PMN基复相弛豫铁电陶瓷电致应变及其温度稳定性的研究

用熔盐法制备的不同居里温度的Pb(Mg1/3Nb2/3)O3基陶瓷预烧粉体和烧结粉体为初始高、低温组元,采用混合烧结法制备出PMN基弛豫铁电复相陶瓷,研究了PMN基复相陶瓷的介电性能和电致伸缩性能及其温度稳定性.结果表明:采用烧结粉体制得的复相陶瓷不仅具有较大的介电常数(室温介电常数为8368)和电致应变2.8×10-4,而且在-10～ 70℃范围内温度稳定性也较好.     

Ferroelectric and dielectric properties of ferroelectromagnet Pb(Fe1/2Nb1/2)O3 ceramics and thin films

The ferroelectric and dielectric properties of ferroelectromagnet Pb(Fe_1/2Nb_1/2)O₃ (PFN) ceramics and thin films prepared by pulsed laser deposition (PLD) have been investigated systematically. PFN ceramics experienced a para-ferroelectric transition and a para-antiferromagnetic transition at 380 K and 145 K, respectively. At room temperature, it has an electrical remnant polarization of 11.5 C/cm² and a coercive field of 4.04 kV/cm. The dielectric behaviors show characteristics of diffusive phase transition at a wide temperature range around 380 K. Anomalies in the dielectric constant and loss tangent have been observed near the Neel temperature of 145 K, indicating a coupling between the ferroelectric and antiferromagnetic orders in PFN ceramics. At room temperature, the PFN films exhibited a remnant electric polarization of 7.4 C/cm², a coercive field of 10.5 kV/cm, and a dielectric constant of 486 at frequency of 10 kHz, indicating their potential applications in memory devices.     

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     

三元陶瓷Pb(In1/2Nb1/2)O3-Pb(Ni1/3Nb2/3)O3-PbTiO3准同型相界附近组分的介电、铁电和压电性能

铅基复合钙钛矿铁电材料广泛应用于机电传感器、致动器和换能器。二元铁电固溶体Pb(Ni_1/3Nb_2/3)O₃- PbTiO₃(PNN-PT)由于其在准同型相界(MPB)区域具有优异的压电、介电性能而备受关注。然而较大的介电损耗和较低的居里温度限制了其在高温高功率器件方面的应用。本研究通过引入Pb(In_1/2Nb_1/2)O₃ (PIN)作为第三组元改善PNN-PT的电学性能, 提高其居里温度; 通过两步法合成了MPB区域的三元铁电陶瓷Pb(In_1/2Nb_1/2)O₃- Pb(Ni_1/3Nb_2/3)O₃-PbTiO₃ (PIN-PNN-PT), 研究了其结构、介电、铁电和压电性能。制备的所有组分陶瓷具有纯的钙钛矿结构。随着PT含量的增加, 陶瓷结构从三方相转变为四方相。通过XRD分析得到了室温下PIN-PNN-PT体系的MPB相图。体系的居里温度由于PIN的加入得到了很大的提高, 更重要的是PIN的引入降低了PNN-PT体系的介电损耗和电导。MPB处的组分展现出了优异的电学性能, 室温下, 性能最优组分为0.30PIN-0.33PNN-0.37PT: d₃₃=417 pC/N, T_C=200 ℃, ε′= 3206, tanδ=0.033, P_r=33.5 μC/cm², E_C=14.1 kV/cm。引入PNN-PT的PIN第三组元使得体系的居里温度和压电性得到提高的同时降低了的介电损耗和电导率, 因此, PIN-PNN-PT三元铁电陶瓷在高温高功率换能器等方面具备一定的应用潜力。     

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.     

Preparation of Pb(Mg1/3Nb2/3)O3–Pb(Zn1/3Nb2/3)O3 ceramics by the B-site precursor method and dielectric characteristics

Powders in the Pb(Mg1/3Nb2/3)O3–Pb(Zn1/3Nb2/3)O3 system, with a high perovskite yield, were prepared by a B-site precursor method. PbO was added to pre-reacted B-site components of Mg1-xZnxNb2O6 solid solution, which was further calcined to form a perovskite structure. Perovskite phase contents and lattice parameters were obtained from X-ray analyses. Weak-field low-frequency dielectric constants and losses of sintered pellets were measured as functions of composition, temperature and frequency. Dielectric relaxation behaviours were investigated in terms of diffuseness coefficients. Microstructures were observed to correlate with other characteristics. © 1998 Chapman & Hall     

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.     

Effect of high pressure on the dielectric properties of relaxor compositions [Pb(Fe1/2Nb1/2)O3]1-x-y-[Pb(Zn1/3Nb2/3)O3]x- [BaTiO3]y

Abstracts are not published in this journal     

不同镁源反应物对反应烧结制备Pb（Mg1/3Nb2/3）O3陶瓷的影响

采用MgO和(MgCO3)4·Mg(OH)2·5H2O为不同镁源反应物,通过高温反应烧结工艺制备Pb(Mg1/3Nb2/3)O0.(PMN)陶瓷,研究不同Mg源反应物对PMN陶瓷物相组成、相对密度及组织形貌的影响.结果表明:以MgO为前驱体时.由于其反应活性差,扩散和反应不均匀,导致烧结样品中有焦绿石相残留,且焦绿石相对晶界的钉扎阻碍作用使得致密化过程进行相对较慢,所得PMN样品致密度相对较低;而以(MgCO3)4·Mg(OH)2·5H2O为前驱体时,因其受热分解可以得到大比表面积、高反应活性的MgO,从而可以制得高致密度且具有单一钙钛矿相组成的PMN陶瓷材料.     

