Ca1-x（Li1/2Sm1/2）xTiO3体系微波介质陶瓷的低温烧结研究

采用传统陶瓷制备工艺,制备了添加10 wt%NCB(Na2O-CaO-B3O3)复合氧化物的Ca1-x(Li1/2Sm1/2)xTiO3(x=0.700～0.875)(CLST-x)体系陶瓷,研究了添加NCB后CLST-x体系的晶相组成、显微结构、烧结性能及微波介电性能与组成关系.研究结果表明,添加复合氧化物NCB后,CLST-x体系各组成主晶相仍呈斜方钙钛矿结构,没有其它杂相.添加10wt%NCB后,CLST-x体系陶瓷均可在950℃下烧结致密,在此温度下材料具有较佳的微波介电性能,其中CLST-0.875陶瓷在950℃保温5 h烧结后具有良好的微波介电性能:εr=63.6,Qf=1591 GHz,τ f=0 ppm/℃,可满足高介多层微波器件的设计要求.     

Ba(Mg1/3Nb2/3)O3-Mg4Nb2O9复相陶瓷微波介电性能研究

采用传统固相法制备了(1?x)Ba(Mg1/3Nb2/3)O3?xMg4Nb2O9 [(1?x)BMN?xM4N2,x = 0.003 ~ 0.125] 微波介质陶瓷,研究了相结构、烧结性能与介电性能随 x 的变化规律。结果表明： BMN 与 M4N2 可以两相共存,且二者间存在有限固溶,BMN 的烧结温度及高温稳定性有所降 低。随着 x 的增大,介电常数 εr和谐振频率温度系数 τf逐渐减小,Q × f 值的变化易受到 BMN 有序参数 S 的影响,高度 1:2 有序的 x = 0.026 陶瓷获得了最大 Q × f 值 125000 GHz。综合来看, 在 1320°C 下保温 4 h 烧结的 x = 0.125 样品表现出最佳的微波介电性能：εr = 26.6,Q × f = 111000 GHz,τf = 5 ppm/ºC。     

前驱体制备(1-x)CaTiO3-xCa(Zn1/3Nb2/3)O3陶瓷的微波介电性能

以ZnNb2O6为前驱体,通过固相反应合成了(1-x)CaTiO_3-xCa(Zn_(1/3)Nb_(2/3))O_3体系微波介质陶瓷。对固溶体进行了结构与性能测试,研究了体系结构与性能随组份变化规律。结果表明,由于Zn,Nb对Ti的B位取代增大了B-O八面体的倾斜角,从而导致随着Ca(Zn_(1/3)Nb_(2/3))O_3含量从0.2增加至0.8,介电常数从109减小为49,Q×f值从8340GHz增至13200GHz,频率温度稳定系数由321ppm/℃降为-18ppm/℃。在x=0.7时获得ε_1≈56,Q×f≈11500GHz,τ_f≈-5ppm/℃的最佳性能。     

Coprecipitation synthesis and sintering property of (YbxSm1-x)2Zr2O7 ceramic powders

Abstract

Abstract

(Yb_xSm_1-x)₂Zr₂O₇ (0<x<1·0) ceramic powders were synthesised with chemical coprecipitation and calcination method. Thermal decomposition behaviour of precipitates was studied by differential scanning calorimetry-thermogravimetry. The powders were characterised by X-ray diffractometry, scanning electron microscopy and transmission electron microscopy with energy dispersive spectroscopy. The synthesised powders have a particle size of about 100?nm, and exhibit to a certain extent agglomeration. The sintering behaviour of (Yb_xSm_1-x)₂Zr₂O₇ powders was studied by pressureless sintering method at 1550-1700°C for 10?h in air. The relative densities of (Yb_xSm_1-x)₂Zr₂O₇ ceramics increase with increasing sintering temperature, and reach above 95% when sintered at 1700°C for 10?h in air. Sm₂Zr₂O₇ and (Yb_0·1Sm_0·9)₂Zr₂O₇ ceramics have a pyrochlore structure; however, (Yb_xSm_1-x)₂Zr₂O₇ (0·3<x<1·0) ceramics exhibit a defective fluorite type structure.     

