CN110668818B - Ultralow temperature sintered composite microwave dielectric ceramic material and preparation method thereof - Google Patents

Ultralow temperature sintered composite microwave dielectric ceramic material and preparation method thereof Download PDF

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CN110668818B
CN110668818B CN201911052856.2A CN201911052856A CN110668818B CN 110668818 B CN110668818 B CN 110668818B CN 201911052856 A CN201911052856 A CN 201911052856A CN 110668818 B CN110668818 B CN 110668818B
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周迪
郝澍钊
郭欢欢
吴芳芳
李文艺
李睿韬
任佳佳
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Xian Jiaotong University
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Abstract

The invention discloses an ultralow temperature sintered composite microwave dielectric ceramic material and a preparation method thereof, wherein the composition expression of the ceramic material is x (Na)0.5Bi0.5)MoO4－(1‑x)Bi2MoO6Wherein x is more than or equal to 0.6 and less than or equal to 0.9, the ceramic material is obtained by sintering at low temperature, can be applied to LTCC technology, and has the advantages of simple preparation method, low cost and high safety.

Description

Ultralow temperature sintered composite microwave dielectric ceramic material and preparation method thereof
Technical Field
The invention belongs to the technical field of electronic ceramics, relates to a microwave dielectric ceramic material and a preparation method thereof, and particularly relates to an ultralow-temperature sintered composite microwave dielectric ceramic material and a preparation method thereof.
Background
In recent years, with the rapid development of wireless communication fields such as mobile communication and satellite communication, higher technical requirements are put on the miniaturization and integration of electronic passive devices, and the development of microwave components as important components thereof is inevitably compliant with the scienceWith the trend of technical development and the urgent need of a series of technological development, large-scale research work on dielectric materials is internationally carried out. In recent years, with the wide use of Low Temperature Co-fired Ceramics (LTCC) technology, high dielectric constant (epsilon) in search, preparation and research is sought, prepared and researchedr>10) Low loss (Qf)>5000GHz), low temperature coefficient of resonance frequency (TCF is approximately equal to 0 ppm/DEG C), lower sintering temperature (lower than the melting point of common metals such as Ag, Cu, Au and Al), low cost (no or little precious metal), and environmental protection (at least no lead, no or little toxic raw materials) become the hot point of research of people.
The development of microwave dielectric ceramics starts in the seventies of the last century and has been going over for forty years, and nowadays, according to the reported situation in the literature, the microwave dielectric ceramics have been developed into hundreds of systems, and more, the microwave dielectric ceramics with excellent performance are more than ten thousands. On such a huge basis, a common situation still exists, that is, most ceramics have higher sintering temperatures (more than or equal to 1000 ℃). For example, the following systems ZrSiO with a Low Medium dielectric constant are of comparative interest4、Al2O3、Li2O-Nb2O5-TiO2、Ba2Ti9O20And A (B)1B2)O3A composite perovskite structure system. The system with the sintering temperature close to 1100 ℃ has the potential of being applied to the field of LTCC, so that the problem of lowering the sintering temperature is solved firstly. The commonly used methods for lowering the sintering temperature of ceramics can be classified into three categories: 1. starting from raw materials, reducing the particle size of the powder by a physical or chemical preparation method, namely reducing the particle size of the required powder to be below 500nm, and then sintering the uniform powder; 2. by adding sintering aids, e.g. low-melting oxides (MoO)3、Bi2O3、B2O3Etc.) or a low softening point glass phase to lower the sintering temperature. 3. The novel sintering process can accelerate the densification of the ceramic and reduce the sintering temperature. First oneThe disadvantages of the method are that: the difficulty in reducing the particle size of the powder is high, the physical method usually adopted is a high-energy ball milling method, the chemical method usually adopts hydrothermal, sol-gel and other methods to obtain fine powder with uniform particle size distribution, the physical method has high energy consumption, and the chemical method has high cost and low efficiency. The second method has the disadvantages that: although the sintering aid reduces the sintering temperature to a certain extent, the components of the sintering aid often have chemical reactions with the ceramic, and meanwhile, even if no chemical reaction occurs, the introduction of the sintering aid also generates impurity phases in the ceramic to a certain extent, so that the microwave dielectric property of the ceramic is inevitably attenuated and even deteriorated, but the method is low in cost and simple to prepare, so that the method is most widely applied to a certain extent. The third method has disadvantages in that: the novel sintering process is accompanied with the development and application of novel sintering equipment, the process still stays in a laboratory stage to a certain extent, a certain time is needed for the process to be converted into actual production, and meanwhile, the high manufacturing cost of the novel equipment also limits the applicability of the method to a certain extent. In recent years, through continuous research, a more effective method is found, namely that a sintering temperature (per se) with low temperature is developed<900 deg.c) and such material systems are generally referred to as low-fire ceramic systems.
