CN114180956B - 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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CN114180956B
CN114180956B CN202111565715.8A CN202111565715A CN114180956B CN 114180956 B CN114180956 B CN 114180956B CN 202111565715 A CN202111565715 A CN 202111565715A CN 114180956 B CN114180956 B CN 114180956B
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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, and a preparation method and application thereof; the microwave dielectric ceramic consists of the following oxide components in mole percent: baO 10-15% and TiO 2 60%~70%、Sm 2 O 3 5%~10%、Bi 2 O 3 5%~10%、La 2 O 3 5% -10% and MnO 2 0.5 to 1 percent; the microwave dielectric ceramic comprises a basic crystal phase and a burn-down crystal phase, wherein the composition expression of the basic crystal phase is Ba 6‑3x (Sm y La 1‑y ) 8+2x (Ti z Mn 1‑z ) 18 O 54 The composition expression of the burn-down crystal phase is Bi 4 Ti 3 O 12 . The microwave dielectric ceramic has the advantages of high quality factor and near-zero resonant frequency temperature coefficient while ensuring high dielectric constant, no toxicity and low price of the preparation raw materials, simple preparation process and wide application prospect in the field of 5G waveguides.

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 a microwave dielectric ceramic 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 novel functional ceramic material, and serve as dielectric materials to perform one or more functions in microwave frequency band circuits. Microwave dielectric properties are determining factors for microwave dielectric ceramic applications, while the relative dielectric constant ε r Quality factor Q x f and resonant frequency temperature coefficient tau f Is three main parameters of microwave dielectric properties.
With the rapid development of the 5G mobile communication system industry, microwave components, particularly filters and resonators, are receiving a great deal of attention from researchers as important devices in communication equipment. In order to meet the use requirements of the electronic equipment with the antenna, the most suitable microwave dielectric ceramic material is a microwave dielectric material distributed between dielectric constants of 60-100. In order to further improve the performance of microwave components and adapt to higher and higher communication frequency in the communication field, the method is used for microwaveThe dielectric material requirements mainly include the following: (1) High dielectric constant epsilon r The method comprises the steps of carrying out a first treatment on the surface of the (2) a quality factor Q x f as high as possible; (3) Near zero resonant frequency temperature coefficient τ f The method comprises the steps of carrying out a first treatment on the surface of the And (4) the selected materials are low in price, nontoxic and environment-friendly. From the later development demands of the current 5G-6G communication field, the microwave dielectric ceramic (epsilon) with high dielectric constant r =90±5) is suitable.
Currently, in a microwave dielectric material system with a dielectric constant of 90+/-5, a Ba-Ln-Ti tungsten bronze system is relatively more researched, 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 important point of realizing the coexistence of the high Q value and the adjustable frequency temperature coefficient, which is the technical problem to be solved by the invention.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide the microwave dielectric ceramic for the high-dielectric-constant 5G waveguide, and the preparation method and the application thereof, wherein the microwave dielectric ceramic has higher quality factor and near-zero resonant frequency temperature coefficient while guaranteeing high dielectric constant and lower sintering temperature, has excellent microwave dielectric property, is nontoxic in preparation raw materials, low in price and simple in preparation process, and has wide application prospect in the application field of the 5G waveguide.
In order to achieve the technical purpose and the technical effect, the invention is realized by the following technical scheme:
the microwave dielectric ceramic for the high-dielectric-constant 5G waveguide consists of the following oxide components in percentage by mole: baO 10-15% and TiO 2 60%~70%、Sm 2 O 3 5%~10%、Bi 2 O 3 5%~10%、La 2 O 3 5% -10% and MnO 2 0.5%~1%;
The microwave dielectric ceramic comprises a basic crystal phase and a burn-down crystal phase, wherein the composition expression of the basic crystal phase is Ba 6-3x (Sm y La 1-y ) 8+2x (Ti z Mn 1-z ) 18 O 54 The composition expression of the burn-down crystal phase is Bi 4 Ti 3 O 12 The mol percent of the basic crystalline phase is 95-99%, and the mol percent of the burn-down crystalline phase is 1-5%; x, y, z in the compositional expression of the base crystalline phase represent molar ratios, respectively, the values of which are determined by the mole percentages of the oxide component.
Further, the dielectric constant of the microwave dielectric ceramic is 85-95, the Q multiplied by f value is more than 7000GHz, and the temperature coefficient of the resonance 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) BaCO is calculated according to mole percent 3 、TiO 2 、Sm 2 O 3 、La 2 O3、Bi 2 O 3 、MnO 2 Mixing materials, ball milling, drying and sieving after ball milling, and then placing the materials into a corundum crucible for heat preservation and presintering to obtain a powder substrate;
(2) Fully ball-milling the powder substrate obtained in the step (1), drying after ball milling, granulating and sieving;
(3) And (3) compacting the sieved mixed powder, and finally sintering to obtain the microwave dielectric ceramic for the high-dielectric-constant 5G waveguide.
