CN101081736A - Niobium-based microwave dielectric ceramic with near-zero resonance frequency temperature coefficient and preparation method thereof - Google Patents

Niobium-based microwave dielectric ceramic with near-zero resonance frequency temperature coefficient and preparation method thereof Download PDF

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CN101081736A
CN101081736A CN 200610095306 CN200610095306A CN101081736A CN 101081736 A CN101081736 A CN 101081736A CN 200610095306 CN200610095306 CN 200610095306 CN 200610095306 A CN200610095306 A CN 200610095306A CN 101081736 A CN101081736 A CN 101081736A
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temperature coefficient
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CN100463878C (en
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田中青
伍光凤
张微
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Chongqing Institute of Technology
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Abstract

The present invention provides one kind of Nb-based microwave dielectric ceramic with temperature coefficient of resonance frequency approaching zero and in the chemical expression of (1-x)BaO.0.33(1-x)CoO.0.33(1-x)Nb2O5.xTiO2.xCaO.yMnO2, where x=0-0.1, and y=0-0.05. The Nb-based microwave dielectric ceramic consists of BaO in 100 molar portions, CoO in 33.33 molar portions, Nb2O5 in 33.33 molar portions, CaO in 0-11.11 molar portions, TiO2 in 0-11.11 molar portions, and MnO2 in 0-5 molar portions. It is prepared through wet milling and mixing the materials including Ba(Co1/3Nb2/3)O3,CaTiO3 and MnO2 based on the material compounding proportion, stoving, adding water solution of PVA, pressing at 150-300 MPa to form, and sintering at 1300-1400 deg.c inside a high temperature furnace. It has temperature coefficient of resonance frequency approaching zero, relatively low sintering temperature and relatively high quality factor.

