CN107986785B - High-quality-factor microwave dielectric ceramic material and preparation method thereof - Google Patents

High-quality-factor microwave dielectric ceramic material and preparation method thereof Download PDF

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CN107986785B
CN107986785B CN201711299592.1A CN201711299592A CN107986785B CN 107986785 B CN107986785 B CN 107986785B CN 201711299592 A CN201711299592 A CN 201711299592A CN 107986785 B CN107986785 B CN 107986785B
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苏聪学
覃杏柳
陈军奇
方亮
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Guilin University of Technology
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Abstract

The invention discloses a high-quality-factor microwave dielectric ceramic material and a preparation method thereof. The main body of the ceramic material is Sr3La2‑xGa1+xM3O15(M ═ Nb, Ta), where x is 0. ltoreq. x.ltoreq.0.6, and 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 1270-1290 ℃, the dielectric constant is 29.4-33.7, the quality factor Qf value is up to 107000-. Meanwhile, the invention discloses Sr for the first time3La2‑xGa1+xM3O15(M ═ Nb, Ta), where 0. ltoreq. x.ltoreq.0.6, have good microwave dielectric properties.

Description

High-quality-factor microwave dielectric ceramic material 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
In recent years, modern communication technology is rapidly developed, and the traditional 2G-4G communication network is difficult to meet the requirement of higher and higher information transmission speed. Research and test of 5G communication networks are accelerated at home and abroad, and the 5G communication networks are different from 2.5GHz communication frequency bands adopted by 2G-4G communication networks, and the 5G communication networks require 28GHz Ka wave bands as communication wave bands. For the microwave dielectric ceramics, to satisfy the communication frequency requirement of 28GHz, the quality factor thereof needs to be more than or equal to 90000GHz, however, there are few microwave dielectric ceramics satisfying such high quality factor, and due to three performance indexes of microwave dielectric ceramics: (rAnd Q.f and τf) Are in a mutually restrictive relationship (see literature: restriction relation among dielectric properties of microwave dielectric ceramic materials, Zhujianhua, Liangfei, Wanghua, Lu text, electronic elements and materials, 3 rd 3 th 2005), and single-phase microwave dielectric ceramics which meet requirements of medium and high dielectric constant, high quality factor and near-zero resonant frequency temperature coefficient are particularly scarce. Such as recently reported Ba3Zn(Nb2-xMox)O9+x/2(CN107382314A)、Mg2.5+xTaNbO7.5+x+ywt％B2O3Quality factor of + zwt% C (CN107382313A) and other ceramics is in90000GHz or more, but Ba3Zn(Nb2-xMox)O9+x/2The sintering temperature is above 1400 ℃, the energy consumption in the process is large, and the value range of x is very narrow (x is 0.006-0.009); mg (magnesium)2.5+xTaNbO7.5+x+ywt％B2O3The proportion of x also needs to be strictly controlled when C is + zwt% (x is more than or equal to 0 and less than or equal to 0.2), the value range of x is narrow, and once the value range exceeds the range, a mixed phase is easy to generate, so that the performance is reduced, and the actual production process is not facilitated, and the dielectric constants of the C and the X are less than 20, so that the miniaturization and the high integration of the devices are not facilitated, and the practical application of the C and the X are severely restricted.
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
In view of the above problems, it is an object of the present invention to provide a novel microwave dielectric ceramic material with a high quality factor and a method for preparing the same. The microwave dielectric ceramic material has good thermal stability and low loss, the sintering temperature is lower than 1330 ℃, 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 high quality factor is characterized in that the ceramic material comprises a main body and BaCu (B) accounting for 0.5-1.5 wt% of the main body2O5) The main body is Sr3La2-xGa1+xM3O15(M ═ Nb, Ta), where 0 ≦ x ≦ 0.6; the microwave dielectric property of the ceramic material is as follows: a dielectric constant of 29.4 to 33.7, a quality factor Qf of 107000 to 139000GHz, and a temperature coefficient of resonance frequency of-22 ppm/DEG C to 12.3 ppm/DEG C;
the preparation method of the high-quality factor constant microwave dielectric ceramic material comprises the following steps:
(1) preparation of the main body: with SrCO3、La2O3、Ga2O3、Nb2O5And Ta2O5Firstly, La is used as raw material2O3Presintering for 8 hours at 880 ℃; then the raw materials are mixed according to Sr3La2-xGa1+xM3O15(M ═ Nb, Ta) where x is 0. ltoreq. x.ltoreq.0.6 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 preserving heat at 1250 ℃ 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 1270-1290 ℃ for 4 hours to obtain the ceramic, thus obtaining the high-quality-factor microwave dielectric ceramic material.
