CN108002833B - Microwave dielectric ceramic material with hexagonal perovskite structure and preparation method thereof - Google Patents

Microwave dielectric ceramic material with hexagonal perovskite structure and preparation method thereof Download PDF

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CN108002833B
CN108002833B CN201711299584.7A CN201711299584A CN108002833B CN 108002833 B CN108002833 B CN 108002833B CN 201711299584 A CN201711299584 A CN 201711299584A CN 108002833 B CN108002833 B CN 108002833B
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苏聪学
覃杏柳
张志伟
方亮
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Guilin University of Technology
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Abstract

The invention discloses a microwave dielectric ceramic material with a hexagonal perovskite structure and a preparation method thereof. The ceramic material main body is ASr3LaM4O15(A ═ Na, K; (M ═ Nb, Ta), 0.5 to 1.5% by weight of BaCu (B)2O5). The material is prepared by a traditional high-temperature solid-phase synthesis method, a small amount of dispersing agent is added in the secondary ball milling process, and then ultrasonic vibration is carried out in a thermal environment, so that sample powder particles are not easy to agglomerate. The material prepared by the method is well sintered at 1230-1260 ℃, the dielectric constant is 30.4-31.9, the quality factor Qf value is as high as 43700-59100GHz, and the temperature coefficient of the resonant frequency is small. Meanwhile, the invention discloses ASr with a B-site vacancy type hexagonal perovskite structure for the first time3LaM4O15The (A ═ Na, K ═ M ═ Nb, Ta) ceramics have good microwave dielectric properties.

Description

Microwave dielectric ceramic material with hexagonal perovskite structure and preparation method thereof
Technical Field
The present invention relates to a dielectric ceramic material, and more particularly, to a dielectric ceramic material for manufacturing microwave components such as ceramic substrates, resonators, and filters used for microwave frequencies, and a method for manufacturing the same.
Background
The rapid development of modern mobile communication has promoted the rapid development of various microwave mobile communication terminal devices toward miniaturization, light weight, multiple functions and low cost. The dielectric ceramic used for manufacturing devices such as dielectric resonators, filters, capacitors, dielectric substrates and the like must satisfy the following conditions: the high relative dielectric constant is used for realizing the miniaturization of the device and improving the integration level, the low dielectric loss is used for improving the frequency selection characteristic, and the temperature coefficient of the resonance frequency approaching zero is used for improving the temperature stability of the device.
Due to three performance indexes of microwave dielectric ceramics: (rAnd Q.f and τf) The dielectric constants of B-site deficient type hexagonal perovskite ceramics such as Ba (Sr) -L a-Ta (Nb), Ba (Sr) -L a-Ti-Ta (Nb), L a-Mg (Zn) -Ti, Ba-Zn (Mg or Ni) -Ta, Ba-Ti-Nb and the like are more than 30, and the dielectric constants of some microwave dielectric ceramics are more than taufSmaller (-20 ppm/. degree.C.. ltoreq.taufLess than or equal to 20 ppm/DEG C), and even taufClose to zero, but the sintering temperature is above 1380 ℃, some sintering temperatures are even as high as 1600 ℃, and most quality factors are less than 40000GHz, which seriously restricts the practical application of the ceramic, so that a plurality of sintering aids (generally accounting for the weight of the ceramic) are required to be added3% -5%) can lower the sintering temperature, but the performance is worsened.
At present, most of the research on the microwave dielectric ceramics is summarized by experience obtained through a large number of experiments, but a complete theory is not provided for explaining the relation between the microstructure and the dielectric property, and the microwave dielectric properties such as the resonant frequency temperature coefficient, the quality factor and the like of the compound cannot be theoretically predicted from the composition and the structure of the compound. More importantly, the preparation process of the microwave dielectric ceramic material is also one of the main factors influencing the microwave dielectric property of the material, from the commercialized microwave dielectric ceramic to the recent microwave dielectric ceramic material with better comprehensive microwave dielectric property, the main preparation method is a high-temperature solid-phase synthesis method, because the method has mature technology, simple process and high production efficiency, and has operability and economic value in industrial production compared with wet chemical methods represented by a sol-gel method, a hydrothermal method and the like, but the inherent defects of the high-temperature solid-phase synthesis method, such as large energy consumption, easy agglomeration of particles after ball milling and the like, still need to draw sufficient attention in the field.
