CN102358698A - Microwave dielectric ceramic material with medium dielectric constant, and preparation method thereof - Google Patents

Microwave dielectric ceramic material with medium dielectric constant, and preparation method thereof Download PDF

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Publication number
CN102358698A
CN102358698A CN2011102157066A CN201110215706A CN102358698A CN 102358698 A CN102358698 A CN 102358698A CN 2011102157066 A CN2011102157066 A CN 2011102157066A CN 201110215706 A CN201110215706 A CN 201110215706A CN 102358698 A CN102358698 A CN 102358698A
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microwave
dielectric ceramic
ceramic material
microwave dielectric
preparation
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陈国华
康晓玲
狄洁昌
徐华蕊
张小文
杨云
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Guilin University of Electronic Technology
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Guilin University of Electronic Technology
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Abstract

The present invention discloses a microwave dielectric ceramic material with a medium dielectric constant, and a preparation method thereof. The preparation method comprises: mixing the following raw powders according to a chemical formula of Ca4La2Ti5-x(Mg1/3Nb2/3) xO17, wherein the raw powders comprise CaCO3, (MgCO3)4.Mg(OH)2.5H2O, TiO2, La2O3 and Nb2O5, the purities of the raw powders are more than 99%, x is more than or equal to 0, and less than or equal to 4; carrying out wet milling and mixing for 12-24 hours, wherein absolute alcohol is adopted as a solvent; drying, and then pre-burning for 4-6 hours at a temperature of 1300 DEG C under air atmosphere; adding an aqueous solution containing 3% of polyvinyl alcohol (PVA) to the pre-burned powders, then mixing and drying; carrying out screening through a sieve with 100 meshes, and pelletizing; pressing into a cylindrical sample under pressure of 100 MPa; finally sintering for 4 hours at the temperature of 1480-1560 DEG C under air atmosphere to obtain the microwave dielectric ceramic material. According to the present invention, the prepared microwave dielectric ceramic has a high-frequency dielectric constant epsilonr of 34-72, high quality factor Q*f and small frequency temperature coefficient tauf, and can be widely used in dielectric resonators, filters, dielectric antennas and other microwave devices.

