CN113072373A - Temperature-stable low-dielectric ceramic material suitable for 5G millimeter wave communication application and preparation method thereof - Google Patents

Temperature-stable low-dielectric ceramic material suitable for 5G millimeter wave communication application and preparation method thereof Download PDF

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CN113072373A
CN113072373A CN202110389330.4A CN202110389330A CN113072373A CN 113072373 A CN113072373 A CN 113072373A CN 202110389330 A CN202110389330 A CN 202110389330A CN 113072373 A CN113072373 A CN 113072373A
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左如忠
刘晓开
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Hefei University of Technology
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Abstract

The invention relates to a temperature stable low-dielectric ceramic material suitable for 5G millimeter wave communication application and a preparation method thereof, and is characterized in that the general formula of the composition is as follows: (1-n) [ (1-x) Ca (Sm)yRz)AlO4+xSr2(TivDt)O4]+ nM. The ceramic can be prepared and synthesized by adopting a conventional ceramic preparation method so as to be combined with CaSmAlO4Having the same K2NiF4Sr of structure2TiO4Material to be reacted with CaSmAlO4The matrix forms solid solution, and is doped and substituted for modification, so that the generation of impurity phase is inhibited and the burning is reduced while the frequency temperature coefficient is adjusted to be nearly zeroThe junction temperature obtains the pure-phase solid solution ceramic with ultralow loss and near-zero frequency temperature coefficient, has good application prospect, and can meet the requirements of the microwave communication industry.

Description

Temperature-stable low-dielectric ceramic material suitable for 5G millimeter wave communication application and preparation method thereof
Technical Field
The invention relates to a microwave dielectric ceramic and a preparation method thereof, in particular to a temperature stable type low dielectric ceramic material (1-n) [ (1-x) Ca (Sm) suitable for 5G millimeter wave communication applicationyRz)AlO4+xSr2(TivDt)O4]+ nM and method of preparation.
Background
In recent years, wireless communication technologies are rapidly developed, especially, the communication dominance of China is about to be updated from a fourth generation communication technology (4G) to a fifth generation communication technology (5G), and communication frequency bands of mobile phones, WIFI, satellites, radars and the like are gradually developing towards the direction of sub-millimeter wave bands. Due to the advantages of low loss, high stability and the like, microwave ceramic materials used as key components such as filters, resonators, oscillators and the like in wireless communication systems become key materials for the development of millimeter wave communication. Unlike 2G/3G/4G communication which works below a 6GHz frequency band, 5G communication ensures extremely fast signal propagation speed in submillimeter wave (24GHz-30GHz) and millimeter wave (60GHz-78GHz) band communication, and requires signal delay time to be less than 1 millisecond. Therefore, the microwave dielectric ceramics used in millimeter wave communication components are required to have a dielectric constant as low as possible to enhance the response of microwave signals and reduce the delay time of transmission signals. Meanwhile, in order to reduce energy transmission loss and enhance the frequency selection characteristic of the device, the microwave dielectric ceramic is required to have a higher Q multiplied by f value (Q multiplied by f is more than 10000 GHz); finally, in order to ensure that microwave components can work normally and stably under different environmental temperatures, the resonant frequency temperature coefficient (tau) of the microwave dielectric ceramic is requiredf) As close to zero as possible. In recent years, with the arrival of 5G business, millimeter wave development advances the construction of small base stations of millions of orders, and the demand of components for the mass construction of communication base stations is rapidly increasing. In order to promote the development of information technology, the development of low-dielectric-constant microwave dielectric ceramics with high signal response speed, high signal transmission quality, low transmission loss and high temperature stability has become an important research focus of research in the communication fields of various countries.
