Enhanced magnetoelectric coupling in La-modified Bi<Subscript>5</Subscript>Co<Subscript>0.5</Subscript>Fe<Subscript>0.5</Subscript>Ti<Subscript>3</Subscript>O<Subscript>15</Subscript> multiferroic ceramics

Multiferroic properties of La-modified four-layered perovskite Bi_5?x La _x Fe_0.5Co_0.5Ti₃O₁₅ (0 ≤ x ≤ 1) ceramics were investigated, by analyzing the magnetodielectric effect, magneto-polarization response and magnetoelectric conversion. X-ray diffraction indicated the formation of pure Aurivillius ceramics, and Raman spectroscopy revealed the Bi ions displacement and the crystal structure variation. The enhancement of ferromagnetic and ferroelectric properties was observed in Bi_5?x La _x Fe_0.5Co_0.5Ti₃O₁₅ after La modification. The evidence for enhanced ME coupling was determined by magnetic field-induced marked variations in the dielectric constant and polarization. A maximum ME coefficient of 1.15 mV/cm·Oe was achieved in Bi_4.25La_0.75Fe_0.5Co_0.5Ti₃O₁₅ ceramic, which provides the possible promise for novel magnetoelectric device application.     

Influence of isovalent and heterovalent substitution for Bi<Superscript>3+</Superscript> and Fe<Superscript>3+</Superscript> on the properties of Bi<Subscript>2</Subscript>Fe<Subscript>4</Subscript>O<Subscript>9</Subscript>-based solid solutions

Bi_2–хLa_хFe₄O₉ and Bi₂Fe_4–2xTi_xCo_xO₉ ferrites have been prepared by solid-state reactions at a temperature of 1073 K. X-ray diffraction data indicate that, in the Bi_2–хLa_хFe₄O₉ system, the limiting degree of La³⁺ substitution for Bi³⁺ ions in Bi₂Fe₄O₉ does not exceed 0.05 and that the limiting degree of substitution in the Bi₂Fe_4–2xTi_xCo_xO₉ system lies in the range 0.05 < x < 0.1. The specific magnetization and specific magnetic susceptibility of the samples have been measured at temperatures from 5 to 300 K in a magnetic field of 0.86 T. The field dependences of magnetization obtained for the Bi_2–хLa_хFe₄O₉ and Bi₂Fe_4–2xTi_xCo_xO₉ ferrites at temperatures of 300 and 5 K demonstrate that partial isovalent substitution of La³⁺ for Bi³⁺ ions in Bi₂Fe₄O₉ and heterovalent substitution of Ti⁴⁺ and Co²⁺ ions for two Fe³⁺ ions leads to partial breakdown of the antiferromagnetic state and nucleation of a ferromagnetic state.     

Diffusion phase transition and impedance spectroscopy of Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>/CuO co-doped BCZT lead-free ceramics

Perovskite type (Ba_0.85Ca_0.15?2x Bi_2x )(Zr_0.1Ti_0.9?x Cu _x )O₃ lead-free ceramics were prepared via a conventional solid-state reaction method. The phase structure, dielectric, ferroelectric properties and complex impedance were investigated in detail. XRD and dielectric measurements determined that single orthorhombic phase displayed in (Ba_0.85Ca_0.15)(Zr_0.1Ti_0.9)O₃ at room temperature. With the introduction of Bi₂O₃/CuO, the phase structure exhibited the mixture of orthorhombic and tetragonal phases, and then turned to single tetragonal phase. In contrast to the sharp dielectric transition of (Ba_0.85Ca_0.15)(Zr_0.1Ti_0.9)O₃ ceramics, a broad dielectric peak coupled with a slight decrease in Curie temperature was observed in (Ba_0.85Ca_0.15?2x Bi_2x )(Zr_0.1Ti_0.9?x Cu _x )O₃ ceramics with increasing x. The observed diffuse phase transition behavior was further confirmed by a couple of measurements with polarization loops and polarization current density curves. The structural and the composition fluctuations induced by ions doping should be responsible for the diffuse phase transition behavior. Furthermore, physical mechanisms of the conduction and relaxation processes were revealed by using impedance spectroscopy analyses. It was concluded that the conduction and relaxation processes were thermally activated, which was closely linked with the singly and doubly ionized oxygen vacancies.     

