Dielectric properties of solid solutions PbMg1/3Nb2/3O3-SrTiO3

Ceramic samples of the solid solutions PbMg_1/3Nb_2/3O₃-SrTiO₃ are synthesized. The dielectric properties are studied and a phase diagram is constructed. The results obtained are discussed in terms of ideas concerning relaxor ferroelectrics for solid solutions on the PMN side and from the standpoint of potential ferroelectrics on the SrTiO₃ side. The introduction of SrTiO₃ into PMN gradually degrades relaxor properties, and the introduction of PMN into SrTiO₃ does not result in initiation of the ferroelectric phase transition, possibly because of the appearance of random fields in the lattice. The possibility of practical applications of the synthesized system is also discussed. Fiz. Tverd. Tela (St. Petersburg) 41, 1091–1095 (June 1999)     

Influence of fabrication processing on phase transition and electrical properties of 0.8Pb(Zr1/2Ti1/2)O3–0.2Pb(Ni1/3Nb2/3)O3 ceramics

The binary system of 0.8Pb(Zr_1/2Ti_1/2)O₃–0.2Pb(Ni_1/3Nb_2/3)O₃ ceramics were synthesized by conventional mixed oxide and columbite method. X-ray diffraction analysis demonstrated the coexistence of both the rhombohedral and tetragonal phases for the columbite prepared sample. Rhombohedral to tetragonal phase transition for columbite method was different compared with those of the mixed oxide method. The permittivity shows a shoulder at the rhombohedral to tetragonal phase transition temperature T_Rho–Tetra = 195 °C, and then a maximum permittivity (36,000 at 10 kHz) at the transition temperature T_m = 277 °C on ceramics prepared with the columbite method. However, piezoelectric coefficient (d₃₃) was measured to be 282 pC/N for the conventional method and higher than the columbite method. The results were related to the phase compositions and porosity of the ceramics.     

铁电磁体Pb(Fe1/2Nb1/2)O3的磁电性能研究

对铁电磁体Pb(Fe1/2Nb1/2)O3单晶样品中的介电和磁性能进行了研究. 认为在其反铁磁相变点观察到的介电常数和损耗的异常来自于自发极化序和自旋序的相互作用引起的磁电耦合. 磁矩与温度的关系曲线在Néel点以下的低温段呈上升趋势,测得的磁滞回线证明有弱铁磁性出现. 对铁电磁体磁电相互作用的Monte Carlo模拟得到与实验类似的结果.     

Specific-heat anomaly caused by ferroelectric nanoregions in Pb(Mg(1/3)Nb(2/3))O3 and Pb(Mg(1/3)Ta(2/3))O3 relaxors

The specific heat of typical relaxors, Pb(Mg(1/3)Nb(2/3))O3 (PMN) and Pb(Mg(1/3)Ta(2/3))O3 (PMT), was measured by adiabatic and relaxation methods between 2 and 420 K. A broad anomaly was found in the specific heat curve over the wide temperature range between 150 and 500 K for PMN, and between 50 and 400 K for PMT, which provides evidence for the formation of ferroelectric nanoregions (FNR) in the paraelectric matrix. The entropy of the anomaly was estimated as 3.3 J K(-1) mol(-1) and 2.9 J K(-1) mol(-1) for PMN and PMT, respectively, which implies an order-disorder-type mechanism for the formation of FNR.     

Electronic properties of Pb(ZrTi)O3 solid solutions

The theoretical backgrounds and some experimental data on the electronic properties of polycrystalline Pb(Zr, Ti)O₃ solid solutions are summarized. These substances occur in the perovskite structure, and so their electronic band structure is presumed to be analogous to other perovskite compounds. Their forbidden gap energy has been determined to be about 3.30–3.56 eV on the basis of optical, photoacoustical, and photoelectrical measurements. Many local levels and traps exist in the forbidden gap because of the polycrystalline character and heterovalent doping. Their actual configurations and states strongly influence the optical, photoelectrical, piezoelectrical, and other physical properties of Pb(Zr, Ti)O₃ solid solutions.     

