CN103553612B - Low-temperature sinterable microwave dielectric ceramic Ba6W2V2O17 and its preparation method - Google Patents

Abstract

The invention discloses a low-temperature sinterable microwave dielectric ceramic Ba ₆ W ₂ V ₂ O ₁₇ and a preparation method thereof. The composition of the low-temperature sinterable microwave dielectric ceramic is Ba ₆ W ₂ V ₂ O ₁₇ . (1) The raw powders of BaCO ₃ , WO ₃ and V ₂ O ₅ with a purity of more than 99.9% are weighed and compounded according to the chemical formula Ba ₆ W ₂ V ₂ O ₁₇ . (2) The raw materials in step (1) were mixed and wet-type ball milled for 12 hours, the solvent was distilled water, dried and pre-fired in an atmosphere at 830°C for 6 hours. (3) Add a binder to the powder prepared in step (2) and granulate it, then press it into shape, and finally sinter it in the air atmosphere at 890-920°C for 4 hours; the binder is used at a mass concentration of 5 % polyvinyl alcohol solution, the dosage accounts for 3% of the total mass of the powder. The ceramic prepared by the present invention is well sintered at 890-920°C, its dielectric constant reaches 25-26, its quality factor Qf value is as high as 88000-94000 GHz, and its resonant frequency temperature coefficient is small. Great application value.

Description

Low-temperature sinterable microwave dielectric ceramic Ba6W2V2O17 and its preparation method

technical field

The invention relates to a dielectric ceramic material, in particular to a microwave dielectric ceramic material for microwave components used at microwave frequencies, such as a dielectric substrate, a resonator, and a filter, and a preparation method thereof.

Background technique

Microwave dielectric ceramics refer to ceramics that are used as dielectric materials in circuits in the microwave frequency band (mainly UHF and SHF bands) and perform one or more functions. They are widely used as resonators, filters, and dielectric substrates in modern communications. Components such as chips and dielectric waveguide circuits are the key basic materials of modern communication technology. They have been used in portable mobile phones, car phones, cordless phones, TV satellite receivers and military radars. They are used in modern communication tools. It is playing an increasingly important role in the process of miniaturization and integration.

Dielectric ceramics used in the microwave frequency band should meet the following requirements for dielectric properties: (1) Serialized dielectric constant ε _r to meet the requirements of different frequencies and different applications; (2) High quality factor Q value or dielectric Loss tanδ to reduce noise, generally requires Qf ≥ 3000 _GHz ; (3) The temperature coefficient τ of the resonant frequency _? ℃. Internationally, since the late 1930s, there have been attempts to apply dielectric materials to microwave technology.

According to the relative permittivity ε _r and the frequency band used, the microwave dielectric ceramics that have been developed and are being developed can usually be divided into 4 categories.

(1) Ultra-low dielectric constant microwave dielectric ceramics, mainly represented by Al ₂ O ₃ -TiO ₂ , Y ₂ BaCuO ₅ , MgAl ₂ O ₄ and Mg ₂ SiO ₄ , etc., whose ε _r ≤ 20, quality factor Q× f≥50000GHz, τ _≤ 10 ppm/°C. Mainly used for microwave substrates and high-end microwave components.

(2) Microwave dielectric ceramics with low ε _r and high Q value, mainly BaO-MgO-Ta ₂ O ₅ , BaO-ZnO-Ta ₂ O ₅ or BaO-MgO-Nb ₂ O ₅ , BaO-ZnO-Nb ₂ O ₅ system or composite system MWDC materials between them. Its ε _r =25～30, Q=(1～2)×10 ⁴ (at f≥10 GHz), τ _? ≈0. It is mainly used as a dielectric resonator device in microwave communication devices such as satellite broadcasting with f≥8 GHz.

(3) Microwave dielectric ceramics with medium ε _r and Q value, mainly MWDC materials based on BaTi ₄ O ₉ , Ba ₂ Ti ₉ O ₂₀ and (Zr, Sn) TiO ₄ , whose ε _r = 35~ 40, Q=(6~9)×10 ³ (at f=3~-4GHz), τ _≤ 5 ppm/°C. It is mainly used as a dielectric resonant device in microwave military radar and communication systems in the frequency range of 4-8 GHz.

(4) Microwave dielectric ceramics with high ε _r and low Q value are mainly used in civil mobile communication systems in the frequency range of 0.8-4GHz, which is also the focus of research on microwave dielectric ceramics. Since the 1980s, Kolar, Kato and others have successively discovered and studied perovskite-like tungsten bronze BaO—Ln ₂ O ₃ —TiO ₂ series (Ln=La, Sm, Nd or Pr, etc., referred to as BLT series), composite calcium Titanite structure CaO—Li ₂ O—Ln ₂ O ₃ —TiO ₂ series, lead-based series materials, Ca _1-x Ln _2x/3 TiO ₃ series and other high ε _r microwave dielectric ceramics, among which BaO—Nd of BLT system The dielectric constant of ₂ O ₃ —TiO ₂ materials reaches 90, and the dielectric constant of lead-based series (Pb,Ca)ZrO ₃ reaches 105.

