CN113149645B - Low-temperature sintering temperature stable composite microwave dielectric ceramic and preparation method thereof - Google Patents
Low-temperature sintering temperature stable composite microwave dielectric ceramic and preparation method thereof Download PDFInfo
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Abstract
The composite microwave dielectric ceramic material comprises the following components: the low-temperature sintering type microwave dielectric ceramic material with the negative resonance frequency temperature coefficient and the low-temperature sintering type microwave dielectric ceramic material with the positive resonance frequency temperature coefficient are prepared by taking the low-temperature sintering type microwave dielectric ceramic material with the negative resonance frequency temperature coefficient or the low-temperature sintering type microwave dielectric ceramic material with the positive resonance frequency temperature coefficient as main materials, adding the low-temperature sintering type microwave dielectric ceramic materials with the same structure and the opposite resonance frequency temperature coefficient as seasonings through a two-phase compounding method, compounding to form a complex-phase ceramic material or solid solution, and obtaining the low-temperature sintering type microwave dielectric ceramic material with the near-zero resonance frequency temperature coefficient. Solves the problems of high sintering temperature and large temperature coefficient of resonant frequency along with the temperature change of the traditional microwave dielectric ceramic. The method has wide application in LTCC low-temperature sintering microwave dielectric ceramic materials.
Description
Technical Field
The invention belongs to the field of electronic components, in particular to the field of microwave electronic components, and further belongs to the field of ceramic materials of microwave electronic components.
Background
The microwave dielectric ceramic (MWDC) refers to a ceramic material which is applied to a microwave frequency band (300 MHz-300 GHz) circuit as a dielectric material and performs one or more functions. In microwave electronic components, microwave dielectric ceramics are used as key materials for manufacturing microwave resonators and filters, and the ideal performance of the microwave dielectric ceramics is as follows: the device is miniaturized by high dielectric constant, high frequency of operation of the device is ensured by high quality factor, and operation stability of the device is ensured by near zero resonance frequency temperature coefficient. At present, the widely adopted microwave dielectric Ceramic material meets the use requirements of some electronic components in performance, but with the continuous upgrading (such as 5G technology) of modern electronic information technology, the development of integration, high frequency, miniaturization, light weight and portability of various mobile communication equipment has become a necessary trend, and the adoption of low temperature cofired Ceramic (LTCC, low Temperature Co-wireless Ceramic) technology is an important means for realizing the technical development of high-density packaging, electronic component integration, miniaturization, light weight, high reliability and the like.
For traditional microwave dielectric ceramics, although the ceramic has higher performance and is widely applied, the application in the technical field of LTCC is limited due to the fact that higher sintering temperature (more than or equal to 1200 ℃) is generally required. In order to lower the sintering temperature of these ceramics, the most efficient and economical method at present is to add low melting point oxides or glasses as sintering aids to lower the sintering temperature. Although the sintering temperature of ceramics is lowered, the microwave dielectric properties thereof are often severely deteriorated. In addition, in practical use, many microwave dielectric materials are limited in use, comprehensively considering the requirements of energy conservation, non-toxicity, low energy consumption and the like. Therefore, the development of the low-temperature sintering microwave dielectric ceramic material which has the advantages of high signal response speed, small loss and strong working environment temperature adaptability, can be widely applied to the fields of mobile communication radars, satellite communication and the like and meets the performance requirements of LTCC devices is a key for solving the technical problems.
In the prior microwave dielectric ceramic material, li 2/3 Ni 2/3 MoO 4 The microwave dielectric ceramic material has excellent microwave dielectric property (epsilon) r =9.2, Q×f =41064GHz, τ f -68.86ppm/°c) with a lower sintering temperature (700 ℃/2 h) (h represents hours) such that Li 2/3 Ni 2/3 MoO 4 Microwave dielectric ceramic materials have become promising candidates for LTCC. However, the temperature coefficient of the resonance frequency is negativeτ f ) Limiting the range of applications for the material. Therefore, how to effectively regulate Li 2/3 Ni 2/3 MoO 4 The temperature coefficient of the resonant frequency of the microwave dielectric ceramic material is close to zero (also called low temperature drift or temperature stability), the service performance is stable, the sintering temperature is low, and the industrial production is convenient to realize 2/3 Ni 2/3 MoO 4 The microwave dielectric ceramic material has positive significance.
