ZnAl_2O_4基低介电常数微波介质陶瓷的结构与性能
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摘要
综观微波介质陶瓷材料的发展历史和应用前景,结合当前微波介质陶瓷的研究现状,确定ZnAl_2O_4基陶瓷为本文的研究对象。利用X射线衍射(XRD)、扫描电镜(SEM)、X射线能谱(EDS)、X射线光电子能谱(XPS)、电子探针(EPMA)和网络分析仪等仪器系统地研究了制备方法(常规固相法和熔盐法)、烧结工艺、相成分、微观组织结构和微波介电性能之间的关系。
首先研究了(1-x)ZnAl_2O_(4-x)TiO_2材料的烧结特性、相成分和微波介电性能。结果表明,TiO_2能有效地改善材料的烧结性能和调节材料的谐振频率温度系数,当x=0.21时,(1-x)ZnAl_2O_(4-x)TiO_2陶瓷具有近零的谐振频率温度系数,体系中包括细小的ZnAl_2O_4尖晶石晶粒和粗大的金红石相晶粒。在此基础上,系统地研究了(1-x)ZnAl_2O_(4-x)TiO_2 (x=0.21)材料的预烧温度、烧结温度和升温速率,并确定了最佳工艺参数,它们分别为1150℃、1500℃和5℃/min,此时的微波介电性能为:εr=11.6、Q·f=74000GHz、τf=-0.4ppm/℃。
利用熔盐法制备了(1-x)ZnAl_2O_(4-x)TiO_2陶瓷,并探索了材料的烧结性能、微观组织和微波介电性能特点。与常规固相法相比,利用LiCl和ZnCl_2熔盐均能制备出颗粒细小均匀、活性高的(1-x)ZnAl_2O_(4-x)TiO_2粉末,并能有效降低材料的烧结温度,但同时也降低了材料的密度和微波介电性能。当熔盐为LiCl、预烧温度为900℃时,(1-x)ZnAl_2O_(4-x)TiO_2(x=0.21)陶瓷的致密化温度为1425℃,微波介电性能分别降到:εr=10.0、Q·f=39970GHz、τf=-21.2ppm/℃。当x=0.25时,(1-x)ZnAl_2O_(4-x)TiO_2陶瓷的致密化温度降低到1300℃,τf值被调节到-7.1ppm/℃,同时,Q·f值降低到27000GHz,而εr值变化很小。当熔盐为ZnCl2、预烧温度为900℃时,(1-x)ZnAl_2O_(4-x)TiO_2(x=0.25)陶瓷的致密化温度为1350℃,此时材料的微波介电性能为:εr=10.0、Q·f=56440GHz、τf=-25.4ppm/℃。
利用MO(M=Co, Mg, Mn)和TiO_2共同改性ZnAl_2O_4时,比较了(1-x)ZnAl_2O_4- xM2TiO_4(x=0.21)与(1-x)ZnAl_2O_(4-x)TiO_2(x=0.21)陶瓷的相成分、微观结构和微波介电性能之间的差异。研究表明,Co~(2+)离子能促使Ti~(4+)离子固溶入ZnAl_2O_4尖晶石晶格中形成单一的固溶体相,能将Q·f值从74000GHz提高到94000GHz。Mg~(2+)和Mn~(2+)离子均不能使Ti~(4+)离子完全固溶入ZnAl_2O_4晶格中,而在体系中分别出现了MgTi_2O_5和ZnMn3O7相,两者的Q·f值分别为188540GHz和23530GHz。与(1-x)ZnAl_2O_4-xTiO_4 (x=0.21)陶瓷相比,(1-x)ZnAl_2O_(4-x)M_2TiO_4(x=0.21)陶瓷的εr和τf值均有所降低,但相互之间的差别很小。
进一步研究了(1-x)ZnAl_2O_(4-x)M_2TiO_4(M=Co, Mg)陶瓷的相变过程和微波介电性能特点。结果表明,对于(1-x)ZnAl_2O_(4-x)Mg_2TiO_4体系,当x=0.1时,ZnAl_2O_4能与Mg2TiO_4形成尖晶石固溶体,当x=0.21～0.8时,体系中包括尖晶石相和MgTi2O5相,当x=0.9和1.0时,体系中存在尖晶石相和MgTiO_3相。对于(1-x)ZnAl_2O_(4-x)Co_2TiO_4体系,当x=0.1～0.3时,ZnAl_2O_4能与Co2TiO_4形成尖晶石固溶体,当x=0.4时,体系中析出少量Co_2TiO_4相,当x=0.5时,体系中同时析出Co_2TiO_4和(Zn, Co)Al_2O_4相,两者相互交替生长在(1-x)ZnAl_2O_(4-x)Co_2TiO_4基体上。随着M_2TiO_4含量的增加,(1-x)ZnAl_2O_(4- x)M_2TiO_4陶瓷的εr值几乎线性增大,Q·f值先减小然后增大,τf值变化很小。
研究了TiO_2、CaTiO_3和SrTiO_3对0.79ZnAl_2O_4-0.21M_2TiO_4(M=Co, Mg)陶瓷谐振频率温度系数的影响。研究发现,TiO_2不能调节0.79ZnAl_2O_4-0.21M_2TiO_4(M=Mg, Co)材料的τf值,因为TiO_2与基体反应生成了具有负温度系数的MTi2O5相。CaTiO_3和SrTiO_3均能有效地调节0.79ZnAl_2O_4-0.21M2TiO_4(M=Co, Mg)材料的τf值。总的来说,随着CaTiO_3(或SrTiO_3)添加量的增多,材料的εr和τf值逐渐增大,而Q?f值具有减小的趋势。
研究了ZnB_2O_4和B_2O_3助烧剂对(1-x)(0.79ZnAl_2O_4-0.21Co2TiO_4)-xCaTiO_3(x=0.08) (ZCC)和(1-x)(0.79ZnAl_2O_4-0.21Mg2TiO_4)-xCaTiO_3(x=0.06)(ZMC)材料的烧结特性、相成分和微波介电性能的影响。ZnB_2O_4助烧剂能将ZCC材料的烧结温度降低到1100℃,降幅为300℃,但ZnB_2O_4助烧剂对ZMC材料以及B_2O_3助烧剂对ZCC和ZMC材料的助烧作用均不显著,仅能降低50～100℃。当掺入助烧剂后,材料的εr值均有所降低,但材料的Q?f和τf值的变化趋势与助烧剂的种类和数量有关。一般而言,ZnB_2O_4助烧剂使ZCC和ZMC材料的Q?f值降低幅度较大,而B_2O_3助烧剂对Q?f值的影响相对较小。
