CN114180956A - Microwave dielectric ceramic for high-dielectric-constant 5G waveguide and preparation method and application thereof - Google Patents

Microwave dielectric ceramic for high-dielectric-constant 5G waveguide and preparation method and application thereof Download PDF

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CN114180956A
CN114180956A CN202111565715.8A CN202111565715A CN114180956A CN 114180956 A CN114180956 A CN 114180956A CN 202111565715 A CN202111565715 A CN 202111565715A CN 114180956 A CN114180956 A CN 114180956A
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吉岸
王晓慧
金镇龙
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WUXI XINSHENG HUILONG NANO CERAMIC TECHNOLOGY CO LTD
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Abstract

The invention discloses a microwave dielectric ceramic for a high-dielectric-constant 5G waveguide, a preparation method and application thereof; the microwave dielectric ceramic is composed of the following oxide components in percentage by mole: 10 to 15 percent of BaO and TiO2 60%~70%、Sm2O3 5%~10%、Bi2O3 5%~10%、La2O35% to 10% and MnO20.5 to 1 percent; the microwave dielectric ceramic comprises a basic crystal phase and a reduced-sintering crystal phase, wherein the composition expression of the basic crystal phase is Ba6‑3x(SmyLa1‑y)8+2x(TizMn1‑z)18O54Composition table of reduced-sintering crystalline phasesThe expression is Bi4Ti3O12. The microwave dielectric ceramic has high quality factor and near-zero temperature coefficient of resonant frequency while ensuring high dielectric constant, has nontoxic and cheap preparation raw materials, simple preparation process and wide application prospect in the field of 5G waveguide.

Description

Microwave dielectric ceramic for high-dielectric-constant 5G waveguide and preparation method and application thereof
Technical Field
The invention belongs to the technical field of electronic ceramics and preparation thereof, and particularly relates to microwave dielectric ceramics for a high-dielectric-constant 5G waveguide, and a preparation method and application thereof.
Background
With the development of recent decades, microwave dielectric ceramics have become a new type of functional ceramic material, and are used as dielectric materials to perform one or more functions in microwave frequency circuit. The dielectric property of microwave is a determining factor of microwave dielectric ceramic application, and the relative dielectric constant epsilonrQuality factor Qxf and resonant frequency temperature coefficient taufAre three main parameters of microwave dielectric performance.
With the rapid development of the 5G mobile communication system industry, microwave components, in particular, filters and resonators, have received much attention from researchers as important components in communication equipment. In order to meet the requirements of thin, thin and small antennas in electronic devices, the most suitable microwave dielectric ceramic material at present is a microwave dielectric material with a dielectric constant of 60-100. In order to further improve the performance of microwave components and adapt to higher and higher communication frequencies in the communication field, the requirements on the microwave dielectric material mainly include the following points: (1) high dielectric constant epsilonr(ii) a (2) A quality factor Qxf as high as possible; (3) near zero temperature coefficient of resonance frequencyf(ii) a (4) The selected material is cheap, non-toxic and environment-friendly. From the requirement of later development in the field of 5G-6G communication, the high dielectric constant microwave dielectric ceramic (epsilon)r90 ± 5) is suitable.
At present, in a microwave dielectric material system with a dielectric constant of 90 +/-5, a Ba-Ln-Ti tungsten bronze system is researched more, but the tungsten bronze system has the problem of a seesaw between a quality factor and a temperature coefficient: i.e. the higher the quality factor is achieved, the greater the degree to which the temperature coefficient deviates from the zero value. Therefore, how to improve the product characteristics of the high-dielectric-constant dielectric material under the precondition of ensuring the high dielectric constant is the technical problem to be solved by the invention, and the key point is to realize the coexistence of the high Q value and the adjustable frequency temperature coefficient.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a microwave dielectric ceramic for a high-dielectric-constant 5G waveguide, and a preparation method and application thereof, wherein the microwave dielectric ceramic has high quality factor and near-zero temperature coefficient of resonant frequency while ensuring high dielectric constant and lower sintering temperature, has excellent microwave dielectric property, is nontoxic and low in price of preparation raw materials, is simple in preparation process, and has wide application prospect in the field of 5G waveguide application.
