Pb(Zn1/3Nb2/3)O_3—Pb(Fe2/3W1/3)O_3二元系陶瓷电容器的介电性质

目前、制备Pb(Zn1/3Nb2/3)O_3(PZN)基陶瓷电容器、最主要的问题是形成有害于介电性质的焦录石相。实验表明、固相反应法很难合成钙钛矿结构的PZN陶瓷。于1000℃经固相反应的产物是含立方焦录石的混合物、在PZN中添加0.25mol的PFW、试样中的钙钛矿相超过97%。通过对Pb(Fe2/3W1/3)O_3(PFW)结晶化学和烧结机理的分析、证明在PZN中添加PFW能减少或抑制焦录石的形成。本文报导了PZN—PFW二元系陶瓷的相关系和介电性质、探讨了钙钛矿相的形成机理。     

Pb(Zn_(1/3)Nb_(2/3))O_3-Pb(Fe_(2/3)W_(1/3))O_3二元系陶瓷的介电性质和钙钛矿相的形成机制

制备 Pb(Zn_(1/3)Nb_(2/3))O_3(PZN)基陶瓷电容器,最主要的问题是形成有害于介电性质的焦录石相。实验表明,固相反应法很难合成钙钛矿结构的 PZN 陶瓷,于1000经固相反应的产物是含立方焦录石的混合物,在 PZN 中添加0.53mol 的 PFW,试样中的钙钛矿相超过97%。通过对 Pb(Fe_(2/3)W_(1/3))O_3(PFW)结晶化学和烧结机理的分析,证明在 PZN 中添加 PFW 能减少或抑制焦录石的形成。本文报导了 PZN-PFW 二元系陶瓷的相关系和介电性质,探讨了钙钛矿相的形成机理。     

锰掺杂对Pb(Zn_(1/3)Nb_(2/3))O_3陶瓷相组成的影响

研究了锰掺杂对合成Pb（Zn_(1／3)Nb_(2／3)）O_3（PZN）陶瓷相组成的影响。用XRD和SEM法探讨了PZN中锰添加量与钙钛矿相形成间的关系，结果表明，仅添加1wt％MnCO_3就能抑制焦绿石的形成，并制成钙钛矿型结构的陶瓷。     

Pb（Zn1／3Nb2／3）O3基陶瓷固相反应中的相变过程

用两次合成工艺,按Pb(Zn_(1/3)Nb_(2/3))O_3(PZN)的化学计量比合成的陶瓷为一种立方焦绿石相和PbO的混合物,其中立方焦绿石相为主晶相。该焦绿石结构的分子式为Pb_2ZnNb_2O_8,Fd3m空间群,Z=6,α=10.62(?)。在PZN基陶瓷中引入钙钛矿结构的子晶(如BaTiO_3),将促进其周围的Pb_2ZnNb_2O_8与PbO结合,形成钙钛矿结构的Pb(Zn_(1/3)Nb_(2/3))O_3。     

Ph(Zn_(1/3)Nb_(2/3))_x(Fe_(1/2)Nb_(1/2))_(0.64-x)(Fe_(2/3)W_(1/3))_(0.36)O_3系陶瓷的介电性质和钙钛矿相的稳定化

本文研究了Ph（Zn_(1/3)Nb_(2/3)）_x（Fe_(1/2)Nb_(1/2)）_(0.64-x)（Fe_(2/3)W_(1/3)）_(0.36)O_3系陶瓷中PZN含量与焦录石相形成间的关系，以及少量添加剂对钙铁矿相的稳定和介电性能的影响。在该系中仅添加0．15wt％MnCO3就可制备100％钙铁矿型结构的陶瓷。文中报导了该系组成的相关系和介电性质。钙铁矿结构的陶瓷，介电常数高，电容温度系数较低。     

(Ba1-xSrx)(Mg1/3 Ta2/3)O3微波陶瓷介电性能研究

Ba(Mg1/3Ta2/3)O3(简称BMT)陶瓷是A(B′1/3B″2/3)O3(A=Ba,Sr;B′=Zn,Mg;B″=Nb,Ta)型复合钙钛矿化合物中的一种,A位由Sr离子取代Ba离子,形成(Ba1-xSrx)(Mg1/3Ta2/3)O3(简称BSMT)固溶体型化合物,也具有复合钙钛矿结构。Sr含量x≥0．6时发生相转变,形成一种新的低温相,这是由于氧八面体畸变造成的。这种低温相结构与BMT六方晶系结构相比具有较低的对称性。低温相的形成．可显著降低BSMT陶瓷的烧结温度．在150℃即可烧结致密(BMT为160℃)。BSMT的微观结构和介电性能(如介电常数ε和介电常数温度系数aε)的变化也与此相转变有关。     