Disclosure of Invention
Based on the problems, the invention aims to provide a novel microwave dielectric ceramic material containing Na or K and having a B-site vacancy type hexagonal perovskite structure and a method for preparing the microwave dielectric ceramic material. The microwave dielectric ceramic material has good thermal stability and low loss, the sintering temperature is lower than 1300 ℃, and the main compound in the material is the compound with good microwave dielectric property reported for the first time.
In order to overcome the defects of the prior art, the technical scheme provided by the invention is as follows:
a microwave dielectric ceramic material with a hexagonal perovskite structure comprises a main body and BaCu (B) accounting for 0.5-1.5 wt% of the main body2O5) The main body is ASr3LaM4O15(A ═ Na, K; M ═ Nb, Ta); the microwave dielectric property of the ceramic material is as follows: the dielectric constant is 30.4 to 31.9, the quality factor Qf is 43700 to 59100GHz, and the temperature coefficient of the resonance frequency is-33.9 ppm/DEG C to 12.6 ppm/DEG C.
Further, in the ceramic material, the main body ASr3LaM4O15The structure of (A ═ Na, K ═ M ═ Nb, Ta) is a hexagonal perovskite structure, the quality factor is 40000-62100 GHz, and the dielectric constant is 32.1-33.5.
The preparation method of the microwave dielectric ceramic material with the hexagonal perovskite structure comprises the following steps:
(1) preparation of the main body: with Na2CO3、K2CO3、SrCO3、La2O3、Nb2O5And Ta2O5L a is firstly used as raw material2O3Presintering for 8 hours at 880 ℃; these raw materials are then processed according to ASr3LaM4O15(A ═ Na, K; M ═ Nb, Ta) are weighed in stoichiometric proportions and mixed; then carrying out wet ball milling on the weighed raw materials for 2 hours; drying after ball milling to obtain raw material mixture powder, pressing the powder into a block body, and keeping the temperature at 1200 ℃ for 4 hours to obtain a sample burning block of a main body;
(2) grinding the sample clinker of the main body in the step (1), and then adding BaCu (B) accounting for 0.5-1.5 wt% of the main body2O5) Mixing the sample with a main sample to be used as a sample and putting the sample into a ball milling tank, wherein zirconia balls and deionized water are filled in the ball milling tank in advance; putting the ball milling tank into a ball mill, setting the revolution speed of the ball mill to be 280rpm, and stopping wet ball milling for 2 hours; adding a small amount of dispersant into the ball milling tank, then carrying out ball milling for 1 hour in a ball milling tank autorotation mode at the rotating speed of 300rpm, and drying after ball milling to obtain sample powder;
(3) putting the dried sample powder into a ball milling tank filled with a proper amount of mixed solution of deionized water and ethanol in a certain ratio, and putting the ball milling tank into an ultrasonic cleaning machine filled with water, wherein the ball milling tank is fixed in the water, and the height of the water is half of the height of the ball milling tank; setting a heating and heat-preserving program of the ultrasonic cleaning machine, heating water in the cleaning machine to 40 ℃, and preserving heat at the temperature; then closing the cover of the ball milling tank, starting ultrasonic vibration, and ultrasonically vibrating the sample powder in a sealed environment at the ultrasonic frequency of 50kHz for 30 minutes; then removing the cover of the ball milling tank, heating the water in the ultrasonic cleaning machine to 95 ℃, keeping the temperature, and ultrasonically vibrating for 30 minutes at the ultrasonic frequency of 30 kHz;
(4) and drying after the ultrasonic vibration is finished to obtain sample powder, then granulating, sieving, pressing and molding the sieved particles, and sintering at 1230-1260 ℃ for 4 hours to obtain the ceramic material of the microwave medium with the hexagonal perovskite structure.