Effect of Bi and Sr doping on morphological and magnetic properties of LaCo<Subscript>0.6</Subscript>Fe<Subscript>0.4</Subscript>O<Subscript>3</Subscript> nanosized perovskites

Nanopowders of La _1?x Bi _x Co_0.6Fe_0.4O₃ (x = 0, 0.1, 0.2) and La _1?2x Bi _x Sr _x Co_0.6Fe_0.4O₃ (x = 0.1) multinary perovskites were synthesized by citrate sol–gel autocombustion method. Crystalline phase and the lattice parameters were obtained from X-ray diffraction pattern. The XRD result shows that all compounds have rhombhohedral crystal structure with \(\bar {\mathbf {R}\mathbf {3}}\)c space group and Bi (x = 0.2) have the presence of secondary peaks. Crystallite size, dislocation density, specific area and strain were calculated from XRD. The elemental composition and micrographs of grain were obtained from EDAX (energy dispersive X-ray analysis) and SEM (scanning electron microscopy), with an average grain size below 400 nm. Surface morphological studies using XPS (X-ray photoelectron spectroscopy) were used to find out the chemical states and surface proportion of oxygen present in samples. Finally, using the vibrating sample magnetometer the room temperature magnetic behaviour of compounds was studied and it was observed that the ferromagnetic behaviour of LaCo_0.6Fe_0.4O₃ was reduced by Bi and Sr doping.     

Crystallization from high-temperature solutions in the K<Subscript>2</Subscript>O-P<Subscript>2</Subscript>O<Subscript>5</Subscript>-V<Subscript>2</Subscript>O<Subscript>5</Subscript>-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> system

We have studied general trends of crystallization from high-temperature solutions in the K₂O-P₂O₅-V₂O₅-Bi₂O₃ system at P/V = 0.5?2.0, K/(P + V) = 0.7?1.4, and Bi₂O₃ contents from 25 to 50 wt % and identified the stability regions of BiPO₄, K₃Bi₅(PO₄)₆, K₂Bi₃O(PO₄)₃, and K₃Bi₂(PO₄)_{3 ? x} (VO₄) _x (x = 0?3) solid solutions. The synthesized compounds have been characterized by X-ray powder diffraction and IR spectroscopy, and the structure of two solid solutions has been determined by single-crystal X-ray diffraction (sp. gr. C ₂/c): K₃Bi₂(PO₄)₂(VO₄), a = 13.8857(8), b = 13.5432(5), c = 6.8679(4) Å, β = 114.031(7)°; K₃Bi₂(PO₄)_1.25(VO₄)_1.75, a = 13.907(4), b = 13.615(2), c = 6.956(2) Å, β = 113.52(4)°.     

Rare-earth-doped PbTiO<Subscript>3</Subscript>-PbZrO<Subscript>3</Subscript> solid solutions

(Pb_{1 ? x} Ln _x )(Zr_0.53Ti_0.47)O₃ and (Pb_{1 ? x} Ln _x )(Zr_0.65Ti_0.35)O₃ (x = 0.02, 0.06; Ln = La, Pr, Gd, Yb) solid solutions have been prepared by modified solid-state synthesis using organic-ligand precursors. The solid solutions have been characterized by thermal analysis, IR spectroscopy, x-ray powder diffraction, and atomic force microscopy. All of them have a rhombohedrally distorted perovskite structure (sp. gr. R3c).     