Solid-state single and triple-quantum 93Nb MAS NMR studies of ferroelectric Pb(Mg1/3Nb2/3)O3 and a related pyrochlore

Pb(Mg1/3Nb2/3)O3 (PMN), a well-known relaxor ferroelectric material, and a related pyrochlore phase have been studied by single- and triple-quantum 93Nb MAS NMR spectroscopy. The assignment of the NMR resonances has been attempted.     

Microstructure and properties of Pb(Mg1/3Nb2/3)O3–Portland cement composites

Lead magnesium niobate, Pb(Mg_1/3Nb_2/3)O₃ (PMN), ceramics particles was mixed with Portland Cement (PC) using a water to cement ratio of 0.50 and PMN content at 40% and 60% by weight to produce 0–3 Pb(Mg_1/3Nb_2/3)O₃–Portland cement (PMN–PC) composites. Microstructure and hydration of the composites were investigated. Calcium silicate hydrate gel can be seen surrounding the PMN particles. Dielectric constant of the composites was found to increase with PMN content. Successful poling of the composites was achieved. Interestingly, SEM micrographs of the PMN40 composite clearly showed calcium silicate hydrate gel (an essential hydration product of Portland cement) surrounding the PMN particles. In PMN60 composite, the gel can also still be seen but of less quantity. This is thought to be due to the increase in the volume ratio of the ceramics where the amount of calcium silicate hydrate gel was reduced in relation to the overall volume.     

Soft phonon anomalies in the relaxor ferroelectric Pb(Zn(1/3)Nb(2/3))0.92Ti0.08O3

Neutron inelastic scattering measurements of the polar transverse optic phonon mode dispersion in the cubic relaxor Pb(Zn(1/3)Nb(2/3))0.92Ti0.08O3 at 500 K reveal anomalous behavior in which the optic branch appears to drop precipitously into the acoustic branch at a finite value of the momentum transfer q = 0.2 A(-1) measured from the zone center. We speculate that this behavior is the result of nanometer-sized polar regions in the crystal.     

Photorefractive effect in the relaxor ferroelectric material 0.91Pb(Zn1/3Nb2/3)O3-0.09PbTiO3

The photorefractive effect in a nominally undoped 0.91Pb(Zn1/3Nb2/3)O3-0.09PbTiO3 single crystal is measured. We report what is, to our knowledge, the first observation of the photorefractive effect in Pb-based relaxor ferroelectric crystals. The crystal is grown by the flux solution method. Then it is cut into a 2 mm x 4 mm x 8 mm piece and electrically poled along the [111] direction. The coupling constant of the two-wave mixing is 17 cm(-1), and the normalized time constant under 1-W/cm(2) illumination is 12 s at a wave-length of 476 nm. The effective trap density is calculated as 5 x 10(16) cm(-3) from the Debye screening length under the assumption of Kukhtarev's band-transport model. The dominant carrier is identified to be holes from the direction of two-wave mixing energy transfer.     

Low- and infralow-frequency dielectric properties of the Pb(Mg1/3Nb2/3)O3 + 2 wt % Li2O ceramics

A dielectric response of the Pb(Mg_1/3Nb_2/3)O₃ ferroelectric ceramics with impurity of 2 wt % Li has been studied. The phase transition has been found to exhibit a relaxor character, as is the case in PMN without Li. However, unlike pure PMN, the dielectric response dispersion in PMN + 2 wt % Li₂O has been described by the Cole-Cole equation at temperatures below the temperature of the low-frequency maximum of the permittivity. An analysis of the dispersion parameters in a wide temperature range has demonstrated that it can be due to the relaxation of domain walls in PMN + 2 wt % Li₂O that appear most likely because of the existence of anomalously coarse grains in PMN + 2 wt % Li₂O.     

