CN114477984A - Microwave dielectric ceramic material and preparation method thereof - Google Patents
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Abstract
The application provides a microwave dielectric ceramic material and a preparation method thereof, wherein the microwave dielectric ceramic material comprises the following components in percentage by mass: 33-38% CaO, 12-14% MgO, 2-3% ZnO, 24-43% SiO2And 3 to 28% GeO2. The application provides Zn for microwave dielectric ceramic material2+Partially replace CaMgSi2O6Mg in (1)2+Formation of CaMg1‑xZnxSi2O6Solid solution, which improves the microwave dielectric property of the ceramic material; additionally using Ge4+Ionic partial substitution of CaMg1‑xZnxSi2O6Si in (1)4+The total ionic polarizability of the ceramic system is increased, the intrinsic loss of the ceramic material is reduced, and the dielectric constant of the microwave dielectric ceramic is 7.8-8.2; the Qxf value is 137000-200000 GHz; the temperature coefficient of the resonance frequency is-53 to-75 ppm/DEG C.
Description
Technical Field
The application relates to the field of electronic functional materials and devices, in particular to a microwave dielectric ceramic material and a preparation method thereof.
Background
The microwave is an electromagnetic wave having a frequency range of 300MHz to 300GHz, and includes a decimetric wave, a centimeter wave, and a millimeter wave. The microwave has a wide frequency band under a certain relative bandwidth, has larger information capacity and higher transmission rate, and is widely applied to mobile communication, satellite communication and radar systems. Microwave dielectric ceramics are key materials for human beings to utilize microwaves. The rapid development of modern mobile communication technology has put higher demands on communication equipment, and miniaturization, high frequency and the like have become development directions of communication equipment, which require that microwave dielectric ceramics have the characteristics of low dielectric constant and low loss and can have adjustability in a certain dielectric constant range.
CaMgSi2O6Is a common low-dielectric silicate ceramic system, and compared with other orthosilicate systems, has the advantages of lower sintering temperature and easy doping modification, and has the disadvantage of higher loss. How to reduce CaMgSi2O6The loss of ceramic systems is a research goal of many researchers, but none of the previous attempts have led to the production of CaMgSi2O6The Q multiplied by f value of the ceramic system reaches more than 130000 GHz.
Disclosure of Invention
The application provides a microwave dielectric ceramic material and a preparation method thereof, and aims to solve the problem of CaMgSi2O6The microwave dielectric ceramic of the system has high loss.
On one hand, the embodiment of the application provides a microwave dielectric ceramic material, which comprises the following components in percentage by mass: 33-38% CaO, 12-14% MgO, 2-3% ZnO, 24-43% SiO2And 3 to 28% GeO2The dielectric constant of the microwave dielectric ceramic is 7.8-8.2; the Qxf value is 137000-200000 GHz; the temperature coefficient of the resonance frequency is-53 to-75 ppm/DEG C.
On the other hand, the embodiment of the application provides a preparation method of a microwave dielectric ceramic material, which comprises the following steps:
(1) weighing raw material powder according to a ratio, and performing first ball milling to obtain a mixture;
(2) carrying out primary drying, screening and presintering treatment on the mixture to obtain a presintering material;
(3) carrying out secondary ball milling, secondary drying, granulation and dry pressing molding on the pre-sintered material to obtain a green body;
(4) and sintering the green body to obtain the microwave dielectric ceramic material.
Preferably, the raw material powder in step (1) includes calcium carbonate, magnesium oxide, zinc oxide, silicon dioxide and germanium dioxide powder.
Preferably, the rotation speed of the first ball milling in the step (1) is 250-350 r/min, and the time is 4-8 hours.
Preferably, the ball milling medium for the first ball milling in the step (1) is alcohol, and the ball-to-material ratio is (8-12): 1.
Preferably, the temperature of the pre-sintering treatment in the step (2) is 1050-1150 ℃ and the time is 4-8 hours.
Preferably, the granulating in the step (3) includes adding an adhesive to the dried pre-sintered material after the second drying, and mixing to prepare the dried pre-sintered material into particles with an average particle size of 0.1-0.5 mm.
Preferably, the pressure of the dry pressing in the step (3) is 100 to 200 MPa.
