Dielectric performance of pyrochlore-type Bi2MgNb2-xTaxO9 ceramics: The effects of tantalum doping

The solid solutions based on the pyrochlore-type system Bi₂MgNb_2-xTa_xO₉ were formed in the compositional range х = 0–2.0 (Bi_1·6Mg_0·8Nb_1.6-tTa_tO_7.2, t = 0–1.6). The Rietveld method was used to refine the structure for Bi₂MgNb_2-xTa_xO₉ (x = 0, 1.0, 2.0). The increasing tantalum content led to the slight decrease in the cubic unit cell parameters from 10.56934 (4) Å for x = 0 and 10.54607 (3) Å for x = 2 (sp.gr. Fd-3m:2). At the same time, tantalum additions suppressed grain growth in the pyrochlore ceramics during sintering and made it possible to obtain materials with an average grain size of 1–2 μm (Bi_1·6Mg_0·8Ta_1·6O_7.2). The increase in the Ta⁵⁺ concentration led to the decrease in the dielectric permeability from 104 (Bi_1·6Mg_0·8Nb_1·6O_7.2) to 20 (Bi_1·6Mg_0·8Ta_1·6O_7.2) at room temperature, while the dielectric loss tangent remained lower than 0.002, which is due to the small grain size and the high porosity of the samples. An increase in temperature has practically no effect on the values of the dielectric permittivity in the entire frequency range. The samples have weak through conductivity. The activation energies of electrical conductivity varied in the range of 0.84–1.00 eV, and the less tantalum, the lower the activation energy. The electrical properties of the samples at 200 Hz to 1 MHz are described by the simplest parallel scheme.     

Fabrication and characterisation of Cr and Co doped Bi1.5Zn0.92Nb1.5O6.92 pyrochlores

Cr and Co doped Bi_1.5Zn_0.92Nb_1.5O_6.92 pyrochlore ceramics were produced by solid state mixing of oxides. Cr and Co were doped into the Nb and Nb-Zn sites considering the compositions of Bi_1.5Zn_0.92Nb_1.5−xCr_xO_6.92−x, (Bi_1.5Zn_0.46)(Zn_0.46−3x/6Nb_1.5−3x/5Cr_x)O_6.92−x/2 for Cr doping and Bi_1.5Zn_0.92Nb_1.5−3x/5Co_xO_6.92, (Bi_1.5Zn_0.46)(Zn_0.46−3x/6Nb_1.5−3x/5Co_x)O_6.92−x/2 for Co doping. The solubility limit of Cr in BZN was higher than that of Co and the solubility limit increased when doping was made both into Nb and Zn sites. The second phases appeared when x > 0.2 for Cr and x > 0.15 for Co doping into the Nb-Zn sites. Simultaneous Cr doping into the Nb- and Zn-sites of BZN pyrochlore gave higher dielectric constant than doping into the Nb-site of pyrochlore. However, Co doping into the Nb- and Zn-sites and only into the Nb-site of BZN gave identical dielectric results in the range of 202-218. The temperature coefficient of dielectric constant decreased with Cr doping and increased with Co doping.     

Dielectric temperature stability of Nb-modified Bi0.5(Na0.78K0.22)0.5TiO3 lead-free ceramics

In this study, the phase structure, microstructure and dielectric properties of Bi_0.5(Na_0.78K_0.22)_0.5(Ti_1-xNb_x)O₃ lead-free ceramics prepared by traditional solid phase sintering method were studied. The second phase pyrochlore bismuth titanate (Bi₂Ti₂O₇) was produced in the system after introduction of Nb⁵⁺. The dielectric constant of the sample (x = 0.03) sintered at 1130 °C at room temperature reached a maximum of 1841, and the dielectric loss was 0.045 minimum. It had been found that the K⁺ and Nb⁵⁺ co-doped Bi_0.5Na_0.5TiO₃ (BNT) lead-free ceramics exhibited outstanding dielectric-temperature stability within 100–400 °C with T_cc ≤±15%. Result of this research provides a valuable reference for application of BNT based capacitors in high temperature field.     