In view of this, the present invention has been made.
Disclosure of Invention
The purpose of the invention is that: solves the problems of high sintering temperature and larger temperature coefficient of resonant frequency of the traditional microwave dielectric ceramic material.
The technical principle adopted is as follows: the low-temperature sintering microwave dielectric ceramic material meeting the LTCC sintering process is taken as a main material, and a material with the same structure and the temperature coefficient of the opposite resonance frequency is added to be compounded into a complex-phase ceramic material or solid solution by a two-phase compounding method, so that the temperature coefficient of the near-zero resonance frequency can be obtained, and the low-temperature sintering can be realized under the action of no sintering auxiliary agent.
Therefore, the invention provides a low-temperature sintering temperature-stable composite microwave dielectric ceramic which has negative resonance frequency temperature coefficientτ f ) Li of (2) 2/3 Ni 2/3 MoO 4 Microwave dielectric ceramic material as main material with positive resonant frequency temperature coefficientτ f ) Of (Li) 1/2 Bi 1/2 )MoO 4 (τ f = +240 ppm/°c) as a flavoring (also known as an additive) by adding to Li 2/3 Ni 2/3 MoO 4 Microwave dielectric ceramic material is added (Li) 1/2 Bi 1/2 )MoO 4 Ceramic material for regulating Li 2/3 Ni 2/3 MoO 4 Temperature coefficient of resonant frequencyτ f ) Near zero, thereby obtaining a low-temperature sintered resonant frequency temperature coefficientτ f ) Microwave dielectric ceramic material close to zero and with composition expression of { (Li) 2(1-x)/3 Bi x/2 )(Li x/2 Ni 2(1-x)/3 )}MoO 4 The saidx=0.2 to 0.6, and can be sintered into porcelain at a temperature lower than 700 ℃ under the action of no sintering aid.
The preparation method of the low-temperature sintering temperature stable composite microwave dielectric ceramic adopts a solid phase synthesis method, firstly, oxides and carbonates are uniformly mixed through primary ball milling, raw materials are subjected to primary reaction through a thermal insulation calcination process to obtain a required phase, the particle size of reactants is refined through secondary ball milling, finally, green bodies are pressed, and the composite ceramic material is prepared through sintering and other processes. The flow chart is shown in fig. 1.
The method comprises the following steps:
(1) Raw material preparation: in high purity (purity is more than or equal to 99 percent) Li 2 CO 3 、NiO、Bi 2 O 3 And MoO 3 As raw material, according to Li 2/3 Ni 2/3 MoO 4 、(Li 1/2 Bi 1/2 )MoO 4 Preparing and weighing the chemical formula stoichiometric ratio;
(2) Ball milling and mixing: the prepared and weighed raw materials are ball-milled for 4 to 6 hours in a high-rotation-speed ball mill with the rotation speed of 250 r/min to 350r/min by taking absolute ethyl alcohol and agate balls as ball-milling media;
(3) Ball milling and mixing and drying: drying the mixture subjected to ball milling and mixing at the temperature of 60-100 ℃;
drying, grinding into powder, and sieving with 80 mesh sieve; then preserving heat for 2-4 hours at the temperature rising rate of 2-5 ℃ per minute at the temperature of 450-650 ℃ to obtain presintering synthesized Li 2/3 Ni 2/3 MoO 4 、(Li 1/2 Bi 1/2 )MoO 4 Ceramic powder;
preparing composite ceramic powder: mixing the presintered ceramic powder with (1-x) Li in proportion 2/3 Ni 2/3 MoO 4 -x(Li 1/2 Bi 1/2 )MoO 4 Batching to get { (Li) 2(1-x)/3 Bi x/2 )(Li x/2 Ni 2(1-x)/3 )}MoO 4 (x is more than or equal to 0.2 and less than or equal to 0.6) composite ceramic powder;
(5) Ball milling of composite ceramic powder: uniformly mixing the prepared composite ceramic powder by taking absolute ethyl alcohol and agate balls as ball milling media, and performing ball milling for 8-12 hours in a high-rotation-speed ball mill with the rotation speed of 250 r-350 r/min;
(6) And (3) ball milling and drying the composite ceramic powder: drying the ball-milled composite ceramic powder at the temperature of 80-100 ℃;
(7) Grinding into powder and sieving: grinding the dried composite ceramic powder into powder, adding a polyvinyl alcohol aqueous solution (PVA) into the composite ceramic powder for manual grinding and granulating, and sieving the granulated powder through a screen with 80-120 meshes;
(8) Preparing a composite ceramic cylindrical green body: pressing the screened composite ceramic powder into a cylindrical green body with the diameter of 15mm and the height of 7 mm-8 mm under the pressure of 5 MPa-10 MPa;
(9) Preparation of composite ceramic material: and (3) placing the composite ceramic cylindrical green compact in a sintering furnace, and preserving heat for 1-4 hours at the temperature rising rate of 3-7 ℃ per minute at the temperature of 500-700 ℃ to obtain the low-temperature sintering temperature-stable composite microwave dielectric ceramic material.
