CN107382305B - Microwave dielectric ceramic material and preparation method thereof - Google Patents

Microwave dielectric ceramic material and preparation method thereof Download PDF

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CN107382305B
CN107382305B CN201710575593.8A CN201710575593A CN107382305B CN 107382305 B CN107382305 B CN 107382305B CN 201710575593 A CN201710575593 A CN 201710575593A CN 107382305 B CN107382305 B CN 107382305B
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唐斌
方梓烜
张星
钟朝位
张树人
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University of Electronic Science and Technology of China
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Abstract

A microwave dielectric ceramic material and a preparation method thereof belong to the technical field of preparation of electronic information functional materials. The chemical general formula of the microwave dielectric ceramic material is Li2/3(1‑x‑y)A1/3(1‑x‑y)MgxByO, wherein A is at least one of Ti, Sn and Zr, and B is at least one of Ca, Zn, Ni and Co; x and y are more than 0 and less than or equal to 4/7, x is more than or equal to 0 and less than 4/7, and y is more than 0 and less than 4/7. The microwave dielectric ceramic material does not contain volatile toxic metals such as Pb, Cd and the like, can be widely applied to microwave devices such as dielectric resonators, filters, oscillators and the like in satellite communication, and is green, environment-friendly and pollution-free.

Description

Microwave dielectric ceramic material and preparation method thereof
Technical Field
The invention belongs to the technical field of preparation of electronic information functional materials.
Background
At present, the methodThe information technology is rapidly developing towards high frequency, high power, integration and multi-functionalization, and with the rapid development of modern mobile communication technology and internet of things technology, the high-frequency microwave technology has wide and important application in systems such as communication, navigation, satellite, bluetooth, sensing internet of things radio frequency technology and the like. In high frequency microwave circuits, many microwave devices require dielectric ceramic materials as substrates, so that the microwave ceramic dielectric substrate materials are becoming more and more the key basic materials used in microwave devices, components and complete machine systems. High-frequency microwave devices using ceramic substrate materials are generally characterized by miniaturization, wide frequency, high reliability, and the like. The importance of developing dielectric ceramics with serialized dielectric constants and excellent microwave dielectric properties is proposed by the file of the outline of electronic information industry adjustment and joy planning of the State Council as early as 2009. The preparation process with adjustable dielectric constant, high quality factor, frequency temperature coefficient close to zero, stability and reliability is the key research and development direction of microwave dielectric ceramics. The performance indexes are important parameters of microwave dielectric materials, the size of a resonator is inversely proportional to the square root of the dielectric constant of the dielectric materials, so that the high dielectric constant is favorable for realizing the miniaturization of components, the higher the quality factor Qxf value of the microwave dielectric ceramic materials is, the lower the loss of a microwave device is, the higher the quality factor is favorable for realizing the good frequency selection of the microwave device, and the frequency temperature coefficient tau close to zerofThe device has small change of the central frequency along with the environmental temperature, high working stability and reliable preparation process, so that the device meets the requirement of large-scale production in the electronic industry. Therefore, the microwave dielectric ceramic material which has adjustable dielectric constant, low loss, frequency temperature coefficient close to zero and reliable preparation process under microwave frequency has great application value.
To meet the requirements of modern microwave communications, Li2O-MgO-BO2(B＝Ti，Sn，Zr)，Li2O-BO2(B＝Ti,Zr,Sn)，Li2O-Nb2O5-TiO2，Li2O-MoO3，Li2O-BO-TiO2(B ═ Mg, Zn, Ca, Co) and Li2O-ZnO-Nb2O5Equal toA series of high-performance microwave ceramic systems are developed successively and subjected to certain modification researches. Wherein, the binary system Li2O-BO2Ceramics and ternary system Li2O-MgO-BO2Ceramics (B ═ Ti, Sn, Zr) have attracted considerable attention for their relatively good properties. For example, in the Journal of the American Ceramic Society, in the microwave dielectric Properties of Low-Firing Li2BO3(B＝Ti,Zr,Sn)Ceramics with B2O3-CuOAddition) of Li reported therein2BO3(B ═ Ti, Zr, Sn) has good microwave properties:r＝12.8～19.7,Q×f＝17,800～23,600GHz,τfplus 26.9-38.5 ppm/DEG C. In the Journal of the European Ceramic Society of China (Journal of the European Ceramic Society) in (Novel series of ultra-low microwave dielectric ceramics: Li2Mg3BO6(B ═ Ti, Sn, Zr)) reported to be Li2Mg3BO6The microwave performance of the microwave ceramic is as follows: li2Mg3BO6(B＝Ti,Sn,Zr)：r＝8.8～15.2,Q×f＝86,000～152,000GHz,τf＝-32～-39ppm/℃。
Although Li2BO3With Li2Mg3BO6The (B ═ Ti, Zr and Sn) microwave ceramics have relatively good microwave performance, but the defects of the sintering process and the temperature coefficient of frequency which cannot be close to zero can not meet the production requirements of the electronic industry application. First, Li in a sintering environment up to 1200 ℃ to 1400 ℃+Severe volatilization of ions at temperatures in excess of 1100 c results in decomposition of the main crystalline phase and the eventual formation of a large number of pores and the formation of a secondary phase, e.g.
