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 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.     

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。     

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.     

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...     

Pr掺杂Sm0.5Sr0.5CoO3阴极的性能研究

固体氧化物燃料电池(SOFC)因能量转换效率高,绿色无污染而备受关注。研究发现,钙钛矿结构的Sm_0.5Sr_0.5CoO_3-δ(SSC)是电子-离子混合导体,具有良好的氧还原活性,以及电导率高、极化电阻低等优点。为了探究镧系元素Pr掺杂对SSC阴极性能的影响,采用溶胶-凝胶法制备Pr_xSm_0.5-xSr_0.5CoO₃(x=0.1,0.2,0.3,0.4,0.5)阴极粉体,对其进行一系列表征和电化学性能测试。电化学阻抗谱(EIS)测试表明,当Pr掺杂量为0.3时,PSSC-30阴极在550～750℃范围内的极化电阻均小于其他掺杂量;在700℃时,全电池的功率密度达到最大,为311.06mW/cm²。     

La掺杂Hf0.5Zr0.5O2薄膜铁电性能研究

铪基氧化物薄膜在超薄膜厚下仍具有优良的铁电性能,非常适用于高密度集成的铁电存储。La掺杂铪基薄膜拥有极为优异的循环写擦特性,但其剩余极化强度(2Pr≤35μC/cm²)还有待进一步提高。本研究采用原子层沉积(ALD)制备La掺杂的Hf_0.5Zr_0.5O₂薄膜(HZLO),通过快速热退火(RTA)对样品进行500℃、550℃和600℃的热处理,研究La掺杂及退火温度对TiN/HZLO/TiN/W结构铁电性能的影响。研究表明,La掺杂促进薄膜四方相转变为正交相,剩余极化强度(49.8μC/cm²)获得极大提高。此外,La掺杂还降低了器件矫顽场(～1.25 MV/cm)并改善矫顽电场对称性。随着退火温度升高至550℃,正交相占比升高至～77%,剩余极化强度高达49.8μC/cm²,而进一步升高退火温度至600℃,正交相、四方相和立方相朝着单斜相转变,器件剩余极化强度降低。     

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.     

LiSbO3含量对BiMnO3掺杂K0.5Na0.5NbO3陶瓷的结构与压电性能的影响研究

采用传统陶瓷常压烧结工艺制备(0.996–x)KNN-0.004BM-xLS(x=0、0.01、0.02、0.03、0.04、0.05、0.06)无铅压电陶瓷,着重研究了LS的含量对(0.996–x)KNN-0.004BM-xLS陶瓷相结构和压电性能的影响。结果表明,当x≤0.02时,陶瓷具有单一的正交相结构;当0.03≤x≤0.05时,陶瓷具有正交相与四方相共存的过渡结构;当x=0.06时,陶瓷具有单一的四方相结构。陶瓷的MPB成分范围在0.03≤x≤0.05。随着LS含量的增加,陶瓷材料的d33和kp均先增加后减小,当x=0.05时,均达到最大值,分别为230 pC/N和0.42;陶瓷的To-t和Tc均向低温方向移动;当x=0时,陶瓷的To-t和Tc分别为455和215℃;当x=0.02时,陶瓷的To-t和Tc分别为385和150℃;当x=0.06时,To-t和Tc分别降至370℃和75℃。     

Li0.5La0.5TiO3包覆LiNil/3Co1/3Mnl/3O2材料的研究

以Li0.5La0.5TiO3为包覆物,制备了固体电解质包覆的LiNil/3Co1/3Mnl/3O2正极材料。采用XRD、SEM对材料进行了表征:XRD显示未包覆的材料具有α-NaFeO2层状结构,粒径在200～300nm之间,包覆后材料粒径略有增大,包覆层具有ABO3型固体电解质结构。包覆层的致密程度及材料的循环稳定性与热处理温度有关。包覆后400℃热处理得到的材料首次放电比容量为185mAh/g,较未包覆材料容量有所提高,50次循环后其容量仍能达到156.5mAh/g,表明包覆物Li0.5La0.5TiO3对LiNil/3Co1/3Mnl/3O2具有保护作用。     

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.     

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.     

不同烧结工艺对K0.5Na0.5NbO3陶瓷微结构的影响

采用普通烧结方法和热压烧结方法制备了K0.5Na0.5NbO3(KNN)无铅压电陶瓷.着重研究了两种烧结工艺对陶瓷的微观结构、晶粒形貌及致密度的影响.研究结果表明,两种烧结方法制备的陶瓷样品都具有单一的正交钙钛矿结构,与普通烧结工艺相比,利用热压烧结工艺制备的样品呈现较高的相对密度(大于98%)、较小的晶粒尺寸(0.6μm左右)及较低的介电损耗(1 kHz,tanδ≤2.8%).实验中发现对于热压烧结的样品,通过改变后期退火温度,样品的晶粒尺寸,致密度可以有规律地变化.     

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.     