Very high thermal stability with excellent dielectric,and non-ohmics properties of Mg-doped CaCu<Subscript>3</Subscript>Ti<Subscript>4.2</Subscript>O<Subscript>12</Subscript> ceramics

In this work, the nominal CaCu_3?xMg_xTi_4.2O₁₂ (0.00, 0.05 and 0.10) ceramics were prepared by sintering pellets of their precursor powders obtained by a polymer pyrolysis solution method at 1100 °C for different sintering time of 8 and 12 h. Very low loss tangent (tanδ)?<?0.009–0.014 and giant dielectric constant (ε′) ～?1.1?×?10⁴–1.8?×?10⁴ with excellent temperature coefficient (Δε′) less than ±?15% in a temperature range of ??60 to 210 °C were achieved. These excellent performances suggested a potent application of the ceramics for high temperature X8R and X9R capacitors. It was found that tanδ values decreased with increasing Mg²⁺ dopants due to the increase of grain boundary resistance (R_gb) caused by the very high density of grain, resulting from the substitution of small ionic radius Mg²⁺ dopants in the structure. In addition, CaCu_3?xMg_xTi_4.2O₁₂ ceramics displayed non-linear characteristics with the significant enhancements of a non-linear coefficient (α) and a breakdown field (E_b) due to Mg²⁺doping. The high values of ε′ (14012), α (13.64) and E_b (5977.02 V/cm) with very low tanδ value (0.009) were obtained in a CaCu_2.90Mg_0.10Ti_4.2O₁₂ ceramic sintered at 1100 °C for 8 h.     

Effects of Ge<Superscript>4+</Superscript> acceptor dopant on sintering and electrical properties of (K<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>)NbO<Subscript>3</Subscript> lead-free piezoceramics

Lead-free (K_0.5Na_0.5)(Nb_1-xGe _x )O₃ (KNN-xGe, where x = 0-0.01) piezoelectric ceramics were prepared by conventional ceramic processing. The effects of Ge⁴⁺ cation doping on the phase compositions, microstructure and electrical properties of KNN ceramics were studied. SEM images show that Ge⁴⁺ cation doping improved the sintering and promoted the grain growth of the KNN ceramics. Dielectric and ferroelectric measurements proved that Ge⁴⁺ cations substituted Nb⁵⁺ ions as acceptors, and the Curie temperature (T_C) shows an almost linear decrease with increasing the Ge⁴⁺ content. Combining this result with microstructure observations and electrical measurements, it is concluded that the optimal sintering temperature for KNN-xGe ceramics was 1020°C. Ge⁴⁺ doping less than 0.4 mol.%can improve the compositional homogeneity and piezoelectric properties of KNN ceramics. The KNN-xGe ceramics with x = 0.2% exhibited the best piezoelectric properties: piezoelectric constant d₃₃ = 120 pC/N, planar electromechanical coupling coefficient k_p = 34.7%, mechanical quality factor Q_m = 130, and tanδ = 3.6%.     

Electrical conductivity of Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-Tm<Subscript>2</Subscript>O<Subscript>3</Subscript>-Nb<Subscript>2</Subscript>O<Subscript>5</Subscript> solid solutions

New solid solutions, Bi_2?x?y Tm _x Nb _y O_3+δ, with tetragonal and cubic structures have been synthesized in the Bi₂O₃-Tm₂O₃-Nb₂O₅ system, and their electrical conductivity has been measured at temperatures from 670 to 1020 K. The 1020-K conductivity of the tetragonal solid solution Bi_1.8Tm_0.15Nb_0.05O_3+δ is comparable to that of Bi_1.75Tm_0.25O₃, the best conductor in the Bi₂O₃-Tm₂O₃ system.     

