Ba（1-x）CaxT0.95Zr0.05O3陶瓷相变和微观结构研究

采用固相合成法制备了系列Ca掺杂的Ba_（1-x）Ca_xT_（0.95）Zr_（0.05）O_3（x=0.1～1.0）（BCZT）陶瓷。通过XRD和SEM研究了Ca掺杂对BCZT陶瓷物相和微观结构的影响。结果表明,当Ca掺杂量较少时（x=0.1～0.2）,BCZT陶瓷为单一四方相钙钛矿结构;当Ca掺杂量较大时（x=0.9～1.0）,BCZT陶瓷为单一正交相钙钛矿结构。当Ca掺杂量为x=0.3～0.9）、时,BCZT陶瓷出现两相共存的过程。随Ca掺杂量增加,BCZT陶瓷晶粒尺寸先变小然后增大,相对密度逐渐增大;当x=1.0时相对密度达到最大值98%。     

碱式碳酸钴掺杂量对BCZT无铅压电陶瓷性能和结构的影响

采用传统固相法制备了碱式碳酸钴掺杂不同量的Ba0.85Ca0.15Ti0.9Zr0.1O3(简称BCZT)系列无铅压电陶瓷,借助扫描电镜(SEM)和X射线衍射仪(XRD)等研究了不同碱式碳酸钴掺杂量(x=0,0.55,0.89,1.3,1.8 wt.％)对BCZT无铅压电陶瓷的物相组成、显微结构及压电性能和介电性能的影响.结果表明:碱式碳酸钴的加入并没有改变所制备陶瓷的相结构,仍为单一斜方相钙钛矿,当x=1.8wt.％时,出现杂相.随着碱式碳酸钴掺杂量(x)的增大,BCZT无铅压电陶瓷的压电系数(d33)、平面机电耦合系数(kp)先增大后减小,介质损耗(tan δ)先减小后增大,而相对介电常数(εr)一直增大.当碱式碳酸钴(x)为1.3wt.％时,BCZT无铅压电陶瓷的综合性能最佳:d33=135 pC/N,εr=3399,kp=0.38,tanδ =0.029.     

Preparation and Properties of （Na0.50＋xK0.50-2xLix）Nb0.9Ta0.1O3 Lead-Free Piezoelectric Ceramics by Sol-Gel Method

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49nm;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=94pC/N）、相对介电常数（εr=684.33）及剩余极化强度（Pr=98.27μC/cm2）较好。     

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。     

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。     

Ba~(2+)和La~(3+)共掺杂对PZN-PNN-PSN-PZT五元系压电陶瓷性能的影响

采用固相烧结法制备了Ba~(2+)和La~(3+)共掺杂的PZN-PNN-PSN-PZT五元系压电陶瓷。通过XRD、SEM研究了组分的微观结构,并研究了不同Ba~(2+)和La~(3+)共掺杂量对组分的密度及压电介电性能的影响。研究表明:组分的相结构均为单一的ABO3型钙钛矿结构;当x≤0.025时,组分的密度变化不大,x0.025时,密度略有下降;不同量的Ba~(2+)、La~(3+)共掺杂到组分中,所有陶瓷样品存在特征双峰和准同型相界。在x=0.025处,陶瓷的特征双峰逐渐向中间靠拢,说明该处的准同型相界结构最为稳定;当x=0.025时,陶瓷的压电介电性能获得最优,即:ε_r=6327、d_(33)=911pC/N、K_p=0.78、tan_δ=2.94%、Q_m=25。     

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。     

Na0.5Bi0.5TiO3-Ba0.5Sr0.5Nb2O6无铅压电陶瓷的研究

采用固相法制备了(1-x)(Na0.5Bi0.5)TiO3-xBa0.5Sr0.5Nb2O6(0≤x≤1.0％)(简称(1-x)NBT-xBSN)无铅压电陶瓷,研究了不同BSN含量(x=0,0.1％,0.3％,0.5％,0.7％,1.0％,摩尔分数)样品的物相组成、显微结构及电性能.结果表明:所有样品均为纯钙钛矿结构,随掺杂量x的增加,陶瓷的相对密度pr、压电常数d33和机电耦合系数kp均先增大后降低,机械品质因子Qm和退极化温度Td则逐渐下降.该体系陶瓷具有弥散相变特征,弥散指数介于1.6～1.7.当x=0.5％时,陶瓷获得最佳性能:d33=92pC/N,kp=0.164,Qm=89,εr=650,tanδ=5.47％,pr=96.5％.     