Based on the development, application and research actuality of microwave dielectric ceramics, ZnAl_2O_4-based ceramics are chosen as research objective in this dissertation. The relationships among preparing methods (including solid-state reaction and molten salt method) and processes, phase compositions, microstructures and microwave dielectric properties have been investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), electron-probe microanalysis (EPMA) and network analyzer, etc.
Sintering characteristic, phase compositions and microwave dielectric properties of (1-x)ZnAl_2O_(4-x)TiO_2 ceramics had been studied. It shows that TiO2 can effectively improve the sintering characteristic and control the temperature coefficient of resonant frequency (τf). (1-x)ZnAl_2O_(4-x)TiO_2 (x=0.21) ceramics with near-zeroτf value includes smaller ZnAl_2O_4 spinel grains and larger rutile grains. And then, the sintering processes such as calcining temperature, sintering temperature and heating rate of the (1-x)ZnAl_2O_(4-x)TiO_2 (x=0.21) system have been researched systematically, and the optimal sintering process parameters have been determined which are 1150℃, 1500℃and 5℃/min, respectively, in which sintering conditions the microwave dielectric properties are as follows:εr=11.6, Q·f=74000GHz,τf=-0.4ppm/℃.
Sintering characteristic, microstructures and microwave dielectric properties of (1-x)ZnAl_2O_(4-x)TiO_2 ceramics synthesized by molten salt method had been explored. In contrast to the solid-state reaction, smaller size, more homogenous and higher activity powder can be synthesized by LiCl and ZnCl_2 molten salt, which lowers the sintering temperature, at the same time, also deteriorates the density and microwave dielectric properties of the (1-x)ZnAl_2O_(4-x)TiO_2 ceramics. (1-x)ZnAl_2O_(4-x)TiO_2 (x=0.21) calcined at 900℃in LiCl molten salt can be fully densified at 1425℃, and the microwave dielectric properties withεr=10.0, Q·f=39970GHz andτf=-21.2ppm/℃can be obtained. When x is equal to 0.25, the densification temperature reduces to 1300℃, andτf value is adjusted to -7.1ppm/℃and theεr value nearly doesn’t change, however, the Q·f value reduces to 27000GHz. (1-x)ZnAl_2O_(4-x)TiO_2 (x=0.25) calcined at 900℃in ZnCl2 molten salt can be fully densified at 1350℃and the ceramics exhibits the microwave dielectric properties withε_r=10.0, Q·f=56440GHz andτf=-25.4ppm/℃.