Synthesis and x-ray diffraction study of solid solutions in the Zn<Subscript>2</Subscript>SnO<Subscript>4</Subscript>-Zn<Subscript>2</Subscript>TiO<Subscript>4</Subscript>-Zn<Subscript>2</Subscript>ZrO<Subscript>4</Subscript> system

The multicomponent refractory oxide system Zn₂(Ti_aSn_b)_{1 ? x} Zr_xO₄ (a + b = 1; a: b = 1: 5, 1: 4, 1: 3, 1: 2, 1: 1, 1: 0, 2: 1, 3: 1, 4: 1; x = 0?1.0; Δx = 0.05) has been studied by x-ray diffraction, using samples prepared by melting appropriate oxide mixtures in a low-temperature hydrogen-oxygen plasma. Two phases, both with wide homogeneity ranges, have been identified: α-phase, with a cubic inverse spinel structure, and β-phase, with a tetragonal spinel structure. The phase boundaries in the system have been determined. Structural data are presented for about 100 solid solutions of different compositions.     

Low temperature sintering and dielectric properties of Ba<Subscript>3</Subscript>(VO<Subscript>4</Subscript>)<Subscript>2</Subscript> microwave ceramics using Co<Subscript>2</Subscript>O<Subscript>3</Subscript> additives

The Ba₃(VO₄)₂–x wt% Co₂O₃ (x?=?0.5–5) ceramics were prepared by the solid state reaction method in order to reduce the sintering temperature. The effects of the Co₂O₃ additions on the phase composition, microstructures, sintering characteristics and microwave dielectric properties of Ba₃(VO₄)₂ ceramics are investigated by an X-ray diffractometer, a scanning electron microscope and a network analyzer. As a result, the Q?×?f value of 54,000 GH, the ε _r of 14.6 and the τ_f value of +58.5 ppm/°C were obtained in the sample of the Ba₃(VO₄)₂–3 wt% Co₂O₃ ceramic sintered at the temperature of 925 °C, which is capable to co-fire with electrode metal of high conductivity such as Ag (961 °C). Moreover, the Q?×?f values of the sample with Co₂O₃ higher than that of 3 wt% additions decreased because of the formation of Ba₂V₂O₇ phase.     

Enhancing the microwave dielectric properties of Sr<Subscript>2</Subscript>Ca<Subscript>3</Subscript>Ta<Subscript>4</Subscript>TiO<Subscript>17</Subscript> ceramics by Zr Substitution

The compositions in Sr₂Ca₃Ta₄Ti_1?xZr_xO₁₇ (0?≤?x?≤?0.12) series were designed and fabricated by solid state sintering method. All the compositions formed single phases and crystallized in an orthorhombic crystal structure. Zr substitution led to the enhancing of the microwave dielectric properties by tuning the τ_f value through zero and increased the Q_uf_o value from 12,540 to 14,970 GHz with a slight decrease in ε_r. In the present study, a good combination of ε_r ~?51, Q_uf_o ~?145,43 GHz and τ_f ~ 3 ppm/°C were obtained for Sr₂Ca₃Ta₄Ti_0.90Zr_0.1O₁₇ ceramic sintered at 1575 °C for 4 h.     

Structural studies of a new electroceramic composite: Pb(Fe<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>)O<Subscript>3</Subscript> (PFN)-Cr<Subscript>0.75</Subscript>Fe<Subscript>1.25</Subscript>O<Subscript>3</Subscript>(CRFO)

A study of the structural characteristics of the composites [Pb(Fe_0.5Nb_0.5)O₃(PFN)] _x -[Cr_0.75Fe_1.25O₃(CRFO)]_100?x (x = 0 (CRFO100), 10, 50, 90, 100) was performed in this work. The compounds PFN100 and CRFO100 were prepared by conventional solid-state method and investigated by X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM), and ⁵⁷Fe Mössbauer Spectroscopy techniques. The X-ray analysis shows that PFN100 is tetragonal and the CRFO100 phase has a trigonal symmetry. The refinement of all the composites was also performed and discussed in this paper. The Mössbauer spectrum for the composite samples shows a paramagnetic doublet and a sextet probably assigned to a magnetic phase associated to Fe⁺³. For the sample PFN100, only a magnetic field of 49.5 T (isomer shift (δ) = 0.21 mm/s) was detected. For the composite sample, the δ and Δ are typical of Fe ions at sites of octahedral coordination.     

