CN111925210B - Metal compound, microwave dielectric ceramic and preparation method thereof - Google Patents

Metal compound, microwave dielectric ceramic and preparation method thereof Download PDF

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CN111925210B
CN111925210B CN202010849336.0A CN202010849336A CN111925210B CN 111925210 B CN111925210 B CN 111925210B CN 202010849336 A CN202010849336 A CN 202010849336A CN 111925210 B CN111925210 B CN 111925210B
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殷旺
凌海强
曹顺顺
马才兵
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Guangdong Gova Advanced Material Technology Co ltd
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Abstract

The application belongs to the technical field of microwave dielectric ceramics. The application provides a metal compound, a microwave dielectric ceramic and a preparation method thereof, and the microwave dielectric ceramic comprises the metal compound with the following general structure: (1-y) Ba3ZnxCo1‑xNb2O9‑yBa8CoNb6O24Wherein x is 0 to 1 and y is 0 to 0.1, and Ba is introduced8CoNb6O24The new object phase with non-stoichiometric ratio can be sintered in a liquid phase, and volatilization of components is inhibited, so that the prepared microwave dielectric ceramic has a stable B-site 1:2 long-range ordered structure, and the Qf value is improved. The dielectric constant of the microwave dielectric ceramic is 32.8-40.2, and Q is multiplied by f>56500GHz, the highest can reach 124300GHz, has the advantages of high Qf value and low dielectric loss, and the temperature coefficient of the resonance frequency is continuously adjustable between-10.6 PPM/DEG C to +28.3 PPM/DEG C. The preparation method is simple, low in manufacturing cost, non-toxic and pollution-free, and meets the environmental protection requirement; the sintering temperature is low, the performance of the product can be ensured without long-time annealing, and the performance deterioration of the prepared product caused by component volatilization is avoided.

Description

Metal compound, microwave dielectric ceramic and preparation method thereof
Technical Field
The application belongs to the technical field of microwave dielectric ceramics, and particularly relates to a metal compound, microwave dielectric ceramics and a preparation method thereof.
Background
With the continuous development of modern communication technology, mobile operators face different standards brought by the fusion networking of 2G networks such as GSM and CDMA, 3G networks such as WCDMA, CDMA2000 and TD-SCDMA, and 4G networks such as TD-LTE and FDD-LTE. The frequency band interference between 1.7GHz and 2.7GHz is particularly obvious because of the serious interference between adjacent frequency bands, which puts higher requirements on the Qf value of the microwave dielectric ceramic material applied to the dielectric filter. Under the frequency band, the microwave dielectric ceramic material with the dielectric constant of about 35 is widely concerned due to the moderate size and excellent performance of the prepared product.
Ba (Zn) is studied more frequently in the preparation of microwave dielectric ceramic materials1/3Nb2/3)O3System, Ba (Co)1/3Nb2/3)O3System sum Ba [ (Zn, Co)1/3Nb2/3]O3The prepared microwave dielectric ceramic material has a high Qf value and is a better candidate system, but the components of the systems are volatile in the preparation process, so that the performance of the prepared product is deteriorated, long-time high-temperature annealing is needed to ensure the performance of the product, the manufacturing cost is high, and the defects limit the large-scale commercial use of the microwave dielectric ceramic material.
Disclosure of Invention
In view of the above, the present application provides a metal compound, which can obtain a microwave dielectric ceramic with a high Qf value and a low manufacturing cost.
The specific technical scheme of the application is as follows:
the present application provides a metal compound having the general structure:
(1-y)Ba3ZnxCo1-xNb2O9-yBa8CoNb6O24wherein x is 0 to 1, and y is 0 to 0.1.
The application also provides a microwave dielectric ceramic which comprises the metal compound.
Preferably, the composition also comprises an additive;
the additive is MgO and Nb2O5ZnO and Yb2O3Two or more of (1);
the content of the additive in the microwave dielectric ceramic is 0-10 wt%.