When MO(M=Co, Mg, Mn) and TiO_2 were added to ZnAl_2O_4, the phase compositions, microstructures and microwave dielectric properties of (1-x)ZnAl_2O_(4-x)M_2TiO_4 (x=0.21) ceramics were compared with those of (1-x)ZnAl_2O_(4-x)TiO_2 (x=0.21) ceramics. It is found that the single phase solid solution appears in the (1-x)ZnAl_2O_(4-x)Co_2TiO_4 (x=0.21) ceramics because Co~(2+) ion can promote Ti~(4+) ion to diffuse into the ZnAl_2O_4 crystal lattice which increases the Q·f value from 74000 to 94000GHz. However, the MgTi_2O_5 and ZnMn_3O_7 phase can be observed in the (1-x)ZnAl_2O_(4-x)Mg_2TiO_4 (x=0.21) and (1-x)ZnAl_2O_(4-x)Mn_2TiO_4 (x=0.21) ceramics, whose Q·f value is 188540GHz and 23530GHz, respectively. Theεr andτf values of the (1-x)ZnAl_2O_(4-x)M_2TiO_4 (x=0.21) are lower than those of (1-x)ZnAl_2O_(4-x)TiO_2 (x=0.21) ceramics, whereas theεr andτf values are weakly dependent on the M element and are equal to about 9.7 and -65ppm/℃, respectively.
Phase transition and microwave dielectric properties of (1-x)ZnAl_2O_(4-x)M_2TiO_4 (M=Co, Mg) ceramics had been further studied. In the (1-x)ZnAl_2O_(4-x)Mg_2TiO_4 system, ZnAl_2O_4 can form a spinel solid solution with Mg2TiO_4 for x=0.1, while the MgTi2O5 and MgTiO_3 second phase exists in the systems for 0.21≤x≤0.8 and 0.9≤x≤1.0, respectively. In the (1-x)ZnAl_2O_(4-x)Co_2TiO_4 system, ZnAl_2O_4 can also form a spinel solid solution with Co2TiO_4 for 0.1≤x≤0.3, however, the Co2TiO_4 second phase appears in the ceramics for x=0.4. When x is equal to 0.5, Co2TiO_4 and (Zn, Co)Al_2O_4 phase coexist and grow alternately in the (1-x)ZnAl_2O_(4-x)Co_2TiO_4 matrix. As the content of M2TiO_4 increases in the (1-x)ZnAl_2O_(4-x)M_2TiO_4 system, theεr value takes on a tendency of linear increase, and the Q·f value increases initially and then decreases, while theτf value only changes slightly.
The effects of TiO_2, CaTiO_3 and SrTiO_3 additions on theτf value of the 0.79ZnAl_2O_4-0.21M2TiO_4 (M=Mg, Co) ceramics had been investigated. TiO_2 cannot control theτf value of the 0.79ZnAl_2O_4-0.21M2TiO_4 (M=Mg, Co) ceramics due to the MTi2O5, formed by the reaction of TiO_2 with the matrix, with relative high negativeτf value, however, CaTiO_3 and SrTiO_3 can adjust effectively theτf value. In general, with the increasing amount of CaTiO_3 (or SrTiO_3), bothεr andτf values increase gradually, while, the Q?f value has a tendency of decrease.
The influences of ZnB_2O_4 and B_2O_3 sintering aids on the sintering characteristic, phase compositions, microwave dielectric properties of (1-x)(0.79ZnAl_2O_4-0.21Co2TiO_4)- xCaTiO_3(x=0.08)(ZCC) and (1-x)(0.79ZnAl_2O_4-0.21Mg_2TiO_4)-xCaTiO_3(x=0.06)(ZMC) ceramics had been studied. When ZnB_2O_4 is added to ZCC system, the sintering temperature is reduced to 1100℃, which is 300℃lower than the sintering temperature of undoped ZCC. When B_2O_3 is added to ZCC system, or ZnB_2O_4 (or B_2O_3 ) is added to ZMC system, the sintering temperature only lowers 50～100℃. In comparison with the undoped ZCC (or ZMC), theεr values of the doped system all reduce, and the Q-f andτf values are dependent on the category and amount of additions. On the whole, ZnB_2O_4 addition greatly reduces the Q-f value of the ZCC (or ZMC) ceramics, while B_2O_3 addition does not affect obviously on the Q-f value.