Temperature–stable dielectrics based on Cu–doped Bi2Mg2/3Nb4/3O7 pyrochlore ceramics for LTCC

Temperature–stable dielectrics based on Cu–doped Bi₂Mg_2/3Nb_4/3O₇ pyrochlore ceramics were prepared by conventional solid–state reaction. Microstructure analysis indicates that all of the specimen maintain the cubic pyrochlore phase, a fluorite–like phase of Bi₃NbO₇ and a Bi₅Nb₃O₁₅ formed for Cu doping. The dielectric constant is dominated by densification of samples and secondary phases, while the dielectric loss is related by the secondary phases, grain boundaries, and leakage current characteristics. The (1-x)BMN - xCuO(x = 0.1 mol%) ceramic sintered at 925 °C shows excellent dielectric properties with dielectric constant of ~184.06, dielectric loss of ~0.0017 and near zero τ_ε (?20 ppm/°C) is obtained at sintering temperature of 925 °C, which could be a promising candidate for LTCC.     

Correlation of La-mediated structural transition and dielectric relaxation in Bi2Mg2/3Nb4/3O7 pyrochlores

Bismuth based pyrochlores have attracted a massive interest in the modern research areas owing to their structural tenability and variety of physical properties. The structural variation and its consequent effects on dielectric relaxation have been presented in this work by synthesizing a series of La-mediated Bi_2-xLa_xMg_2/3Nb_4/3O₇ (x = 0.00, 0.05, 0.10, 0.15, 0.20 and 0.25) ceramics using sol–gel auto-combustion technique. Coexistence of fluorite and cubic pyrochlore phases in the parent composition and gradual enrichment of pyrochlore phase with increase of substitution contents was observed from the structural analysis. Distortion of spherical symmetry of grains with reduced grain size from 950 to 500 nm was revealed by field emission scanning electron microscope. The presence of required constituent elements with their correct proportion was analysed using energy dispersive X-ray spectroscopy. Complex impedance study and frequency dependent dielectric dispersion analysis was performed to check ac-conductivity and to explore potential of material for energy storage applications. With the help of complex modulus analysis, the range of carrier transportation inside the material was distinguished in different frequency regimes.     

Magnetic and electrical properties of Mg1-xCoxFe2O4 (x = 0-0.15) ceramics prepared by the solid-state method

Mg_1-xCo_xFe₂O₄ (x = 0?0.15) ferrite powders were synthesized by the solid-state reaction followed by a liquid phase sintering at 1050 °C using 3 wt% Bi₂O₃ as a sintering aid. The grain size and density increased upon cobalt doping due to the higher ionic mobility of cobalt than magnesium ions. The microstructure revealed that, upon cobalt doping, the average grain size increased from 2.43 $\pm$ 1.52–3.59 $\pm$ 2.05 μm. The highest density of 4.52 $\pm$ 20 g/cm³ was obtained for x = 0.11. The saturation magnetizations of the samples progressively increased from 23 to 52 emu/g by increasing the cobalt content. The DC resistivity increased up to 6.45 × 10⁺¹⁰ Ω.cm for x = 0.11. The dielectric behavior was explained based on the Maxwell-Wagner two-layer model. The samples with x = 0; 0.03; 0.07; and 0.15 showed a high-lossy behavior, whereas with x = 0.11 exhibited a low tanδ of 0.048 and the dielectric constant of 16.8 at 1 kHz.     