The quality of the microwave dielectric ceramic depends on the properties of the selected material. Article of 2004 in the Journal of the American Ceramic Society, having Square K2NiF4CaRAlO of structure4The microstructure and microwave dielectric properties of (R ═ Nd, Sm, Y) ceramics were first reported in CaRAlO4(R ═ Nd, Sm, Y) microwave dielectric properties. Article CaSmAlO in 20084Base ceramicFurther reports of small adjustments of CaSmAlO in the microstructure and microwave dielectric Properties4The molar ratio of Ca in the dielectric ceramic can greatly improve the dielectric property (Q multiplied by f-120,000 GHz, epsilon)r～19，andτf10ppm/° c), the excellent performance is that CaSmAlO4Have received much attention from researchers. In order to meet the practical requirements of microwave dielectric ceramics, a near-zero temperature coefficient of frequency is indispensable. Among the methods of adjusting the temperature coefficient of frequency of a material by composition, the solid solution method is preferred to the complex phase method which greatly increases the loss of ceramics. In 2009 there were researchers "Ca2TiO4"form pair carries out Ca and Ti substitution to form solid solution, but because of Ca2TiO4It is not a stable substance, so it can promote the generation of impurity phase and increase the loss, and the Q x f value is lower than 100000 GHz. 2016, American ceramic Association and periodical, reports again that K has positive temperature coefficient and excellent dielectric property2NiF4Structural material Sr2TiO4It can be used as an excellent candidate for the solid solution adjusting method.
In conclusion, CaSmAlO is used as the active ingredient in the invention4And have the same K2NiF4Structure and excellent performance of Sr2TiO4The material is a modified solid solution formed on a substrate, excellent dielectric property is obtained while the frequency temperature coefficient is adjusted to be close to zero, the sintering temperature is reduced to reduce the cost, the solid solution ceramic with ultralow loss and close to zero frequency temperature coefficient is obtained, the application prospect is good, and the requirements of the microwave communication industry can be met.
Disclosure of Invention
In order to meet the application requirements of the mobile communication technology under a higher frequency band, the invention provides a temperature stable type low dielectric ceramic material (1-n) [ (1-x) Ca (Sm) suitable for 5G millimeter wave communication applicationyRz)AlO4+xSr2(TivDt)O4]+ nM and method of preparation. The system has proper dielectric constant, ultrahigh quality factor and near-zero temperature coefficient of resonant frequency.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a temperature stable low-dielectric ceramic material suitable for 5G millimeter wave communication application and a preparation method thereof comprise the following steps:
(1) preparing materials: the raw materials are respectively Ca (Sm)yRz)AlO4And Sr2(TivDt)O4Proportioning the components according to the stoichiometric ratio;
(2) mixing materials: putting the materials obtained by burdening into a ball mill, and carrying out wet ball milling by taking absolute ethyl alcohol as a medium to obtain a slurry raw material;
(3) drying: putting the slurry raw material into a drying oven to be dried to constant weight to obtain a dry mixture;
(4) pre-burning: grinding and dispersing the mixture, and then placing the mixture into a high-temperature furnace for presintering to prepare Ca (Sm)yRz)AlO4And Sr2(TivDt)O4Powder, wherein the presintering temperature is respectively 1300 ℃ and 1200 ℃;
(5) preparing materials: ca (Sm) is preparedyRz)AlO4And Sr2(TivDt)O4The powder is prepared from (1-n) [ (1-x) Ca (Sm)yRz)AlO4+xSr2(TivDt)O4]+ nM stoichiometric ratio;
(6) ball milling: mixing (1-n) [ (1-x) Ca (Sm)yRz)AlO4+xSr2(TivDt)O4]Adding absolute ethyl alcohol into the nM powder, and grinding in a ball mill to form uniform slurry;
(7) drying: drying the obtained slurry in an oven to constant weight to obtain mixture powder;
(8) and (3) granulation: grinding the mixture powder, adding a polyvinyl alcohol solution, uniformly mixing and pressing into a cylindrical green body;
(9) rubber discharging: placing the cylindrical green body in a high-temperature furnace to raise the temperature for glue discharging treatment
(10) And (3) sintering: sintering the cylindrical green body after the glue discharging treatment to obtain the microwave dielectric ceramic (1-n) [ (1-x) Ca (Sm)yRz)AlO4+xSr2(TivDt)O4]+nM。
Preferably, the ball mill is a planetary ball mill, and the rotating speed is set to 360 r/min.
Preferably, in the step (2), the ball milling time is 4 h.
