La2O3对Nd3+掺杂氧化钇透明陶瓷性能的影响

采用传统无压烧结工艺,在氢气气氛下制备了(Nd0.01Y0.99-xLax)2O3(摩尔含量x=0,0.05,0.10)透明陶瓷,研究了La2O3的含量对其性能的影响。结果表明:随着La2O3含量的增加,陶瓷的晶粒尺寸减小,密度和透过率增大;同时,Raman光谱特征峰发生红移,声子能量略有降低,最大声子能量分别为378,375,372cm-1,半高宽增大,相对强度减小。当La2O3含量继续增加时,样品晶粒尺寸和立方相结构保持不变。当x=0.10时,在烧结温度为1680℃和保温时间为50h的条件下,Nd3+掺杂的氧化镧钇透明陶瓷的直线透过率最高达到80%。     

W6+掺杂对Na0.5Bi2.5Ta2O9陶瓷的结构与电学性能影响

采用传统固相法制备Na0.5Bi2.5Ta2-xWxO9 (NBTO-x,0≤x≤0.05)无铅压电陶瓷,研究W6+掺杂对NBTO陶瓷结构和电学性能的影响.XRD结果显示,所有陶瓷样品均生成了m=2的铋层状结构化合物,随着掺杂量的增加,样品的正交畸变先减小后增大;W6+掺杂提高了样品的压电与铁电性能,当x=0.03时,...     

Ho~(3+)掺杂Na_(0.25)K_(0.25)Bi_(2.5)Nb_2O_9陶瓷的结构、电学和上转换发光性能

采用传统固相法制备了Na_(0.25)K_(0.25)Bi_(2.5–x)Ho_xNb_2O_9(NKBN–x Ho~(3+),0.000≤x≤0.030)铋层状陶瓷,研究了Ho~(3+)掺杂对NKBN陶瓷结构、电学和上转换发光性能的影响。X射线衍射谱表明Ho~(3+)进入NKBN晶格形成了固溶体。随着Ho3+掺杂量的增加,NKBN陶瓷的晶粒尺寸降低,当x=0.020时,样品的压电和铁电性能均达到最佳:d_(33)=21.8pC/N2Pr=1.84μC/cm。(d_(33)为压电常数,Pr为剩余极化强度)所有样品在400℃均未出现明显的退极化现象,在高温下表现出良好的压电稳定性。在980 nm激光激发下,所有陶瓷样品均表现出上转换荧光发光特性,表明NKBN–x Ho~(3+)陶瓷在光电多功能材料领域具有潜在的应用价值。随着极化电压的增加,陶瓷样品的晶格结构对称性提高,上转换荧光发光强度降低。     

Ca2+掺杂对BiFeO3陶瓷结构和磁、介电性能的影响

以Bi(NO3)3·5H2O、Fe(NO3)3·9H2O和Ca(NO3)2·4H2O为原料、乙二醇甲醚为溶剂、柠檬酸为络合剂,采用溶胶–凝胶法制备Bi1–x Cax FeO3(x=0、0.05、0.10、0.15、0.20)陶瓷样品。结果表明:所有样品的主衍射峰与纯相BiFeO3相吻合,样品晶粒尺寸随Ca2+掺杂量的增加而减小,在室温下各样品均具有完整的磁滞回线,样品铁磁性显著提高。当x=0.10时,剩余比磁化强度达到最大值(0.11A·m2/kg)。在外加磁场为398 kA/m时,样品的比磁化强度在644 K附近出现明显的反铁磁相变,反铁磁相变温度TN随掺杂量的增加而升高。在300~900 K,样品顺磁相变温度TP,以及TN和TP处比磁化强度的差值随Ca2+的增加均呈现先上升,在x=0.10时达到最大值,之后又呈下降趋势。样品在850K时比磁化强度出现明显变化,变化幅度随Ca2+掺杂量的增加而减小,在x=0.10时最小,之后又增大。不同磁场下样品剩余比磁化强度随温度变化表明:Bi1–x Cax FeO3陶瓷样品存在变磁性,当x=0.10时,变磁性最为明显。磁电耦合效应观测结果表明:样品的磁电耦合系数为负值,介电常数随外磁场变化反应灵敏,在x=0.10时磁电耦合效应为–14.2%,是纯相BiFeO3(其磁电耦合效应为–5%)的近3倍,表明掺杂适量Ca2+可增强样品的磁电耦合性能。     