Electric-field effect on crystal growth in the Li<Subscript>3</Subscript>PO<Subscript>4</Subscript>-Li<Subscript>4</Subscript>GeO<Subscript>4</Subscript>-Li<Subscript>2</Subscript>MoO<Subscript>4</Subscript>-LiF system

We have studied the electric-field effect on crystallization processes in the Li₃PO₄-Li₄GeO₄-Li₂MoO₄-LiF system. In zero field, Li_3+x P_1?x Ge _x O₄ (x = 0.31) crystals were grown on the cathode under the conditions of this study. At low applied voltages (≤ 0.5 V), we obtained Li₂MoO₄, Li₂GeO₃, and Li_1.3Mo₃O₈. In the range V = 0.5–1 V, crystals of Li_3+x P_1?x Ge _x O₄ solid solutions with x = 0.17, 0.25, 0.28, 0.29, and 0.36 were obtained. An applied electric field was shown to reduce the melting temperature of the starting mixtures and the crystallization onset temperature.     

Effect of high pressures and temperatures on the structure and properties of CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript>

We have prepared ceramic CaCu₃Ti₄O₁₂ samples by solid-state reaction and investigated the effect of high-pressure/high-temperature processing (p = 8.0 GPa, t = 1100°C) on the structure and electrical properties of CaCu₃Ti₄O₁₂.     

Structural and dielectric properties of PbMg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>O<Subscript>3</Subscript>-PbZrO<Subscript>3</Subscript> solid solutions synthesized at high pressures and temperatures

(1 ? x)PbMg_1/3Nb_2/3O₃ · xPbZrO₃ (1 ? x)PMN · xPZ) solid solutions have been synthesized at a pressure of 5 GPa and temperatures from 1300 to 1700 K, and their structural and dielectric properties have been studied. The composition dependences of the average unit-cell parameter and dielectric permittivity for the solid solutions indicate that the PMN-PZ system has a morphotropic phase boundary near x = 0.65. The solid solutions have a cubic structure for x < 0.65, a rhombohedral structure in the range 0.65 < x < 0.9, and an orthorhombic structure (similar to that of PbZrO₃) for x > 0.9. The temperature and frequency dependences of dielectric permittivity suggest that the (1 ? x)PMN · xPZ samples with x < 0.65 consist of two ferroelectric phases: a relaxor with antipolar dipole order and a normal ferroelectric with a diffuse phase transition. The effect of annealing temperature on the ferroelectric state of the samples with x < 0.65 is examined. In the composition range 0.65 < x < 0.9, the samples have normal ferroelectric properties, independent of annealing temperature.     

Low temperature sintering and microwave dielectric properties of Li<Subscript>6</Subscript>Mg<Subscript>7</Subscript>Ti<Subscript>3</Subscript>O<Subscript>16</Subscript> ceramics with LiF additive for LTCC applications

Li₆Mg₇Ti₃O₁₆ ceramics were prepared by the conventional solid-state method with 1–5 wt% LiF as the sintering aid. Effects of LiF additions on the phase compositions, sintering characteristics, micro-structures and microwave dielectric properties of Li₆Mg₇Ti₃O₁₆ ceramics were investigated. The LiF addition could effectively lower the sintering temperature of Li₆Mg₇Ti₃O₁₆ ceramics from 1550 to 900 °C. For different LiF-doped compositions, the optimum dielectric permittivity (ε _r ) and quality factor (Q·f) values first increased and then decreased with the increase of LiF contents, whereas the temperature coefficient of resonant frequency (τ _f ) fluctuated between ??14.39 and ??8.21 ppm/°C. Typically, Li₆Mg₇Ti₃O₁₆ ceramics with 4 wt% LiF sintered at 900 °C exhibited excellent microwave dielectric properties of ε _r ?=?16.17, Q·f?=?80,921 GHz and τ _f ?=???8.21 ppm/°C, which are promising materials for the low temperature co-fired ceramics applications.     

