(Ba1-xSrx)La4Ti4O15（x=0.8～0.95）陶瓷的微结构及微波介电性能研究

采用固相反应法制备了(Ba1-xSrx)La4Ti4O15(x=0.8~0.95)复合体系微波介质陶瓷,并对其进行物相组成、晶体结构分析以及微波介电性能的研究.研究结果表明,(Ba1-xSrx)La4Ti4O15陶瓷主晶相为SrLa4Ti4O15,并伴随有第二相SrLa8Ti9O15.SEM观察表明,Ba0.2Sr0.8La4Ti4O15陶瓷内部微观结构致密,晶粒尺寸在10~20μm之间,晶界清晰.随着x值逐渐增大,(Ba1-xSrx)La4Ti4O15陶瓷中晶粒形态发生变化,气孔增多.在x=0.8时,(Ba1-xSrx)La4Ti4O15陶瓷具有优良的微波介电性能,即εr=40.86,Q×f≈62806 GHz,τf=20×10 6/℃.随着Ba2+的含量逐渐增加,该陶瓷的介电常数εr单调上升,品质因子Q×f值增加,说明适量的Ba2+替代Sr2+能改善陶瓷的微波介电性能.     

Fe2O3掺杂MgTiO3-CaTiO3微波陶瓷的介电性能研究

采用固相法制备0.93MgTiO3-0.07CaTiO3-xFe_2O_3(摩尔分数x=0.01~0.025)微波介质陶瓷材料,研究添加Fe_2O_3后,体系的晶体结构、显微结构和微波介电性能之间的变化规律。利用XRD、SEM、网络分析仪对样品的相组成、微观结构、介电性能进行测试分析。研究表明:该复合陶瓷样品的致密度、介电常数和Q·f值随Fe_2O_3含量的增加先增大后减小。当x(Fe_2O_3)为0.015,在1290℃烧结4h时,获得最优的介电性能:εr=21.32,Q·f=37448GHz,τf=0.577×10-6/℃。     

PbTiO3+Bi2Ti2O7掺杂的Ba4.5Nd9Ti18O54微波介质陶瓷

研究了PbTiO3 Bi2Ti2O7掺杂的Ba4.5Nd9Ti18O54微波介质陶瓷材料的结构和介电性能.结果表明,随着掺杂量的增加,陶瓷材料的密度呈现出轻微下降的趋势,介电常数则保持较高的数值,Q值及τf随掺杂量的增加而下降.当PbTiO3 Bi2Ti2O7掺杂量为20%时,材料的εr≈93,Q.f≈5800 GHz,τf≈3×10-5/℃.XRD分析表明,当PbTiO3 Bi2Ti2O7掺杂量小于24%时,Ba4.5Nd9Ti18O54材料仍呈现出单相结构.利用电介质极化理论初步解释了材料介电性能变化的原因.     

添加La2O3对Mg2TiO4陶瓷的显微结构与微波介电性能的影响

采用传统烧结工艺,制备了具有不同La2O3含量的镁钛镧陶瓷,并研究了La2O3组份对材料晶相构成、晶粒、晶界的演变、介电常数和品质因数的影响。结果表明,不含La2O3的钛酸镁陶瓷主晶相为Mg2TiO4,其平均晶粒尺寸＞60μm;引入La2O3后,出现新晶相La0.66TiO2.99,材料的晶粒尺寸明显下降;随La2O3含量的增加,材料的介电常数线性增加,材料的品质因数Q在10GHz出现最大值（16558）。     