Li2Mg3SnO6And Li2Mg3ZrO6Respectively in the presence of second phase Mg2SnO4And ZrO2The presence of a large number of pores and secondary phases can lead to Li2Mg3SnO6And Li2Mg3ZrO6The microwave performance of the base material is seriously deteriorated, and the phase composition of a material system is complicated and is difficult to control; second, Li2BO3With Li2Mg3BO6In the sintering and heating process of the (B ═ Ti, Zr and Sn) microwave ceramics, the internal stress distribution of the ceramics is not uniform due to the evolution of phase components and phase structures, and microcracks or broken lines appear; third, the temperature coefficient of frequency, which cannot approach zero, makes Li2BO3With Li2Mg3BO6The microwave ceramic can not meet the actual application requirements. At present, in order to solve the problem of volatilization of lithium element, sintering temperature is generally reduced by adding sintering aid into ceramic base material and non-stoichiometric ratio of lithium element is achieved, such as numerous et al (Microwave Dielectric Properties of Low-fire Li)2MO3(M＝Ti,Zr,Sn)Ceramics with B2O3-CuO Addition) with Addition of B2O3-CuO sintering aid to Li2SnO3The sintering temperature is greatly reduced, so that the volatilization of lithium element is well inhibited, the microstructure is improved, and the dielectric property is greatly deteriorated while the temperature is reduced; bian et al (Sintering behavor, microstructure and microwave properties of Li)2+xTiO3(0. ltoreq. x. ltoreq.0.2)) achieved by the nonstoichiometric ratio of Li elements2+xTiO3The comprehensive microwave performance of the ceramic is greatly improved, but the micro appearance of the ceramic with multiple pores and microcracks is not improved; aiming at microcracks or cracks caused by the evolution of phases, most of the existing researches do not solve the problem; the method for adjusting the frequency temperature coefficient is more effective by firstly synthesizing a phase opposite to the frequency temperature coefficient of a base material system and then adding the ceramic base material, but with the introduction of a second phase, the quality factor of the ceramic base material is also deteriorated while the temperature coefficient is improved. Therefore, the existing ceramic preparation process and the introduction of a second phase have failed to further improve Li2O-MgO-BO2And Li2O-BO2(B ═ Ti, Zr, Sn) microstructure and overall microwave performance.
In summary, Li is used2O-MgO-BO2And Li2O-BO2Based on (B ═ Ti, Zr and Sn) (B ═ Ti, Sn and Zr) ceramic materials, a highly dense microscopic ceramic was investigated by ion substitution using a novel processThe novel microwave dielectric ceramic has the advantages of high appearance, high quality factor (ultralow loss), frequency temperature coefficient close to zero, and capability of adjusting dielectric property within a certain range, has great scientific research value, and can meet the application requirements of the microwave communication industry.
Disclosure of Invention
The invention aims to solve the technical problem of providing a microwave dielectric ceramic material with high compact microscopic appearance, high quality factor, adjustable dielectric constant and adjustable resonant frequency temperature coefficient near zero and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is that the microwave dielectric ceramic material is characterized in that the chemical general formula is Li2/3(1-x-y)A1/3(1-x-y)MgxByO, wherein A is at least one of Ti, Sn and Zr, and B is at least one of Zn, Ni and Co; x and y are more than 0 and less than or equal to 4/7, x is more than or equal to 0 and less than 4/7, and y is more than 0 and less than 4/7.
