Ga<Subscript>2</Subscript>O<Subscript>3</Subscript> doping and vacancy effect in KNN—LT lead-free piezoceramics

Ga₂O₃ was doped into 0.95(K_0.48Na_0.52)NbO₃—0.05LiTaO₃ (KNN—LT) ceramics and its influences on the sintering behavior, phase structure and electrical properties of ceramics were studied. Firstly, SEM observation exhibits that more and more glass phase appears in ceramics with the gradual addition of Ga₂O₃, which determines the continuous decrease in sintering temperatures. And the addition of Ga₂O₃ is also found to increase the orthorhombic—tetragonal transition temperature (T_O—T) of system to a higher level. Secondly, both the density and the coercive field (E_C) of ceramics increase firstly and then decrease with increasing the Ga₂O₃ content, and the KNN—LT—xGa sample at x = 0.004 shows a pinched P—E hysteresis loop. Finally, the impedance characteristics of KNN—LT—xGa ceramics were investigated at different temperatures, revealing a typical vacancy related conduction mechanism. This work demonstrates that Ga₂O₃ is a good sintering aid for KNN-based ceramics, and the vacancy plays an important role in the sintering and electrical behaviors of ceramics.     

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%.     

Structure and electrical properties of MnO doped (Ba<Subscript>0.96</Subscript>Ca<Subscript>0.04</Subscript>)(Ti<Subscript>0.92</Subscript>Sn<Subscript>0.08</Subscript>)O<Subscript>3</Subscript> lead free ceramics

In this work, (Ba_0.96Ca_0.04)(Ti_0.92Sn_0.08)O₃–xmol MnO (BCTS–xMn) lead-free piezoelectric ceramics were fabricated by the conventional solid-state technique. The composition dependence (0 ≤ x ≤ 3.0 %) of the microstructure, phase structure, and electrical properties was systematically investigated. An O–T phase structure was obtained in all ceramics, and the sintering behavior of the BCTS ceramics was gradually improved by doping MnO content. In addition, the relationship between poling temperature and piezoelectric activity was discussed. The ceramics with x = 1.5 % sintering at temperature of 1330 °C demonstrated an optimum electrical behavior: d ₃₃ ~ 475 pC/N, k _p ~ 50 %, ε _r ~ 4060, tanδ ~ 0.4 %, P _r ~ 10.3 μC/cm², E _c ~ 1.35 kV/mm, T _C ~ 82 °C, strain ~0.114 % and \(d_{33}^{*}\) ~ 525 pm/V. As a result, we achieved a preferable electric performance in BaTiO₃-based ceramics with lower sintering temperature, suggesting that the BCTS–xMn material system is a promising candidate for lead-free piezoelectric ceramics.     

Photoluminescence and electrical properties of Eu3+-doped Na0.5Bi4.5Ti4O15-based ferroelectrics under blue light excitation

Na_0.5Bi_4.5?x Eu _x Ti₄O₁₅ (NBT- _x Eu³⁺) ceramics with x = 0, 0.05, 0.10, 0.15, 0.20, 0.25, 0.30 and 0.40 were prepared by conventional ceramics processing. NBT-0.25Eu³⁺ ceramics show the strongest red and orange emissions corresponding to the ⁵D₀ → ⁷F₂ (617 nm) and ⁵D₀ → ⁷F₁ (596 nm) transitions, respectively. The strongest excitation band around 465 nm matches well with the emission wavelength of commercial InGaN-based blue LED chip, indicating that Eu³⁺-doped NBT ceramics may be used as potential environmental friendly red-orange phosphor for W-LEDs application. As an inherent ferroelectric and piezoelectric material, the electrical properties of this potentially multifunctional electro-optical material have been also studied. The introduction of Eu³⁺ distinctly increased the Curie temperature (T _C ) of NBT- _x Eu³⁺ ceramics from 640°C to 711°C as x ranges from 0 to 0.40. For higher temperature applications, the electrical conductivity was also investigated. The conduction of charge carriers in high-temperature range originates from the conducting electrons from the ionization of oxygen vacancies. High T _C and low tanδ makes Eu³⁺-doped NBTceramic also suitable for high temperature piezoelectric sensor applications and electro-optical integration.     