Dielectric properties of Sm, Nd and Fe doped Bi1.5Zn0.92Nb1.5O6.92 pyrochlores

New pyrochlore ceramics have been produced by doping Sm and Nd into the Bi site and Fe into the Nb site in the Bi_1.5Zn_0.92Nb_1.5O_6.92 (BZN) pyrochlore. Doped pyrochlore ceramics were produced by conventional solid state mixing of oxides at different doping levels using the compositions of Bi_1.5−xSm_xZn_0.92Nb_1.5O_6.92, Bi_1.5−xNd_xZn_0.92Nb_1.5O_6.92 and Bi_1.5Zn_0.92Nb_1.5−xFe_xO_6.92−x. The solubility limit of cations was determined as x = 0.13, 0.18 and 0.15 for Sm, Nd and Fe, respectively. While Sm and Nd increased the dielectric constant (?), Fe doping led a decrease in ?. Dielectric constant of Sm and Nd doped BZN increased to 199 at x = 0.13 (Sm) and to 219 at x = 0.18 (Nd). At low Fe dopings (x = 0.05), the dielectric constant of BZN increased to 242 but decreased to 211 at x = 0.15. The dielectric losses were lower for Sm and Nd dopings than Fe but in all cases it was lower than 0.006. The dielectric constant of Sm, Nd and Fe doped BZN ceramics was nearly independent of frequency within the frequency range between 1 kHz and 2 MHz, but decreased considerably with temperature between 20 and 200 °C. Temperature coefficient of Sm doped BZN (−354 ppm/°C) was lower than Nd and Fe doped BZN ceramics at solubility limits (−538 ppm/°C for Nd and −565 ppm/°C for Fe).     

Low-temperature firing and microwave dielectric properties of MgNb2-xVx/2O6-1.25x ceramics

MgNb_2-xV_x/2O_6-1.25x (0.1≤x≤0.6) ceramics with orthorhombic columbite structures were prepared at low-temperature by a solid-phase process. The phase component, microscopic morphology, low-temperature sintering mechanism and microwave dielectric performance of MgNb_2-xV_x/2O_6-1.25x ceramics were comprehensively investigated. Low-temperature sintering densification of dielectric ceramics was achieved via the nonstoichiometric substitution of vanadium (V) at the Nb-site. In contrast to pure MgNb₂O₆ ceramics, the sintering temperature of MgNb_2-xV_x/2O_6-1.25x (x = 0.2) ceramics was reduced by nearly 300 °C owing to the liquid-phase assisted sintering mechanism. The liquid phase arises from the autogenous low-melting-point phase. Meanwhile, MgNb_2-xV_x/2O_6-1.25x (x = 0.2) samples with nonstoichiometric substitution could achieve a more than 900% improvement in the Q × f value, compared with stoichiometrically MgNb_2-xV_xO₆ (x = 0.1, 0.2) ceramics. Finally, MgNb_2-xV_x/2O_6-1.25x dielectric ceramics possess outstanding microwave dielectric properties: ε_r = 20.5, Q × f = 91000, and τ_f = -65 ppm/°C when sintered at 1030 °C for x = 0.2, which provides an alternative material for LTCC technology and an effective approach for low-temperature sintering of Nb-based microwave dielectric ceramics.     

Processing and dielectric properties of (Pb,Bi)(Mg,Nb,Ti)O3 ceramics

Powders of the Pb(Mg_1/3Nb_2/3)O₃–Bi(Mg_2/3Nb_1/3)O₃ (PMN–BMN) system with PbTiO₃ (PT) substitution levels of 20 and 30 mol% were prepared by a B-site precursor method. Phase development as well as dielectric properties were examined. Two major phases, i.e., MgNb₂O₆ and [(Mg_1/3Nb_2/3)_1/2Ti_1/2]O₂ (with small fractions of Mg₄Nb₂O₉), developed in the B-site precursor compositions, whereas only monophasic perovskite formed after the addition of PbO/Bi₂O₃. Maximum dielectric constant values of the two systems decreased rapidly with increasing BMN concentration, but corresponding temperatures were lowest at intermediate compositions.     