Ca掺杂对Ba0.8Sr0．2TiO3本征热释电性能的影响

以尿素（Urea）为添加剂,用溶胶一凝胶工艺在较低温（550℃）合成了钛酸锶钡粉末,在1300℃烧结成陶瓷。研究了Ca掺杂量对陶瓷结构、介电、铁电以及本征热释电性能的影响。研究显示：陶瓷样品均形成了单一的钙钛矿结构固溶体。陶瓷的本征热释电性能受Ca掺杂量影响显著。当Ca掺杂量为2at％时,陶瓷在居里点附近的本征热释电系数达670nC·cm^-1·k^-1。     

Y_2O_3,Fe_2O_3掺杂(Na_(0.5)Bi_(0.5))TiO_3无铅压电陶瓷的研究

采用固相法制备了(Na0.5Bi0.5)TiO3+xmol%Y2O3+xmol%Fe2O3(0≤x≤1.25)(简称NBTYF)无铅压电陶瓷。XRD衍射结果表明,所有陶瓷样品均为单一的钙钛矿结构。SEM表明,掺杂后陶瓷的晶粒尺寸增大。介电温谱表明该体系陶瓷具有弛豫特性,随掺杂量的增加,退极化温度Td向低温方向移动,而居里温度Tc向高温方向移动。陶瓷的密度和压电常数d33和随x的增加先增大后减小,而机械品质因子Qm一直下降。当x=1.00时,该体系陶瓷具有最佳压电性能,d33=106pC/N,Qm=93,kp=16.08%,εr=594,tanδ=5.33%,ρ=5.699g/cm3。     

(Mg1–xCax)2Al4Si5O18陶瓷的相演变与微波介电性能

采用固相烧结反应法制备(Mg1–x,Cax)2Al4Si5O18陶瓷。XRD测试结果表明:0≤x<0.2时,陶瓷以(Mg,Ca)2Al4Si5O18堇青石单一相固溶体形式存在;0.2≤x<0.8时,陶瓷以Mg2Al4Si5O18/CaAl2Si2O8两相复合形式存在;0.8≤x<1.0时,陶瓷以单一相(Ca,Mg)Al2Si2O8固溶体形式存在。SEM结果显示:Ca2+掺杂可以有效地降低堇青石陶瓷的气孔率与微裂纹,并能有效地控制Mg2Al4Si5O18/CaAl2Si2O8复相陶瓷的颗粒分布与晶粒尺寸。微波介电性能测试结果表明:0≤x≤0.4时,(Mg1–xCax)2Al4Si5O18陶瓷介电常数εr为7.0左右;0.6≤x≤1.0时,εr从7.0增加到8.6,然后又降低到6.9。随着x增加,品质因数Qf值从24100GHz降低到4400GHz。但是,在x=0.6时,由于[Si,AlO4]四面体中Al/Si原子排列的有序化,(Mg0.4,Ca0.6)2Al4Si5O18陶瓷Qf值(Qf=5500GHz)比两侧x值成分点Qf值有较大提高。(Mg1–x,Cax)2Al4Si5O18陶瓷谐振频率温度系数在整个x值范围内保持在–20×10–6～–35×10–6℃–1。     

