Structure and electrical properties of Bi0.5Na0.5TiO3–Bi0.5K0.5TiO3–BiCoO3 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics (1 − x − y)Bi_0.5Na_0.5TiO₃–xBi_0.5K_0.5TiO₃–yBiCoO₃ (x = 0.12–0.24, y = 0–0.04) have been fabricated by a conventional solid-state reaction method, and their structure and electrical properties have been investigated. The XRD analysis shows that samples with y ≤ 0.03 exhibit a pure perovskite phase and very weak impurity reflections can be detected in the sample with y = 0.04. With x increasing from 0.12 to 0.24 and y increasing from 0 to 0.04, the ceramics transform gradually from a rhombohedral phase to a tetragonal phase and rhombohedral–tetragonal phase coexistence to a pseudocubic phase, respectively. The morphotropic phase boundary (MPB) of the system between rhombohedral and tetragonal locates in the range of x = 0.18–0.21, y = 0–0.03. The ceramics near the composition of the MPB have good performances with piezoelectric constant d ₃₃ = 156 pC/N and electromechanical coupling factor k _p = 0.34 at x = 0.21 and y = 0.01, which attains a maximum value in this ternary system. Adding content of BiCoO₃ leads to a disappearance of the response in the curves of dielectric constant-temperature to the ferroelectric–antiferroelectric transition. The temperature dependence of dielectric properties suggests that the ceramics are relaxor ferroelectrics. The results show that (1 − x − y)Bi_0.5Na_0.5TiO₃–xBi_0.5K_0.5TiO₃–yBiCoO₃ ceramics are good candidate for use as lead-free ceramics.     

Piezoelectric and dielectric properties of Bi0.5Na0.5TiO3–Bi0.5K0.5TiO3–Ba0.77Ca0.23TiO3 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics (1 − x)Bi_0.5(Na_0.84K_0.16)_0.5TiO₃–xBa_0.77Ca_0.23TiO₃ (BNKT–xBCT, x = 0–0.04) were synthesized by conventional solid-state reaction method. The piezoelectric, dielectric, and ferroelectric characteristics of the ceramics are investigated and discussed. The XRD results show that Ba_0.77Ca_0.23TiO₃ (BCT) has diffused into Bi_0.5(Na_0.84K_0.16)_0.5TiO₃ (BNKT) lattices to form a new solid solution. It is shown that moderate additive of BCT (x ≤ 0.025) in BNKT–xBCT ceramics can enhance their piezoelectric and ferroelectric properties. Three dielectric anomalies are observed in BNKT–xBCT (x ≤ 0.03) ceramics. The piezoelectric measurements and P–E hysteresis loops reveal that BNKT–0.025BCT ceramic has the highest piezoelectric performance and strongest ferroelectricity in all the samples. Piezoelectric constants d ₃₃, k _p, and k _t of 175 pC/N, 29.1, and 54% are, respectively, achieved. Remnant polarization P _r and coercive field E _c reach 28.3 μC/cm² and 24.2 kV/cm, respectively.     

Structure and piezoelectric properties of new (Bi0.5Na0.5)1?x?yBax(Yb0.5Na0.5)yTiO3 lead-free ceramics

New lead-free ceramics (Bi_0.5Na_0.5)_1−x−yBa_x(Yb_0.5Na_0.5)_yTiO₃ (x = 0.02–0.10 and y = 0–0.04) have been prepared by an ordinary sintering technique and their structure and piezoelectric properties have been studied. X-ray diffraction shows that Ba²⁺ and Yb³⁺ diffuse into the Bi_0.5Na_0.5TiO₃ lattices to form a solid solution with a pure perovskite structure and a morphotropic phase boundary (MPB) between rhombohedral and tetragonal phases is formed at 0.04 < x < 0.10. The partial substitutions of Ba²⁺ and Yb³⁺ for A-site ions of Bi_0.5Na_0.5TiO₃ decrease effectively the coercive field E _c and improve significantly the remanent polarization P _r. The ceramics with x = 0.06 and y = 0–0.02 situate within the MPB and possess the lower E _c and larger P _r, and thus exhibit optimum piezoelectric properties: d ₃₃ = 155–171 pC/N and k _p = 29.2–36.7%. The temperature dependences of the dielectric and ferroelectric properties suggest that the ceramics may contain both the polar and non-polar regions at temperatures near/above T _d.     

