?x (Y2O3)x and (Bi2O3)1?x (Gd2O3)x solid solutions

Solid solution series, (Bi₂O₃)_1−x (Y₂O₃)_x and (Bi₂O₃)_1−x (Gd₂O₃)_x, forx = 0.10, 0.20, 0.30 and 0.40 were synthesized by standard ceramic technique. The structural phase characterization was carried out using X-ray powder diffraction technique. It was found that the solid solution containing 20–40 mole% of Y₂O₃ had face-centred cubic structure. All samples of the solid solution series, (Bi₂O₃)_1−x (Gd₂O₃)_x, had rhombohedral single phase in the concentration range 0.10 ≤x ≤ 0.40. Lattice parameters offcc phase of Y₂O₃ doped samples were calculated from the X-ray diffraction data. The lattice constant ‘a’ gradually decreases with increasing content of dopant concentration (x) for the Y₂O₃ doped system and obeys Vegard’s rule. The unit cell parameters for the (Bi₂O₃)_1−x (Gd₂O₃)_x doped samples showing rhombohedral phase were obtained on hexagonal setting.     

Microstructures, ferromagnetic, and ferroelectric properties in polyvinylpyrrolidone-assisted CoFe2O4/Pb(Zr0.53Ti0.47)O3 multiferroic composite thick films

CoFe₂O₄/Pb(Zr_0.53Ti_0.47)O₃ (CFO/PZT) multiferroic composite thick films with different CFO mass fractions have been prepared onto Pt/Ti/SiO₂/Si substrate by a hybrid sol–gel process and spin coating technique. Polyvinylpyrrolidone (PVP) was employed to be an assistance to the sol–gel solution for enhancing the film thickness and promising a crack-free film surface. After annealing at 650 °C in air for 1 h, phase structure, microstructure, magnetic and ferroelectric properties as well as leakage current of multiferroic thick films were investigated. X-ray diffraction indicated a deeply buried distribution of CFO particles in the PZT matrix. Scanning electronic microscopes showed crack-free surfaces and a decreasing film thickness from 7.2 μm to 6.2 μm with increasing CFO content. Furthermore, the saturated magnetization and remanent magnetization were also hence increased. In addition, mass fraction of CFO in PZT matrix was also estimated from 0.36% to 4.58% according to the relationship between M _s and magnetic content. Ferroelectric hysteresis loops revealed saturated polarization (P _s) and remanent polarization (P _r) were diluted by CFO till its mass fraction rising to 1.8%. After that, polarization was increased with further increasing CFO content. Enhanced leakage was demonstrated to be partially contributed to them. A critical content of 1.8% was hence confirmed, where ferroelectric and magnetic properties can be balanced, indicating a possible stress-transferred magnetoelectric coupling effect in this composite.     

Electrical conduction, dielectric behavior and magnetoelectric effect in (x)BaTiO3 + (1 − x)Ni0.94Co0.01Mn0.05Fe2O4 ME composites

Electrical and magnetoelectric properties of magnetoelectric (ME) composites containing barium titanate as electrical component and a mixed Ni-Co-Mn ferrite as the magnetic component are reported. The ME composites with a general formula (x)BaTiO₃ + (1 − x)Ni_0.94Co_0.01Mn_0.05Fe₂O₄ where x varies as 0, 0.55, 0.70, 0.85 and 1 were prepared by standard double sintering ceramic method. The presence of both the phases was confirmed by X-ray diffraction technique. The dc resistivity was measured as a function of temperature. The variation of dielectric constant (?) and loss tangent (tan δ) with frequency (100 Hz-1 MHz) and with temperature was studied. The conduction is explained on the basis of small polaron model based on ac conductivity measurements. The static value of ME conversion factor i.e. dc (ME)_H was studied as function of intensity of magnetic field. The changes were observed in dielectric properties as well as ME effect as the molar ratio of the components was varied. A maximum value of ME conversion factor of 610 μV/cm Oe was observed in the case of a composite containing 15 mol% ferrite phase.     

Dielectric, ferromagnetic and ferroelectric properties of the (1 ? x)Ba0.8Sr0.2TiO3–xCoFe2O4 multiferroic particulate ceramic composites

The (1 − x)Ba_0.8Sr_0.2TiO₃–xCoFe₂O₄ ceramic composites (x = 0–1) were prepared by standard solid state reaction method. X-ray diffraction and SEM indicate the Ba_0.8Sr_0.2TiO₃ (BST) phase and CoFe₂O₄ (CFO) phase coexist in the composites. The dielectric constant and dielectric loss for the composites were studied as a function of frequency (40 Hz–1 MHz) and temperature (30–600 °C). Magnetic and ferroelectric tests show that the ceramic composites display ferromagnetic and ferroelectric properties simultaneously. The saturated polarization of the composites decrease with ferrite concentration increasing, while the remnant polarization of the composites increase with increasing ferrite concentration. The enhanced ferroelectricity of composites may be attributed to space charge contribution in the composites.     

