0.08Pb(Fe1/3Sb2/3)O3-yPbTiO3-(1-0.08-y)PbZrO3压电陶瓷性能研究

合成了钙钛矿结构的0.08Pb(Fe1/3 Sb2/3)O3-yPb-TiO3-(1-0.08-y)PbZrO3三元系压电陶瓷材料,测量并计算了不同y值时的压电常数(d33)、机电耦合系数kp、k33)、机械品质因数(Qm)以及极化前后的介电常数(εT33/ε0),对实验现象进行了简单的讨论,得出一些有益的结论;实验结果表明当选取合适的y值时可以获得压电性能良好的压电材料,如y=0.45时材料的平面机电耦合系数kp、纵向机电耦合系数k33和压电常数d33分别达到0.64×10-12C/N、0.72×10-12C/N和365×10-12C/N.     

Kinetics of Fe(3)O(4)-CoO/Al(2)O(3) catalytic ozonation of the herbicide 2-(2,4-dichlorophenoxy) propionic acid

The presence of Fe(3)O(4)-CoO/Al(2)O(3) can improve degradation efficiency significantly during the ozonation of the herbicide 2-(2,4-dichlorophenoxy) propionic acid (2,4-DP). The main factors affecting degradation efficiency, such as pH, the catalyst concentration and addition of the scavenger, were investigated. The kinetics of the catalytic ozonation are also discussed. The results indicate that two factors, the oxidation after adsorption of 2,4-DP and the oxidation of hydroxyl radicals (OH), lead to a great enhancement in ozonation efficiency during the catalytic ozonation of 2,4-DP in the presence of Fe(3)O(4)-CoO/Al(2)O(3), in which the oxidation of the OH plays an important role. Under controlled conditions, the apparent reaction rate constants for the degradation of 2,4-DP were determined to be 2.567 × 10(-4)s(-1) for O(3) and 1.840 × 10(-3)s(-1) for O(3)/Fe(3)O(4)-CoO/Al(2)O(3). The results from the analysis of the reaction kinetics using the relative method showed that O(3)/Fe(3)O(4)-CoO/Al(2)O(3) possessed a larger R(ct) (R(ct) is defined as the ratio of the ·OH exposure to the O(3) exposure, R(ct) = ∫C(t)(OH) dt/C(t)O(3)dt) than O(3), indicating that O(3)/Fe(3)O(4)-CoO/Al(2)O(3) produced more hydroxyl radicals.     

Role of Mn in controlling the dielectric loss and ageing effect in Pb(Zn1/3Nb2/3)O3–Pb(Fe2/3W1/3)O3–Pb(Fe1/2Nb1/2)O3

Compositions in the Pb(Zn1/3Nb2/3)O3–Pb(Fe2/3W1/3)O3–Pb(Fe1/2Nb1/2)O3 (PZN–PFW–PFN) system show a high dielectric constant, insulation resistance and bend strength. In addition they can be sintered at very low temperatures. Hence they find technological applications as multilayer capacitors with low cost Ag-based internal electrodes. The dielectric loss in these ceramics was controlled by doping with Mn in the form of Mn-acetate, MnO2, and Pb(Mn1/3Nb2/3)O3. The subtle differences in the dielectric properties of PZN–PFW–PFN, when Mn is taken in these forms are reported in this paper. A possible way of controlling the ageing effect is highlighted. © 1998 Chapman & Hall     

冷冻干燥合成ZrO2-(Al2O3,Fe203)及其微观组织的变化

通过冷冻干燥方法制备了ZrO2-Al2O3,ZrO2-Fe2O3二元及ZrO2-(Al2O3,Fe2O3)三元体系的前驱物粉末,研究了不同温度下的相变及微观组织结构,证明Fe2O3具有球化晶粒的作用,并获得了具有均匀细小显微组织的三元体系.     

Crystallization kinetics of amorphous Pb (Fe2/3W1/3) O3

Kinetic data analyses on the crystallization behaviour of amorphous lead iron tungstate (PFW) were carried out. A low value of the glass transition/melting point ratio (0.52) and a high value of the frequency factor (2 × 10³⁷ s^–1) of the first crystallization exotherm may indicate a high degree of metastability of the prepared PFW in the amorphous state. The Avrami exponent was determined to be 3.0, which suggests a bulk nucleation. The activation energy for crystallization was averaged to be 520 kJ mol^–1 for the first exotherm. The validity of the estimated values of the Avrami exponent and the activation energy were confirmed by comparing with an independently obtained product of the two parameters.     