Preferably, the step (3) further comprises a rubber discharge treatment after the dry pressing treatment, wherein the rubber discharge temperature is 550-650 ℃, and the time is 4-8 hours.
Preferably, the sintering treatment temperature in the step (4) is 1150-1250 ℃ and the time is 4-8 hours.
The invention provides Zn for microwave dielectric ceramic material2+Partially substitute CaMgSi2O6Mg in (1)2+Formation of CaMg1-xZnxSi2O6Solid solution with Zn2+The content is increased, the density of the ceramic is improved, and the porosity is reduced, so that the microwave dielectric property of the ceramic material is directly improved; in addition, with Ge4+Ionic partial substitution of CaMg1-xZnxSi2O6Si in (1)4+The total ionic polarizability of a ceramic system is increased, the intrinsic loss of the ceramic material is reduced, the dielectric constant of the ceramic material is changed within 7.8-8.2, and the ceramic material has a higher Q x f value which can be up to 200000GHz maximally. The microwave dielectric ceramic materialThe preparation process is simple and is expected to be applied to the manufacture of microwave devices such as microwave integrated circuit substrates, resonators, electronic product packaging and the like.
Drawings
Features, advantages and technical effects of exemplary embodiments of the present application will be described below with reference to the accompanying drawings.
FIG. 1 is a surface microtopography of a microwave dielectric ceramic material of example 1;
FIG. 2 is an X-ray diffraction (XRD) spectrum of the microwave dielectric ceramic material of example 1.
Detailed Description
In order to make the objects, technical solutions and advantageous technical effects of the present invention more clear, the present invention is further described in detail with reference to the following embodiments. It should be understood that the embodiments described in this specification are only for the purpose of explaining the present invention and are not intended to limit the present invention.
For the sake of brevity, only some numerical ranges are explicitly disclosed herein. However, any lower limit may be combined with any upper limit to form ranges not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and similarly any upper limit may be combined with any other upper limit to form a range not explicitly recited. Also, although not explicitly recited, each point or individual value between endpoints of a range is encompassed within the range. Thus, each point or individual value can form a range not explicitly recited as its own lower or upper limit in combination with any other point or individual value or in combination with other lower or upper limits.
In the description herein, it is to be noted that, unless otherwise specified, "above" and "below" are inclusive, and "a plurality" of "one or more" means two or more.
The above summary of the present invention is not intended to describe each disclosed embodiment or every implementation of the present invention. The following description more particularly exemplifies illustrative embodiments. At various points throughout this application, guidance is provided through a list of embodiments that can be used in various combinations. In various embodiments, the lists are provided as representative groups and should not be construed as exhaustive.
Microwave dielectric ceramic material
The embodiment of the first aspect of the invention provides a microwave dielectric ceramic material, which comprises the following components in percentage by mass: 33-38% CaO, 12-14% MgO, 2-3% ZnO, 24-43% SiO2And 3 to 28% GeO2The dielectric constant of the microwave dielectric ceramic is 7.8-8.2; the Qxf value is 137000-200000 GHz; the temperature coefficient of the resonance frequency is-53 to-75 ppm/DEG C.
According to the examples of the present application, in CaMgSi2O62-3% of ZnO is doped in the ceramic material to form a solid solution, so that the sintering temperature of the ceramic material is reduced by 50-150 ℃, and the Qxf value of the ceramic material is improved; when ZnO is doped in an amount exceeding 3%, a second phase is formed, which lowers the Q × f value of the ceramic material and increases the loss of the material. In CaMgSi doped with 2-3% of ZnO2O63-28% of GeO is doped in the ceramic2Solid solution can be formed, the intrinsic loss of the ceramic material is reduced, and the Q multiplied by f value of the ceramic material is further improved; if the doping exceeds 28% GeO2A second phase is generated, resulting in a decrease in the Q × f value of the ceramic material and an increase in the loss of the material.
In order to comprehensively improve CaMgSi2O6The Q multiplied by f value of the microwave dielectric ceramic material system and the mass percentage of CaO are selected to be 33-38%, for example, 33%, 34%, 36%, 37% or 38%.