The low-temperature sintering temperature stable composite microwave dielectric ceramic material has the following characteristics:
the sintering temperature is low and adjustable. Typical sintering temperature range: 500-700 ℃;
high temperature stability and adjustable property. Typical resonant frequency temperature coefficient range: -30 ppm/. Degree.C. 30 ppm/DEG C;
the dielectric constant is moderate and adjustable. Typical dielectric constant range: 9-25;
the quality factor is high and adjustable. Typical figures of merit range: 18000 GHz-40000 GHz.
Can meet the requirements of LTCC technology. Meanwhile, the lower sintering temperature (500-700 ℃) greatly reduces the energy consumption in industrial production.
The low-temperature sintering temperature-stable composite microwave dielectric ceramic material is widely applied to the modern microwave electronic communication fields such as mobile communication, electronic countermeasure, satellite communication, beidou system (GPS), bluetooth technology, wireless local area network (MLAN), internet of things and the like.
Drawings
FIG. 1 is a flow chart of a preparation process of a composite ceramic material.
Description of the embodiments
The composition expression of the low-temperature sintering temperature-stable composite microwave dielectric ceramic material is { (Li) 2(1-x)/3 Bi x/2 )(Li x/2 Ni 2(1-x)/3 )}MoO 4 Different numerical values are taken for x in the expression, and with reference to fig. 1, the preparation methods and material properties of different embodiments are as follows:
example 1:x=0.2
the preparation method comprises the following steps:
li with purity more than or equal to 99.9% 2 CO 3 、NiO、Bi 2 O 3 And MoO 3 As raw material, according to Li 2/3 Ni 2/3 MoO 4 、(Li 1/2 Bi 1/2 )MoO 4 Stoichiometric proportion is prepared and weighed, absolute ethyl alcohol and agate balls are used as ball milling media, ball milling is carried out for 4-6 hours at the rotating speed of 300r/min, drying is carried out at 80 ℃, and then heat preservation is carried out at the heating rate of 2-5 ℃ per minute for 2-4 hours at the temperature of 500-600 ℃ to obtain presintered Li 2/3 Ni 2/3 MoO 4 、(Li 1/2 Bi 1/2 )MoO 4 Ceramic powder.
Proportionally (1-x) Li the ceramic powder synthesized by presintering in the step 1) 2/3 Ni 2/3 MoO 4 -x(Li 1/2 Bi 1/2 )MoO 4 Batching to get { (Li) 1.6/3 Bi 0.2/2 )(Li 0.2/2 Ni 1.6/3 )}MoO 4 Composite ceramic powder; uniformly mixing the prepared composite ceramic powder by taking absolute ethyl alcohol and agate balls as ball milling media, and performing ball milling for 8-12 hours in a high-rotation-speed ball mill with the rotation speed of 250 r-350 r/min; drying at 80 ℃, grinding into powder, sieving, adding polyvinyl alcohol aqueous solution (PVA) into the composite ceramic powder, carrying out manual grinding and granulating, sieving the granulated powder with a 80-120 mesh screen, and pressing into a cylindrical green body with the diameter of 15mm and the height of 7-8 mm under the pressure of 5-10 MPa;
3) And (3) carrying out heat preservation on the green body obtained in the step (2) in a muffle furnace at the temperature rising rate of 3-7 ℃ per minute at the temperature of 600-700 ℃ for 1-4 hours to obtain the composite ceramic material.