High-pressure synthesis,structure, and electrical properties of Li<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Na<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>NbO<Subscript>3</Subscript> solid solutions

The dielectric permittivity of Li _x Na_{1 ? x} NbO₃ ferroelectric solid solutions prepared at high pressures has been measured as a function of temperature and frequency, and their structural properties have been studied. The results demonstrate that ceramics samples of the Li _x Na_{1 ? x} NbO₃ (x = 0.17, 0.25) ferroelectric perovskite solid solutions exhibit superionic conduction at relatively low temperatures (T ≥ 400 K). In the temperature range of superionic conduction, we observe significant dielectric dispersion and anomalies in permittivity, corresponding to structural transformations of the high-pressure solid solutions.     

Influence of the Preparation Conditions and Percolation Threshold on the Properties of Lead Zirconate Titanate/Cobalt Nickel Ferrite Magnetoelectric Composites

We have prepared magnetoelectric (ME) composite ceramics, free of foreign phases, in the lead zirconate titanate–cobalt nickel ferrite two-phase system: xPZT-36 + (100–x)Ni_0.9Co_0.1Fe₂O₄. The sol–gel derived ferrite powder used in our preparations seems to be doped with titanium cations from the PZT-36. The ceramics have a percolation threshold at x = 50–70 wt %, which is due to the increased electrical conductivity of Ni_0.9Co_0.1Fe₂O₄. As a consequence, the piezoelectric parameters of the ME ceramics drop sharply at x < 50–70 wt %: the piezoelectric moduli |d_ij| and piezoelectric voltage coefficients |g_ij| decrease by a factor of 3–5 in this composite range. The piezoelectric parameters |d_ij| and |g_ij| of the composites produced using the fine ferrite powder exceed those of the materials prepared using macrocrystalline Ni_0.9Co_0.1Fe₂O₄ powder by more than a factor of 2. The piezoelectric voltage coefficient g33 correlates with the ME coefficient ΔE/ΔH. The highest ME conversion efficiency (up to 45 mV/(cm Oe)) is offered by the 80 wt % PZT-36 + 20 wt % Ni_0.9Co_0.1Fe₂O₄ composites, whose composition lies in a subpercolation region. Even though the composites produced using the fine ferrite powder possess improved piezoelectric properties, they have smaller ΔE/ΔH coefficients (no greater than 25 mV/(cm Oe)), which can be tentatively attributed to the degradation of the properties of the ferrite as a consequence of doping with Ti⁴⁺ cations during the sintering of the composite ceramics.     

Effects of Nb doping on the microstructure,ferroelectric and piezoelectric properties of 0.7BiFeO<Subscript>3</Subscript>–0.3BaTiO<Subscript>3</Subscript> lead-free ceramics

Donor-doped lead-free Bi_0.7Ba_0.3(Fe_0.7Ti_0.3)_1?x Nb_0.66x O₃ + 1 mol% MnO₂ ceramics were prepared by a conventional oxide-mixed method and the effects of Nb-doping on microstructure, piezoelectric and ferroelectric properties of the ceramics were investigated. All the ceramics exhibit a pure perovskite structure with rhombohedral symmetry. The grain growth of the ceramics is inhibited after the addition of Nb doping. High electric insulation (R = 10⁹–10¹⁰ Ω?cm) and the poor piezoelectric performance and weak ferroelectricity are observed after the addition of Nb₂O₅ in the ceramics. Different from the donor effect of Pb-based perovskite ceramics, the introduction of Nb into 0.7BiFeO₃–0.3BaTiO₃ degrades the piezoelectricity and ferroelectricity of the ceramics. The Bi_0.7Ba_0.3(Fe_0.7Ti_0.3)_1?x Nb_0.66x O₃ + 1 mol% MnO₂ ceramic with x = 0 exhibits the optimum piezoelectric properties with d ₃₃ = 133 pN C^?1 and k _p = 0.29 and high Curie temperature (T_C = 603^°C).     

