A位复合铁电陶瓷Bi0.5(Na0.82K0.18)0.5TiO3-BiCrO3的介电弛豫

采用固相反应法制备了A位复合铁电陶瓷(1-x)Bi_0.5(Na_0.82K_0.18)_0.5TiO₃-xBiCrO₃(BNKT-BCx). 研究了该陶瓷在室温至500℃温度范围内的介电性能. 结果表明该陶瓷的介电温谱存在两个介电反常峰和一个介电损耗峰, 低温介电反常峰温度附近具有明显的介电常数频率依赖性, 但居里峰随频率增加基本不变, 与典型弛豫铁电体的特征不同. 将弛豫铁电体分为本征弛豫和非本征弛豫铁电体, 通过分析极化前和极化后陶瓷的介电温谱, 发现该体系低温介电反常峰温度附近的介电频率依赖性为空间电荷和缺陷偶极子极化引起的非本征弛豫.     

Na0.5 Bi0.5 TiO3-K0.5 Bi0.5 TiO3系铁电体的相变研究

研究了(Na1-xKx)0.5Bi0.5TiO3体系x分别为0、0.08、0.16和0.20时陶瓷不同频率下的介电温谱,发现材料为弛豫型铁电体,材料的介电谱在室温到500℃的温度范围内存在一个介电常数-温度"台阶",一个介电常数-温度峰和一个介电损耗-温度峰,通过分析陶瓷不同温度下的电滞回线验证陶瓷在升温过程中产生了铁电-反铁电-顺电相变,采用铁电体成分起伏理论和内电场理论解释了这类弛豫型铁电体相变的原因.     

铌酸锶钡铁电陶瓷的介电弛豫行为

铌酸锶钡Sr_1－xBa_xNb₂O₆（0．25＜x＜075）陶瓷固溶体是典型的钨青铜结构弛豫型铁电体,其介电行为与钙钛矿结构弛豫型铁电体的介电行为极为相似,即射频介电温谱呈现弥散的居里温区.通过对Sr_1－xBa_xNb₂O₆（x＝0．4、0.5、06）在─170～＋400℃的介电温谱进行详细测定;与其热释电测量结果进行对比,发现它们在低温区的介电响应存在一个不同于钙钛矿结构弛豫型铁电体的弛豫过程,高于居里温区的介电响应很好地符合居里-外斯定律．结合钨青铜结构铁电体存在无公度相的特征,初步探讨了钨青铜结构弛豫型铁电体中局域极化的产生、增大和凝聚特点．     

La2O3掺杂（Na0．5 Bi0．5）0．94 Ba0.06 TiO3无铅压电陶瓷的介电弛豫研究

采用固相合成法制备了La2O3掺杂(Na0.5Bi0.5)0.94Ba0.06TiO3无铅压电陶瓷.研究了La2O3掺杂对(Na1/2Bi1/2)TiO3陶瓷晶体结构、介电性能与介电弛豫行为的影响.XRD分析表明,在所研究的组成范围内陶瓷材料均能够形成纯钙钛矿固溶体.材料的介电常数-温度曲线显示陶瓷具有两个介电反常峰Tf和Tm.修正的居里-维斯公式较好的描述了陶瓷弥散相变特征,弥散指数随La2O3掺杂量的增加而增加.掺杂量较低的陶瓷仅在低温介电反常峰Tf附近表现出明显的频率依赖性,随掺杂量的增加,陶瓷材料在室温和低温介电反常峰Tf之间都表现出明显的频率依赖性.并根据宏畴-微畴转变理论探讨了该体系陶瓷介电弛豫特性的机理.     

BaNb2O6掺杂Na1/2Bi1/2TiO3无铅压电陶瓷的介电弛豫

采用传统陶瓷制备方法,制备了无铅新压电陶瓷材料Na1/2Bi1/2TiO3-xBaNb2O6.研究了BaNb2O6掺杂对(Na1/2Bi1/2)TiO3陶瓷晶体结构、介电性能与介电弛豫行为的影响.XRD分析表明,在所研究的组成范围内陶瓷材料均能够形成纯钙钛矿固溶体.材料的介电常数-温度曲线显示陶瓷具有两个介电反常峰Tf和Tm,修正的居里一外斯公式较好的描述了陶瓷弥散相变特征,弥散指数随BaNb2O6掺杂量的增加而增加.该体系陶瓷表现出与典型弛豫铁电体明显不同的弛豫行为,低掺杂量的陶瓷仅在低温介电反常峰Tf附近表现出明显的频率依赖性,而高掺杂的陶瓷材料在室温和Tf之间都表现出明显的频率依赖性.并根据宏畴一微畴转变理论探讨了该体系陶瓷产生介电弛豫的机理.     

