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.     

Hydrothermal synthesis of nanocrystalline MxZn1−xFe2O4 (M=Ni, Mn, Co; x=0.40-0.60) powders

A series of nanocrystalline M_xZn_1−xFe₂O₄ (M=Ni, Mn and Co; x=0.40-0.60) powders have been successfully prepared via hydrothermal process and characterized by XRD, TEM and IR techniques. The effects of reaction temperature and the initial pH value of the starting suspension solution on the particulate properties such as the particle size and morphology are discussed. IR spectra indicate that there are no hydroxyl in as-prepared Ni_xZn_1−xFe₂O₄ and Co_xZn_1−xFe₂O₄ powders, while there are obvious hydroxyl adsorption on the IR spectrum of Mn_xZn_1−xFe₂O₄ powder.     

Microstructure and microwave dielectric characteristics of (1 − x)Ba(Zn1/3Ta2/3)O3-xBaTi4O9 ceramics

(1 − x)Ba(Zn_1/3Ta_2/3)O₃-xBaTi₄O₉ (0.1 ≤ x ≤ 0.85) composites are prepared by mixing 1150 °C-calcined BaTi₄O₉ with 1150 °C-calcined Ba(Zn_1/3Ta_2/3)O₃ powders. The crystal structure, microwave dielectric properties and sinterabilites of the (1 − x)Ba(Zn_1/3Ta_2/3)O₃-xBaTi₄O₉ ceramics have been investigated. X-ray diffraction patterns reveal that BaTi₄O₉, ordered and disordered Ba(Zn_1/3Ta_2/3)O₃ phases exist independently over the whole compositional range. The sintering temperatures of (1 − x)Ba(Zn_1/3Ta_2/3)O₃-xBaTi₄O₉ ceramics are about 1240 - 1320 °C and obviously lower than those of Ba(Zn_1/3Ta_2/3)O₃ ceramics. The dielectric constants (?_r) and the temperature coefficient of resonant frequency (τ_f) of (1 − x)Ba(Zn_1/3Ta_2/3)O₃-xBaTi₄O₉ ceramics increase with the increase of BaTi₄O₉ content. Nevertheless, the bulk densities and the quality values (Q × f) of (1 − x)Ba(Zn_1/3Ta_2/3)O₃-xBaTi₄O₉ ceramics increase with the increase of Ba(Zn_1/3Ta_2/3)O₃ content. The results are attributed to the higher density and quality value of Ba(Zn_1/3Ta_2/3)O₃ ceramics, the better grain growth, and the densification of sintered specimens added a small BaTi₄O₉ content. The (1 − x)Ba(Zn_1/3Ta_2/3)O₃-xBaTi₄O₉ ceramic with x = 0.1 sintered at 1320 °C exhibits a ?_r value of 31.5, a maximum Q × f value of 68500 GHz and a minimum τ_f value of 4.1 ppm/°C.     

New dielectric material system of x(Mg0.95Zn0.05Ti)O3-(1 − x)Ca0.8Sm0.4/3TiO3 at microwave frequency

The microstructures and the microwave dielectric properties of the x(Mg_0.95Zn_0.05)TiO₃-(1 − x) Ca_0.8Sm_0.4/3TiO₃ ceramic system were investigated. In order to achieve a temperature-stable material, we studied a method of combining a positive temperature coefficient material with a negative one. Ca_0.8Sm_0.4/3TiO₃ has dielectric properties of dielectric constant ε_r ~ 120, Q × f value ~ 13,800 GHz and a large positive τ_f value ~ 400 ppm/°C. (Mg_0.95Zn_0.05)TiO₃ possesses high dielectric constant (ε_r ~ 16.21), high quality factor (Q × f value ~ 210,000 at 9 GHz) and negative τ_f value (− 59 ppm/°C). Sintering at 1300 °C with x = 0.9, 0.9(Mg_0.95Zn_0.05Ti)O₃ − 0.1 Ca_0.8Sm_0.4/3TiO₃ has a dielectric constant (ε_r) of 22.7, a Q × f value of 124,000 GHz and a temperature coefficient of resonant frequency (τ_f) of − 6.3 ppm/°C.     