MgO掺杂Ca_(0.85)Sr_(0.15)Cu_3Ti_(4.01)O_(12)陶瓷的制备及介电性能

首先研究了Ti缺失和过量对Ca_(0.85)Sr_(0.15)Cu_3Ti_(4+x)O_(12)陶瓷粉体(x=-0.005～0.020)相结构的影响,再采用传统固相法制备了MgO掺杂(0～25 mol%)Ca_(0.85)Sr_(0.15)Cu_3Ti_(4.01)O_(12)陶瓷,主要研究了MgO含量变化对Ca_(0.85)Sr_(0.15)Cu_3Ti_(4.01)O_(12)陶瓷晶相结构、显微结构和介电性能的影响。结果表明:x=-0.005～0.005时有少量的CuO杂相存在,当x=0.010时得到了单一的类钙钛矿结构,Ti含量进一步增加出现了少量的TiO_2杂相;随着MgO掺量的增加,晶粒尺寸逐渐增大,在MgO掺量为1 mol%时,体积密度达到最大为4.98 g/cm~3,相对密度为98.76%。陶瓷的室温介电常数和介电损耗均是先增大后减小,在MgO掺量为5 mol%时,陶瓷的介电常数达到最大值1.01×10~5(10 kHz),介电损耗为0.183。在40～100 kHz频率范围内,介电常数均在4.78×10~4以上,具有良好的频率稳定性。     

Mn含量对Al掺杂PMN-PMS-PZT陶瓷介电性能的影响

采用传统的固相烧结法制备了Pb1.07[(Mn1/3Nb2/3)1/2(Mn1/3Sb2/3)1/2]0.08(Zr0.828Ti0.092)O3+x wt%Al2O3+y wt%MnO2(x=0.1,0.3,0.5,0.7;y=0.00,0.02,0.04,0.06,0.08,0.10,0.12)热释电陶瓷,在对不同组分Al掺杂PMNPMS-PZT陶瓷材料介电性能对比寻优的基础上,逐步增加Mn的含量,研究不同Mn增量下,对最优Al掺杂PMNPMS-PZT热释电陶瓷相结构、晶粒生长以及介电性能的影响。通过X射线衍射仪(XRD)分析显示Al掺杂PMNPMS-PZT陶瓷和在最优Al掺杂基础上增加Mn的含量都不会引入新的杂相,扫描电子显微镜(SEM)分析表明当x=0.30,适当增加Mn的含量,有助于陶瓷晶体的均匀致密,但一旦添加过量则又会产生不好的影响。实验结果表明:采用530℃排塑,烧结1190℃,保温2 h,当x=0.30,y=0.08时,PMN-PMS-PZT热释电陶瓷具有较好的相结构和介电性能,其中介电常数εr约为210,介电损耗tanδ约为0.16%,压电系数d33约为66.00 pC/N。     

La~(3+)掺杂对焦绿石型Bi_2O_3—ZnO-Nb_2O_5陶瓷结构和介电性能的影响

采用固相反应法制备(Bi1.5LaxZn0.5—x)(Zn0.5+xNb1.5—x)O7(BZNL,x=0.01~0.07mol)焦绿石型陶瓷。利用X射线衍射仪和高阻抗分析仪(LCR)对样品结构、结晶化学特性与介电性能进行表征。结果表明:所有陶瓷样品均保持单一的立方焦绿石相;随La3+替代量的增加,陶瓷样品中A位阳离子与8b位O′的平均键长r(O′—A)从0.228 36nm增加到0.228 46nm;键价和AV(O′)[Bi3La]、AV(O′)[Bi2ZnLa]、AV(O′)[Bi2La2]、AV(O′)[BiZn2La]随之减小;48f位氧的坐标ζ从0.028 27nm增加到0.029 03nm;样品的介电弛豫峰值温度Tm向低温方向移动,峰值介电常数εm依次减小,当替代量x=0.07mol时,介电弛豫峰值温度Tm降低到最低温度(—107.4℃),峰值介电常数εm为136.35。样品介电弥散性的增强与八面体结构的转变有关。     