Preferably, the pre-firing treatment process includes: the temperature is increased to 1200 ℃ and 1300 ℃ at the speed of 5 ℃/min for calcining for 4h, then the temperature is reduced to 500 ℃ at the speed of 10 ℃/min, and finally the temperature is naturally reduced.
Preferably, in the step (6), the ball milling time is 6 h.
Preferably, the polyvinyl alcohol solution is added in the step (9) in an amount of (1-n) [ (1-x) Ca (Sm)yRz)AlO4+xSr2(TivDt)O4]+ nM compound powder 3-5 wt%.
Preferably, the diameter of the cylindrical green body is 10mm, and the height of the cylindrical green body is 6 mm.
Preferably, in the step (9), the process of the glue discharging treatment includes: heating to 550 ℃ at the speed of 3 ℃/min, preserving heat for 4h, and then continuing to perform the sintering step.
Preferably, in the step (10), the sintering process includes: heating to 1250-1425 ℃ at the speed of 5 ℃/min, and sintering for 4 h; then the temperature is reduced to 500 ℃ at the speed of 10 ℃/min, and finally the temperature is cooled to the room temperature along with the furnace.
Preferably, the step (10) further comprises the following steps:
(11) and (3) later-stage mechanical processing: and grinding and polishing the sintered microwave dielectric ceramic.
Compared with the prior art, the invention has the characteristics and beneficial effects that:
1. the solid solution ceramic material (1-n) [ (1-x) Ca (Sm) of the inventionyRz)AlO4+xSr2(TivDt)O4]The preparation method of the + nM is a traditional solid-state reaction method, and has simple process and lower cost.
2. The solid solution ceramic material does not contain volatile toxic metals such as Pb, Cd, Bi and the like, can be widely applied to microwave devices such as dielectric resonators, filters, oscillators and the like in satellite communication, and meets the strict standard requirements of green and environment-friendly RHOS (instruction for limiting the use of certain harmful substances in electrical and electronic equipment) and recovery processing management regulations (WEEE).
3. By designing (1-n) [ (1-x) Ca (Sm)yRz)AlO4+xSr2(TivDt)O4]Composition of + nM solid solution ceramic, excellent temperature stability (tau) can be obtainedf4.9- +3.05ppm/° c) and ultra-low dielectric lossr＝17.1～19.2，Q×f＝46000～140400GHz)。
Drawings
FIG. 1 shows a microwave dielectric ceramic 0.8832Ca (Sm) in example 1 of the present invention0.875La0.125)AlO4+0.0768Sr2(Ti0.93Zr0.07)O4+0.04CaF2An XRD pattern of (a);
FIG. 2 shows a microwave dielectric ceramic 0.9306Ca (Sm) in example 2 of the present invention0.9Nd0.1)AlO4+0.0594Sr2(Ti0.95Zr0.05)O4+0.01ZnF2An XRD pattern of (a);
FIG. 3 shows a microwave dielectric ceramic 0.8955Ca (Sm) in example 4 of the present invention0.8Nd0.2)AlO4+0.0995Sr2(Ti0.95Sn0.05)O4+0.005LiF sample of hot corrosion surface scanning electron microscope;
Detailed Description
The technical solution of the present invention is further described and illustrated by the following specific examples:
example 1
The microwave dielectric ceramic 0.8832Ca (Sm) of the present example0.875La0.125)AlO4+0.0768Sr2(Ti0.93Zr0.07)O4+0.04CaF2The preparation method comprises the following steps:
(1) preparing materials:CaCO3(99.99％)、Sm2O3(99.9％)、La2O3(99.9％)、Al2O3(99.99%) according to Ca (Sm)0.875La0.125)AlO4Proportioning the components according to the stoichiometric ratio; SrCO3(99.9％)、TiO2(99.0%) according to Sr2TiO4Proportioning the components according to the stoichiometric ratio;
(2) mixing materials: pouring the mixture into a ball milling tank respectively, and mixing the materials, a ball milling medium and absolute ethyl alcohol according to the proportion of 1: 5: 3, placing the mixture in a planetary ball mill, and ball-milling the mixture for 4 hours at a rotating speed of 360r/min to obtain slurry;
(3) drying: pouring out the ball-milled slurry, and placing the slurry into an oven to be dried to constant weight at 100 ℃ to obtain a dried mixture;
(4) pre-burning: grinding and dispersing the mixture, then placing the mixture into a high-temperature furnace for presintering, wherein the presintering temperature is respectively 1300 ℃ and 1200 ℃, and the heating rate is 5 ℃/min, thus obtaining Ca (Sm)0.875La0.125)AlO4And 0.05Sr2(Ti0.93Zr0.07)O4Powder;