As a preferable technical scheme of the invention, the heat preservation presintering process in the step (1) is to heat preservation roasting for 3-5 hours at 1000-1100 ℃.
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 invention, the granulation in the step (2) is to mix the dried powder with a polyvinyl alcohol aqueous solution and then prepare micron-sized spherical particles.
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 preparing a microwave device.
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 uses Ba 6-3x (Sm y La 1-y ) 8+2x (Ti z Mn 1-z ) 18 O 54 Is a base crystal phase and takes the best matching burn-down crystal phase Bi 4 Ti 3 O 12 The ceramic material is filled among ceramic grains, and the basic crystal phase and the burn-down crystal phase are mutually matched, so that the sintering temperature can be reduced, the higher dielectric constant is ensured, the higher Q value is obtained, and the adjustable resonant frequency temperature coefficient is realized. The dielectric constant of the microwave dielectric ceramic is 85-95, the Q multiplied by f value is more than 7000GHz, the temperature coefficient of the resonant frequency is near zero and is-5 ppm/DEG C, and the temperature stability is good. The microwave dielectric ceramic has excellent microwave dielectric property, nontoxic raw materials, low price and simple preparation process, and has wide application prospect in the field of 5G waveguide application.
Detailed Description
The following description of the embodiments of the present invention will be made more apparent and fully by reference to the accompanying drawings, in which it is shown, by way of illustration, only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a microwave dielectric ceramic for a high dielectric constant 5G waveguide, which comprises the following oxide components in percentage by mole: baO 10-15% and TiO 2 60%~70%、Sm 2 O 3 5%~10%、Bi 2 O 3 5%~10%、La 2 O 3 5% -10% and MnO 2 0.5%~1%;
The microwave dielectric ceramic comprises a basic crystal phase and a burn-down crystal phase, wherein the composition expression of the basic crystal phase is Ba 6-3x (Sm y La 1-y ) 8+2x (Ti z Mn 1-z ) 18 O 54 The composition expression of the burn-down crystal phase is Bi 4 Ti 3 O 12 The mol percent of the basic crystalline phase is 95-99%, and the mol percent of the burn-down crystalline phase is 1-5%; x, y, z in the compositional expression of the base crystalline phase represent molar ratios, respectively, the values of which are determined by the mole percentages of the oxide component.
The dielectric constant of the microwave dielectric ceramic is 85-95, the Q multiplied by f value is more than 7000GHz, and the temperature coefficient of 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) BaCO is calculated according to mole percent 3 、TiO 2 、Sm 2 O 3 、La 2 O3、Bi 2 O 3 、MnO 2 Mixing materials, ball milling, drying and sieving after ball milling, and then placing the materials into a corundum crucible for heat preservation and presintering to obtain a powder substrate;
(2) Fully ball-milling the powder substrate obtained in the step (1), drying after ball milling, granulating and sieving;
(3) And (3) compacting the sieved mixed powder, and finally sintering to obtain the microwave dielectric ceramic for the high-dielectric-constant 5G waveguide.
The heat preservation presintering process in the step (1) of the method is to heat preservation roasting for 3 to 5 hours at the temperature of 1000 to 1100 ℃.
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 the polyvinyl alcohol aqueous solution and then prepare the micron-sized spherical particles.
In 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 preparing a microwave device. In this application, the microwave device is a filter or resonator.
The invention further provides a microwave device which comprises the microwave dielectric ceramic for the high-dielectric-constant 5G waveguide.
The following examples will illustrate the invention further, but are not intended to limit it.
Example 1
The oxide mole percent composition expression of the microwave dielectric ceramic for the high dielectric constant 5G waveguide of this example 1 is: 10% BaO-60% TiO 2 -10%Sm 2 O 3 -10%Bi 2 O 3 -9.5%La 2 O 3 -0.5%MnO 2
The preparation method of the microwave dielectric ceramic for the high-dielectric-constant 5G waveguide of the embodiment 1 comprises the following steps:
(1) BaCO is calculated as mole percent of oxides in the compositional expression 3 、TiO 2 、Sm 2 O 3 、La 2 O3、Bi 2 O 3 、MnO 2 Proportioning, fully mixing, performing ball milling, drying and sieving after ball milling, and then placing the mixture into a corundum crucible for heat preservation and roasting for 3 hours at 1000 ℃ to obtain a powder substrate;
(2) Fully ball-milling the powder substrate obtained in the step (1), drying after ball milling, granulating and sieving; the granulating process is to mix the dried powder with polyvinyl alcohol water 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, preserving heat and sintering for 5 hours at the temperature of 1300 ℃ to obtain the microwave dielectric ceramic for the high dielectric constant 5G waveguide.