In order to comprehensively improve CaMgSi2O6The Q multiplied by f value of the microwave dielectric ceramic material system and the weight percentage of MgO are selected to be 12-14%, for example, the weight percentage is 12%, 13% or 14%.
In order to comprehensively improve CaMgSi2O6Q multiplied by f value, SiO of system microwave dielectric ceramic material2The content of (b) is selected from 24 to 43% by mass, for example, 24%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 43% by mass or the like.
In order to comprehensively improve CaMgSi2O6The Q multiplied by f value of the microwave dielectric ceramic material system and the mass percentage of ZnO are selected to be 2-3%, for example, the mass percentage is 2%, 3% or 4%.
In order to comprehensively improve CaMgSi2O6Q multiplied by f value, GeO of system microwave dielectric ceramic material2The content of (b) is selected from 3 to 28% by mass, for example, 3%, 5%, 10%, 15%, 20%, 25%, 26%, 28% by mass or the like.
The invention provides Zn for microwave dielectric ceramic material2+Partially replace CaMgSi2O6Mg in (1)2+Formation of CaMg1-xZnxSi2O6Solid solution with Zn2+The content is increased, the density of the ceramic is improved, and the porosity is reduced, so that the microwave dielectric property of the ceramic material is directly improved; in addition, with Ge4+Ionic partial substitution of CaMg1-xZnxSi2O6Si in (1)4+The total ionic polarizability of the ceramic system is increased, the intrinsic loss of the ceramic material is reduced, the dielectric constant of the ceramic material is changed within 7.8-8.2, and the Qxf value is 137000-200000 GHz.
Preparation method of microwave dielectric ceramic material
The embodiment of the second aspect of the invention provides a preparation method of a microwave dielectric ceramic material, which comprises the following steps:
(1) weighing raw material powder according to a ratio, and performing first ball milling to obtain a mixture;
(2) carrying out primary drying, screening and presintering treatment on the mixture to obtain a presintering material;
(3) carrying out secondary ball milling, secondary drying, granulation and dry pressing forming treatment on the pre-sintered material to obtain a green body;
(4) and sintering the green body to obtain the microwave dielectric ceramic material.
In an embodiment of the present application, the raw material powder in step (1) includes calcium carbonate, magnesium oxide, zinc oxide, silicon dioxide, and germanium dioxide powder. The raw material powder can be uniformly mixed by the first ball milling.
In the embodiment of the application, the rotation speed of the first ball milling in the step (1) is 250-350 r/min, and the time is 4-8 hours. The first ball milling may be planetary ball milling, for example, at a speed of 250 rpm, 280 rpm, 300 rpm, 320 rpm, or 350 rpm.
The ball milling medium of the first ball milling is alcohol, and the ball-to-material ratio is (8-12): 1. For example, the ball to feed ratio may be 8:1, 9:1, 10:1, 11:1, or 12: 1.
In the ball milling process, the impact force generated when the zirconium balls do centrifugal motion and the friction force between the zirconium balls and the inner wall of the ball milling tank are utilized to crush the raw materials to achieve the effect of refining the raw materials, alcohol is added as a ball milling medium, and a mixture is obtained after ball milling.
In some embodiments, the mixture is dried and sieved, and then is subjected to pre-sintering treatment, wherein the pre-sintering temperature is 1050-1150 ℃ and the pre-sintering time is 4-8 hours. For example, the pre-firing temperature may be 1050 ℃, 1080 ℃, 1100 ℃, 1120 ℃, or 1150 ℃; the pre-firing time may be 4 hours, 5 hours, 6 hours, 7 hours, or 8 hours.
A series of physical and chemical reactions occur in the pre-sintering process to synthesize the required crystal form and phase, the pre-sintering can also remove internal stress in the mixture to cause volume shrinkage, and partial impurities can be removed at high temperature, so that the purity of the mixture is improved.
According to the embodiment of the application, after the pre-sintering, the pre-sintering material is subjected to secondary ball milling (which can be planetary ball milling), so that the particle size of the pre-sintering material is further reduced, and the particle distribution is more uniform.
According to the embodiment of the application, the pre-sintered material after the second ball milling is dried and granulated, so that the flowability of the material can be improved after granulation, and the subsequent dry pressing molding is facilitated.