Dielectric and piezoelectric properties of BiMnO3 doped 0.95Na0.5K0.5NbO3–0.05LiSbO3 ceramics

The piezoelectric properties of (1 − x)(0.95K_0.5Na_0.5NbO₃–0.05LiSbO₃)–x BiMnO₃ (x = 0, 0.002, 0.004, 0.006, 0.008, 0.01) lead-free piezoelectric ceramics were investigated as a function of x. These ceramics were fabricated by conventional ceramics sintering processing. BiMnO₃ (BM)-doping was found to increase the Curie temperature, T _c, from 370 °C at x = 0–380 °C at x = 0.002, and clearly increase the d ₃₃, Q _m and k _p values, showing “hard” characteristic. The good piezoelectric and electromechanical properties of d ₃₃ = 226pC/N, k _p = 40.8%, tan θ = 2.60% and T _c = 370 °C appear at x = 0.004.     

Frequency and temperature dependent dielectric and conductivity behavior of 0.95(K0.5Na0.5)NbO3–0.05BaTiO3 ceramic

Dielectric and conductivity measurements were carried out on the 0.95(K_0.5Na_0.5)NbO₃–0.05BaTiO₃ (KNN–5BT) ceramic both as a function of temperature (∼350–850 K) and frequency (40 Hz to 100 MHz). A high-temperature dielectric relaxation above Curie temperature (∼590 K) was observed and analyzed with the Cole–Cole function. Frequency dependent conductivity was analyzed with an augmented Jonscher relation and exhibited a universal conductivity behavior. The activation energy of dielectric relaxation was estimated to be 1.09 eV. It could be attributed to the thermal motion of double ionized oxygen vacancy or to the formation of defect dipoles between the acceptor ion and charge compensating oxygen vacancies. The mechanism for both the high-temperature dielectric relaxation and the frequency dependent conductivity was proposed based on a possible mode of incorporation of Ba²⁺ and Ti⁴⁺ ions into the KNN lattice sites.     

Structure and electrical properties of (Bi0.5Na0.5)0.94Ba0.06TiO3–Bi0.5(Na0.82K0.18)0.5TiO3–BiAlO3 lead free piezoelectric ceramics

0.09(Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃–(0.01 − x) Bi_0.5(Na_0.82K_0.18)_0.5TiO₃–x BiAlO₃ (BNBKT–xBA) lead-free piezoelectric ceramics were synthesized by conventional solid-state reaction processes. Structure, ferroelectric and piezoelectric properties of BNBKT–xBA ceramics were investigated. X-ray diffraction data shows that BNBKT–xBA ceramics form the pure perovskite phases and the ceramics have the morphotropic phase boundary when x ≤ 0.030. At room temperature, the BNBKT–xBA ceramics at x = 0.030 have better electrical properties, the piezoelectric constant d₃₃ and planar coupling factor k_p of BNBKT–xBA ceramics reaches peak values at x = 0.030: d₃₃ = 217 pC N⁻¹, k_p = 0.308. The remnant polarization P_r, mechanical quality factor Q_m and relative dielectric constant ?_r of BNBKT–xBA ceramics at x = 0.030 attains 33.8 μC cm⁻², 133 and 928 (100 KHz), respectively. As BA content increase, the depolarization temperature T_d shift toward lower temperature, and T_d of BNBKT–xBA ceramics with x = 0.030 decreased to 55 °C.     

Proton conduction and chemical stability of (La0.5Sr0.5)(Mg0.5+yNb0.5−y)O3−δ

Electrical conduction properties of complex perovskite-type oxides in the (La_0.5Sr_0.5)(Mg_0.5+yNb_0.5−y)O_3−δ (y = 0.02-0.06) series at intermediate-high temperatures were investigated; introduction of protons by hydration of oxide-ion vacancies was expected by increasing the Mg/Nb ratio from unity. The conductivity depended on y and a maximum conductivity was obtained at y = 0.04: σ = 4.9 × 10⁻⁶ S cm⁻¹ at 400 °C in wet H₂ atmospheres. From electromotive force measurements of hydrogen and water vapor concentration cells, electrical conduction in wet H₂ atmospheres can be attributed to ionic conduction, and proton conduction is dominant below 700 °C. Unlike other perovskite-type proton conductors, (La_0.5Sr_0.5)(Mg_0.54Nb_0.46)O_3−δ was stable in CO₂ atmospheres even in the low-intermediate temperature region due to dilution of reactive strontium by lanthanum.     