In general, ceramics made from oxides should themselves be sintered at temperatures near their melting point (between 80% and 95%). The reason for this is that when the oxide approaches the melting point temperature, various internal atomic bonds and ionic bonds become very active, which accelerates the transmission of energy among various particles to a certain extent, thereby promoting the reaction among the particles and accelerating the ceramic forming progress of the ceramic. Thus, the melting point of the oxide used in the ceramic composition determines to some extent the sintering temperature of the ceramic. The following are melting point data for several common low melting point oxides: TeO2(733℃)、MoO3(795℃)、Bi2O3(817℃)、B2O3(450℃)、V2O5(690 ℃) and Na2CO3(851 ℃), and the like. In systems of the above-mentioned oxidesIn TeO2Bate prepared for the main composition4O9The ceramic has excellent microwave performance, a dielectric constant of 17.5, a Qf value of 54700GHz and a TCF of-90 ppm/DEG C, and meanwhile, the sintering temperature is only 550 ℃, and the ceramic does not react with or diffuse with an Al electrode, and a series of reports attract extensive attention of researchers. However TeO2The high price and the strong toxicity of the raw materials determine the difficulty of large-scale application in industrial production to a great extent.
In summary, with the urgent need of the modern communication technology for the miniaturization, integration and high frequency of the microwave communication device, it is always the current research focus and emphasis to explore and develop the microwave dielectric ceramic material with low sintering temperature. The ultra-low temperature sintering microwave dielectric ceramic material rich in low melting point oxide is a novel research hotspot promoted in the field of LTCC, and the development of the series of ceramics fundamentally solves the bottleneck of reducing the sintering temperature of the microwave dielectric ceramic material, and simultaneously can introduce an Al electrode into the LTCC process, which undoubtedly is a great revolution on the LTCC process.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an ultralow-temperature sintered composite microwave dielectric ceramic material and a preparation method thereof.
In order to achieve the purpose, the composition expression of the ultralow-temperature sintered composite microwave dielectric ceramic material is x (Na)0.5Bi0.5)MoO4－(1-x)Bi2MoO6Wherein x is more than or equal to 0.6 and less than or equal to 0.9.
The ceramic material is composed of Na+And Bi3+Ion association occupies A site and Mo6+The ions occupying the B position (Na)0.5Bi0.5)MoO4And Bi3+Ion occupies A site and Mo6+Bi with ions occupying B position2MoO6And (4) forming.
Microwave dielectric constant of the ceramic materialNumber epsilonr31.8 to 33.4, a temperature coefficient TCF of resonance frequency of-7 ppm/DEG C to +4 ppm/DEG C, and a high quality factor Qf of 11600GHz to 14400 GHz.
The preparation method of the ultralow temperature sintered composite microwave dielectric ceramic material comprises the following steps:
1) according to the composition expression x (Na)0.5Bi0.5)MoO4－(1-x)Bi2MoO6Weighing raw material Na2CO3、Bi2O3And MoO3；
2) Mixing Na2CO3、Bi2O3And MoO3Mixing, ball-milling, drying, sieving and pressing into blocks in sequence, and then preserving heat at 550-600 ℃ to obtain sample baked blocks;
3) sequentially crushing, ball-milling and drying the sample fired block obtained in the step 2), and then preserving heat at 550-600 ℃ to obtain a secondary sample fired block;
4) and 3) sequentially crushing, ball-milling, drying, granulating and sieving the secondary sample fired block obtained in the step 3), then pressing and forming, and then sintering at 660-740 ℃ to obtain the ultralow temperature sintering composite microwave dielectric ceramic material.