The invention also provides a preparation method of the microwave dielectric ceramic material, which is characterized by comprising the following steps:
step 1: the starting material is selected from Mg (OH)2·4MgCO3·5H2O、Li2CO3、TiO2、SnO2、ZrO2ZnO, NiO and Co2O3According to the chemical formula Li2/3(1-x-y)A1/3(1-x-y)MgxByMixing O to form a mixture, wherein A is at least one of Ti, Sn and Zr, and B is at least one of Zn, Ni and Co; x and y are more than 0 and less than or equal to 4/7, x is more than or equal to 0 and less than 4/7, and y is more than 0 and less than 4/7;
step 2: ball milling, namely uniformly mixing the mixture and alcohol to obtain a ball grinding material;
and step 3: drying and sieving the ball-milled material to obtain dry powder;
and 4, step 4: pre-sintering the dried powder at 900-1200 ℃ to obtain pre-sintered powder;
and 5: performing secondary ball milling on the pre-sintered powder and alcohol to obtain a secondary ball grinding material which is uniformly mixed;
step 6: drying and sieving the secondary ball-milled material to obtain dry pre-sintered powder;
and 7: mixing the dried pre-sintered powder with a polyvinyl alcohol aqueous solution, granulating, controlling the granulation size to be 80-100 meshes, and then carrying out dry pressing forming to obtain a green body;
and 8: placing the green body on the compacted zirconium dioxide powder in a small container, continuously adding a certain amount of zirconium dioxide powder and pressurizing to form a buried part of the green body; placing the small container filled with the green body in a large container, burying the small container with lithium carbonate powder, and covering the large container with a covering plate with stable temperature to make the large container airtight, so as to form a green body burying device;
and step 9: and heating the green body burying device at a heating rate of 4-6 ℃/min and sintering at 1200-1400 ℃ for 2-6 hours to obtain the final microwave dielectric ceramic material.
Further, in the step 2, zirconium dioxide balls are used as ball milling media, and the mixing ratio is as follows: grinding balls: the absolute ethyl alcohol is mixed and ground for 5-7 hours according to the mass ratio of 1 (5-7) to 2-4 to obtain the uniformly mixed ball-milling material.
In the step 3 and the step 6, sieving is to pass through a 100-mesh sieve;
in the step 4, the pre-sintering time is 3-5 hours.
In the step 5, the zirconia balls are used as ball milling media for the second ball milling, and the mixing ratio is as follows: grinding balls: the mass ratio of the absolute ethyl alcohol is 1 (3-5) to 1-2, and the mixture is ground for 2-4 hours to obtain the uniformly mixed secondary ball grinding material.
The step 8 is as follows: putting zirconium dioxide powder into a small aluminum oxide crucible, pressurizing to compact and flatten the zirconium dioxide powder, putting the green body obtained in the step 7 on the compacted zirconium dioxide powder, continuously adding the zirconium dioxide powder for pressurizing, compacting and flattening the zirconium dioxide powder, repeatedly laminating to form a burying part of the green body, putting the crucible containing the green body into a large aluminum oxide crucible, pouring lithium carbonate powder into the large crucible, completely burying the small crucible by lithium carbonate, covering the large crucible with a zirconium oxide covering plate with stable temperature to ensure that the large crucible is airtight, and forming the burying device of the green body.
Compared with the prior art, the invention has the following beneficial effects:
1. in the sintering link, the green body is wrapped in the pure zirconium dioxide powder and placed under the lithium carbonate, so that a protective atmosphere and a lithium-rich atmosphere are provided for the green body, namely, the atmosphere is controlled and sintered to provide a good growth environment for the green body. In the formula, the content proportion of Li, A, Mg and B ions is adjusted by comprehensively adjusting the values of x and y so as to achieve the purpose of improving the comprehensive microwave dielectric property of the formula, the formula has a highly compact microstructure and high quality factor, the frequency temperature coefficient is-5 ppm/DEG C to +4 ppm/DEG C, the dielectric constant is adjustable, the microstructure and the comprehensive property are completely superior to the existing formula without any atmosphere control and substitution modification, the performance is stable, and the application requirements of modern microwave devices can be met
2. The microwave dielectric ceramic material does not contain volatile toxic metals such as Pb, Cd and the like, can be widely applied to microwave devices such as dielectric resonators, filters, oscillators and the like in satellite communication, is green, environment-friendly and pollution-free, and meets the strict standard requirements of the latest RHOS (instruction for limiting the use of certain harmful substances in electrical and electronic equipment) and the recycling treatment management regulations (WEEE) in the European Union.
