CN103467091A

CN103467091A - Low-sintering microwave dielectric ceramic Ba4Nb2V2O14 and preparation method of microwave dielectric ceramic

Info

Publication number: CN103467091A
Application number: CN2013103781291A
Authority: CN
Inventors: 苏聪学; 方亮; 苏和平
Original assignee: Guilin University of Technology
Current assignee: YANCHENG LIYAN NEW MATERIAL Co.,Ltd.
Priority date: 2013-08-27
Filing date: 2013-08-27
Publication date: 2013-12-25
Anticipated expiration: 2033-08-27
Also published as: CN103467091B

Abstract

The invention discloses low-sintering microwave dielectric ceramic Ba4Nb2V2O14 and a preparation method of the microwave dielectric ceramic. The low-sintering vanadate microwave dielectric ceramic is made of Ba4Nb2V2O14. The preparation method comprises the steps of (1) weighing and batching original powder of BaCO3, Nb2O5 and V2O5 according to a chemical formula of Ba4Nb2V2O14, (2) performing wet ball milling and mixture for 12h by taking distilled water as a solvent, drying and presintering for 6h in an atmosphere at 750 DEG C, and (3) adding an adhesive agent into powder prepared in Step (2), pelleting, then performing compression molding, and finally sintering for 4h in the atmosphere at 870-900 DEG C, wherein the purities of BaCO3, Nb2O5 and V2O5 are above 99.9%; the adhesive agent is a polyvinyl alcohol solution at a mass concentration of 5%; and the amount of the adhesive agent accounts for 3% of the total mass of the powder. The prepared ceramic is sintered well at 870-900 DEG C, a dielectric constant of the ceramic reaches 13-14, a quality factor (Qf) of the ceramic is up to 84000-97000 GHz, a temperature coefficient of resonance frequency of the ceramic is small, and the ceramic can be sintered together with an Ag electrode at the low temperature, and has a very high application value industrially.

Description

Low temperature sintering microwave dielectric ceramic Ba 4nb 2v 2o 14and preparation method thereof

Technical field

The present invention relates to dielectric ceramic material, particularly relate to microwave dielectric ceramic material of the microwave devices such as medium substrate, resonator and wave filter that use in microwave frequency and preparation method thereof.

Background technology

Microwave dielectric ceramic refers to and is applied in microwave frequency band (being mainly UHF, SHF frequency range) circuit as dielectric material and completes the pottery of one or more functions, be widely used as the components and parts such as resonator, wave filter, dielectric substrate and medium guided wave loop in modern communication, it is the key foundation material of modern communication technology, at aspects such as portable mobile phone, automobile telephone, cordless telephone, telestar susceptor and military radars, very important application is arranged, in the miniaturization of modern communication instrument, integrated process, just bringing into play increasing effect.

Be applied to the dielectric ceramic of microwave frequency band, should meet the requirement of following dielectric characteristics: (1) seriation DIELECTRIC CONSTANT ε _rto adapt to the requirement of different frequency and different application occasion; (2) high quality factor q value or dielectric loss tan δ are to reduce noise, general requirement Qf>=3000 GHz; (3) the temperature factor τ of resonant frequency _?the as far as possible little thermostability to guarantee that device has had, general requirement-10/ ℃≤τ _?≤+10 ppm/ ℃.From late 1930s, just someone attempts dielectric substance is applied to microwave technology in the world.

According to relative permittivity ε _rsize from use the different of frequency range, usually the microwave-medium ceramics be developed He developing can be divided into to 4 classes.

(1) ultralow dielectric microwave dielectric ceramic, main representative is Al ₂o ₃-TiO ₂, Y ₂baCuO ₅, MgAl ₂o ₄and Mg ₂siO ₄deng, its ε _r≤ 20, quality factor q * f>=50000GHz, τ _?≤ 10 ppm/ ° C.Be mainly used in microwave base plate and high-end microwave device.

(2) low ε _rwith the microwave dielectric ceramic of high Q value, be mainly BaO-MgO-Ta ₂o ₅, BaO-ZnO-Ta ₂o ₅or BaO-MgO-Nb ₂o ₅, BaO-ZnO-Nb ₂o ₅system or the composite system MWDC material between them.Its ε _r=25～30, Q=(1～2) * 10 ⁴(under f>=10 GHz), τ _?≈ 0.Be mainly used in the microwave communication equipments such as direct broadcasting satellite of f >=8 GHz as the dielectric resonance device.

(3) medium ε _rwith the microwave dielectric ceramic of Q value, be mainly with BaTi ₄o ₉, Ba ₂ti ₉o ₂₀(Zr, Sn) TiO ₄deng the MWDC material that is base, its ε _r=35 ~ 40, Q=(6～9) * 10 ³(f=3～-4GHz under), τ _?≤ 5 ppm/ ° C.Be mainly used in the interior microwave military radar of 4～8 GHz range of frequency and communication system as the dielectric resonance device.