The ball milling time in the step 2), the step 3) and the step 4) is 4-6 h.
The temperature in the drying process in the step 2), the step 3) and the step 4) is 180-200 ℃.
The screen used in the sieving in the step 2) is 200 meshes; the screen used in the sieving in the step 4) is a double-layer screen with 60 meshes and 120 meshes.
The sintering in step 4) is performed in an air atmosphere.
The pressing in the step 4) is formed into a cylindrical shape.
The heat preservation time in the step 2) is 4-6 h;
the heat preservation time in the step 3) is 4-6 h;
the sintering time in the step 4) is 2-4 h.
The invention has the following beneficial effects:
the ultra-low of the inventionThe composite microwave dielectric ceramic material sintered at a high temperature and the preparation method thereof are specifically operated by using low-melting-point oxide Bi2O3And MoO3As a main element, the dielectric ceramic material of the invention can be sintered at low temperature, and has higher safety and lower cost. The invention is based on the principles of crystal chemistry and dielectric medium, as ABO4Based on scheelite structure, adopts Na in a two-phase composite mode respectively+、Bi3+Ion association occupies A site and Mo6+The ions occupying the B position (Na)0.5Bi0.5)MoO4And Bi3+Ion occupies A site and Mo6+Bi with ions occupying B position2MoO6On the premise of not adding any sintering aid, a compact composite microwave dielectric ceramic material with excellent microwave dielectric property is sintered at the temperature of 660-740 ℃, the sintering temperature is low, and no sintering aid is required to be added in the sintering process.
Detailed Description
The present invention is described in further detail below with reference to examples:
example one
The composition expression of the ultralow temperature sintered composite microwave dielectric ceramic material is x (Na)0.5Bi0.5)MoO4－(1-x)Bi2MoO6Wherein x is 0.6.
The preparation method of the ultralow temperature sintered composite microwave dielectric ceramic material comprises the following steps:
1) according to the composition expression x (Na)0.5Bi0.5)MoO4－(1-x)Bi2MoO6Weighing raw material Na2CO3、Bi2O3And MoO3；
2) Mixing Na2CO3、Bi2O3And MoO3Mixing, ball-milling, drying, sieving and pressing into blocks in sequence, and then preserving heat at 550 ℃ to obtain sample baked blocks;
3) sequentially crushing, ball-milling and drying the sample fired block obtained in the step 2), and then preserving heat at 550 ℃ to obtain a secondary sample fired block;
4) and 3) sequentially crushing, ball-milling, drying, granulating and sieving the secondary sample fired block obtained in the step 3), then pressing and forming, and then sintering at 660-700 ℃ to obtain the ultralow temperature sintering composite microwave dielectric ceramic material.
The ball milling time in the step 2), the step 3) and the step 4) is 4 h.
The temperature in the drying process in the step 2), the step 3) and the step 4) is 180 ℃.
The screen used in the sieving in the step 2) is 200 meshes; the screen used in the sieving in the step 4) is a double-layer screen with 60 meshes and 120 meshes.
The sintering in step 4) is performed in an air atmosphere.
The pressing in the step 4) is formed into a cylindrical shape.
The heat preservation time in the step 2) is 4 hours;
the heat preservation time in the step 3) is 4 hours;
the sintering time in the step 4) is 4 h.
The performance of the group of ceramic materials reaches the following indexes:
sintering the ceramic in air at 660-700 ℃ to form the ceramic with dielectric property epsilon under microwaver31.8(6.5GHz), quality factor Q1780, Qf 11600GHz, and temperature coefficient of resonance frequency TCF-7 ppm/° c (25-85 ℃).
Example two
The composition expression of the ultralow temperature sintered composite microwave dielectric ceramic material is x (Na)0.5Bi0.5)MoO4－(1-x)Bi2MoO6Wherein x is 0.7.
