CN111689771A - Microwave dielectric ceramic material and preparation method thereof - Google Patents

Microwave dielectric ceramic material and preparation method thereof Download PDF

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CN111689771A
CN111689771A CN202010598495.8A CN202010598495A CN111689771A CN 111689771 A CN111689771 A CN 111689771A CN 202010598495 A CN202010598495 A CN 202010598495A CN 111689771 A CN111689771 A CN 111689771A
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ceramic material
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张军志
杨和成
罗超
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Xiamen Sunyear Electronics Co ltd
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Abstract

The invention provides a microwave dielectric ceramic material, and relates to the field of information functional materials. The ceramic material comprises a main material and a modified additive. The main material has a chemical formula of Mg2‑3xCaxTiO4‑2x·yCaSiO3Wherein x is more than or equal to 0.01 and less than or equal to 0.50 and 0.00<y is less than or equal to 0.20; the mass fraction of the main material in the microwave dielectric ceramic material is 99.2-99.8 wt%; the mass fraction of the modified additive in the microwave dielectric ceramic material is 0.2-0.8 wt%. The modifying additive is selected from BaCO3、SrCO3、ZnO、MnCO3、Sb2O3、SiO2And MnO2One or more of them. The ceramic dielectric material is a lead-free environment-friendly material, and Mg is synthesized by adopting a solid-phase synthesis method2‑3xCaxTiO4‑2xWith CaSiO3As the main material, modified additive is doped and reasonably designedThe method optimizes the synthesis process, the average particle size of the prepared powder is 0.4-1.0um, the electronic ceramic device manufactured by the powder can be sintered into ceramic within the temperature range of 1300-1380 ℃, the dielectric constant is 18-23, the quality factor Qf value is more than or equal to 40000GHz, and the temperature coefficient tau f (-40-85 ℃): 10 ppm/DEG C.

Description

Microwave dielectric ceramic material and preparation method thereof
Technical Field
The invention relates to the field of information functional materials, in particular to a microwave dielectric ceramic material with medium and low dielectric constants and a preparation method thereof.
Background
Microwave dielectric ceramic materialIs a novel functional ceramic material which is rapidly developed in recent years. It has the characteristics of low dielectric loss, high dielectric constant, stable dielectric constant temperature coefficient tau f and the like. The material is a core basic material of a novel microwave circuit and a device including a dielectric resonator, a filter, an oscillator, a duplexer, an antenna, a dielectric substrate and the like, and has wide application in modern microwave communication and satellite navigation systems and equipment. In recent years, microwave devices have been rapidly developed in a direction of miniaturization, integration, and low power consumption, especially, mass production and low price for civil use, and thus a large number of microwave dielectric ceramic materials suitable for various microwave frequency bands have been developed. However, the dielectric constant of the existing microwave dielectric ceramic material is higher, and the microwave dielectric ceramic material is general>23, or dielectric constant<23 but temperature coefficient τ f>+ -10 ppm/DEG C, the performance is unstable. For example, magnesium metatitanate (MgO. TiO) having an ilmenite structure2) The microwave dielectric ceramic material is an important microwave dielectric ceramic material due to relatively cheap raw materials and excellent microwave performance, but the high-temperature coefficient is-50 ppm/DEG C, so that the practical application of the microwave dielectric ceramic material is influenced.
Disclosure of Invention
The invention aims to provide a microwave dielectric ceramic material and a preparation method thereof, which are used for solving the problems of high dielectric constant and unstable performance of the conventional microwave dielectric ceramic material.
The invention adopts the following scheme to achieve the aim.
The invention provides a microwave dielectric ceramic material, which comprises a main material and a modified additive, wherein the chemical formula of the main material is Mg2-3xCaxTiO4-2x·yCaSiO3Wherein x is more than or equal to 0.01 and less than or equal to 0.50 and 0.00<y is less than or equal to 0.20; the mass fraction of the main material in the microwave dielectric ceramic material is 99.2-99.8 wt%; the mass fraction of the modified additive in the microwave dielectric ceramic material is 0.2-0.8 wt%.
Preferably, the modifying additive is selected from BaCO3、SrCO3、ZnO、MnCO3、Sb2O3、SiO2And MnO2One or more than one mixture.
Preference is given toAnd the mass fraction range of each modified additive in the microwave dielectric ceramic material is as follows: BaCO30 to 0.35% of SrCO30 to 0.2% of ZnO, 0 to 0.2% of MnCO30 to 0.4% of Sb2O30 to 0.3% of SiO20 to 0.1% of MnO20 to 0.3%.
