CN113754424A - Low-dielectric-constant microwave dielectric ceramic material and preparation method thereof - Google Patents

Low-dielectric-constant microwave dielectric ceramic material and preparation method thereof Download PDF

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CN113754424A
CN113754424A CN202110940704.7A CN202110940704A CN113754424A CN 113754424 A CN113754424 A CN 113754424A CN 202110940704 A CN202110940704 A CN 202110940704A CN 113754424 A CN113754424 A CN 113754424A
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张启龙
王浩
董娇娇
杨辉
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Zhejiang University ZJU
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Abstract

The invention relates to the field of material science, and aims to provide a low-dielectric-constant microwave dielectric ceramic material and a preparation method thereof. The microwave dielectric ceramic material with the low dielectric constant is provided, and the chemical expression of the microwave dielectric ceramic material is as follows: (100-x) wt% Ca3Sn2SiGa2O12+x wt％CaTiO3+a wt％CaF2(ii) a Wherein a is CaF2Is in Ca3Sn2SiGa2O12With CaTiO3Mass fraction of total mass, wherein 0<x is less than or equal to 10, and a is less than or equal to 5 and more than or equal to 2. The microwave dielectric ceramic material prepared by the invention has the advantages of low dielectric constant, high Q multiplied by f value, stable temperature coefficient of resonant frequency and low sintering temperature. Compared with the existing Ca3Sn2SiGa2O12The invention is a ceramic material, and has remarkable superiority in practical application. The invention has simple preparation process and good repeatabilityThe method has strong universality and wide application prospect in microwave devices such as filters, antennas, dielectric substrates and the like.