In order to achieve the technical purpose and achieve the technical effect, the invention is realized by the following technical scheme:
a microwave dielectric ceramic for a high dielectric constant 5G waveguide is composed of the following oxide components in percentage by mole: 10 to 15 percent of BaO and TiO2 60%~70%、Sm2O3 5%~10%、Bi2O3 5%~10%、La2O35% to 10% and MnO2 0.5%~1%;
The microwave dielectric ceramic comprises a basic crystal phase and a reduced-sintering crystal phase, wherein the composition expression of the basic crystal phase is Ba6-3x(SmyLa1-y)8+2x(TizMn1-z)18O54The composition expression of the reduced-sintering crystalline phase is Bi4Ti3O12The molar percentage of the basic crystalline phase is 95-99%, and the molar percentage of the reduced-sintering crystalline phase is 1-5%; x, y, z in the composition expression of the base crystal phase respectively represent molar ratios, the values of which are determined by the molar percentages of the oxide components.
Furthermore, the dielectric constant of the microwave dielectric ceramic is 85-95, the Qxf value is more than 7000GHz, and the temperature coefficient of the resonant frequency is-5 ppm/DEG C.
The invention further provides a preparation method of the microwave dielectric ceramic for the high-dielectric-constant 5G waveguide, which comprises the following steps:
(1) according to the molar percentage ratio of BaCO3、TiO2、Sm2O3、La2O3、Bi2O3、MnO2Burdening, fully mixing, performing ball milling, drying and sieving after ball milling, and then putting into a corundum crucible for heat preservation and presintering to obtain a powder base material;
(2) fully ball-milling the powder base material obtained in the step (1), drying, granulating and sieving after ball-milling;
(3) and pressing and molding the sieved mixed powder, and finally sintering to obtain the microwave dielectric ceramic for the high-dielectric-constant 5G waveguide.
As the preferable technical scheme of the invention, the heat-preservation pre-sintering process in the step (1) is heat-preservation roasting at 1000-1100 ℃ for 3-5 hours.
As a preferable technical scheme of the invention, the sintering temperature in the step (3) is 1300-1350 ℃.
As a preferable technical scheme of the present invention, the granulation in the step (2) is to mix the dried powder with a polyvinyl alcohol aqueous solution, and then to prepare micron-sized spherical particles.
As a preferred technical scheme of the invention, in the step (3), the sieved mixed powder is pressed into a cylinder with the diameter of 10mm and the height of 6 mm.
The invention further provides application of the microwave dielectric ceramic for the high-dielectric-constant 5G waveguide in preparation of microwave devices.
In the above application, the microwave device is a filter or a resonator.
The invention further provides a microwave device which comprises the microwave dielectric ceramic for the high-dielectric-constant 5G waveguide.
Compared with the prior art, the invention has the following beneficial effects: the microwave dielectric ceramic of the invention is prepared from Ba6-3x(SmyLa1-y)8+2x(TizMn1-z)18O54Based on a base crystalline phase and with the best-matched reduced-sintering crystalline phase Bi4Ti3O12The ceramic material is filled among ceramic crystal grains, and the basic crystal phase and the reduced sintering crystal phase are matched with each other, so that a higher Q value can be obtained while the sintering temperature is reduced and a higher dielectric constant is ensured, and an adjustable resonant frequency temperature coefficient is realized. The microwave dielectric ceramic has the dielectric constant of 85-95, the Qxf value of more than 7000GHz, the temperature coefficient of resonant frequency of near zero, namely-5 ppm/DEG C, and good temperature stability. The microwave dielectric ceramic disclosed by the invention is excellent in microwave dielectric property, nontoxic and low in price of raw materials, simple in preparation process and wide in application prospect in the field of 5G waveguide application.
Detailed Description
The technical solutions in the present invention will be described clearly and completely with reference to specific embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a microwave dielectric ceramic for a high-dielectric-constant 5G waveguide, which consists of the following oxide components in percentage by mole: 10 to 15 percent of BaO and TiO2 60%~70%、Sm2O3 5%~10%、Bi2O3 5%~10%、La2O35% to 10% and MnO2 0.5%~1%;
The microwave dielectric ceramic comprises a basic crystal phase and a reduced-sintering crystal phase, wherein the composition expression of the basic crystal phase is Ba6-3x(SmyLa1-y)8+2x(TizMn1-z)18O54The composition expression of the reduced-sintering crystalline phase is Bi4Ti3O12The molar percentage of the basic crystalline phase is 95-99%, and the molar percentage of the reduced-sintering crystalline phase is 1-5%; x, y, z in the composition expression of the base crystal phase respectively represent molar ratios, the values of which are determined by the molar percentages of the oxide components.