Effect of gradient composite structure in cofired bilayer composites of Pb(Zr0.56Ti0.44)O3–Ni0.6Zn0.2Cu0.2Fe2O4 system on magnetoelectric coefficient

This study investigates the ferroelectric, ferromagnetic, and magnetoelectric properties of the cofired bilayer composites consisting of piezoelectric phase with formulation 0.9 Pb(Zr_0.56Ti_0.44)O₃–0.1 Pb[(Zn_0.8/3Ni_0.2/3)Nb_2/3] + 2 (mol%) MnO₂ and 40 mol% ferrite phase with formulation Ni_0.6Zn_0.2Cu_0.2Fe₂O₄ (NCZF). A bulk composite of the same composition was also synthesized for comparison. Scanning electron microscope (SEM) investigation using quadrant back scattering detector (QBSD) shows migration of ferrite phases through the interface and energy dispersive X-ray spectroscopy (EDX) analysis with X-ray mapping clarifying these as Cu-rich phases. Improved piezoelectric (d ₃₃ ~ 80 pC/N), ferroelectric (polarization of 60 μC/cm² and 0.1% strain), higher magnetization (25 emu/g) and lower coercive field (2.8 Oe) were recorded for bilayer composite. The results indicate that the gradient bilayer composites with tailored composition such that the fraction of the secondary phase is higher may lead to better magnetoelectric material.     

Dielectric and ferromagnetic properties of BaTiO<Subscript>3</Subscript>/Ni<Subscript>0.93</Subscript>Co<Subscript>0.02</Subscript>Cu<Subscript>0.05</Subscript>Fe<Subscript>2</Subscript>O<Subscript>4</Subscript> composites

xBaTiO₃ + (1 − x)Ni_0.93Co_0.02Cu_0.05Fe₂O₄ (x = 0.5, 0.6, 0.7, 0.8) composites with ferroelectric–ferromagnetic characteristics were synthesized by the ceramic sintering technique. The presence of constituent phases in the composites was confirmed by X-ray diffraction studies. The average grain size was calculated by using a scanning electron micrograph. The dielectric characteristics were studied in the 100 kHz to 15 MHz. The dielectric constant changed higher with ferroelectric content increasing; and it was constant in this frequency range. The relation of dielectric constant with temperature was researched at 1, 10, 100 kHz. The Curie temperature would be higher with frequency increasing. The hysteresis behavior was studied to understand the magnetic properties such as saturation magnetization (M _s). The composites were a typical soft magnetic character with low coercive force. Both the ferroelectric and ferromagnetic phases preserve their basic properties in the bulk composite, thus these composites are good candidates as magnetoelectric materials.     

Microstructure, hysteresis and microwave absorption analysis of Ba(1 − x)SrxFe12O19 ferrite

M-type hexagonal ferrite series, Ba_(1−x)Sr_xFe₁₂O₁₉ (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0), has been synthesized by conventional ceramic method. Hysteresis parameters have been investigated at an applied field of 10 kOe and absorption has been studied at X-band as a function of thickness, substitution and frequency. Microstructure and X-ray diffraction confirmed hexagonal structure of ferrite. The substitution causes profound increase in absorption, coercivity and magnetization. The magnetic parameters have been characterized by taking into account microstructure and preferential site occupancy. Curie temperature decreases with substitution due to the formation of spin canting structure.     

Magnetoelectric and dielectric properties of Ni0.5Cu0.5Fe2O4–Ba0.5Pb0.5Ti0.5Zr0.5O3 ME composites

The (x) Ni_0.5Cu_0.5Fe₂O₄ + (1−x) Ba_0.5Pb_0.5Ti_0.5Zr_0.5O₃ ME composites have been synthesized by a standard ceramic method. The presence of single phase in x = 0 and x = 1 as well as two phases in x = 0.15, 0.30 and 0.45 composites has been confirmed by XRD. The dielectric constant (ε′) and dielectric loss (tan δ) have been studied as a function of temperature and frequency. These composite materials exhibit maximum dielectric constant with a variation of frequency and temperature. The composite 15% Ni_0.5Cu_0.5Fe₂O₄ + 85% Ba_0.5Pb_0.5Ti_0.5Zr_0.5O₃ had the highest magnetoelectric voltage coefficient of 0.248 mV/cm Oe at room temperature among the studied composites.     

Ba(Zn1/3Nb2/3)O3/Ni0.8Zn0.2Fe2O4 magneto-dielectric composite with large dielectric constant and high permeability

Ba(Zn_1/3Nb_2/3)O₃/Ni_0.8Zn_0.2Fe₂O₄ (BZN/NZO) composites were synthesized via the conventional solid-state reaction method. The phase composition and surface morphology of the composites were investigated using XRD and SEM, respectively. The dielectric and magnetic properties of the composites were studied. The results show that the BZN/NZO composites have large dielectric constants and very high permeabilities. For the 20%BZN/80%NZO composite, the dielectric constant and permeability in low frequency range are about 8,000 and 18, respectively. The large dielectric behavior of the BZN/NZO composites is mainly attributed to the Maxwell–Wagner polarization.     