(Sn_(1-x),Ni_(2x))O_2纳米颗粒膜的制备及半导体性能

为提高SnO2的半导体性能,以分析纯SnCl2.2H2O和NiCl2.6H2O为主要原料,控制不同n(Ni2+)/n(Sn2+),利用溶胶凝胶-浸渍提拉法制备了(Sn1-x,Ni2x)O2纳米颗粒膜及半导体元件。用XRD、AFM对样品的结构、形貌进行了分析,并测试了(Sn1-x,Ni2x)O2元件的半导体性能。结果表明,(Sn1-x,Ni2x)O2纳米颗粒膜表面椭球形颗粒排列致密,尺寸约30 nm,(Sn1-x,Ni2x)O2为金红石型结构,但Ni2+代替了SnO2晶格中的部分Sn4+,使其晶胞参数a轴长平均减小0.000 4 nm,c轴长平均减小0.000 3 nm;随n(Ni2+)/n(Sn2+)由0.006增大到0.03,(Sn1-x,Ni2x)O2的晶粒尺寸由约45 nm减小至约18 nm;随温度由30℃上升至150℃,n型(Sn1-x,Ni2x)O2半导体元件的电阻约减小至其10%,而纯净SnO2元件的电阻仅约减小至其15%;随n(Ni2+)/n(Sn2+)的增大,离子化杂质散射增强,(Sn1-x,Ni2x)O2内部载流子迁移率下降,元件在150℃左右的电阻也由4.8 kΩ增大至12.1 MΩ,提高了元件的半导体性能。     

(K,Na) (Nb,Ta,Sb)O3粉体制备及陶瓷介电性能研究

Ta/Sb掺杂的K0.5Na0.5Nb0.7TaxSb0.3-xO3(KNNSTx,x＝0.06,0.09,0.12,0.15,0.18,0.21, 0.24)粉体经水热合成,Ta、Sb对粉体物相、微观结构的影响被系统研究,烧结后陶瓷的微观结构、介电性能表明:陶瓷物相均具有纯钙钛矿结构;随着Ta含量的增加陶瓷晶粒尺寸逐渐增大,x＝0.09、0.12时较小粒径颗粒均匀分布在大颗粒的空隙之间,陶瓷密度增加;样品的介电常数随着Ta含量的增加x＝0.06～0.12逐渐降低,x＝0.15～0.24逐渐增加,居里温度均在350 ℃左右,且x＝0.09、0.12时陶瓷介电损耗较小.     

(Mg4-xLi2x)(Nb1.92V0.08)O9陶瓷微波介电性能

采用固相合成法制备了(Mg_(4-x)Li_(2x))(Nb_(1.92)V_(0.08))O_9系列微波介质陶瓷。通过XRD、SEM以及HP网络分析仪等测试手段对其烧结特性、晶体结构和微波介电性能进行了系统研究。结果表明:x<0.3时形成了(Mg_(4-x)Li_(2x))(Nb_(1.92)V_(0.08))O_9固溶体;x≥0.3时,除主相(Mg_(4-x)Li_(2x))(Nb_(1.92)V_(0.08))O_9外,还有少量第二相Li3Mg2NbO6生成。微波介电常数ε随x的增大持续升高,品质因数Q则先增大后减小。x=0.2,950℃,5h烧结样品的微波介电性能达到最佳:ε=12.7,Q.f=14078GHz(f0=8GHz)。     

Nb2O5掺杂对BaTiO3陶瓷介电常数的影响

BaTiO3陶瓷以其优异的铁电、压电和绝缘性能广泛应用于体积小、容量大的电子器件材料,但其在一定的工作温度区间介电常数却呈现不稳定变化。对其常用的改性方法进行了分类和阐述,同时对Nb2O5掺杂改性对BaTiO3陶瓷介电性能的影响作了简单介绍,最后讨论了Nb2O5在多层陶瓷电容器制备领域的应用和重要性。     

低温烧结Mg4Nb2O9微波介质陶瓷

研究了V2O5对Mg4Nb2O9陶瓷的烧结温度、相结构和微波介电性能的影响.结果表明,添加1％～8％的V2O5,能使该陶瓷的烧结温度降低到1000～1050℃而对其微波介电性能的影响很小,材料的主晶相为有序型刚玉结构的Mg4 Nb2O9,存在Mg4Nb2O6和Mg5Nb4O15杂相而没有检测到V2O5的存在.陶瓷的密度对微波介电性能起着决定性作用,介电常数e1与密度成线性关系(在99.99％的置信限内,其相关系数为0.98252),Q·f值与密度的关系较复杂.添加1％的v2O5,将Mg4Nb2O9陶瓷的烧结温度降低到了1050℃,得到了εr=12.72,Q·f=151040GHz的优异性能.     