The preparation method of the ultralow temperature sintered composite microwave dielectric ceramic material comprises the following steps:
1) according to the composition tableExpression x (Na)0.5Bi0.5)MoO4－(1-x)Bi2MoO6Weighing raw material Na2CO3、Bi2O3And MoO3；
2) Mixing Na2CO3、Bi2O3And MoO3Mixing, ball-milling, drying, sieving and pressing into blocks in sequence, and then preserving heat at 550 ℃ to obtain sample baked blocks;
3) sequentially crushing, ball-milling and drying the sample fired block obtained in the step 2), and then preserving heat at 550 ℃ to obtain a secondary sample fired block;
4) and 3) sequentially crushing, ball-milling, drying, granulating and sieving the secondary sample fired block obtained in the step 3), then pressing and forming, and then sintering at 660-700 ℃ to obtain the ultralow temperature sintering composite microwave dielectric ceramic material.
The ball milling time in the step 2), the step 3) and the step 4) is 5 h.
The temperature in the drying process in the step 2), the step 3) and the step 4) is 180 ℃.
The screen used in the sieving in the step 2) is 200 meshes; the screen used in the sieving in the step 4) is a double-layer screen with 60 meshes and 120 meshes.
The sintering in step 4) is performed in an air atmosphere.
The pressing in the step 4) is formed into a cylindrical shape.
The heat preservation time in the step 2) is 4 hours;
the heat preservation time in the step 3) is 4 hours;
the sintering time in the step 4) is 3 h.
The performance of the group of ceramic materials reaches the following indexes:
sintering the ceramic in air at 660-700 ℃ to form the ceramic with dielectric property epsilon under microwaver32.2(6.48GHz), 1900, 12200GHz, and-4 ppm/deg.c (25-85 deg.c) of temperature coefficient of resonance frequency TCF under microwave.
EXAMPLE III
The composition expression of the ultralow temperature sintered composite microwave dielectric ceramic material is x (Na0.5Bi0.5)MoO4－(1-x)Bi2MoO6Wherein x is 0.8.
The preparation method of the ultralow temperature sintered composite microwave dielectric ceramic material comprises the following steps:
1) according to the composition expression x (Na)0.5Bi0.5)MoO4－(1-x)Bi2MoO6Weighing raw material Na2CO3、Bi2O3And MoO3；
2) Mixing Na2CO3、Bi2O3And MoO3Mixing, ball-milling, drying, sieving and pressing into blocks in sequence, and then preserving heat at 580 ℃ to obtain sample burning blocks;
3) sequentially crushing, ball-milling and drying the sample fired block obtained in the step 2), and then preserving heat at 580 ℃ to obtain a secondary sample fired block;
4) and 3) sequentially crushing, ball-milling, drying, granulating and sieving the secondary sample fired block obtained in the step 3), then pressing and forming, and then sintering at 680-720 ℃ to obtain the ultralow temperature sintering composite microwave dielectric ceramic material.
The ball milling time in the step 2), the step 3) and the step 4) is 6 hours.
The temperature in the drying process in the step 2), the step 3) and the step 4) is 200 ℃.
The screen used in the sieving in the step 2) is 200 meshes; the screen used in the sieving in the step 4) is a double-layer screen with 60 meshes and 120 meshes.
The sintering in step 4) is performed in an air atmosphere.
The pressing in the step 4) is formed into a cylindrical shape.
The heat preservation time in the step 2) is 6 hours;
the heat preservation time in the step 3) is 6 hours;
the sintering time in the step 4) is 3 h.
The performance of the group of ceramic materials reaches the following indexes:
sintering the ceramic in air at 680-720 ℃ to form the ceramic, wherein the dielectric property of the ceramic is epsilon under microwaver32.5(6.45GHz), 2200, 14400GHz, and-1 ppm/° c (25-85 ℃) resonant frequency temperature coefficient TCF under microwave.
Example four
The composition expression of the ultralow temperature sintered composite microwave dielectric ceramic material is x (Na)0.5Bi0.5)MoO4－(1-x)Bi2MoO6Wherein x is 0.9.