Preferably, in the preparation method of the high-quality factor constant microwave dielectric ceramic material, 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% 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 high-quality-factor microwave dielectric ceramic material, the deionized water and ethanol mixed solution 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, Sr with good microwave dielectric property is reported for the first time3La2-xGa1+xM3O15(M ═ Nb, Ta) where x is 0. ltoreq. x.ltoreq.0.6 as a main component, and a very small amount of BaCu (B) added2O5) The microwave dielectric ceramic material with high quality factor, good temperature stability 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, the 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 water and ethanol mixed solution is volatilized at a high temperature, so that the sample is subjected to ultrasonic vibration in the high-temperature water environmentThe liquid can better avoid molecular agglomeration, the sample particles are finer, the dispersing agent added by secondary ball milling can be primarily separated, and the microwave dielectric ceramic obtained by sintering the obtained sample 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 SrCO3、La2O3、Ga2O3And Nb2O5Firstly, La is used as raw material2O3Presintering for 8 hours at 880 ℃; then the raw materials are mixed according to Sr3La2GaNb3O15Weighing 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 preserving heat at 1250 ℃ 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 then sintering at 1270 ℃ for 4 hours to obtain the ceramic, thus obtaining the high-quality factor constant microwave dielectric ceramic material.
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 30.6, the quality factor is 107000GHz, and the temperature coefficient of the resonance frequency is-22 ppm/DEG C.
Example 2
In step (1) of example 1, according to Sr3La1.5Ga1.5Nb3O15Weighing a preparation main body according to a stoichiometric ratio; in step (2) of example 1, BaCu (B)2O5) Accounts for 1 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 1280 ℃ for 4 hours to make porcelain; the other steps (including raw materials) 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 microwave dielectric ceramic material with high quality factor is obtained.
The microwave dielectric properties of the group of ceramic materials are as follows: the dielectric constant is 33.7, the quality factor is 127000GHz, and the temperature coefficient of the resonance frequency is-13.2 ppm/DEG C.
Example 3
In step (1) of example 1, according to Sr3La1.4Ga1.6Nb3O15Stoichiometric weighing of the preparation body, in example 1In the step (2), 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 1285 ℃ for 4 hours to make porcelain; the other steps (including raw materials) are the same as those in 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 in example 1, so that the high-quality factor constant microwave dielectric ceramic material is obtained.
The microwave dielectric properties of the group of ceramic materials are as follows: the dielectric constant is 32.3, the quality factor is 116300GHz, and the temperature coefficient of the resonance frequency is-7.1 ppm/DEG C.
Example 4
In step (1) of example 1, according to Sr3La2GaTa3O15Stoichiometric ratio weighing preparation of main body and raw material Ta2O5Replacing Nb2O5(ii) a In step (2) of example 1, BaCu (B)2O5) Accounts for 1.5 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 high-quality-factor microwave dielectric ceramic material is obtained.
The microwave dielectric properties of the group of ceramic materials are as follows: the dielectric constant is 29.4, the quality factor is 116000GHz, and the temperature coefficient of the resonant frequency is-13.9 ppm/DEG C.
Example 5
In step (1) of example 1, according to Sr3La1.5Ga1.5Ta3O15Stoichiometric ratio weighing preparation of main body and raw material Ta2O5Replacing Nb2O5(ii) a In step (2) of example 1, BaCu (B)2O5) Accounts for 1.2 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 for 4 hours at 1280 ℃ 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 microwave dielectric ceramic material with high quality factor is obtainedAnd (5) feeding.
The microwave dielectric properties of the group of ceramic materials are as follows: the dielectric constant is 30.6, the quality factor is 139000GHz, and the temperature coefficient of the resonance frequency is-4.3 ppm/DEG C.
Example 6
In step (1) of example 1, according to Sr3La1.4Ga1.6Ta3O15Stoichiometric 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 the example 1, the sieved particles are pressed and molded, and then sintered at 1290 ℃ 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 those of the example 1, so that the high-quality-factor microwave dielectric ceramic material is obtained.
The microwave dielectric properties of the group of ceramic materials are as follows: the dielectric constant is 31.4, the quality factor is 122000GHz, and the temperature coefficient of the resonance frequency is 12.3 ppm/DEG C.
Example 7
In step (1) of example 1, Sr is followed, respectively3La2GaNb3O15、Sr3La1.5Ga1.5Nb3O15、Sr3La1.4Ga1.6Nb3O15、Sr3La2GaTa3O15、Sr3La1.5Ga1.5Ta3O15And Sr3La1.4Ga1.6Ta3O15The main body is prepared by stoichiometric weighing, and the raw material is taken from SrCO3、La2O3、Ga2O3、Nb2O5And Ta2O5(ii) a In step (4) of example 1, the sieved granules were press-molded and then sintered at 1325 ℃ 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 dispersing agent, the deionized water and the ethanol mixed solution are the same as the example 1And obtaining the microwave dielectric ceramic material with high quality factor.
The microwave dielectric properties of the group of ceramic materials are as follows: a dielectric constant of 31 to 35.1, a quality factor of 113000 to 152000GHz, and a temperature coefficient of resonance frequency of-14.4 ppm/DEG C to 27.5 ppm/DEG C
XRD testing of the bulk of all the above examples revealed no impurity phase and Sr was found by TEM and structural refinement3La2-xGa1+xM3O15(M ═ Nb, Ta), where 0. ltoreq. x.ltoreq.0.6, is one of the intrinsic causes for the high quality factors of this series of ceramics.
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 (3)