Preferably, in the preparation method of the microwave dielectric ceramic material with the hexagonal perovskite structure, the dispersant is a mixture liquid of sodium polyacrylate, sodium hexametaphosphate, sodium pyrophosphate and polyethylene glycol, and the addition amount of the dispersant is 0.1% of the mass of the sample; the mass ratio of the sodium polyacrylate, the sodium hexametaphosphate, the sodium pyrophosphate and the polyethylene glycol is 3:1:1: 1.
Preferably, in the preparation method of the microwave dielectric ceramic material with the hexagonal perovskite structure, the mixed solution of deionized water and ethanol in the step (3) is composed of the following components in proportion: deionized water weight: ethanol weight 1: 9.
compared with the prior art, the invention has the advantages that: 1. by adopting the technical scheme of the invention, the ASr with good microwave dielectric property is reported for the first time3LaM4O15Mainly (A ═ Na, K; M ═ Nb, Ta), and a very small amount of BaCu (B) added2O5) The microwave dielectric ceramic material with medium dielectric constant, high quality factor and good comprehensive microwave dielectric property can be obtained by high-temperature sintering. 2. The technical scheme adopted by the invention is further improved on the traditional high-temperature solid-phase synthesis method, a proper amount of ceramic powder dispersing agent with a proper formula is added in the secondary ball milling process, so that the powder particles of a ball-milled sample are not easy to agglomerate, then the sample is subjected to ultrasonic vibration in a high-temperature water environment, and simultaneously the mixed solution of water and ethanol is volatilized at high temperature, so that the sample is better prevented from molecular agglomeration in the liquid, the particles of the sample are finer, the dispersing agent added in the secondary ball milling can be primarily separated, and the obtained sample is sintered to obtain the microwave dielectric ceramic which is more compact and has more excellent performance.
Detailed Description
The above-described scheme is further illustrated below with reference to specific examples. It should be understood that these examples are for illustrative purposes and are not intended to limit the scope of the present invention.
Example 1
(1) Preparation of the main body: with Na2CO3、SrCO3、La2O3And Nb2O5L a is firstly used as raw material2O3Presintering for 8 hours at 880 ℃; then the raw materials are mixed according to NaSr3LaNb3O15Weighing and mixing according to a stoichiometric ratio; then carrying out wet ball milling on the weighed raw materials for 2 hours; drying after ball milling to obtain raw material mixture powder, pressing the powder into a block body, and keeping the temperature at 1200 ℃ for 4 hours to obtain a sample burning block of a main body;
(2) grinding the sample sintered block of the main body in the step (1), and then adding BaCu (B) accounting for 1.5 percent of the weight of the main body2O5) Mixing the sample with a main sample to be used as a sample and putting the sample into a ball milling tank, wherein zirconia balls and deionized water are filled in the ball milling tank in advance; putting the ball milling tank into a ball mill, setting the revolution speed of the ball mill to be 280rpm, and stopping wet ball milling for 2 hours; adding a small amount of dispersant into the ball milling tank, then carrying out ball milling for 1 hour in a ball milling tank autorotation mode at the rotating speed of 300rpm, and drying after ball milling to obtain sample powder;
(3) putting the dried sample powder into a ball milling tank filled with a proper amount of mixed solution of deionized water and ethanol in a certain ratio, and putting the ball milling tank into an ultrasonic cleaning machine filled with water, wherein the ball milling tank is fixed in the water, and the height of the water is half of the height of the ball milling tank; setting a heating and heat-preserving program of the ultrasonic cleaning machine, heating water in the cleaning machine to 40 ℃, and preserving heat at the temperature; then closing the cover of the ball milling tank, starting ultrasonic vibration, and ultrasonically vibrating the sample powder in a sealed environment at the ultrasonic frequency of 50kHz for 30 minutes; then removing the cover of the ball milling tank, heating the water in the ultrasonic cleaning machine to 95 ℃, keeping the temperature, and ultrasonically vibrating for 30 minutes at the ultrasonic frequency of 30 kHz;
(4) and drying after the ultrasonic vibration is finished to obtain sample powder, then granulating, sieving, pressing and molding the sieved particles, and sintering at 1240 ℃ for 4 hours to obtain the ceramic, thus obtaining the microwave dielectric ceramic material with the hexagonal perovskite structure.