溶胶–凝胶法制备(Na0.50+xK0.50-2xLix)Nb0.9Ta0.1O3无铅压电陶瓷及其性能

采用溶胶–凝胶法制备Li+取代(K0.5Na0.5)+及Ta5+取代Nb5+的(K0.5Na0.5)NbO3陶瓷粉体,采用无压烧结工艺制备(Na0.50+xK0.50–2xLix)Nb0.9Ta0.1O3(x=0,0.02,0.04)陶瓷样品。研究了前驱体煅烧温度对陶瓷粉体物相组成的影响。分析了不同Li+掺杂量对样品物相组成、微观结构、体积密度及电学性能的影响。结果表明:前驱体的最佳煅烧温度为600℃,通过透射电子显微镜分析陶瓷粉体的粒径为49 nm;不同Li+掺杂量制备的(Na0.50+xK0.50–2xLix)Nb0.9Ta0.1O3陶瓷样品均为正交相钙钛矿结构;随着Li+掺杂量的增加,(Na0.50+xK0.50–2xLix)Nb0.9Ta0.1O3陶瓷的体积密度先增大后减小,介电常数逐渐升高,压电常数先降低再升高,剩余极化强度逐渐升高。Li+掺杂量x为0.04时样品的压电常数(d33=94 pC/N)、相对介电常数(εr=684.33)及剩余极化强度(Pr=98.27μC/cm2)较好。     

Er~(3+)掺杂对Na_(0.25)K_(0.25)Bi_(2.5)Nb_2O_9压电陶瓷电学和光学性能的影响

采用传统固相法制备Na0.25K0.25Bi2.5Nb2O9+x Er(NKBN–x Er,0≤x≤0.06)铋层状无铅压电陶瓷,研究了不同Er3+掺杂量对NKBN–x Er陶瓷显微结构、电学性能及上转换荧光性能的影响。结果表明:所有样品均为单一的铋层状结构;随着Er3+掺杂量x从0增加到0.06,样品的晶粒尺寸逐渐增大,Curie温度TC升高,适量的Er3+掺杂能提高陶瓷的压电性能;电导率与温度的关系在高温区域,热激活氧空位二级电离电子电导起主导作用;在980 nm激光激发下,所有样品在513~570和644~679 nm处可观察到绿光和红光发射峰,分别对应于Er3+的2H11/2→4I15/2、4S3/2→4I15/2和4F9/2→4I15/2能级跃迁。当x=0.02时,电学性能最佳:压电常数d33=22 p C/N,介电损耗tanδ=0.38%,品质因子Qm=2 324,且样品均具有良好的荧光性能,表明该组分陶瓷可作为高温应用光—电多功能材料。     

Fe_2O_3掺杂BaZr_(0.1)Ti_(0.9)O_3陶瓷介电性能的研究

采用传统固相法分别于1250℃、1280℃、1300℃、1330℃下制备了BaZr_(0.1)Ti_(0.9)O_3+xmol%Fe_2O_3(0≤x≤1.25)陶瓷样品。XRD结果表明,Fe~(3+)掺杂后的陶瓷样品均为钙钛矿结构。SEM表明,掺杂Fe~(3+)后陶瓷的晶粒尺寸减小。随着掺杂量的增加,陶瓷样品的体积密度ρv和介电常数ε先增大后减小,介质损耗tanδ先减小后增大。1300℃烧结,x=1.00%的陶瓷样品介电性能最好,ρv=6.03 g/cm3,ε=4560,tanδ=0.004。     

超声压电马达用陶瓷材料的研究

研究了钡锶锑锰等离子掺杂对锆钛酸铅(PZT)系压电陶瓷的介电、压电性能和体积密度的影响。实验结果表明:对于Pb0.95Ba0.03Sr0.02(Zr1-yTiy)O3+xwt%MnSb2O6(PBSZTMS),在x=1.5、Zr/Ti=52/48附近获得了优越的压电活性。对于Pb0.95Ba0.03Sr0.02(MnSb2O6)x/3(Zr54Ti46)1-xO3(PBSMSZT),综合性能较好的组成点出现在x=0.05处。对于PbaBabSrc(MnSb2O6)x/3(Zr1-yTiy)1-xO3+zwt%MnSb2O6系列配方,发现Sr2+和Ba2+的共同添加会使样品致密度降低,介电常数、介质损耗和压电常数增加;当a=1,b=0,c=0,x=0.03,y=0.48,z=0.76时,获得了综合性能较好的陶瓷材料,有望应用于大功率超声压电马达器件领域。     