含铅弛豫铁电材料中焦绿石相形成的研究

含铅弛豫铁电材料中焦绿石相的存在是影响材料性能的重要因素,也是制造工艺中遇到的难题之一。本文以Pb(Zn_(1/3)Nb_(2/3))O_3(PZN)及Pb(Mg_(1/3)Nb(2/3))O_2(PMN)为例证实了非化学配比有序畴的形成会促进焦绿石相的生成,二者存在着密切关系。对PZN、PMN材料的钙钛矿结构的稳定性提出了新看法。这一结果可很好解释在PZN及PMN研究中出现的一些实验现象,对工艺控制也有指导意义。     

复合氧化物PZN结晶化学特性及其合成

用ＸＲＤ法研究了掺杂少量锰对合成钙钛矿型结构的铌锌酸铅陶瓷的影响、讨论了ＰＺＮ的结晶化学参数，认为锌的配位数是影响ＰＺＮ形成钙钛矿型结构的关键因素，掺杂少量锰能有效地抑制焦录石相的生成，进入Ｂ的三阶锰离子能促使Ｚｎ＾２＋的配位数由４变成６，从而形成钙钛生矿型结构的ＰＺＮ。     

锰锑酸铅-锌铌酸铅-锆钛酸铅陶瓷的压电性能

以同时位于准同型相界的Pb(Mn1/3Sb2/3)0.05(Zr1/2Ti1/2)0.95O3(PMnS-PZT)与Pb(Zn1/3Nb2/3)0.28(Zr1/2Ti1/2)0.72O3(PZN-PZT)组合而成的xPb(Mn1/3Sb2/3)0.05(Zr1/2Ti1/2)0.95O3-(1-x)Pb(Zn1/3Nb2/3)0.28(Zr1/2Ti1/2)0.72O3[xPMnS-(1-x)PZN]四元系压电陶瓷为研究对象,研究了PZN和PMnS含量的变化对xPMnS-(1-x)PZN材料结构与性能的影响,制备了具有高性能的四元系xPMnS-(1-x)PZN陶瓷材料.结果表明:性能最好的组成位于准同型相界附近靠近四方相含量较高的区域.Ba2 ,Sr2 取代显著提高了材料的压电性能,Ba2 取代0.5PMnS-0.5PZN的性能为压电系数da3=406 pC/N,机电耦合系数kp=0.55,介电常数εT33/ε0=2 183,机械品质因数Qm=1 077和介电损耗tan δ=2.7%;Sr2 取代0.6 PMnS-0.4 PZN的性能为d33=438 pC/N,kp=0.55,εT33/ε0=2 701,Qm=1 073和tan δ=3.3%.     

高压电活性PNN–PZN–PBSZT陶瓷的结构及性能

采用铌铁矿预合成及固相法制备xPb(Ni_(1/3)Nb_(2/3))O_3–0.01Pb(Zn_(1/3)Nb_(2/3))O_3–(0.99–x)Pb_(0.82)Ba_(0.08)Sr_(0.10)Zr_(0.56)Ti_(0.44)O_3(x PNN–PZN–PBSZT)压电陶瓷。研究了不同铌酸镍NiNb_2O_6含量(x=0、0.01、0.015、0.02)对x PNN–PZN–PBSZT压电陶瓷的晶相结构以及压电和介电等性能的影响。结果表明:制备的压电陶瓷均为钙钛矿结构,处在准同型相界处,且随着x的增大,晶体结构逐渐向四方相转变。PNN的引入可以提高x PNN–PZN–PBSZT陶瓷的压电、机电和介电性能,当x=0.015时,样品的综合性能最佳,压电性能和室温介电性能达到最大,d33和εr分别达到998 pC/N和5 498,此时的机电转换因子k_p为74.61%,Curie温度TC为140℃,kp的最大值出现在x=0.02处,为76.26%。     

Thermodynamic Stability and Mechanisms of Formation and Decomposition of Perovskite Pb(Zn1/3Nb2/3)O3 Prepared by the PbO Flux Method

The mechanisms of formation and decomposition of the ferroelectric perovskite PZN [Pb(Zn_1/3Nb_2/3)O₃] were examined. The formation of perovskite PZN from the excess molten PbO environment is characterized by an inititial rapid formation of pyrochlore phase, followed by a subsequent reaction between the intermediate pyrochlore phase, ZnO, and liquid PbO to produce perovskite phase. The pure perovskite PZN crystal prepared by the PbO flux method is thermodynamically unstable over a wide range of temperature (600° to 1400°C), yielding pyrochlore phase and PbO as the decomposition products. The decomposition reaction of perovskite PZN proceeded uniformly with a spatial homogeneity throughout the specimen. The estimated activation energy of the decomposition reaction is approximatley 18 kcal/mol.     