SnO2掺杂对BMN陶瓷结构及介电性能的影响

采用固相烧结法制备Ba(Mg_(1/3)Nb_(2/3))O_3+x(x=0~8)%SnO_2(BMSN,x为质量分数)微波介质陶瓷,并研究SnO_2掺杂对Ba(Mg_(1/3)Nb_(2/3))O_3(BMN)微波介质陶瓷结构及介电性能的影响。XRD分析表明,陶瓷体系中存在两种相,主晶相Ba(Mg_(1/3)-Nb_(2/3))O_3和附加相Ba_5Nb_4O_(15)。随着x的增大,BMSN陶瓷体系的相结构逐渐由钙钛矿六方结构转变为立方结构,同时有序相逐渐由1∶2有序结构转变为1∶1有序结构。研究表明:添加适量的SnO_2可以促进液相烧结,当SnO_2掺杂质量分数为6%时,BMN陶瓷致密化烧结温度由纯相时的1 550℃以上降低至1 200℃,表观密度ρ=6.39g/cm3,相对理论密度为99.1%,此时BMSN陶瓷体系拥有优良的微波介电性能——高相对介电常数(ε_r=33.6),接近于零的谐振频率温度系数(τ_f=0.15×10~(-6)℃~(-1)),高品质因数与谐振频率的乘积(Q·f=112 300GHz(8GHz))。     

微波和真空烧结制备La2O3掺杂Al2O3透明陶瓷

通过共沉淀法制备La2O3掺杂Al_2O_3纳米粉,粉体经压制后分别采用微波和真空烧结制备Al_2O_3透明陶瓷。结果表明:Al_2O_3粉末颗粒大小均匀,近似球形,为40~60nm;两种烧结方式制备的试样XRD图中均为α-Al_2O_3,未检测到其它相。La2O3掺杂量为1%时,随烧结温度升高,两种烧结方法得到的Al_2O_3陶瓷的相对密度和抗弯强度均呈上升趋势,且微波烧结陶瓷的相对密度和抗弯强度明显高于真空烧结。1500℃烧结时,随La2O3掺杂量的增加,Al_2O_3陶瓷的相对密度均先增大后减小,当La2O3掺杂量为1%时,Al_2O_3陶瓷的相对密度和抗弯强度均最大。微波烧结陶瓷的透光率明显高于真空烧结,且其断口晶粒比真空烧结明显细少。     

MnO2对Ba(Mg1/3Nb2/3)O3微观结构和微波介电性能的影响

研究了MnO2助烧剂对Ba(Mg1/3Nb2/3)O3陶瓷的微观结构和微波介电性能.MnO2可以有效地使Ba(Mg1/3Nb2/3)O3陶瓷的致密化温度由1550℃降低到1400℃左右.随MnO2掺量的增加,Ba(Mg1/3Nb2/3)O3陶瓷的12超晶格衍射峰的强度减弱,但是没有第二相出现.1400℃烧结4h陶瓷的晶粒尺寸在1.5μm左右.MnO2的掺入改善了Ba(Mg1/3Nb2/3)O3陶瓷的微波介电性能,MnO2掺量为1%mol的Ba(Mg1/3Nb2/3)O3陶瓷具有最好的微波介电性能εr≈31.5,Qf=68000,τf=3.11×10-5/℃,这可归功于陶瓷具有相当高的相对密度.     

Ba5 Nb1-x(Al1/3Mo2/3)x 4O15陶瓷的结构和微波介电性能

移动通信的全面快速发展迫切需要研究开发频率温度系数小的中等ε_r、高Q值的微波介质陶瓷新材料。本工作通过固相反应法,将(Al_1/3-Mo_2/3)⁵⁺引入缺位型六方钙钛矿陶瓷Ba₅Nb₄O₁₅的B位,研究离子掺杂对其相组成、微结构和微波介电性能的影响。分析表明：适量的(Al_1/3-Mo_2/3)⁵⁺有利于Ba₅Nb₄O₁₅陶瓷的致密化烧结,然而当掺入量过多时,并未完全形成固溶体,出现了第二相BaMoO₄,这在一定程度上会影响陶瓷基体的微波介电性能。随着取代量的增加,Ba₅[Nb_1-x(Al_1/3Mo_2/3)_x]₄O₁₅陶瓷的介电常数及Q×f值均表现出下降的趋势,但是复合取代令τ_f值朝负方向移动。当x=0.1时,1 385℃下烧结的陶瓷样品具有最优的微波介电性能：ε_r=37,Q×f=10 300 GHz,τ_f=6.5×10^-6/℃。结果表明,改性的Ba₅Nb₄O₁₅陶瓷介质可作为候选材料应用于高可靠性的移动通信器件。     

