CN104446436B - A kind of low temperature sintering temperature-stable dielectric constant microwave dielectric ceramic - Google Patents

Abstract

The invention discloses a kind of low temperature sintering temperature-stable dielectric constant microwave dielectric ceramic Bi ₅ti ₂wO ₁₄cl and preparation method thereof.(1) be 99.9%(percentage by weight by purity) more than Bi ₂o ₃, TiO ₂, WO ₃bi is pressed with the starting powder of BiOCl ₅ti ₂wO ₁₄the composition weigh batching of Cl; (2) step (1) raw material wet ball-milling is mixed 12 hours, ball-milling medium is absolute ethyl alcohol, pre-burning 6 hours in 700 DEG C of air atmosphere after oven dry; (3) in the powder that step (2) is obtained, binding agent is added and after granulation, more compressing, finally in 750 ~ 800 DEG C of air atmosphere, sinter 4 hours; Described binding agent adopts mass concentration to be the poly-vinyl alcohol solution of 5%, and the addition of polyvinyl alcohol accounts for 3% of powder gross mass.Ceramic post sintering prepared by the present invention is good, and dielectric constant reaches 28.6 ~ 29.7, and its quality factor q f value is up to 62200-69100GHz, and temperature coefficient of resonance frequency is little, industrially has great using value.

Description

A kind of low temperature sintering temperature-stable dielectric constant microwave dielectric ceramic

Technical field

The present invention relates to dielectric ceramic material, particularly relate to dielectric ceramic material of the microwave devices such as ceramic substrate, resonator and the filter used for the manufacture of microwave frequency and preparation method thereof.

Background technology

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

Be applied to the dielectric ceramic of microwave frequency band, the requirement of following dielectric property should be met: (1) seriation DIELECTRIC CONSTANT ε _rto adapt to the requirement of different frequency and different application occasion; (2) high quality factor q value or low dielectric loss tan δ to reduce noise, General Requirements Qf>=3000GHz; (3) the temperature coefficient τ of resonance frequency _?little of as far as possible to ensure the thermal stability that device has had, General Requirements-10ppm/ DEG C≤τ _?≤+10ppm/ DEG C.From late 1930s, just someone attempts dielectric substance to be applied to microwave technology in the world, and prepares TiO ₂microwave dielectric filter, but its temperature coefficient of resonance frequency τ _?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 ε _rsize from use frequency range different, usually the microwave-medium ceramics be developed and developing can be divided into 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 _?≤ 10ppm/ ° of C.Be mainly used in microwave base plate and high-end microwave device.

(2) low ε _rwith the microwave dielectric ceramic of high q-factor, mainly BaO-MgO-Ta ₂o ₅, BaO-ZnO-Ta ₂o ₅or BaO-MgO-Nb ₂o ₅, BaO-ZnO-Nb ₂o ₅system or the hybrid system MWDC material between them.Its ε _r=20 ~ 35, Q=(1 ~ 2) × 10 ⁴(under f>=10GHz), τ _?≈ 0.Be mainly used in the microwave communication equipments such as the direct broadcasting satellite of f >=8GHz as dielectric resonance device.

(3) medium ε _rwith the microwave dielectric ceramic of Q value, mainly with BaTi ₄o ₉, Ba ₂ti ₉o ₂₀(Zr, Sn) TiO ₄deng the MWDC material for base, its ε _r=35 ~ 45, Q=(6 ~ 9) × 10 ³(under f=3 ~-4GHz), τ _?≤ 5ppm/ ° of C.Be mainly used in microwave military radar in 4 ~ 8GHz frequency range and communication system as dielectric resonance device.

(4) high ε _rand the microwave dielectric ceramic that Q value is lower, be mainly used in civilian mobile communcations system in 0.8 ~ 4GHz frequency range, this is also the emphasis of microwave dielectric ceramic research.Since the eighties, the people such as Kolar, Kato in succession find and have studied perovskite-like tungsten bronze type BaO-Ln 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 ₃dielectric constant reaches 105.

