弛豫铁电晶体PZNT生长的几个关键问题

新型弛豫铁电晶体(1-x)Pb(Zn1 3Nb2 3)O3-xPbTiO3(PZNT)是一种复合钙钛矿结构的固溶体晶体,具有比传统压电陶瓷PZT远为优越的压电性能,在医用超声成像、声纳、微位移器等方面有着广阔的应用前景。由于该晶体组成复杂,熔体析晶时存在钙钛矿与焦绿石两相的竞争,且PbO组分对Pt坩埚和籽品均能产生腐蚀．采用提拉法等传统生长工艺很难获得钙钛矿结构的实用化的PZNT晶体。目前普遍采用助熔剂来抑制焦绿石相的生成,并且在传统生长工艺的基础上发展了多种改进工艺。结合作者实验室近儿年来在PZNT晶体生长方面的研究结果和实践经验,讨论了助熔剂及其配比的选择、生长技术的发展、工艺参数与晶体性能优化等关键技术问题。     

新型弛豫铁电单晶(1-x)Pb(Zn_(1/3)Nb_(2/3))O_(3-x)PbTiO_3生长的技术创新

(1-x)Pb(Zn_(1/3)Nb_(2/3))O_(3-x)PbTiO_3(PZNT)晶体是弛豫铁电体Pb(Zn_(1/3)Nb_(2/3)O_3与普通铁电体PbTiO_3组成的具有钙钛矿结构的固溶体,其准同型相界成分(x=0.09)附近表现出极其优异的压电性能,在医用超声成像、声纳、微位移器等方面具有广阔的应用前景,分析了PZNT-PbO赝二元系的析晶行为和相关系,总结了PZNT晶体的压电性能,讨论了生长工艺和成分对晶体性能的影响。针对PZNT晶体生长中存在的问题,发展了助熔剂-坩埚下降法、通气诱导成核技术、两步法生长工艺、区熔凝固技术、底部籽晶高温溶液法等多种生长技术,生长出大尺寸的PZNT晶体,并比较了这些生长技术的特点。     

预烧温度对LaAlO3和SrTiO3晶相结构及介电性能的影响

以La2O3和Al2O3、SrCO3和TiO2为原材料,用常规的固相法制备了LaAlO3及SrTiO3粉体,研究了预烧温度对LaAlO3及SrTiO3粉体主晶相形成的影响。XRD衍射实验结果表明:La2O3和Al2O3可以在预烧温度1250℃保温时间10h得到单相的LaAlO3晶体;SrCO3和TiO2在预烧温度1150℃保温时间4h可以得到单相的SrTiO3晶体。另外,LaAlO3与SrTiO3组分与性能的关系研究证明,当其摩尔比为0.5∶0.5时,得到了介电常数为38,介质损耗为1.48×10-4,温度系数为-20.5×10-6/℃的介质材料。     

助熔剂法生长的锆钛锡酸铅镧(PLZST)晶体及生长余料的组分分析

以PbO-PbF2复合体作为助熔剂,采有助熔剂自发成核缓冷法率先制备出成分为（Pb0.94La0.04)(Zr0.37Ti0.18Sn0.45)O3的驰豫型复合钙钛矿结构锆钛锡酸铅镧（PLZST）晶体,合适的生长工艺为：助熔剂中PbO与PbF2的摩尔比为0.55:0.45,原料与助熔剂的摩尔比为1：1,保温温度1250℃,保温时间12h,快降温速率为50－100℃／h,慢降温速率为1－5℃/h,快速降温与慢速降温的转变温度为1150℃,本工作对晶体及晶体生长余料中的组分进行了分析,结果表明：对一定组成的初始配料,PLZST晶体组成相对富La,Ti和Zr,生长后的余料相对富Sn,PLZST晶体中存在两种包裹体缺陷,晶体除包裹体以外各元素分布均匀,生长余料中各元素分布较均匀,存在某些元素的相对富集区域。     

