CN111484328A - Microwave dielectric ceramic material and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a microwave dielectric ceramic material, which comprises a main material and an additive, wherein the mass percent of each component is as follows: 95-98 wt% of main material and 2-5 wt% of additive, and the structural expression of the main material is (Pb)x/4Bix/2)(Alx/3Mo2x/3V1‑x)O4Wherein x is more than or equal to 0.05 and less than or equal to 0.85, and the additive is Ni (CH)3COO)2、Mg(CH3COO)2And In (CH)3COO)3. Wherein the main material is ABO4Structure based, Pb2+And Bi3+The ion association occupies A site, Al3+And Mo6+The composite particles of (2) occupy the B site, and Ni (CH) is added3COO)2、Mg(CH3COO)2And In (CH)3COO)3As additive, sintered microwave mediumThe ceramic material has a relative dielectric constant of 75-85, good microwave performance and low loss, and the temperature coefficient of resonance frequency can meet the requirement of 0 ppm/DEG C. The invention also provides a preparation method and application of the microwave dielectric ceramic material, the sintering temperature is lower in the preparation process, the microwave dielectric ceramic material is suitable for multilayer low-temperature co-fired ceramic electronic components such as microwave dielectric ceramic antennas and the like, the microwave dielectric ceramic material has the characteristics of good stability and excellent performance, and can be widely applied to the field of 5G communication.
Description
Technical Field
The invention relates to the field of electronic ceramic materials, in particular to a microwave dielectric ceramic material and a preparation method and application thereof.
Background
With the rapid development of information technology, the demands of communication electronic products in terms of miniaturization, light weight, high reliability, high integration and low cost are met, and the multilayer structure design based on the low-temperature co-fired ceramic (L TCC) technology can effectively reduce the volume of the device, and is an important technical means for meeting the demands.
L TCC technology is to use low temperature sintering ceramic material to burn the base plate, electronic element, electrode material and so on in one time according to the designed pattern structure, which greatly improves the production efficiency, compared with other component integration technologies, L TCC technology has many advantages, L TCC technology sintering temperature is generally lower than 950 ℃, can use high conductivity metal such as gold, silver, copper as conductive medium, reduces the process difficulty and improves the signal transmission speed, L TCC material dielectric constant can change in a large range, which makes the circuit design more flexible, the temperature characteristic is excellent, such as smaller thermal expansion coefficient, smaller resonance frequency temperature coefficient, which can meet the requirements of large current and high temperature resistance, higher reliability, which can be used in severe environment, and can obtain finer line width and line spacing, which improves the integration level.
The microwave dielectric ceramic material is one of key materials of L TCC technology, and refers to a ceramic material which is used as a dielectric material in a microwave frequency band circuit and completes one or more functions.
For example, personal communication terminal modules tend to be increasingly portable, light, thin, short and small, which is the design focus currently and for a long time in the future, so that the antenna needs to be supported by small but high-performance antennas, and wireless local area networks (W L AN) and Bluetooth, household radio frequency technologies and the like which appear in industrial scientific frequency bands (2.402GH-2.480GHz), wherein the conventional antenna is too large to be applied to such environments due to the fact that the conventional antenna is too large in size.
The dielectric constant of the microwave dielectric ceramic material in the existing microwave dielectric ceramic antenna is generally between 7 and 30, which causes the volume of the microwave antenna to be larger and limits the application thereof, so that the performance of the microwave dielectric ceramic material needs to be improved, the size of a microwave device needs to be reduced, and the application portability needs to be improved.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a microwave dielectric ceramic material which has the characteristics of high relative dielectric constant, good microwave performance, continuous and adjustable temperature coefficient of resonant frequency and low sintering temperature.
The second purpose of the present invention is to provide a method for preparing the microwave dielectric ceramic material.