In the application, the sintering temperature is further reduced by introducing the additive, the volatilization of components is inhibited, the Qf value is improved, and the preparation cost is reduced.
Preferably, among the additives, MgO and Nb2O5ZnO and Yb2O3In a molar ratio of4:1:(0～0.05):(0～0.03)。
The third aspect of the present application provides a method for preparing microwave dielectric ceramic, comprising the following steps:
s1: mixing BaCO3、ZnO、Co3O4And Nb2O5Performing primary ball milling, drying and presintering to obtain a microwave dielectric ceramic presintering material; the microwave dielectric ceramic pre-sintering material has the following general structure:
(1-y)Ba3ZnxCo1-xNb2O9-yBa8CoNb6O24wherein x is 0-1, and y is 0-0.1;
s2: carrying out secondary ball milling on the microwave dielectric ceramic pre-sintered material, and drying to obtain microwave dielectric ceramic powder;
s3: and adding a binder into the microwave dielectric ceramic powder, granulating, molding and sintering to obtain the microwave dielectric ceramic.
Preferably, the additive is also added in S2;
the additive is made of MgO and Nb2O5ZnO and Yb2O3Mixing, ball milling, drying and pre-sintering.
More preferably, the pre-sintering is followed by mixing, ball milling and drying.
Preferably, the mass ratio of the mixing ball mill is as follows: material preparation: ball: water (1), (3-4) and (2-3), wherein the rotation speed of the mixing ball milling is 200-300 r/min, and the time of the mixing ball milling is 20-24 hours;
the drying temperature is 80-150 ℃, and more preferably 120 ℃;
the pre-sintering temperature is 1100-1300 ℃, and the time is 1-3 h.
Preferably, the mass ratio of the primary ball milling in the step S1 is: material preparation: ball: water (1), (3-4) and (2-3), wherein the rotation speed of the primary ball milling is 200-300 r/min, and the time of the primary ball milling is 3-5 hours;
the pre-sintering temperature is 900-1100 ℃, and the time is 3-4 hours.
More preferably, the primary ball milling is planetary ball milling, zirconium balls are used as milling balls, deionized water is used as a ball milling medium, and the mass ratio of the primary ball milling is as follows: material preparation: ball: and (3) adding water in a ratio of 1:3:2, wherein the rotation speed of one-time ball milling is 250 r/min. The pre-burning conditions are as follows: heating to 900-1100 ℃ at a heating rate of 3-8 ℃/min, preserving heat for 3-4 hours, and cooling.
Preferably, the mass ratio of the secondary ball milling in the step S2 is: material preparation: ball: and (3) water (1), (3-4) and (2-3), wherein the rotation speed of the secondary ball milling is 200-300 r/min, and the time of the secondary ball milling is 3-5 hours.
More preferably, the secondary ball milling is planetary ball milling, zirconium balls are used as milling balls, deionized water is used as a ball milling medium, and the mass ratio of the ball milling is as follows: material preparation: ball: and (3) adding water to the mixture in a ratio of 1:3:2, and performing ball milling at a rotating speed of 250 r/min.
Preferably, the binder in S3 is a polyvinyl alcohol aqueous solution, and the mass concentration of the polyvinyl alcohol aqueous solution is 6-8 wt%;
the using amount of the binder is 15-25 wt% of the microwave dielectric ceramic powder;
the sintering temperature is 1300-1500 ℃, and the sintering time is 2-4 hours.
More preferably, the sintering conditions are as follows: heating to 1300-1500 ℃ at a heating rate of 3-8 ℃/min, preserving heat for 2-4 hours, and cooling.
In this application, polyvinyl alcohol is sintered at high temperature to become CO2And H2O can be completely volatilized, so that residual impurities of the binder are not left in the blank, no post-treatment is needed, the prepared product is non-toxic, and the environment-friendly requirement is met.