(5) preparing materials: ca (Sm) is prepared0.875La0.125)AlO4And Sr2(Ti0.93Zr0.07)O4Powder and CaF2(99.0%) raw powder 0.8832Ca (Sm) in molar ratio0.875La0.125)AlO4+0.0768Sr2(Ti0.93Zr0.07)O4+0.04CaF2Proportioning;
(6) ball milling: adding absolute ethyl alcohol into the prepared powder, and placing the powder in a ball mill to perform ball milling for 4 hours at the rotating speed of 360r/min to form uniform slurry;
(7) drying: taking out the slurry obtained in the last step, and drying the slurry in a drying oven at 100 ℃ until the weight is constant to obtain mixture powder;
(8) and (3) granulation: grinding the mixture powder, adding the mixture powder into a polyvinyl alcohol solution (PVA) according to the mass ratio of the mixture of 4%, uniformly mixing, and putting the powder into a mould to press the powder into a cylindrical green body with the diameter of 10mm and the thickness of about 6mm under the pressure of 200 Mpa;
(9) rubber discharging: heating the cylinder green compact to 550 ℃ at the speed of 3 ℃/min in a high-temperature furnace, and preserving heat for 4h to remove PVA in the cylinder;
(10) and (3) sintering: after the glue is discharged, the temperature is raised to 1300 ℃ at the speed of 5 ℃/min for sintering for 4h, then the temperature is lowered to 500 ℃ at the speed of 10 ℃/min, and finally the temperature is naturally lowered;
(11) and (3) later-stage mechanical processing: and grinding and polishing the sintered microwave dielectric ceramic to obtain a ceramic finished product with a smooth surface.
Example 2
The microwave dielectric ceramic 0.9306Ca (Sm) of the present example0.9Nd0.1)AlO4+0.0594Sr2(Ti0.95Zr0.05)O4+0.01ZnF2The preparation method comprises the following steps:
(1) preparing materials: CaCO3(99.99％)、Sm2O3(99.9％)、Nd2O3(99.9％)、Al2O3(99.99%) according to Ca (Sm)0.9Nd0.1)AlO4Proportioning the components according to the stoichiometric ratio; SrCO3(99.9％)、TiO2(99.0％)、ZrO2(99.0%) according to Sr2(Ti0.95Zr0.05)O4Proportioning the components according to the stoichiometric ratio;
(2) mixing materials: pouring the mixture into a ball milling tank respectively, and mixing the materials, a ball milling medium and absolute ethyl alcohol according to the proportion of 1: 5: 3, placing the mixture in a planetary ball mill, and ball-milling the mixture for 4 hours at a rotating speed of 360r/min to obtain slurry;
(3) drying: pouring out the ball-milled slurry, and placing the slurry into an oven to be dried to constant weight at 100 ℃ to obtain a dried mixture;
(4) pre-burning: grinding and dispersing the mixture, then placing the mixture into a high-temperature furnace for presintering, wherein the presintering temperature is respectively 1300 ℃ and 1200 ℃, and the heating rate is 5 ℃/min, thus obtaining Ca (Sm)0.9Nd0.1)AlO4And Sr2(Ti0.95Zr0.05)O4Powder;
(5) preparing materials: ca (Sm) is prepared0.9Nd0.1)AlO4And Sr2(Ti0.95Zr0.05)O4Powder and ZnF2(99.0%) raw powder 0.9306Ca (Sm) in molar ratio0.9Nd0.1)AlO4-0.0594Sr2(Ti0.95Zr0.05)O4+0.01ZnF2Proportioning;
(6) ball milling: adding absolute ethyl alcohol into the prepared powder, and placing the powder in a ball mill to perform ball milling for 4 hours at the rotating speed of 360r/min to form uniform slurry;
(7) drying: taking out the slurry obtained in the last step, and drying the slurry in a drying oven at 100 ℃ until the weight is constant to obtain mixture powder;
(8) and (3) granulation: grinding the mixture powder, adding the mixture powder into a polyvinyl alcohol solution (PVA) according to the mass ratio of the mixture of 4%, uniformly mixing, and putting the powder into a mould to press the powder into a cylindrical green body with the diameter of 10mm and the thickness of about 6mm under the pressure of 200 Mpa;
(9) rubber discharging: heating the cylinder green compact to 550 ℃ at the speed of 3 ℃/min in a high-temperature furnace, and preserving heat for 4h to remove PVA in the cylinder;
(10) and (3) sintering: after the glue is discharged, the temperature is raised to 1325 ℃ at the speed of 5 ℃/min for sintering for 4h, then the temperature is lowered to 500 ℃ at the speed of 10 ℃/min, and finally the temperature is naturally lowered;
(11) and (3) later-stage mechanical processing: and grinding and polishing the sintered microwave dielectric ceramic to obtain a ceramic finished product with a smooth surface.