Description

Low-dielectric-constant microwave dielectric ceramic material and preparation method thereof
Technical Field
The invention belongs to the field of material science, and particularly relates to a low-dielectric-constant microwave dielectric ceramic material and a preparation method thereof.
Background
With the rapid development of 5G mobile communication, satellite communication, wireless network and other technologies, microwave devices are continuously moving towards high frequencyThe development of high speed and light weight, which puts higher requirements on microwave dielectric ceramic materials: low dielectric constant to satisfy high signal transmission rate; the Q multiplied by f value of the quality factor is high, and the signal transmission loss in the device is reduced; the sintering temperature is low, the microstructure of the material is effectively controlled, and energy is saved; stable temperature coefficient of resonance frequency. Ca3Sn2SiGa2O12The microwave dielectric material has low dielectric constant and extremely high quality factor, meets the requirements of the existing microwave devices very well, and has wide application prospect. But Ca3Sn2SiGa2O12The system has high sintering temperature (1430 ℃) and poor temperature coefficient of resonance frequency (46 ppm/DEG C), thereby limiting the practical application. Therefore, development of Ca having a low sintering temperature and a stable temperature coefficient of resonant frequency3Sn2SiGa2O12The microwave dielectric ceramic with low dielectric constant has very important significance.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects of the existing material system and technology and provide a low-dielectric-constant microwave dielectric ceramic material with low sintering temperature and stable resonant frequency temperature coefficient and a preparation method thereof.
In order to solve the technical problem, the solution provided by the invention is as follows:
the microwave dielectric ceramic material with the low dielectric constant is provided, and the chemical expression of the microwave dielectric ceramic material is as follows: (100-x) wt% Ca3Sn2SiGa2O12+x wt％CaTiO3+a wt％CaF2(ii) a Wherein a is CaF2Is in Ca3Sn2SiGa2O12With CaTiO3Mass fraction of total mass, wherein 0<x≤10，2≤a≤5。
The invention further provides a preparation method of the microwave dielectric ceramic material, which comprises the following steps:
(1) according to Ca3Sn2SiGa2O12The raw material CaCO is weighed according to the molar ratio of the elements3、SnO2、SiO2And Ga2O3Powder of ethanolPerforming ball milling and mixing for 6h as a medium; baking, pre-sintering at 1300 deg.C for 5h, and ball-milling for the second time to obtain Ca3Sn2SiGa2O12Ceramic powder;
(2) according to Ca3Sn2SiGa2O12With CaTiO3The mass ratio of (100-x) to (x) weighing CaTiO3，0<x is less than or equal to 10; according to CaF2With Ca3Sn2SiGa2O12With CaTiO3Ratio of total mass a: 100 weighing of CaF2A is more than or equal to 2 and less than or equal to 5; adding Ca3Sn2SiGa2O12、CaTiO3And CaF2Ball milling and mixing the powder, and drying to obtain ceramic mixed powder;
(3) adding a polyvinyl alcohol solution into the ceramic mixed powder prepared in the step (2), and uniformly mixing; pressing under the pressure of 100MPa to prepare a cylindrical blank; the polyvinyl alcohol is added to ensure that the ceramic particles have cohesiveness so as to maintain the strength of the ceramic body;
(4) and (4) sintering the blank obtained in the step (3) for 6 hours at the temperature of 900-1050 ℃ to obtain the low-dielectric-constant microwave dielectric ceramic material.
Preferably, in the step (2), the ball milling time is 6 hours, and the drying temperature is 80 ℃.
Preferably, in the step (3), the mass fraction of the polyvinyl alcohol solution is 15%, and the mass percentage of the polyvinyl alcohol in the ceramic powder is 10%.
Preferably, in the step (3), the cylindrical billet has a diameter of 20mm and a height of 10 mm.
Preferably, in the step (4), the temperature rise rate in the sintering process is 10 ℃/min.
Description of the inventive principles:
Ca3Sn2SiGa2O12has a negative temperature coefficient of resonance frequency, and needs to be improved by adding a ceramic having a positive temperature coefficient of resonance frequency. In a ceramic system with a plurality of satisfied conditions, CaTiO containing calcium element3The ceramic can greatly reduce the introduction of impurity elements, andCaTiO3the ceramic also has excellent dielectric properties. CaTiO compared to other ceramic systems3Can improve the temperature coefficient and simultaneously maintain the excellent dielectric property of the original ceramic system. CaF2The invention introduces Ca into the flux based on the characteristics of lower melting point and calcium element content3Sn2SiGa2O12The system can realize low-temperature sintering of the ceramic.
Compared with the prior art, the invention has the beneficial effects that:
1. the microwave dielectric ceramic material prepared by the invention has the advantages of low dielectric constant (between 8.5 and 9.2), high Q x f value (between 35000 and 51000 GH), stable temperature coefficient of resonance frequency (between-10 and +10 ppm/DEG C) and low sintering temperature (between 900 and 1050 ℃).
Compared with the existing Ca3Sn2SiGa2O12The dielectric constant (9.0), Q x f value (54000GHz), temperature coefficient of resonance frequency (-46 ppm/DEG C) of the system ceramic material and the performance of high sintering temperature (1430 ℃) in the preparation process have obvious superiority in the aspect of practical application.
2. The invention has simple preparation process, good repeatability and strong universality, and has wide application prospect in microwave devices such as filters, antennas, dielectric substrates and the like.
Detailed Description
The following examples are presented to enable those skilled in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Example 1:
step (1): according to Ca3Sn2SiGa2O12The raw material CaCO is weighed according to the molar ratio of the elements3、SnO2、SiO2And Ga2O3Ball milling and mixing the powder for 6h by taking ethanol as a medium, drying, pre-sintering at 1300 ℃ for 5h, and carrying out secondary ball milling to obtain Ca3Sn2SiGa2O12Ceramic powder;
step (2): according to Ca3Sn2SiGa2O12With CaTiO3Weighing CaTiO in a mass ratio of 90:103According to CaF2With Ca3Sn2SiGa2O12With CaTiO3The ratio of the total mass 2: 100 weighing of CaF2(ii) a Adding Ca3Sn2SiGa2O12、CaTiO3And CaF2Ball milling and mixing the powder for 6 hours, and then drying at 80 ℃;