Dual relaxation behaviors and large electrostrictive properties of Bi<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>–Sr<Subscript>0.85</Subscript>Bi<Subscript>0.1</Subscript>TiO<Subscript>3</Subscript> ceramics

Lead-free ceramics (1???x)Bi_0.5Na_0.5TiO₃–xSr_0.85Bi_0.1TiO₃ (BNT–xSBT, x?=?0.4, 0.5, 0.6 and 0.7) were prepared by a solid-state reaction process. Coexistence of ferroelectric relaxation at low temperature and Maxwell–Wagner dielectric relaxation at high temperature was revealed for the first time in this system. Meanwhile, hysteresis-free P–E loops combined with a very high piezoelectric strain coefficient (d₃₃) of 1658 pC/N concurrently with large electrostrictive coefficient Q?=?0.287 m⁴C^?2 were achieved. The ferroelectric relaxor behavior and large electrostrictive strain might be linked to easy reorientation and reversal of ergodic PNRs and the combined effect of Bi off-center position and lone pair electrons.     

Effects of Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> doping on the microstructure and electrical properties of (Ba,Ca)(Zr,Ti)O<Subscript>3</Subscript> lead-free ceramics

Lead-free ceramics (Ba_0.85Ca_0.15)(Zr_0.1Ti_0.9)O₃?x wt.%Cr₂O₃ (BCZT-xCr) were prepared via the conventional solid-state reaction method. The microstructure and electrical properties of BCZT-xCr samples were systematically studied. XRD and Raman results showed that all samples possessed a single phased perovskite structure and were close to the morphotropic phase boundary (MPB). With the increase of the Cr content, the rhombohedral-tetragonal phase transition temperature (T _R-T) increases slightly, and the Curie temperature (T _C) shifts towards the low temperature side. XPS analysis reveals that Cr³⁺ and Cr^{5 +} ions co-existed in Cr-doped BCZT ceramics, indicating the different impact on the electrical properties from Cr ions as “acceptor” or “donor”. For the x = 0.1 sample, relative high piezoelectric constants d ₃₃ (～316 pC/N) as well as high Q _m (～554) and low tanδ (～0.8%) were obtained. In addition, the AC conductivity was also investigated. Hopping charge was considered as the main conduction mechanism at low temperature. As the temperature increases, small polarons and oxygen vacancies conduction played important roles.     

Improved electrical properties of Co-doped 0.92NBT–0.04KBT–0.04BT lead-free ceramics

The (1???2x)NBT–xKBT–xBT ternary piezoelectric system has been extensively studied in recent years. However, its electrical performance is far inferior to lead-based counterparts, and could not meet the requirements for practical applications. In this contribution, the 0.92NBT–0.04KBT–0.04BT (abbreviated as NKBT4) ceramics were prepared by traditional solid-state method. The effects of doped cobalt content on the structure and electrical performance of NKBT4 ceramics were studied systematically. The content of Co₂O₃ affects the average grain size, maximum dielectric constant, piezoelectric properties and the ferroelectric responses of the ceramics. It was found that the introduction of cobalt did not affect the phase structure of the ceramics, but is beneficial for the improvement of the dielectric and piezoelectric properties. When x?=?0.2, the piezoelectric coefficient (d₃₃) is around 130 pC/N, which is greatly improved compared to pure NKBT4 ceramics. Besides, a relatively high dielectric constant (ε_r?=?1150) was obtained at the same composition. This work paves a new way for the further development of high performance lead-free piezoelectric ceramics.     

Good electrical performances and impedance analysis of (1 − <Emphasis Type="Italic">x</Emphasis>)KNN–<Emphasis Type="Italic">x</Emphasis>BMM lead-free ceramics

(1 ? x)(K_0.5Na_0.5)NbO₃–xBi(Mg_0.75Mo_0.25)O₃ [(1 ? x)KNN–xBMM] (x?=?0.005, 0.01, 0.02) ceramics were prepared via a solid-state reaction method. X-ray diffraction patterns (XRD) and Raman spectrum showed that a solid solution was formed between the BMM and KNN, which improved the electrical properties of KNN. With increasing the BMM content, the grain firstly increased and then decreased. When x?=?0.01, the ceramics exhibited the optimized microstructure, indicating that there exits an optimal doping component. Temperature dependence of relative permittivity also increases firstly and then decreases. The relative permittivity (ε_r) of ~?1418 in stabilization zone, ε_max?~?4861 at the Curie temperature T _C ~ 394 °C, good temperature stability ?ε/ε_123 °C?≤?±?15% from 123 °C to 348 °C, and the dielectric loss tanδ?≤?0.036 from 109 to 348 °C were obtained for 0.99KNN-0.01BMM ceramics. Conductivity behavior of the (1 ? x)KNN–xBMM was investigated as a function of temperature from 420 to 520 °C and frequency from 40 to 106 Hz, showing that the basic mechanisms of conduction and relaxation processes were thermally activated, and oxygen vacancies were the possible ionic charge transport carriers at higher temperatures.     