Perovskite Pb(Sc1/2Nb1/2)O3 nanopowders synthesized by surfactant-modulated precipitation

A novel surfactant-modulated precipitation method is proposed to produce pure perovskite Pb(Sc_1/2Nb_1/2)O₃ (PSN) nanopowders at a low temperature of 700 °C. The samples were characterized by XRD, SEM, TEM, and HRTEM, respectively. The results indicate that the powders exhibit a granular shape of 80 nm in diameter. It is believed that the nanosize of as-prepared PSN powders is dependent on the well-dispersed performance, which arouse from the combined effects of both precipitant TMAH and surfactant CTAB. The mechanism of the formation of the pure perovskite PSN nanopowders is discussed in detail. Our method is expected to create a new, low-cost route to produce the promising nanopowders of multi-component perovskite systems.     

Control of the properties of Pb(TixZr1-x )O3 solid solutions by external disturbances

The influence of x-ray irradiation to absorbed radiation doses D = (0.5?12) × 10⁸ rad on the properties of ferroelectric ceramic Pb(Ti_xZr_1?x )O₃ solid solutions with compositions close to the morphotropic phase boundary was studied. The effects of x-ray radiation on the electrical conductivity of ferroelectric ceramics are shown to differ with x ranging from 0.42 to 0.60. Using empirical equations and numerical techniques, quantitative relations are established between the composition, absorbed radiation dose, and electrical conductivity for Pb(Ti_xZr_1?x )O₃.     

Effects of strontium on the characteristics of Pb(Zr1/2Ti1/2)O3--Pb(Zn1/3Nb2/3)O3 ceramics

The dielectric and piezoelectric properties of pyrochlore-free lead zirconate titanate-lead zinc niobate ceramics were investigated systematically as a function of Sr doping. The powders of Pb_{(1? x )}Sr _x [0.7(Zr_{1 / 2}Ti_{1 / 2})–0.3(Zn_{1 / 3}Nb_{2 / 3})]O₃, where x?=?0–0.06 were prepared using the columbite-(wolframite) precursor method. The ceramic materials were characterized using X-ray diffraction, dielectric spectra, hysteresis and electromechanical measurements. The phase-pure perovskite phase of Sr-doped PZN--PZT ceramics was obtained over a wide compositional range. The results showed that the optimized electrical properties were also achieved at composition x?=?0.0, which were K _P?=?0.69, d ₃₃?=?670?pC?N^?1, P _r?=?31.9?µC?cm^?2 and ε_rmax?=?18600. Maximum dielectric constant values of the systems decreased rapidly with increasing Sr concentration. Moreover, with increasing Sr concentration dielectric constant versus temperature curves become gradually broader. The diffuseness parameter increased significantly with Sr doping. Furthermore, Sr doping has been shown to produce a linear reduction in the transition temperature (T _m)?=?294.1–12.7x°C with concentration (x). Sr shifts the transition temperature of this system at a rate of 12.7°C?mol^?1%.     

铁电单晶0.62Pb(Mg1/3Nb2/3)O3-0.38PbTiO3折射率的研究

用最小偏向角法在20℃下精确测量了0.62Pb(Mg1/3Nb2/3)O3-0.38PbTiO3(0.62PMN-0.38PT)单晶的折射率,给出了该温度下折射率色散的Sellmeier方程.研究了能带结构与折射率的关系,计算了样品的Sellmeier光学系数:对no,E0=5.50eV,λ0=0.226μm,S0=1.004×1014m-2,Ed=28.10eV;对ne,E0=5.57eV,λ0=0.223μm,S0=1.017×1014m-2,Ed=28.10eV.ABO3型钙钛矿材料中,BO6八面体基元决定了晶体的能带结构,对折射率产生重要影响.     