Pb(Zn1/3Nb2/3)O3基陶瓷预合成和烧结工艺的研究

基于Swartz and Shrout的二次合成法,采用改进的两步法,将部分原料预合成,一次烧结合成具有100%钙钛矿结构的75Pb(Zn1/3Nb2/3)O3-10PbTiO3-15BaTiO3固溶体陶瓷.首先一次性称量PbO,然后和ZnNb2O6混合,在660～800℃预合成,将预合成产物粉碎后再与TiO2和BaCO3按化学计量称量,充分混合后,在1060～1140℃保温1～2h烧结成陶瓷试样.实验结果表明:改进的两步法工艺能够将预合成温度降为660℃,烧结温度能被拓宽到80℃获得100%钙钛矿结构的固溶体陶瓷.不同于传统的预合成和烧结,改进的两步法工艺简单、有效,在预合成阶段没有形成钙钛矿相,烧结阶段陶瓷的成瓷和致密化同时进行,完成了中间相向钙钛矿相的转变,获得了介电性能优良的陶瓷试样.     

NdAlO_3及CaTiO_3粉末合成工艺与性能的研究

为满足NdAlO3-CaTiO3体系陶瓷材料介电性能的要求,以Nd2O3和Al2O3、CaCO3和TiO2为原材料,用常规的电子陶瓷合成工艺制备了NdAlO3及CaTiO3粉末,研究了粉末合成温度对NdAlO3及CaTiO3主晶相形成的影响。XRD衍射实验结果表明:Nd2O3和Al2O3可以在合成温度1200℃保温时间10h得到单相的NdAlO3晶体;CaCO3和TiO2在合成温度1150℃保温时间4h可以得到单相的CaTiO3晶体。另外,分析了NdAlO3与CaTiO3比例对NdAlO3-CaTiO3介质陶瓷性能的影响,得到了介电常数为44、介质损耗为2.23×10-4、温度系数为-17.5×10-6/℃的介质材料。     

BaO-Nd2O3-TiO2系陶瓷材料的研究

以BaO-Nd2O3-TiO2为主要研究体系,以Bi2O3,PbO为添加剂,研究了系统的成分配比和工艺对瓷料的介电性能的影响,成功研制出了性能优良的高频、高Q的MLC陶瓷材料.研究结果表明,当BaO:Nd2O3:TiO2的摩尔比为1:1:5时,可在中温范围内(≈1160℃)制成介电常数ε≈98, 介电损耗tg δ≈1.3×10-4(Q≈8000), 电容量的温度系数αc≈30ppm/℃,绝缘电阻IR>1013Ω的高频、高Q的MLC陶瓷材料;当BaO:Nd2O3:TiO2的摩尔比为1:1:4.5时,可在较高温度范围内(≈1200℃)制成介电常数ε≈93,介电损耗tg δ≈0.8×10-4(Q≈10000),电容量的温度系数αc≈10ppm/℃,绝缘电阻IR>1013Ω的高频、高Q的MLC陶瓷材料.     

溶胶-凝胶法制备Li2O-ZnO-B2O3-SiO2系低温玻璃料

以有机锌盐、有机锂盐、正硅酸乙酯、硼酸为原料,乙醇为溶剂,采用溶胶-凝胶法成功制备出Li2O-ZnO-B2O3-SiO2系微晶玻璃料,通过TG-DTA、FTIR、XRD等材料测试方法对Li2O-ZnO-B2O3-SiO2系玻璃料进行分析.结果表明:最佳pH值是4.5,反应温度是40℃,最佳配比Li2O∶ ZnO∶B2O3:SiO2=15∶ 15∶ 10∶ 60;干凝胶开始析出晶体的温度为480℃;当热处理温度为660℃时,能够生成稳定的SiO2晶体,样品晶粒粒径为55.1 nm.     