Phase Formation and Phase Transitions in Nonstoichiometric Sodium Bismuth Titanate Ceramics

We have studied the phase formation, microstructure, and dielectric and ferroelectric properties of (Na_0.5–xBi_0.5)TiO₃ and (Na_0.5Bi_{0.5 + x})TiO₃ nonstoichiometric ceramics with Na/Bi < 1 and x = 0–0.1. The grain size of the ceramics has been shown to decrease with increasing x. The temperature dependences of dielectric permittivity for the samples studied have anomalies near ~400 K and peaks at ~600 K, corresponding to ferroelectric phase transitions. The phase transitions near 400 K demonstrate relaxor behavior, indicative of the presence of polar regions in a nonpolar matrix, as supported by laser second harmonic generation measurements. In addition, the (Na_0.5Bi_{0.5 + x})TiO₃ samples with x > 0.05 have anomalies near 900 K, confirming the presence of Bi₄Ti₃O₁₂ as an impurity phase, which is accompanied by an increase in the spontaneous polarization of these samples.     

Effects of LiNbO<Subscript>3</Subscript> doping on the microstructures and electrical properties of BiScO<Subscript>3</Subscript>–PbTiO<Subscript>3</Subscript> piezoelectric system

Piezoelectric ceramics xLiNbO₃–yBiScO₃–(1?x?y)PbTiO₃ (LN–BS–PT, 0.00?≤?x?≤?0.10, 0.30?≤?y?≤?0.36) were synthesized and their phase diagram and morphotropic phase boundary between rhombohedral and tetragonal phases have been confirmed. The optimal properties were found at the composition of 0.03LN–0.36BS–0.61PT with piezoelectric coefficient d₃₃^* value of 702 pm/V, d₃₃ of 551 pC/N, planar electromechanical coupling factor k_p of 0.51, remnant polarization P_r of 46.5 µC/cm², Curie temperature T_c of 337 °C, and a large strain of 0.351% at an electric field of 50 kV/cm and frequency of 2 Hz with a low strain hysteresis of 5.9%. The Curie temperature of the ternary system presents a linear relationship with LiNbO₃ and BiScO₃ contents. The optimization of these electric properties was probably ascribed to the enhancement in domain walls and the improving mobility of domain switching due to LiNbO₃ doping.     

Microwave dielectric properties of ZnO–Nb<Subscript>2</Subscript>O<Subscript>5</Subscript>–<Emphasis Type="Italic">x</Emphasis>TiO<Subscript>2</Subscript> ceramics prepared by reaction-sintering process

The ZnO–Nb₂O₅–xTiO₂ (1 ≤ x ≤ 2) ceramics were fabricated by reaction-sintering process, and the effects of TiO₂ content and sintering temperature on the crystal structure and microwave dielectric properties of the ceramics were investigated. The XRD patterns of the ceramics showed that ZnTiNb₂O₈ single phase was formed as x ≤ 1.6 and second phase Zn_0.17Nb_0.33Ti_0.5O₂ appeared at x ≥ 1.8. With the increase of TiO₂ content and sintering temperature, the amount of the second phase Zn_0.17Nb_0.33Ti_0.5O₂ increased, resulting in the increase of dielectric constant, decrease of Q × f value, and the temperature coefficient of resonant frequency (τ _f ) shifted to a positive value. The optimum microwave dielectric properties were obtained for ZnO–Nb₂O₅–2TiO₂ ceramics sintered at 1075 °C for 5 h: ε _r  = 45.3, Q × f = 23,500 GHz, τ _f  = +4.5 ppm/°C.     