Preparation and Magnetic Properties of?(La1?xSr1+x)(Mn0.5Co0.5)O4

A series of single phase (La_1−x Sr_1+x ) (Mn_0.5Co_0.5)O₄ (0≤x≤0.40) materials with a tetragonal K₂NiF₄ structure was prepared by a solid state reaction method at 1400 or 1450 °C with a short period of heating time. Powder X-ray diffraction (XRD) and the Rietveld refinement method were employed for the structural analysis. Unit cell a- and c-axes decrease with increasing amount of Sr substitution. A discrepancy between the zero-field-cooled and the field-cooled magnetization is observed in all samples investigated below a characteristic temperature, T ^*, which likely arises from the canted nature of spins or the random freezing of spins. It appears that T ^* decreases with increasing amount of Sr substitution, which is possibly due to the enhancement of chemical pressure induced by Sr and a corresponding increases of the valence of Mn and/or Co.     

Phase diagram and electric properties of the (Mn, K)-modified Bi0.5Na0.5TiO3–BaTiO3 lead-free ceramics

In this study, the phase diagram and electric properties were demonstrated for a (Mn, K)-modified Bi_0.5Na_0.5TiO₃ (BNT)-based solid solution. (0.935−x) Bi_0.5Na_0.5TiO₃−xBi_0.5K_0.5TiO₃−0.065BaTiO₃ with 0.5% mol Mn doping was prepared by a conventional solid-state reaction method. A morphotropic phase boundary (MPB) formed between the ferroelectric rhombohedral and tetragonal phases around x of 0.04 with the MPB tolerance factor t of 0.984–0.986. The temperature and composition dependence of the dielectric, piezoelectric, ferroelectric properties along with the strain characteristics were investigated in detail and a phase diagram was presented. Around the MPB region, the maximum values of piezoelectric constant d₃₃^* d_{33}^{*} of 290 pC/N, d ₃₃ of 155 pC/N, dielectric constant e₃₃^T /e₀ \varepsilon_{33}^{T} /\varepsilon_{0} of 1059 and low dielectric loss tangent tan δ of 0.017 were obtained. In addition, the authors also suggest that the solid solution with composition x of 0.24, exhibiting both high-depolarization temperature T _d of 182 °C, d₃₃^* d_{33}^{*} of 156 pC/N, d ₃₃ of 130 pC/N, will be favorable for high-temperature actuator and sensor applications.     

Effects of ball milling on microstructure and electrical properties of sol–gel derived (Bi0.5Na0.5)0.94Ba0.06TiO3 piezoelectric ceramics

A citrate sol–gel method was investigated for synthesizing lead-free piezoelectric compositions of (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ (BNT) and the effect of ball milling on the sintering, microstructure and electrical properties of BNT ceramics was emphasized. The thermal analysis and X-ray diffraction results show that crystalline powders with a single perovskite structure can be obtained when calcined at 600 °C for 3 h. The average particle size of as-calcined powder and electrical properties of sintered samples were obviously dependent on an additional ball milling. Because of well-dispersed superfine powders (∼100 nm), the BNT ceramics can be well densified at temperature 50 °C lower than that by mixed-oxide method and conventional sol–gel method and as a result exhibit enhanced electrical properties of a piezoelectric constant d₃₃ ∼ 180 pC/N and a planar electromechanical coupling factor k_p ∼ 0.29.     

Preparation and magnetic properties of SrFe12O19/Ni0.5Zn0.5Fe2O4 nanocomposite ferrite microfibers via sol–gel process

SrFe₁₂O₁₉/Ni_0.5Zn_0.5Fe₂O₄ nanocomposite ferrite microfibers with diameters of 1–2 μm have been prepared by the sol–gel process. The SrFe₁₂O₁₉/Ni_0.5Zn_0.5Fe₂O₄ nanocomposite ferrites are formed after the precursor calcined at 850 °C for 2 h, fabricating from nanosized particles with a uniform phase distribution. The ferrite grain size increases with the calcination temperature. The magnetic properties for the nanocomposite ferrite microfibers are mainly influenced by the chemical composition and grain size. The nanocomposite ferrite microfibers obtained at 900 °C show the enhanced specific saturation magnetization (M_sh) of 64.8 Am² kg⁻¹, coercivity (H_c) of 146.5 kA m⁻¹ and remanence (M_r) of 33.6 Am² kg⁻¹ owing to the exchange–coupling interaction. This exchange–coupling interaction in the SrFe₁₂O₁₉/Ni_0.5Zn_0.5Fe₂O₄ nanocomposite ferrite microfibers has been discussed.     