Description

A kind of medium dielectric constant microwave medium microwave dielectric ceramic material and preparation method thereof
Technical field
The present invention relates to a kind of dielectric ceramic material, particularly a kind of medium dielectric constant microwave medium microwave dielectric ceramic material and preparation method thereof.
Background technology
Microwave generally is meant frequency between 300MHz～3000GHz, and wavelength is between the hertzian wave of 0.1mm～1m.Microwave dielectric ceramic is meant and is applied in microwave frequency band (mainly being UHF, the SHF frequency range) circuit as dielectric materials and accomplishes the pottery of one or more functions.Along with the fast development of microwave integrated circuit, need a large amount of microwave dielectric materials to be used for commercial microwave regime day by day with middle and high specific inductivity, near-zero resonance frequency temperature coefficient and low-dielectric loss.Be applied to the dielectric ceramic material of microwave frequency band, should satisfy the requirement of following dielectric characteristics: the relative permittivity ε that (1) is high r, be beneficial to miniaturization of devices, general requirement ε r>=25; (2) high quality factor (high Q * fValue) or low dielectric loss tan δ reducing noise, general requirement Q * f>=10000GHz; (3) temperature coefficient of resonance frequency τ f As far as possible little of to guarantee that device has good thermostability, general requirement-10ppm/ ℃≤τ f ≤+10ppm/ ℃.Yet the microwave dielectric ceramic that the present overwhelming majority has high-k has big positive frequency-temperature coefficient τ f , like CaTiO 3The dielectric properties of pottery are: ε r=162, Q * f=12000 GHz, τ f =850 ppm/ ℃.Reducing frequency-temperature coefficient, to make it be bordering on zero effective ways be to utilize the compound of negative frequency-temperature coefficient to compensate or on the B position, substitute formation sosoloid to change the degree of reversing of oxygen octahedra, thereby reduce frequency-temperature coefficient.To maintain higher dielectric constant and quality factor simultaneously, to satisfy the practicability requirement of micro-wave dielectric resonator, micro-wave dielectric antenna and wave filter.
In sum, along with the fast development of short-wave communication tedhnology, the demand of centering dielectric constant microwave dielectric ceramic material constantly increases, and therefore develops the focus that chemical constitution and the simple novel medium dielectric constant microwave medium microwave ceramics of preparation technology become research.
Summary of the invention
The objective of the invention is to overcome the existing big shortcoming of microwave dielectric ceramic frequency-temperature coefficient, provide a kind of
Have medium dielectric constant microwave medium, hi-q and little frequency-temperature coefficient, can be at≤1560 ℃ of agglomerating dielectric ceramic materials and preparation method thereof.
Microwave dielectric ceramic material of the present invention is made up of oxide form Ca, La, Ti, Mg and Nb, and its chemical constitution is Ca 4La 2Ti 5-x(Mg 1/3Nb 2/3) xO 17, 0≤x≤4 wherein..
The preparation method of microwave dielectric ceramic material comprises the steps:
(1) with purity greater than 99% CaCO 3, (MgCO 3) 4Mg (OH) 25H 2O, TiO 2, La 2O 3And Nb 2O 5Starting powder according to Ca 4La 2Ti 5-x(Mg 1/3Nb 2/3) xO 17Chemical formula weigh batching, wherein 0≤x≤4;
(2) mix 12～24h with the absolute ethyl alcohol wet ball-milling;
(3) oven dry back pre-burning 4～6h in 1300 ℃ of air atmospheres;
(4) in preburning powder, add 3% Z 150PH (PVA) aqueous solution then, mix, dry, cross 100 mesh sieve granulations;
(5) depress to cylindric sample at 100MPa;
(6) sintering 4h in 1480～1560 ℃ of air atmospheres.
The performance of the microwave dielectric ceramic material of the present invention's preparation is following: ε r=34～72, Q * f=14500～21280 GHz, τ f =+125～-16.7ppm/ ℃, can be widely used in the microwave device such as dielectric resonator, wave filter, dielectric antenna of different occasions.
Description of drawings:
Fig. 1 is an X ray diffracting spectrum of the present invention.(a) is Ca among the figure 4La 2Ti 5O 17(x=0) XRD spectrum; (b) is Ca among the figure 4La 2Ti 2.5(Mg 1/3Nb 2/3) 2.5O 17(x=2.5) XRD spectrum; (c) is Ca among the figure 4La 2Ti (Mg 1/3Nb 2/3) 4O 17(x=4) XRD spectrum.
Fig. 2 is the SEM figure of the embodiment of the invention 4.
Embodiment
The preparation method of a kind of medium dielectric constant microwave medium microwave dielectric ceramic material of the present invention can obtain more clearly describing through following indefiniteness embodiment.
Embodiment 1
The chemical constitution formula of microwave dielectric ceramic is Ca 4La 2Ti 5-x(Mg 1/3Nb 2/3) xO 17, x=0 wherein.
With purity greater than 99% CaCO 3, TiO 2And La 2O 3Starting powder according to Ca 4La 2Ti 5O 17The chemical formula weigh batching; Wet ball-milling mixing 24h; Solvent is an absolute ethyl alcohol, and oven dry back pre-burning 6h in 1300 ℃ of air atmospheres adds 3% Z 150PH (PVA) aqueous solution then in preburning powder; Mix, dry; After crossing 100 mesh sieve granulations, depress to cylindric sample at 100MPa again, at last sintering 4h in 1540 ℃ of air atmospheres.The microwave dielectric property of this material is: ε r=71.8, Q * f=15070GHz, τ f =+125ppm/ ℃.
Embodiment 2
The chemical constitution formula of microwave dielectric ceramic is Ca 4La 2Ti 5-x(Mg 1/3Nb 2/3) xO 17, x=2 wherein.