One of the purposes of the invention is realized by adopting the following technical scheme:
a microwave dielectric ceramic material comprises a main material and an additive, wherein the mass percent of each component is as follows: 95-98 wt% of main material and 2-5 wt% of additive, wherein the structural expression of the main material is (Pb)x/4Bix/2)(Alx/3Mo2x/3V1-x)O4Wherein x is more than or equal to 0.05 and less than or equal to 0.85, and the additive is Ni (CH)3COO)2、Mg(CH3COO)2And In (CH)3COO)3。
Further, the additive comprises the following components in percentage by weight: ni (CH)3COO)21-2.5wt％、Mg(CH3COO)20.5-1.5wt％、In(CH3COO)30.5-1wt％。
Further, the relative dielectric constant of the microwave dielectric ceramic materialr75-85, Q × f value of 9800-10100 GHz, and resonant frequency temperature coefficient of-20- +20 ppm/DEG C.
The second purpose of the invention is realized by adopting the following technical scheme:
the preparation method of the microwave dielectric ceramic material comprises the following steps:
(1) preparation of the major Material
A: according to (Pb)x/4Bix/2)(Alx/3Mo2x/3V1-x)O4Taking PbO and Bi2O3、Al2O3、V2O5、MoO3Mixing materials, wherein x is more than or equal to 0.05 and less than or equal to 0.85;
b: b, fully ball-milling the mixture obtained in the step A, drying, sieving and pressing into blocks;
c: sintering the block in the step B at the temperature of 550-600 ℃ for 4-8h to obtain a sample sintered block;
d: c, crushing the sample clinker in the step C, performing secondary ball milling, drying, granulating, sieving, pressing and molding the sieved powder, and sintering at the temperature of 600-650 ℃ for 6-8 hours to obtain a main material;
(2) and (2) adding an additive into the main material prepared in the step (1), uniformly mixing, performing ball milling again, drying, granulating, sieving, performing compression molding on the sieved powder, and sintering at the temperature of 700-.
Further, ethanol is added in the step (1) for ball milling, and the ball milling time is 4-6 h.
Further, the drying temperature in the step (1) and the step (2) is 100-120 ℃.
Further, the step B in the step (1) is passed through a 200-mesh screen, the step D is passed through a 60-mesh and 100-mesh double-layer screen, and the step (2) is passed through an 80-mesh and 120-mesh double-layer screen.
The third purpose of the invention is realized by adopting the following technical scheme:
the microwave dielectric ceramic material is applied to the preparation of microwave dielectric ceramic antennas.
Compared with the prior art, the invention has the beneficial effects that: the invention provides a microwave dielectric ceramic material, which comprises a main material and an additive, wherein the main material (Pb) isx/4Bix/2)(Alx/3Mo2x/3V1-x)O4With ABO4Structure based, Pb2+And Bi3+The ion association occupies A site, Al3+And Mo6+The composite particles of (2) occupy the B site, and Ni (CH) is added3COO)2、Mg(CH3COO)2And In (CH)3COO)3As an additive, the microwave dielectric ceramic material obtained by sintering has the relative dielectric constant of 75-85, good microwave performance and low loss, and the temperature coefficient of the resonance frequency is adjustable between-20 and +20 ppm/DEG C, thus meeting the requirement of 0 ppm/DEG C.
The invention also provides a preparation method and application of the microwave dielectric ceramic material, the sintering temperature is lower in the preparation process of the microwave dielectric ceramic material, the microwave dielectric ceramic material can be co-sintered with Ag electrodes, the microwave dielectric ceramic material is suitable for multilayer low-temperature co-sintered ceramic (L TCC) electronic components such as microwave dielectric ceramic antennas, the microwave dielectric ceramic material has the characteristics of good stability and excellent performance, the size of the microwave dielectric ceramic antenna can be reduced, the development requirements of miniaturization and chip type of electronic components are met, and the microwave dielectric ceramic material can be widely applied to the field of 5G communication.
