CN104387057B

CN104387057B - A kind of temperature-stable titanio spinelle microwave-medium ceramics and low temperature preparation method thereof

Info

Publication number: CN104387057B
Application number: CN201410634291.XA
Authority: CN
Inventors: 周焕福; 龚健章; 郝澍钊; 陈秀丽
Original assignee: Guilin University of Technology
Current assignee: Guilin University of Technology
Priority date: 2014-11-12
Filing date: 2014-11-12
Publication date: 2016-08-17
Anticipated expiration: 2034-11-12
Also published as: CN104387057A

Abstract

The invention discloses a kind of temperature-stable titanio spinelle microwave-medium ceramics and low temperature preparation method thereof.The chemical constitution formula of this microwave dielectric ceramic materials is: (100y)wt% Li_(1+x/3)Zn_(0.5‑0.5x)Ti_(1.5+x/6)O₄ + ywt%B₂O₃, wherein 0.2≤x≤0.8;0.05≤y≤2；Li with purity >=99%₂CO₃、ZnO、TiO₂And B₂O₃For primary raw material, press Li the most respectively_(1+x/3)Zn_(0.5‑0.5x)Ti_(1.5+x/6)O₄Dispensing, closes main powder body in 900 DEG C of calcining 8h after ball milling mixing, then adds B in main powder body₂O₃Reduce its sintering temperature, thus obtain dielectric constant moderate,Q×fHeight, the LTCC microwave dielectric material of temperature coefficient of resonance frequency nearly zero.Microwave-medium ceramics prepared by the present invention, its sintering temperature is in 850 ~ 950 DEG C, dielectric constant moderate (25.2 ~ 32.5),Q×fValue is high (10500 ~ 24900GHz), temperature coefficient of resonance frequency (τ_f) little；Can be used for the manufacture of the microwave devices such as resonator, antenna, wave filter.

Description

A kind of temperature-stable titanio spinelle microwave-medium ceramics and low temperature preparation method thereof

Technical field

The invention belongs to electronic ceramics and manufacture field thereof, relate to medium substrate, the dielectric ceramic material of microwave device such as antenna resonator of using in microwave frequency and preparation method thereof.

Background technology

Microwave-medium ceramics refers to be applied in microwave frequency band circuit as medium the material that completes one or more functions, mainly for the preparation of microwave devices such as resonator, wave filter, diectric antennas.In recent years, along with microwave mobile communication technology constantly develops to high frequency and digitized direction, the requirement to component module is more and more urgent.LTCC Technology (LTCC, Low Temperature Co-fired Ceramics) with electricity, machinery, calorifics and the operational characteristic of its excellence, one of major technique having become as electronic-component module.The sintering temperature of LTCC system is low, the low metal of available resistivity is as the conductor material of multilayer wiring, packing density, signaling rate can be improved, and bury the various laminar microwave electronic devices of multilager base plate once-firing in can, be therefore widely used in high-speed and high-density and interconnect among polynary ceramic component (MCM).LTCC altogether burning technology has that packing density is high, dielectric loss is low, can be used for high microwave frequency band, reliability is high and the thermally matched feature such as good of IC, therefore has extremely wide application prospect.

The key technology of LTCC require microwave dielectric material must excellent performance, there is low sintering temperature (≤900 DEG C) and compatibility can be burnt altogether with Ag electrode.Although current most microwave dielectric ceramic have excellence performance, but its sintering temperature the highest (>=1300 DEG C), such as (Zr, Sn) TiO₄、Ba(Zn_1/3Ta_2/3)O₃、Ba(Mg_1/3Ta_2/3)O₃Deng, therefore cannot be applied on LTCC device.Therefore increasing research be placed on and explored that sintering temperature is low, excellent performance and can realize burning on compatible material system altogether with Ag electrode.LiZn_0.5Ti_1.5O₄Spinel compound have excellence microwave dielectric property:ε _r=26.5,Q × f=62000 GHz, τ_f=-15ppm/ DEG C, but big τ_fValue and higher sintering temperature limit its application in terms of LTCC device.By adulterating, the second phase can effectively regulate its τ_fValue, the sintering aid adding low melting point on this basis can reduce its sintering temperature, but the phase structure of complexity is still unfavorable for application.

Summary of the invention

The present invention has the Li of same picket spinel structure by introducing_4/3Ti_5/3O₄With LiZn_0.5Ti_1.5O₄Form solid solution to regulate the τ of material_fValue, adds a small amount of B on this basis₂O₃Sintering aid, thus obtain the temperature-stable LTCC microwave dielectric ceramic materials of a kind of low cost, excellent performance.