Elimination of pyrochlore phase in high-concentration Sm3+-doped PMN-PT piezoelectric ceramics by excessive MgO

Undesirable pyrochlore phase often appears in Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (PMN-PT)-based ceramics with high rare-earth ion (RE³⁺) doping concentration, which greatly limits their development. In this study, 0–5 mol% Sm³⁺-doped Pb(Mg_1/3Nb_2/3)O₃-29PbTiO₃ (PMN-29PT:0-5Sm) ceramics were first synthesized using traditional precursor method. In the X-ray diffraction spectra and scanning electron microscope images of PMN-29PT:3-5Sm ceramics, the diffraction peaks of pyrochlore phase and pyrochlore grains with octahedral morphology were observed, respectively. The reason for the appearance of the pyrochlore phase is that Sm³⁺ doping causes the Nb-rich regions. To eliminate the pyrochlore phase, PMN-29PT:3-5Sm ceramics were resynthesized by an improved precursor method in which an excess of 4 mol% MgO was added to the reactants before pre-sintering. After adding an excess of 4 mol% MgO, the concentration ratio of Nb⁵⁺ and Mg²⁺ in the pyrochlore grains returned to the value in the perovskite grains, and the pyrochlore phase was transformed into the perovskite phase PMN. The dielectric, ferroelectric, and electromechanical properties were compared before and after eliminating the pyrochlore phase. The results show that the comprehensive performance of the ceramics is improved after eliminating the pyrochlore phase.     

Dielectric and Electrical Conductivity Properties of PMS–PZT Ceramics

The dielectric and electrical conductivity properties of x Pb(Mn_1/3Sb_2/3)O₃–(1− x )Pb(Zr_0.52Ti_0.48)O₃ (PMS–PZT) ceramics were studied. X-ray diffraction indicated that all samples exhibit a single-phase perovskite structure. Dielectric study revealed that the dielectric relaxor behavior was induced by co-doping Mn²⁺ and Sb⁵⁺ into Pb(Zr_0.52Ti_0.48)O₃ ceramics. Electrical conductivity measurements showed that the concentration of carriers are increased with the increase in PMS contents. After annealing in an oxygen atmosphere for 30 h, the direct current conductivity of PMSZ15 was much lower than that of the as-sintered sample. The reason why this phenomenon occurs may be the reduction of oxygen-vacancy concentration.     

Structure and Dielectric Properties of Pb(Sc2/3W1/3)O3–Pb(Zr/Ti)O3 Relaxors

The structure and dielectric properties of (1− x )Pb(Sc_2/3W_1/3)O₃–( x )Pb(Zr/Ti)O₃ ceramics have been investigated over a full substitution range. All compositions with x < 0.5 adopt a cubic perovskite structure; however, for x ≤ 0.25 a doubled cell results from a 1:1 ordered distribution of the B-site cations. The structural order in Pb(Sc_2/3W_1/3)O₃ (PSW) can be described by a random-site model with one cation site occupied by Sc³⁺ and the other by a random distribution of (Sc_1/3³⁺W_2/3⁶⁺). The ordering is destabilized in solid solutions of PSW with PbZrO₃ (PSW–PZ), but stabilized by PbTiO₃ in the (1− x )PSW–( x )PT system. The changes in order are accompanied by alterations in the dielectric response of the two systems. For PSW–PZ the temperature of the permittivity maximum ( T _ɛ,max) increases linearly with x ; however, for PSW–PT T _ɛ,max decreases in the ordered region (up to x = 0.25) and then increases rapidly as the order is lost. Similar effects were produced by modifying the degree of order of (0.75)PSW–(0.25)PT; when the order parameter was reduced from ∼1.0 to ∼0.65, T _ɛ,max increased by more than 60°C.     