The invention also provides a preparation method of the microwave dielectric ceramic material, which comprises the following steps:
s1, Synthesis of Mg2-3xCaxTiO4-2x: putting magnesium hydroxide, calcium carbonate and titanium dioxide into a ball mill according to a ratio, adding water, uniformly mixing, carrying out wet ball milling, calcining at the temperature of 1050-1300 ℃ for 2-4 hours in air atmosphere to obtain Mg2-3xCaxTiO4-2x(ii) a The specific surface area of the magnesium hydroxide is more than 7.0m2The specific surface area of the titanium dioxide is more than 5.0m2/g；
S2, Synthesis of CaSiO3: proportionally placing calcium carbonate and silicon dioxide in a ball mill, adding water, uniformly mixing, carrying out wet ball milling, calcining at 1050-1100 ℃ for 1-2 hours in air atmosphere to obtain CaSiO3；
S3, mixing the Mg obtained in the step S12-3xCaxTiO4-2xCaSiO obtained in step S23And the modified additives are put into a ball mill together according to the formula requirements, water is added for wet ball milling, homogenization treatment is carried out, and then the ball-milled materials are dried to obtain the microwave dielectric ceramic material in a powder state.
Further, in step S3, the particle size of the ball-milled material is 0.4-1.0 um.
Further, the preparation method also comprises the following steps:
s4, adding an adhesive, a plasticizer, a dispersing agent and the like into the microwave dielectric ceramic material in a powder state, performing ball milling for 1-2 hours to obtain slurry, drying to obtain powder, and pressing the powder into a green body;
s5, removing glue: placing the green body in a temperature range of 500-650 ℃, and preserving heat for 16-32 hours to obtain a green body;
s6, sintering: keeping the blank subjected to the binder removal at 1300-1380 ℃ for 3-5 hours in an air atmosphere;
s7, annealing: and after sintering, keeping the temperature for 1-2 hours at 950-1050 ℃ to obtain the formed microwave dielectric ceramic material.
Preferably, the adhesive is polyvinyl alcohol, the plasticizer is polyethylene glycol, and the dispersant is carboxylic acid ammonium salt.
Preferably, in the glue discharging process of the step S5, the temperature rising speed is less than 10 ℃/hour.
Preferably, in the sintering process of step S6, the temperature rise rate is 150 to 200 ℃/hr.
The formed microwave dielectric ceramic material has a temperature dielectric constant of 18-23 and a temperature coefficient tau f (-40-85 ℃): +/-10 ppm/deg.C, and Qf value greater than or equal to 40000 GHz.
Magnesium metatitanate (MgO. TiO) having ilmenite structure2) The high temperature coefficient of (2) is-50 ppm/DEG C, and the temperature coefficient can be adjusted by compounding with other materials with positive temperature coefficients according to a mixing rule. By predoping Ca, it can be mixed with TiO2Formation of CaTiO3. And CaTiO3Is a twisted orthogonal perovskite structure, has the dielectric constant of 170 at room temperature, has a very high positive temperature coefficient of 800 ppm/DEG C, can realize the adjustment of a high-temperature coefficient, and synthesizes CaSiO for realizing sintering at a lower temperature3，CaSiO3Besides being a low-dielectric-constant ceramic material with good performance, the ceramic material is also a cosolvent. Mixing Mg2-3xCaxTiO4-2xWith CaSiO3The ceramic material which is sintered at 1300-1380 ℃ and has microwave performance can be obtained by compounding the two according to a certain proportion. The ceramic material can form a ceramic material with a room temperature dielectric constant of 18-23, a Qf value of more than or equal to 40000GHz and a temperature coefficient tau f (-40-85 ℃): 10 ppm/DEG C.
The invention has the beneficial effects that: mixing Mg2-3xCaxTiO4-2x、CaSiO3And compounding with modified additivesThe prepared microwave dielectric ceramic material has good material uniformity and meets the requirements of microwave devices. The microwave dielectric ceramic material with microwave performance is obtained after the powder is sintered at 1300-1380 ℃. The ceramic material can form a ceramic material with a room temperature dielectric constant of 18-23, a Qf value of more than or equal to 40000GHz and a temperature coefficient tau f (-40-85 ℃): +/-10 ppm/DEG C, and can meet the microwave performance requirement of the microwave device.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The invention provides a microwave dielectric ceramic material, which comprises a main material and a modified additive, wherein the chemical formula of the main material is Mg2-3xCaxTiO4-2x·yCaSiO3Wherein x is more than or equal to 0.01 and less than or equal to 0.50 and 0.00<y is less than or equal to 0.20; the mass fraction of the main material in the microwave dielectric ceramic material is 99.2-99.8 wt%; the mass fraction of the modified additive in the microwave dielectric ceramic material is 0.2-0.8 wt%.
The modifying additive is selected from BaCO3、SrCO3、ZnO、MnCO3、Sb2O3、SiO2And MnO2One or more than one mixture.