In an embodiment of the application, the granulating in the step (3) includes adding an adhesive to the dried pre-sintered material after the second drying, and mixing to prepare the dried pre-sintered material into particles with an average particle size of 0.1-0.5 mm.
In some embodiments, the adhesive may be selected from an aqueous solution of polyvinyl alcohol at a concentration of 5 wt%.
In the embodiment of the application, the pressure of the dry pressing in the step (3) is 100 to 200 MPa, and the pressure applying mode is axial pressure. For example, the pressure may be 100 megapascals, 120 megapascals, 150 megapascals, 180 megapascals, or 200 megapascals. After the pressure dry pressing molding, the pre-sintering material particles become compact green bodies.
In some embodiments, the dry-pressing process further comprises a glue-removing process, wherein the glue-removing process is used for removing the adhesive added in the granulation process. The glue discharging temperature is 550-650 ℃, and the time is 4-8 hours. For example, the degumming temperature is 550 ℃, 580 ℃, 600 ℃, 620 ℃ or 650 ℃; the gel removal time may be 4 hours, 5 hours, 6 hours, 7 hours, or 8 hours.
In the embodiment of the application, the green body is sintered at 1150-1250 ℃ for 4-8 hours. For example, the temperature of the sintering process may be 1150 ℃, 1180 ℃, 1200 ℃, 1220 ℃ or 1250 ℃; the sintering treatment time may be 4 hours, 5 hours, 6 hours, 7 hours, or 8 hours. In the sintering process, crystal grains fully grow, the size of the air holes is reduced, the porosity is reduced, the volume is shrunk, and the density is improved.
Examples
Example 1
(1) According to mass fraction 37% CaO, 14% MgO, 3% ZnO, 42% SiO2And 3% GeO2Weighing calcium carbonate, magnesium oxide, zinc oxide, silicon dioxide and germanium dioxide, adding alcohol with proper content, and carrying out planetary ball milling for 4 hours;
(2) drying the slurry, sieving, and presintering at 1100 deg.C for 4 hr;
(3) and ball-milling the obtained powder for 4 hours, drying, sieving, adding a proper amount of polyvinyl alcohol (PVA) aqueous solution, grinding, granulating, and performing dry pressing and molding.
(4) Finally, the green body is degummed for 4 hours at 600 ℃, and then sintered for 4 hours at 1200 ℃, so as to obtain the ceramic material with the required chemical component ratio.
As shown in FIG. 1, the surface morphology of the SEM of the ceramic shows that the density of the ceramic is high, the number of pores is small, and the volume density is 3.4g/cm3The average crystal grain size was 1.5. mu.m. The XRD pattern of the ceramic is shown in fig. 2, and no significant second phase is present in the ceramic. The dielectric constant measured by a network analyzer was 7.8, the Qxf value was 200000GHz, and the temperature coefficient of the resonance frequency was-53 ppm/deg.C.
Example 2
(1) According to mass fraction 37% CaO, 13% MgO, 3% ZnO, 39% SiO2And 8% GeO2Weighing calcium carbonate, magnesium oxide, zinc oxide, silicon dioxide and germanium dioxide, adding alcohol with proper content, and carrying out planetary ball milling for 4 hours;
(2) drying the slurry, sieving, and presintering at 1100 deg.C for 4 hr;
(3) and ball-milling the obtained powder for 4 hours, drying, sieving, adding a proper amount of polyvinyl alcohol (PVA) aqueous solution, grinding, granulating, and performing dry pressing and molding.
(4) Finally, the green body is degummed for 4 hours at 600 ℃, and then sintered for 4 hours at 1200 ℃, so as to obtain the ceramic material with the required chemical component ratio.
The bulk density of the ceramic was 3.4g/cm3. The dielectric constant was 7.9, the Q x f value was 167600GHz, and the temperature coefficient of the resonance frequency was-55 ppm/deg.C as measured by a network analyzer.
