(Ba1-αSrα)4.8(Sm0.7La0.3)8.8Ti18O54陶瓷的微波介电性能

采用固相合成法制备了(Ba(1-α)Srα)4.8(Sm0.7La0.3)8.8Ti18O54(α=0.1～0.5)系陶瓷,表征了该陶瓷的相组成和显微结构,测试了微波介电性能.结果表明:α=0.3时,(Ba(1-α)Srα)4.8(Sm0.7La0.3)8.8Ti18O54系陶瓷为单相的新钨青铜结构固溶体.α>0.3时,相继出现了第二相BaLa2Ti4O12和La0.66TiO2.993.随α的增加,(Ba(1-α)Srα)4.8(Sm0.7La0.3)8.8Ti18O54系陶瓷的相对介电常数(εr)先增大后有所波动,品质因数(Qf)先增大后减小,谐振频率温度系数(τf)单调减小.α=0.3时,在1 350℃烧结的陶瓷的微波介电性能最佳:εr=98.77,Qf=5184GHz,τf=10.9×10-6/℃,优于不掺杂的BaO-Sm2O3-TiO2陶瓷的.     

微波介质陶瓷

微波介质陶瓷作为广泛应用于微波谐振器、滤波器、介质基板、移相器等现代移动通信设备的核心材料,大大促进了现代通信事业的飞速发展。本文综述了近几十年来微波介质陶瓷的研究现状,以及各类体系微波介质陶瓷发展的最新进展,同时对微波介质陶瓷的发展趋势进行了讨论。     

高介电常数微波介质陶瓷

近年来，微波介质陶瓷作为现代通信技术中关键的核心材料，广泛应用于微波谐振器、滤波器、介质基板、移相器等微波元器件，极大的促进了现化通信事业的飞速发展。本文综述了高介电常数微波介质陶瓷近几十年来的研究进展，并对高介电常数微波介质陶瓷的发展趋势进行了讨论和展望。     

(1-y)Ca1-xLa2x/3TiO3-yCa(Mg1/3Nb2/3)O3复合微波介质陶瓷的研究

采用固相合成法制备了 ( 1-y)Ca1 -xLa2x/ 3 TiO3 -yCa(Mg1 / 3 Nb2 / 3 )O3 系列微波介质陶瓷材料 ,研究了复合系统的微波介电性能、烧结性能和微观结构。研究结果表明 :在y =0 .4～ 0 .6范围内 ,体系形成了单一的钙钛矿结构 ;当复合体系组成 0 .5Ca0 .6La0 .2 67TiO3 -0 .5Ca(Mg1 / 3 Nb2 / 3 )O3 时 ,在 14 0 0℃下烧结保温 4小时所得到材料的微波介电性能最佳 ;εf=5 5 ,Q×f =45 0 0 0GHz( 7.6GHz下 ) ,τf=0 .0 4ppm/℃。     

水热法制备Ba6-3xNd8+2xTi18O54微波介质陶瓷

利用水热法合成了Ba6-3xNd8 2xTi18O54微波介质陶瓷,并对合成的微波介质陶瓷进行了X射线衍射分析和性能测试.结果表明:选择活性较大的前驱物[如Nd(OH)3,TiCl4],用水热法在360℃保温12h,能合成纯的Ba6-3xNd8 2xTi18O54粉体,极大地降低了粉体的合成温度.用水热法合成的Ba6-3xNd8 2xTi18O54粉体制备陶瓷,其烧结温度为1 250℃,比传统固相法要低100℃左右,陶瓷的介电常数(εr)稍大于用固相法制备的陶瓷,品质因数(Q)也有较大的提高,谐振频率温度系数(τf)也有所改善,当x=2/3时,水热法制备的Ba6-3xNd9 2xTi18O54陶瓷具有最佳微波介电性能:εr=88,Q与谐振频率(f)的乘积Q×f=8 890 GHz,τf=24x10-6/℃.     

Pr2O3取代Sm2O3对CLST微波介质陶瓷介电性能的影响

论述了使用Pr2O3取代Sm2O3对CaO-Li2O-Sm2O2—TiO2（CLST）微波介质陶瓷介电性能的影响。采用传统固相反应法制备16CaO-9Li2O-xPr2O3-（12-x）Sm2O3-63TiO2（简写为CLPST-x）陶瓷。XRD分析结果表明，不同取代量的CLPST-x呈现单一的正交钙钛矿结构。当CaO：Li2O：Pr2O3：Sm2O3：TiO2=16：9：4：8：63，烧结温度为1300℃时．CLPST-x能够取得良好的介电性能。εr=101，tanδ=0．00923，τr=85ppm／℃（1MHz），此时，晶粒大小均匀，晶界清晰。     