(5 − x)BaO-xMgO-2Nb2O5 ceramics prepared using a reaction-sintering process

(5 − x)BaO-xMgO-2Nb₂O₅ (x = 0.5 and 1; 5MBN and 10MBN) microwave ceramics prepared using a reaction-sintering process were investigated. Without any calcinations involved, the mixture of BaCO₃, MgO, and Nb₂O₅ was pressed and sintered directly. MBN ceramics were produced after 2-6 h of sintering at 1350-1500 °C. The formation of (BaMg)₅Nb₄O₁₅ was a major phase in producing 5MBN ceramics, and the formation of Ba(Mg_1/3Nb_2/3)O₃ was a major phase in producing 10MBN ceramics. As CuO (1 wt%) was added, the sintering temperature dropped by more than 150 °C. We produced 5MBN ceramics with these dielectric properties: ?_r = 36.69, Qf = 20,097 GHz, and τ_f = 61.1 ppm/°C, and 10MBN ceramics with these dielectric properties: ?_r = 39.2, Qf = 43,878 GHz, and τ_f = 37.6 ppm/°C. The reaction-sintering process is a simple and effective method for producing (5 − x)BaO-xMgO-2Nb₂O₅ ceramics for applications in microwave dielectric resonators.     

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.     

Solution calorimetric study of mixing enthalpy in 0.8[xB2O3-(1 − x)SiO2]-0.2K2O glasses at 298 K

The mixing enthalpies in the 0.8[xB₂O₃-(1 − x)SiO₂]-0.2K₂O glassy system with 0 ≤ x ≤ 1 have been deduced from accurate calorimetric measurements of solution enthalpies in acidic solvent at 298 K. The substitution of SiO₂ by B₂O₃ corresponds to a negative enthalpic effect and suggests the absence of some glassy miscibility gap. The mixing enthalpies are of the same order of magnitude as mixing enthalpies usually found in molten salts.     

Synthesis of perovskite-type (La1−xCax)FeO3 (0 ≤ x ≤ 0.2) at low temperature

Gel formation was realized by adding citric acid to a solution of La(NO₃)₃·5H₂O, Ca(NO₃)₂·4H₂O, and Fe(NO₃)₂·9H₂O. Perovskite-type (La_1−xCa_x)FeO₃ (0 ≤ x ≤ 0.2) was synthesized by firing the gel at 500 °C in air for 1 h. The crystallite size (D_1 2 1) decreased with increasing x, while the specific surface area was 6.8-9.4 m²/g and independent of x. The XPS measurement of the (La_1−xCa_x)FeO₃ surface indicated that the Ca²⁺ ion content increased with increasing x, while the Fe ion content was independent of x. Catalytic activity for CO oxidation increased with increasing x.     

Structure, dielectric, ferroelectric, and optical properties of (1 − x)Ba(Zr0.2Ti0.8)O3 − x(Ba0.7Ca0.3)TiO3 thin films prepared by sol-gel method

We report high dielectric tunabilities of (1 − x)Ba(Zr_0.2Ti_0.8)O₃ − x(Ba_0.7Ca_0.3)TiO₃ (BZT-xBCT) (x = 0.15, 0.30, 0.40, 0.45, 0.50, and 0.55) thin films prepared by a sol-gel method. The films show a pure perovskite structure with random orientation. They have moderate dielectric constant ranging from 350 to 500 and low dielectric loss near 3.0% at 1 kHz with 0 V bias at room temperature. The dielectric tunability of the BZT-0.55BCT thin films is up to 65% at 400 kV/cm and 100 kHz. The films exhibit a high optical transmission in the range of 420 nm-1500 nm. Their optical band gap energies are about 3.90 eV.     

Microwave dielectric properties of (Pb1−3x/2Lax)(Mg1/2W1/2)O3

La modified Pb(Mg_1/2W_1/2)O₃ were prepared by solid-state reaction process, and the sintering behavior, microstructure and microwave dielectric properties were investigated by X-ray powder diffraction (XRD), Raman scattering and HP network analyzer in this paper. A series of single phase perovskite type solid solutions with A-site vacancies (Pb_1−3x/2La_x(Mg_1/2W_1/2)O₃ (0 ≤ x ≤ 2/3)) were formed. The solid solution took cubic perovskite type structure (Fm3m) with random distribution of A-site vacancies when 0 < x < 0.5, and tetragonal or orthorhombic structure with the ordering of A-site vacancies when 0.5 ≤ x ≤ 2/3. The dielectric constant and temperature coefficient of resonant frequency decrease with increasing La content. Relatively good combination microwave dielectric properties were obtained for x = 0.56: ?_r = 28.7; Q × f = 18098; and τ_f = −5.8 ppm/°C.     