Preparation and characterization of Pb(Lu1/2Nb1/2)O3–Pb(In1/2Nb1/2)O3–PbTiO3 ternary ferroelectric ceramics with high phase transition temperatures

To explore new relaxor‐PbTiO₃ systems for high‐power and high‐temperature electromechanical applications, a ternary ferroelectric ceramic system of Pb(Lu_1/2Nb_1/2)O₃–Pb(In_1/2Nb_1/2)O₃–PbTiO₃ (PLN–PIN–PT) have been investigated. The phase structure, dielectric, piezoelectric, and ferroelectric properties of the as‐prepared PLN–PIN–PT ceramics near the morphotropic phase boundary (MPB) were characterized. A high rhombohedral‐tetragonal phase transition temperature T_R‐T of 165°C and a high Curie temperature T_C of 345°C, together with a good piezoelectric coefficient d₃₃ of 420 pC/N, were obtained in 0.38PLN–0.20PIN–0.42PT ceramics. Furthermore, for (0.8?x)PLN–0.2PIN–xPT ceramics, the temperature‐dependent piezoelectric coefficients, coercive fields and electric‐field‐induced strains were further studied. At 175°C, their coercive fields were found to be above 9.5 kV/cm, which is higher than that of PMN–PT and soft P5H ceramics at room temperature, indicating PLN–PIN–PT ceramics to be one of the promising candidates in piezoelectric applications under high‐driven fields. The results presented here could benefit the development of relaxor‐PbTiO₃ with enhanced phase transition temperatures and coercive fields.     

(K0.5Na0.5)(TaxNb1-x)O3无铅压电陶瓷的性能特征

采用传统电子陶瓷制备工艺制备了(K0.5Na0.5)(TaxNb1-x)O3无铅压电陶瓷。研究了不同Ta含量下(K0.5Na0.5)(TaxNb1-x)O3陶瓷的晶相组成及性能特征。结果表明,(K0.5Na0.5)(TaxNb1-x)O3陶瓷在低Ta含量时形成单一斜方相固溶体,但Ta含量达到0.08mol后则有K6Ta10.8O30次晶相产生。随着Ta的加入,陶瓷的体积密度逐渐增大,居里温度(Tc)逐渐降低。当Ta含量为0.08mol时陶瓷具有良好的铁电、压电性能和介电稳定性能,其压电常数d33为76pC/N。     

Effect of cation vacancies on the optical and dielectric properties of KSr2Nb5O15: A first-principles study

Using first-principles calculations, the effect of cation vacancies on the electronic structures and optical characters of KSr₂Nb₅O₁₅ (KSN) lead-free ferroelectrics are investigated. The calculated dielectric properties are demonstrated by the experimental results. The cation vacancies involve K⁺ vacancies (KSN-K), Sr²⁺ vacancies (KSN-Sr), and coexisting K⁺ and Sr²⁺ vacancies (KSN-K&Sr). When these cation vacancies exist in KSN, the unit cell volumes decrease, leading to phase transition from tetragonal to orthorhombic, and the cation vacancies show strong effects on the band gap of KSN, declining by 1.46%-9.46%. The optical properties including the static dielectric constants, refraction, and extinction coefficient of KSN-K, KSN-Sr, and KSN-K&Sr increase more than those of KSN without vacancies, but the reflectivity and loss function decrease. All structures with cation vacancies are mainly refractive in the 0-4 eV photon energy range and are reflective at 5-8 eV. The refractivity increases and reflectivity decreases after vacancies occur. KSN-Sr has the largest static dielectric constant while KSN-K&Sr has the smallest values. The dielectric constant can be adjusted in the range of 25% by controlling the cation vacancies. The calculated dielectric properties are in good agreement with the experimental results. The results pave the way to regulate the optical and dielectric properties of lead-free ferroelectrics by controlling different cation vacancies.     

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.     

Boosting dielectric temperature stability in BNBST-based energy storage ceramics by Nb2O5 modification

Exploring environment-friendly energy storage ceramics simultaneously featuring large recoverable energy storage density (W_rec), high-energy storage efficiency (ƞ), and excellent temperature stability is highly desirable for the application of pulsed power systems. Herein, Nb₂O₅ was introduced to modify BNBST-based lead-free relaxor ferroelectric ceramics in an effort to enhance the dielectric temperature stability. (Bi_0.5Na_0.5)_0.65(Ba_0.3Sr_0.7)_0.35(Ti_0.98Ce_0.02)O₃ (BNBSTC) + x wt%Nb₂O₅ (0 ≤ x ≤ 4) ceramics were prepared by a solid-state reaction method. The phase structure, microstructure, dielectric, and energy storage properties of the ceramics have been systematically studied. It was found that the ε_r–T curve was flattened, and the dielectric temperature stability was effectively improved due to the addition of Nb₂O₅. A noticeable W_rec (1.44 J/cm³) with high η (84.1%) was obtained in BNBSTC + 2 wt%Nb₂O₅ ceramics at a low electric field of 90 kV/cm, which was mainly due to a refined P–E loop induced by Nb₂O₅. In addition to excellent frequency and anti-fatigue cycle stability, this ceramic provides a new solution for designing pulsed power capacitors with high energy density and high temperature stability under low voltage driving conditions.     