Example 3
The microwave dielectric ceramic of this example 0.882Ca (Sm)0.9La0.1)AlO4+0.098Sr2(Ti0.95Zr0.05)O4The preparation method of +0.02NaF comprises the following steps:
(1) preparing materials: CaCO3(99.99％)、Sm2O3(99.9％)、Al2O3(99.99％)、La2O3(99.9%) according to Ca (Sm)0.9La0.1)AlO4Proportioning the components according to the stoichiometric ratio; SrCO3(99.9％)、TiO2(99.0％)、ZrO2(99.0%) according to Sr2(Ti0.95Zr0.05)O4Proportioning the components according to the stoichiometric ratio;
(2) mixing materials: pouring the mixture into a ball milling tank respectively, and mixing the materials, a ball milling medium and absolute ethyl alcohol according to the proportion of 1: 5: 3, placing the mixture in a planetary ball mill, and ball-milling the mixture for 4 hours at a rotating speed of 360r/min to obtain slurry;
(3) drying: pouring out the ball-milled slurry, and placing the slurry into an oven to be dried to constant weight at 100 ℃ to obtain a dried mixture;
(4) pre-burning: grinding and dispersing the mixture, then placing the mixture into a high-temperature furnace for presintering, wherein the presintering temperature is respectively 1300 ℃ and 1200 ℃, and the heating rate is 5 ℃/min, thus obtaining Ca (Sm)0.9La0.1)AlO4And Sr2(Ti0.95Zr0.05)O4Powder;
(5) preparing materials: ca (Sm) is prepared0.9La0.1)AlO4And Sr2(Ti0.95Zr0.05)O4Powder and NaF (99.0%) raw material powder according to the molar ratio of 0.882Ca (Sm)0.9La0.1)AlO4+0.098Sr2(Ti0.95Zr0.05)O4+0.02 NaF;
(6) ball milling: adding absolute ethyl alcohol into the prepared powder, and placing the powder in a ball mill to perform ball milling for 4 hours at the rotating speed of 360r/min to form uniform slurry;
(7) drying: taking out the slurry obtained in the last step, and drying the slurry in a drying oven at 100 ℃ until the weight is constant to obtain mixture powder;
(8) and (3) granulation: grinding the mixture powder, adding the mixture powder into a polyvinyl alcohol solution (PVA) according to the mass ratio of the mixture of 4%, uniformly mixing, and putting the powder into a mould to press the powder into a cylindrical green body with the diameter of 10mm and the thickness of about 6mm under the pressure of 200 Mpa;
(9) rubber discharging: heating the cylinder green compact to 550 ℃ at the speed of 3 ℃/min in a high-temperature furnace, and preserving heat for 4h to remove PVA in the cylinder;
(10) and (3) sintering: after the glue is discharged, the temperature is raised to 1300 ℃ at the speed of 5 ℃/min for sintering for 4h, then the temperature is lowered to 500 ℃ at the speed of 10 ℃/min, and finally the temperature is naturally lowered;
(11) and (3) later-stage mechanical processing: and grinding and polishing the sintered microwave dielectric ceramic to obtain a ceramic finished product with a smooth surface.