The optimal performance indexes of the ceramic materials are as follows: a dielectric constant of 10.9, a quality factor of 34538GHz,the temperature coefficient of resonance frequency is-33.15 ppm/°C.
Example 2:x=0.3
li with purity more than or equal to 99.9% 2 CO 3 、NiO、Bi 2 O 3 And MoO 3 As raw material, according to Li 2/3 Ni 2/3 MoO 4 、(Li 1/2 Bi 1/2 )MoO 4 Stoichiometric proportion is prepared and weighed, absolute ethyl alcohol and agate balls are used as ball milling media, ball milling is carried out for 4-6 hours at the rotating speed of 300r/min, drying is carried out at 80 ℃, and then heat preservation is carried out at the heating rate of 2-5 ℃ per minute for 2-4 hours at the temperature of 500-600 ℃ to obtain presintered Li 2/3 Ni 2/3 MoO 4 、(Li 1/2 Bi 1/2 )MoO 4 Ceramic powder.
Proportionally (1-x) Li the ceramic powder synthesized by presintering in the step 1) 2/3 Ni 2/3 MoO 4 -x(Li 1/2 Bi 1/2 )MoO 4 Batching to get { (Li) 1.4/3 Bi 0.3/2 )(Li 0.3/2 Ni 1.4/3 )}MoO 4 Composite ceramic powder; uniformly mixing the prepared composite ceramic powder by taking absolute ethyl alcohol and agate balls as ball milling media, and performing ball milling for 8-12 hours in a high-rotation-speed ball mill with the rotation speed of 250 r-350 r/min; drying at 80 ℃, grinding into powder, sieving, adding polyvinyl alcohol aqueous solution (PVA) into the composite ceramic powder, carrying out manual grinding and granulating, sieving the granulated powder with a 80-120 mesh screen, and pressing into a cylindrical green body with the diameter of 15mm and the height of 7-8 mm under the pressure of 5-10 MPa;
and (3) placing the green body obtained in the step (2) in a muffle furnace, and preserving heat at 580-680 ℃ for 1-4 hours at a heating rate of 3-7 ℃/min to obtain the composite ceramic material.
The optimal performance indexes of the ceramic materials are as follows: the dielectric constant is 13.5, the quality factor is 24538GHz, and the temperature coefficient of resonance frequency is-20.15 ppm/°C.
Example 3:x=0.4
the preparation method comprises the following steps:
in purity of99.9% or more of Li 2 CO 3 、NiO、Bi 2 O 3 And MoO 3 As raw materials, press Li 2/3 Ni 2/3 MoO 4 、(Li 1/2 Bi 1/2 )MoO 4 Stoichiometric ratio of chemical formula is prepared and weighed, anhydrous ethanol and agate balls are used as ball milling media, ball milling is carried out for 4-6 hours at the rotating speed of 300r/min, drying is carried out at 80 ℃, and then heat preservation is carried out at the heating rate of 2-5 ℃/min at 500-600 ℃ for 2-4 hours, so that presintering synthesized Li is obtained 2/3 Ni 2/3 MoO 4 、(Li 1/2 Bi 1/2 )MoO 4 Ceramic powder.
Proportionally (1-x) Li the ceramic powder synthesized by presintering in the step 1) 2/3 Ni 2/3 MoO 4 -x(Li 1/2 Bi 1/2 )MoO 4 Compounding to obtain composite ceramic powder; uniformly mixing the prepared composite ceramic powder by taking absolute ethyl alcohol and agate balls as ball milling media, and ball milling in a high-rotation-speed ball mill with the rotation speed of 250 r-350 r/min for 8-12 hours; drying at 80 ℃, grinding into powder, sieving, adding polyvinyl alcohol aqueous solution (PVA) into the composite ceramic powder, carrying out manual grinding and granulating, sieving the granulated powder with a 80-120 mesh screen, and pressing into a cylindrical green body with the diameter of 15mm and the height of 7-8 mm under the pressure of 5-10 MPa;
and (3) placing the green body obtained in the step (2) in a muffle furnace, and preserving heat at 560-660 ℃ for 1-4 hours at a heating rate of 3-7 ℃/min to obtain the composite ceramic material.