Synthesis of 0.4Pb(Mg1/3Nb2/3)O3–0.3Pb(Mg1/2W1/2)O3–0.3PbTiO3 Ceramics by Metal Alkoxide Method, and Its Dielectric Properties

0.4Pb(Mg_1/3Nb_2/3)O₃–0.3Pb(Mg_1/2W_1/2)O₃–0.3PbTiO₃+ x MgO ( x = 0 to 0.04) were prepared by a metal alkoxide method. The percent of perovskite phase of the calcined powders increased with increased calcination temperatures. About 89% of perovskite phase was obtained at 1050°C. The dielectric constant of the pellets fired at 1100°C was increased by the addition of 10 wt% excess Mg(OC₂H₅)₂ and had a maximum value of 7532 at 1 kHz.     

硼铅锌系玻璃对细晶BaTiO3基陶瓷系统介电性能影响的研究

研究了硼铅锌系玻璃对细晶BaTiO     

Fundamental Material Aspects Underlying the Preparation of High-Temperature Superconducting (Bi,Pb)2+xSr2Ca2Cu3O10+d Ceramics

Phase equilibria of the quasi-quinary system Bi₃O₃-PbO-SrO-CaO-CuO were studied between 650° and 900°C in air with emphasis on the high-temperature superconducting phase (Bi,Pb)_{2+ x} Sr₂Ca₂Cu₃O_{10+ d} (2223). The 2223 phase lies in equilibrium with a number of nonsuperconducting phases and also with the superconducting phase (Bi,Pb)₂Sr₂CaCu₂O_{8+ d} (2212). The single-phase region was found to be very limited. The Pb solubility of the 2223 phase is strongly temperature dependent. The phase relations are very sensitive to variations of the cation concentration and temperature. This effect significantly influences the preparation of 2223 ceramics.     

Defect engineering toward the structures and dielectric behaviors of (Nb,Zn) co-doped SrTiO3 ceramics

Defect engineering is applied to induce controllable changes in structures and dielectric behaviors in oxides. SrTiO₃ ceramics modified by complex ions (Nb, Zn)^x+ (x = 2, 3, 4 and 5) with variable valence states are prepared by standard solid state method. Phase structures, microstructures, defect structures and dielectric properties of the (Nb, Zn) co-doped SrTiO₃ ceramics have been systematically investigated. In acceptor co-doping, M2 ceramics (x = 2) exhibits extremely low dielectric loss (≤0.001). M3 ceramics (x = 3) shows low conductivity and excellent thermal stability. In equivalent co-doping, M4 ceramics (x = 4) possesses giant permittivity and low dielectric loss. In donor co-doping, M5 ceramics (x = 5) presents improved permittivity while deteriorated dielectric loss. Further investigations reveal that oxygen vacancy is beneficial to the localization of charge carriers and then the low tangent loss, while excess electrons not only contribute to the improved permittivity but also result in high dielectric loss. Appropriate concentrations of oxygen vacancy and electron are significantly important for the formation of multiple defect dipoles or defect clusters, and therefore the greatly modified dielectric properties. The findings may facilitate the ability to engineer the advanced electronic materials.     

Vacuum sintering of highly transparent La1+xYb1+yZr2O7 ceramics with excess La and Yb contents

In this study, a series of transparent ceramics with chemical composition of La_1+xYb_1+yZr₂O₇ (x, y = 0.1?0.5) were successfully prepared by vacuum sintering using combustion synthesized powders. The effects of excess contents on the phase composition, microstructure and in-line transmittance have been studied. The detailed results indicate that the in-line transmittance increases at first and then decreases as La content be elevated. It was also determined that the highest in-line transmittance of La_1+xYb_1+yZr₂O₇ (x, y = 0.1?0.5) ceramics is 84.1 % at 1100 nm when the excess amount of co-doped La-Yb is 30 %. Compared with stoichiometric LaYbZr₂O₇ ceramic, the nonstoichiometric La_1+xYb_1+yZr₂O₇ (x, y = 0.1?0.5) ceramics exhibit much higher transparency. In addition, the high excess amount of La, Yb and co-doped La-Yb also shows effects on the phase composition and crystal structure.