Properties of fluorine-doped PbMg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>O<Subscript>3</Subscript> ceramics

We report the first fluorine doping of lead magnesium niobate in the PbMg _{(1 + x)/3}Nb_{(2 ? x)/3}O_{3 ? x} F _x system in a wide composition range, x = 0.025 to 0.625. The fluorine content of the samples is shown to be substantially lower than the intended one because of the fluorine volatilization in the form of HF during synthesis and sintering in air. The ceramics consist of magnesium and lead oxides undetectable by x-ray diffraction, and a perovskite phase whose composition can be represented by the formula PbMg_{(1 + m)/3}Nb_{(2 ? m)/3}O_{3 ? m} F _m , where the fluorine content after sintering is m ≤ 0.12. The PbO and MgO contents of the ceramics depend on the starting mixture composition (x) and heat-treatment conditions (hydrogen fluoride and lead oxide volatilization). As a result of the low fluorine content, the diffraction patterns of the samples show no superlattice reflections, and their lattice parameter varies insignificantly with x. Data are presented on the temperaturedependent dielectric permittivity of ceramic samples sintered and annealed under different conditions.     

Synthesis and microwave dielectric properties of Zn<Subscript>1+<Emphasis Type="Italic">x</Emphasis></Subscript>Nb<Subscript>2</Subscript>O<Subscript>6+<Emphasis Type="Italic">x</Emphasis></Subscript>

We have studied the formation of zinc niobate, ZnNb₂O₆, with the columbite structure and the microstructure and microwave dielectric properties of Zn_1+x Nb₂O_6+x ceramics. The results demonstrate that, in the range 0.005 ≤ x ≤ 0.03, the excess zinc reduces the porosity of the material and increases its microwave quality factor Q. For x ≥ 0.03, the Q of the ceramics decreases because of the formation of an additional, zinc-enriched phase. Sintering in an oxygen atmosphere is shown to improve the dielectric properties of stoichiometric ZnNb₂O₆.     

Good thermal stability and improved piezoelectric properties of (K<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>)NbO<Subscript>3</Subscript>–Bi(Mg<Subscript>0.75</Subscript>W<Subscript>0.25</Subscript>)O<Subscript>3</Subscript> solid solutions

In this paper, (1 ? x)(K_0.5Na_0.5)NbO₃–xBi(Mg_0.75W_0.25)O₃ (x = 0–0.015) lead-free dielectric ceramics were investigated. XRD analysis certified that the Bi(Mg_0.75W_0.25)O₃ has diffused into (K_0.5Na_0.5)NbO₃ to fabricate a new solid solution. The addition of Bi(Mg_0.75W_0.25)O₃ depressed the orthorhombic–tetragonal phase transition temperature from 210 to 176 °C and tetragonal–pseudocubic phase transition temperature (Curie point) from 419 to 400 °C. As x = 0.005, the ceramics exhibited high relative permittivity (ε ~ 1325), low dielectric loss (tan δ < 2.9%) tan δ stability (Δε/ε_168°C ≤ ±15%) in the temperature range of 168 ~ 369 °C. Especially, the ceramics also showed optimized piezoelectric constant (d ₃₃ = 122 pC N^?1) and remnant polarization (P_r = 32.57 μC cm^–2). These results indicated that the BMW added ceramics have potential applications in ferroelectric and thermal stability devices.     

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.     

Synthesis and investigation of superconducting properties of heterosubstituted magnesium diborides

The properties of magnesium diborides with the composition Mg_{1 ? x} M _x B₂, where M = Al, Ga, In, and Tl, and Mg (B_{1 ? x} E _x ), where E = N, P, and Si (0.05 ≤ x ≤ 0.3), made by sintering of calculated amounts of boron, magnesium, and a substituent element or by a solid-phase exchange reaction of a corresponding halogenide of a metal with MgB₂ at 1070–1170 K are studied. Using RFA technique, it is shown that, from all employed heterosubstituents, only the atoms of aluminum, gallium, and silicon in the amount x ≤ 0.2 are incorporated into magnesium and boron sublatticies. Here, the temperature of the superconducting transition T _c = 39 ± 1K determined for pure magnesium diboride hardly changes.