The optimal performance indexes of the ceramic materials are as follows: the dielectric constant is 15.1, the quality factor is 22564GHz, and the temperature coefficient of resonance frequency is +1.12 ppm/°C.
Example 4:x=0.5
the preparation method comprises the following steps:
li with purity more than or equal to 99.9% 2 CO 3 、NiO、Bi 2 O 3 And MoO 3 As raw material, according to Li 2/3 Ni 2/3 MoO 4 、(Li 1/2 Bi 1/2 )MoO 4 Weighing by stoichiometric proportion, ball milling for 4-6 hours at a rotating speed of 300r/min by taking absolute ethyl alcohol and agate balls as ball milling media, drying at 80 ℃, and then using 2 ℃/miKeeping the temperature at 500-600 ℃ for 2-4 hours at a heating rate of n-5 ℃/min to obtain presintered Li 2/3 Ni 2/3 MoO 4 、(Li 1/2 Bi 1/2 )MoO 4 Ceramic powder.
Proportionally (1-x) Li the ceramic powder synthesized by presintering in the step 1) 2/3 Ni 2/3 MoO 4 -x(Li 1/2 Bi 1/2 )MoO 4 Batching to get { (Li) 1.2/3 Bi 0.4/2 )(Li 0.4/2 Ni 1.2/3 )}MoO 4 Composite ceramic powder; the prepared composite ceramic powder is ball-milled for 8-12 hours and uniformly mixed in a high-rotation-speed ball mill with the rotation speed of 250 r-350 r/min by taking absolute ethyl alcohol and agate balls as ball-milling media; drying at 80 ℃, grinding into powder, sieving, adding polyvinyl alcohol aqueous solution (PVA) into the composite ceramic powder, carrying out manual grinding and granulating, sieving the granulated powder with a 80-120 mesh screen, and pressing into a cylindrical green body with the diameter of 15mm and the height of 7-8 mm under the pressure of 5-10 MPa;
and (3) placing the green body obtained in the step (2) in a muffle furnace, and preserving heat at the temperature of 540-640 ℃ for 1-4 hours at the heating rate of 3-7 ℃/min to obtain the composite ceramic material.
The optimal performance indexes of the ceramic materials are as follows: the dielectric constant was 18.4, the quality factor was 20304GHz, and the temperature coefficient of resonance frequency was +12.18ppm/°C.
Example 5:x=0.6
the preparation method comprises the following steps:
li with purity more than or equal to 99.9% 2 CO 3 、NiO、Bi 2 O 3 And MoO 3 As raw material, according to Li 2/3 Ni 2/3 MoO 4 、(Li 1/2 Bi 1/2 )MoO 4 Stoichiometric proportion is prepared and weighed, absolute ethyl alcohol and agate balls are used as ball milling media, ball milling is carried out for 4-6 hours at the rotating speed of 300r/min, drying is carried out at 80 ℃, and then heat preservation is carried out at the heating rate of 2-5 ℃ per minute for 2-4 hours at the temperature of 500-600 ℃ to obtain presintered Li 2/3 Ni 2/3 MoO 4 、(Li 1/2 Bi 1/2 )MoO 4 Ceramic powder.