Nao．5 Bio．5 TiO3 -Ko．5 Bi0．5 TiO3系铁电体的相变研究

研究了(Na1-xKx)0.5 Bi0．5 TiO3体系x分别为0、0．08、0．16和0．20时陶瓷不同频率下的介电温谱，发现材料为弛豫型铁电体，材料的介电谱在室温到500℃的温度范围内存在一个介电常数-温度“台阶”，一个介电常数-温度峰和一个介电损耗一温度峰，通过分析陶瓷不同温度下的电滞回线验证陶瓷在升温过程中产生了铁电-反铁电-顺电相变，采用铁电体成分起伏理论和内电场理论解释了这类弛豫型铁电体相变的原因。     

A位Sm掺杂对0.93Na0.5Bi0.5TiO3-0.07BaTiO3陶瓷微结构及电学性能的影响

采用固相反应烧结方法制备了Sm掺杂的[(Na_0.5Bi_0.5)_0.93Ba_0.07]_1-xSm_xTiO₃(BNBST)无铅介电储能陶瓷, 系统研究了Sm掺杂含量对BNBST陶瓷的相结构、微观结构、铁电、介电、储能和交、直流电导的影响。研究结果表明: 制备的陶瓷样品具有单一的钙钛矿结构, Sm掺杂固溶于(Na_0.5Bi_0.5)_0.93Ba_0.07TiO₃基材的晶格A位; 晶粒生长被Sm掺杂抑制, 平均晶粒尺寸在2 μm内, 且均匀致密; Sm掺杂显著降低了剩余极化和矫顽场, 表现出双电滞回线特性, 但饱和极化也略有降低; 储能密度和效率随Sm掺杂量增加先增大后减小, 在x=0.02和电场为70 kV/cm时获得最大储能密度0.70 J/cm³, 其效率为40%; BNBST陶瓷具有明显的弛豫铁电体特征, 其介电常数峰T_m随掺杂量增加而降低且平坦化; BNBST陶瓷的绝缘性有较强的温度依赖性, 300℃以下具有良好的绝缘性。     

(Na0.8K0.2)0.5Bi0.5TiO3陶瓷的介电压电性能

研究了(Na0.8K0.2)0.5Bi0.5TiO3陶瓷的介电和压电性能,发现陶瓷从室温到500℃温度范围的介电谱中存在两个介电峰,电滞回线显示第一个介电峰由铁电-反铁电相变引起的,温度继续升高,反铁电相由宏畴变为微畴,微畴向顺电相转变导致了第二个介电峰,该峰对应的相变为弥散型相变.室温下陶瓷具有较高的剩余极化强度Pr=29.4μC/cm2和相对低的矫顽电场Ec=2.8kV/mm,极化后的陶瓷显示出较高的压电常数d33=120pC/N和机电耦合系数Kp=28.5%,以及高的频率常数Nφ=2916Hz.m,120℃具有最小的谐振频率温度系数.     

(Na0.5Bi0.5)TiO3基弛豫铁电体相变的研究进展

钛酸铋钠((Na0.5Bi0.5)TiO3,NBT)是一种典型的A位复合钙钛矿结构弛豫铁电体,具有复杂的相变序列,介电温度峰呈现明显的弛豫性.总结了NBT弛豫铁电体的相变及NBT基复合铁电体准同型相界的研究进展;从晶体结构出发,通过与B位复合型钙钛矿结构弛豫铁电体类比,对A位复合型NBT的弛豫机理进行了探讨,提出NBT弛豫性来源于其A位离子有序-无序引起的B位离子位移的变化.     

Nd3+A位置换对(Pb0.5Ca0.5)(Fe0.5Nb0.5)O3陶瓷微波介电性能的影响

研究了Nd³⁺离子A位置换改性(Pb_0.5Ca_0.5)(Fe_0.5Nb_0.5)O₃陶瓷的微波介电性能.[(Pb_0.5Ca_0.5)_1-xNd_x](Fe_0.5Nb_0.5)O₃(PCNFN)陶瓷的微波介电性能得到改善是由于少量过剩的Nd³⁺与(Pb,Ca)²⁺的固溶能够消除氧空位.当x=0.02时,能够形成单相的钙钛矿相,随着Nd³⁺置换量的增加,过剩的Nd³⁺将导致第二相焦绿石的形成,焦绿石会恶化PCNFN的微波介电性能.PCNFN介电性能随x的增加而下降是由于焦绿石相随x增加的结果.当x=0.02-0.05,PCNFN陶瓷有很好的微波介电性能,介电常数K>100,Qf值为5385-5797GHz,频率温度系数TCF随Nd³⁺含量的增加从正的变为负的.     