Example 3
(1) According to mass fraction of 36% CaO, 13% MgO, 2% ZnO, 36% SiO2And 13% GeO2Weighing calcium carbonate, magnesium oxide, zinc oxide, silicon dioxide and germanium dioxide, adding alcohol with proper content, and carrying out planetary ball milling for 4 hours;
(2) drying the slurry, sieving, and presintering at 1100 deg.C for 4 hr;
(3) and ball-milling the obtained powder for 4 hours, drying, sieving, adding a proper amount of polyvinyl alcohol (PVA) aqueous solution, grinding, granulating, and performing dry pressing and molding.
(4) Finally, the green body is degummed for 4 hours at 600 ℃, and then sintered for 4 hours at 1200 ℃, so as to obtain the ceramic material with the required chemical component ratio.
The bulk density of the ceramic was 3.5g/cm3. The dielectric constant was 8.0, the Q x f value was 137000GHz, and the temperature coefficient of the resonance frequency was-58 ppm/deg.C as measured by a network analyzer.
Example 4
(1) According to the mass fraction of 33 percent of CaO, 12 percent of MgO, 2 percent of ZnO and 24 percent of SiO2And 28% GeO2Weighing calcium carbonate, magnesium oxide, zinc oxide, silicon dioxide and germanium dioxide, adding alcohol with proper content, and carrying out planetary ball milling for 4 hours;
(2) drying the slurry, sieving, and presintering at 1100 deg.C for 4 hr;
(3) and ball-milling the obtained powder for 4 hours, drying, sieving, adding a proper amount of polyvinyl alcohol (PVA) aqueous solution, grinding, granulating, and performing dry pressing and molding.
(4) Finally, the green body is degummed for 4 hours at 600 ℃, and then sintered for 4 hours at 1200 ℃, so as to obtain the ceramic material with the required chemical component ratio.
The bulk density of the ceramic was 3.5g/cm3. The dielectric constant was 8.2, the Qxf value was 173000GHz, and the temperature coefficient of the resonance frequency was-75 ppm/deg.C as measured by a network analyzer.
Comparative example
Comparative example 1
(1) According to the mass fraction of 38 percent of CaO, 14 percent of MgO, 3 percent of ZnO and 45 percent of SiO2Weighing calcium carbonate, magnesium oxide, zinc oxide and silicon dioxide, adding alcohol with proper content, and carrying out planetary ball milling for 4 hours;
(2) drying the slurry, sieving, and presintering at 1100 deg.C for 4 hr;
(3) and ball-milling the obtained powder for 4 hours, drying, sieving, adding a proper amount of polyvinyl alcohol (PVA) aqueous solution, grinding, granulating, and performing dry pressing and molding.
(4) Finally, the green body is degummed for 4 hours at 600 ℃, and then sintered for 4 hours at 1200 ℃, so as to obtain the ceramic material with the required chemical component ratio.
Comparative example 1In which only ZnO and GeO are doped2The preparation process is the same as the example. The bulk density of the ceramic in comparative example 1 was 3.3g/cm3. The dielectric constant was 7.8, the Qxf value was 117100GHz, and the temperature coefficient of the resonance frequency was-54 ppm/deg.C as measured by a network analyzer.
The results show that the Q x f value of comparative example 1 is significantly lower than that of example, and the dielectric constant and resonance frequency are comparable to those of example. Thus, Ge doping4+The Q multiplied by f value of the ceramic material can be obviously improved, namely the loss of the ceramic material is reduced, and the influence on the dielectric constant and the temperature coefficient of the resonant frequency is small.
While the invention has been described with reference to specific embodiments, the scope of the invention is not limited thereto, and those skilled in the art can easily conceive various equivalent modifications or substitutions within the technical scope of the invention. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims (10)
1. The microwave dielectric ceramic material is characterized by comprising the following components in percentage by mass: 33-38% CaO, 12-14% MgO, 2-3% ZnO, 24-43% SiO2And 3 to 28% GeO2The dielectric constant of the microwave dielectric ceramic is 7.8-8.2; the Qxf value is 137000-200000 GHz; the temperature coefficient of the resonance frequency is-53 to-75 ppm/DEG C.
2. A method for preparing a microwave dielectric ceramic material as claimed in claim 1, comprising the steps of:
(1) weighing raw material powder according to a ratio, and performing first ball milling to obtain a mixture;
(2) carrying out primary drying, screening and presintering treatment on the mixture to obtain a presintering material;
(3) carrying out secondary ball milling, secondary drying, granulation and dry pressing molding on the pre-sintered material to obtain a green body;
(4) and sintering the green body to obtain the microwave dielectric ceramic material.