3. The raw materials for preparing the microwave dielectric ceramic material are sufficiently supplied at home, the price is relatively low, and the cost reduction of the high-performance microwave ceramic becomes possible, so the microwave dielectric ceramic material has important industrial application value; the sintering temperature of the microwave dielectric ceramic material is about 1200-1300 ℃, the sintering temperature range is wide, and the microwave dielectric ceramic material has good process adaptability.
4. The raw materials used in the formula of the invention are all simple carbonates and oxides, do not need additional process synthesis, and are completely superior to the raw materials which need additional independent synthesis; the invention adopts a secondary ball milling process to realize the particle size control of the material.
5. The invention realizes great improvement on the microscopic appearance: the sample prepared by the existing sintering technology has a large amount of air hole microcracks, and the performance is greatly improved: the temperature coefficient of resonance frequency of the prior art basic formula is far less than-32 ppm/DEG C or more than 20 ppm/DEG C; the microwave dielectric ceramic material provided by the invention has a highly compact and reliable microstructureHigh in performance, has a near-zero adjustable resonant frequency temperature coefficient which meets the requirement of tau being less than or equal to minus 5 ppm/DEG CfThe dielectric constant is less than or equal to +4 ppm/DEG C, has high quality factor and adjustable dielectric, and can meet the application requirements of modern microwave devices.
Drawings
FIG. 1 is a schematic view of the atmosphere controlled sintering process for preparing microwave ceramic dielectric material according to the present invention.
FIG. 2 shows the result of XRD analysis of the microwave ceramic dielectric material prepared in example 4 of the present invention.
FIG. 3 is a SEM image of a microwave ceramic dielectric material prepared in example 4 of the present invention.
Detailed Description
The invention provides a microwave dielectric ceramic material prepared by ball-milling mixing, granulation, molding, binder removal and novel atmosphere control sintering process and a preparation method thereof, wherein the microwave dielectric ceramic material has high compactness in microscopic appearance, no air holes and no microcracks, a high quality factor Qxf is between 50000GHz and 100000GHz, and a relative dielectric constant isrBetween 10 and 20, the temperature coefficient of frequency taufBetween-5 ppm/DEG C and +4 ppm/DEG C.
The general chemical formula of the material of the microwave dielectric ceramic material is Li2/3(1-x-y)A1/3(1-x-y)MgxByO, wherein A is at least one of Ti, Sn and Zr, and B is at least one of Zn, Ni and Co; x and y are more than 0 and less than or equal to 4/7, x is more than or equal to 0 and less than 4/7, and y is more than 0 and less than 4/7. The raw material of the microwave dielectric ceramic material can comprise Mg (OH)2·4MgCO3·5H2O，Li2CO3Titanium, tin or zirconium dioxide and one or more of ZnO, NiO or Co2O3。
The preparation method comprises the following steps: preparing the components of the microwave ceramic material according to the chemical general formula, performing first ball milling and mixing, pre-sintering at 900-1200 ℃, performing second ball milling and mixing, and performing atmosphere control sintering at 1200-1300 ℃ to prepare the microwave ceramic material; the microscopic appearance is highly compact, no air holes or microcracks exist, the high-quality factor Qxf is between 50000GHz and 100000GHz, and the relative dielectric constantrBetween 10 and 20, the temperature coefficient of frequency taufBetween-5 ppm/DEG C and +4 ppm/DEG C. Atmosphere(s)The material for wrapping the green body sample in the control device is pure zirconium dioxide powder and pure lithium carbonate powder for providing a lithium-rich atmosphere outside.