In summary, the present application provides a metal compound by introducing Ba8CoNb6O24The new object phase with non-stoichiometric ratio can be sintered in a liquid phase, and volatilization of components is inhibited, so that the prepared microwave dielectric ceramic has a stable B-site 1:2 long-range ordered structure, and the Qf value is improved. The microwave dielectric ceramic has a dielectric constant of 32.8-40.2 and a dielectric constant of Qxf>56500GHz (up to 124300 GHz), high Qf value and low dielectric loss, and has a temperature coefficient of resonance frequency of-10.6 PPM/deg.C to +28.3PThe PM/DEG C is continuously adjustable. The preparation method is simple, low in manufacturing cost, non-toxic and pollution-free, and meets the environmental protection requirement; the sintering temperature is low, the performance of the product can be ensured without long-time annealing, and the performance deterioration of the prepared product caused by component volatilization is avoided.
Detailed Description
In order to make the objects, features and advantages of the present application more obvious and understandable, the technical solutions in the embodiments of the present application are clearly and completely described, and it is obvious that the embodiments described below are only a part of the embodiments of the present application, and not all 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 application.
The reagents used in the examples of this application are all commercially available.
Example 1
1. 126.191g of BaCO were weighed out3、5.182g ZnO、11.935g Co3O4And 56.692g Nb2O5Wet ball milling the weighed raw materials, zirconium balls and deionized water for 4 hours by a planetary mill according to the mass ratio of 1:3:2, drying at 120 ℃, pre-sintering at 1050 ℃ for 3 hours (in atmospheric atmosphere), wherein the heating rate is 3 ℃/min, and then cooling along with a furnace to obtain a pre-sintered material;
2. carrying out ball milling on the pre-sintered material, zirconium balls and deionized water for 4 hours by a planetary wet method according to the mass ratio of 1:3:2, and drying at 120 ℃ to obtain microwave dielectric ceramic powder;
3. adding 20% of adhesive in the mass of the powder into the microwave dielectric ceramic powder, granulating and grinding for 1 hour, sieving by a 80-mesh sieve, pressing the powder under the pressure of 100MPa into a thin cylindrical blank with the thickness of 6mm and the diameter of 13mm, sintering at the temperature rise rate of 3 ℃/min at 1500 ℃ to form ceramic, preserving heat for 3 hours, and then cooling along with a furnace to obtain the microwave dielectric ceramic.
The prepared microwave dielectric ceramic is tested as follows:
the microwave medium ceramic sample is subjected to metallographic phase and flannelette medium surface polishing, and Agilent 5 is adopted061B network analyzer, dielectric constant epsilon is measured according to Hakki-Coleman methodrAnd tan delta, and the quality factor Qf is calculated, and the test results are shown in table 1.
In addition, the prepared microwave dielectric ceramic is also subjected to measurement of the temperature coefficient of resonance frequency. Directly connecting a network analyzer with a constant temperature box, testing the change value of the resonance frequency within the temperature range of 20-85 ℃, and then calculating tau according to the following formulafThe values, test results are shown in table 1.
Figure BDA0002644188630000041
Example 2
1. 126.215g of BaCO were weighed out3、5.158g ZnO、11.89g Co3O4And 56.736g Nb2O5Wet ball milling the weighed raw materials, zirconium balls and deionized water for 4 hours by a planetary mill according to the mass ratio of 1:3:2, drying at 120 ℃, pre-sintering at 1050 ℃ for 3 hours (in atmospheric atmosphere), wherein the heating rate is 3 ℃/min, and then cooling along with a furnace to obtain a pre-sintered material;
2. carrying out ball milling on the pre-sintered material, zirconium balls and deionized water for 4 hours by a planetary wet method according to the mass ratio of 1:3:2, and drying at 120 ℃ to obtain microwave dielectric ceramic powder;
3. adding 20% of adhesive in the mass of the powder into the microwave dielectric ceramic powder, granulating and grinding for 1 hour, sieving by a 80-mesh sieve, pressing the powder under the pressure of 100MPa into a thin cylindrical blank with the thickness of 6mm and the diameter of 13mm, sintering at the temperature rise rate of 3 ℃/min at 1500 ℃ to form ceramic, preserving heat for 3 hours, and then cooling along with a furnace to obtain the microwave dielectric ceramic.