BaAlBO3F2晶体的生长与形貌

以NaF为助熔剂,BaAlBO3F2和NaF摩尔比为11.5,采用熔盐籽晶生长方法,沿[001]方向生长出尺寸为18 mm×18 mm×12 mm的BaAlBO3F2(BABF)晶体.晶体生长参数降温速率为2～4℃/d,晶体旋转速率为15 r/min.研究了BABF晶体的生长形貌,BABF晶体生长过程中,呈现出(001)和(100)晶面.测试了BABF的粉末倍频效应,其倍频系数约为KDP晶体倍频系数的0.8倍.室温下测试了BABF晶体的显微硬度,其(001)面与(100)面显微硬度分别为10.99 GPa和8.137 GPa.     

BaO-Al2O3-B2O3-SiO2系微晶玻璃低温共烧陶瓷研究

采用烧结法制备了BaO-Al2O3-B2O3-SiO2系微晶玻璃低温共烧陶瓷。通过差热分析仪、影像式烧结点试验仪、X射线衍射仪等方法研究了玻璃组成以及烧结制度对微晶玻璃结构和性能的影响。结果表明:随着B2O3替代Al2O3量的增加,玻璃转变温度和烧结温度逐渐降低,析晶能力增强,有利于重硅酸钡晶体的析出,但不利于钡长石晶体的析出。烧结制度对析出晶体的种类和数量有很大影响。在850℃烧结2 h,微晶玻璃低温共烧陶瓷的气孔率低于1%,热膨胀系数在(7.05～12.78)×10-6/℃之间变化。     

Ferroelectric Ceramics in the PbMg1/3Nb2/3O3-PbCd1/3Nb2/3O3 System

Solid solutions (1-x)PbMg_1/3Nb_2/3O₃ + xPbCd_1/3Nb_2/3O₃ with x = 0-0.30 are investigated with purpose to work out a capacitor ceramics with good dielectric properties and low sintering temperature. It is found that the perovskite phase forms at sintering near to 980°C and begins to decompose at higher temperatures. When x grows from 0 to 0.30, the Curie temperature linearly grows from -10°C to +25°C, the dielectric permittivity ε_m in the Curie point T_C decreases from 18000 to 6800 and the phase transition becomes more diffused. The dielectric permittivity at room temperature is rather high and the temperature stability is improved. The system is of interest, because it can serve as a base for working out some ceramic materials for capacitors with low sintering temperature, which needs of no special atmosphere at burning.     

Structure Evolution from Pb(Mg1/3Nb2/3)O3 to La(Mg2/3Nb1/3)O3

The crystal structure of lanthanum-modified lead magnesium niobates having composition (Pb_{1− x} La _x ) (Mg_{(1+ x )/3}-Nb_{(2− x )/3})O₃ with X = 0 to 1 was investigated by X-ray powder diffraction. It was found that the fundamental reflections from perovskite structure remain in the whole range of composition. The superlattice reflections from the A(B'_1/2-B"_1/2)O₃ ordered structure are also well preserved for La content greater than 50 at.%; however, a series of extra peaks of mixing indices appears, with intensities gradually enhanced with the increase of La content. For the complete substitution of Pb by La, a splitting of some reflections can be observed in the diffraction pattern. The results indicate that the crystal structure evolves continuously with the La content, from disordered cubic perovskite of space group Pm 3 m for X = 0, to ordered cubic perovskite of space group Fm 3 m for X = 0.5, distorted cubic perovskite of space group Pa 3 for 0.5 < X < 0.9, and finally to a rhombohedral perovskite, possibly belonging to the space group R 3 , for X ≥ 0.9. In the evolution of structure, a linear reduction of the lattice constant of the perovskite cell from 4.048 to 3.964 Å was observed.     