Synthesis and Characterization of(Na0.5K0.5)NbO3（NKN） Thin Films Formed by a Diol-based Sol-gel Process

Lead-free(Na_(0.5)K_(0.5))NbO_3(NKN) thin films were fabricated by spin coating on Pt/Ti/SiO2/Si substrates by a diol-based sol-gel process.Na-acetate,K-acetate,Nb-pentaethoxide and 1,3 propanediol were used to prepare the NKN precursor solution.Thermal analysis showed two characteristic temperatures of 360 and 600 ℃.Based on these temperatures,a heat treatment program with pyrolysis at 360 ℃ and calcination at 600 ℃ after every layer was used.To avoid inhomogeneities and secondary phases,an excess of sodium and potassium was necessary.To evaluate the proper excess amount of sodium and potassium secondary ion mass spectrometry(SIMS) lateral element maps and X-ray diffraction(XRD) patterns were recorded.An excess amount of 20% led to homogeneous distribution of the elements and to single phase perovskite NKN films with random crystal orientation.Scanning electron microscopy(SEM) images showed a pore free surface with 100 nm grains.The leakage current measurements showed a current of 1×10~(-3) A/cm~2 at 150 kV/cm.     

Evidence of phase heterogeneity in sol–gel Na0.5K0.5NbO3 system

Na_0.5K_0.5NbO₃ thin films have been synthesised via a sol–gel route using commercially available ethoxides of sodium, potassium and niobium. X-ray diffraction confirmed that film crystallisation occurred at ≥600 °C, but extra peaks indicated the presence of secondary phase(s). The thin films displayed non-ferroelectric polarisation hysteresis loops. Evidence of phase heterogeneity was found from detailed analyses of the thermochemistry of the NKN precursor gels which showed multiple heating DTA exotherms for crystallisation around 480–550 °C. Additionally, heating DTA endotherms and cooling exotherms for NKN gels around 800–850 °C confirm the presence of a second phase.     

Structural, spectroscopic and microwave characterizations of (Sm0.5Y0.5)Ti(Nb1?xTax)O6 ceramics

Microwave dielectric ceramics of the type (Sm_0.5Y_0.5)Ti(Nb_1−x Ta _x )O₆ were prepared for x = 0, 0.2, 0.4, 0.6, 0.8 and 1 through the conventional solid state ceramic route. The ball-milled compositions were calcined at 1,250 °C. The cylindrical pellets were sintered at temperatures between 1,385 and 1,450 °C. The densities were determined by Archimedes method. The structure was analyzed using X-ray diffraction method. The microwave dielectric properties of the polished pellets were measured using cavity resonator method. The morphological studies were done using Scanning Electron Microscopy and Transmission Electron Microscopy. The Raman spectra were recorded and analyzed to confirm the structural change. The photoluminescence spectra were also taken and the emission lines were identified. A correlation study was done among the measured properties and parameters. Most of the samples have high dielectric constant, high quality factor and low temperature coefficient of resonant frequency and hence suitable for microwave applications.     

La0.5Y0.5Ni4.8Mn0.1Al0.1和La0.5Y0.5Ni4.8Al0.2合金的储氢性能研究

针对两种新型稀土型储氢合金La0.5Y0.5Ni4.8Mn0.1Al0.1和La0.5Y0.5Ni4.8Al0.2的储氢特性进行研究分析。实验表明,相同温度下,La0.5Y0.5Ni4.8Mn0.1Al0.1和La0.5Y0.5Ni4.8Al0.2合金的PCT曲线基本重合,且都具有优良的吸氢动力学性能;相比之下,后者的滞后系数要小于前者,吸氢量较大,吸氢速率也较快,故其储氢性能较优。300次吸放氢循环实验结果表明,La0.5Y0.5Ni4.8Al0.2合金的吸氢动力学性能虽然略有下降,但抗粉化性能较好。     

Microstructures and dielectric properties of Ba0.5Sr0.5TiO3–Zn2TiO4 composite ceramics with low sintering temperature for tunable device applications

Ba_0.5Sr_0.5TiO₃–Zn₂TiO₄ composite ceramics with low dielectric constant and high tunability are fabricated at a relatively low sintering temperature of 1200 °C via the conventional solid-state reaction route. Zn₂TiO₄ and Ba_0.5Sr_0.5TiO₃ can be friendly coexistent in the composite material system. The dielectric constant is tailored from 2500 to 83 by manipulating the addition of Zn₂TiO₄ content from 0 wt.% to 80 wt.% weight ratio. The dielectric loss still keeps around 0.002 and the tunability is 10.3% under a DC-applied electric field of 30 kV/cm at 10 kHz for the 80 wt.% Zn₂TiO₄ added Ba_0.5Sr_0.5TiO₃ composite ceramics. These composite ceramics are promising candidates for multilayer low-temperature co-fired ceramics (LTCC) and potential tunable devices applications.     