The prepared microwave dielectric ceramic is subjected to performance test, the test method is the same as that of the example 1, and the test results are shown in the table 1.
Comparative example 1
1. 126.17g of BaCO were weighed out3、5.203g ZnO、11.975g Co3O4And 56.652g Nb2O5The weighed raw materials, zirconium balls and deionized water are ground by a planet mill according to the mass ratio of 1:3:2Ball-milling for 4 hours, drying at 120 ℃, presintering for 3 hours (in atmospheric atmosphere) at 1050 ℃, heating at the rate of 3 ℃/min, and cooling along with a furnace to obtain a presintering material;
2. carrying out ball milling on the pre-sintered material, zirconium balls and deionized water for 4 hours by a planetary wet method according to the mass ratio of 1:3:2, and drying at 120 ℃ to obtain microwave dielectric ceramic powder;
3. adding 20% of adhesive in the mass of the powder into the microwave dielectric ceramic powder, granulating and grinding for 1 hour, sieving by a 80-mesh sieve, pressing the powder under the pressure of 100MPa into a thin cylindrical blank with the thickness of 6mm and the diameter of 13mm, sintering at the temperature rise rate of 3 ℃/min at 1500 ℃ to form ceramic, preserving heat for 3 hours, and then cooling along with a furnace to obtain the microwave dielectric ceramic.
The prepared microwave dielectric ceramic is subjected to performance test, the test method is the same as that of the example 1, and the test results are shown in the table 1. As can be seen from Table 1, by introducing Ba8CoNb6O24The component can improve the Qf value.
TABLE 1 Performance results for the microwave dielectric ceramics of comparative example 1 and examples 1-2
Numbering x y εr Qf(GHz) τf(PPM/℃)
Comparative example 1 0.3 0 35 56500 0
Example 1 0.3 0.05 34.8 81400 -1.3
Example 2 0.3 0.1 34.5 64700 -3.2
Example 3
Preparing an additive: mixing MgO and Nb2O5ZnO and Yb2O3Mixing the raw materials according to a molar ratio of 4:1:0.05:0.03, ball-milling the weighed raw materials, zirconium balls and deionized water for 24 hours according to a mass ratio of 1:3:2, drying at 80 ℃, and presintering at 1100 ℃ for 3 hours to obtain the additive.
Example 4
1. 126.191g of BaCO were weighed out3、5.182g ZnO、11.935g Co3O4And 56.692g Nb2O5Wet ball milling the weighed raw materials, zirconium balls and deionized water for 4 hours by a planetary mill according to the mass ratio of 1:3:2, drying at 120 ℃, pre-sintering at 1050 ℃ for 3 hours (in atmospheric atmosphere), heating at the rate of 3 ℃/min, and furnace cooling to obtain a pre-sintered material;
2. mixing the pre-sintering material with the additive of example 3, wherein the dosage of the additive is 0.2% of the mass of the pre-sintering material, ball-milling the mixture of the pre-sintering material and the additive, zirconium balls and deionized water for 4 hours by a planetary wet method according to the mass ratio of 1:3:2, and drying at 120 ℃ to obtain microwave dielectric ceramic powder;
3. adding an adhesive accounting for 20 percent of the mass of the powder into microwave medium ceramic powder, granulating and grinding for 1 hour, sieving by a 80-mesh sieve, pressing the powder into a thin cylindrical blank with the thickness of 6mm and the diameter of 13mm under the pressure of 100MPa, sintering the blank into ceramic at 1450 ℃ at the heating rate of 3 ℃/min, preserving heat for 3 hours, and then cooling along with a furnace to obtain the microwave medium ceramic.