Fabrication of perovskite Pb(Fe2/3W1/3)x(Fe1/2Nb1/2)0.9−xTi0.1O3 by double calcination process

Perovskite, Pb(Fe_2/3W_1/3) _x (Fe_1/2Nb_1/2)_09–x Ti_0.1O₃ (abbreviated as PFW _x PFN_0.9–x PT_0.1 where PFW = 3PbO-Fe₂O₃-WO₃, PFN = 4PbO-Fe₂O₃-Nb₂O₃ and PT = PbO-TiO₂), can be fabricated by the so-called double calcination process. The process is to first partially calcine PFW, PFN and PT separately and then calcine the mixture of PFW, PFN and PT. A bulk density of at least 90% can be achieved with a sintering temperature of 900 to 930° C. The higher the molar proportion of PFW is, the lower the sintering temperature of PFW _x PFN_0.9–x PT_0.1 will be. This system shows a high dielectric constant (32000) and a low loss tangent (1%). The effects of processing temperature on the sinterability and dielectric properties of PFW _x PFN_09–x PT_0.1 are also given.     

Pb(Fe2/3W1/3)O3的制备及其介电性能研究

本文采用半化学法,即硝酸铁代替传统氧化物混合法中的三氧化二铁与PbO和WO3浆料混合,经850℃,2h预烧,一步合成了钙钛矿单相的Pb(Fe2/3W1/3)O3(PFW)预烧粉体;再经870℃和2h烧结,得到了纯钙钛矿相的PFW陶瓷,其理论密度大于98%,在1kHz时的最大介电常数εmax为8000,高于二次合成法和传统氧化物法制备的PFW陶瓷,表明半化学法对制备PFW陶瓷是可行的.     

Structural and electrical characteristics of Sr(Fe2/3W1/3)O3 ceramics

The polycrystalline samples of Sr(Fe_2/3W_1/3)O₃ (SFW) were prepared by a high-energy ball-milling followed by solid-state reaction technique. The X-ray structural analysis showed the formation of single-phase compound in the tetragonal system, which is a distorted structure of an ideal cubic perovskite. The temperature–frequency dependence of dielectric constant and loss tangent exhibited relaxation behavior of the compound. The studies of impedance parameters (Z′, Z″) as a function of temperature and frequency have confirmed the contribution of bulk resistance of SFW. The small value of activation energy of the compound (～ 0.35 eV) can be explained by mixed ionic–polaronic conductivity mechanism.     

(La2/3Ca1/3)(Mn(3-x)/3)Fex/3)O3体系磁电阻行为的研究

通过系统地测量（La_2/3Ca_1/3）（Mn_{（3-x）／3}Fe_x／3）O₃（x＝0、0.1、0．2、0．3的体系样品的电阻率-温度关系以及一定温度下磁电阻率与磁场的关系,发现随x的变化其磁电阻率峰和电阻率峰均发生位移,磁电阻率峰值增大,并伴生磁电阻率峰展宽效应．作者认为由于Fe的替代,引起体系中Mn³⁺／Mn⁴⁺比率及磁矩的变化,加之外场对磁有序结构的调制作用,从而影响了Mn³⁺－O^－Mn⁴⁺的双交换作用,最终导致磁电阻行为发生变化．     

溶胶-凝胶燃烧法制备La_2O_3和La(OH)_3纳米晶的研究

采用燃烧法合成纳米La(OH)3材料,分别以硝酸镧和柠檬酸为镧源和络合剂,以氨水调节pH值为2～4、柠檬酸与硝酸镧的物质的量比为1～1.2∶1之间,加热凝胶至自蔓延燃烧后并在700～750℃煅烧1～2 h,得到膨松粉末状产物,即La2O3纳米晶。利用X射线衍射和透射电镜等测试方法对凝胶热分解过程及最终形成的La2O3纳米晶颗粒进行分析和表征。结果表明:用该方法得到的纳米La2O3产物的平均粒径在30～100 nm之间可控;纳米La2O3在空气中是不稳定的,在自然吸潮情况下和空气中的H2O发生反应生成La(OH)3,控制湿度即可得到纯La(OH)3纳米晶。     

The crystal structures of Ba2R2/3V2O8 (R = La, Nd) and Sr2La2/3V2O8; palmierite derivatives

