CN105645947A - Temperature-stable microwave dielectric ceramic Bi2TiGe3O11 allowing low temperature sintering and preparation method thereof - Google Patents

Abstract

The invention discloses a temperature-stable microwave dielectric ceramic Bi2TiGe3O11 allowing low temperature sintering and a preparation method thereof. The method is as below: (1) weighing analytically pure raw materials of Bi2O3, TiO and GeO2 powders according to a stoichiometric formula Bi2TiGe3O11; (2) mixing the raw materials in the step (1) by wet ball milling for 12 h by using a milling medium of distilled water, drying and pre-sintering in the atmosphere at 700 DEG C for 6 h; and (3) adding a binder into the powder obtained in the step (2) and pelletizing, then pressing for forming, and finally sintering in the atmosphere at 750-800 DEG C for 4 h, wherein the binder is a polyvinyl alcohol solution with mass concentration of 5%, and the addition of the polyvinyl alcohol accounts for 3 wt.% of the total amount of the powder. The ceramic prepared by the invention has the advantages of good sintering property at the temperature below 800 DEG C, dielectric constant of 16.7-17.8, quality factor Qf of up to 84000-141000 GHz, small resonance frequency temperature coefficient, and a great application value in industry.

Description

Low temperature sintering temperature-stable microwave dielectric ceramic Bi2TiGe3O11And preparation method thereof

Technical field

The present invention relates to dielectric ceramic material, particularly relate to for manufacturing dielectric ceramic materials of microwave device such as the ceramic substrate of microwave frequency use, resonator and wave filter and preparation method thereof.

Background technology

Microwave dielectric ceramic refers to and is applied in microwave frequency band (mainly UHF and SHF frequency range) circuit as dielectric material the pottery completing one or more functions, modern communication is widely used as the components and parts such as resonator, wave filter, dielectric substrate and medium wave circuit, it it is the key foundation material of modern communication technology, in portable mobile phone, automobile telephone, wireless phone, television satellite accepter and military radar etc., there is highly important application, in the miniaturization of modern communication instrument, integrated process, just playing increasing effect.

It is applied to the dielectric ceramic of microwave frequency band, the requirement of following dielectric property should be met: (1) seriation DIELECTRIC CONSTANT ��_rTo adapt to different frequency and the requirement of different application occasion; (2) high quality factor q value or low dielectric loss tan ��, to reduce noise, generally require Qf >=3000GHz; (3) the temperature coefficient �� of resonant frequency_?Little of as far as possible to ensure the heat stability that device has had ,-10ppm/ DEG C�ܦ� of general requirement_?��+10ppm/ DEG C. Just have tried to be applied to dielectric substance microwave technology in the world from late 1930s, and prepare TiO₂Microwave dielectric filter, but its temperature coefficient of resonance frequency ��_?Too greatly cannot be practical. Since the seventies in last century, start the large-scale development to medium ceramic material, according to relative dielectric constant ��_rSize different from what use frequency range, generally can will have been developed that and the microwave-medium ceramics developed be divided into 4 classes.

(1) ultralow dielectric microwave dielectric ceramic, main representative is Al₂O₃-TiO₂��Y₂BaCuO₅��MgAl₂O₄And Mg₂SiO₄Deng, its ��_r�� 20, quality factor q �� f >=50000GHz, ��_?�� 10ppm/ �� of C. It is mainly used in microwave base plate and high-end microwave device.

(2) low ��_rWith the microwave dielectric ceramic of high q-factor, mainly BaO-MgO-Ta₂O₅,BaO-ZnO-Ta₂O₅Or BaO-MgO-Nb₂O₅,BaO-ZnO-Nb₂O₅System or the hybrid system MWDC material between them.Its ��_r=20��35, Q=(1��2) �� 10⁴(under f >=10GHz), ��_?�� 0. As dielectric resonance device in the microwave communication equipments such as the direct broadcasting satellite being mainly used in f >=8GHz.

(3) medium ��_rWith the microwave dielectric ceramic of Q-value, mainly with BaTi₄O₉��Ba₂Ti₉O₂₀(Zr, Sn) TiO₄Deng the MWDC material for base, its ��_r=35 ~ 45, Q=(6��9) �� 10³(under f=3��-4GHz), ��_?�� 5ppm/ �� of C. It is mainly used in the microwave military radar in 4��8GHz frequency range and in communication system as dielectric resonance device.

(4) high ��_rAnd the microwave dielectric ceramic that Q-value is relatively low, it being mainly used in 0.8��4GHz frequency range civilian mobile communcations system, this is also the emphasis of microwave dielectric ceramic research. Since the eighties, Kolar, Kato et al. find and have studied perovskite-like tungsten bronze type BaO Ln in succession₂O₃��TiO₂Series (Ln=La, Sm, Nd or Pr etc. are called for short BLT system), complex perovskite structure CaO Li₂O��Ln₂O₃��TiO₂Series, lead base series material, Ca_1-xLn_2x/3TiO₃It is contour ��_rMicrowave dielectric ceramic, wherein the BaO Nd of BLT system₂O₃��TiO₂Material dielectric constant reaches 90, lead base series (Pb, Ca) ZrO₃Dielectric constant reaches 105.