Example 2
The oxide mole percent composition expression of the microwave dielectric ceramic for high dielectric constant 5G waveguide of this example 2 is: 10% BaO-70% TiO 2 -5%Sm 2 O 3 -9%Bi 2 O 3 -5%La 2 O 3 -1%MnO 2
The preparation method of the microwave dielectric ceramic for the high-dielectric-constant 5G waveguide of the embodiment 2 comprises the following steps:
(1) BaCO is calculated as mole percent of oxides in the compositional expression 3 、TiO 2 、Sm 2 O 3 、La 2 O3、Bi 2 O 3 、MnO 2 Proportioning, fully mixing, performing ball milling, drying and sieving after ball milling, and then placing the mixture into a corundum crucible for heat preservation and roasting for 3 hours at 1000 ℃ to obtain a powder substrate;
(2) Fully ball-milling the powder substrate obtained in the step (1), drying after ball milling, granulating and sieving; the granulating process is to mix the dried powder with polyvinyl alcohol water 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, preserving heat and sintering for 5 hours at the temperature of 1300 ℃ to obtain the microwave dielectric ceramic for the high dielectric constant 5G waveguide.
Example 3
The oxide mole percent composition expression of the microwave dielectric ceramic for high dielectric constant 5G waveguide of this example 3 is: 15% BaO-60% TiO 2 -10%Sm 2 O 3 -9%Bi 2 O 3 -5%La 2 O 3 -1%MnO 2
The preparation method of the microwave dielectric ceramic for the high-dielectric-constant 5G waveguide of the embodiment 3 comprises the following steps:
(1) BaCO is calculated as mole percent of oxides in the compositional expression 3 、TiO 2 、Sm 2 O 3 、La 2 O3、Bi 2 O 3 、MnO 2 Proportioning, fully mixing, performing ball milling, drying and sieving after ball milling, and then placing the mixture into a corundum crucible for heat preservation and roasting for 3 hours at 1000 ℃ to obtain a powder substrate;
(2) Fully ball-milling the powder substrate obtained in the step (1), drying after ball milling, granulating and sieving; the granulating process is to mix the dried powder with polyvinyl alcohol water 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, preserving heat and sintering for 5 hours at the temperature of 1320 ℃ to obtain the microwave dielectric ceramic for the high dielectric constant 5G waveguide.
Example 4
The oxide mole percent composition expression of the microwave dielectric ceramic for high dielectric constant 5G waveguide of this example 4 is: 14% BaO-65% TiO 2 -10%Sm 2 O 3 -5%Bi 2 O 3 -5%La 2 O 3 -1%MnO 2
The preparation method of the microwave dielectric ceramic for the high-dielectric-constant 5G waveguide of the embodiment 4 comprises the following steps:
(1) BaCO is calculated as mole percent of oxides in the compositional expression 3 、TiO 2 、Sm 2 O 3 、La 2 O3、Bi 2 O 3 、MnO 2 Proportioning, fully mixing, performing ball milling, drying and sieving after ball milling, and then placing the mixture into a corundum crucible for heat preservation and roasting for 3 hours at 1000 ℃ to obtain a powder substrate;
(2) Fully ball-milling the powder substrate obtained in the step (1), drying after ball milling, granulating and sieving; the granulating process is to mix the dried powder with polyvinyl alcohol water 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, preserving heat and sintering for 5 hours at the temperature of 1320 ℃ to obtain the microwave dielectric ceramic for the high dielectric constant 5G waveguide.
Example 5
The oxide mole percent composition expression of the microwave dielectric ceramic for high dielectric constant 5G waveguide of this example 5 is: 14% BaO-70% TiO 2 -5%Sm 2 O 3 -5%Bi 2 O 3 -5%La 2 O 3 -1%MnO 2
The preparation method of the microwave dielectric ceramic for the high-dielectric-constant 5G waveguide of the embodiment 5 comprises the following steps:
(1) BaCO is calculated as mole percent of oxides in the compositional expression 3 、TiO 2 、Sm 2 O 3 、La 2 O3、Bi 2 O 3 、MnO 2 Proportioning, fully mixing, performing ball milling, drying and sieving after ball milling, and then placing the mixture into a corundum crucible for heat preservation and roasting for 3 hours at 1000 ℃ to obtain a powder substrate;
(2) Fully ball-milling the powder substrate obtained in the step (1), drying after ball milling, granulating and sieving; the granulating process is to mix the dried powder with polyvinyl alcohol water 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, preserving heat and 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 oxide mole percent composition expression thereof is: 20% BaO-65% TiO 2 -5%Sm 2 O 3 -5%Bi 2 O 3 -4.5%La 2 O 3 -0.5%MnO 2 . The preparation method is the same as in example 5, and the sintering temperature is 1340 ℃.