Detailed Description
The present invention is further described below with reference to specific embodiments, and it should be noted that, without conflict, any combination between the embodiments or technical features described below may form a new embodiment.
Example 1
The microwave dielectric ceramic material comprises 95 wt% of main material and 5 wt% of additive, wherein the structural expression of the main material is (Pb)x/4Bix/2)(Alx/3Mo2x/3V1-x)O4Wherein x is 0.05, and the additive is Ni (CH)3COO)22.5wt％、Mg(CH3COO)21.5 wt% and In (CH)3COO)31wt％。
The preparation method of the microwave dielectric ceramic material comprises the following steps:
(1) preparation of the major Material
A: according to (Pb)x/4Bix/2)(Alx/3Mo2x/3V1-x)O4Taking PbO and Bi2O3、Al2O3、V2O5、MoO3Preparing materials, wherein x is 0.05;
b: b, putting the mixture obtained in the step A into a ball mill, adding ethanol, fully ball-milling for 6 hours, drying at 100 ℃, sieving with a 200-mesh sieve, and pressing into blocks;
c: b, sintering the block in the step B at 550 ℃ for 8h to obtain a sample sintered block;
d: c, crushing the sample clinker in the step C, adding ethanol into a ball mill, performing secondary ball milling, drying at 110 ℃, granulating, sieving by a 60-mesh and 100-mesh double-layer screen, pressing and molding part of powder between the two layers of screens, and sintering at 600 ℃ for 8 hours to obtain a main material;
(2) and (2) adding additives into the main material prepared in the step (1), uniformly mixing, performing ball milling again, drying at 100 ℃, granulating, sieving by a double-layer screen of 80 meshes and 120 meshes, performing compression molding on the sieved powder, and sintering at 700 ℃ for 6 hours to obtain the microwave dielectric ceramic material.
Example 2
The microwave dielectric ceramic material comprises 97 wt% of main material and 3 wt% of additive, wherein the structural expression of the main material is (Pb)x/4Bix/2)(Alx/3Mo2x/3V1-x)O4Wherein x is 0.65, and the additive is Ni (CH)3COO)21.5wt％、Mg(CH3COO)20.5 wt% and In (CH)3COO)31wt％。
The preparation method of the microwave dielectric ceramic material comprises the following steps:
(1) preparation of the major Material
A: according to (Pb)x/4Bix/2)(Alx/3Mo2x/3V1-x)O4Taking PbO and Bi2O3、Al2O3、V2O5、MoO3Preparing materials, wherein x is 0.65;
b: b, putting the mixture obtained in the step A into a ball mill, adding ethanol, fully ball-milling for 4 hours, drying at 110 ℃, sieving with a 200-mesh sieve, and pressing into blocks;
c: b, sintering the block in the step B at 580 ℃ for 6 hours to obtain a sample sintered block;
d: c, crushing the sample clinker in the step C, adding ethanol into a ball mill, performing secondary ball milling, drying at 110 ℃, granulating, sieving by a 60-mesh and 100-mesh double-layer screen, pressing and molding part of powder between the two layers of screens, and sintering at 630 ℃ for 7 hours to obtain a main material;
(2) and (2) adding additives into the main material prepared in the step (1), uniformly mixing, performing ball milling again, drying at 110 ℃, granulating, sieving by a double-layer screen of 80 meshes and 120 meshes, performing compression molding on the sieved powder, and sintering at 730 ℃ for 5 hours to obtain the microwave dielectric ceramic material.