The prepared microwave dielectric ceramic is subjected to performance test, the test method is the same as that of the example 1, and the test results are shown in a table 2.
Example 5
1. 126.191g of BaCO were weighed out3、5.182g ZnO、11.935g Co3O4And 56.692g Nb2O5Wet ball milling the weighed raw materials, zirconium balls and deionized water for 4 hours by a planetary mill according to the mass ratio of 1:3:2, drying at 120 ℃, pre-sintering at 1050 ℃ for 3 hours (in atmospheric atmosphere), heating at the rate of 3 ℃/min, and furnace cooling to obtain a pre-sintered material;
2. mixing the pre-sintering material with the additive of example 3, wherein the dosage of the additive is 0.6 percent of the mass of the pre-sintering material, ball-milling the mixture of the pre-sintering material and the additive, zirconium balls and deionized water for 4 hours by a planetary wet method according to the mass ratio of 1:3:2, and drying at 120 ℃ to obtain microwave dielectric ceramic powder;
3. adding 20% of adhesive in the mass of the powder into the microwave dielectric ceramic powder, granulating and grinding for 1 hour, sieving by a 80-mesh sieve, pressing the powder under the pressure of 100MPa into a thin cylindrical blank with the thickness of 6mm and the diameter of 13mm, sintering at the temperature rise rate of 3 ℃/min at 1400 ℃ to form ceramic, preserving heat for 3 hours, and then cooling along with a furnace to obtain the microwave dielectric ceramic.
The prepared microwave dielectric ceramic is subjected to performance test, the test method is the same as that of the example 1, and the test results are shown in a table 2.
Example 6
1. 126.191g of BaCO were weighed out3、5.182g ZnO、11.935g Co3O4And 56.692g Nb2O5Weighing the aboveWet ball milling the raw materials, zirconium balls and deionized water for 4 hours by a planetary mill at a mass ratio of 1:3:2, drying at 120 ℃, pre-sintering at 1050 ℃ for 3 hours (in an atmospheric atmosphere), heating at a rate of 3 ℃/min, and furnace cooling to obtain a pre-sintered material;
2. mixing the pre-sintering material with the additive of example 3, wherein the using amount of the additive is 1% of the mass of the pre-sintering material, ball-milling the mixture of the pre-sintering material and the additive, zirconium balls and deionized water for 4 hours by a planetary wet method according to the mass ratio of 1:3:2, and drying at 120 ℃ to obtain microwave dielectric ceramic powder;
3. adding an adhesive accounting for 20 percent of the mass of the powder into microwave dielectric ceramic powder, granulating and grinding for 1 hour, sieving by a 80-mesh sieve, pressing the powder into a thin cylindrical blank with the thickness of 6mm and the diameter of 13mm under the pressure of 100MPa, sintering the blank into ceramic at the temperature of 1300 ℃ at the heating rate of 3 ℃/min, preserving the heat for 3 hours, and then cooling along with a furnace to obtain the microwave dielectric ceramic.
The prepared microwave dielectric ceramic is subjected to performance test, the test method is the same as that of the example 1, and the test results are shown in a table 2. As can be seen from Table 2, the introduction of the additives helps to lower the sintering temperature while increasing the Qf value.