Example 4
The microwave dielectric ceramic 0.8955Ca (Sm) of the present example0.8Nd0.2)AlO4+0.0995Sr2(Ti0.95Sn0.05)O4+0.005LiF preparation method, comprising the following steps:
(1) preparing materials: CaCO3(99.99％)、Sm2O3(99.9％)、Al2O3(99.99％)、Nd2O3(99.9%) according to Ca (Sm)0.8Nd0.2)AlO4Proportioning the components according to the stoichiometric ratio; SrCO3(99.9％)、TiO2(99.0％)、SnO2(99.99%) according to Sr2(Ti0.95Sn0.05)O4Proportioning the components according to the stoichiometric ratio;
(2) mixing materials: pouring the mixture into a ball milling tank respectively, and mixing the materials, a ball milling medium and absolute ethyl alcohol according to the proportion of 1: 5: 3, placing the mixture in a planetary ball mill, and ball-milling the mixture for 4 hours at a rotating speed of 360r/min to obtain slurry;
(3) drying: pouring out the ball-milled slurry, and placing the slurry into an oven to be dried to constant weight at 100 ℃ to obtain a dried mixture;
(4) pre-burning: grinding and dispersing the mixture, then placing the mixture into a high-temperature furnace for presintering, wherein the presintering temperature is respectively 1300 ℃ and 1200 ℃, and the heating rate is 5 ℃/min, thus obtaining Ca (Sm)0.8Nd0.2)AlO4And Sr2(Ti0.95Sn0.05)O4Powder;
(5) preparing materials: ca (Sm) is prepared0.8Nd0.2)AlO4And Sr2(Ti0.95Sn0.05)O4Powder and LiF (99.0%) raw material powder according to a molar ratio of 0.8955Ca (Sm)0.8Nd0.2)AlO4+0.0995Sr2(Ti0.95Sn0.05)O4+0.005 LiF;
(6) ball milling: adding absolute ethyl alcohol into the prepared powder, and placing the powder in a ball mill to perform ball milling for 4 hours at the rotating speed of 360r/min to form uniform slurry;
(7) drying: taking out the slurry obtained in the last step, and drying the slurry in a drying oven at 100 ℃ until the weight is constant to obtain mixture powder;
(8) and (3) granulation: grinding the mixture powder, adding the mixture powder into a polyvinyl alcohol solution (PVA) according to the mass ratio of the mixture of 4%, uniformly mixing, and putting the powder into a mould to press the powder into a cylindrical green body with the diameter of 10mm and the thickness of about 6mm under the pressure of 200 Mpa;
(9) rubber discharging: heating the cylinder green compact to 550 ℃ at the speed of 3 ℃/min in a high-temperature furnace, and preserving heat for 4h to remove PVA in the cylinder;
(10) and (3) sintering: after the binder is discharged, the temperature is raised to 1350 ℃ at the speed of 5 ℃/min for sintering for 4h, then the temperature is lowered to 500 ℃ at the speed of 10 ℃/min, and finally the temperature is naturally lowered;
(11) and (3) later-stage mechanical processing: and grinding and polishing the sintered microwave dielectric ceramic to obtain a ceramic finished product with a smooth surface.