Description

Niobium-based microwave dielectric ceramic of near-zero resonance frequency temperature coefficient and preparation method thereof
Technical field
The present invention relates to a kind of based on oxide compound be the ceramic compound of feature with the composition, or rather, be about a kind of be the ceramic compound of main component with niobium base complex perovskite compound.
Background technology
Microwave-medium ceramics is the core material of microwave device.Recently for over ten years, because microwave technology equipment to miniaturization and integrated, especially to the big output of the product for civilian use, the fast development of low price direction, makes the research of microwave-medium ceramics and practicability develop rapidly.Be applied to the media ceramic of microwave circuit, should satisfy the requirement of following dielectric characteristics: the relative permittivity ε that (1) is high rTo reduce device size, general requirement ε r〉=20; (2) high quality factor q is to reduce noise, general requirement Qf 〉=3000GHz; (3) near zero temperature coefficient of resonance frequency τ fTo guarantee the temperature stability of device, general requirement-5ppm/ ℃≤τ f≤ 5ppm/ ℃.
Ba (Co 1/3Nb 2/3) O 3Microwave-medium ceramics (ε r≈ 32, Qf=63000GHz, τ f=-13ppm/ ℃) the quality factor height, cost is low, is mainly used in the field that is used for microwave high-frequency section (more than the 8GHz).But its main drawback is: (1) temperature coefficient of resonance frequency absolute value is bigger than normal; (2) sintering temperature up to 1450 ℃ about.This has limited its use, generally need regulate its temperature coefficient of resonance frequency or reduce sintering temperature to reach service requirements by the material that mixes other components.As " European ceramic association proceedings " (Journal of the European Ceramic Society) at one piece of article in 2003 " low cost, high-performance Ba (Zn that microwave resonator is used 1/3Nb 2/3O 3) exploitation of sill " (Development of low cost, highperformance Ba (Zn 1/3Nb 2/3O 3) based materials for microwave resonator applications) middle report, adopt Ba (Zn with positive temperature coefficient 1/3Nb 2/3) O 3(τ f=30ppm/ ℃) and the Ba (Co of negative temperature coefficient 1/3Nb 2/3) O 3Formation solid solution compound pottery is as Ba (Zn 1/3Nb 2/3) O 3Incorporation when being 60mol%, just obtained τ fBe zero microwave dielectric ceramic materials (ε r=35.6, Qf=86000 GHz, τ f=0 ± 3ppm/ ℃).
Summary of the invention
The objective of the invention is to overcome existing Ba (Co 1/3Nb 2/3) O 3The shortcoming that the microwave-medium ceramics temperature coefficient of resonance frequency is bigger than normal and sintering temperature is high is by mixing CaTiO 3And MnO 2Material and the microwave-medium ceramics that obtains a kind of near-zero resonance frequency temperature coefficient, lower sintering temperature and have the higher quality factor; Ba (Co is provided simultaneously 1/3Nb 2/3) O 3The method of the compositing formula of base microwave dielectric ceramics and this media ceramic product of manufacturing.
The object of the present invention is achieved like this: the niobium-based microwave dielectric ceramic of near-zero resonance frequency temperature coefficient, it is characterized in that forming by Ba, Co, Nb, Ca, Ti and the Mn of oxide form, and its chemical formula is:
(1-x) BaO0.33 (1-x) CoO0.33 (1-x) Nb 2O 5XTiO 2XCaOyMnO 2, x=0-0.1 in the formula, y=0-0.05.
Described microwave-medium ceramics, its component mole deal ratio is: BaO 100:CoO 33.33:Nb 2O 533.33:CaO0-11.11:TiO 20-11.11:MnO 20-5.
Pottery of the present invention (1-x) BaO0.33 (1-x) CoO0.33 (1-x) Nb 2O 5XTiO 2XCaOyMnO 2(x=0-0.1 in the formula, preparation method y=0-0.05) comprises the steps:
1, with purity 99%BaCO 3, 99%CoO and 99.99%Nb 2O 5Be starting raw material, 1100-1200 ℃ of insulation 2-4 hour, synthetic Ba (Co 1/3Nb 2/3) O 3Powder;
2, with purity 99%CaCO 3And 99%TiO 2Be starting raw material, 1200-1300 ℃ of insulation 4-8 hour, synthetic CaTiO 3Powder;
3, then by (1-x) Ba (Co 1/3Nb 2/3) O 3-x CaTiO 3-yMnO 2(x=0-0.1, proportioning y=0-0.05) is with Ba (Co 1/3Nb 2/3) O 3, CaTiO 3And MnO 2The powder wet-milling mixes, it is the polyvinyl alcohol water solution of 5-10% that the oven dry back adds concentration, and add-on accounts for the 2-20% of powder gross weight, is 150-300Mpa compression moulding in pressure then, in temperature is 1300-1400 ℃ of high temperature kiln roasting, makes microwave-medium ceramics.
Described microwave-medium ceramics preparation method, its firing time is 4-24 hour.
The present invention has overcome Ba (Co 1/3Nb 2/3) O 3The shortcoming that the microwave-medium ceramics temperature coefficient of resonance frequency is bigger than normal and sintering temperature is high is by mixing CaTiO 3And MnO 2And the microwave-medium ceramics that has obtained a kind of near-zero resonance frequency temperature coefficient, lower sintering temperature and had the higher quality factor.
Embodiment
The present invention adopts solid state reaction manufactured (1-x) Ba (Co 1/3Nb 2/3) O 3-x CaTiO 3-yMnO 2The niobium-based microwave dielectric ceramic of near-zero resonance frequency temperature coefficient.
The present invention is with purity 99%BaCO 3, 99%CoO and 99.99%Nb 2O 5Be starting raw material, press Ba (Co 1/3Nb 2/3) O 3Chemistry than batching, in dehydrated alcohol, grind oven dry after 12 hours, at 2-4 hour synthetic Ba (Co of 1100-1200 ℃ of insulation 1/3Nb 2/3) O 3Powder; With purity 99%CaCO 3And 99%TiO 2Be starting raw material, press CaTiO 3Chemistry than batching, in dehydrated alcohol, grind oven dry after 24 hours, 4-8 hour synthetic CaTiO of 1200-1300 ℃ of insulation 3Powder.By (1-x) Ba (Co 1/3Nb 2/3) O 3-x CaTiO 3-yMnO 2(x=0-0.1, y=0-0.05) batching are grinding medium rewetting mill about 24 hours then with distilled water.It is the polyvinyl alcohol water solution of 5-10% that material after the oven dry adds concentration, and add-on accounts for the 2-20% of powder gross weight, uses the pressure compression moulding of 150-300Mpa then, burns till 4-24 hour in 1300-1400 ℃.The microwave-medium ceramics that makes can be used for making microwave-medium wave filter, resonator etc.
Embodiment 1-3:
The first step:
Ba (Co 1/3Nb 2/3) O 3Synthetic: get BaCO 363.65g, CoO8.06g, Nb 2O 528.29g in dehydrated alcohol, grind oven dry after 12 hours, then at 2 hours synthetic Ba (Co of 1100 ℃ of insulations 1/3Nb 2/3) O 3
Second step:
CaTiO 3Synthetic: get CaCO 355.61g, TiO 244.39g in dehydrated alcohol, grind oven dry after 24 hours, then at 6 hours synthetic CaTiO of 1250 ℃ of insulations 3
The 3rd step:
Get Ba (Co in ratio in the table 1 1/3Nb 2/3) O 3, CaTiO 3Powder and MnO 2, wet-milling 24 hours.Material adding concentration after the oven dry is 5% polyvinyl alcohol water solution 5g granulation, uses the pressure compression moulding of 200MPa then, burns till 6 hours in 1350 ℃ of temperature, makes microwave-medium ceramics, and its dielectric properties detected result about 8GHz sees Table 2:
The composition of table 1 microwave-medium ceramics
Figure A20061009530600051
Dielectric properties under the table 2 microwave-medium ceramics 8GHz
Figure A20061009530600052
Innovation of the present invention is to select suitable Ba (Co 1/3Nb 2/3) O 3, CaTiO 3Powder and MnO 2Proportioning, the niobium-based microwave dielectric ceramic of near-zero resonance frequency temperature coefficient of the Technology Need of systems such as mobile communication, satellite communications is satisfied in the manufacturing of making various microwave devices such as being widely used in various dielectric resonators, wave filter.