The dielectric constant of the microwave dielectric ceramic is 85-95, the Qxf value is more than 7000GHz, and the temperature coefficient of the resonant frequency is-5 ppm/DEG C.
The invention further provides a preparation method of the microwave dielectric ceramic for the high-dielectric-constant 5G waveguide, which comprises the following steps:
(1) according to the molar percentage ratio of BaCO3、TiO2、Sm2O3、La2O3、Bi2O3、MnO2Burdening, fully mixing, performing ball milling, drying and sieving after ball milling, and then putting into a corundum crucible for heat preservation and presintering to obtain a powder base material;
(2) fully ball-milling the powder base material obtained in the step (1), drying, granulating and sieving after ball-milling;
(3) and pressing and molding the sieved mixed powder, and finally sintering to obtain the microwave dielectric ceramic for the high-dielectric-constant 5G waveguide.
The heat-preservation pre-sintering process in the step (1) of the method is heat-preservation roasting at 1000-1100 ℃ for 3-5 hours.
The sintering temperature in the step (3) of the method is 1300-1350 ℃.
The granulation in the step (2) of the method is to mix the dried powder with a polyvinyl alcohol aqueous solution and then prepare micron-sized spherical particles.
In the step (3) of the above method, the sieved mixed powder is pressed into a cylinder with a diameter of 10mm and a height of 6 mm.
The invention further provides application of the microwave dielectric ceramic for the high-dielectric-constant 5G waveguide in preparation of microwave devices. In this application, the microwave device is a filter or a resonator.
The invention further provides a microwave device which comprises the microwave dielectric ceramic for the high-dielectric-constant 5G waveguide.
The following examples further illustrate the invention but are not intended to limit the invention thereto.
Example 1
The composition expression of the microwave dielectric ceramic for the high dielectric constant 5G waveguide in mole percent of oxides in example 1 is as follows: 10% BaO-60% TiO2-10%Sm2O3-10%Bi2O3-9.5%La2O3-0.5%MnO2
The preparation method of the microwave dielectric ceramic for the high-dielectric-constant 5G waveguide in the embodiment 1 includes the following steps:
(1) according to the mole percentage of oxides in the composition expression to BaCO3、TiO2、Sm2O3、La2O3、Bi2O3、MnO2Proportioning, mixing, ball grinding, baking and passingSieving, and then placing the powder into a corundum crucible to be roasted for 3 hours at the temperature of 1000 ℃ to obtain a powder base material;
(2) fully ball-milling the powder base material obtained in the step (1), drying, granulating and sieving after ball-milling; wherein, the granulation process is to mix the dried powder with a polyvinyl alcohol aqueous solution and then prepare micron-sized spherical particles;
(3) and pressing the sieved mixed powder into a cylinder with the diameter of 10mm and the height of 6mm, and finally, carrying out heat preservation sintering at 1300 ℃ for 5h to obtain the microwave dielectric ceramic for the high-dielectric-constant 5G waveguide.
Example 2
The composition expression of the microwave dielectric ceramic for the high dielectric constant 5G waveguide in mole percent of oxides in example 2 is as follows: 10% BaO-70% TiO2-5%Sm2O3-9%Bi2O3-5%La2O3-1%MnO2
The preparation method of the microwave dielectric ceramic for the high-dielectric-constant 5G waveguide in example 2 includes the steps of:
(1) according to the mole percentage of oxides in the composition expression to BaCO3、TiO2、Sm2O3、La2O3、Bi2O3、MnO2Proportioning, fully mixing, performing ball milling, drying and sieving after ball milling, and then putting into a corundum crucible to perform heat preservation roasting for 3 hours at 1000 ℃ to obtain a powder base material;
(2) fully ball-milling the powder base material obtained in the step (1), drying, granulating and sieving after ball-milling; wherein, the granulation process is to mix the dried powder with a polyvinyl alcohol aqueous solution and then prepare micron-sized spherical particles;
(3) and pressing the sieved mixed powder into a cylinder with the diameter of 10mm and the height of 6mm, and finally, carrying out heat preservation sintering at 1300 ℃ for 5h to obtain the microwave dielectric ceramic for the high-dielectric-constant 5G waveguide.