The chemical constitution formula of the microwave dielectric ceramic materials that the present invention relates to is: (100-y)wt% Li_(1+x/3)Zn_(0.5-0.5x)Ti_(1.5+x/6)O₄ +ywt%B₂O₃, wherein 0.2≤x≤0.8; 0.05≤y≤ 2, xFor mol ratio,yFor mass ratio.

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

(1) by the Li of purity >=99%₂CO₃, ZnO and TiO₂As primary raw material, press Li the most respectively_(1+x/3)Zn_(0.5-0.5x)Ti_(1.5+x/6)O₄, wherein 0.2≤x≤ 0.8 weighs, then batch mixing；In powder body, dehydrated alcohol is added with powder quality than the ratio for 1:1 according to dehydrated alcohol, wet grinding is used to mix 4 hours, dry at 120～140 DEG C after levigate, sieve with the screen cloth of 80 mesh, bulk it is pressed into after sieving, then with the heating rate of 5 DEG C/min, the block stock of compacting is risen to 900 DEG C respectively by room temperature, and insulation 8 hours at this temperature, make main powder body；

(2) step (1) is made powder body by (100-y)wt% Li_(1+x/3)Zn_(0.5-0.5x)Ti_(1.5+x/6)O₄ +ywt%B₂O₃Proportioning by pulverize burning block and B₂O₃It is mixed into powder, wherein 0.2≤x≤0.8; 0.05≤y≤2；In powder, dehydrated alcohol is added with powder quality than the ratio for 1:1 according to dehydrated alcohol, put into ball milling in nylon tank to take out after 4 hours, put into baker to dry at 120～140 DEG C, being pressed into a diameter of 12mm thickness after pelletize is the small column of 6mm, in 500～600 DEG C of binder removals 4 hours, obtain porcelain after furnace cooling, then porcelain is sintered 4 hours at 850 ~ 950 DEG C i.e. obtain titanio temperature-stable LTCC microwave dielectric ceramic materials.

Microwave-medium ceramics prepared by the present invention, its sintering temperature low (~ 900 DEG C), microwave property is excellent: dielectric constant (ε_r) moderate,Q × fValue height and τ_fNearly zero；Can be used for the manufacture of the LTCC microwave devices such as resonator, microwave antenna, wave filter.

Detailed description of the invention

Embodiment :

Table 1 lists 20 specific embodiments and the microwave dielectric property thereof of the heterogeneity 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 electron components and parts such as various medium substrate, antenna and wave filter, meets the technology needs of Modern Mobile Communications Systems.

Table 1:

Claims

1. a temperature-stable titanio spinelle microwave dielectric ceramic materials, it is characterised in that the chemical constitution formula of this microwave dielectric ceramic materials is: (100-y)wt% Li_(1+x/3)Zn_(0.5-0.5x)Ti_(1.5+x/6)O₄ +ywt%B₂O₃, wherein 0.2≤x≤0.8; 0.05≤y≤ 2,xFor mol ratio,yFor mass ratio；

The synthesis step of described microwave dielectric ceramic materials is:

(1) by the Li of purity >=99%₂CO₃, ZnO and TiO₂As primary raw material, first press Li_(1+x/3)Zn_(0.5-0.5x)Ti_(1.5+x/6)O₄, wherein 0.2≤x≤ 0.8 weighs, then batch mixing；In powder body, dehydrated alcohol is added with powder quality than the ratio for 1:1 according to dehydrated alcohol, wet grinding is used to mix 4 hours, dry at 120～140 DEG C after levigate, sieve with the screen cloth of 80 mesh, bulk it is pressed into after sieving, then with the heating rate of 5 DEG C/min, the block stock of compacting is risen to 900 DEG C by room temperature, and insulation 8 hours at this temperature, make main powder body；

(2) step (1) is made main powder body by (100-y)wt% Li_(1+x/3)Zn_(0.5-0.5x)Ti_(1.5+x/6)O₄ +ywt%B₂O₃Proportioning by main powder body and B₂O₃It is mixed into powder, wherein 0.2≤x≤0.8; 0.05≤y≤2；In powder, dehydrated alcohol is added with powder quality than the ratio for 1:1 according to dehydrated alcohol, put into ball milling in nylon tank to take out after 4 hours, put into baker to dry at 120～140 DEG C, being pressed into a diameter of 12mm thickness after pelletize is the small column of 6mm, in 500～600 DEG C of binder removals 4 hours, obtain porcelain after furnace cooling, then porcelain is sintered 4 hours at 850 ~ 950 DEG C i.e. obtain titanio temperature-stable LTCC microwave dielectric ceramic materials.