3. The method for preparing a microwave dielectric ceramic material as claimed in claim 2, wherein the raw material powder in step (1) comprises calcium carbonate, magnesium oxide, zinc oxide, silicon dioxide and germanium dioxide powder.
4. The preparation method of the microwave dielectric ceramic material as claimed in claim 2, wherein the rotation speed of the first ball milling in the step (1) is 250-350 r/min, and the time is 4-8 hours.
5. The preparation method of the microwave dielectric ceramic material as claimed in claim 2, wherein the ball milling medium for the first ball milling in the step (1) is alcohol, and the ball-to-material ratio is (8-12): 1.
6. The preparation method of the microwave dielectric ceramic material as claimed in claim 2, wherein the temperature of the pre-sintering treatment in the step (2) is 1050-1150 ℃ for 4-8 hours.
7. The preparation method of the microwave dielectric ceramic material as claimed in claim 2, wherein the granulating in the step (3) includes adding an adhesive to the dried pre-sintered material after the second drying, and mixing to prepare the dried pre-sintered material into particles with an average particle size of 0.1-0.5 mm.
8. The preparation method of the microwave dielectric ceramic material as claimed in claim 2, wherein the pressure of the dry pressing in the step (3) is 100 to 200 MPa.
9. The preparation method of the microwave dielectric ceramic material as claimed in claim 2, wherein the step (3) further comprises a glue removing treatment after the dry pressing treatment, wherein the glue removing temperature is 550-650 ℃, and the time is 4-8 hours.
10. A preparation method of a microwave dielectric ceramic material as claimed in claim 2, wherein the sintering temperature in the step (4) is 1150-1250 ℃ for 4-8 hours.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002211971A (en) * | 2000-11-17 | 2002-07-31 | Nippon Electric Glass Co Ltd | Glass-ceramics dielectric material, sintered body and circuit member for microwave |
| CN103193389A (en) * | 2012-01-05 | 2013-07-10 | 东莞华科电子有限公司 | Microwave dielectric glass ceramic material and composition thereof |
| CN110723965A (en) * | 2019-08-23 | 2020-01-24 | 电子科技大学 | Fluxing agent-free LTCC microwave ceramic material and preparation method thereof |
| CN112876229A (en) * | 2021-03-22 | 2021-06-01 | 南宁国人射频通信有限公司 | Microwave ceramic and preparation method thereof |
-
2022
- 2022-01-26 CN CN202210096241.5A patent/CN114477984B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002211971A (en) * | 2000-11-17 | 2002-07-31 | Nippon Electric Glass Co Ltd | Glass-ceramics dielectric material, sintered body and circuit member for microwave |
| CN103193389A (en) * | 2012-01-05 | 2013-07-10 | 东莞华科电子有限公司 | Microwave dielectric glass ceramic material and composition thereof |
| CN110723965A (en) * | 2019-08-23 | 2020-01-24 | 电子科技大学 | Fluxing agent-free LTCC microwave ceramic material and preparation method thereof |
| CN112876229A (en) * | 2021-03-22 | 2021-06-01 | 南宁国人射频通信有限公司 | Microwave ceramic and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| JIE ZHANG等: ""Low-temperature sintering and microwave dielectric properties of LiF-doped CaMg1-xZnxSi2O6 ceramics"", 《CERAMICS INTERNATIONAL》 * |
| JIE ZHANG等: "Low-temperature sintering and microwave dielectric properties of LiF-doped CaMg1-xZnxSi2O6 ceramics" * |
| KANG DU等: "Crystal structure, far-infrared spectra, and microwave dielectric properties of bazirite-type BaZr(Si1-xGex)3O9 ceramics" * |
| 杨辉等: "低温共烧微波介质陶瓷及其器件的研究进展", 《硅酸盐学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116354700A (en) * | 2023-03-03 | 2023-06-30 | 深圳顺络电子股份有限公司 | Low dielectric constant microwave ceramic material, microwave ceramic filter and preparation method |
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