The preparation method of the ultralow temperature sintered composite microwave dielectric ceramic material comprises the following steps:
1) according to the composition expression x (Na)0.5Bi0.5)MoO4－(1-x)Bi2MoO6Weighing raw material Na2CO3、Bi2O3And MoO3；
2) Mixing Na2CO3、Bi2O3And MoO3Mixing, ball-milling, drying, sieving and pressing into blocks in sequence, and then preserving heat at 600 ℃ to obtain sample baked blocks;
3) sequentially crushing, ball-milling and drying the sample fired block obtained in the step 2), and then preserving heat at 600 ℃ to obtain a secondary sample fired block;
4) and 3) sequentially crushing, ball-milling, drying, granulating and sieving the secondary sample fired block obtained in the step 3), then pressing and forming, and then sintering at 700-740 ℃ to obtain the ultralow temperature sintering composite microwave dielectric ceramic material.
The ball milling time in the step 2), the step 3) and the step 4) is 5 h.
The temperature in the drying process in the step 2), the step 3) and the step 4) is 200 ℃.
The screen used in the sieving in the step 2) is 200 meshes; the screen used in the sieving in the step 4) is a double-layer screen with 60 meshes and 120 meshes.
The sintering in step 4) is performed in an air atmosphere.
The pressing in the step 4) is formed into a cylindrical shape.
The heat preservation time in the step 2) is 4 hours;
the heat preservation time in the step 3) is 4 hours;
the sintering time in the step 4) is 2 h.
The performance of the group of ceramic materials reaches the following indexes:
sintering the ceramic in air at 700-740 ℃ to form ceramic with dielectric property epsilon under microwaver33.4(6.42GHz), 2020, 12800GHz, and +3ppm/° c (25-85 ℃) resonant frequency temperature coefficient TCF under microwave.
EXAMPLE five
The composition expression of the ultralow temperature sintered composite microwave dielectric ceramic material is x (Na)0.5Bi0.5)MoO4－(1-x)Bi2MoO6Wherein x is 0.7.
The preparation method of the ultralow temperature sintered composite microwave dielectric ceramic material comprises the following steps:
1) according to the composition expression x (Na)0.5Bi0.5)MoO4－(1-x)Bi2MoO6Weighing raw material Na2CO3、Bi2O3And MoO3；
2) Mixing Na2CO3、Bi2O3And MoO3Mixing, ball-milling, drying, sieving and pressing into blocks in sequence, and then preserving heat at 600 ℃ to obtain sample baked blocks;
3) sequentially crushing, ball-milling and drying the sample fired block obtained in the step 2), and then preserving heat at 600 ℃ to obtain a secondary sample fired block;
4) and 3) sequentially crushing, ball-milling, drying, granulating and sieving the secondary sample fired block obtained in the step 3), then pressing and forming, and then sintering at 740 ℃ to obtain the ultralow-temperature sintered composite microwave dielectric ceramic material.
The ball milling time in the step 2), the step 3) and the step 4) is 6 hours.
The temperature in the drying process in the step 2), the step 3) and the step 4) is 200 ℃.
The screen used in the sieving in the step 2) is 200 meshes; the screen used in the sieving in the step 4) is a double-layer screen with 60 meshes and 120 meshes.
The sintering in step 4) is performed in an air atmosphere.
The pressing in the step 4) is formed into a cylindrical shape.
The heat preservation time in the step 2) is 6 hours;
the heat preservation time in the step 3) is 6 hours;
the sintering time in the step 4) is 4 h.
EXAMPLE six
The composition expression of the ultralow temperature sintered composite microwave dielectric ceramic material is x (Na)0.5Bi0.5)MoO4－(1-x)Bi2MoO6Wherein x is 0.8.
The preparation method of the ultralow temperature sintered composite microwave dielectric ceramic material comprises the following steps:
1) according to the composition expression x (Na)0.5Bi0.5)MoO4－(1-x)Bi2MoO6Weighing raw material Na2CO3、Bi2O3And MoO3；
2) Mixing Na2CO3、Bi2O3And MoO3Mixing, ball-milling, drying, sieving and pressing into blocks in sequence, and then preserving heat at 550 ℃ to obtain sample baked blocks;
3) sequentially crushing, ball-milling and drying the sample fired block obtained in the step 2), and then preserving heat at 550 ℃ to obtain a secondary sample fired block;
4) and 3) sequentially crushing, ball-milling, drying, granulating and sieving the secondary sample fired block obtained in the step 3), then pressing and forming, and then sintering at 660 ℃ to obtain the ultralow temperature sintering composite microwave dielectric ceramic material.