Low dielectric loss ceramics in the Mg4Nb2O9-ZnAl2O4-TiO2 ternary system

This study used a traditional solid-state reaction method to prepare a series of composite ceramics in the 0.7Mg₄Nb₂O₉-(0.3-x)ZnAl₂O₄-xTiO₂ ternary system. Crystalline phases and microstructure of Mg₄Nb₂O₉-ZnAl₂O₄-TiO₂ dielectric ceramic composites were investigated and correlated with the relevant dielectric properties. It was observed that the addition of Ti⁴⁺ substituted Nb⁵⁺ in the Mg₄Nb₂O₉ structure, which promoted the decomposition of Mg₄Nb₂O₉ to form the second phase, Mg₅Nb₄O₁₅, during sintering. The synergistic effect of ZnAl₂O₄-TiO₂ co-doping promoted the Mg₄Nb₂O₉ ceramic densification. The sample (0.7Mg₄Nb₂O₉-(0.3-x)ZnAl₂O₄-xTiO₂) with x = 0.15?0.2 exhibited dielectric constants of 13–14, larger than those of ZnAl₂O₄, Mg₄Nb₂O₉ and Mg₅Nb₄O₁₅, due to the NbO₆ octahedra distortion resulting from the substitution of Al³⁺/Ti⁴⁺ for Nb⁵⁺ in Mg₄Nb₂O₉ and Mg₅Nb₄O₁₅. The long-range order of the NbO₆ octahedra was enhanced by co-doping ZnAl₂O₄ and TiO₂, thereby enhancing the Qxf value. A dielectric constant of 13.1, Qxf value of 366,000 GHz and a τ_f of ?60.8 ppm/°C were obtained from 1300 °C sintered 0.7Mg₄Nb₂O₉-0.15ZnAl₂O₄-0.15TiO₂. These results show that 0.7Mg₄Nb₂O₉-0.15 ZnAl₂O₄-0.15TiO₂ ceramic is a good candidate for microwave electronic device applications.     

Effect of magnesium content on structure and dielectric properties of cubic bismuth magnesium niobate pyrochlores

Structure and dielectric properties of cubic pyrochlore Bi_1.5Mg_NNb_2.5−NO_8.5−1.5N (BMN) compositions with N=0.6–1.3 have been studied. X-ray diffraction (XRD), infrared reflectivity spectra and Raman spectra were employed to analyze the crystal structures and phonon vibration modes of BMN compositions. The vibration spectra were sensitive to the content of Mg²⁺ ions, which is caused by the randomness of Mg²⁺ ions partially filling both the cubic pyrochlore A and B sites. The intensity of A3O stretching vibrations became stronger with increasing Mg²⁺ content, but B3O stretching vibrations were quite opposite. With the increase of Mg²⁺ content, the dielectric constant and loss tangent both increased. Temperature dependent dielectric constant was observed in the samples with N>0.8. The tendency of the dielectric constant with the increasing temperature showed a quick drop in the samples with higher Mg²⁺ content, which seems to be associated with the disorder in the A₂O′ network.     

Enhanced sinterability and conductivity of cobalt doped lanthanum niobate as electrolyte for proton-conducting solid oxide fuel cell

La_0.95Ca_0.05Nb_1-xCo_xO₄ (x?=?0, 0.01, 0.02, 0.03, 0.05) compounds have been synthesized by a conventional solid state reaction method at 1150?°C. Co and Ca have been simultaneously introduced into LaNbO₄ solid solution for the first time, taking the place of La and Nb sites, respectively. Dense ceramic pellets of La_0.95Ca_0.05Nb_1-xCo_xO₄ have been prepared by sintering at 1300?°C with the utilization of cobalt as the sintering aid. The conductivity measurement has been carried out for all the samples in wet air. The results demonstrate that conductivity of La_0.95Ca_0.05Nb_1-xCo_xO₄ compounds are higher than that of LaNbO₄ attributed to additional oxygen vacancies generated by Co and Ca co-doping. The strategy of doping cobalt as a sintering aid proposed in this work could be served as a valid way to enhance the sinterability and electrical conductivity of LaNbO₄ based proton conducting oxides.     