Comparative example 2
In the microwave dielectric ceramic of comparative example 2, the oxide mole percent composition expression thereof is: 15% BaO-75% TiO 2 -3%Sm 2 O 3 -3%Bi 2 O 3 -3.5%La 2 O 3 -0.5%MnO 2 . The preparation method is the same as in example 5, and the sintering temperature is 1340 ℃.
Comparative example 3
In the microwave dielectric ceramic of comparative example 3, the oxide mole percent composition expression thereof is: 10% BaO-65% TiO 2 -15%Sm 2 O 3 -5%Bi 2 O 3 -4.5%La 2 O 3 -0.5%MnO 2 . The preparation method is the same as in 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 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 TiO 2 C represents Sm 2 O 3 D represents Bi 2 O 3 E represents La 2 O 3 In mol percent, f represents MnO 2 Is a mole percent of (c).
Table 1 results of performance testing of microwave dielectric ceramics of examples and comparative examples
As can be seen from Table 1, compared with the microwave dielectric ceramics of comparative examples 1-3, the microwave dielectric ceramics of examples 1-5 of the present invention have higher quality factor and near-zero tunable vibration frequency temperature coefficient while ensuring higher dielectric constant and lower sintering temperature, and have better temperature stability and better comprehensive microwave dielectric properties.
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes or direct or indirect application in other related arts 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 consists of the following oxide components in mole percent: baO 10-15% and TiO 2 60%~70%、Sm 2 O 3 5%~10%、Bi 2 O 3 5%~10%、La 2 O 3 5% -10% and MnO 2 0.5%~1%;
The microwave dielectric ceramic comprises a basic crystal phase and a burn-down crystal phase, wherein the composition expression of the basic crystal phase is Ba 6-3x (Sm y La 1-y ) 8+2x (Ti z Mn 1-z ) 18 O 54 The composition expression of the burn-down crystal phase is Bi 4 Ti 3 O 12 The mol percent of the basic crystalline phase is 95-99%, and the mol percent of the burn-down crystalline phase is 1-5%; x, y, z in the compositional expression of the base crystalline phase represent molar ratios, respectively, the values of which are determined by the mole percentages of the oxide component.
2. The microwave dielectric ceramic for high dielectric constant 5G waveguides of claim 1, wherein: the dielectric constant of the microwave dielectric ceramic is 85-95, the Q multiplied by f value is more than 7000GHz, and the temperature coefficient of resonant frequency is-5 ppm/DEG C.
3. A method for preparing the microwave dielectric ceramic for high dielectric constant 5G waveguides according to claim 1 or 2, comprising the steps of:
(1) BaCO is calculated according to mole percent 3 、TiO 2 、Sm 2 O 3 、La 2 O3、Bi 2 O 3 、MnO 2 Mixing materials, ball milling, drying and sieving after ball milling, and then placing the materials into a corundum crucible for heat preservation and presintering to obtain a powder substrate;
(2) Fully ball-milling the powder substrate obtained in the step (1), drying after ball milling, granulating and sieving;
(3) And (3) compacting 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 a microwave dielectric ceramic for a high dielectric constant 5G waveguide according to claim 3, wherein the thermal insulation pre-sintering process in the step (1) is thermal insulation roasting for 3-5 hours at 1000-1100 ℃.
5. The method for producing a microwave dielectric ceramic for high-permittivity 5G waveguides according to claim 3, wherein the sintering temperature in step (3) is 1300 to 1350 ℃.
6. The method for preparing microwave dielectric ceramic for high dielectric constant 5G waveguide according to claim 3, wherein the granulating in the step (2) is to mix the dried powder with polyvinyl alcohol aqueous solution and then prepare micron-sized spherical particles.
7. The method for producing a microwave dielectric ceramic for high-permittivity 5G waveguides according to claim 3, wherein in step (3), the sieved mixed powder is pressed into a cylinder having a diameter of 10mm and a height of 6 mm.
8. Use of a microwave dielectric ceramic for high dielectric constant 5G waveguides according to claim 1 or 2 in the manufacture of a microwave device.
9. The 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 high-k 5G waveguide according to claim 1 or 2.
CN202111565715.8A 2021-12-20 2021-12-20 Microwave dielectric ceramic for high-dielectric-constant 5G waveguide and preparation method and application thereof Active CN114180956B (en)

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