TABLE 2 Performance results for the microwave dielectric ceramics of examples 4-6
Figure BDA0002644188630000071
Comparative example 2
126.236g of BaCO were weighed out3、17.052g Co3O4And 56.713g Nb2O5Wet ball milling the weighed raw materials, zirconium balls and deionized water for 4 hours by a planetary mill according to the mass ratio of 1:3:2, drying at 120 ℃, pre-sintering at 950 ℃ for 3 hours (in atmospheric atmosphere), heating at the rate of 3 ℃/min, and furnace cooling to obtain a pre-sintered material;
2. mixing the pre-sintering material with the additive of example 3, wherein the dosage of the additive is 0.6 percent of the mass of the pre-sintering material, ball-milling the mixture of the pre-sintering material and the additive, zirconium balls and deionized water for 4 hours by a planetary wet method according to the mass ratio of 1:3:2, and drying at 120 ℃ to obtain microwave dielectric ceramic powder;
3. adding 20% of adhesive in the mass of the powder into the microwave dielectric ceramic powder, granulating and grinding for 1 hour, sieving by a 80-mesh sieve, pressing the powder under the pressure of 100MPa into a thin cylindrical blank with the thickness of 6mm and the diameter of 13mm, sintering at the temperature rise rate of 3 ℃/min at 1400 ℃ to form ceramic, preserving heat for 3 hours, and then cooling along with a furnace to obtain the microwave dielectric ceramic.
The prepared microwave dielectric ceramic was subjected to a performance test in the same manner as in example 1, and the test results are shown in table 3.
Example 7
1. 126.206g of BaCO were weighed out3、3.455g ZnO、13.64g Co3O4And 56.699g Nb2O5Wet ball milling the weighed raw materials, zirconium balls and deionized water for 4 hours by a planetary mill according to the mass ratio of 1:3:2, drying at 120 ℃, pre-sintering at 950 ℃ for 3 hours (in atmospheric atmosphere), heating at the rate of 3 ℃/min, and furnace cooling to obtain a pre-sintered material;
2. mixing the pre-sintering material with the additive of example 3, wherein the dosage of the additive is 0.6 percent of the mass of the pre-sintering material, ball-milling the mixture of the pre-sintering material and the additive, zirconium balls and deionized water for 4 hours by a planetary wet method according to the mass ratio of 1:3:2, and drying at 120 ℃ to obtain microwave dielectric ceramic powder;
3. adding 20% of adhesive in the mass of the powder into the microwave dielectric ceramic powder, granulating and grinding for 1 hour, sieving by a 80-mesh sieve, pressing the powder under the pressure of 100MPa into a thin cylindrical blank with the thickness of 6mm and the diameter of 13mm, sintering at the temperature rise rate of 3 ℃/min at 1400 ℃ to form ceramic, preserving heat for 3 hours, and then cooling along with a furnace to obtain the microwave dielectric ceramic.
The prepared microwave dielectric ceramic was subjected to a performance test in the same manner as in example 1, and the test results are shown in table 3.
Example 8
1. 126.176g of BaCO were weighed3、6.908g ZnO、10.23g Co3O4And 56.686g Nb2O5Ball-milling the weighed raw materials, zirconium balls and deionized water for 4 hours by a planetary mill wet method according to the mass ratio of 1:3:2After drying at 120 ℃, presintering at 1050 ℃ for 3 hours (in atmospheric atmosphere), heating at the rate of 3 ℃/min, and furnace cooling to obtain a presintering material;
2. mixing the pre-sintering material with the additive of example 3, wherein the dosage of the additive is 0.6 percent of the mass of the pre-sintering material, ball-milling the mixture of the pre-sintering material and the additive, zirconium balls and deionized water for 4 hours by a planetary wet method according to the mass ratio of 1:3:2, and drying at 120 ℃ to obtain microwave dielectric ceramic powder;
3. adding 20% of adhesive in the mass of the powder into the microwave dielectric ceramic powder, granulating and grinding for 1 hour, sieving by a 80-mesh sieve, pressing the powder under the pressure of 100MPa into a thin cylindrical blank with the thickness of 6mm and the diameter of 13mm, sintering at the temperature rise rate of 3 ℃/min at 1400 ℃ to form ceramic, preserving heat for 3 hours, and then cooling along with a furnace to obtain the microwave dielectric ceramic.
The prepared microwave dielectric ceramic was subjected to a performance test in the same manner as in example 1, and the test results are shown in table 3.