Potential of pyrochlore structure materials in solid oxide fuel cell applications

Pyrochlore structure material (A₂B₂O₇) has gained interest in diverse applications like catalysis, nuclear waste encapsulation, sensors, and various electronic devices due to the unique crystal structure, electrical property, and thermal stability. This review deals with the ionic/electronic conductivity of numerous pyrochlore structure materials (titanates, zirconates, hafnates, stannates, niobates, ruthenates, and tantalite based pyrochlore) as electrolyte and electrode materials for solid oxide fuel cells (SOFCs). The impact of cation radius ratio (r_A/r_B) on the lattice constant and oxygen ‘x’ parameter of different pyrochlore structure materials obtained by various synthesis methods are reported. Higher ionic conductivity is essential for better ion transport in an electrolyte, and mixed ionic and electronic conductivity in electrode is essential for attaining higher efficiency in a typical SOFC. Gd_xTi₂O_7-δ, Gd_2-xCa_xTi₂O_7-δ, Nd_2-yGd_yZr₂O₇, Y₂Zr₂O₇, Y₂Zr_2-xMn_xO_7-δ, SmDy_1-xMg_xZr₂O_7-x/2, Gd_2-xCa_xTi₂O_7-δ pyrochlore are reported as electrolytes for fuel cell applications. Some pyrochlore material (La_2-xCa_xZr₂O₇, Sm_2-xM_xTi₂O₇ (M = Mg, Co, and Ni) pyrochlore) shows protonic conductivity at lower temperatures and ionic conductivity at higher temperature condition. Also, the mixed ionic-electronic conductivity behavior is reported in electrode materials for SOFC such as R₂MnTiO₇ (R = Er and Y), R₂MnRuO₇ (R = Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y), R₂Ru₂O₇ (R = Bi, Pb and Y), Y_2-xPr_xRu₂O₇, Ni-(Gd_0.9Ca_0.1)₂Ti₂O_7-δ, (Gd_0.9Ca_0.1)₂Ti₂O_7-δ, Gd₂(Ti_0.8Ru_0.2)₂O_7-δ, (Sm_0.9Ca_0.1)₂Ti₂O_7-δ and (Y_0.9Ca_0.1)₂Ti₂O_7-δ pyrochlore. The detailed study of the electronic behavior of these pyrochlore system confirms the necessity of defect structure with high oxygen mobility, lower activation energy, ionic radii ratio criterion should satisfy, and possess notable ion-ion interaction. Ionic conductivity in pyrochlore is increased by enhancing the oxygen migration through 48f-48f site with the formation of oxygen vacancy. Vacancy formation can be achieved by adding a suitable dopant that creates oxygen vacancy by charge compensation mechanism or as anion Frenkel defects. Similarly, the electrical conductivity is improved while adding suitable dopant (Ce, Pr, Ru, etc.) due to disordered structure and anti-Frenkel defect formation which leads to oxygen vacancy formation and thus improves conductivity.     

Effects of W6+ substitution on crystal structure and microwave dielectric properties of Li3Mg2NbO6 ceramics

Li₃Mg₂(Nb_1-xW_x)O_6+x/2 (0 ≤ x ≤ 0.08) ceramics were synthesized by the solid-state reaction route. The effects of W⁶⁺ substitution on the phase composition, microstructure and microwave dielectric properties of Li₃Mg₂NbO₆ ceramics were investigated systematically. The XRD results showed that all the samples formed a pure solid solution in the whole doping range. The SEM iamges and relative density revealed the dense structure of Li₃Mg₂(Nb_1-xW_x)O_6+x/2 ceramics. The relationship between the crystal structure and dielectric properties of Li₃Mg₂(Nb_1-xW_x)O_6+x/2 ceramics was researched through polarizability, average bond valence, and bond energy. The substitution of W⁶⁺ for Nb⁵⁺ in Li₃Mg₂(Nb_1-xW_x)O_6+x/2 ceramics significantly promoted the Q × f values. In addition, the increase of W⁶⁺ content improved the thermal stability of the Li₃Mg₂(Nb_1-xW_x)O_6+x/2 ceramics. The Li₃Mg₂(Nb_0.94W_0.06)O_6.03 ceramics sintered at 1175 °C for 6h possessed excellent properties: ε_r ~ 15.82, Q × f ~ 124,187 GHz, τ_f ~ −18.28 ppm/°C.     