Dielectric properties of Pb(Mg1/4Zn1/4Nb1/2)O11/4

Polycrystalline samples of Pb(Mg_1/4Zn_1/4Nb_1/2)O_11/4 have been synthesized by high temperature columbite precursor solid state reaction technique. Using X-ray diffraction (XRD) technique, compound formation in single phase cubic structure was observed and XRD analysis provided preliminary structural data. Detailed studies of dielectric properties of the compound reveal that this compound has high dielectric constant and diffuse phase transition in a wide range of temperatures around the Curie temperature. The charge deficiency of the compound presumably gets compensated in the high temperature columbite precursor process of sample preparation which is supported by single phasic form of the material.     

化学溶液法制备的Pb(Mg1/3 Nb2/3)O3-PbTiO3薄膜的光学性能

用化学溶液方法在宝石衬底及有LaNiO3缓冲层的Pt/TiO2/SiO2/Si衬底上制备了92%Pb(Mg1/3 Nb2/3)O3-8%PbTiO3(PMNT)薄膜,X射线衍射测试结果表明:在有LaNiO3缓冲层的Pt/TiO2/SiO2/Si衬底上制备的PMNT薄膜几乎是纯钙钛矿相,且薄膜呈现(110)择优取向.通过对Pt/TiO2/SiO2/Si衬底上的PMNT薄膜在2.5-12.6μm波长范围内的红外椭圆偏振光谱测试,并拟合得到了PMNT薄膜在2.5-12.6μm波长范围内的光学常数(n和k),通过对宝石衬底上的PMNT薄膜在200-1100nm波长范围内的可见-紫外透过率测试,并拟合得到了PMNT薄膜在200-1100nm波段的光学常数(n和k)和吸收系数α,进而推导出PMNT薄膜的禁带宽度为4.03eV.     

Transparent ferroelectric ceramics PbMg1/3Nb2/3O3-xPbZr0.53Ti0.47O3: Dielectric and electro-optical properties

Lanthanum-free high-transparency ferroelectric ceramics PbMg_1/3Nb_2/3O₃?xPbZr_0.53Ti_0.47O₃ (PMN-xPZT) have been prepared for the first time by a two-stage sintering method. The dielectric and electro-optical properties of the PMN-xPZT ceramics of different compositions, with the values of x both far from the morphotropic phase boundary (x = 10, 16, 23%) and close to it (x = 33%), have been studied. It has been shown that, in compositions lying closer to the morphotropic phase boundary (x = 23 and 33%), one observes, with no electric field applied, a first-order phase transition to a macrodomain ferroelectric phase, whereas the compositions far from the boundary (x = 10, 16%) persist in the relaxor cubic phase down to the low-temperature domain. It has been found that, in the ceramic with x = 33%, the quadratic electro-optical coefficients have at high temperatures (T > 340 K) the largest value among the relaxor systems, which expands the temperature interval of applicability of these solid solutions in industry.     

Piezoresponse imaging and local characterization of ferroelectric domains in Pb(Zn1/3Nb2/3)O3–7%PbTiO3 single crystals

Ferroelectric domain structures of (001)‐oriented Pb(Zn_1/3Nb_2/3)O₃–7%PbTiO₃ (PZN‐7%PT) single crystals were visualized and characterized by piezoresponse force microscopy (PFM). Locally regular domain configurations are found to be possibly related to the stable macroscopic properties in the PZN‐7%PT single crystals. Nanoscale piezoresponse hysteresis loops measured by PFM tip revealed no evidence of local domain switching behavior in the PZN‐7%PT single crystal. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Pb-driven anti-ferroelectric phase in Pb(Mg1/3Nb2/3)O3 : First-principle study

Density functional calculations are used to investigate the role of Pb displacement in the formation of anti-ferroelectric phase in Pb(Mg_1/3Nb_2/3)O₃. Order and disordered supercells, both are used. Through geometry optimization without symmetry imposed, the two supercells are found to be anti-ferroelectric. Displacement of cations are analyzed and it is shown that asymmetry of Pb’s next-nearest B-site shell is probably the reason for anti-parallel displacement of Pb. A–B-site, B-site–O bond distances and O₆ octahedral volumes are also calculated.