Preferably, the mass fraction of each modified additive in the microwave dielectric ceramic material is as follows: BaCO30 to 0.35% of SrCO30 to 0.2% of ZnO, 0 to 0.2% of MnCO30 to 0.4% of Sb2O30 to 0.3% of SiO20 to 0.1% of MnO20 to 0.3%.
The invention also provides a preparation method of the microwave dielectric ceramic material, which comprises the following steps:
① preparation of Mg as one of the principal materials2-3xCaxTiO4-2xPowder: weighing high-purity and superfine Mg (OH) with corresponding mass according to the proportion of each metal element in the compound2、CaCO3、TiO2Placing the mixture into a ball mill, and taking the solid materials according to the mass ratio: water 1: (1.0-2.0), adding water, performing ball milling and mixing uniformly, performing sand milling treatment to reach a certain particle size, drying by using a spray drying tower or other methods, calcining for 2-4 hours in an air atmosphere furnace at the temperature of 1050-1300 ℃, and finally obtaining Mg2-3xCaxTiO4-2xAnd (3) powder. Wherein, Mg (OH)2Has a specific surface area of more than 7.0m2/g，TiO2Has a specific surface area of more than 5.0m2/g。
② preparation of CaSiO as another component of the main material3Powder: mixing high-purity, ultra-fine CaCO3And SiO2Weighing the materials according to a molar ratio of 1:1, placing the materials in a ball mill, and mixing the materials according to the mass ratio: deionized water 1: (1.0-2.0), adding water, ball-milling, uniformly mixing, drying by using a spray drying tower or other methods after reaching a certain particle size, calcining for 1-2 hours at 1050-1100 ℃ in an air atmosphere furnace to finally obtain CaSiO3And (3) powder.
③ preparing formula powder by mixing ① and ② two main materials with various modified additives BaCO3、MnCO3、MnO2、SrCO3、ZnO、SiO2、Sb2O3One or more of the microwave dielectric ceramic materials are weighed according to the formula of the microwave dielectric ceramic materials, placed in a ball mill and prepared into solid materials according to the mass ratio: water 1: (0.6-1.0) adding water for wet sanding, wherein the materials are required to be uniformly mixed, and the average particle size of the sanded powder is 0.40-1.0um measured by a laser particle sizer. And drying the mixture by using a spray drying tower or other methods after the ball milling is finished to obtain the powdery microwave dielectric ceramic material.
Further, the preparation method of the microwave dielectric ceramic material of the invention also comprises the following steps:
and fourthly, adding a proper amount of adhesive, plasticizer, dispersant and the like into the microwave dielectric ceramic material in the powder state, using zirconia balls as grinding media to perform ball milling for 1-2 hours in a ball milling tank to obtain slurry, and performing centrifugal spray drying to obtain spherical particle powder with good fluidity. In a preferred mode, the adhesive is polyvinyl alcohol, the plasticizer is polyethylene glycol, and the dispersant is ammonium carboxylate.
Pressing the spherical particle powder into a green device.
Sixthly, placing the green device in the temperature range of 500-650 ℃, preserving heat for 16-32 hours, removing organic matters in the green sheet, and requiring the temperature rise speed in the whole glue removing process to be less than 10 ℃/hour.
And (c) sintering: and sintering the green body after the binder removal in air, heating to 1300-1380 ℃ at a heating rate of 150-200 ℃/h, and keeping the temperature for 3-5 hours. The sintering temperature is preferably 1350 ℃. Sintering can move the grain boundary of the powder particles in the ceramic body, the air holes are gradually eliminated, and the body shrinks into a compact ceramic body with certain strength.
And eighthly, annealing treatment: and (3) after high-temperature sintering, keeping the furnace temperature within the range of 950-1050 ℃ for 1-2 hours to obtain the formed microwave dielectric ceramic material. Annealing can reduce the internal stress of the blank, refine crystal grains, close microcracks, improve the tissue structure of the material and improve the mechanical property of the ceramic.
Ninthly, testing the device: and performing microwave performance test at the frequency of 5-8GHz by adopting an Agilent network.
According to the test result: the formed microwave dielectric ceramic material has a temperature dielectric constant of 18-23 and a temperature coefficient tau f (-40-85 ℃): +/-10 ppm/deg.C, and Qf value greater than or equal to 40000 GHz.
Examples
The present embodiment provides a microwave dielectric ceramic material and a method for preparing the same, and the scheme of the present invention is not limited to the embodiments.