Bi1.5+xZn1.0Nb1.5O7+1.5x（x=0.075,0.15）陶瓷的结构和介电性能

采用固相反应法,以立方焦绿石Bi_1.5Zn_1.0Nb_1.5O₇（BZN）为配方基础,通过改变Bi³⁺离子与O^2-离子的浓度,形成非化学计量比Bi_1.5+xZN_1.0Nb_1.5O_7+1.5x（x=0.075,0.15）陶瓷。研究了不同Bi含量和烧结温度对BZN陶瓷的结构、微观形貌以及介电性能的影响。结果表明制备的非化学计量比BZN陶瓷在不高于1050℃时,呈现焦绿石单相结构;随着烧结温度增加到1100℃,x=0.075,出现ZnO杂相;x=0.15,出现Bi₂O₃杂相。随着x值的增大,BZN陶瓷样品的晶格常数、密度以及介电常数都逐渐增加。     

Structure and Microwave Dielectric Characteristics of Ca1+xNd1−xAl1−xTixO4 Ceramics

CaNdAlO₄ microwave dielectric ceramics were modified by Ca/Ti co-substitution, and their dielectric characteristics were evaluated along with their structure and microstructures. Ca_{1+ x} Nd_{1− x} Al_{1− x} Ti _x O₄ ( x =0, 0.025, 0.05, 0.10, 0.15, 0.20) ceramics with the relative density of over 95% theoretical density were obtained by sintering at 1400°–1450°C in air for 3 h, where the K₂NiF₄-type solid solution single phase was determined from the compositions of x <0.20, while a small amount of CaTiO₃ secondary phase was detected for x =0.20. With Ca/Ti co-substitution in CaNdAlO₄ ceramics, the dielectric constant (ɛ_r) increased with increasing x , and the temperature coefficient of resonant frequency (τ_f) was adjusted from negative to positive, while the Q × f ₀ value increased significantly at first and reached an extreme value at x =0.025 and the maximum at x =0.15. The best combination of microwave dielectric characteristics were achieved at x =0.15 (ɛ_r=19.5, Q × f ₀=93 400 GHz, τ_f=−2 ppm/°C). The improvement of the Q × f ₀ value primarily originated from the reduced interlayer polarization with Ca/Ti co-substitution, while the decreased tolerance factor, the subsequent increased interlayer stress, and the appearance of CaTiO₃ secondary phase brought negative effects upon the Q × f ₀ value.     

Effects of La on Dielectric and Piezoelectric Properties of Pb1−xLa2x/3(Nb0.95Ti0.0625)2 O6 Ceramics

Ceramics with the chemical compositions of Pb_{1− x} La_{2 x /3}(Nb_0.95Ti_0.0625)₂O₆ (0≤ x ≤0.060) (PLTN) were prepared by the conventional solid-state reaction method. X-ray diffraction analysis indicated that Ti and La doping not only decreased the rhombohedral–tetragonal phase transformation temperature, but also stabilized the orthorhombic phase of PLTN ceramics. All ceramics sintered at 1190°–1250°C had shown the pure orthorhombic ferroelectric phase. La doping suppresses grain growth and inhibits the formation of pores and cracks, resulting in an increase in relative density up to 97%. The amount of La doping to PLTN ceramics obviously affect ceramics' piezoelectric constant ( d ₃₃) and dielectric loss (tanδ). The sample with x =0.015 possesses high Curie temperature ( T _c=560°C), low dielectric loss (tanδ=0.0054), and excellent piezoelectric constant ( d ₃₃=92 pC/N), presenting a high potential to be used in high-temperature applications as piezoelectric transducers.     

Microstructure and Microwave Dielectric Properties of (1−x)Ca(Mg1/3Ta2/3)O3/xCaTiO3 Ceramics

Dense (1− x )Ca(Mg_1/3Ta_2/3)O₃/ x CaTiO₃ ceramics (0.1≤ x ≤0.9) were prepared by a solid-state reaction process. The crystal structures and microstructures were characterized by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. Single-phase solid solutions were obtained in the entire composition range. Long-range 1:2 ordering of B-site cations and oxygen octahedra tilting lead to the monoclinic symmetry with space group P 2₁/ c for x =0.1. For x above 0.1, the long-range ordering was destroyed and the crystal structure became the orthorhombic with space group Pbnm . The microwave dielectric properties showed a strong dependence on the composition and microstructure. The dielectric constant and temperature coefficient of resonant frequency increased nonlinearly as the CaTiO₃ content increased while the Qf values decreased approximately linearly. Good combination of microwave dielectric properties was obtained at x =0.45, where ɛ_r=45.1, Qf =34 800 GHz, and τ_f=17.4 ppm/°C.     