Pb(Zn1/3Nb2/3)O3-Ba(Zn1/3Nb2/3)O3铁电陶瓷结构与性能的研究

采用固相反应的方法系统地研究了BZN稳定PZN基陶瓷的相结构与介电性能.随着BZN含量的增加,PZN-BZN陶瓷中钙钛矿相的稳定性增强,居里温度近似呈线性下降,室温介电常数和介质损耗随也显著降低,最小值分别为380和0.002.为获得100%钙钛矿结构的PZN基陶瓷所需BZN的最小用量为8mol%～10mol%,当BZN的mol%超过15mol%时,PZN基陶瓷中钙钛矿相所占的百分比不再受烧结工艺的影响,基本保持100%.1kHz时Pb0.9Ba0.1Zn1/3Nb2/3O3陶瓷的最大介电常数Kmax=8680,tgδ=0.02,相应的居里温度Tm为24℃.     

高居里温度铁电体0.20Pb(Fe1/2Nb1/2)O3-0.32PbZrO3-0.48PbTiO3的性能

用传统的陶瓷工艺、通过B位氧化物预合成法制备了高质量、钙钛矿结构的0.20Pb(Fe1/2Nb1/2)O3-0.32PbZrO3-0.48PbTiO3(PFN20-PZ32-PT48)铁电陶瓷,该条件下制备的铁电陶瓷呈现相当均匀的微结构和良好的电学性能.PFN20-PZ32-PT48具有较大的室温介电常数(～410)、高的居里温度(TC,～350℃),在295K＜T＜525K温度区间,具有较小的介电常数温度梯度(a)ε/(a)T=2.8/℃,并且介电常数与频率无关,特别适合高温电容器工业的应用.虽然PFN20-PZ32-PT48呈现较为典型的一级铁电相变,其介电性能在顺电相区呈现明显的频率色散现象,并伴随着介电常数和损耗的反常增加.该反常现象的产生可能与陶瓷烧结过程中Fe3 被部分还原成Fe2 离子所诱导产生的热激发的空穴导电机制有关.PFN20-PZ32-PT48的剩余极化(Pr)与频率的关系可以很好地用随机场模型模拟,表明其弛豫行为的产生与短程化学有序所诱导产生的极性簇和/或纳米尺寸的非均匀性有关.     

Temperature and pressure dependence of dielectric properties of ceramic Pb(Fe(1/2)Ta(1/2))O(3)

Dielectric properties such as the real epsilon" and imaginary epsilon" parts of the complex permittivity and the spontaneous polarization P(N) of ceramic Pb(Fe(1/2)Ta(1/2))O(3) with the diffuse phase transition (DPT) were measured under pressures up to 6 kbar. The value of epsilon" shows a broad maximum at a temperature T(m) (mean Curie temperature). As the pressure increases, T(m) of the maximum epsilon" (epsilon"(max)) and the value of epsilon"(max) decrease, and the shape of the maximum in epsilon" around T(m) becomes broader. The pressure coefficient of T(m) is about -3.4 K/kbar. The small heat effect associated with the DPT was observed around T(m). The temperature and pressure dependence of epsilon" and P(s ) is explained in terms of a phenomenological theory using statistical treatments based on a Gaussian distribution of the local Curie temperature. The value of the standard deviation sigma describing the intensity of the DPT is 25 K and increases with increasing pressure.     

Dielectric properties of Pb(Zn1/3, Nb2/3)O3 ceramics modified by Ba(Zn1/3, Nb2/3)O3 and BaTiO3

Dielectric properties of lead zinc niobate (PZN) ceramics modified by barium zinc niobate (BZN) and BaTiO₃ (BT) were investigated. By adding the modifier of BT and BZN, the stabilization of perovskite phase of PZN increased, but its Curie temperature decreased linearly with the amount of added modifier. Room temperature dielectric constant of PZN increased by addition of stabilizers up to 12 and 15 mol% of BZN and BT, respectively. The maximum room temperature dielectric constant was observed to be 7800 at 12 mol% of BZN, and 9800 at 15 mol% of BT, respectively.     

Intermediate Temperature Sintering of La-Modified Pb(Zn1/3Nb2/3)O3-PbZrO3-PbTiO3 Piezoelectric Ceramics

In order to realize the co-firing with Ag/Pd electrodes in multilayer devices, Pb(Zn1/3Nb2/3)1-,-yZrxTiyO3(0.25＜x＜0.35, 0.25＜y＜0.35) piezoelectric ceramics (hereafter designated PZN-PZT)modified by La2O3 has been prepared by conventional technique with sintering temperature from 1100℃ to 1140℃. X-ray diffraction patterns demonstrated that pure perovskite phase was obtained. Secondary electron image (SEI) showed that crystalline grains in ceramics were well grown. d33 of manufactured sample was as high as 560×10-12C/N. kp was about 0.61 and tgδabout 30×10-3. The existence of liquid phase examined by electron diffraction in PZN-PZT sample is beneficial to sintering of the ceramic.     

Perovskite formation and dielectric responses in Pb(Zn1/3Nb2/3)O3-modified Pb(Zn1/3Ta2/3)O3-PbTiO3 ceramics

Pb(Zn_1/3Ta_2/3)O₃-PbTiO₃ ceramic compositions were modified by the introduction of Nb to the octahedral lattice sites. Resultant tendencies in the perovskite formation and dielectric properties were examined. System powders were prepared using a B-site precursor method. Developed structures and lattice parameters of the system compositions were investigated by powder X-ray diffractometry, from which the parameter of a hypothetical perovskite Pb(Zn_1/3Ta_2/3)O₃ is proposed. Weak-field low-frequency dielectric responses of the system ceramics were measured.