Example 5
The microwave dielectric ceramic 0.9185Ca (Sm) of the present example0.85Y0.15)AlO4+0.0745Sr2(Ti0.95Sn0.05)O4+0.007B2O3The preparation method comprises the following steps:
(1) preparing materials: CaCO3(99.99％)、Sm2O3(99.9％)、Al2O3(99.99％)、Y2O3(99.9%) according to Ca (Sm)0.8Y0.2)AlO4Proportioning the components according to the stoichiometric ratio; SrCO3(99.9％)、TiO2(99.0％)、SnO2(99.99%) according to Sr2(Ti0.95Sn0.05)O4Proportioning the components according to the stoichiometric ratio;
(2) mixing materials: pouring the mixture into a ball milling tank respectively, and mixing the materials, a ball milling medium and absolute ethyl alcohol according to the proportion of 1: 5: 3, placing the mixture in a planetary ball mill, and ball-milling the mixture for 4 hours at a rotating speed of 360r/min to obtain slurry;
(3) drying: pouring out the ball-milled slurry, and placing the slurry into an oven to be dried to constant weight at 100 ℃ to obtain a dried mixture;
(4) pre-burning: grinding and dispersing the mixture, then placing the mixture into a high-temperature furnace for presintering, wherein the presintering temperature is respectively 1300 ℃ and 1200 ℃, and the heating rate is 5 ℃/min, thus obtaining Ca (Sm)0.8Y0.2)AlO4And Sr2(Ti0.95Sn0.05)O4Powder;
(5) preparing materials: ca (Sm) is prepared0.8Y0.2)AlO4And Sr2(Ti0.95Sn0.05)O4Powder and B2O3(99.0%) raw powder 0.9185Ca (Sm) in molar ratio0.85Y0.15)AlO4+0.0745Sr2(Ti0.95Sn0.05)O4+0.007B2O3Proportioning;
(6) ball milling: adding absolute ethyl alcohol into the prepared powder, and placing the powder in a ball mill to perform ball milling for 4 hours at the rotating speed of 360r/min to form uniform slurry;
(7) drying: taking out the slurry obtained in the last step, and drying the slurry in a drying oven at 100 ℃ until the weight is constant to obtain mixture powder;
(8) and (3) granulation: grinding the mixture powder, adding the mixture powder into a polyvinyl alcohol solution (PVA) according to the mass ratio of the mixture of 4%, uniformly mixing, and putting the powder into a mould to press the powder into a cylindrical green body with the diameter of 10mm and the thickness of about 6mm under the pressure of 200 Mpa;
(9) rubber discharging: heating the cylinder green compact to 550 ℃ at the speed of 3 ℃/min in a high-temperature furnace, and preserving heat for 4h to remove PVA in the cylinder;
(10) and (3) sintering: after the binder is discharged, the temperature is raised to 1350 ℃ at the speed of 5 ℃/min for sintering for 4h, then the temperature is lowered to 500 ℃ at the speed of 10 ℃/min, and finally the temperature is naturally lowered;
(11) and (3) later-stage mechanical processing: and grinding and polishing the sintered microwave dielectric ceramic to obtain a ceramic finished product with a smooth surface.
Table 1 shows the performance parameters of the microwave dielectric ceramic material prepared by the listed examples of the invention.
TABLE 1
Figure BDA0003015911810000101
FIG. 1 shows a microwave dielectric ceramic 0.8832Ca (Sm) in example 1 of the present invention0.875La0.125)AlO4+0.0768Sr2(Ti0.93Zr0.07)O4+0.04CaF2XRD pattern of (a). All peaks were associated with CaSmAlO4The PDF cards of the ceramic are consistent and have no hetero-phase peaks, which indicates that the ceramic forms a single pure-phase solid solution.
FIG. 2 shows a microwave dielectric ceramic 0.9306Ca (Sm) in example 2 of the present invention0.9Nd0.1)AlO4+0.0594Sr2(Ti0.95Zr0.05)O4+0.01ZnF2XRD pattern of (a). All peaks were associated with CaSmAlO4The PDF cards are consistent and have no hetero-phase peak, which shows that the matrix component can still maintain a single phase under the conditions of no trace change of the substituted elements and doping.
FIG. 3 shows 0.8955Ca (Sm) in example 4 of the present invention0.8Nd0.2)AlO4+0.0995Sr2(Ti0.95Sn0.05)O4+0.005LiF sample scanning electron micrograph of hot-corroded surface. It can be seen that the sample has uniform grain morphology and size, few pores, few liquid phase traces on the grain boundary, and a very compact microstructure.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core ideas. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.