High-Temperature Thermoelectric Properties in the La2−xRxCuO4 (R: Pr, Y, Nb) Ceramics

La_{2− x} R _x CuO₄ (R: Pr, Y, Nb) polycrystalline ceramics have been prepared by a spark plasma sintering process. Analysis of the microstructure and phase composition shows that pure La₂CuO₄ ceramics with a high density can be obtained, and no impurity phases appear. All the samples exhibit a metal–semiconductor transition behavior at ∼750 K, which could be ascribed to the decreasing charge density as a result of loss of oxygen atoms and various conduction mechanisms in these La₂CuO₄-based ceramics. Our results indicate that the La_1.98Y_0.02CuO₄ ceramics show large thermoelectric power ∼1.0 × 10⁻³μW·(m·K²)⁻¹, and the evaluated ZT can reach 0.17 at 330 K, which potentially make them useful for thermoelectric applications.     

Phase Structure, Microstructure, and Electrical Properties of Sb-Modified (K, Na, Li) (Nb, Ta) O3 Piezoelectric Ceramics

Lead-free (K_0.44Na_0.52Li_0.04)(Nb_{0.80− x} Ta_0.20Sb _x )O₃ piezoelectric ceramics were prepared by the ordinary sintering method. The much higher Pauling electronegativity of Sb compared with Nb makes the ceramics more covalent. By increasing x from 0.00 to 0.06, the phase structure of the ceramics changed from the tetragonal to the pseudocubic phase, and both the bands in the Raman scattering spectra shifted to lower frequency numbers. The grain growth of the ceramics was improved by substituting Sb⁵⁺ for Nb⁵⁺. By increasing x , the dielectric properties were optimized and the variation of dielectric constants before and after poling became smaller. Only the tetragonal–cubic phase transition was observed above room temperature in all the ɛ_r– T curves. The degree of diffuseness increased from 1.29 at x =0.00 to 1.96 at x =0.06, indicating that the ceramics at x =0.06 changed to an approximate ideal relaxor ferroelectric. The temperature dependences of f _r and k _p became better by increasing x properly. Significantly, the ceramics with x between 0.00 and 0.04 had high density and outstanding electrical properties ( d ₃₃=241–272pC/N, k _p=0.42–0.52, ɛ_r=1258–1591, tan δ=0.015–0.025, T _c=280°–355°C, E _c=10.62–12.60 kV/cm, and P _r=16.19–20.13 μC/cm²). Besides, the underlying mechanism for variations of the electrical properties due to Sb⁵⁺ substitution was explained in this work.     

Microstructure and Piezoelectric Properties of (1−x)(Na0.5K0.5)NbO3–xLiNbO3 Ceramics

(1− x )(Na_0.5K_0.5)NbO₃– x LiNbO₃ [(1− x )NKN– x LN] ceramics were produced by the conventional solid-state sintering method, and their microstructure and piezoelectric properties were investigated. The formation of the liquid phase and K₆Li₄Nb₁₀O₃₀ second phase that were observed in the (1− x )NKN– x LN ceramics was explained by the evaporation of Na₂O during the sintering. A morphotropic phase boundary (MPB) was observed in the specimens with 0.05< x <0.08. Promising piezoelectric properties were obtained for the specimens with x =0.07. Therefore, the piezoelectric properties of this 0.93NKN–0.07LN ceramic were further investigated and were found to be influenced by their relative density and grain size. In particular, grain size considerably affected the d ₃₃ value. Two-step sintering was conducted at different temperatures to increase the grain size. Piezoelectric properties of d ₃₃=240 (pC/N) and k _p=0.35 were obtained for the 0.93NKN–0.07LN ceramics sintered at 1030°C and subsequently annealed at 1050°C.