Morphotropic Phase Boundary in the Pb(Zn1/3Nb2/3O3)-BaTiO3-PbTiO3 System

The morphotropic phase boundary (MPB) in the relaxor ferroelectric system Pb(Zn_1/3Nb_2/3O₃)-BaTiO₃-PbTiO₃ (PZN-BT-PT) with 15 mol% BT was investigated through dielectric permittivity and high-temperature X-ray diffraction measurements. It was revealed that MPB is a broad composition region extending from 12 to 18 mol% PT, within which the temperatures of the permittivity maximum are close to the ending temperatures for the phase transformation from coexisting rhombohedral and tetragonal phases to cubic phase on heating. When the specimen is cooled, the starting temperatures for the rhombohedral-to-tetragonal phase transition increase with increasing PT content. The large thermal hysteresis observed by X-ray diffraction is caused by the phase transformation between rhombohedral and tetragonal phases. On cooling, the MPB curves toward the PT-rich side, so that ceramics within this composition range undergoe successive phase transitions from cubic to rhombohedral and from rhombohedral to tetragonal phase. The diffuseness of the paraelectric-to-ferroelectric phase transition is remarkably decreased by the addition of PT. The enhanced dielectric permittivity peak values for the MPB compositions are correlated with the reduced lattice distortion and phase coexistence.     

Sintering of glass-added BaZn1/3Nb2/3O3 ceramics

The complex perovskite oxide Ba(Zn_1/3Nb_2/3)O₃ (BZN) has been studied for its attractive dielectric properties which place this material interesting for applications as multilayer ceramics capacitors or hyperfrequency resonators. This material is sinterable at low temperature with combined glass phase–lithium salt additions, and exhibits, at 1 MHz very low dielectric losses combined with relatively high dielectric constant and a good stability of this later versus temperature. The 2 wt.% of ZnO–SiO₂–B₂O₃ glass phase and 1 wt.% of LiF-added BZN sample sintered at 900 °C exhibits a relative density higher than 95% and attractive dielectric properties: a dielectric constant ?_r of 39, low dielectrics losses (tan(δ) < 10⁻³) and a temperature coefficient of permittivity τ_? of 45 ppm/°C⁻¹. The 2 wt.% ZnO–SiO₂–B₂O₃ glass phase and 1 wt.% of B₂O₃-added BZN sintered at 930 °C exhibits also attractive dielectric properties (?_r = 38, tan(δ) < 10⁻³) and it is more interesting in terms of temperature coefficient of the permittivity (τ_? = −5 ppm/°C). Their good dielectric properties and their compatibility with Ag electrodes, make these ceramics suitable for L.T.C.C applications.     

Cation Ordering Transformations in the Ba(Zn1/3Nb2/3)O3-La(Zn2/3Nb1/3)O3 System

Single-phase perovskites were formed in the (1−_x)Ba(Zn_1/3Nb_2/3)O₃-( _x )La(Zn_2/3Nb_1/3)O₃ system for compositions with 0.0≤ x ≤0.6. Although the stability of the trigonal "1:2" ordered structure of the Ba(Zn_1/3Nb_2/3)O₃ end member is very limited (0.0≤ x ≤0.05), low levels of lanthanum induce a transformation to a cubic, "1:1" ordered structure that has a broad range of homogeneity (0.05≤ x ≤0.6). Samples with x > 0.6 were comprised of La₃NbO₇, ZnO, and a perovskite with x = 0.6. The cubic 1:1 phases were fully ordered and no evidence was found for a compositionally segregated microstructure. These observations could not be reconciled in terms of a "space-charge" model; rather, they supported a charge-balanced, "random-site" structure for the 1:1 cation-ordered Ba(β_1/2'β_1/2")O₃ phases.     