Studies on magnetic and magnetoelectric properties of the NiFe2O4–Ba0.7Sr0.3TiO3 composites

The magnetic and magnetoelectric properties of magnetoelectric (ME) composites consisting of with nickel ferrite (NiFe₂O₄) and barium strontium titanate (Ba_0.7Sr_0.3TiO₃) were investigated. The composites were prepared by standard double sintering ceramic method. The X-ray diffraction analysis was carried out to confirm the phases formed during sintering and also to calculate the lattice parameters. The hysteresis measurements were done to determine saturation magnetization (M_s), remenance magnetization (M_r) and coercivity (H_c) of the samples. The magnetoelectric voltage coefficient (dE/dH)_H was studied as a function of intensity of the magnetic field. The measured magnetoelectric (ME) response demonstrated strong dependence on the volume fraction of NiFe₂O₄ and the applied magnetic field. A large ME voltage coefficient of about 560 μVcm⁻¹Oe⁻¹ was observed for 15% NiFe₂O₄ + 85% Ba_0.7Sr_0.3TiO₃ composite.     

Magnetic susceptibility, spin transition, and electrical conductivity of LaCo1 + xO3 and NdCo1 + xO3

The magnetic susceptibility of Nd₂O₃, NdCo_{1 + x} O₃, and LaCo_{1 + x} O₃ (x = 0, 0.05, 0.1, 0.15) has been measured at temperatures from 80 to 950 K, and the electrical conductivity of the neodymium and lanthanum cobaltites (enriched in cobalt relative to neodymium or lanthanum) with the general formulas Nd(La)Co_{1 + x} O_{3 + 1.5x} , or Nd_{1/(1 + x)}(La)_{1/(1 + x)}CoO_{(3 + 1.5x)/(1 + x)}, has been measured between 300 and 1050 K. The effective magnetic moments of paramagnetic ions have been determined in the temperature ranges of CurieWeiss behavior and have been used to evaluate the fractions of low-, intermediate-, and high-spin Co³⁺ ions. Raising the temperature from 320 to 660 K (non-Curie—Weiss behavior) increases the fraction of high-spin Co³⁺ ions in LaCo_{1 + x} O_{3 + 1.5x} (La_{1/(1 + x)}CoO_{(3 + 1.5x)/(1 + x)} from 27–43 to 56–61%. Moreover, in this temperature range the conductivity of the lanthanum cobaltites rises most steeply. In the range 660–950 K, no spin transition occurs in LaCo_{1 + x} O_{3 + 1.5x} , the slope of the conductivity versus temperature curves gradually decreases, and the conductivity gradually saturates. The conductivity of NdCo_{1 + x} O_{3 + 1.5x} (Nd_{1/(1 + x)}CoO_{(3 + 1.5x)/(1 + x)}) varies considerably in the range 550–950 K, and the spin transition in these cobaltites takes place between 260 and 760 K. Above 760 K, the NdCo_{1 + x} O_{3 + 1.5x} cobaltites with x = 0.05 and 0.10 contain, respectively, 72 and 83% high-spin Co³⁺ ions and 28 and 17% high-spin Co⁴⁺ ions, whereas neodymium cobaltite with x = 0.15 contains 83% high-spin and 17% intermediate-spin Co³⁺ ions. Original Russian Text ? S.V. Shevchenko, L.A. Bashkirov, G.S. Petrov, S.S. Dorofeichik, N.N. Lubinskii, 2008, published in Neorganicheskie Materialy, 2008, Vol. 44, No. 1, pp. 88–94.     

Dielectric properties of Pb[(1?x)(Zr1/2Ti1/2)?x(Zn1/3Ta2/3)]O3 ceramics prepared by columbite and wolframite methods

Polycrystalline samples of Pb[(1 − x)(Zr_1/2Ti_1/2) − x(Zn_1/3Ta_2/3)]O ₃ , where x = 0.1–0.5 were prepared by the columbite and wolframite methods. The crystal structure, microstructure, and dielectric properties of the sintered ceramics were investigated as a function of composition via X-ray diffraction (XRD), scanning electron microscopy (SEM), and dielectric spectroscopy. The results indicated that the presence of Pb(Zn_1/3Ta_2/3)O₃ (PZnTa) in the solid solution decreased the structural stability of overall perovskite phase. A transition from tetragonal to pseudo-cubic symmetry was observed as the PZnTa content increased and a co-existence of tetragonal and pseudo-cubic phases was observed at a composition close to x = 0.1. Examination of the dielectric spectra indicated that PZT–PZnTa exhibited an extremely high relative permittivity at the MPB composition. The permittivity showed a ferroelectric to paraelectric phase transition at 330 °C with a maximum value of 19,600 at 100 Hz at the MPB composition.