1. A microwave dielectric ceramic material with high quality factor is characterized in that the ceramic material comprises a main body and BaCu (B) accounting for 0.5-1.5 wt% of the main body2O5) The main body is Sr3La2-xGa1+xM3O15M is Nb or Ta, wherein x is more than or equal to 0 and less than or equal to 0.6; the microwave dielectric property of the ceramic material is as follows: a dielectric constant of 29.4 to 33.7, a quality factor Qf of 107000 to 139000GHz, and a temperature coefficient of resonance frequency of-22 ppm/DEG C to 12.3 ppm/DEG C;
the preparation method of the microwave dielectric ceramic material with high quality factor comprises the following steps:
(1) preparation of the main body: with SrCO3、La2O3、Ga2O3、Nb2O5And Ta2O5Firstly, La is used as raw material2O3Presintering for 8 hours at 880 ℃; then the raw materials are mixed according to Sr3La2-xGa1+xM3O15M is Nb or Ta, wherein x is not less than 0 and not more than 0.6, and are weighed and mixed in 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 preserving heat at 1250 ℃ 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 1270-1290 ℃ for 4 hours to obtain the ceramic, thus obtaining the high-quality-factor microwave dielectric ceramic material.
2. The high-Q microwave dielectric ceramic material as claimed in claim 1, wherein in the preparation method of the high-Q 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 sample mass; the mass ratio of the sodium polyacrylate, the sodium hexametaphosphate, the sodium pyrophosphate and the polyethylene glycol is 3:1:1: 1.
3. The high-Q microwave dielectric ceramic material of claim 1, wherein in the preparation method of the high-Q microwave dielectric ceramic material, the mixed solution of deionized water and ethanol in step (3) comprises the following components in percentage by weight: deionized water weight: ethanol weight 1: 9.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1557770A (en) * 2004-01-14 2004-12-29 浙江大学 Low-loss microwave dielectric ceramic
CN1759067A (en) * 2003-03-31 2006-04-12 科学与工业研究委员会 Mg2mm' 06+x, ( m=y, rare earth metal, and m'=sn, sb, zr, hf, and ta) compounds and a method for the production of the same
CN101538158A (en) * 2009-04-11 2009-09-23 桂林工学院 Composite niobate microwave dielectric ceramic material sintered at low temperature and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1759067A (en) * 2003-03-31 2006-04-12 科学与工业研究委员会 Mg2mm' 06+x, ( m=y, rare earth metal, and m'=sn, sb, zr, hf, and ta) compounds and a method for the production of the same
CN1557770A (en) * 2004-01-14 2004-12-29 浙江大学 Low-loss microwave dielectric ceramic
CN101538158A (en) * 2009-04-11 2009-09-23 桂林工学院 Composite niobate microwave dielectric ceramic material sintered at low temperature and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CaTiO3-LaGaO3系微波介质陶瓷结构及微波介电性能的研究;倪猛;《中国优秀硕士学位论文全文数据库》;20161215(第12期);1-60页 *

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