Example 3
Mole percent of oxide of the microwave dielectric ceramic for high-permittivity 5G waveguide of example 3The composition expression is as follows: 15% BaO-60% TiO2-10%Sm2O3-9%Bi2O3-5%La2O3-1%MnO2
The preparation method of the microwave dielectric ceramic for a high-dielectric-constant 5G waveguide in example 3 includes the steps of:
(1) according to the mole percentage of oxides in the composition expression to BaCO3、TiO2、Sm2O3、La2O3、Bi2O3、MnO2Proportioning, fully mixing, performing ball milling, drying and sieving after ball milling, and then putting into a corundum crucible to perform heat preservation roasting for 3 hours at 1000 ℃ to obtain a powder base material;
(2) fully ball-milling the powder base material obtained in the step (1), drying, granulating and sieving after ball-milling; wherein, the granulation process is to mix the dried powder with a polyvinyl alcohol aqueous solution and then prepare micron-sized spherical particles;
(3) and pressing the sieved mixed powder into a cylinder with the diameter of 10mm and the height of 6mm, and finally, carrying out heat preservation sintering at the temperature of 1320 ℃ for 5 hours to obtain the microwave dielectric ceramic for the high-dielectric-constant 5G waveguide.
Example 4
The composition expression of the microwave dielectric ceramic for the high dielectric constant 5G waveguide in mole percent of oxides in example 4 is as follows: 14% BaO-65% TiO2-10%Sm2O3-5%Bi2O3-5%La2O3-1%MnO2
The preparation method of the microwave dielectric ceramic for a high-dielectric-constant 5G waveguide of example 4 includes the steps of:
(1) according to the mole percentage of oxides in the composition expression to BaCO3、TiO2、Sm2O3、La2O3、Bi2O3、MnO2Proportioning, fully mixing, performing ball milling, drying and sieving after ball milling, and then putting into a corundum crucible to perform heat preservation roasting for 3 hours at 1000 ℃ to obtain a powder base material;
(2) fully ball-milling the powder base material obtained in the step (1), drying, granulating and sieving after ball-milling; wherein, the granulation process is to mix the dried powder with a polyvinyl alcohol aqueous solution and then prepare micron-sized spherical particles;
(3) and pressing the sieved mixed powder into a cylinder with the diameter of 10mm and the height of 6mm, and finally, carrying out heat preservation sintering at the temperature of 1320 ℃ for 5 hours to obtain the microwave dielectric ceramic for the high-dielectric-constant 5G waveguide.
Example 5
The composition expression of the microwave dielectric ceramic for the high dielectric constant 5G waveguide in mole percent of oxides in example 5 is as follows: 14% BaO-70% TiO2-5%Sm2O3-5%Bi2O3-5%La2O3-1%MnO2
The preparation method of the microwave dielectric ceramic for a high-dielectric-constant 5G waveguide of example 5 includes the steps of:
(1) according to the mole percentage of oxides in the composition expression to BaCO3、TiO2、Sm2O3、La2O3、Bi2O3、MnO2Proportioning, fully mixing, performing ball milling, drying and sieving after ball milling, and then putting into a corundum crucible to perform heat preservation roasting for 3 hours at 1000 ℃ to obtain a powder base material;
(2) fully ball-milling the powder base material obtained in the step (1), drying, granulating and sieving after ball-milling; wherein, the granulation process is to mix the dried powder with a polyvinyl alcohol aqueous solution and then prepare micron-sized spherical particles;
(3) and pressing the sieved mixed powder into a cylinder with the diameter of 10mm and the height of 6mm, and finally, carrying out heat preservation sintering for 5 hours at the temperature of 1340 ℃ to obtain the microwave dielectric ceramic for the high-dielectric-constant 5G waveguide.
Comparative example 1
In the microwave dielectric ceramic of comparative example 1, the composition expression of mole percent of oxides is: 20% of BaO-65% of TiO2-5%Sm2O3-5%Bi2O3-4.5%La2O3-0.5%MnO2. The preparation method is the same as example 5, and the sintering temperature is 1340 ℃.
Comparative example 2
In the microwave dielectric ceramic of the comparative example 2, the composition expression of mole percent of oxides is as follows: 15% BaO-75% TiO2-3%Sm2O3-3%Bi2O3-3.5%La2O3-0.5%MnO2. The preparation method is the same as example 5, and the sintering temperature is 1340 ℃.