Ba3ZnTa2−xNbxO9 and Ba3MgTa2−xNbxO9 (0≤x≤1): synthesis, structure and dielectric properties

Oxides belonging to the families Ba₃ZnTa_2−xNb_xO₉ and Ba₃MgTa_2−xNb_xO₉ were synthesized by the solid state reaction route. Sintering temperatures of 1300°C led to oxides with disordered (cubic) perovskite structure. However, on sintering at 1425°C hexagonally ordered structures were obtained for Ba₃MgTa_2−xNb_xO₉ over the entire range (0≤x≤1) of composition, while for Ba₃ZnTa_2−xNb_xO₉ the ordered structure exists in a limited range (0≤x≤0.5). The dielectric constant is close to 30 for the Ba₃ZnTa_2−xNb_xO₉ family of oxides while the Mg analogues have lower dielectric constant of ∼18 in the range 50 Hz to 500 kHz. At microwave frequencies (5-7 GHz) dielectric constant increases with increase in niobium concentration (22-26) for Ba₃ZnTa_2−xNb_xO₉; for Ba₃MgTa_2−xNb_xO₉ it varies between 12 and 14. The “Zn” compounds have much higher quality factors and lower temperature coefficient of resonant frequency compared to the “Mg” analogues.     

Dielectric relaxation related to single-ionized oxygen vacancies in (Pb1−xLax)(Zr0.90Ti0.10)1−x/4O3 ceramics

The dielectric relaxation phenomenon has been studied in lanthanum modified lead zirconate titanate ceramics in the high temperature paraelectric phase. The high temperature dielectric response revealed an anomalous behavior, which is characterized by an increase of the real component of the dielectric permittivity with the increase of the temperature. At the same time, a similar behavior, with very high values, has been observed in the imaginary component of the dielectric permittivity, which can be associated with conduction effects related to the conductivity losses. The frequency and temperature behavior of the complex dielectric permittivity has been analyzed considering the semi-empirical complex Cole-Cole equation. The activation energy value, obtained from the Arrhenius’ dependence for the relaxation time, was found to decreases with the increase of the lanthanum concentration and has been associated with single-ionized oxygen vacancies. The short-range hopping of oxygen vacancies is discussed as the main cause of the dielectric relaxation.     

X-ray Rietveld analysis and Fourier transform infrared spectra of the solid solutions [Eu2−xMx][Sn2−xMx]O7−3x/2 (M = Mg or Zn)

Two series of mixed oxides with formula [Eu_2−xM_x][Sn_2−xM_x]O_7−3x/2 (M = Mg or Zn) have been synthesized. The study by X-ray diffraction and Fourier transform infrared spectroscopy shows that the solids obtained are new non-stoichiometric solid solutions with the pyrochlore type structure. For both series a decrease of the cell parameter is observed when the degree of substitution, x, increases. The structural refinements (X-ray studies) were achieved in the space group Fd-3m, no. 227 (origin at center -3m) by using the Fullprof software. The Rietveld refinements show that the divalent cations M²⁺ (Mg²⁺, Zn²⁺) substitute isomorphically for Eu³⁺ and Sn⁴⁺ ions producing vacancies in the anionic sublattice.     

Rietveld refinements of the solid solution Li(1−2x)NixTiO(PO4) (0 ≤ x ≤ 0.50)

Li_(1−2x)Ni_xTiO(PO₄) oxyphosphates with 0 ≤ x ≤ 0.10 crystallize in the orthorhombic system with the space group Pnma, those with 0.10 < x ≤ 0.25 crystallize in the monoclinic system with the space group P2₁/c and compositions with 0.25 < x < 0.50 present a mixture of the limit of the solid solution Li_0.50Ni_0.25TiO(PO₄) and Ni_0.50TiO(PO₄). The structure of the compositions 0 ≤ x ≤ 0.25 is based on a three-dimensional anionic framework constructed of chains of alternating TiO₆ octahedra and PO₄ tetrahedra, with the lithium and nickel atoms in the cavities in the framework. The dominant structural units in the compositions are chains of tilted corner-sharing TiO₆ octahedra running parallel to one of the axis. The oxygen atoms of the shared corners, not implied in (PO₄) tetrahedra, justify the oxyphosphate designation. Titanium atoms are displaced from the geometrical center of the octahedra resulting in alternating long (≈2.25 Å) and short (≈1.71 Å) TiO(1) bonds. The four remaining TiO bond distances have intermediate values ranging from 1.91 to 2.06 Å.     

Preparation and characterization of Ba1 − xSrxTiO3 thin films deposited on Pt/SiO2/Si by sol-gel method

BST thin films have been investigated as potential candidates for use in frequency agile microwave circuit devices. Stoichiometric (Ba_1 − xSr_x)TiO₃ (BST) thin films have been prepared on Pt/SiO₂/Si substrates using sol-gel method. The BST films were characterized by X-ray fluorescence (XRF) spectroscopy analysis, X-ray diffraction (XRD), scanning electron microscope (SEM) and electrical measurements. The relationships of processing parameters, microstructures, and dielectric properties are discussed. The results show that the films exhibit pure perovskite phase through rapid thermal anneal at 700 °C and their grain sizes are about 20-40 nm. The dielectric constants of BST5, BST10, BST15 and BST20 are 323, 355, 382 and 405, respectively, at 80 kHz.     