Dielectric and Ferroelectric Properties of Ceramics in the Pb(Zn 1/3Nb2/3)O3-BaTiO3-PbTiO3 System

The use of Pb(Zn_1/3Nb_2/3)O₃ ceramics is restricted by the formation of a pyrochlore phase detrimental to both dielectric and piezoelectric properties. Recently it has been shown that a 6 mol% addition of BaTiO₃ to PZN suppresses the formation of pyrochlore phase. Phase relations and dielectric properties of ceramics in the PZN-BT-PT system are reported here. Compositions with the perovskite structure, having high dielectric constant and low temperature coefficient of capacitance, have been identified.     

Formation of the Perovskite Phase in the PbMg1/3Nb2/3O3─PbTiO3 System

The reaction sequences during calcination of oxide mixtures were studied for the PbMg_1/3Nb_2/3O₃─PbTiO₃ (PMN-PT) system. The effect of reactivity and composition of the starting mixtures was investigated. In the present study, a B-site-deficient, cubic pyrochlore phase in the PbO-Nb₂O₅ system was formed at 500°C. The perovskite phase of PMN was formed at 7007deg;C through the diffusion of MgO into the pyrochlore phase. The lattice parameter of the pyrochlore phase decreased as this transformation to perovskite progressed.     

铌锌酸铅基陶瓷相变的热力学分析

ＰＺＮ基陶瓷在烧结过程中都要经历由焦绿石相朝钙钛矿相的转变。ＰＺＮ基陶瓷中钙钛矿相含量的多少与添加剂的种类及数量密切相关，本工作根据化学热力学理论，讨论了内应力对化学势的影响，建立了一个热力学模型，并用该模型讨论了ＰＺＮ基陶瓷在烧结时的相变过程。     

Estimation of Phase Stability in Pb(Mg1/3Nb2/3)O3 and Pb(Zn1/3Nb2/3)O3 Using the Bond Valence Approach

The structure stability of perovskite-type compounds has been quantitatively estimated by applying bond valence calculations to Pb(Mg_1/3Nb_2/3)O₃ (PMN) and Pb(Zn_1/3Nb_2/3)O₃ (PZN). The bond valence calculations revealed that the bond strength between oxygen and cations in the pyrochlore-type compounds is greater than that in the perovskite PMN. It is found that the absolute value of the bond valence sum of oxygen, | V _O|, for a PZN single crystal is smallest in reported Pb-containing perovskite-type compounds, corresponding to the fact that it is impossible to synthesize PZN by solid-state reaction under atmospheric pressure. The calculated amount of additives required for stabilizing PZN under atmospheric pressure agreed well with the experimental values.     

Synthesizing Nanocrystalline Pb(Zn1/3Nb2/3)O3 Powders from Mixed Oxides

The attempt to synthesize a Pb(Zn_1/3Nb_2/3)O₃ (PZN) powder of perovskite structure via both traditional ceramic and chemistry-based novel processing routes over the last three decades has failed. Difficult-to-synthesize nanocrystallite PZN powders have, for the first time, been successfully prepared via a mechanochemical reaction either among PbO, ZnO, and Nb₂O₅ or between PbO and pre-reacted ZnNb₂O₆ from ZnO and Nb₂O₅ for more than 15 h in a high-energy mechanochemical reaction chamber. The resulting PZN powders exhibit a well-established perovskite structure and their crystallite sizes are in the range of 10 to 15 nm, as has been indicated from the peak broadening of X-ray diffraction and direct observation using a high-resolution transmission electron microscope.     

PZN－PFN－PFW系陶瓷的介电性质和钙钛矿相的稳定作用

研究了Ｐｈ（Ｚｎ１／３Ｎｂ２／３）ｘ（Ｆｅ１／２Ｎｂ１／２）０．６４－ｘ（Ｆｅ２／３Ｗ１／３）０．３６Ｏ３（ＰＺＮ－ＰＦＮ－ＰＦＷ）系陶瓷中ＰＺＮ含量与焦录石相形成间的关系，以及少量添加剂对钙钛矿相的稳定和介电性能的影响。在该系中仅添加０．１５ｗｔ％ＭｎＣＯ３就可制备１００％钙钛矿型结构的陶瓷。文中报导了该系组成的相关系和介电性质。钙钛矿结构的陶瓷介电常数高，电容温度系数较低。     

镧钾离子掺杂对0.85PZN-0.10BT-0.05PT陶瓷相结构和介电性能的影响

对0.85PZN-0.10BT-0.05PT弛豫铁电陶瓷进行施主和受主掺并，并用二次合成法制备出镧钾离子共掺的PZN基复相陶瓷，研究了镧，钾离子对陶瓷的相结合和介电性能的影响。结果表明，施主掺杂镧产生有利于焦绿石相生成的富Nb区，并导致材料的介电常数降低；受主掺杂钾引起的电荷不平衡可以通过产生氧空位得到补偿；镧，钾离子掺杂均可使居里温度向低温方向,工提高材料的温度稳定性；镧钾离子共掺会使各自独立掺杂引起的电荷不平衡得到抵消，消除陶瓷中的焦绿石相，并获得具有优异介温性且无焦绿石相的PZN基复相陶瓷。