Claims (4)

1, the niobium-based microwave dielectric ceramic of near-zero resonance frequency temperature coefficient is characterized in that, is made up of Ba, Co, Nb, Ca, Ti and the Mn of oxide form, and its chemical formula is:
(1-x) BaO0.33 (1-x) CoO0.33 (1-x) Nb 2O 5XTiO 2XCaOyMnO 2, x=0-0.1 in the formula, y=0-0.05.
2, microwave-medium ceramics according to claim 1 is characterized in that, its component mole deal ratio is: BaO 100:CoO 33.33:Nb 2O 533.33:CaO 0-11.11:TiO 2O-11.11:MnO 20-5.
3, microwave-medium ceramics preparation method according to claim 1 is characterized in that comprising the steps:
(1) with purity 99%BaCO 3, 99%CoO and 99.99%Nb 2O 5Be starting raw material, at 2-8 hour synthetic Ba (Co of 1100-1200 ℃ of insulation 1/3Nb 2/3) O 3Powder;
(2) with purity 99%CaCO 3And 99%TiO 2Be starting raw material, 2-10 hour synthetic CaTiO of 1200-1300 ℃ of insulation 3Powder;
(3) by (1-x) Ba (Co 1/3Nb 2/3) O 3-x CaTiO 3-yMnO 2(x=0-0.1, proportioning y=0-0.05) is with Ba (Co 1/3Nb 2/3) O 3, CaTiO 3And MnO 2The powder wet-milling mixes, it is the polyvinyl alcohol water solution of 3-15% that the oven dry back adds concentration, and add-on accounts for the 2-20% of powder gross weight, is 150-300Mpa compression moulding in pressure then, in temperature is 1300-1400 ℃ of high temperature kiln roasting, makes microwave-medium ceramics.
4, preparation method according to claim 3 is characterized in that, described firing time is 4-24 hour.
CNB2006100953065A 2006-12-15 2006-12-15 Niobium-based microwave dielectric ceramic with near-zero resonance frequency temperature coefficient and preparation method thereof Expired - Fee Related CN100463878C (en)