Example 3
The microwave dielectric ceramic material comprises 98 wt% of main material and 2 wt% of additive, wherein the structural expression of the main material is (Pb)x/4Bix/2)(Alx/3Mo2x/3V1-x)O4Wherein x is 0.85, and the additive is Ni (CH)3COO)21wt％、Mg(CH3COO)20.5 wt% and In (CH)3COO)30.5wt％。
The preparation method of the microwave dielectric ceramic material comprises the following steps:
(1) preparation of the major Material
A: according to (Pb)x/4Bix/2)(Alx/3Mo2x/3V1-x)O4Taking PbO and Bi2O3、Al2O3、V2O5、MoO3Preparing materials, wherein x is 0.85;
b: b, putting the mixture obtained in the step A into a ball mill, adding ethanol, fully ball-milling for 6 hours, drying at 120 ℃, sieving with a 200-mesh sieve, and pressing into blocks;
c: b, sintering the block in the step B at 600 ℃ for 4h to obtain a sample sintered block;
d: c, crushing the sample clinker in the step C, adding ethanol into a ball mill, performing secondary ball milling, drying at 120 ℃, granulating, sieving by a 60-mesh and 100-mesh double-layer screen, pressing and molding part of powder between the two layers of screens, and sintering at 650 ℃ for 6 hours to obtain a main material;
(2) and (2) adding additives into the main material prepared in the step (1), uniformly mixing, performing ball milling again, drying at 120 ℃, granulating, sieving by a double-layer screen of 80 meshes and 120 meshes, performing compression molding on the sieved powder, and sintering at 750 ℃ for 4 hours to obtain the microwave dielectric ceramic material.
Example 4
The microwave dielectric ceramic material comprises 97.5 wt% of main material and 2.5 wt% of additive, wherein the structural expression of the main material is (Pb)x/4Bix/2)(Alx/3Mo2x/3V1-x)O4Wherein x is 0.68, and the additive is Ni (CH)3COO)21.5wt％、Mg(CH3COO)20.5 wt% and In (CH)3COO)30.5wt％。
The preparation method of the microwave dielectric ceramic material comprises the following steps:
(1) preparation of the major Material
A: according to (Pb)x/4Bix/2)(Alx/3Mo2x/3V1-x)O4Taking PbO and Bi2O3、Al2O3、V2O5、MoO3Preparing materials, wherein x is 0.68;
b: b, putting the mixture obtained in the step A into a ball mill, adding ethanol, fully ball-milling for 6 hours, drying at 110 ℃, sieving with a 200-mesh sieve, and pressing into blocks;
c: b, sintering the block in the step B at 570 ℃ for 6h to obtain a sample sintered block;
d: c, crushing the sample clinker in the step C, adding ethanol into a ball mill, performing secondary ball milling, drying at 120 ℃, granulating, sieving by a 60-mesh and 100-mesh double-layer screen, pressing and molding part of powder between the two layers of screens, and sintering at 640 ℃ for 6.5 hours to obtain a main material;
(2) and (2) adding additives into the main material prepared in the step (1), uniformly mixing, performing ball milling again, drying at 120 ℃, granulating, sieving by a double-layer screen of 80 meshes and 120 meshes, performing compression molding on the sieved powder, and sintering at 740 ℃ for 4.5 hours to obtain the microwave dielectric ceramic material.
Example 5
The microwave dielectric ceramic material comprises 98 wt% of main material and 2 wt% of additive, wherein the structural expression of the main material is (Pb)x/4Bix/2)(Alx/3Mo2x/3V1-x)O4Wherein x is 0.32, and the additive is Ni (CH)3COO)21wt％、Mg(CH3COO)20.5 wt% and In (CH)3COO)30.5wt％。
The preparation method of the microwave dielectric ceramic material comprises the following steps:
(1) preparation of the major Material
A: according to (Pb)x/4Bix/2)(Alx/3Mo2x/3V1-x)O4Taking PbO and Bi2O3、Al2O3、V2O5、MoO3Preparing materials, wherein x is 0.32;
b: b, putting the mixture obtained in the step A into a ball mill, adding ethanol, fully ball-milling for 6 hours, drying at 100 ℃, sieving with a 200-mesh sieve, and pressing into blocks;
c: b, sintering the block in the step B at 600 ℃ for 4h to obtain a sample sintered block;
d: c, crushing the sample clinker in the step C, adding ethanol into a ball mill, performing secondary ball milling, drying at 110 ℃, granulating, sieving by a 60-mesh and 100-mesh double-layer screen, pressing and molding part of powder between the two layers of screens, and sintering at 630 ℃ for 7 hours to obtain a main material;
(2) and (2) adding additives into the main material prepared in the step (1), uniformly mixing, performing ball milling again, drying at 120 ℃, granulating, sieving by a double-layer screen of 80 meshes and 120 meshes, performing compression molding on the sieved powder, and sintering at 750 ℃ for 4 hours to obtain the microwave dielectric ceramic material.