首先研究了(1-x)ZnAl_2O_(4-x)TiO_2材料的烧结特性、相成分和微波介电性能。结果表明,TiO_2能有效地改善材料的烧结性能和调节材料的谐振频率温度系数,当x=0.21时,(1-x)ZnAl_2O_(4-x)TiO_2陶瓷具有近零的谐振频率温度系数,体系中包括细小的ZnAl_2O_4尖晶石晶粒和粗大的金红石相晶粒。在此基础上,系统地研究了(1-x)ZnAl_2O_(4-x)TiO_2 (x=0.21)材料的预烧温度、烧结温度和升温速率,并确定了最佳工艺参数,它们分别为1150℃、1500℃和5℃/min,此时的微波介电性能为:εr=11.6、Q·f=74000GHz、τf=-0.4ppm/℃。
利用熔盐法制备了(1-x)ZnAl_2O_(4-x)TiO_2陶瓷,并探索了材料的烧结性能、微观组织和微波介电性能特点。与常规固相法相比,利用LiCl和ZnCl_2熔盐均能制备出颗粒细小均匀、活性高的(1-x)ZnAl_2O_(4-x)TiO_2粉末,并能有效降低材料的烧结温度,但同时也降低了材料的密度和微波介电性能。当熔盐为LiCl、预烧温度为900℃时,(1-x)ZnAl_2O_(4-x)TiO_2(x=0.21)陶瓷的致密化温度为1425℃,微波介电性能分别降到:εr=10.0、Q·f=39970GHz、τf=-21.2ppm/℃。当x=0.25时,(1-x)ZnAl_2O_(4-x)TiO_2陶瓷的致密化温度降低到1300℃,τf值被调节到-7.1ppm/℃,同时,Q·f值降低到27000GHz,而εr值变化很小。当熔盐为ZnCl2、预烧温度为900℃时,(1-x)ZnAl_2O_(4-x)TiO_2(x=0.25)陶瓷的致密化温度为1350℃,此时材料的微波介电性能为:εr=10.0、Q·f=56440GHz、τf=-25.4ppm/℃。
利用MO(M=Co, Mg, Mn)和TiO_2共同改性ZnAl_2O_4时,比较了(1-x)ZnAl_2O_4- xM2TiO_4(x=0.21)与(1-x)ZnAl_2O_(4-x)TiO_2(x=0.21)陶瓷的相成分、微观结构和微波介电性能之间的差异。研究表明,Co~(2+)离子能促使Ti~(4+)离子固溶入ZnAl_2O_4尖晶石晶格中形成单一的固溶体相,能将Q·f值从74000GHz提高到94000GHz。Mg~(2+)和Mn~(2+)离子均不能使Ti~(4+)离子完全固溶入ZnAl_2O_4晶格中,而在体系中分别出现了MgTi_2O_5和ZnMn3O7相,两者的Q·f值分别为188540GHz和23530GHz。与(1-x)ZnAl_2O_4-xTiO_4 (x=0.21)陶瓷相比,(1-x)ZnAl_2O_(4-x)M_2TiO_4(x=0.21)陶瓷的εr和τf值均有所降低,但相互之间的差别很小。
进一步研究了(1-x)ZnAl_2O_(4-x)M_2TiO_4(M=Co, Mg)陶瓷的相变过程和微波介电性能特点。结果表明,对于(1-x)ZnAl_2O_(4-x)Mg_2TiO_4体系,当x=0.1时,ZnAl_2O_4能与Mg2TiO_4形成尖晶石固溶体,当x=0.21～0.8时,体系中包括尖晶石相和MgTi2O5相,当x=0.9和1.0时,体系中存在尖晶石相和MgTiO_3相。对于(1-x)ZnAl_2O_(4-x)Co_2TiO_4体系,当x=0.1～0.3时,ZnAl_2O_4能与Co2TiO_4形成尖晶石固溶体,当x=0.4时,体系中析出少量Co_2TiO_4相,当x=0.5时,体系中同时析出Co_2TiO_4和(Zn, Co)Al_2O_4相,两者相互交替生长在(1-x)ZnAl_2O_(4-x)Co_2TiO_4基体上。随着M_2TiO_4含量的增加,(1-x)ZnAl_2O_(4- x)M_2TiO_4陶瓷的εr值几乎线性增大,Q·f值先减小然后增大,τf值变化很小。
研究了TiO_2、CaTiO_3和SrTiO_3对0.79ZnAl_2O_4-0.21M_2TiO_4(M=Co, Mg)陶瓷谐振频率温度系数的影响。研究发现,TiO_2不能调节0.79ZnAl_2O_4-0.21M_2TiO_4(M=Mg, Co)材料的τf值,因为TiO_2与基体反应生成了具有负温度系数的MTi2O5相。CaTiO_3和SrTiO_3均能有效地调节0.79ZnAl_2O_4-0.21M2TiO_4(M=Co, Mg)材料的τf值。总的来说,随着CaTiO_3(或SrTiO_3)添加量的增多,材料的εr和τf值逐渐增大,而Q?f值具有减小的趋势。
研究了ZnB_2O_4和B_2O_3助烧剂对(1-x)(0.79ZnAl_2O_4-0.21Co2TiO_4)-xCaTiO_3(x=0.08) (ZCC)和(1-x)(0.79ZnAl_2O_4-0.21Mg2TiO_4)-xCaTiO_3(x=0.06)(ZMC)材料的烧结特性、相成分和微波介电性能的影响。ZnB_2O_4助烧剂能将ZCC材料的烧结温度降低到1100℃,降幅为300℃,但ZnB_2O_4助烧剂对ZMC材料以及B_2O_3助烧剂对ZCC和ZMC材料的助烧作用均不显著,仅能降低50～100℃。当掺入助烧剂后,材料的εr值均有所降低,但材料的Q?f和τf值的变化趋势与助烧剂的种类和数量有关。一般而言,ZnB_2O_4助烧剂使ZCC和ZMC材料的Q?f值降低幅度较大,而B_2O_3助烧剂对Q?f值的影响相对较小。