The ceramic powder synthesized by presintering in the step 1) is mixed according to the proportion (1-x)Li 2/3 Ni 2/3 MoO 4 -x(Li 1/2 Bi 1/2 )MoO 4 Batching to get { (Li) 1/3 Bi 0.6/2 )(Li 0.6/2 Ni 1/3 )}MoO 4 Composite ceramic powder; uniformly mixing the prepared composite ceramic powder by taking absolute ethyl alcohol and agate balls as ball milling media, and performing ball milling for 8-12 hours in a high-rotation-speed ball mill with the rotation speed of 250 r-350 r/min; drying at 80 ℃, grinding into powder, sieving, adding polyvinyl alcohol aqueous solution (PVA) into the composite ceramic powder, carrying out manual grinding and granulating, sieving the granulated powder with a 80-120 mesh screen, and pressing into a cylindrical green body with the diameter of 15mm and the height of 7-8 mm under the pressure of 5-10 MPa;
and (3) carrying out heat preservation on the green body obtained in the step (2) in a muffle furnace at the temperature rising rate of 3-7 ℃/min at 520-620 ℃ for 1-4 hours to obtain the composite ceramic material.
The optimal performance indexes of the ceramic materials are as follows: the dielectric constant was 20.11, the quality factor was 18304GHz, and the temperature coefficient of resonance frequency was +22.01ppm/°C.
Finally, it should be noted that: the above examples are only illustrative and the invention includes, but is not limited to, the above examples, which need not and cannot be exhaustive of all embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. All embodiments meeting the requirements of the invention are within the protection scope of the invention.
Claims (7)
1. The low-temperature sintering temperature-stable composite microwave dielectric ceramic material is characterized by comprising the following components: the low-temperature sintering type microwave dielectric ceramic material with the negative resonance frequency temperature coefficient and the low-temperature sintering type microwave dielectric ceramic material with the positive resonance frequency temperature coefficient are adopted as main materials, the low-temperature sintering type microwave dielectric ceramic material with the same structure and the opposite resonance frequency temperature coefficient is added as a seasoning through a two-phase compounding method, and a complex phase ceramic material or solid solution is compounded to obtain the low-temperature sintering type microwave dielectric ceramic material with the near-zero resonance frequency temperature coefficient;
the main material is Li with negative resonance frequency temperature coefficient 2/3 Ni 2/3 MoO 4 The flavoring is a microwave dielectric ceramic material with positive resonant frequency temperature coefficient (Li 1/2 Bi 1/2 )MoO 4 Microwave dielectric ceramic material prepared by introducing Li 2/3 Ni 2/3 MoO 4 Microwave dielectric ceramic material is added (Li) 1/2 Bi 1/2 )MoO 4 Microwave dielectric ceramic material, forming a microwave dielectric ceramic material (1-x) Li with low-temperature sintering and resonance frequency temperature coefficient close to zero 2/3 Ni 2/3 MoO 4 -x(Li 1/2 Bi 1/2 )MoO 4 ；
The (1-x) Li 2/3 Ni 2/3 MoO 4 -x(Li 1/2 Bi 1/2 )MoO 4 X=0.2-0.6 in the microwave dielectric ceramic material;
the (1-x) Li 2/3 Ni 2/3 MoO 4 -x(Li 1/2 Bi 1/2 )MoO 4 Temperature coefficient range of resonant frequency of microwave dielectric ceramic material: -30 ppm/-DEG C; dielectric constant range: 9-25; quality factor range: 18000 GHz-40000 GHz.
2. The low temperature sintering temperature stable composite microwave dielectric ceramic material according to claim 1, wherein: the Li is 2/3 Ni 2/3 MoO 4 The resonant frequency temperature coefficient of the microwave dielectric ceramic material is-68.86 ppm/°c, the (Li 1/ 2 Bi 1/2 )MoO 4 The resonant frequency temperature coefficient of the microwave dielectric ceramic material is +240 ppm/°c.
3. The low temperature sintering temperature stable composite microwave dielectric ceramic material according to claim 1, wherein: the (1-x) Li 2/3 Ni 2/3 MoO 4 -x(Li 1/2 Bi 1/2 )MoO 4 Sintering temperature range of microwave dielectric ceramic material: 500-700 ℃.