氧化气氛对CaCu3Ti4O12陶瓷显微结构及介电性能的影响

采用固相法合成了CaCu₃Ti₄O₁₂陶瓷, 研究了氧化气氛热处理对其显微结构和介电性能的影响。结果表明, 氧化气氛热处理后, CaCu₃Ti₄O₁₂陶瓷的介电常数略微下降, 介电损耗角正切值得到有效抑制, 降至0.03~0.04。在183~273 K温度范围内, CaCu₃Ti₄O₁₂陶瓷总的介电损耗可以分解成低频电导损耗和高频的两个弛豫损耗峰, 氧化气氛热处理后低频电导损耗的贡献下降较为明显。对CaCu₃Ti₄O₁₂陶瓷的晶粒、晶界进行阻抗分析, 发现在393 K时晶界电阻值从1.8×10⁴ Ω增大到8.6×10⁴ Ω。伏安特性(J-E)结果表明氧化气氛热处理使CaCu₃Ti₄O₁₂陶瓷的击穿场强和非线性系数分别从226 V/mm、3.52上升到397 V/mm、4.51, 晶界势垒高度从0.56 eV增大到0.63 eV。     

Bi2O3助熔剂对CaO-B2O3-SiO2/Al2O3玻璃陶瓷复合材料性能的影响

以CaO-B₂O₃-SiO₂(CBS)玻璃粉体和Al₂O₃陶瓷粉体为原料,通过在CBS与Al₂O₃的质量比固定为50:50的玻璃-陶瓷复合材料中添加适量的Bi₂O₃作为烧结助熔剂,探讨了Bi₂O₃助熔剂对CBS/Al₂O₃复合材料的烧结性能、介电性能、抗弯强度和热膨胀系数的影响规律.研究表明:Bi₂O₃助熔剂能通过降低CBS玻璃的转变温度和黏度促进CBS/Al₂O₃复合材料的致密化进程,于880 ℃下烧结即能获得结构较致密、气孔较少的CBS/Al₂O₃复合材料.然而,过量添加Bi₂O₃将使玻璃的黏度过低,从而恶化CBS/Al₂O₃复合材料的烧结性能、介电性能及抗弯强度.当Bi₂O₃的添加量为CBS/Al₂O₃复合材料的1.5wt%时,于880 ℃下烧结即能获得最为致密的CBS/Al₂O₃复合材料,密度为2.82 g·cm^-3,这一材料具有良好的介电性能(介电常数为7.21,介电损耗为1.06×10^-3),抗弯强度为190.34 MPa,0~300 ℃的热膨胀系数为3.52×10^-6 K^-1.     

Influence of Fabrication Parameters on the Phase Formation and Dielectric Properties of CaCu3Ti4O12 Ceramics

The giant dielectric permittivity materials CaCu 3 Ti 4 O 12(CCTO) were synthesized by conventional solid-state reaction techniques.X-ray diffraction and Raman scattering for the powder indicate that the powder calcined at 950 C for 12 h has been completely transformed into the purer CCTO phase.Furthermore,the morphology and size of the grains of the ceramics sintered at 1090 C in the dwell time range from 0 to 26 h were observed by scanning electron microscopy(SEM).Dielectric properties of the polycrystalline CCTO ceramics were characterized in a broad frequency range(100 Hz-1 MHz) and at a temperature ranged from 300 to 500 K.The longer sintering time may lead to more defect structures and the enhanced conductivity,also leads to substantial improvements in permittivity.Grain size and density differences were not large enough to account for the enhancement in dielectric permittivity.Based on the observations,it is believed that the primary factor affecting dielectric behavior is the development of internal defects.The CCTO ceramics sintered at 1090 C for 15 h exhibit lower dielectric loss(～0.05) near room temperature,and the dielectric relaxation behavior above 1 kHz was observed to follow the Arrhenius law.The activation energy(E a) of 0.65 eV indicates that the doubly ionized oxygen vacancies in the grain boundaries are responsible for the dielectric relaxation of the CCTO ceramics.     