用不对称二羟基化反应合成光学纯( )-(1R,2R)和(-)-(1S,2S)-1,2-二苯基-1,2-乙二胺

以（Ｅ）－１,２－二苯基乙烯为原料,经催化不对称二羟基化反应,生成相应的对映体纯１,２－乙二醇,再分别与甲基磺酰氯和叠氮钠作用,最后催化氢化,生成光学纯１,２－乙二胺,总产率７０％。     

Relaxor‐like behaviors in Na1/2Bi1/2Cu3Ti4O12 ceramics

Dielectric properties of Na_1/2Bi_1/2Cu₃Ti₄O₁₂ ceramics were evaluated over the temperature range 300‐720 K. Two relaxor‐like dielectric anomalies were found. The low‐temperature anomaly was confirmed to be an oxygen‐vacancy‐related relaxation process. It is a pseudo‐relaxor behavior caused by a bulk relaxation and a Maxwell‐Wagner relaxation. The high‐temperature one was evidenced to be an electric ferroelectric phase‐transition process resulting from the oxygen‐vacancy ordering.     

V2O5掺杂对(Bi1.5Zn1.0Nb1.5)O7介质陶瓷性能的影响

采用传统的固相反应法制备陶瓷试样,借助XRD,SEM和LCR测试仪,研究了V2O5掺杂对(Bi1.5Zn1.0Nb1.5)O7介质陶瓷的烧结特性和介电性能的影响.结果表明,掺杂适量V2O5后试样的烧结温度明显降低,相结构仍为立方焦绿石单相,且具有良好的介电性能:介电常数(εr)为135～154,介电损耗(tan δ)为0.0033～0.0007,频率温度系数(τf)为-442～-387(2MHz).     

Nb2O5纳米材料在催化氢化肉桂醛中的影响

使用Nb2O5纳米线（W-Nb2O5）和介孔Nb2O5（S-Nb2O5）两种载体负载金属Pd,制备了Pd/W-Nb2O5和Pd/S-Nb2O5两种催化剂对肉桂醛(CMA)进行催化还原,考察了催化剂的活性和选择性。以乙醇为反应溶剂,催化剂用量0.10 g,80 oC,2MPa H2压力下反应6 h,Pd/W-Nb2O5对CMA的转化率为99%,HCMA的选择性为65%。Pd/S-Nb2O5在相同条件下反应, CMA转化率为98%,HCMA选择性为84%。W-Nb2O5表面酸性过强,导致HCMA选择性变低。继续考察Pd/S-Nb2O5在不同条件下对CMA加氢反应的影响。结果显示温度,H2压力,催化剂载体Nb2O5的晶化温度对反应均有影响。     

Ba缺位和烧结工艺对Ba1-xZn1/3Nb2/3O3陶瓷离子有序度和微波介电性能的影响

利用常规固相法制备了Ba1-xZn1/3Nb2/303(x=O～0.02)陶瓷,研究了Ba缺位对Ba1-xZn1/3Nb2/3O3陶瓷的相成分、B位离子长程有序度(LRO)和微波介电性能的影响规律.X射线衍射(XRD)结果显示,适量的Ba缺位可以提高材料的阳离子有序度,x=0.01时陶瓷具有最大的阳离子有序度;Ba缺位...     

Structural and electrical properties of lead free ceramic: Ba(La1/2Nb1/2)O3

Abstract

Abstract

Lead free perovskite Ba(La_1/2Nb_1/2)O₃ was prepared by conventional ceramic fabrication technique at 1375°C for 7?h in air atmosphere. The crystal symmetry, space group and unit cell dimensions were estimated using Rietveld analysis. X-ray diffraction analysis indicated the formation of a single phase monoclinic structure with space group P2/m. Energy dispersive X-ray analysis and scanning electron microscopy studies were carried to study the quality and purity of the compound. Permittivity data showed low temperature coefficient of capacitance (T _CC = 11%) up to 100°C. The circuit model fittings were carried out using the impedance data to find the correlation between the response of real system and idealised model electrical circuit. Complex impedance analyses suggested the dielectric relaxation to be of non-Debye type. The correlated barrier hopping model was employed to successfully explain the mechanism of charge transport in Ba(La_1/2Nb_1/2)O₃. The AC conductivity data were used to evaluate the density of states at Fermi level, minimum hopping length and apparent activation energy.