Example 9
1. 126.146g of BaCO were weighed out3、10.36g ZnO、6.821g Co3O4And 56.672g Nb2O5Wet ball milling the weighed raw materials, zirconium balls and deionized water for 4 hours by a planetary mill according to the mass ratio of 1:3:2, drying at 120 ℃, pre-sintering at 1050 ℃ for 3 hours (in atmospheric atmosphere), heating at the rate of 3 ℃/min, and furnace cooling to obtain a pre-sintered material;
2. mixing the pre-sintering material with the additive of example 3, wherein the dosage of the additive is 0.6 percent of the mass of the pre-sintering material, ball-milling the mixture of the pre-sintering material and the additive, zirconium balls and deionized water for 4 hours by a planetary wet method according to the mass ratio of 1:3:2, and drying at 120 ℃ to obtain microwave dielectric ceramic powder;
3. adding 20% of adhesive in the mass of the powder into the microwave dielectric ceramic powder, granulating and grinding for 1 hour, sieving by a 80-mesh sieve, pressing the powder under the pressure of 100MPa into a thin cylindrical blank with the thickness of 6mm and the diameter of 13mm, sintering at the temperature rise rate of 3 ℃/min at 1400 ℃ to form ceramic, preserving heat for 3 hours, and then cooling along with a furnace to obtain the microwave dielectric ceramic.
The prepared microwave dielectric ceramic was subjected to a performance test in the same manner as in example 1, and the test results are shown in table 3.
Example 10
1. 126.117g of BaCO were weighed out3、13.81g ZnO、3.415g Co3O4And 56.659g Nb2O5Wet ball milling the weighed raw materials, zirconium balls and deionized water for 4 hours by a planetary mill according to the mass ratio of 1:3:2, drying at 120 ℃, pre-sintering at 1050 ℃ for 3 hours (in atmospheric atmosphere), heating at the rate of 3 ℃/min, and furnace cooling to obtain a pre-sintered material;
2. mixing the pre-sintering material with the additive of example 3, wherein the dosage of the additive is 0.6 percent of the mass of the pre-sintering material, ball-milling the mixture of the pre-sintering material and the additive, zirconium balls and deionized water for 4 hours by a planetary wet method according to the mass ratio of 1:3:2, and drying at 120 ℃ to obtain microwave dielectric ceramic powder;
3. adding 20% of adhesive in the mass of the powder into the microwave dielectric ceramic powder, granulating and grinding for 1 hour, sieving by a 80-mesh sieve, pressing the powder under the pressure of 100MPa into a thin cylindrical blank with the thickness of 6mm and the diameter of 13mm, sintering at the temperature rise rate of 3 ℃/min at 1400 ℃ to form ceramic, preserving heat for 3 hours, and then cooling along with a furnace to obtain the microwave dielectric ceramic.
The prepared microwave dielectric ceramic was subjected to a performance test in the same manner as in example 1, and the test results are shown in table 3.
Example 11
1. 126.087g of BaCO were weighed out3、17.258g ZnO、0.09g Co3O4And 56.646g Nb2O5Wet ball milling the weighed raw materials, zirconium balls and deionized water for 4 hours by a planetary mill according to the mass ratio of 1:3:2, drying at 120 ℃, pre-sintering at 1050 ℃ for 3 hours (in atmospheric atmosphere), heating at the rate of 3 ℃/min, and furnace cooling to obtain a pre-sintered material;
2. mixing the pre-sintering material with the additive of example 3, wherein the dosage of the additive is 0.6 percent of the mass of the pre-sintering material, ball-milling the mixture of the pre-sintering material and the additive, zirconium balls and deionized water for 4 hours by a planetary wet method according to the mass ratio of 1:3:2, and drying at 120 ℃ to obtain microwave dielectric ceramic powder;
3. adding 20% of adhesive in the mass of the powder into the microwave dielectric ceramic powder, granulating and grinding for 1 hour, sieving by a 80-mesh sieve, pressing the powder under the pressure of 100MPa into a thin cylindrical blank with the thickness of 6mm and the diameter of 13mm, sintering at the temperature rise rate of 3 ℃/min at 1400 ℃ to form ceramic, preserving heat for 3 hours, and then cooling along with a furnace to obtain the microwave dielectric ceramic.