The dispersing agent is a mixture liquid of sodium polyacrylate, sodium hexametaphosphate, sodium pyrophosphate and polyethylene glycol, and the addition amount of the dispersing agent is 0.1 percent of the mass of the sample; the mass ratio of the sodium polyacrylate, the sodium hexametaphosphate, the sodium pyrophosphate and the polyethylene glycol is 3:1:1: 1. The deionized water and ethanol mixed solution in the step (3) is composed of the following components in parts by weight: deionized water weight: ethanol weight 1: 9.
the microwave dielectric properties of the group of ceramic materials are as follows: the dielectric constant is 30.4, the quality factor is 49400GHz, and the temperature coefficient of the resonance frequency is-26.4 ppm/DEG C.
Example 2
In step (1) of example 1, as NaSr3LaNb3O15Weighing a preparation main body according to a stoichiometric ratio; in step (2) of example 1, BaCu (B)2O5) Accounts for 0.5 percent of the weight of the main body; in the step (4) of example 1, the sieved granules were press-molded and then sintered at 1250 ℃ for 4 hours to form porcelain; the other steps (including raw materials) are the same as the example 1, and the composition and the addition amount of the dispersant, the deionized water and the ethanol mixed solution are the same as the example 1, so that the microwave dielectric ceramic material with the hexagonal perovskite structure is obtained.
The microwave dielectric properties of the group of ceramic materials are as follows: the dielectric constant is 30.9, the quality factor is 52000GHz, and the temperature coefficient of the resonance frequency is-8.6 ppm/DEG C.
Example 3
In step (1) of example 1, as NaSr3LaTa3O15Stoichiometric ratio weighing preparation of main body and raw material Ta2O5Replacing Nb2O5(ii) a In the step (4) of example 1, the sieved granules were press-molded and then sintered at 1230 ℃ for 4 hours to form porcelain; the other steps (including raw materials) are the same as the example 1, the composition and the addition amount of the dispersant, the deionized water and the ethanol mixed solution are the same as the example 1, and the hexagonal perovskite structure microwave medium is obtainedA ceramic material.
The microwave dielectric properties of the group of ceramic materials are as follows: the dielectric constant is 30.9, the quality factor is 50000GHz, and the temperature coefficient of the resonance frequency is-13.9 ppm/DEG C.
Example 4
In step (1) of example 1, as NaSr3LaTa3O15Stoichiometric ratio weighing preparation of main body and raw material Ta2O5Replacing Nb2O5(ii) a In step (2) of example 1, BaCu (B)2O5) Accounts for 0.5 percent of the weight of the main body; in the step (4) of example 1, the sieved granules were press-molded and then sintered at 1260 ℃ for 4 hours to form porcelain; the other steps (including raw materials) are the same as the example 1, and the composition and the addition amount of the dispersant, the deionized water and the ethanol mixed solution are the same as the example 1, so that the microwave dielectric ceramic material with the hexagonal perovskite structure is obtained.
The microwave dielectric properties of the group of ceramic materials are as follows: the dielectric constant is 31.9, the quality factor is 59100GHz, and the temperature coefficient of the resonance frequency is 12.6 ppm/DEG C.
Example 5
In step (1) of example 1, according to KSr3LaNb3O15Stoichiometric weighing of the preparation body, raw material K2CO3Substitution of Na2CO3(ii) a In step (4) of example 1, the sieved granules were press-molded and then sintered at 1240 ℃ for 4 hours to form porcelain, except that BaCu (B) was not added in the whole process2O5) The other steps are the same as the example 1, and the composition and the addition amount of the dispersant, the deionized water and the ethanol mixed solution are the same as the example 1, so that the microwave dielectric ceramic material with the hexagonal perovskite structure is obtained.
The microwave dielectric properties of the group of ceramic materials are as follows: the dielectric constant is 30.8, the quality factor is 49700GHz, and the temperature coefficient of the resonance frequency is-33.9 ppm/DEG C.