Specifically, the preparation method of the microwave dielectric ceramic material comprises the following steps:
step 1: preparing materials; the raw material is selected from basic magnesium carbonate and Li2CO3，TiO2，SnO2，ZrO2ZnO, NiO or Co2O3According to the general formula Li2/3(1-x)A1/3(1-x-y)MgxByO, wherein A is Ti4+,Sn4+Or Zr4+(ii) a B is Zn2+,Ni2+Or Co2+X is more than or equal to 0 and less than 4/7, and y is more than 0 and less than 4/7 to form a mixture;
step 2: performing primary ball milling; taking zirconium dioxide balls as a ball milling medium, and mixing the materials according to the following ratio: grinding balls: the mass ratio of the absolute ethyl alcohol is 1 (5-7) to 2-4, and the absolute ethyl alcohol is ground for 5-7 hours to obtain a ball milling material which is uniformly mixed;
and step 3: drying and sieving; drying the ball-milled material obtained in the step 2 and sieving the ball-milled material with a 100-mesh sieve to obtain dry powder;
and 4, step 4: pre-burning; placing the dried powder obtained in the step 3 in an alumina crucible, and presintering for 3-5 hours at 900-1200 ℃ to obtain presintering powder;
and 5: performing secondary ball milling; and (4) performing secondary ball milling on the base material obtained in the step (4), taking zirconium dioxide balls as ball milling media, and mixing the materials: grinding balls: grinding the high-purity alcohol for 2-4 hours to obtain a uniformly mixed secondary ball grinding material, wherein the mass ratio of the high-purity alcohol is 1 (3-5) to 1-2;
step 6: drying and sieving; drying the ball-milled material obtained in the step 5 and sieving the ball-milled material with a 100-mesh sieve to obtain dry powder;
and 7: granulating and compression molding; mixing the pre-sintered powder obtained in the step 6 with a polyvinyl alcohol aqueous solution, granulating, controlling the granulation size to be 80-100 meshes, and putting the granules into a forming die for dry pressing and forming to obtain a green body;
and 8: and (3) stacking the green bodies, putting a certain amount of pure zirconium dioxide powder into a 200ml rectangular aluminum oxide small crucible, and applying a certain pressure to compact and flatten the pure zirconium dioxide powder. And (3) placing the green body obtained in the step (7) on the compacted zirconium dioxide powder, continuously adding a certain amount of zirconium dioxide powder, and applying a certain pressure to compact and flatten the zirconium dioxide powder. This was repeated 5 times to form the buried part of the green article. Placing the crucible filled with the green body into a 500ml rectangular alumina large crucible, pouring a certain amount of fine pure lithium carbonate powder into the 500ml large crucible, burying 200ml small crucible completely with lithium carbonate, and finally covering the 500ml large crucible with a zirconium oxide covering plate with stable temperature to form a closed space.
And step 9: sintering; and (4) placing the green body burying device obtained in the step (8) in a sintering furnace, heating at a heating rate of 4-6 ℃/min, and sintering at 1200-1400 ℃ for 2-6 hours to obtain the final microwave dielectric ceramic material.
The present invention can use any suitable starting material to form compounds of the general chemical formula Li2/3(1-x-y)A1/3(1-x-y)MgxByO, wherein A is Ti4+,Sn4+Or Zr4+(ii) a B is Zn2+,Ni2+Or Co2+X is more than or equal to 0 and less than 4/7, y is more than 0 and less than 4/7; the invention provides a good growth environment for green bodies through atmosphere control sintering, and comprehensively regulates and controls the x and y values to control the contents of Li, A, Mg and B ions so as to achieve the aim of comprehensively improving the microwave dielectric property, thereby ensuring that the prepared microwave dielectric ceramic material has high-density microscopic appearance, no air holes and no microcracks, high quality factor Qxf between 50000GHz and 100000GHz and relative dielectric constantrBetween 10 and 20, the temperature coefficient of frequency taufBetween-5 ppm/DEG C and +4 ppm/DEG C.
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
FIG. 1 is an atmosphere controlled sintering process for preparing microwave ceramic dielectric material according to the present inventionReferring to the schematic diagram, as can be seen from fig. 1: the sample is deeply buried in ZrO2Medium, ZrO2Providing a protective atmosphere, Li2CO3A lithium-rich atmosphere is provided to suppress volatilization of lithium. FIG. 2 shows the XRD analysis result of the microwave ceramic dielectric material prepared in example 3, and it can be seen from FIG. 2 that the main crystal phase of the prepared sample is made of Li with excellent properties2SnO3And Li2Mg3SnO6A complex phase system is formed. FIG. 3 is a SEM image of the microwave ceramic dielectric material prepared in example 3, and it can be seen from FIG. 3 that the ceramic has a highly dense microstructure, no pores and no microcracks.
Examples
The microwave dielectric ceramic material has a chemical general formula of Li2/3(1-x)A1/3(1-x-y)MgxByO, wherein (A ═ Ti, Sn, Zr; B ═ Zn, Ni, Co; 0 < x + y ≦ 4/7), wherein A is Ti4+,Sn4+Or Zr4+Tetravalent ion, B being Zn2+,Ni2+Or Co2+One or more of divalent ions; x is more than or equal to 0 and less than 4/7, and y is more than 0 and less than 4/7. The adopted protective materials required in the atmosphere control sintering link are pure zirconium dioxide powder and pure lithium carbonate powder for providing a lithium-rich atmosphere.