Synthesis and characterization of Ca3-xLaxCo4-yCuyO9+δ cathodes for intermediate temperature solid oxide fuel cells

The calcium cobaltite Ca_3-xLa_xCo_4-yCu_yO_9+δ with x and y = 0 and 0.1 were synthesized and the electrical, thermal, and catalytic behaviors for the oxygen reduction reaction (ORR) for use as air electrodes in intermediate-temperature solid oxide fuel cells (IT-SOFCs) were evaluated. X?ray diffraction confirms the Ca_3-xLa_xCo_4-yCu_yO_9+δ samples were crystallized in a monoclinic structure and scanning electron microscopic image shows lamella-like grain formation. Introduction of dopants decreases slightly the loss of lattice oxygen and thermal expansion co-efficient. The Ca_3-xLa_xCo_4-yCu_yO_9+δ samples exhibit good phase stability for long-term operation, thermal expansion, and chemical compatibility with the Ce_0.8Gd_0.2O_2-δ electrolyte. Among the studied samples, Ca_2.9La_0.1Co₄O_9+δ shows a maximum conductivity of 176 Scm^?1 at 800 °C. Although the doped samples exhibit a higher total electrical conductivity, an improved symmetrical cell performance is displayed by the undoped sample. Comparing the sintering temperatures, the composite cathode Ca₃Co₄O_9+δ + Ce_0.8Gd_0.2O_2-δ sintered at 800 °C exhibit the lowest area specific resistance of 0.154 Ω cm² at 800 °C in air. In the Ca_3-xLa_xCo_4-yCu_yO_9+δ + GDC composite cathodes, the charge-transfer process at high frequencies presents a major rate limiting step for the oxygen reduction reaction.     

Effect of yttrium solubility on the structural and optical properties of Bi1.5−xYxZn0.92Nb1.5O6.92 pyrochlore ceramics

In this article, the yttrium solubility effects on the structural, dielectric and optical properties of the Bi_1.5?xY_xZn_0.92Nb_1.5O_6.92 (Y–BZN) solid solutions are investigated. The yttrium content (x) was varied in the range of 0.04–0.6. The scanning electron microscopy and energy dispersion analysis have shown that the single phase of the yttrium doped pyrochlore is possible up to yttrium content of 0.06. At x=0.07 YNbO₄ minor phase appears and at x=0.08 YNbO₄ and ZnO dominates in the Y–BZN. Due to the very rare amount and the random distribution of the minor phases in the pyrochlore, the X-ray diffraction technique was not able to detect these minor phases at low yttrium doping levels. While the nonstoichiometric phase evaluated at x=0.07 displayed no role on the relative density, the dielectric constant, dielectric loss, the temperature coefficient of dielectric constant, the absorbance and the energy band gap are observed to be sharply altered. The energy band gap of the pure BZN widened from 3.30 eV to 3.60 eV when the BZN was doped with Y content of 0.04. It then sharply shrunk to 2.75 eV for Y content of 0.07.     

Superior ultra-high temperature multilayer ceramic capacitors based on polar nanoregion engineered lead-free relaxor

The assembly of high-temperature electronic equipment places great demands on ultra-high temperature multilayer ceramic capacitors (UHT-MLCCs). However, the relatively low dielectric constant and inferior reliability associated with the protruding ferroelectric phase transition for existing dielectric materials have hindered the development of UHT-MLCCs. Here, these concerns have been addressed by the strategy of composition modulation of different types of polar nanoregions (PNRs) in bismuth-based perovskite relaxor. A new lead-free dielectric system (1-x)(0.8Na_0.5Bi_0.5TiO₃-0.2K_0.5Bi_0.5TiO₃)-xBi(Mg_2/3Nb_1/3)O₃ (NBT-KBT-xBMN) dominated by P4bm PNRs has been built and the corresponding UHT-MLCCs with 70Ag/30Pd inner electrodes are fabricated by tape casting and cofiring processes. A record-high dielectric constant (ε_r = 1800 ± 15%) together with low dielectric loss (tanδ ≤ 0.025) is achieved over a wide range of 100 °C–440 °C for NBT-KBT-0.2BMN MLCC, which consists of nine dielectric layers with the single-layer thickness of 70 μm. The excellent results suggest that NBT-KBT-0.2BMN MLCC can provide realistic solutions for next-generation UHT-MLCC applications and the material design strategy can be generalized for the construction of more high performance capacitor dielectrics.     