and (3): adding the mixed powder prepared in the step (2) into 15% of polyvinyl alcohol solution by mass percent, and uniformly mixing, wherein the polyvinyl alcohol accounts for 10% of the ceramic powder by mass percent; pressing under the pressure of 100MPa to prepare a cylindrical blank with the diameter of 20mm and the height of 10 mm;
and (4): and (4) sintering the blank obtained in the step (3) at 900 ℃ for 6h, and controlling the temperature rise rate in the sintering process to be 10 ℃/min to prepare the low-dielectric-constant microwave dielectric ceramic material.
The medium-temperature sintered low-dielectric microwave dielectric ceramic material prepared according to the formula and the steps has the following performance indexes: dielectric constant εrQuality factor Q × f 35000GHz, temperature coefficient of resonance frequency tauf＝+10ppm/℃。
Example 2:
step (1): according to Ca3Sn2SiGa2O12The raw material CaCO is weighed according to the molar ratio of the elements3、SnO2、SiO2And Ga2O3Ball milling and mixing the powder for 6h by taking ethanol as a medium, drying, pre-sintering at 1300 ℃ for 5h, and carrying out secondary ball milling to obtain Ca3Sn2SiGa2O12Ceramic powder;
step (2): according to Ca3Sn2SiGa2O12With CaTiO3The mass ratio of the CaTiO is 95:53According to CaF2With Ca3Sn2SiGa2O12With CaTiO3The proportion of the total mass is 5: 100 weighing of CaF2(ii) a Adding Ca3Sn2SiGa2O12、CaTiO3And CaF2Ball milling and mixing the powder for 6 hours, and then drying at 80 ℃;
and (3): adding the mixed powder prepared in the step (2) into 15% of polyvinyl alcohol solution by mass percent, and uniformly mixing, wherein the polyvinyl alcohol accounts for 10% of the ceramic powder by mass percent; pressing under the pressure of 100MPa to prepare a cylindrical blank with the diameter of 20mm and the height of 10 mm;
and (4): and (4) sintering the blank obtained in the step (3) at 1050 ℃ for 6h, and controlling the temperature rise rate in the sintering process to be 10 ℃/min to prepare the low-dielectric-constant microwave dielectric ceramic material.
The medium-temperature sintered low-dielectric microwave dielectric ceramic material prepared according to the formula and the steps has the following performance indexes: dielectric constant εrQuality factor Qxf 51000GHz, temperature coefficient of resonance frequency tauf＝-10ppm/℃。
Example 3:
step (1): according to Ca3Sn2SiGa2O12The raw material CaCO is weighed according to the molar ratio of the elements3、SnO2、SiO2And Ga2O3Ball milling and mixing the powder for 6h by taking ethanol as a medium, drying, pre-sintering at 1300 ℃ for 5h, and carrying out secondary ball milling to obtain Ca3Sn2SiGa2O12Ceramic powder;
step (2): according to Ca3Sn2SiGa2O12With CaTiO3Weighing CaTiO in a mass ratio of 92:83According to CaF2With Ca3Sn2SiGa2O12With CaTiO3Ratio of total mass 3: 100 weighing of CaF2(ii) a Adding Ca3Sn2SiGa2O12、CaTiO3And CaF2Ball milling and mixing the powder for 6 hours, and then drying at 80 ℃;
and (3): adding the mixed powder prepared in the step (2) into 15% of polyvinyl alcohol solution by mass percent, and uniformly mixing, wherein the polyvinyl alcohol accounts for 10% of the ceramic powder by mass percent; pressing under the pressure of 100MPa to prepare a cylindrical blank with the diameter of 20mm and the height of 10 mm;
and (4): and (4) sintering the blank obtained in the step (3) at 1000 ℃ for 6h, and controlling the temperature rise rate in the sintering process to be 10 ℃/min to prepare the low-dielectric-constant microwave dielectric ceramic material.
The medium-temperature sintered low-dielectric microwave dielectric ceramic material prepared according to the formula and the steps has the following performance indexes: dielectric constant εrQuality factor Q × f 48000GHz, resonant frequency temperature coefficient τ 9f＝-6ppm/℃。
Example 4:
step (1): according to Ca3Sn2SiGa2O12The raw material CaCO is weighed according to the molar ratio of the elements3、SnO2、SiO2And Ga2O3Ball milling and mixing the powder for 6h by taking ethanol as a medium, drying, pre-sintering at 1300 ℃ for 5h, and carrying out secondary ball milling to obtain Ca3Sn2SiGa2O12Ceramic powder;
step (2): according to Ca3Sn2SiGa2O12With CaTiO3Weighing CaTiO with the mass ratio of 98:23According to CaF2With Ca3Sn2SiGa2O12With CaTiO3The ratio of the total mass 4: 100 weighing of CaF2(ii) a Adding Ca3Sn2SiGa2O12、CaTiO3And CaF2Ball milling and mixing the powder for 6 hours, and then drying at 80 ℃;
and (3): adding the mixed powder prepared in the step (2) into 15% of polyvinyl alcohol solution by mass percent, and uniformly mixing, wherein the polyvinyl alcohol accounts for 10% of the ceramic powder by mass percent; pressing under the pressure of 100MPa to prepare a cylindrical blank with the diameter of 20mm and the height of 10 mm;
and (4): and (4) sintering the blank obtained in the step (3) at 950 ℃ for 6h, and controlling the temperature rise rate in the sintering process to be 10 ℃/min to prepare the low-dielectric-constant microwave dielectric ceramic material.
The medium-temperature sintered low-dielectric microwave dielectric ceramic material prepared according to the formula and the steps has the following performance indexes: dielectric constant εrQuality factor Qxf 39000GHz, temperature coefficient of resonance frequency τ 8.8f＝+1.3ppm/℃。
Example 5:
step (1): according to Ca3Sn2SiGa2O12The raw material CaCO is weighed according to the molar ratio of the elements3、SnO2、SiO2And Ga2O3Ball milling and mixing the powder for 6h by taking ethanol as a medium, drying, pre-sintering at 1300 ℃ for 5h, and carrying out secondary ball milling to obtain Ca3Sn2SiGa2O12Ceramic powder;
step (2): according to Ca3Sn2SiGa2O12With CaTiO3Weighing CaTiO with the mass ratio of 96:43According to CaF2With Ca3Sn2SiGa2O12With CaTiO3Ratio of total mass 3: 100 weighing of CaF2(ii) a Adding Ca3Sn2SiGa2O12、CaTiO3And CaF2Ball milling and mixing the powder for 6 hours, and then drying at 80 ℃;
and (3): adding the mixed powder prepared in the step (2) into 15% of polyvinyl alcohol solution by mass percent, and uniformly mixing, wherein the polyvinyl alcohol accounts for 10% of the ceramic powder by mass percent; pressing under the pressure of 100MPa to prepare a cylindrical blank with the diameter of 20mm and the height of 10 mm;
and (4): and (4) sintering the green body obtained in the step (3) for 6 hours at 980 ℃, and controlling the heating rate of the sintering process to be 10 ℃/min to prepare the low-dielectric-constant microwave dielectric ceramic material.
The medium-temperature sintered low-dielectric microwave dielectric ceramic material prepared according to the formula and the steps has the following performance indexes: dielectric constant εrQuality factor Q × f 42000GHz, temperature coefficient of resonance frequency τ 8.6f＝+3.3ppm/℃。