Due to three performance index (ε of microwave dielectric ceramic _rwith Qf and τ _?) between be that the relation of mutually restriction is (see document: the restricting relation between microwave dielectric ceramic materials dielectric property, Zhu Jianhua, Liang Fei, Wang little Hong, Lv Wenzhong, electronic component and material, phase March the 3rd in 2005), meet the single-phase microwave-medium ceramics of three performance requirements considerably less, mainly their temperature coefficient of resonance frequency is usually excessive or quality factor are on the low side and cannot application request.Current is the summary of experience drawn by great many of experiments to the research major part of microwave-medium ceramics, but complete theory is not had to set forth the relation of microstructure and dielectric property, therefore, in theory also cannot predict its microwave dielectric property such as temperature coefficient of resonance frequency and quality factor from the composition of compound and structure, explore and exploitation near-zero resonance frequency temperature coefficient (-10ppm/ DEG C≤τ _?≤+10ppm/ DEG C) be that those skilled in the art thirst for solving always but are difficult to the difficult problem that succeeds all the time with the serial differing dielectric constant microwave dielectric ceramic of higher figure of merit, which greatly limits the development of microwave dielectric ceramic and device.We are to composition Bi ₅ti ₂wO ₁₄cl, Bi ₅ti ₂moO ₁₄cl, Bi ₅ti ₂wO ₁₄the series compound of F has carried out the research of microwave dielectric property, finds that their sintering temperature is lower than 900 DEG C, wherein only has Bi ₅ti ₂wO ₁₄cl has near-zero resonance frequency temperature coefficient and high quality factor.Bi ₅ti ₂moO ₁₄the temperature coefficient of resonance frequency τ of Cl pottery _?(being-33ppm/ DEG C) bigger than normal and cannot as practical microwave-medium ceramics; And Bi ₅ti ₂wO ₁₄f cannot as microwave-medium ceramics because dielectric loss is too large under microwave frequency band.

Summary of the invention

The object of this invention is to provide a kind of low temperature sintering, there is good thermal stability and low-loss dielectric constant microwave dielectric ceramic material and preparation method thereof.

The chemical composition of microwave dielectric ceramic material of the present invention is Bi ₅ti ₂wO ₁₄cl.

Preparation method's step of this microwave dielectric ceramic material is:

(1) be 99.9%(percentage by weight by purity) more than Bi ₂o ₃, TiO ₂, WO ₃bi is pressed with the starting powder of BiOCl ₅ti ₂wO ₁₄the composition weigh batching of Cl.

(2) step (1) raw material wet ball-milling is mixed 12 hours, ball-milling medium is absolute ethyl alcohol, pre-burning 6 hours in 700 DEG C of air atmosphere after oven dry.

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

Advantage of the present invention: Bi ₅ti ₂wO ₁₄cl ceramic dielectric constant reaches 28.6 ~ 29.7, the temperature coefficient τ of its resonance frequency _?little, temperature stability is good; Quality factor q f value, up to 62200-69100GHz, can be widely used in the manufacture of the microwave devices such as various dielectric resonator and filter, can meet the technology needs of low temperature co-fired technology and microwave multilayer device, industrially have great using value.

Embodiment

Embodiment:

Table 1 shows 3 specific embodiments and microwave dielectric property thereof that form different sintering temperature of the present invention.Its preparation method is described above, carries out the evaluation of microwave dielectric property by cylindrical dielectric resonator method.

This pottery can be widely used in the manufacture of the microwave devices such as various medium substrate, resonator and 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 dielectric constant microwave dielectric ceramic, is characterized in that the chemical composition of described microwave dielectric ceramic is: Bi ₅ti ₂wO ₁₄cl;

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

(1) be 99.9%(percentage by weight by purity) more than Bi ₂o ₃, TiO ₂, WO ₃bi is pressed with the starting powder of BiOCl ₅ti ₂wO ₁₄the composition weigh batching of Cl;

(2) step (1) raw material wet ball-milling is mixed 12 hours, ball-milling medium is absolute ethyl alcohol, pre-burning 6 hours in 700 DEG C of air atmosphere after oven dry;

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