The sintering temperature of the above material systems is generally higher than 1300°C, and cannot be directly co-fired with low melting point metals such as Ag and Cu to form multilayer ceramic capacitors. In recent years, with the development of low temperature co-fired ceramics (Low Temperature Co-fired Ceramics, LTCC) and the requirements of the development of microwave multilayer devices, researchers at home and abroad have carried out extensive exploration and research on some low-temperature co-fired materials, mainly It adopts glass-ceramic or glass-ceramic composite material system, because the low melting point glass phase has a relatively high dielectric loss, the existence of the glass phase greatly improves the dielectric loss of the material. Therefore, the development of low-temperature sinterable microwave dielectric ceramics without glass phase is the focus of current research. We studied the sintering characteristics and microwave dielectric properties of ceramics with compositions of Ba ₆ W ₂ V ₂ O ₁₇ , Ba ₆ W ₂ Nb ₂ O ₁₇ , Sr ₆ W ₂ Nb ₂ O ₁₇ and Sr ₆ W ₂ V ₂ O ₁₇ , it was found that the sintering temperature of the above ceramics is lower than 950 ° C, but only Ba ₆ W ₂ V ₂ O ₁₇ has excellent comprehensive microwave dielectric properties, and can be widely used in the manufacture of microwave devices such as various resonators and filters. It meets the needs of low-temperature co-firing technology and microwave multilayer devices.

Contents of the invention

The object of the present invention is to provide a microwave dielectric ceramic with low loss, good thermal stability, low sintering temperature, and co-fired with Ag at low temperature and its preparation method.

The chemical composition of the low-temperature sinterable microwave dielectric ceramics involved in the present invention is: Ba ₆ W ₂ V ₂ O ₁₇ .

The specific steps of the preparation method of the low-temperature sinterable microwave dielectric ceramic are:

(1) The raw powders of BaCO ₃ , WO ₃ and V ₂ O ₅ with a purity of more than 99.9% are weighed and compounded according to the chemical formula Ba ₆ W ₂ V ₂ O ₁₇ .

(2) The raw materials in step (1) were mixed and wet-type ball milled for 12 hours, the solvent was distilled water, dried and pre-fired in an atmosphere at 830°C for 6 hours.

(3) Add a binder to the powder prepared in step (2) and granulate it, then press it into shape, and finally sinter it in the air atmosphere at 890-920°C for 4 hours; the binder is used at a mass concentration of 5 % polyvinyl alcohol solution, the dosage accounts for 3% of the total mass of the powder.

The ceramic prepared by the present invention is well sintered at 890-920°C, its dielectric constant reaches 25-26, its quality factor Qf value is as high as 88000-94000 GHz, and its resonant frequency temperature coefficient is small. Great application value.

Detailed ways

Example:

Table 1 shows four specific examples of different sintering temperatures constituting the present invention and their microwave dielectric properties. The preparation method is as above, and the microwave dielectric performance is evaluated by the cylindrical dielectric resonator method. Ba ₆ W ₂ V ₂ O ₁₇ powder was mixed with Ag powder accounting for 20% of the powder mass, pressed and molded, and then sintered at 920°C for 4 hours; X-ray diffraction phase analysis and scanning electron microscope observation showed that Ba ₆ W ₂ V ₂ O ₁₇ has no chemical reaction with Ag, that is, Ba ₆ W ₂ V ₂ O ₁₇ can be co-fired with Ag electrode at low temperature.

The present invention is by no means limited to the above examples. The upper and lower limits and range values of the sintering temperature can all realize the present invention, and the examples are not listed one by one here.

The ceramics can be widely used in the manufacture of microwave devices such as various dielectric substrates, resonators and filters, and can meet the technical needs of mobile communication, satellite communication and other systems.

Table 1:

Claims (1)

1. The application of a composite oxide as a low-temperature sinterable microwave dielectric ceramic, characterized in that the chemical composition formula of the composite oxide is: Ba ₆ W ₂ V ₂ O ₁₇ ; The specific steps of the preparation method of the composite oxide are: (1) Weigh the raw powders of BaCO ₃ , WO ₃ and V ₂ O ₅ with a purity of more than 99.9% according to the chemical formula Ba ₆ W ₂ V ₂ O ₁₇ ; (2) Mix the raw materials of step (1) with wet ball milling for 12 hours, the solvent is distilled water, and after drying, pre-fire in the atmosphere at 830°C for 6 hours; (3) Add a binder to the powder prepared in step (2) and granulate it, then press it into shape, and finally sinter it in the air atmosphere at 890-920°C for 4 hours; the binder is used at a mass concentration of 5 % polyvinyl alcohol solution, the dosage accounts for 3% of the total mass of the powder.