Example 6
In step (1) of example 1, according to KSr3LaNb3O15Stoichiometric weighing of the preparation body, raw material K2CO3Replacement ofNa2CO3(ii) a In step (2) of example 1, BaCu (B)2O5) Accounts for 0.5 percent of the weight of the main body; in the step (4) of the embodiment 1, the sieved particles are pressed and molded, and then sintered at 1260 ℃ for 4 hours to form porcelain, the other steps are the same as the embodiment 1, and the composition and the addition amount of the dispersing agent, the deionized water and the ethanol mixed solution are the same as those of the embodiment 1, so that the microwave dielectric ceramic material with the hexagonal perovskite structure is obtained.
The microwave dielectric properties of the group of ceramic materials are as follows: the dielectric constant is 31.5, the quality factor is 45100GHz, and the temperature coefficient of the resonance frequency is-9.4 ppm/DEG C.
Example 7
In step (1) of example 1, according to KSr3LaTa3O15Stoichiometric weighing of the preparation body, raw material K2CO3Substitution of Na2CO3，Ta2O5Replacing Nb2O5(ii) a In the step (4) of the example 1, the sieved particles are pressed and molded, and then sintered for 4 hours at 1245 ℃ to form porcelain, the other steps are the same as the example 1, and the composition and the addition amount of the dispersant, the deionized water and the ethanol mixed solution are the same as those of the example 1, so that the microwave dielectric ceramic material with the hexagonal perovskite structure is obtained.
The microwave dielectric properties of the group of ceramic materials are as follows: the dielectric constant is 30.8, the quality factor is 52300GHz, and the temperature coefficient of the resonance frequency is-11.4 ppm/DEG C.
Example 8
In step (1) of example 1, according to KSr3LaTa3O15Stoichiometric weighing of the preparation body, raw material K2CO3Substitution of Na2CO3，Ta2O5Replacing Nb2O5(ii) a In step (2) of example 1, BaCu (B)2O5) Accounts for 0.5 percent of the weight of the main body; in the step (4) of the example 1, the sieved particles are pressed and molded, and then sintered at 1260 ℃ for 4 hours to form porcelain, the other steps are the same as the example 1, and the composition and the addition amount of the dispersing agent, the deionized water and the ethanol mixed solution are the same as the example 1, so that the hexagonal calcium is obtainedA titanium ore structure microwave dielectric ceramic material.
The microwave dielectric properties of the group of ceramic materials are as follows: the dielectric constant is 31.3, the quality factor is 55500GHz, and the temperature coefficient of the resonant frequency is 6.2 ppm/DEG C.
Example 9
In step (1) of example 1, NaSr is followed, respectively3LaNb3O15、NaSr3LaTa3O15、KSr3LaNb3O15And KSr3LaTa3O15Stoichiometric weighing preparation body, and raw material is taken from Na2CO3、K2CO3、SrCO3、La2O3、Nb2O5And Ta2O5(ii) a In step (4) of example 1, the sieved granules were press-molded and then sintered at 1300 ℃ for 4 hours to form porcelain, except that BaCu (B) was not added in the whole process2O5) The other steps are the same as the example 1, and the composition and the addition amount of the dispersant, the deionized water and the ethanol mixed solution are the same as the example 1, so that the microwave dielectric ceramic material with the hexagonal perovskite structure is obtained.
The microwave dielectric properties of the group of ceramic materials are as follows: a dielectric constant of 32.1 to 33.5, a quality factor of 40000 to 62100GHz, and a temperature coefficient of resonance frequency of-26.6 ppm/DEG C to 16.9 ppm/DEG C
Phase structure analysis of the host of all the above examples revealed that the host was a hexagonal perovskite structure.