Comparative example 1
Comparative example 1 provides a microwave dielectric ceramic material, which is different from example 1 in that: omitting Ni (CH) from the additive3COO)2Otherwise, the same as in example 1 was repeated.
Comparative example 2
Comparative example 2 provides a microwave dielectric ceramic material, which is different from example 1 in that: omitting Mg (CH) from the additives3COO)2Otherwise, the same as in example 1 was repeated.
Comparative example 3
Comparative example 3 provides a microwave dielectric ceramic material, which is different from example 1 in that: omitting In (CH) from the additive3COO)3Otherwise, the same as in example 1 was repeated.
Comparative example 4
Comparative example 4 provides a microwave dielectric ceramic material, which is different from example 1 in that: omitting Ni (CH) from the additive3COO)2And Mg (CH)3COO)2In (CH)3COO)3The amount of the catalyst was adjusted to 5% by weight, and the rest was the same as in example 1.
Comparative example 5
Comparative example 5 provides a microwave dielectric ceramic material, which is different from example 1 in that: omitting Ni (CH) from the additive3COO)2And In (CH)3COO)3Mixing Mg (CH)3COO)2The amount of the catalyst was adjusted to 5% by weight, and the rest was the same as in example 1.
Comparative example 6
Comparative example 6 provides a microwave dielectric ceramic material, which is different from example 1 in that: omitting Mg (CH) from the additives3COO)2And In (CH)3COO)3Mixing Ni (CH)3COO)2The amount of the catalyst was adjusted to 5% by weight, and the rest was the same as in example 1.
Comparative example 7
Comparative example 7 provides a microwave dielectric ceramic material, which is different from example 1 in that: mixing Ni (CH)3COO)2The substitution with NiO was conducted in the same manner as in example 1.
Comparative example 8
Comparative example 8 provides a microwave dielectric ceramic material, which is different from example 1 in that: mixing Mg (CH)3COO)2The procedure of example 1 was repeated except that MgO was used instead.
Comparative example 9
Comparative example 9 provides a microwave dielectric ceramic material, which is different from example 1 in that: in (CH)3COO)3Substitution with In2O3Otherwise, the same as in example 1 was repeated.
The dielectric properties of the microwave dielectric ceramic materials of examples 1 to 5 and comparative examples 1 to 9 were measured, respectively, and the results are shown in table 1.
TABLE 1
As can be seen from Table 1, the microwave dielectric ceramic materials of embodiments 1 to 5 of the present invention have high relative dielectric constant and quality factor, small temperature coefficient of resonant frequency, good microwave performance and high reliability. In comparative examples 1 to 6, the composition of the additive was adjusted, and the dielectric constant and quality factor of the ceramic material prepared by omitting one or both of the components were lower than those of examples 1 to 5 under the same sintering conditions, and the ceramic material had a high temperature coefficient of resonance frequency and unstable properties. Similarly, in comparative examples 7 to 9, the additives were replaced with the corresponding metal oxides, and the prepared microwave dielectric ceramic material was inferior to examples 1 to 5 of the present invention in terms of properties, both dielectric constant and quality factor, to the present inventionInventive examples 1 to 5 further illustrate that the microwave dielectric ceramic material of the present invention is made of a main material and an additive, and specifically the composition of the additive is limited to Ni (CH)3COO)2、Mg(CH3COO)2And In (CH)3COO)3Compared with the addition of metal oxide, the prepared microwave dielectric ceramic material has higher dielectric constant and quality factor under the condition of lower sintering temperature, lower temperature coefficient of resonance frequency and stable performance, can be co-fired with Ag electrodes, is used in a microwave dielectric ceramic antenna, contributes to reducing the size of the microwave dielectric ceramic antenna, is suitable for the development requirements of miniaturization and chip type of electronic elements, and can be widely applied to the field of 5G communication.