Dielectric properties and high-temperature dielectric relaxation of Ba3Ti4Nb4O21 ceramic

A₃B₈O₂₁ hexagonal perovskite-like Ba₃Ti₄Nb₄O₂₁ ceramics were synthesized by a conventional solid-state reaction technique, which exhibit high dielectric constant at room temperature. A high-temperature dielectric relaxation was observed in frequency range from 40 Hz to 1 MHz above the Curie temperature. The real and imaginary parts of the impedance (Z′ and Z″) as functions of frequency indicate the presence of two relaxation processes at high temperatures, which are attributed to grain and grain boundary responses. The conductivities of both grain and grain boundary obey the Arrhenius law with activation energies of 1.04 eV and 1.27 eV, respectively. The dielectric relaxation processes are related to the oxygen vacancies inside the ceramic, indicating that the Q × f value of Ba₃Nb₄Ti₄O₂₁ might be improved via eliminating oxygen vacancies.     

Dielectric and non-Ohmic properties of CaCu3Ti4O12 ceramics modified with NiO, SnO2, SiO2, and Al2O3 additives

In order to conciliate dielectric and non-Ohmic properties of CaCu₃Ti₄O₁₂ (CCTO) ceramics, NiO, SnO₂, SiO₂, and Al₂O₃ were added as sintering aids to promote the grain growth of CCTO ceramics. Microstructure, dielectric properties, and non-Ohmic behavior of the CCTO ceramics were investigated. Among them, NiO-modified CCTO exhibits good dielectric and non-Ohmic properties (ε = 69833, tanδ = 0.073, α = 3.66 and E _B = 296.7 V/cm), due to NiO is also one of giant dielectric materials. Therefore, it is suitable for applying semiconductor circuits. The relationship between electrical current density (J) and electrical field (E) demonstrated that Schottky barrier should exist at grain boundaries. Non-linear coefficient α was directly proportional to the height of barrier. Depressing barrier width would improve significantly dielectric permittivity but decrease breakdown voltage.     

Ba2Ti9O20-Ba1.85Sm4.1Ti9O24 layered dielectric resonators with adjustable effective dielectric constant

The layered dielectric resonator structures composed of Ba₂Ti₉O₂₀ (BTO) and Ba_1.85Sm_4.1Ti₉O₂₄ (BSTO) ceramic pellets were introduced to design new microwave dielectric materials with adjustable dielectric constant between 50 and 70. Good combination of microwave dielectric properties (?_r,eff = 50 ~ 70, Qf = 11,700-19,100 GHz and τ_f = − 4.3 to − 1.5 ppm/°C) was obtained by the present approach, and such combination could be optimized by adjusting the volume fraction of BSTO and stacking scheme. For practical applications, the BTO and BSTO layers could be bonded by low-loss adhesive, and the effects of the adhesive on the microwave dielectric properties were limited.     