Comparative example 3
In the microwave dielectric ceramic of the comparative example 3, the composition expression of mole percent of oxides is as follows: 10% BaO-65% TiO2-15%Sm2O3-5%Bi2O3-4.5%La2O3-0.5%MnO2. The preparation method is the same as example 5, and the sintering temperature is 1340 ℃.
The microwave dielectric ceramics prepared in examples 1 to 5 and comparative examples 1 to 3 were subjected to the performance test, and the results of the performance test are shown in table 1. In Table 1, a represents the mole percentage of BaO and b represents TiO2C represents Sm2O3D represents Bi2O3E represents La2O3F represents MnO2Mole percent of (c).
TABLE 1 results of performance test of microwave dielectric ceramics of examples and comparative examples
Figure BDA0003421895570000101
As can be seen from table 1, compared with the microwave dielectric ceramics of comparative examples 1 to 3, the microwave dielectric ceramics of examples 1 to 5 of the present invention have higher quality factor and tunable temperature coefficient of oscillation frequency close to zero, better temperature stability, and more excellent comprehensive microwave dielectric properties while ensuring higher dielectric constant and lower sintering temperature.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims (10)

1. A microwave dielectric ceramic for a high dielectric constant 5G waveguide is characterized in that: the microwave dielectric ceramic is composed of the following oxide components in percentage by mole: 10 to 15 percent of BaO and TiO2 60%~70%、Sm2O35%~10%、Bi2O35%~10%、La2O35% to 10% and MnO2 0.5%~1%;
The microwave dielectric ceramic comprises a basic crystal phase and a reduced-sintering crystal phase, wherein the composition expression of the basic crystal phase is Ba6-3x(SmyLa1-y)8+2x(TizMn1-z)18O54The composition expression of the reduced-sintering crystalline phase is Bi4Ti3O12The molar percentage of the basic crystalline phase is 95-99%, and the molar percentage of the reduced-sintering crystalline phase is 1-5%; x, y, z in the composition expression of the base crystal phase respectively represent molar ratios, the values of which are determined by the molar percentages of the oxide components.
2. A microwave dielectric ceramic for a high dielectric constant 5G waveguide according to claim 1, wherein: the dielectric constant of the microwave dielectric ceramic is 85-95, the Qxf value is more than 7000GHz, and the temperature coefficient of the resonant frequency is-5 ppm/DEG C.
3. A method for preparing a microwave dielectric ceramic for a high dielectric constant 5G waveguide as claimed in claim 1 or 2, comprising the steps of:
(1) according to the molar percentage ratio of BaCO3、TiO2、Sm2O3、La2O3、Bi2O3、MnO2Proportioning, mixing, ball milling, drying, sieving, putting in corundum crucible, and presintering to obtain powder baseTimber;
(2) fully ball-milling the powder base material obtained in the step (1), drying, granulating and sieving after ball-milling;
(3) and pressing and molding the sieved mixed powder, and finally sintering to obtain the microwave dielectric ceramic for the high-dielectric-constant 5G waveguide.
4. The method for preparing microwave dielectric ceramic for a high-dielectric-constant 5G waveguide according to claim 3, wherein the heat-preservation pre-sintering process in the step (1) is heat-preservation roasting at 1000-1100 ℃ for 3-5 hours.
5. The method for preparing a microwave dielectric ceramic for a high-k 5G waveguide according to claim 3, wherein the sintering temperature in the step (3) is 1300-1350 ℃.
6. The method according to claim 3, wherein the granulating in step (2) is carried out by mixing the dried powder with an aqueous solution of polyvinyl alcohol and then making micron-sized spherical particles.
7. The method according to claim 3, wherein in the step (3), the sieved powder mixture is pressed into a cylinder having a diameter of 10mm and a height of 6 mm.
8. Use of the microwave dielectric ceramic for high dielectric constant 5G waveguides as claimed in claim 1 or 2 in the preparation of microwave devices.
9. Use according to claim 8, wherein the microwave device is a filter or a resonator.
10. A microwave device comprising the microwave dielectric ceramic for a high dielectric constant 5G waveguide according to claim 1 or 2.
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CN116102347A (en) * 2022-12-23 2023-05-12 无锡鑫圣慧龙纳米陶瓷技术有限公司 High-dielectric-constant microwave dielectric ceramic for MLCC (multi-layer ceramic) and preparation method thereof

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