Claims (10)

1. A temperature stable low-dielectric ceramic material suitable for 5G millimeter wave communication application and a preparation method thereof are characterized in that the microwave dielectric ceramic can be represented by the following general formula:
(1-n)[(1-x)Ca(SmyRz)AlO4+xSr2(TivDt)O4]+nM
in the general formula, n, v, t, x, y and z are mole fractions of all substances, and values are less than 1;
n is more than or equal to 0, x is more than 0, y is more than 0, z is more than or equal to 0, v is more than or equal to 0, and t is more than or equal to 0; y + z =1, 4v + at =4, wherein a is a valence number of D, R or an average valence number;
r is selected from La3+、Nd3+、Y3+One or more of rare earth metal ions;
d is selected from Mg2+、Zn2+、Zr4+、Sn4+、Nb5+、Ta5+One or more of metal ions;
m is selected from B2O3、ZnO、CuO、LiF、ZnF2、CaF2One or more of a sintering aid.
2. A temperature stable low-dielectric ceramic material suitable for 5G millimeter wave communication application and a preparation method thereof comprise the following steps:
(1) preparing materials: the raw materials are respectively Ca (Sm)yRz)AlO4And Sr2(TivDt)O4Proportioning the components according to the stoichiometric ratio;
(2) mixing materials: putting the materials obtained by burdening into a ball mill, and carrying out wet ball milling by taking absolute ethyl alcohol as a medium to obtain a slurry raw material;
(3) drying: putting the slurry raw material into a drying oven to be dried to constant weight to obtain a dry mixture;
(4) pre-burning: grinding and dispersing the mixture, and then placing the mixture into a high-temperature furnace for presintering to prepare Ca (Sm)yRz)AlO4And Sr2(TivDt)O4Powder, wherein the presintering temperature is respectively 1300 ℃ and 1200 ℃;
(5) preparing materials: ca (Sm) is preparedyRz)AlO4And Sr2(TivDt)O4The powder is prepared from (1-n) [ (1-x) Ca (Sm)yRz)AlO4+xSr2(TivDt)O4]Conversion to + nMProportioning according to a stoichiometric ratio;
(6) ball milling: mixing (1-n) [ (1-x) Ca (Sm)yRz)AlO4+xSr2(TivDt)O4]Adding absolute ethyl alcohol into the nM powder, and grinding in a ball mill to form uniform slurry;
(7) drying: drying the obtained slurry in an oven to constant weight to obtain mixture powder;
(8) and (3) granulation: grinding the mixture powder, adding a polyvinyl alcohol solution, uniformly mixing and pressing into a cylindrical green body;
(9) rubber discharging: placing the cylindrical green body in a high-temperature furnace, and heating to carry out glue discharging treatment;
(10) and (3) sintering: sintering the cylindrical green body after the glue discharging treatment to obtain the microwave dielectric ceramic (1-n) [ (1-x) Ca (Sm)yRz)AlO4+xSr2(TivDt)O4]+nM。
3. The production method according to claim 2, wherein the ball mill is a planetary ball mill, and the rotation speed is set to 360 r/min.
4. The preparation method according to claim 2, wherein in the step (2), the ball milling time is 4 h.
5. The manufacturing method according to claim 2, wherein in the step (4), the pre-firing treatment process comprises: the temperature is increased to 1200 ℃ and 1300 ℃ at the speed of 5 ℃/min for calcining for 4h, then the temperature is reduced to 500 ℃ at the speed of 10 ℃/min, and finally the temperature is naturally reduced.
6. The preparation method according to claim 2, wherein in the step (6), the ball milling time is 6 h.
7. The method according to claim 2, wherein the polyvinyl alcohol solution is added in an amount of (1-n) [ (1-x) Ca (Sm) in step (8)yRz)AlO4+xSr2(TivDt)O4]+ nM compound powder 3-5 wt%.
8. The preparation method according to claim 2, wherein in the step (9), the process of the glue discharging treatment comprises the following steps: heating to 550 ℃ at the speed of 3 ℃/min, preserving heat for 4h, and then continuing to perform the sintering step.
9. The method according to claim 2, wherein in the step (10), the sintering treatment comprises: heating to 1250-1425 ℃ at the speed of 5 ℃/min, and sintering for 4 h; then the temperature is reduced to 500 ℃ at the speed of 10 ℃/min, and finally the temperature is cooled to the room temperature along with the furnace.
10. The method for preparing according to claim 2, characterized by further comprising the following step after the step (10):
(11) and (3) later-stage mechanical processing: and grinding and polishing the sintered microwave dielectric ceramic.
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