Polar nanodomains and relaxor behaviour in (1 − x)Pb(Mg1/3Nb2/3)O3–xPbTiO3 crystals with x = 0.3–0.5

Phase transitions and dielectric properties of the (1 − x)Pb(Mg_1/3Nb_2/3)O₃–xPbTiO₃ crystals with x = 0.3–0.5 are studied. The solid solutions in this composition range are shown to be relaxor ferroelectrics. The crystals with low x demonstrate a diffused maximum in the temperature dependences of the dielectric permittivity at T_m. T_m varies with frequency according to the Vogel–Fulcher law. The polarizing microscopy investigations reveal a first-order phase transition from the relaxor phase to the low-temperature ferroelectric phase at T_C, which is several degrees below T_m. The permittivity peak in the crystals with x = 0.5 is sharp, and T_m is equal to T_C and does not depend on frequency, as is typical of the transition from a ferroelectric to an ordinary paraelectric phase. Nevertheless, the relaxor, but not the paraelectric, phase is observed at T > T_m. This conclusion is confirmed by the observation of the temperature behaviour of complex dielectric permittivity at T > T_m, which is typical of relaxors and related to the existence of polar nanodomains.     

Na0.5Bi0.5TiO3-BaTiO3陶瓷的介电和压电性能研究

研究了Ｎａ_０．５Ｂｉ_０．５ＴｉＯ_３和（Ｎａ_０．５Ｂｉ_０．５）_０．９４Ｂａ_０．０６ＴｉＯ_３陶瓷的电滞回线、压电性能和热滞现象·得到（Ｎａ_０．５Ｂｉ_０．５）_０．９４Ｂａ_０．０６ＴｉＯ_３陶瓷的剩余极化Ｐ_ｒ＝１９ｕＣ／ｃｍ^２、矫顽场Ｅ_ｃ＝４．７ｋＶ／ｍｍ．发现用适量的Ｂａ^２＋取代（Ｎａ_０．５Ｂｉ_０．５）^２＋尽管压电性能有所提高,但同时使得材料的温度稳定性大大降低．     

Abnormal electrocaloric effect of Na0.5Bi0.5TiO3–BaTiO3 lead-free ferroelectric ceramics above room temperature

We demonstrate the electrocaloric effect (ECE) of Na_0.5Bi_0.5TiO₃–BaTiO₃ (NBT–BT) lead-free ferroelectric ceramics, which were fabricated by the solid-state reaction method. Based on a Maxwell relation, the ECE was characterized via P–T curves under different electric fields. The polarization of NBT increases monotonically within the temperature range of 25–145 °C. It indicates that the NBT has an abnormal ECE with a negative temperature change (ΔT₁₄₀ = −0.33 K at E = 50 kV/cm) opposite to that of the normal ferroelectrics. The 0.92NBT–0.08BT composition near the morphotropic phase boundary has a normal ECE under low electric fields and an abnormal ECE under high electric fields. The abnormal ECE character originates from the relaxor characteristic between ferroelectric and antiferroelectric phases, while the common ECE is always related to the normal ferroelectric–paraelectric phase transition.     

(Bi0.5Na0.5)0.935Ba0.065TiO3-xBiScO3陶瓷储能及应变性能研究

本研究采用BiScO₃组分对固相烧结工艺制备的(1-x)(Bi_0.5Na_0.5)_0.935Ba_0.065TiO₃-xBiScO₃(BNBT-xBS)无铅陶瓷进行改性, 考察了BiScO₃掺杂含量对陶瓷的微观结构、储能、场致应变和介电等性能的影响。结果表明: 随着BiScO₃掺杂含量的增加, BNBT-xBS陶瓷的相结构由三方相与四方相共存演变为伪立方相, 无杂相形成, 且平均晶粒尺寸略有增大; BiScO₃组分的引入破坏了BNBT陶瓷铁电畴的长程有序, 表现出弱极化, 且伴随有铁电相到弛豫铁电相的相变过程。BiScO₃组分提高了储能和应变性能, 在70 kV/cm电场下其最大储能密度为0.46 J/cm³, 电致应变达到0.25%。介电常数随着掺杂含量的增加逐渐降低, 其介电行为也表明陶瓷具有弛豫铁电体特征; BNBT-xBS陶瓷表现出负温度系数效应, 且在450℃以下具有较好的绝缘性。     