Based on the development, application and research actuality of microwave dielectric ceramics, ZnAl_2O_4-based ceramics are chosen as research objective in this dissertation. The relationships among preparing methods (including solid-state reaction and molten salt method) and processes, phase compositions, microstructures and microwave dielectric properties have been investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), electron-probe microanalysis (EPMA) and network analyzer, etc.
Sintering characteristic, phase compositions and microwave dielectric properties of (1-x)ZnAl_2O_(4-x)TiO_2 ceramics had been studied. It shows that TiO2 can effectively improve the sintering characteristic and control the temperature coefficient of resonant frequency (τf). (1-x)ZnAl_2O_(4-x)TiO_2 (x=0.21) ceramics with near-zeroτf value includes smaller ZnAl_2O_4 spinel grains and larger rutile grains. And then, the sintering processes such as calcining temperature, sintering temperature and heating rate of the (1-x)ZnAl_2O_(4-x)TiO_2 (x=0.21) system have been researched systematically, and the optimal sintering process parameters have been determined which are 1150℃, 1500℃and 5℃/min, respectively, in which sintering conditions the microwave dielectric properties are as follows:εr=11.6, Q·f=74000GHz,τf=-0.4ppm/℃.
Sintering characteristic, microstructures and microwave dielectric properties of (1-x)ZnAl_2O_(4-x)TiO_2 ceramics synthesized by molten salt method had been explored. In contrast to the solid-state reaction, smaller size, more homogenous and higher activity powder can be synthesized by LiCl and ZnCl_2 molten salt, which lowers the sintering temperature, at the same time, also deteriorates the density and microwave dielectric properties of the (1-x)ZnAl_2O_(4-x)TiO_2 ceramics. (1-x)ZnAl_2O_(4-x)TiO_2 (x=0.21) calcined at 900℃in LiCl molten salt can be fully densified at 1425℃, and the microwave dielectric properties withεr=10.0, Q·f=39970GHz andτf=-21.2ppm/℃can be obtained. When x is equal to 0.25, the densification temperature reduces to 1300℃, andτf value is adjusted to -7.1ppm/℃and theεr value nearly doesn’t change, however, the Q·f value reduces to 27000GHz. (1-x)ZnAl_2O_(4-x)TiO_2 (x=0.25) calcined at 900℃in ZnCl2 molten salt can be fully densified at 1350℃and the ceramics exhibits the microwave dielectric properties withε_r=10.0, Q·f=56440GHz andτf=-25.4ppm/℃.