The title phases Ba₂R_2/3V₂O₈ (R = La, Nd) and Sr₂La_2/3V₂O₈, synthesised by solid state reaction of oxides at 1350°C, have structures derived from that of the palmierite-type of Ba₃V₂O₈; the stoichiometry is often written as A₃RV₃O₁₂. Ba₂La_2/3V₂O₈ is hexagonal, spacegroup R3m, a = 5.75271(7), c = 21.0473(5) Å, Z = 3; cation ordering was determined by joint Rietveld refinement using X-ray and neutron powder diffraction data, R _wp = 4.45%, R _p = 6.33%, ² = 6.847. In the Ba₃V₂O₈ structure, Ba occupies two sites: 3a and 6c. In Ba₂La_2/3V₂O₈, Ba wholly occupies the 3a site; the 6c site contains both Ba, La and vacancies. Bond valence analysis was inconclusive, but tends to support the presence of Ba on the 3a site. Sr₂La_2/3V₂O₈ and Ba₂Nd_2/3V₂O₈ are isostructural, as confirmed by Rietveld refinement using X-ray powder diffraction data. Ba₂R_2/3V₂O₈ phases could not be synthesised for lanthanides, R, smaller than Sm.     

Multiferroic and fatigue behavior of BiFe(0.95)Mn(0.05)O3/Bi(0.90)La(0.10)Fe(0.85)Zn(0.15)O3 bilayered thin films

Bilayered thin films consisting of BiFe(0.95)Mn(0.05)O(3) (BFMO) and Bi(0.90)La(0.10)Fe(0.85)Zn(0.15O3) (BLFZO) layers were prepared on Pt-coated silicon substrates without any buffer layers by RF sputtering. The (110) orientation was induced with a high phase purity for all bilayers as a result of the introduction of the bottom (110)-oriented BLFZO layer. The low leakage current density of BFMO/BLFZO bilayers could be attributed to a combined effect of the BFMO and BLFZO layers. The dielectric constant increases, the remanent polarization decreases, and the coercive field slightly increases with increasing thickness of the BLFZO layer in BFMO/BLFZO bilayers. Magnetic properties in BFMO/BLFZO bilayers are improved by increasing the BFMO layer thicknesses. A large polarization value of 2Pr ~ 189.5 μC/cm2 is obtained for the BFMO/ BLFZO bilayer with a thickness ratio of 3:1, which is much larger than those reported for BFO-based single layers or multilayers, and a good fatigue behavior is demonstrated with an increase in measurement frequencies and driving electric fields.     

Room temperature multiferroic properties of (Bi0.95La0.05)(Fe0.97Mn0.03)O3/NiFe2O4 double layered thin film

(Bi_0.95La_0.05)(Fe_0.97Mn_0.03)O₃/NiFe₂O₄ double layered thin film was prepared on a Pt(111)/Ti/SiO₂/Si(100) substrate by a chemical solution deposition method. X-ray diffraction and Raman scattering spectroscopy studies confirmed the formation of the distorted rhombohedral perovskite and the inverse spinel cubic structures for the (Bi_0.95La_0.05)(Fe_0.97Mn_0.03)O₃/NiFe₂O₄ double layered thin film. The (Bi_0.95La_0.05)(Fe_0.97Mn_0.03)O₃/NiFe₂O₄ double layered thin film exhibited well saturated ferromagnetic (2 M_r of 18.1 emu/cm³ and 2H_c of 0.32 kOe at 20 kOe) and ferroelectric (2P_r of 60 μC/cm² and 2E_c of 813 kV/cm at 866 kV/cm) hysteresis loops with low order of leakage current density (4.5 × 10⁻⁶ A/cm² at an applied electric field of 100 kV/cm), which suggest the ferroelectric and ferromagnetic multi-layers applications in real devices.     

Effect of Fe2O3 crystallite size on its mechanochemical reaction with La2O3 to form LaFeO3

Fe₂O₃ powders with different crystallite sizes prepared by heating FeOOH at various temperatures were ground with La₂O₃ powder using a planetary ball mill to investigate the effect of crystallite size on mechanochemical synthesis of LaFeO₃. Fe₂O₃ powder with smaller crystallite size obtained by heating at lower temperature reacts more easily with La₂O₃ than that with larger size. The mechanochemical reaction proceeds with an increase in grinding time. Specific surface area of the LaFeO₃ powder synthesized has a large value of over 11 m²/g. The mechanochemical process can be also applied to synthesize other iron complex oxides with rare earth elements such as Pr, Nd and Sm.