4. The low temperature sintering temperature stable composite microwave dielectric ceramic material according to claim 1, wherein (1-x) Li 2/3 Ni 2/3 MoO 4 -x(Li 1/2 Bi 1/2 )MoO 4 The microwave dielectric ceramic material comprises the following components:
xwhen=0.2, the dielectric constant is 10.9, the quality factor is 34538GHz, and the temperature coefficient of resonance frequency is-33.15 ppm/°c;
xwhen=0.3, the dielectric constant is 13.5, the quality factor is 24538GHz, and the temperature coefficient of resonance frequency is-20.15 ppm/°c;
xwhen=0.4, the dielectric constant is 15.1, the quality factor is 22564GHz, and the temperature coefficient of resonance frequency is +1.12 ppm/°c;
xwhen=0.5, the dielectric constant is 18.4, the quality factor is 20304GHz, and the temperature coefficient of resonance frequency is +12.18ppm/°c;
xwhen=0.6, the dielectric constant is 20.11, the quality factor is 18304GHz, and the temperature coefficient of resonance frequency is +22.01ppm/°c.
5. The method for preparing the low-temperature sintering temperature-stable composite microwave dielectric ceramic material according to claim 1, which is characterized by comprising the following steps: the preparation method adopts a solid-phase synthesis method, firstly, oxides and carbonates are uniformly mixed through primary ball milling, the raw materials are subjected to primary reaction through a heat preservation calcination process to obtain a required phase, the particle size of reactants is refined through secondary ball milling, and finally, green bodies are pressed, and the composite ceramic material is prepared through a sintering process.
6. The method for preparing the low-temperature sintering temperature-stable composite microwave dielectric ceramic material according to claim 5, which is characterized by comprising the following steps:
(1) Raw material preparation: high purity of 99% or moreDegree Li 2 CO 3 、NiO、Bi 2 O 3 And MoO 3 As raw material, according to Li 2/ 3 Ni 2/3 MoO 4 、(Li 1/2 Bi 1/2 )MoO 4 Preparing and weighing the chemical formula stoichiometric ratio;
(2) Ball milling and mixing: the prepared and weighed raw materials are ball-milled for 4 to 6 hours in a high-rotation-speed ball mill by taking absolute ethyl alcohol and agate balls as ball-milling media;
(3) Ball milling, mixing and drying, presintering: drying the mixture subjected to ball milling and mixing at the temperature of 80-100 ℃, grinding the dried mixture into powder, and sieving the powder with a 80-mesh sieve; then preserving heat for 2-4 hours at the temperature rising rate of 2-5 ℃/min at the temperature of 450-650 ℃ to obtain presintering synthesized Li 2/3 Ni 2/3 MoO 4 、(Li 1/2 Bi 1/2 )MoO 4 Ceramic powder;
(4) Preparing composite ceramic powder: mixing the presintered ceramic powder with (1-x) Li in proportion 2/3 Ni 2/3 MoO 4 -x(Li 1/2 Bi 1/2 )MoO 4 Batching to obtain (1-x) Li 2/3 Ni 2/3 MoO 4 -x(Li 1/2 Bi 1/2 )MoO 4 Composite ceramic powder;
(5) Ball milling of composite ceramic powder: the prepared composite ceramic powder is ball-milled for 8-12 hours in a high-rotation-speed ball mill by taking absolute ethyl alcohol and agate balls as ball-milling media, and uniformly mixed;
(6) And (3) ball milling and drying the composite ceramic powder: drying the ball-milled composite ceramic powder at the temperature of 80-100 ℃;
(7) Grinding into powder and sieving: grinding the dried composite ceramic powder into powder, adding a polyvinyl alcohol aqueous solution into the composite ceramic powder for manual grinding and granulating, and sieving the granulated powder through a 80-120-mesh screen;
(8) Preparing a composite ceramic cylindrical green body: pressing the screened composite ceramic powder into a cylindrical green body with the diameter of 15mm and the height of 7 mm-8 mm under the pressure of 5 MPa-10 MPa;
(9) Preparation of composite ceramic material: and (3) placing the composite ceramic cylindrical green compact in a sintering furnace, and preserving heat for 1-4 hours at the temperature rising rate of 3-7 ℃ per minute at the temperature of 500-700 ℃ to obtain the low-temperature sintering temperature-stable composite microwave dielectric ceramic material.
7. The method for preparing the low-temperature sintering temperature-stable composite microwave dielectric ceramic material according to claim 6, wherein the high purity is 99.9% -99.99%; the rotating speed of the ball mill is 200 r/min-300 r/min.
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