With purity greater than 99% CaCO 3, TiO 2And La 2O 3Nb 2O 5Starting powder according to Ca 4La 2Ti 3(Mg 1/3Nb 2/3) 2O 17The chemical formula weigh batching; Wet ball-milling mixes 12 h; Solvent is an absolute ethyl alcohol, and oven dry back pre-burning 5h in 1300 ℃ of air atmospheres adds 3% Z 150PH (PVA) aqueous solution then in preburning powder; Mix, dry; After crossing 100 mesh sieve granulations, depress to cylindric sample at 100MPa again, at last sintering 4h in 1540 ℃ of air atmospheres.The microwave dielectric property of this material is: ε r=49.2, Q * f=16046GHz, τ f =31.5ppm/ ℃.
Embodiment 3
The chemical constitution formula of microwave dielectric ceramic is Ca 4La 2Ti 5-x(Mg 1/3Nb 2/3) xO 17, x=4 wherein.
With purity greater than 99% CaCO 3, TiO 2And La 2O 3Nb 2O 5Starting powder according to Ca 4La 2Ti (Mg 1/3Nb 2/3) 4O 17The chemical formula weigh batching; Wet ball-milling mixing 20h; Solvent is an absolute ethyl alcohol, and oven dry back pre-burning 4h in 1300 ℃ of air atmospheres adds 3% Z 150PH (PVA) aqueous solution then in preburning powder; Mix, dry; After crossing 100 mesh sieve granulations, depress to cylindric sample at 100MPa again, at last sintering 4h in 1540 ℃ of air atmospheres.The microwave dielectric property of this material is: ε r=35.3, Q * f=21277GHz, τ f =-16.7ppm/ ℃.
Embodiment 4
The chemical constitution formula of microwave dielectric ceramic is Ca 4La 2Ti 5-x(Mg 1/3Nb 2/3) xO 17, x=3 wherein.
With purity greater than 99% CaCO 3, TiO 2And La 2O 3Nb 2O 5Starting powder according to Ca 4La 2Ti 2(Mg 1/3Nb 2/3) 3O 17The chemical formula weigh batching; Wet ball-milling mixes 16 h; Solvent is an absolute ethyl alcohol, and oven dry back pre-burning 4h in 1300 ℃ of air atmospheres adds 3% Z 150PH (PVA) aqueous solution then in preburning powder; Mix, dry; After crossing 100 mesh sieve granulations, depress to cylindric sample at 100MPa again, at last sintering 4h in 1540 ℃ of air atmospheres.The microwave dielectric property of this material is: ε r=40.5, Q * f=19123GHz, τ f =1.6ppm/ ℃.
Embodiment 5
The chemical constitution formula of microwave dielectric ceramic is Ca 4La 2Ti 5-x(Mg 1/3Nb 2/3) xO 17, x=2.5 wherein.
With purity greater than 99% CaCO 3, TiO 2And La 2O 3Nb 2O 5Starting powder according to Ca 4La 2Ti 2.5(Mg 1/3Nb 2/3) 2.5O 17The chemical formula weigh batching; Wet ball-milling mixes 12 h; Solvent is an absolute ethyl alcohol, and oven dry back pre-burning 4h in 1300 ℃ of air atmospheres adds 3% Z 150PH (PVA) aqueous solution then in preburning powder; Mix, dry; After crossing 100 mesh sieve granulations, depress to cylindric sample at 100MPa again, at last sintering 4h in 1520 ℃ of air atmospheres.The microwave dielectric property of this material is: ε r=44.3, Q * f=15896GHz, τ f =17.6ppm/ ℃.
Embodiment 6
The chemical constitution formula of microwave dielectric ceramic is Ca 4La 2Ti 5-x(Mg 1/3Nb 2/3) xO 17, x=1 wherein.
With purity greater than 99% CaCO 3, TiO 2And La 2O 3Nb 2O 5Starting powder according to Ca 4La 2Ti 4(Mg 1/3Nb 2/3) O 17The chemical formula weigh batching; Wet ball-milling mixes 12 h; Solvent is an absolute ethyl alcohol, and oven dry back pre-burning 5h in 1300 ℃ of air atmospheres adds 3% Z 150PH (PVA) aqueous solution then in preburning powder; Mix, dry; After crossing 100 mesh sieve granulations, depress to cylindric sample at 100MPa again, at last sintering 4h in 1500 ℃ of air atmospheres.The microwave dielectric property of this material is: ε r=59.2, Q * f=14592GHz, τ f =68.2ppm/ ℃.
Embodiment 7
The chemical constitution formula of microwave dielectric ceramic is Ca 4La 2Ti 5-x(Mg 1/3Nb 2/3) xO 17, x=3 wherein.
With purity greater than 99% CaCO 3, TiO 2And La 2O 3Nb 2O 5Starting powder according to Ca 4La 2Ti 2(Mg 1/3Nb 2/3) 3O 17The chemical formula weigh batching; Wet ball-milling mixes 12 h; Solvent is an absolute ethyl alcohol, and oven dry back pre-burning 4h in 1300 ℃ of air atmospheres adds 3% Z 150PH (PVA) aqueous solution then in preburning powder; Mix, dry; After crossing 100 mesh sieve granulations, depress to cylindric sample at 100MPa again, at last sintering 4h in 1480 ℃ of air atmospheres.The microwave dielectric property of this material is: ε r=40.1, Q * f=15157GHz, τ f =2.5ppm/ ℃.
Embodiment 8
The chemical constitution formula of microwave dielectric ceramic is Ca 4La 2Ti 5-x(Mg 1/3Nb 2/3) xO 17, x=2.5 wherein.
With purity greater than 99% CaCO 3, TiO 2And La 2O 3Nb 2O 5Starting powder according to Ca 4La 2Ti 2.5(Mg 1/3Nb 2/3) 2.5O 17The chemical formula weigh batching; Wet ball-milling mixing 18h; Solvent is an absolute ethyl alcohol, and oven dry back pre-burning 4h in 1300 ℃ of air atmospheres adds 3% Z 150PH (PVA) aqueous solution then in preburning powder; Mix, dry; After crossing 100 mesh sieve granulations, depress to cylindric sample at 100MPa again, at last sintering 4h in 1560 ℃ of air atmospheres.The microwave dielectric property of this material is: ε r=44.3, Q * f=14888GHz, τ f =13.2ppm/ ℃.
Embodiment 9
The chemical constitution formula of microwave dielectric ceramic is Ca 4La 2Ti 5-x(Mg 1/3Nb 2/3) xO 17, x=4 wherein.
With purity greater than 99% CaCO 3, TiO 2And La 2O 3Nb 2O 5Starting powder according to Ca 4La 2Ti (Mg 1/3Nb 2/3) 4O 17The chemical formula weigh batching; Wet ball-milling mixes 16 h; Solvent is an absolute ethyl alcohol, and oven dry back pre-burning 4h in 1300 ℃ of air atmospheres adds 3% Z 150PH (PVA) aqueous solution then in preburning powder; Mix, dry; After crossing 100 mesh sieve granulations, depress to cylindric sample at 100MPa again, at last sintering 4h in 1480 ℃ of air atmospheres.The microwave dielectric property of this material is: ε r=34.1, Q * f=16584GHz, τ f =-13.8ppm/ ℃.
It is pointed out that according to technical scheme of the present invention the foregoing description can also be enumerated a lot, confirm,, all can reach the object of the invention in the scope that claims of the present invention proposed according to applicant's lot of experiment results.