Na0.5Bi0.5TiO3纳米纤维的制备及形成机理研究

以Bi(NO3)3 5H2O、板状钛酸(H1.07Ti1.73O4 nH2O)、NaOH为原料,采用水热法合成了具有钙钛矿结构的Na0.5Bi0.5TiO3纳米纤维.利用X射线衍射仪(XRD)、场发射扫描电镜(FESEM)、透射电镜(TEM)和X射线能谱仪(EDS)对产物进行表征.通过考察在200℃下水热反应不同时间的产物的相结构、微观形貌及化学组成,对Na0.5Bi0.5TiO3纳米纤维的形成机理进行了探讨.结果表明:钛酸H1.07Ti1.73O4 nH2O是一类具有层板结构的化合物,在水热反应过程中,板状钛酸的层间H3O+可与Na+、Bi3+进行离子交换,通过原位生长的方式形成了板状Na0.5Bi0.5TiO3颗粒,随着水热反应的进行,板状Na0.5Bi0.5TiO3颗粒裂解形成纳米纤维.所得的Na0.5Bi0.5TiO3纳米纤维分散性好,具有钙钛矿结构,直径为30~150 nm,长度为几个微米到十几个微米.     

聚吡咯/Ni0.5Zn0.5Fe2O4复合物的合成与表征

采用超声场下原位聚合法制备聚吡咯/Ni0.5Zn0.5Fe2O4(PPy/NZFO)复合物。分别采用X射线衍射仪(XRD)、扫描电镜(SEM)、四探针测试仪和矢量网络分析仪对其结构、形貌、电性能和吸波性能进行研究。结果表明:APS/Py摩尔比为0.75的条件下可获得团聚程度较小、粒径大小比较均匀的聚吡咯颗粒。随着超声聚合反应时间的延长,聚吡咯颗粒的粒径呈现增大趋势。PPy/NZFO复合物的电导率与PPy含量成正比。复合物的吸波性能较纯PPy有很大提高,在5~20GHz频率范围内,NZFO含量为40%(质量分数)的复合物反射损耗都在-12dB以上,在18.15GHz处具有最大的反射损耗-16.76dB,-15dB有效带宽为1.65GHz。     

Bi4Ti3O12–(Ni0.5Zn0.5)Fe2O4 dielectric–ferromagnetic ceramic composites synthesized with nanopowders

Bi₄Ti₃O₁₂ and (Ni_0.5Zn_0.5)Fe₂O₄ nanopowders were prepared by co-precipitation and hydrothermal methods, respectively. It was found that ethanolamine is effective as a precipitating agent in the synthesis of Bi₄Ti₃O₁₂ nanopowders via co-precipitation, and it also plays an important role in the synthesis of (Ni_0.5Zn_0.5)Fe₂O₄ nanopowders. Bi₄Ti₃O₁₂–(Ni_0.5Zn_0.5)Fe₂O₄ multiferroic ceramics were obtained by sintering the as-prepared nanopowders. Lower sintering temperatures (800–900 °C) were available when compared with the traditional solid state method and ceramic composites with higher density and limited interfacial reaction were obtained. The ceramics also showed lower dielectric loss and higher magnetic moments. Both the ferroelectric and magnetic phases preserve their individual properties in bulk composite form and thus, these types of composite ceramics appear to be good candidate multiferroic materials.     

纳米Ce1-x(Eu0.5La0.5)xO2固溶体对Mg2Ni合金储氢性能催化作用研究

采用水热法合成纳米Ce1-x(Eu0.5La0.5)xO2(x=0、0.04)固溶体,系统研究固溶体在球磨条件下对Mg2Ni合金储氢性能的催化作用。XRD结果表明,随着Ce1-x(Eu0.5La0.5)xO2添加量的增大及球磨时间的延长,样品的非晶纳米晶含量增加;SEM结果显示,催化剂均匀分布在合金表面,随着球磨时间延长,团聚现象减少;催化剂对球磨样品的活性、最大放电容量和高倍率放电性能均有良好的催化作用,掺杂固溶体比纯CeO2具有更好的催化活性。     

Sr、Nb掺杂(Bi0.5Na0.5)0.94Ba0.06TiO3陶瓷的介电性能研究

采用固相反应法制备Sr、Nb掺杂BNBT无铅压电陶瓷,利用X射线衍射仪(XRD)、扫描电子显微镜(SEM)和介电谱仪表征了样品的晶体结构,表面形貌及介电性能,研究了陶瓷的相结构,微观形貌和介电响应。结果表明,BNBT陶瓷为单一的钙钛矿结构,而BNBT-3SN、BNBT-3SN-3Sr和BNBT-3SN-1Nb陶瓷除了主相钙钛矿结构,存在少量第二相。形貌结构显示出样品相对比较致密,晶粒尺寸分布均匀。SrNb₂O₆的引入使介电峰T_s向低温方向移动,增强弛豫相变程度从而提高了陶瓷基体的介电温度稳定性,BNBT-3SN陶瓷在40～406℃内表现出良好的温度稳定性。通过阻抗图谱分析可知,所有样品主要为晶界传导机制。而且研究表明Sr、Nb掺杂可通过对BNBT-3SN陶瓷氧空位浓度的作用,实现对电导率的调控。随着Sr²⁺的增加,样品的氧空位浓度增加,电导率增大;而Nb⁵⁺的增加,填充了氧空位导致氧空位浓度减小促使电导率降低。