Dielectric characterization of (1-x)PMN-xPT (x = 0.07 and 0.10) ceramics synthesized by an ethylene glycol-based soft chemical route

Materials based on relaxor ferroelectrics have become one of the most important families of functional materials being explored for such applications as sensors/actuators, micro-electromechanical systems (MEMS), non-volatile random access memories, and high-energy-density capacitors. Fabrication of high-quality relaxor-based ceramics remains, however, a challenging task. In this work, a new soft chemical synthetic method for the preparation of the complex perovskite-based relaxor ferroelectric solid solutions, (1-x)Pb(Mg(1/3)Nb(2/3))O(3)-xPbTiO(3) was developed using ethylene glycol as the solvent. Ceramics with compositions of x = 0.07 and 0.10 were prepared and it was found that a 10% stoichiometric excess of Pb(2+) was required to compensate for lead oxide volatility at the high temperatures used for sintering. The ceramics produced by this method show excellent dielectric properties at room temperature, such as a high dielectric constant (~20 000) and low loss over a large temperatures range (tan δ < 0.01 between 20 and 200°C). The temperature dependence of the dielectric constant exhibits typical relaxor ferroelectric behavior, fitting a quadratic law which describes the high-temperature slope of ε'(T) peak. The frequency dispersion of the temperature of maximum permittivity satisfies the Vogel-Fulcher law.     

烧结工艺对B2O3掺杂Ba1-xSrxTiO3梯度陶瓷介电性能的影响

研究了烧结温度及升温速率对氧化硼(B₂O₃)掺杂钛酸锶钡梯度陶瓷(Ba_1-xSr_xTiO₃,x=0-0.4,步长0.02)的致密化、晶粒尺寸及介电性能的影响.结果表明,随着烧结温度的升高,在氧化硼挥发的同时致密化程度提高,从而居里峰提高且变得尖锐;随着氧化硼含量的增加,晶粒尺寸均匀长大、介电常数和介电损耗都增加;升温速率适中时,掺杂物的挥发、致密化进程及晶粒长大同步完成,梯度陶瓷介电性能才有效提高.此外,钛酸锶钡梯度陶瓷掺杂适量氧化硼明显降低烧结温度,比未掺杂相同成分的陶瓷烧结温度至少降低150℃,且介电损耗明显减小;梯度陶瓷的居里峰温度区间显著展宽,大大降低了该温区的介温系数,可望提高该系列陶瓷元器件精度及稳定性.     

Dielectric properties and relaxation of Bi<Subscript>0·5</Subscript>Na<Subscript>0·5</Subscript>TiO<Subscript>3</Subscript>-BaNb<Subscript>2</Subscript>O<Subscript>6</Subscript> lead-free ceramics

A new member of lead-free piezoelectric ceramics of the BNT-based group, (1 − x)Bi_0·5Na_0·5TiO_3−x BaNb₂O₆, was prepared by conventional solid state reaction and its dielectric properties and relaxation was investigated. X-ray diffraction showed that BaNb2O6 diffused into the lattice of Bi_0·5Na_0·5TiO₃ to form a solid solution with perovskite-type structure. A diffuse character was proved by the linear fitting of the modified Curie-Weiss law. The temperature dependence of dielectric constant at different frequencies revealed that the solid solution exhibited relaxor characteristics different from classic relaxor ferroelectrics. The samples with x = 0·002 and 0·006 exhibited obvious relaxor characteristics near the low temperature dielectric abnormal peak, T _f, and the samples with x = 0·010 and 0·014 exhibited obvious relaxor characteristics between room temperature and T _f. The mechanism of relaxor behaviour was also discussed according to the macro-domain to micro-domain transition theory.     

(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．     

La0.5Ca0.5MnO3中Ca位上Ba掺杂效应研究

用固态反应法制备了具有单相结构的La_0.5Ca_0.5-xBa_xMnO₃系列样品,其结构随Ba含量增加由立方晶系转变为典型的正交晶系．零场下输运性质实验表明,在较低掺杂量时,系统在整个温区显示半导体型导电特征,而当掺杂量超过0.14时,系统发生由半导体到金属的转变,且转变的温度随掺杂量增加而移向高温瑞．基于对实验结果的分析,就Ca位上Ba掺杂所起的作用进行了初步探讨．