Dielectric and Electrical Transport Properties of the Fe3+-doped CaCu3Ti4O12

CaCu(3-x)FexTi4O(12)(x=0, 0.015, 0.03, 0.045, 0.06) ceramics were synthesized by sol-gel method. The electrical conduction and dielectric measurements show that the doping of a very small amount of Fe(3+) ions greatly reduces the low-frequency dielectric constants and leakage, and enhances grain resistivity. For the doped samples, the appearance of the strong low-frequency peaks in the spectra of dielectric loss confirms that the doping of Fe(3+) ions induces the contact-electrode effect on ceramic surface. These great changes of electrical properties may originate from the reduced amount of oxygen vacancies by doping Fe(3+)     

Properties of tungsten-doped Bi4Ti3O12-SrBi4Ti4O15 intergrowth ferroelectrics

Ferroelectric and dielectric properties of tungsten-doped Bi₄Ti₃O₁₂-SrBi₄Ti₄O₁₅ ceramics were investigated. A pure phase of all the samples is confirmed by X-ray diffraction patterns. The remanent polarization (2P_r) of the samples increases initially and reaches its maximum value of 43.2 μC/cm² when W content is 0.03, which is over twice as large as that of non-doped one, then decreases with further doping. The coercive field (E_c) shows a weak tungsten content dependency. It is considered that the enlarged 2P_r could be mainly attributed to the restraint of oxygen vacancies as well as the weakening of their mobility. The Curie temperature decreases a little with increasing doping content, which indicates the good thermal stability is not deteriorated by tungsten doping.     

Polymeric precursor synthesis of Ba2Ti9O20

Ba₂Ti₉O₂₀ was synthesized by Pechini method using citric acid as a chelating agent and ethylene glycol as an esterification agent. The effects, of the pH of the starting solutions and the molar ratio of citric acid to total metal cations concentration on the formation of Ba₂Ti₉O₂₀, were investigated. Increasing the pH of the starting solutions enhances the formation of Ba₂Ti₉O₂₀, but the increase of the molar ratio of citric acid to total metal cations concentration retards the formation of Ba₂Ti₉O₂₀ due to increased diffusion distances. Single-phase Ba₂Ti₉O₂₀ was obtained at 1200 °C for 4 h when the molar ratio of citric acid to total metal cations concentration was unity, regardless of the pH of the starting solutions. Increasing the molar ratio of citric acid to total metal cations concentration up to 2, single-phase Ba₂Ti₉O₂ was synthesized at 1200 °C for 6 h for the precursors with pH 3.5 and 6, but not for the precursors with pH 2.0. DTA, TG, XRD, FT–IR spectroscopy and Raman spectroscopy were used to characterize the precursors and the derived oxide powders. Details of the synthesis and characterizations of the resultant products were given.     

CoAl2O4/Al2O3纳米复合陶瓷的结构与表征

利用溶胶-凝胶方法制备了的CoAl2O4/Al2O3纳米复合陶瓷,并用X-ray分析(XRD)、红外光谱(IR)和扫描电镜分析(SEM)对其结构进行了分析.结果表明,随Al2O3含量增多,CoAl2O4尖晶石相从CoAl2O4/Al2O3凝胶中的析晶温度升高.SEM形貌也说明,随Al2O3含量增多,CoAl2O4/Al2O3陶瓷中形成一定的层状结构.     

Sm2O3掺杂(Ba0.7Ca0.3)TiO3-Ba(Zr0.2Ti0.8)O3无铅压电陶瓷的制备与性能

采用固相合成法制备了Sm2O3掺杂的(Ba0.7Ca0.3)TiO3-Ba(Zr0.2Ti0.8)O3(BCZT)无铅压电陶瓷.借助XRD、SEM等手段对该陶瓷的显微结构与电性能进行了研究.结果表明,Sm2O3的掺杂降低了BCZT无铅压电陶瓷的烧结温度并使居里温度点Tc从85℃提高到95℃.当Sm2O3掺杂量为0.02wt%～0.1wt%时,样品具有典型ABO3型钙钛矿结构.Sm2O3掺杂量为0.02wt%时,所得陶瓷样品具有最优综合电性能,其压电常数d33、机电耦合系数kp、机械品质因子Qm、介电损耗tanδ和介电常数εr分别为590 pC/N、0.52、43、1.3%和3372.