(4) high ε _rand the lower microwave dielectric ceramic of Q value is mainly used in civilian mobile communcations system in 0.8～4GHz range of frequency, this is also the emphasis of microwave dielectric ceramic research.Since the eighties, the people such as Kolar, Kato find and have studied perovskite-like tungsten bronze type BaO-Ln in succession ₂o ₃-TiO ₂series (Ln=La, Sm, Nd or Pr etc. are called for short BLT system), complex perovskite structure CaO-Li ₂o-Ln ₂o ₃-TiO ₂series, lead base series material, Ca _1-xln _2x/3tiO ₃be contour ε _rmicrowave dielectric ceramic, the wherein BaO-Nd of BLT system ₂o ₃-TiO ₂material dielectric constant reaches 90, lead base series (Pb, Ca) ZrO ₃specific inductivity reaches 105.

The sintering temperature of above these material systems is generally higher than 1300 ° of C, can not be directly and the low melting point metals such as Ag and Cu burn altogether the formation laminated ceramic capacitor.In recent years, along with LTCC Technology (Low Temperature Co-fired Ceramics, the requirement of development LTCC) and the development of microwave multilayer device, researchist both domestic and external has carried out exploring widely and studying to some low fever's system materials, mainly to adopt devitrified glass or glass-ceramic composite system, because low melting glass has relatively high dielectric loss mutually, the existence of glassy phase has improved the dielectric loss of material greatly.Therefore development is the emphasis of current research without the low fired microwave dielectric ceramic material of glassy phase.

In exploration and development of new can be hanged down the process of fired microwave dielectric ceramic materials, the material systems such as the Li based compound that intrinsic sintering temperature is low, Bi based compound, tungstate architecture compound and tellurate architecture compound get the attention and study, due to easy and Ag electrode generation surface reaction and raw material TeO containing compounds such as Bi, Te and Mo ₂poisonously make the application of these Bi, Te and Mo sill be restricted, but therefore low fever's high performance microwave media ceramic system is still very limited, this has limited the development of low temperature co-fired technology and microwave multilayer device to a great extent.

Summary of the invention

The purpose of this invention is to provide a kind of have low-loss and good thermostability, microwave dielectric ceramic material that sintering temperature is low simultaneously and preparation method thereof.

The chemical constitution of the low temperature sintering microwave dielectric ceramic material the present invention relates to is: Ba ₄nb ₂v ₂o ₁₄.

Preparation method's concrete steps of described low temperature sintering microwave dielectric ceramic are:

(1) by purity, be the BaCO more than 99.9% ₃, Nb ₂o ₅and V ₂o ₅starting powder press Ba ₄nb ₂v ₂o ₁₄the chemical formula weigh batching.

(2) step (1) raw material wet ball-milling is mixed 12 hours, solvent is distilled water, pre-burning 6 hours in 750 ℃ of air atmosphere after oven dry.

(3) after adding binding agent granulation in the powder made in step (2), then compression moulding, last sintering 4 hours in 870 ~ 900 ℃ of air atmosphere; Described binding agent adopts the polyvinyl alcohol solution that mass concentration is 5%, and dosage accounts for 3% of powder total mass.

Pottery prepared by the present invention is good at 870-900 ℃ of sintering, its specific inductivity reaches 13～14, and quality factor q f value is up to 84000-97000GHz, and temperature coefficient of resonance frequency is little, and can be low temperature co-fired with the Ag electrode, therefore industrial great using value arranged.

Embodiment

Embodiment:

Table 1 shows 3 specific embodiments and the microwave dielectric property thereof that forms different sintering temperatures of the present invention.Its preparation method as mentioned above, carries out the evaluation of microwave dielectric property by the cylindrical dielectric resonator method; By powder with the Ag powder that accounts for powder quality 20%, mix, after compression moulding, at 900 ℃ of sintering; X ray diffraction material phase analysis and scanning electron microscopic observation all show Ba ₄nb ₂v ₂o ₁₄with Ag, chemical reaction, i.e. Ba do not occur ₄nb ₂v ₂o ₁₄can be low temperature co-fired with the Ag electrode.

The present invention never is limited to above embodiment.The bound of sintering temperature, interval value can realize the present invention, at this, do not enumerate embodiment.

This pottery can be widely used in the manufacture of the microwave devices such as various medium substrates, resonator and wave filter, can meet the Technology Need of the systems such as mobile communication, satellite communications.

Table 1:

Claims

1. but a vanadate, as the application of low-temperature sintered microwave dielectric ceramic, is characterized in that the chemical constitution formula of described vanadate is: Ba ₄nb ₂v ₂o ₁₄;

Preparation method's concrete steps of described vanadate are:

(1) by purity, be the BaCO more than 99.9% ₃, Nb ₂o ₂and V ₂o ₅starting powder press Ba ₄nb ₂v ₂o ₁₄the chemical formula weigh batching;

(2) step (1) raw material wet ball-milling is mixed 12 hours, solvent is distilled water, pre-burning 6 hours in 750 ℃ of air atmosphere after oven dry;