The raw material of the microwave dielectric ceramic material can comprise Mg (OH)2·4MgCO3·5H2O，Li2CO3The carbonate of calcium, tetravalent oxide of titanium, tin or zirconium, dioxide of zinc oxide, nickel oxide or cobalt oxide, i.e. the starting material for the microwave dielectric ceramic material, may also be in the form: mg (OH)2·4MgCO3·5H2O，Li2CO3Titanium, tin or zirconium dioxide and one or more of ZnO, NiO or Co2O3(ii) a Preparing the components of the microwave ceramic material according to the chemical general formula, performing first ball milling and mixing, pre-sintering at 900-1200 ℃, performing second ball milling and mixing, and performing atmosphere control sintering at 1200-1300 ℃ to prepare the microwave ceramic material; the micro-morphology of the ceramic material is highly compact, has no air holes and no microcracks, the microwave dielectric ceramic material is a two-phase composite system with opposite frequency temperature coefficients, and has a high quality factor Qxf between 50000GHz and 100000GHzTo dielectric constantrBetween 10 and 20, the temperature coefficient of frequency taufBetween-5 ppm/DEG C and +4 ppm/DEG C.
Table 1 shows the mass percentage of each raw material in each example in the total amount of the raw materials, and the raw materials are weighed according to the mass percentage in table 1, and subjected to ball milling and mixing processes twice, and then subjected to atmosphere control sintering at 1200-1400 ℃.
The embodiment specifically controls the content of Li, A, Mg and B ions by adjusting and comprehensively regulating the values of x and y, thereby obtaining excellent comprehensive microwave performance;
the method specifically comprises the following steps:
step 1: li2/3(1-x)A1/3(1-x-y)MgxByO, raw material is selected from Mg (OH)2·4MgCO3·5H2O (basic magnesium carbonate), Li2CO3，TiO2，SnO2，ZrO2ZnO, NiO or Co2O3In each example, various raw materials are accurately weighed according to the mass percentage in table 1;
step 2: performing primary ball milling; performing ball milling on the mixture obtained in the step 1 to obtain a primary ball milling base material;
and step 3: drying and sieving; drying the ball-milled material obtained in the step 2 and sieving the ball-milled material with a 100-mesh sieve to obtain dry powder;
and 4, step 4: pre-burning; placing the dried powder obtained in the step 3 in an alumina crucible, and presintering for 3-5 hours at 900-1200 ℃ to obtain presintering powder;
and 5: performing secondary ball milling; and (4) performing secondary ball milling on the base material obtained in the step (4), taking zirconium dioxide balls as ball milling media, and mixing the materials: grinding balls: grinding the high-purity alcohol for 2-4 hours to obtain a uniformly mixed secondary ball grinding material, wherein the mass ratio of the high-purity alcohol is 1 (3-5) to 1-2;
step 6: drying and sieving; drying the ball-milled material obtained in the step 5 and sieving the ball-milled material with a 100-mesh sieve to obtain dry powder;
and 7: granulating and compression molding; mixing the pre-sintered powder obtained in the step 6 with a polyvinyl alcohol aqueous solution, granulating, controlling the granulation size to be 80-100 meshes, and putting the granules into a forming die for dry pressing and forming to obtain a green body;
and 8: and (3) stacking the green bodies, putting a certain amount of pure zirconium dioxide powder into a 200ml rectangular aluminum oxide small crucible, and applying a certain pressure to compact and flatten the pure zirconium dioxide powder. And (4) placing the green body obtained in the step (7) on the compacted zirconium dioxide powder, continuously filling a certain amount of zirconium dioxide powder, and applying a certain pressure to compact and flatten the zirconium dioxide powder. This was repeated 5 times to form the buried part of the green article. Placing the crucible filled with the green body into a 500ml rectangular alumina large crucible, pouring a certain amount of fine pure lithium carbonate powder into the 500ml large crucible, burying 200ml small crucible completely with lithium carbonate, and finally covering the 500ml large crucible with a zirconium oxide covering plate with stable temperature to form a closed space.