When MO(M=Co, Mg, Mn) and TiO_2 were added to ZnAl_2O_4, the phase compositions, microstructures and microwave dielectric properties of (1-x)ZnAl_2O_(4-x)M_2TiO_4 (x=0.21) ceramics were compared with those of (1-x)ZnAl_2O_(4-x)TiO_2 (x=0.21) ceramics. It is found that the single phase solid solution appears in the (1-x)ZnAl_2O_(4-x)Co_2TiO_4 (x=0.21) ceramics because Co~(2+) ion can promote Ti~(4+) ion to diffuse into the ZnAl_2O_4 crystal lattice which increases the Q·f value from 74000 to 94000GHz. However, the MgTi_2O_5 and ZnMn_3O_7 phase can be observed in the (1-x)ZnAl_2O_(4-x)Mg_2TiO_4 (x=0.21) and (1-x)ZnAl_2O_(4-x)Mn_2TiO_4 (x=0.21) ceramics, whose Q·f value is 188540GHz and 23530GHz, respectively. Theεr andτf values of the (1-x)ZnAl_2O_(4-x)M_2TiO_4 (x=0.21) are lower than those of (1-x)ZnAl_2O_(4-x)TiO_2 (x=0.21) ceramics, whereas theεr andτf values are weakly dependent on the M element and are equal to about 9.7 and -65ppm/℃, respectively.
Phase transition and microwave dielectric properties of (1-x)ZnAl_2O_(4-x)M_2TiO_4 (M=Co, Mg) ceramics had been further studied. In the (1-x)ZnAl_2O_(4-x)Mg_2TiO_4 system, ZnAl_2O_4 can form a spinel solid solution with Mg2TiO_4 for x=0.1, while the MgTi2O5 and MgTiO_3 second phase exists in the systems for 0.21≤x≤0.8 and 0.9≤x≤1.0, respectively. In the (1-x)ZnAl_2O_(4-x)Co_2TiO_4 system, ZnAl_2O_4 can also form a spinel solid solution with Co2TiO_4 for 0.1≤x≤0.3, however, the Co2TiO_4 second phase appears in the ceramics for x=0.4. When x is equal to 0.5, Co2TiO_4 and (Zn, Co)Al_2O_4 phase coexist and grow alternately in the (1-x)ZnAl_2O_(4-x)Co_2TiO_4 matrix. As the content of M2TiO_4 increases in the (1-x)ZnAl_2O_(4-x)M_2TiO_4 system, theεr value takes on a tendency of linear increase, and the Q·f value increases initially and then decreases, while theτf value only changes slightly.
The effects of TiO_2, CaTiO_3 and SrTiO_3 additions on theτf value of the 0.79ZnAl_2O_4-0.21M2TiO_4 (M=Mg, Co) ceramics had been investigated. TiO_2 cannot control theτf value of the 0.79ZnAl_2O_4-0.21M2TiO_4 (M=Mg, Co) ceramics due to the MTi2O5, formed by the reaction of TiO_2 with the matrix, with relative high negativeτf value, however, CaTiO_3 and SrTiO_3 can adjust effectively theτf value. In general, with the increasing amount of CaTiO_3 (or SrTiO_3), bothεr andτf values increase gradually, while, the Q?f value has a tendency of decrease.
The influences of ZnB_2O_4 and B_2O_3 sintering aids on the sintering characteristic, phase compositions, microwave dielectric properties of (1-x)(0.79ZnAl_2O_4-0.21Co2TiO_4)- xCaTiO_3(x=0.08)(ZCC) and (1-x)(0.79ZnAl_2O_4-0.21Mg_2TiO_4)-xCaTiO_3(x=0.06)(ZMC) ceramics had been studied. When ZnB_2O_4 is added to ZCC system, the sintering temperature is reduced to 1100℃, which is 300℃lower than the sintering temperature of undoped ZCC. When B_2O_3 is added to ZCC system, or ZnB_2O_4 (or B_2O_3 ) is added to ZMC system, the sintering temperature only lowers 50～100℃. In comparison with the undoped ZCC (or ZMC), theεr values of the doped system all reduce, and the Q-f andτf values are dependent on the category and amount of additions. On the whole, ZnB_2O_4 addition greatly reduces the Q-f value of the ZCC (or ZMC) ceramics, while B_2O_3 addition does not affect obviously on the Q-f value.
引文
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