While the invention has been described in further detail with reference to specific preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (4)

1. The microwave dielectric ceramic material with the hexagonal perovskite structure is characterized by comprising a main body and a ceramic material occupying the weight of the main bodyBaCu (B) in an amount of 0.5 to 1.5% by weight2O5) The main body is ASr3LaM4O15Wherein: a is Na, K; m ═ Nb, Ta; the microwave dielectric property of the ceramic material is as follows: a dielectric constant of 30.4 to 31.9, a quality factor Qf of 43700 to 59100GHz, and a temperature coefficient of resonance frequency of-33.9 ppm/DEG C to 12.6 ppm/DEG C;
the preparation method of the microwave dielectric ceramic material with the hexagonal perovskite structure comprises the following steps:
(1) preparation of the main body: with Na2CO3、K2CO3、SrCO3、La2O3、Nb2O5And Ta2O5L a is firstly used as raw material2O3Presintering for 8 hours at 880 ℃; these raw materials are then processed according to ASr3LaM4O15Wherein: a is Na, K; m ═ Nb, Ta; weighing and mixing according to a stoichiometric ratio; then carrying out wet ball milling on the weighed raw materials for 2 hours; drying after ball milling to obtain raw material mixture powder, pressing the powder into a block body, and keeping the temperature at 1200 ℃ for 4 hours to obtain a sample burning block of a main body;
(2) grinding the sample clinker of the main body in the step (1), and then adding BaCu (B) accounting for 0.5-1.5 wt% of the main body2O5) Mixing the sample with a main sample to be used as a sample and putting the sample into a ball milling tank, wherein zirconia balls and deionized water are filled in the ball milling tank in advance; putting the ball milling tank into a ball mill, setting the revolution speed of the ball mill to be 280rpm, and stopping wet ball milling for 2 hours; adding a small amount of dispersant into the ball milling tank, then carrying out ball milling for 1 hour in a ball milling tank autorotation mode at the rotating speed of 300rpm, and drying after ball milling to obtain sample powder;
(3) putting the dried sample powder into a ball milling tank filled with a proper amount of mixed solution of deionized water and ethanol in a certain ratio, and putting the ball milling tank into an ultrasonic cleaning machine filled with water, wherein the ball milling tank is fixed in the water, and the height of the water is half of the height of the ball milling tank; setting a heating and heat-preserving program of the ultrasonic cleaning machine, heating water in the cleaning machine to 40 ℃, and preserving heat at the temperature; then closing the cover of the ball milling tank, starting ultrasonic vibration, and ultrasonically vibrating the sample powder in a sealed environment at the ultrasonic frequency of 50kHz for 30 minutes; then removing the cover of the ball milling tank, heating the water in the ultrasonic cleaning machine to 95 ℃, keeping the temperature, and ultrasonically vibrating for 30 minutes at the ultrasonic frequency of 30 kHz;
(4) and drying after the ultrasonic vibration is finished to obtain sample powder, then granulating, sieving, pressing and molding the sieved particles, and sintering at 1230-1260 ℃ for 4 hours to obtain the ceramic material of the microwave medium with the hexagonal perovskite structure.
2. A hexagonal perovskite structure microwave dielectric ceramic material as claimed in claim 1, characterized in that in the ceramic material, the main body ASr3LaM4O15Wherein: a is Na, K; m ═ Nb, Ta; the structure is a hexagonal perovskite structure, the quality factor is 40000-62100 GHz, and the dielectric constant is 32.1-33.5.
3. The hexagonal perovskite structure microwave dielectric ceramic material as claimed in claim 1, wherein in the preparation method of the hexagonal perovskite structure microwave dielectric ceramic material, the dispersant is a mixture liquid of sodium polyacrylate, sodium hexametaphosphate, sodium pyrophosphate and polyethylene glycol, and the addition amount of the dispersant is 0.1% of the mass of the sample; the mass ratio of the sodium polyacrylate, the sodium hexametaphosphate, the sodium pyrophosphate and the polyethylene glycol is 3:1:1: 1.
4. The hexagonal perovskite structure microwave dielectric ceramic material as claimed in claim 1, wherein in the preparation method of the hexagonal perovskite structure microwave dielectric ceramic material, the mixed solution of deionized water and ethanol in step (3) is composed of the following components in proportion: deionized water weight: ethanol weight 1: 9.
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