The sintering temperature of the above material system is generally greater than 1300 �� of C, it is impossible to directly and the low-melting-point metal such as Ag and Cu burn formation multilayer ceramic capacitor altogether. In recent years, along with LTCC Technology (LowTemperatureCo-firedCeramics, the requirement of development LTCC) and the development of microwave multilayer device, some low grade fever's system materials have been carried out exploring widely and research by research worker both domestic and external, mainly adopt devitrified glass or glassceramic composites system, have of a relatively high dielectric loss mutually because of low-melting glass, the existence of glassy phase substantially increases the dielectric loss of material. Therefore the emphasis that the low fired microwave dielectric ceramic material without glassy phase is current research is developed.

Can in the process of low fired microwave dielectric ceramic materials with development of new exploring, the material systems such as Li based compound, Bi based compound, tungstates architecture compound and tellurate architecture compound that intrinsic sintering temperature is low get the attention and research, but due to three performance indications (�� of microwave dielectric ceramic_rWith Q f and ��_?) between be that the relation of mutually restriction is (see document: the restricting relation between microwave dielectric ceramic materials dielectric properties, Zhu Jianhua, Liang Fei, Wang little Hong, Lv Wenzhong, electronic component and material, phase March the 3rd in 2005), meet three performance requirements and the single-phase microwave-medium ceramics of low temperature sintering be considerably less, mainly their temperature coefficient of resonance frequency generally excessive or quality factor are on the low side and cannot application request. Research major part to microwave-medium ceramics is the summary of experience drawn by great many of experiments at present, but there is no complete theory to set forth the relation of microstructure and dielectric properties, therefore, in theory also its microwave dielectric property such as temperature coefficient of resonance frequency and quality factor be cannot predict from the composition of compound and structure, low temperature co-fired technology and the development of microwave multilayer device which greatly limits. Explore and low-temperature sintering can have near-zero resonance frequency temperature coefficient (-10ppm/ DEG C�ܦ� with exploitation simultaneously_?��+10ppm/ DEG C) it is that those skilled in the art thirst for solving always but are difficult to the difficult problem succeeded all the time with the microwave dielectric ceramic of higher figure of merit.

Summary of the invention

It is an object of the invention to provide a kind of have good heat stability and low-loss, simultaneously low temperature sintering ultralow dielectric microwave dielectric ceramic material and preparation method thereof.

The chemical composition of the microwave dielectric ceramic material of the present invention is Bi₂TiGe₃O₁₁��

The preparation method step of this microwave dielectric ceramic material is:

(1) by analytical pure chemical raw material Bi₂O₃��TiO₂And GeO₂Powder press Bi₂TiGe₃O₁₁Composition weigh dispensing.

(2) by step (1) raw material wet ball-milling mix 12 hours, ball-milling medium is distilled water, after drying in 700 DEG C of air atmosphere pre-burning 6 hours.

(3) after adding binding agent pelletize in the powder that step (2) prepares, more compressing, finally sinter 4 hours in 750 ~ 800 DEG C of air atmosphere; Described binding agent adopts mass concentration to be the poly-vinyl alcohol solution of 5%, and polyvinyl alcohol addition accounts for the 3% of powder gross mass.

Advantages of the present invention: Bi₂TiGe₃O₁₁Ceramic sintering temperature is low, and cost of material is low; Its quality factor q f value is up to 84000-141000GHz, and dielectric constant reaches 16.7��17.8, the temperature coefficient �� of its resonant frequency_?Little, temperature stability is good; Can be widely used for the manufacture of the microwave devices such as various medium substrate, resonator and wave filter, the technology needs of low temperature co-fired technology and microwave multilayer device can be met.

Detailed description of the invention

Embodiment:

Table 1 illustrates 3 specific embodiments and the microwave dielectric property thereof of the different sintering temperatures constituting the present invention. Its preparation method as it has been described above, carry out the evaluation of microwave dielectric property by cylindrical dielectric resonator method.

This pottery can be widely used for the manufacture of the microwave devices such as various medium substrate, resonator and wave filter, can meet the technology needs of the system such as mobile communication and satellite communication.

Table 1:

Claims (1)

1. a low temperature sintering temperature-stable high quality factor microwave dielectric ceramic, it is characterised in that the chemical composition of described microwave dielectric ceramic is: Bi₂TiGe₃O₁₁;

The preparation method of described microwave dielectric ceramic concretely comprises the following steps:

(1) by analytical pure chemical raw material Bi₂O₃��TiO₂And GeO₂Powder press Bi₂TiGe₃O₁₁Composition weigh dispensing;

(2) by step (1) raw material wet ball-milling mix 12 hours, ball-milling medium is distilled water, after drying in 700 DEG C of air atmosphere pre-burning 6 hours;

(3) after adding binding agent pelletize in the powder that step (2) prepares, more compressing, finally sinter 4 hours in 750 ~ 800 DEG C of air atmosphere; Described binding agent adopts mass concentration to be the poly-vinyl alcohol solution of 5%, and polyvinyl alcohol addition accounts for the 3% of powder gross mass.