Sm掺杂对Ba4La19.33Ti18O54陶瓷结构和介电性能的影响分析

主要研究了不同Sm掺杂浓度对Ba4La19.33Ti18O54陶瓷的微波介电性能和微观结构的影响。首先利用常规固相反应技术制备了Sm含量y分别为0、0．1、0．3、0．5和0．7的5种Bat（La1-y,Smy）9.33T18O54陶瓷样品;室温下在0．373．0GHz频率范围内,利用网格分析仪测量了这些样品的介电常数和介电损耗因子;结果表明随着Sm掺杂含量的增大,样品介电损耗明显减小,而介电常数只有微小减少。当Sm掺杂含量y=0．5时,样品的介电性能最好。此外,还利用X射线衍射仪和扫描电子显微镜研究了样品的微观结构及随微波介电性能的变化。     

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。     

(1-x)Ca_(15/16)Sr_(1/16)TiO_3-xLi_(1/2)Nd_(1/2)TiO_3陶瓷的相组成、显微结构及微波介电性能

采用传统固相法合成了(1-x)Ca_(15/16)Sr_(1/16)TiO_3-xLi_(1/2)Nd_(1/2)TiO_3(CST-LNT)系列微波介质陶瓷材料,研究了该系列材料的物相组成、显微结构及微波介电性能。XRD分析结果表明所有样品均为钙钛矿结构,无二次相出现。随着Li_(1/2)Nd_(1/2)TiO_3的加入,陶瓷平均晶粒尺寸下降,表明Li_(1/2)Nd_(1/2)TiO_3会抑制晶粒生长。随着x的增加,介电常数下降,频率温度系数向负方向移动。当x=0.85时,1250℃保温4 h可以得到优良的微波介电性能:ε_r=125.4,Q×f=2230GHz,τ_f=+14.4 ppm/℃。     

(1-y)Ca1-xLa2x/3TiO3-yCa(Mg1/3Nb2/3)O3复合体系的微波介电性能

采用固相合成法制备了(1-y)Ca1-xLa2x/3TiO3-yCa(Mg1/3Nb2/3)O3系列微波介质陶瓷材料.研究了复合系统的微波介电性能和微观结构.研究结果表明在y=0.4～0.6范围内,体系形成了单一的钙钛矿结构.当复合体系组成为0.5Ca0.6La0.267TiO3-0.5Ca(Mg1/3·Nb2/3)O3时,在1 400℃下烧结保温4 h所制备的材料表现出良好的微波介电性能εr=55,Q×f=45 000 GHz(7.6 GHz下),τf=0.04×10-6/℃.     

(1-x)Ba(Mg1/3Nb2/3)O3-xBaSnO3陶瓷的微波介电性能

用传统陶瓷制备方法制备了(1-x)Ba(Mg1/3Nb2/3)O3-xBaSnO3[0.0≤x≤0.3,(1-x)BMN-xBS]体系微波介质陶瓷,研究了该陶瓷的微观结构和微波介电性能.用X射线衍射仪研究陶瓷的晶体结构.用扫描电镜观察陶瓷的显微结构.用网络分析仪测试陶瓷的微波介电性能.结果表明:晶格常数c和a均随x值的增加而增加;晶格常数比(c/a)随x值的增加而减小.当x≥0.1时,1∶2有序衍射峰消失.陶瓷的平均晶粒尺寸在0.7～2 μm之间.随x值的增加,陶瓷的相对介电常数(εr)和谐振频率温度系数(τr)呈线性减小;品质因数与谐振频率的乘积(Qf)呈非线性变化.当x=0.15时,Qf达到最大值,为86 200 GHz.当x=0.3时,在此体系中可以获得τf接近零的微波介质陶瓷Ba(Sn0.3Mg0.233Nb0.467)O3,其微波介电性能如下:εr=26.1;Qf=42 500GHz;τr=4.3×10-6/℃.     

添加SrO或SnO2对Ba4.5(Nd0.84,Bi0.16)9Ti18O54微波陶瓷介电性能的影响

对Ba4.5(Nd0.84，Bi0.16)9Ti18O54(BNBT)系微波陶瓷进行了组成改性的研究。添加不同量的SrO或SnO2于主相材料中，分别替代Ba或者Ti,合成条件为1100℃下保温3h，粉碎、成型后，在1270℃下保温3h烧成。在10GHz下用谐振腔法测量了材料的介电常数ετ。和机械品质因数Q，在20～90℃范围测量了频率温度系数τf。结果表明：Sr，Bi复合掺杂能够使BNBT材料保持较高的介电常数，同时Qf值（机械品质因数Q与测量频率之积)由5899GHz上升到9259GHz，而少量的SnO2添加有助于提高系统的介电常数并使τf值减小。     