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CN101786879B (en) * 2010-01-05 2013-07-17 湖北大学 Low-loss microwave medium ceramic with complex-phase structure and preparation method thereof
CN103482971A (en) * 2013-09-18 2014-01-01 重庆理工大学 Microwave dielectric ceramic and preparing method
CN103496964A (en) * 2013-09-23 2014-01-08 桂林理工大学 Low-temperature sintering microwave dielectric ceramic Ca3Bi(PO4)3 and preparation method thereof
CN103496978A (en) * 2013-09-23 2014-01-08 桂林理工大学 Low-temperature sintering microwave dielectric ceramic Ba2BiV3O11 and preparation method thereof
CN103570349A (en) * 2012-07-26 2014-02-12 深圳市国华新材料科技股份有限公司 Doped modified composite perovskite microwave dielectric ceramic Ba (Co, nb) O3and its prepn
CN104649665A (en) * 2014-12-28 2015-05-27 桂林理工大学 Microwave medium ceramic Li2La3NdV2O12 with near zero temperature coefficient of resonant frequency
CN106747412A (en) * 2016-12-14 2017-05-31 电子科技大学 A kind of Ti bases LTCC microwave dielectric ceramic materials and preparation method thereof
CN111908920A (en) * 2020-07-31 2020-11-10 东莞市翔通光电技术有限公司 Barium-cobalt-zinc-niobium-based microwave dielectric ceramic and preparation method thereof
CN114315344A (en) * 2021-12-09 2022-04-12 太原师范学院 Negative temperature coefficient ceramic dielectric material and preparation method thereof
CN114349504A (en) * 2022-01-07 2022-04-15 湖南省美程陶瓷科技有限公司 Doped perovskite relay electronic ceramic material and preparation method thereof

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CN101786879B (en) * 2010-01-05 2013-07-17 湖北大学 Low-loss microwave medium ceramic with complex-phase structure and preparation method thereof
CN103570349A (en) * 2012-07-26 2014-02-12 深圳市国华新材料科技股份有限公司 Doped modified composite perovskite microwave dielectric ceramic Ba (Co, nb) O3and its prepn
CN103482971A (en) * 2013-09-18 2014-01-01 重庆理工大学 Microwave dielectric ceramic and preparing method
CN103496964A (en) * 2013-09-23 2014-01-08 桂林理工大学 Low-temperature sintering microwave dielectric ceramic Ca3Bi(PO4)3 and preparation method thereof
CN103496978A (en) * 2013-09-23 2014-01-08 桂林理工大学 Low-temperature sintering microwave dielectric ceramic Ba2BiV3O11 and preparation method thereof
CN104649665A (en) * 2014-12-28 2015-05-27 桂林理工大学 Microwave medium ceramic Li2La3NdV2O12 with near zero temperature coefficient of resonant frequency
CN106747412A (en) * 2016-12-14 2017-05-31 电子科技大学 A kind of Ti bases LTCC microwave dielectric ceramic materials and preparation method thereof
CN106747412B (en) * 2016-12-14 2019-07-19 电子科技大学 A kind of Ti base LTCC microwave dielectric ceramic material and preparation method thereof
CN111908920A (en) * 2020-07-31 2020-11-10 东莞市翔通光电技术有限公司 Barium-cobalt-zinc-niobium-based microwave dielectric ceramic and preparation method thereof
CN114315344A (en) * 2021-12-09 2022-04-12 太原师范学院 Negative temperature coefficient ceramic dielectric material and preparation method thereof
CN114349504A (en) * 2022-01-07 2022-04-15 湖南省美程陶瓷科技有限公司 Doped perovskite relay electronic ceramic material and preparation method thereof
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