The ball milling time in the step 2), the step 3) and the step 4) is 4 h.
The temperature in the drying process in the step 2), the step 3) and the step 4) is 180 ℃.
The screen used in the sieving in the step 2) is 200 meshes; the screen used in the sieving in the step 4) is a double-layer screen with 60 meshes and 120 meshes.
The sintering in step 4) is performed in an air atmosphere.
The pressing in the step 4) is formed into a cylindrical shape.
The heat preservation time in the step 2) is 4 hours;
the heat preservation time in the step 3) is 4 hours;
the sintering time in the step 4) is 2 h.
EXAMPLE seven
The composition expression of the ultralow temperature sintered composite microwave dielectric ceramic material is x (Na)0.5Bi0.5)MoO4－(1-x)Bi2MoO6Wherein x is 0.9.
The preparation method of the ultralow temperature sintered composite microwave dielectric ceramic material comprises the following steps:
1) according to the composition expression x (Na)0.5Bi0.5)MoO4－(1-x)Bi2MoO6Weighing raw material Na2CO3、Bi2O3And MoO3；
2) Mixing Na2CO3、Bi2O3And MoO3Mixing, ball-milling, drying, sieving and pressing into blocks in sequence, and then preserving heat at 560 ℃ to obtain sample baked blocks;
3) sequentially crushing, ball-milling and drying the sample fired block obtained in the step 2), and then preserving heat at 560 ℃ to obtain a secondary sample fired block;
4) and 3) sequentially crushing, ball-milling, drying, granulating and sieving the secondary sample fired block obtained in the step 3), then pressing and forming, and then sintering at 700 ℃ to obtain the ultralow temperature sintering composite microwave dielectric ceramic material.
The ball milling time in the step 2), the step 3) and the step 4) is 5 h.
The temperature in the drying process in the step 2), the step 3) and the step 4) is 190 ℃.
The screen used in the sieving in the step 2) is 200 meshes; the screen used in the sieving in the step 4) is a double-layer screen with 60 meshes and 120 meshes.
The sintering in step 4) is performed in an air atmosphere.
The pressing in the step 4) is formed into a cylindrical shape.
The heat preservation time in the step 2) is 5 hours;
the heat preservation time in the step 3) is 5 hours;
the sintering time in the step 4) is 3 h.
Example eight
The composition expression of the ultralow temperature sintered composite microwave dielectric ceramic material is x (Na)0.5Bi0.5)MoO4－(1-x)Bi2MoO6Wherein x is 0.6.
The preparation method of the ultralow temperature sintered composite microwave dielectric ceramic material comprises the following steps:
1) according to the composition expression x (Na)0.5Bi0.5)MoO4－(1-x)Bi2MoO6Weighing raw material Na2CO3、Bi2O3And MoO3；
2) Mixing Na2CO3、Bi2O3And MoO3Mixing, ball-milling, drying, sieving and pressing into blocks in sequence, and then preserving heat at 570 ℃ to obtain sample burning blocks;
3) sequentially crushing, ball-milling and drying the sample fired block obtained in the step 2), and then preserving heat at 570 ℃ to obtain a secondary sample fired block;
4) and 3) sequentially crushing, ball-milling, drying, granulating and sieving the secondary sample fired block obtained in the step 3), then pressing and forming, and then sintering at 720 ℃ to obtain the ultralow temperature sintering composite microwave dielectric ceramic material.
The ball milling time in the step 2), the step 3) and the step 4) is 4.5 h.
The temperature in the drying process in the step 2), the step 3) and the step 4) is 185 ℃.
The screen used in the sieving in the step 2) is 200 meshes; the screen used in the sieving in the step 4) is a double-layer screen with 60 meshes and 120 meshes.
The sintering in step 4) is performed in an air atmosphere.
The pressing in the step 4) is formed into a cylindrical shape.