CaLa4Ti4O15微波介电陶瓷的制备和性能

采用固相法制备了Cata4Ti4O15系微波介质陶瓷.研究了不同预烧温度对CaLa4Ti4O15陶瓷烧结特性和微波介电性能的影响.在1 200℃预烧caLa4Ti4O15粉末.除CaLa4Ti4O15主相外,还存在部分CaTiO3,La2Ti2O7和La2TiO5混合相.在1 300℃和1 400℃预烧后.获得了六方类钙钛矿CaLa4Ti4O15单相.CaLa4Ti4O15粉末预烧后可饶结成高致密陶瓷(相对密度约97%),同时具有高机械品质因数与谐振频率的乘积(Q×f)值和近零谐振频率温度系数(Tf).1 550℃烧结的CaLa4Ti4O15陶瓷具有优异的微波介电性能:相对介电常数εr=45.1,Q×f=46087GHz,tf=-14.1 × 10-6/℃(预烧温度1 200℃);εr=-45.9,Q×f=48871GHz,tf=-14.4 ×10-6/℃(预烧温度1 300℃).     

(Zr0.8Sn0.2)TiO4(ZST)微波介质陶瓷微波烧成工艺研究

分别采用传统的电热烧结和微波烧结制备了ZST微波介质陶瓷,研究了烧结温度对介质陶瓷烧结性能、微观结构、相组成和微波介电性能的影响。结果表明:与传统电热烧结相比,在所得材料密度近似的情况下,微波烧结能降低烧结温度约70℃、缩短烧结时间2.5h,所获材料密度分布的标准差大大减小;微波烧结后材料由(Zr0.8Sn0.2)TiO4斜方晶单一晶相组成,随温度升高,无新相产生;微波烧结所得材料的晶粒尺寸均匀、结构致密;材料的介电常数和品质因数随着微波烧结温度的提高而增大,对应数值分别比传统烧结方式提高17.5%和14.3%左右。     

Microwave dielectric properties and thermally stimulated depolarization of Al-doped Ba4(Sm,Nd)9.33Ti18O54 ceramics

Ba₄(Sm_0.15Nd_0.85)_9.33Ti_18-zAl_3z/4O₅₄ (BSNT-zAl, 0.0 ≤ z ≤ 2.5) ceramics were prepared via a solid-state reaction, and the effects of Al doping on the microwave dielectric properties and defect behavior of the title compound were studied. X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM) photographs suggested that Al ions successfully entered the lattice to form tungsten-bronze-like solid solutions. With a small amount of Al substitution, the relative dielectric constant (ε_r), and the temperature coefficient of resonant frequency (τ_f) values decreased, whereas the quality factor (Q × f) substantially increased by approximately 50%. The defect-related extrinsic dielectric loss was clarified via the thermally stimulated depolarization current (TSDC) technique. With Al doping, the TSDC relaxation of across-grain-boundary oxygen vacancies () vanished, whereas that of defect dipoles () appeared at relatively low temperatures. Therefore, in the BSNT-zAl ceramics, oxygen vacancies were more inclined to interconnect with to form defect dipoles. This could reduce the activity of and account for the notable improvement in the Q × f values. In particular, the excellent characteristics of ε_r = 67.33, Q × f = 16 530 GHz, and τ_f = +0.87 ppm/°C were achieved in the specimens with z = 1.5 sintered at 1350°C for 4 hours.     

Microwave and terahertz properties of porous Ba4(Sm,Nd,Bi)28/3Ti18O54 ceramics obtained by sacrificial template method

Microwave and terahertz communications are increasingly significant, however, the lack of material information in terahertz band limits their development. Moreover, few lightweight materials with a high relative dielectric constant () are found suited for satellite communication and wearable devices. In this study, we developed lightweight porous Ba₄[(Sm_0.1Nd_0.9)_0.9Bi_0.1]_28/3Ti₁₈O₅₄ (BSNBT) ceramics exhibiting a total porosity ranging from 6.3% to 26.5% (bulk density ranging from 5.47 to 4.29 g/cm³) and relatively high ranging from 85.6 to 56.8, which were obtained by sacrificial template method using polymethyl methacrylate spheres (PMMAs) of varying average particle sizes, from 9 to 34 μm, as sacrificial materials. A high refractive index ranging between 7.5 and 8.9 and a low absorption coefficient of approximately 17 cm⁻¹ at 0.3 THz were obtained for the porous ceramics with different total porosities derived from PMMAs with average particle sizes of 9 and 19 μm. Furthermore, effective medium and Mie scattering theories were applied to understand the effects of porous structure on the dielectric properties in microwave and terahertz frequency ranges, respectively, owing to the different wavelengths in the BSNBT matrix. The results of this study suggest that introducing a porous structure can effectively exploit lightweight microwave dielectric ceramic materials and provide valuable information on their terahertz response mechanism.     

(Zr,Sn)TiO4系微波介质陶瓷的研究进展

本文从晶体结构、固溶体性质、组成改性、制备、性能等方面对(Zr,Sn)TiO4系微波陶瓷的发展现状进行了详细介绍,并指出了研究和应用前景。