Claims (6)

1. A microwave dielectric ceramic material with low dielectric constant is characterized in that the chemical expression of the microwave dielectric ceramic material is as follows: (100-x) wt% Ca3Sn2SiGa2O12+x wt％CaTiO3+a wt％CaF2(ii) a Wherein a is CaF2Is in Ca3Sn2SiGa2O12With CaTiO3Mass fraction of total mass, wherein 0<x≤10，2≤a≤5。
2. A method for preparing a microwave dielectric ceramic material as claimed in claim 1, characterized by comprising the steps of:
(1) according to Ca3Sn2SiGa2O12The raw material CaCO is weighed according to the molar ratio of the elements3、SnO2、SiO2And Ga2O3Powder is mixed by ball milling for 6 hours by taking ethanol as a medium; baking, pre-sintering at 1300 deg.C for 5h, and ball-milling for the second time to obtain Ca3Sn2SiGa2O12Ceramic powder;
(2) according to Ca3Sn2SiGa2O12With CaTiO3The mass ratio of (100-x) to (x) weighing CaTiO3，0<x is less than or equal to 10; according to CaF2With Ca3Sn2SiGa2O12With CaTiO3Ratio of total mass a: 100 weighing of CaF2A is more than or equal to 2 and less than or equal to 5; adding Ca3Sn2SiGa2O12、CaTiO3And CaF2Ball milling and mixing the powder, and drying to obtain ceramic mixed powder;
(3) adding a polyvinyl alcohol solution into the ceramic mixed powder prepared in the step (2), and uniformly mixing; pressing under the pressure of 100MPa to prepare a cylindrical blank;
(4) and (4) sintering the blank obtained in the step (3) for 6 hours at the temperature of 900-1050 ℃ to obtain the low-dielectric-constant microwave dielectric ceramic material.
3. The method according to claim 2, wherein in the step (2), the ball milling time is 6h, and the drying temperature is 80 ℃.
4. The method according to claim 2, wherein in the step (3), the mass fraction of the polyvinyl alcohol solution is 15%, and the mass percentage of the polyvinyl alcohol in the ceramic powder is 10%.
5. The method according to claim 2, wherein in the step (3), the cylindrical billet has a diameter of 20mm and a height of 10 mm.
6. The method according to claim 2, wherein in the step (4), the temperature rise rate in the sintering process is 10 ℃/min.
CN202110940704.7A 2021-08-17 2021-08-17 Low-dielectric-constant microwave dielectric ceramic material and preparation method thereof Active CN113754424B (en)

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