Decomposition of (Ti2xFe1−xSb1−x)O4 solid solutions below 1673 K

The pseudo-binary TiO₂-FeSbO₄ system was investigated by means of thermogravimetric analysis below 1673 K in O₂. Rutile-type solid solutions were synthesised at 1373 K in O₂ by means of a solid state reaction between the two pure end members TiO₂ (rutile) and FeSbO₄ mixed in stoichiometric amounts. Thermal stability of the (Ti_2xFe_1−xSb_1−x)O₄ solid solution increases with rutile content; equimolar (Ti_1.00Fe_0.50Sb_0.50)O₄ solid solutions decompose at about 1673 K forming a TiO₂-enriched solid solution and FeSbO₄, that subsequently decomposes into Fe₂O₃ (hematite) and a volatile Sb oxide, probably Sb₄O₆. For compositions characterised by higher Ti content the decomposition temperature is higher than 1673 K.     

Structure and electrical properties of (1 − x)Bi0.5Na0.5TiO3-xBi0.5K0.5TiO3 ceramics near morphotropic phase boundary

The binary lead-free piezoelectric ceramics with the composition of (1 − x)Bi_0.5Na_0.5TiO₃-xBi_0.5K_0.5TiO₃ were synthesized by conventional mixed-oxide method. The phase structure transformed from rhombohedral to tetragonal phase in the range of 0.16 ≤ x ≤ 0.20. The grain sizes varied with increasing the Bi_0.5K_0.5TiO₃ content. Electrical properties of ceramics are significantly influenced by the Bi_0.5K_0.5TiO₃ content. Two phase transitions at T_t (the temperature at which the phase transition from rhombohedral to tetragonal occurs) and T_c (the Curie temperature) were observed in all the ceramics. Adding Bi_0.5K_0.5TiO₃ content caused the variations of T_t and T_c. A diffuse character was proved by the linear fitting of the modified Curie-Weiss law. Besides, the ceramics with homogeneous microstructure and excellent electrical properties were obtained at x = 0.18 and sintered at 1170 °C. The piezoelectric constant d₃₃, the electromechanical coupling factor K_p and the dielectric constant ?_r reached 144 pC/N, 0.29 and 893, respectively. The dissipation factor tan δ was 0.037.     

Diffuse transition and piezoelectric properties of Pb[(Zr1−xTix)0.74(Mg1/3Nb2/3)0.20(Zn1/3Nb2/3)0.06]O3 Ceramics

In this work, the piezoelectric ceramic system of Pb[(Zr_1−xTi_x)_0.74(Mg_1/3Nb_2/3)_0.20(Zn_1/3Nb_2/3)_0.06]O₃, 0.47≤x≤0.57, with composition close to the morphotropic phase boundary, was studied. From the results of X-ray diffraction and piezoelectric measurement, ceramics near x=0.51 were found at the morphotropic phase boundary (MPB) between the tetragonal and pseudocubic perovskite. The planar coupling factor (k_p=0.72) is high at compositions near the MPB, but the mechanical quality factor (Q_m=75) is low. The calculation of the diffuseness of phase transition shows that the region of phase coexistence of this system is broader than that of the ternary system.     

Structural and electrical properties of La2−xBaxMo2O9−x/2 (x = 0-0.18)

La_2−xBa_xMo₂O_9−x/2 (x ≤ 0.18) have been prepared by solid state reaction method. The lattice parameter of La_2−xBa_xMo₂O_9−x/2 (x ≤ 0.18) determined by XRD data refinement shows a linear dependence on the dopant Ba content x. For the specimen with a La/Ba molar ratio of 0.18-0.2, additional reflection of secondary phase exists in the XRD pattern, so the value of solubility limit for Ba in La₂Mo₂O₉ is defined in range of 0.18 < x < 0.2. As the replacement degree of La³⁺ by Ba²⁺ increases, the bulk conductivity of La_2−xBa_xMo₂O_9−x/2 (x ≤ 0.18) decreases initially and then increases, a minimum value at La_1.9Ba_0.1Mo₂O_8.95 exists. Hebb-Wagner studies in argon atmosphere, which use an oxide-ion blocking electrode, show that La_2−xBa_xMo₂O_9−x/2 (x ≤ 0.18) are predominantly oxide-ion conducting in the temperature ranging from 773 to 1173 K. The average thermal expansion coefficient of La_1.84Ba_0.16Mo₂O_8.92 determined by high-temperature XRD was deduced as great as 17.5 × 10⁻⁶ K⁻¹ between 298 and 1173 K.