The prepared microwave dielectric ceramic was subjected to a performance test in the same manner as in example 1, and the test results are shown in table 3. As can be seen from Table 3, when Ba is present3ZnxCo1-xNb2O9And Ba8CoNb6O24When the two phases exist simultaneously, the dielectric ceramic has the advantages of high Qf value and low dielectric loss.
TABLE 3 Performance results for microwave dielectric ceramics of examples 7-11 and comparative example 2
Figure BDA0002644188630000101
The above embodiments are only used for illustrating the technical solutions of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions in the embodiments of the present application.

Claims (6)

1. A microwave dielectric ceramic is characterized by comprising a metal compound and an additive;
the metal compound has the following general structure:
(1-y) Ba3ZnxCo1-xNb2O9-yBa8CoNb6O24wherein x = 0.2-1, y = 0.05-0.1;
the additive is MgO and Nb2O5ZnO and Yb2O3；
The content of the additive in the microwave dielectric ceramic is 0.2-1 wt%;
among the additives, MgO and Nb2O5ZnO and Yb2O3In a molar ratio of 4:1:0.05: 0.03.
2. A method for preparing a microwave dielectric ceramic as claimed in claim 1, comprising the steps of:
s1: mixing BaCO3、ZnO 、Co3O4And Nb2O5Performing primary ball milling, drying and presintering to obtain a microwave dielectric ceramic presintering material; the microwave dielectric ceramic pre-sintering material has the following general structure:
(1-y) Ba3ZnxCo1-xNb2O9-yBa8CoNb6O24wherein x = 0.2-1, y = 0.05-0.1;
s2: carrying out secondary ball milling on the microwave dielectric ceramic pre-sintered material, and drying to obtain microwave dielectric ceramic powder;
s3: adding a binder into the microwave dielectric ceramic powder, granulating, molding and sintering to obtain the microwave dielectric ceramic;
the additive is also added into S2;
the additive is made of MgO and Nb2O5ZnO and Yb2O3Mixing, ball milling, drying and pre-sintering.
3. The production method according to claim 2,
the mass ratio of the mixed ball milling is as follows: material preparation: ball: water =1, (3-4) and (2-3), wherein the rotation speed of the mixing ball mill is 200-300 r/min, and the time of the mixing ball mill is 20-24 hours;
the drying temperature is 80-150 ℃;
the pre-sintering temperature is 1100-1300 ℃, and the time is 1-3 h.
4. The preparation method of claim 2, wherein the mass ratio of the primary ball milling in the S1 is as follows: material preparation: ball: water =1, (3-4), (2-3), the rotation speed of the primary ball milling is 200-300 r/min, and the time of the primary ball milling is 3-5 hours;
the pre-sintering temperature is 900-1100 ℃, and the time is 3-4 hours.
5. The preparation method of claim 2, wherein the mass ratio of the secondary ball milling in the S2 is as follows: material preparation: ball: and (3-4) and (2-3) in the presence of water, wherein the rotation speed of the secondary ball milling is 200-300 r/min, and the time of the secondary ball milling is 3-5 hours.
6. The preparation method according to claim 2, wherein the binder in S3 is a polyvinyl alcohol aqueous solution, and the mass concentration of the polyvinyl alcohol aqueous solution is 6-8 wt%;
the using amount of the binder is 15-25 wt% of the microwave dielectric ceramic powder;
the sintering temperature is 1300-1500 ℃, and the sintering time is 2-4 hours.
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