And step 9: sintering; and (3) placing the green body burying device obtained in the step (8) in a sintering furnace, heating at the heating rate of 4-6 ℃/min, and sintering at 1200-1300 ℃ for 2-6 hours to obtain the final microwave dielectric ceramic material, wherein the process parameters and performance detection results adopted in each embodiment are shown in table 2.
As can be seen from Table 2, the microwave dielectric ceramic material of each example has a high Q x f quality factor ranging from 50000GHz to 100000GHz and a relative dielectric constantrBetween 10 and 20, the temperature coefficient of frequency taufBetween-5 ppm/DEG C and +4 ppm/DEG C.
Table 1 mass percentage of each raw material in each example
Figure BDA0001350873150000081
Figure BDA0001350873150000091
TABLE 2 Process and microwave dielectric Properties used in the examples
Figure BDA0001350873150000092

Claims (5)

1. The preparation method of the microwave dielectric ceramic material is characterized by comprising the following steps:
step 1: the starting material is selected from Mg (OH)2·4MgCO3·5H2O、Li2CO3、TiO2、SnO2、ZrO2ZnO, NiO and Co2O3According to the chemical formula Li2/3(1-x-y)A1/3(1-x-y)MgxByMixing O to form a mixture, wherein A is at least one of Ti, Sn and Zr, and B is at least one of Zn, Ni and Co; x and y are more than 0 and less than or equal to 4/7, x is more than or equal to 0 and less than 4/7, and y is more than 0 and less than 4/7;
step 2: ball milling, namely uniformly mixing the mixture and alcohol to obtain a ball grinding material;
and step 3: drying and sieving the ball-milled material to obtain dry powder;
and 4, step 4: pre-sintering the dried powder at 900-1200 ℃ to obtain pre-sintered powder;
and 5: performing secondary ball milling on the pre-sintered powder and alcohol to obtain a secondary ball grinding material which is uniformly mixed;
step 6: drying and sieving the secondary ball-milled material to obtain dry pre-sintered powder;
and 7: mixing the dried pre-sintered powder with a polyvinyl alcohol aqueous solution, granulating, controlling the granulation size to be 80-100 meshes, and then carrying out dry pressing forming to obtain a green body;
and 8: placing the green body on the compacted zirconium dioxide powder in a small container, continuously adding a certain amount of zirconium dioxide powder and pressurizing to form a buried part of the green body; placing the small container filled with the green body in a large container, burying the small container with lithium carbonate powder, and covering the large container with a covering plate with stable temperature to make the large container airtight, so as to form a green body burying device;
and step 9: and heating the green body burying device at a heating rate of 4-6 ℃/min and sintering at 1200-1400 ℃ for 2-6 hours to obtain the final microwave dielectric ceramic material.
2. A method for preparing a microwave dielectric ceramic material as claimed in claim 1, wherein in the step 2, zirconia balls are used as a ball milling medium, and the mixing ratio is as follows: grinding balls: the absolute ethyl alcohol is mixed and ground for 5-7 hours according to the mass ratio of 1 (5-7) to 2-4 to obtain the uniformly mixed ball-milling material.
3. A method for preparing a microwave dielectric ceramic material as claimed in claim 1,
in the step 3 and the step 6, sieving is to pass through a 100-mesh sieve;
in the step 4, the pre-sintering time is 3-5 hours.
4. A method for preparing a microwave dielectric ceramic material as claimed in claim 1, wherein in the step 5, zirconia balls are used as a ball milling medium for the second ball milling, and the mixing ratio is as follows: grinding balls: the mass ratio of the absolute ethyl alcohol is 1 (3-5) to 1-2, and the mixture is ground for 2-4 hours to obtain the uniformly mixed secondary ball grinding material.
5. A method for preparing a microwave dielectric ceramic material as claimed in claim 1, wherein the step 8 is: putting zirconium dioxide powder into a small aluminum oxide crucible, pressurizing to compact and flatten the zirconium dioxide powder, putting the green body obtained in the step 7 on the compacted zirconium dioxide powder, continuously adding the zirconium dioxide powder for pressurizing, compacting and flattening the zirconium dioxide powder, repeatedly laminating to form a burying part of the green body, putting the crucible containing the green body into a large aluminum oxide crucible, pouring lithium carbonate powder into the large crucible, completely burying the small crucible by lithium carbonate, covering the large crucible with a zirconium oxide covering plate with stable temperature to ensure that the large crucible is airtight, and forming the burying device of the green body.
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