Sintering Behavior and Surface Microstructure of PbO-Rich PbNi1/3Nb2/3O3–PbTiO3–PbZrO3 Ceramics

The sintering behavior and surface microstructure of PbNi_1/3Nb_2/3O₃–PbTiO₃–PbZrO₃ (PNiNb-PT-PZ) ceramics were investigated. The PNiNb-PT-PZ ceramics with the stoichiometric composition and the addition of excess lead oxide (PbO-rich ceramics) were sintered by liquid-phase sintering in accordance with the solution-reprecipitation mechanism at temperatures below the melting point of PbO. The temperature at which the liquid phase forms fell to near the eutectic point of the PbO–Nb₂O₅ and the PbO–TiO₂ system (868°C) with the addition of 5 mol% PbO. As the calcination temperature influenced the sinterability of the stoichiometric PNiNb-PT-PZ ceramic, unreacted PbO was considered to be the source of the liquid phase in the sintering of the stoichiometric powder. The secondary phase was observed at the surface of PbO-rich ceramics and was suggested to be a liquid phase expelled from inside the ceramic. A sintering scheme of PNiNb-PT-PZ ceramics was proposed, and the high sinterability of PNiNb-PT-PZ ceramics was attributed to the low formation temperature of the liquid phase.     

Effect of the hydrogen spillover on the selectivity of dibenzothiophene hydrodesulfurization over CoSx/γ-Al2O3, NiSx/γ-Al2O3 and MoS2/γ-Al2O3 catalysts

Dibenzothiophene (DBT) hydrodesulphurization (HDS) reaction at 3 MPa and 325–375 °C on Mo/γ-Al₂O₃ single-bed and Me/γ-Al₂O₃//SiO₂//Mo/γ-Al₂O₃ (Me = Co or Ni) double-bed catalysts were investigated. Results indicate that ratio cyclohexylbenzene (CHB)/biphenyl (BP) or selectivity is higher when using double-beds rather than a single-bed. Synergy in dibenzothiophene hydrodesulphurization on Co//Mo and Ni//Mo double-beds is also detected. Changes in selectivity and conversion are attributed to the action of spillover hydrogen (Hso) formed in the first bed that reaches the second bed.     

Dielectric and Piezoelectric Properties of Pb(Co1/3Nb2/3)O3-PbTiO3-PbZrO3 Solid Solution Ceramics

Ceramic and piezoelectric properties of the Pb(Co_1/3Nb_2/3)O₃-PbTiO₃-PbZrO₃ system were investigated. The system contains rhombohedral, tetragonal, and pseudocubic phases at room temperature. The triple point is at 0.07Pb(Co_1/3Nb_2/3)O₃-0.43PbTiO₃-0.50PbZrO₃. High dielectric constants (750 to 1500) and radial coupling coefficients (40 to 45%) and low average temperature coefficients of resonant frequency (of the order of 10^-6°C) were obtained for compositions near the morphotropic phase boundary.     

Electromechanical Testing and Modeling of a Pb(Mg1/3Nb2/3)O3-PbTiO3-BaTiO3 Relaxor Ferroelectric

Compressive prestress effects on the electrical and mechanical properties of relaxor ferroelectric materials were studied as a function of temperature for several formulations of Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃-BaTiO₃ (PMN-PT-BT) ceramics. Experimentally measured polarization and strain, induced by an ac electric field, decreased as compressive stress increased. Effective Young's moduli also were measured under constant dc electric fields. A significant decrease in modulus was observed with increasing field. The prestress and modulus experiments were modeled analytically using a proposed relaxor ferroelectric constitutive law. In general, excellent agreement between the model and experiments was obtained, indicating that the model accurately predicted the coupled behavior of this relaxor ferroelectric material.     

Low-Temperature Synthesis of 0.65 PbMg1/3Nb2/3O3–0.35PbTiO3 Ceramics

Nanocrystalline 0.65 PbMg_1/3Nb_2/3O₃–0.35PbTiO₃ powders were synthesized by citrate gel method. The gel was prepared using citrate (titanium and niobium) and nitrate (lead and magnesium) salts. The hard gel obtained after completion of the reaction was treated to get the desired phase. Thermal analysis of the gel was done to optimize the calcination temperature. The calcined powders were characterized by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The crystallite size and the effective strain were found to be 50 nm and 0.03584 N, respectively.