In conclusion, the main material (Pb) of the microwave dielectric ceramic material of the inventionx/2Bix/2)(Alx/3Mo2x/3V1-x)O4With ABO4Structure based, adding Ni (CH)3COO)2、Mg(CH3COO)2And In (CH)3COO)3As an additive, the microwave dielectric ceramic material obtained by sintering has high relative dielectric constant, good microwave performance and low loss, meets the requirements of low-temperature co-fired ceramic electronic elements, is applied to microwave dielectric ceramic antennas, and has the characteristics of good stability and excellent performance.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (8)
1. The microwave dielectric ceramic material is characterized by comprising a main material and an additive, wherein the mass percent of each component is as follows: 95-98 wt% of main material and 2-5 wt% of additive, wherein the structural expression of the main material is (Pb)x/4Bix/2)(Alx/3Mo2x/3V1-x)O4Wherein x is more than or equal to 0.05 and less than or equal to 0.85, and the additive is Ni (CH)3COO)2、Mg(CH3COO)2And In (CH)3COO)3。
2. A microwave dielectric ceramic material as claimed in claim 1, wherein the additive comprises the following components in percentage by weight: ni (CH)3COO)21-2.5wt％、Mg(CH3COO)20.5-1.5wt％、In(CH3COO)30.5-1wt％。
3. A microwave dielectric ceramic material according to claim 1, wherein the microwave dielectric ceramic material has a relative dielectric constantr75-85, Q × f value of 9800-10100 GHz, and resonant frequency temperature coefficient of-20- +20 ppm/DEG C.
4. A method for preparing a microwave dielectric ceramic material as claimed in claim 1, comprising the steps of:
(1) preparation of the major Material
A: according to (Pb)x/4Bix/2)(Alx/3Mo2x/3V1-x)O4Taking PbO and Bi2O3、Al2O3、V2O5、MoO3Mixing materials, wherein x is more than or equal to 0.05 and less than or equal to 0.85;
b: b, fully ball-milling the mixture obtained in the step A, drying, sieving and pressing into blocks;
c: sintering the block in the step B at the temperature of 550-600 ℃ for 4-8h to obtain a sample sintered block;
d: c, crushing the sample clinker in the step C, performing secondary ball milling, drying, granulating, sieving, pressing and molding the sieved powder, and sintering at the temperature of 600-650 ℃ for 6-8 hours to obtain a main material;
(2) and (2) adding an additive into the main material prepared in the step (1), uniformly mixing, performing ball milling again, drying, granulating, sieving, performing compression molding on the sieved powder, and sintering at the temperature of 700-.
5. The preparation method of the microwave dielectric ceramic material as claimed in claim 4, wherein the ethanol is added in the step (1) for ball milling for 4-6 h.
6. The method for preparing microwave dielectric ceramic material as claimed in claim 4, wherein the drying temperature in the steps (1) and (2) is 100-120 ℃.
7. The method for preparing microwave dielectric ceramic material according to claim 4, wherein step B is performed by using a 200-mesh screen in step (1), step D is performed by using a 60-mesh and 100-mesh double-layer screen, and step (2) is performed by using an 80-mesh and 120-mesh double-layer screen.
8. Use of the microwave dielectric ceramic material as claimed in claim 1 for the manufacture of a microwave dielectric ceramic antenna.
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