Strong up-conversion luminescence and electrical properties of SrBi<Subscript>4</Subscript>Ti<Subscript>4</Subscript>O<Subscript>15</Subscript> multifunctional ceramics by Er<Superscript>3+</Superscript> doping

Novel green-emitting piezoelectric ceramics of SrBi_4?x Er _x Ti₄O₁₅ (SBT-xEr) were prepared. Strong up-conversion with bright green (524 and 548 nm) and a relatively weak red (660 nm) emission bands were obtained under 980 nm excitation at room temperature, which is attributed to the intra 4f–4f electronic transition of (²H_11/2, ⁴S_3/2)–⁴I_15/2 and the transition from ⁴F_9/2 to ⁴I_15/2 of Er³⁺ ions, respectively. Simultaneously, Er³⁺ doping promotes the electrical properties. At 0.8 mol%Er, the optimal electric properties with high Curie temperature of T _c?~527?°C, large remanent polarization of 2P _r?~14.92 μC/cm² and piezoelectric constant of d ₃₃?~17 pC/N was achieved. As a multifunctional material, Er³⁺ doped SBT showed a great potential to be used in 3D-display, bio-imaging, solid state laser and optical temperature sensor.     

Solid-state reactions in the system Li<Subscript>2</Subscript>CO<Subscript>3</Subscript>-Na<Subscript>2</Subscript>CO<Subscript>3</Subscript>-Nb<Subscript>2</Subscript>O<Subscript>5</Subscript>-Ta<Subscript>2</Subscript>O<Subscript>5</Subscript>

The formation mechanisms of Li _x Na_{1 ?x} Ta _y Nb_{1 ? y} O₃ perovskite solid solutions in the Li₂CO₃-Na₂CO₃-Nb₂O₅-Ta₂O₅ system have been studied by x-ray diffraction, differential thermal analysis, thermogravimetry, IR spectroscopy, and mass spectrometry at temperatures from 300 to 1100°C. The results indicate that the synthesis of Li _x Na_{1 ? x} Ta _y Nb_{1 ? y} O₃ solid solutions involves a complex sequence of consecutive and parallel solid-state reactions. An optimized synthesis procedure for Li _x Na_{1 ? x} Ta _y Nb_{1 ? y} O₃ solid solutions is proposed.     

Dielectric responses of Na<Subscript>0.65</Subscript>Bi<Subscript>0.45</Subscript>Cu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> ceramics based on the composition design of changing the Na/Bi ratio

Na_0.65Bi_0.45Cu₃Ti₄O₁₂ ceramics were successful prepared by the conventional solid-state reaction technique. Compared to Na_0.50Bi_0.50Cu₃Ti₄O₁₂ (NBCTO), the composition of Na_0.65Bi_0.45Cu₃Ti₄O₁₂ was designed in terms of changing the Na/Bi ratio. Colossal dielectric permittivity of ~1.2 × 10⁴ at 1 kHz was obtained in Na_0.65Bi_0.45Cu₃Ti₄O₁₂ ceramics. Interestingly, three frequency dispersions were observed in the frequency dependence of dielectric constant measured at different temperatures. The investigation of electric modulus displayed that the giant low-frequency dielectric constant was attributed to Maxwell–Wagner polarization at the grain boundaries and the frequency dispersion in middle-frequency range was due to the grain polarization. Except grain response and grain boundaries response reflected by two semicircles in the impedance spectroscopy, another electrical response associated with nonzero high frequency intercept was found. The grain resistance Rg and grain boundaries resistance R _gb was ~600 Ω and 3.9 × 10⁵ Ω, respectively. The large intrinsic permittivity as high as ~700 was obtained. Furthermore, two dielectric anomalies observed in the temperature dependent of dielectric constant were discussed in detail. The results indicated change in the Na/Bi ratio had a significant effect on the electrical properties of NBCTO ceramics.