The heat preservation time in the step 2) is 4.5 h;
the heat preservation time in the step 3) is 4.5 h;
the sintering time in the step 4) is 2.5 h.
The invention adopts a simple and effective solid-phase reaction sintering method, firstly adopts a formula with a proper proportion, selects corresponding oxides and carbonates, puts powder into a ball milling tank for primary ball milling to enable the oxides to be uniformly mixed, then carries out primary sintering on the ball-milled powder to enable the oxides to carry out primary reaction, then carries out secondary ball milling on the powder to further refine the particle size of reactants, promotes the reactant phases to be uniformly dispersed through secondary sintering, further refines the powder size through third ball milling, and finally obtains a required ceramic sample through sintering, and through the simple and effective preparation method, the dielectric constant of the obtained ceramic sample is changed along with the components between 31.8 and 33.4, the Qf is distributed between 11600GHz and 14400GHz, the temperature coefficient of resonance frequency is adjustable between-7 and +4 ppm/DEG C, the sintering temperature is 660 to 740 ℃, the method is suitable for the requirements of LTCC technology, and the application range of the LTCC technology is expanded.

Claims (8)

1. The ultralow temperature sintered composite microwave dielectric ceramic material is characterized in that the composition expression of the ceramic material is x (Na)0.5Bi0.5)MoO4－(1-x)Bi2MoO6Wherein x is more than or equal to 0.6 and less than or equal to 0.9;
the preparation process of the ultralow temperature sintered composite microwave dielectric ceramic material comprises the following steps:
1) according to the composition expression x (Na)0.5Bi0.5)MoO4－(1-x)Bi2MoO6Weighing raw material Na2CO3、Bi2O3And MoO3；
2) Mixing Na2CO3、Bi2O3And MoO3Mixing, ball-milling, drying, sieving and pressing into blocks in sequence, and then preserving heat at 550-600 ℃ to obtain sample baked blocks;
3) sequentially crushing, ball-milling and drying the sample fired block obtained in the step 2), and then preserving heat at 550-600 ℃ to obtain a secondary sample fired block;
4) sequentially crushing, ball-milling, drying, granulating and sieving the secondary sample fired block obtained in the step 3), then pressing and forming, and then sintering at 660-740 ℃ to obtain the ultralow temperature sintering composite microwave dielectric ceramic material;
the temperature in the drying process in the step 2), the step 3) and the step 4) is 180-200 ℃.
2. The ultra-low temperature sintered composite microwave dielectric ceramic material as claimed in claim 1, wherein the ball milling time in step 2), step 3) and step 4) is 4-6 h.
3. The ultra-low temperature sintered composite microwave dielectric ceramic material as claimed in claim 1, wherein the screen used in the sieving in step 2) is 200 mesh; the screen used in the sieving in the step 4) is a double-layer screen with 60 meshes and 120 meshes.
4. The ultra-low temperature sintered composite microwave dielectric ceramic material as claimed in claim 1, wherein the sintering in step 4) is performed in an air atmosphere.
5. The ultra-low temperature sintered composite microwave dielectric ceramic material as claimed in claim 1, wherein the press molding in step 4) is press-molding into a cylindrical shape.
6. The ultra-low temperature sintered composite microwave dielectric ceramic material as claimed in claim 1, wherein the heat preservation time in step 2) is 4-6 h;
the heat preservation time in the step 3) is 4-6 h;
the sintering time in the step 4) is 2-4 h.
7. The ultra-low temperature sintered composite microwave dielectric as claimed in claim 1A ceramic material, characterized in that the ceramic material is composed of Na+And Bi3+Ion association occupies A site and Mo6+The ions occupying the B position (Na)0.5Bi0.5)MoO4And Bi3+Ion occupies A site and Mo6+Bi with ions occupying B position2MoO6And (4) forming.
8. The ultra-low temperature sintered composite microwave dielectric ceramic material as claimed in claim 1, wherein the ceramic material has a microwave dielectric constant ∈r31.8 to 33.4, a temperature coefficient TCF of resonance frequency of-7 ppm/DEG C to +4 ppm/DEG C, and a high quality factor Qf of 11600GHz to 14400 GHz.
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