Densification behavior, microstructure, and electrical properties of sol–gel-derived niobium-doped (Bi0.5Na0.5)0.94Ba0.06TiO3 ceramics

Superfine powders (~100 nm) with compositions of (1 − x)(Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ + xNb⁵⁺ (BNTBT6 + xNb) with x from 0 to 0.02 were synthesized by an improved citrate sol–gel method using Nb₂O₅ as Nb⁵⁺ source. The sintering behavior, microstructure, and various electrical properties of BNTBT6 + xNb ceramics were investigated. The results indicated that the addition of a small amount of Nb⁵⁺ has no remarkable effect on the crystal structure and grain morphology, but the electrical properties of the ceramics are obviously influenced. The BNTBT6 + 0.005Nb compositions exhibit enhanced densification behavior and improved electrical properties of a piezoelectric constant d ₃₃ ~ 205 pC/N and a planar electromechanical coupling factor k _p ~ 33%.     

Structural and dielectric properties of Na1?xBaxNb1?x(Sn0.5Ti0.5)xO3 ceramics

Lead-free (1 − x)NaNbO₃/xBa(Ti_0.5Sn_0.5)O₃ (x = 0.1, 0.125, 0.15, 0.175, 0.2, and 0.3) ceramics were elaborated by the conventional ceramic technique. Sintering has been made at 1523 K for 2 h. The crystal structure was investigated by X-ray diffraction with CuKα radiation at room temperature. As a function of composition, these compounds crystallize with tetragonal or cubic symmetry. Dielectric measurements show that the materials have a classical ferroelectric behavior for compositions in the range 0.10 ≤ x ≤ 0.15 and relaxor one for compositions in the range 0.15 < x ≤ 0.30. Temperatures T _C or T _m decrease as x content increases. The ferroelectric behavior has been confirmed by hysteresis characterization. For x = 0.1, a piezoelectric coefficient d ₃₁ of 42.146 pC N⁻¹ was obtained at room temperature. The evolution of the Raman spectra was studied as a function of temperature for x = 0.1.     

Improvement of the Irreversibility Line of the 1212 Compound Tl0.5Pb0.5Sr2CaCu2O7?δ

The superconducting properties and the irreversibility line of the Tl_0.5Pb_0.5Sr₂CaCu₂O_7– were studied by ac susceptibility on both ceramic and powder samples prepared in sealed quartz tube at 960°C. In parallel, carefull investigations by DTA/Tg, X rays diffraction and plasma emission spectroscopy were performed on each sample after each thermal treatment. It is shown that the superconducting properties are strongly dependent on further heat treatments and that the irreversibility line may be optimized. Nevertheless, the results obtained suggest that further improvement of the irreversibility line might be expected.     

Bi0.5Na0.5TiO3和Bi0.5K0.5TiO3含量对三元固溶体系无铅PTC热敏陶瓷性能的影响

PTC热敏陶瓷的无铅化是绿色智能加热及电路智能保护元件研制的重要前提。为了获得可在空气气氛下烧结且兼具高居里温度和高升阻比的无铅化PTC热敏陶瓷,本工作采用固相法制备了(1-x)BaTiO₃-0.5xBi_0.5Na_0.5TiO₃-0.5xBi_0.5K_0.5TiO₃和0.98BaTiO₃-0.02yBi0_.5Na_0.5TiO₃-0.02(1-y)Bi_0.5K_0.5TiO₃三元固溶体系无铅PTC热敏陶瓷材料,研究了不同含量的Na和K元素对无铅PTC热敏陶瓷材料的烧结特性和电学性能的影响。结果表明,BNT和BKT均与BaTiO₃形成固溶体,随着BNT含量的增加,PTC陶瓷平均晶粒尺寸减小;当BNT和BKT含量相同时,PTC陶瓷可以在较宽的烧结温度范围内实现半导化,且在...