Claims (2)

1. the preparation method of a medium dielectric constant microwave medium microwave dielectric ceramic material is characterized in that: comprise the steps:
(1) with purity greater than 99% CaCO 3, (MgCO 3) 4Mg (OH) 25H 2O, TiO 2, La 2O 3And Nb 2O 5Starting powder according to chemical formula Ca 4La 2Ti 5-x(Mg 1/3Nb 2/3) xO 17, wherein prepare burden in 0≤x≤4;
(2) mix 12～24h with the absolute ethyl alcohol wet ball-milling;
(3) oven dry back pre-burning 4～6h in 1300 ℃ of air atmospheres;
(4) in preburning powder, add 3% polyvinyl alcohol water solution, mix, dry, cross 100 mesh sieve granulations;
(5) depress to cylindric sample at 100MPa;
(6) sintering 4h in 1480～1560 ℃ of air atmospheres.
2. the microwave dielectric ceramic material for preparing with the described preparation method of claim 1.
CN2011102157066A 2011-07-29 2011-07-29 Microwave dielectric ceramic material with medium dielectric constant, and preparation method thereof Pending CN102358698A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111752012A (en) * 2020-06-24 2020-10-09 湖北第二师范学院 Temperature-insensitive terahertz wave metamaterial-based biosensing device
CN111995392A (en) * 2020-09-08 2020-11-27 中物院成都科学技术发展中心 Low-cost ceramic filter powder for 5G base station and preparation method thereof
CN112851333A (en) * 2021-03-31 2021-05-28 中国振华集团云科电子有限公司 high-Q-value microwave dielectric ceramic material and preparation method thereof
CN116751056A (en) * 2023-06-14 2023-09-15 云南贵金属实验室有限公司 Titanium dioxide doped calcium niobate ceramic material and preparation method and application thereof

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CHENG-LIANG HUANG ET AL.: "Improved high Q value of CaTiO3–Ca(Mg1/3Nb2/3)O3 solid solution with near zero temperature coefficient of resonant frequency", 《MATERIALS RESEARCH BULLETIN》 *
FEI ZHAO ET AL.: "Microstructure and microwave dielectric properties of Ca[Ti1-x(Mg1/3Nb2/3)x]O3 ceramics", 《JOURNAL OF THE EUROPEAN CERAMIC SOCIETY》 *
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111752012A (en) * 2020-06-24 2020-10-09 湖北第二师范学院 Temperature-insensitive terahertz wave metamaterial-based biosensing device
CN111995392A (en) * 2020-09-08 2020-11-27 中物院成都科学技术发展中心 Low-cost ceramic filter powder for 5G base station and preparation method thereof
CN112851333A (en) * 2021-03-31 2021-05-28 中国振华集团云科电子有限公司 high-Q-value microwave dielectric ceramic material and preparation method thereof
CN112851333B (en) * 2021-03-31 2022-07-26 中国振华集团云科电子有限公司 high-Q-value microwave dielectric ceramic material and preparation method thereof
CN116751056A (en) * 2023-06-14 2023-09-15 云南贵金属实验室有限公司 Titanium dioxide doped calcium niobate ceramic material and preparation method and application thereof

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Application publication date: 20120222