Phase development and dielectric responses in PMN–BNT ceramics

(1 − x)Pb(Mg_1/3Nb_2/3)O₃–x(Bi_0.5Na_0.5)TiO₃ ceramics were prepared by the conventional mixed-oxide method. All compositions show complete perovskite solid solutions and the structure to change from cubic to rhombohedral at x = 0.5. The dielectric constant and dielectric loss tangent were measured as a function of both temperature and frequency. The results indicated a relaxor ferroelectric behavior for all ceramics. The temperature at maximum of the dielectric constant of PMN–BNT ceramics were seen to increase with increasing BNT content. Moreover, the broadest dielectric peak occurs at x = 0.9, which leads to a morphotropic phase boundary in this system.     

Phase transition and energy storage properties of Bi0.5Na0.5TiO3–Bi(Mg2/3Nb1/3)O3 lead-free ceramics

Bi_0.5Na_0.5TiO₃ (BNT) lead-free ceramics have been extensively studied due to their excellent dielectric, piezoelectric and ferroelectric properties. The phase structure and functionalities of BNT can be feasibly adjusted by doping/forming solid solutions with other elements/components. In this work, Bi(Mg_2/3Nb_1/3)O₃ (BMN) was introduced into BNT by a conventional solid-state reaction to form a homogeneous solid solution of (1-x)(Bi_0.5Na_0.5)TiO₃-xBi(Mg_2/3Nb_1/3)O₃ (BNT-xBMN) with a perovskite structure. With the increase of BMN content, a phase transition from rhombohedral R3c to tetragonal P4bm has been confirmed by XRD, along with shifting the ferroelectric-paraelectric phase transition temperature to lower temperatures with broadening dielectric peaks. Furthermore, an optimized recoverable energy density of 1.405 J/cm³ was achieved for BNT-0.10BMN ceramics under a low applied electric field of 140 kV/cm, which is mainly attributed to the transformation from ferroelectric to ergodic relaxor phase.     

Effect of Bismuth substitution on the enhancement of thermoelectric power factor of nanostructured BixCo3-xO4

Bismuth Cobalt Oxide (Bi_xCo_3-xO₄) nanoparticles with different compositions (x?=?0, 0.025, 0.05, 0.1, 0.2) were prepared by chemical precipitation method. The structural, morphological and thermal properties of the prepared samples were studied by XRD, SEM, FTIR and TG&DTA analysis. X-ray diffraction analysis shows that pure phase of Cobalt oxide was formed till x?≤?0.05 and while increasing the Bi concentration (0.05?≤ x?≤?0.2) mixed phases of Co₃O₄, Co₂O₃, CoO and separate phase of Bi₂O₃ were formed. The diffraction peaks were reasonably shifted due to substitution of Bi²⁺ ions. XPS analysis conforms the presence of mixed valance states of Co and presence of Bi with their binding states in the samples. The electrical resistivity and Seebeck coefficient were measured for Bi_xCo_3-xO₄ (0?≤ x?≤?0.2) at different temperatures. It was observed that the electrical resistivity decrease till x?≤?0.05 due to the substitution of Bi ions in Cobalt lattice and increases at higher x values (0.05?≤ x?≤?0.2) due to the formation of Bi₂O₃ phase. The Bi substitution has considerably reduced the electrical resistivity by one order when completely dissolved in the cobalt oxide lattice at lower x values. The Seebeck coefficient value gradually increased for all samples of Bi_xCo_3-xO₄ (0?≤ x?≤?0.2). The power factor was calculated from electrical resistivity and Seebeck coefficient and the maximum power factor of 0.025 µWm^?1K^?2 was obtained for Bi_0.2Co_2.8O₄ sample at 530?K. The experimental results revealed that the Bi substitution have promising effect on the thermoelectric properties of nanostructured Bi_xCo_3-xO₄ (0?≤ x?≤?0.2).