(1) According to Mg2-3xCaxTiO4-2xWherein x is more than or equal to 0.01 and less than or equal to 0.50, and three groups of Mg (OH) with corresponding mass are weighed according to the raw material formula shown in Table 12、CaCO3And TiO2Sequentially placing the materials in a ball mill, wherein each group of solid materials comprises the following components in percentage by mass: deionized water 1: 1.5, adding deionized water for wet ball milling, drying by a spray drying tower after ball milling, and calcining for 3 hours in an air furnace at 1200 ℃. In each group of samples: MCT1, x is 0.05; MCT2, x is 0.25; in MCT3, x is 0.50.
TABLE 1 Mg2-3xCaxTiO4-2xEXAMPLES formulations
Figure BDA0002558302620000061
(2) According to CaSiO3The method comprises the following steps of (1) preparing calcium carbonate and silicon dioxide in a ball mill according to a molar ratio of 1:1, wherein the calcium carbonate and the silicon dioxide are solid materials in mass ratio: deionized water 1: deionized water is added according to the proportion of 1.5 for wet ball milling, the mixture is evenly mixed, dried by a spray drying tower and calcined for 1.5 hours in an air furnace at the temperature of 1080 ℃.
(3) According to Mg2-3xCaxTiO4-2x·yCaSiO3(wherein x is not less than 0.01 and not more than 0.50, 0.00<y is less than or equal to 0.20), weighing the Mg obtained in the step (1) according to the chemical composition of the samples in the table 22-3xCaxTiO4-2xCaSiO obtained in (2)3And various modified additives are placed in a ball mill in groups, and the modified additives are solid materials according to the mass ratio of each group: deionized water 1: deionized water is added in a proportion of 0.8 for wet sanding, the materials are required to be uniformly mixed, and the average particle size of the sanded powder is 0.40-1.0um measured by a laser particle sizer. After sanding, adding a polyvinyl alcohol adhesive, a polyethylene glycol plasticizer and an ammonium carboxylate dispersant which respectively account for 0.5-3% of the total mass, drying by using a spray drying tower after uniform dispersion, and pressing the dried powder into a cylindrical green compact wafer; setting a temperature curve, and firstly placing the temperature curve in 600 ℃ for heat preservation for 24 hours to carry out glue discharging, wherein the heating rate of the whole glue discharging process is 8 ℃/hour; heating to 1310-1375 ℃ at the heating rate of 150 ℃/h, and preserving heat for 3 hours for sintering; and (3) after high-temperature sintering, keeping the temperature at 1000 ℃ for 1.5 hours to obtain the formed microwave dielectric ceramic material wafer.
TABLE 2 chemical composition of microwave dielectric ceramic material samples
Figure BDA0002558302620000071
The microwave performance test was performed on the formed microwave dielectric ceramic material, and the test results are shown in table 3. The samples No. 1 to 15 in Table 3 were taken from the samples No. 1 to 15 in Table 2, and the same numbers correspond one to one.
TABLE 3 test results of various electrical properties of wafers prepared by sintering microwave dielectric ceramic material samples
Figure BDA0002558302620000072
Figure BDA0002558302620000081
As can be seen from Table 3, the ceramic material produced by the above process can be in the temperature range of 1300 ℃ to 1380 ℃. By adjusting the compounding ratio of the materials, the material can form a material with the room temperature dielectric constant of 18-23 and the temperature coefficient tau f (-40-85 ℃): the ceramic material of the system has +/-10 ppm/DEG C, a Qf value of more than or equal to 40000GHz and continuously adjustable microwave performance parameters, and can meet the application requirements of medium-low room temperature dielectric constant and narrow fluctuation range temperature coefficient tau f (-40-85 ℃) of microwave devices.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the claims, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Claims (10)

1. A microwave dielectric ceramic material comprises a main material and a modified additive, and is characterized in that: the main material has a chemical formula of Mg2-3xCaxTiO4-2x·yCaSiO3Wherein x is more than or equal to 0.01 and less than or equal to0.50，0.00<y is less than or equal to 0.20; the mass fraction of the main material in the microwave dielectric ceramic material is 99.2-99.8 wt%; the mass fraction of the modified additive in the microwave dielectric ceramic material is 0.2-0.8 wt%.
2. A microwave dielectric ceramic material according to claim 1, wherein: the modifying additive is selected from BaCO3、SrCO3、ZnO、MnCO3、Sb2O3、SiO2And MnO2One or more than one mixture.
3. A microwave dielectric ceramic material as claimed in claim 2, wherein the mass fraction of each of the modifying additives in the microwave dielectric ceramic material is: BaCO30 to 0.35% of SrCO30 to 0.2% of ZnO, 0 to 0.2% of MnCO30 to 0.4% of Sb2O30 to 0.3% of SiO20 to 0.1% of MnO20 to 0.3%.
4. A method for preparing a microwave dielectric ceramic material as claimed in any one of claims 1 to 3, comprising the following steps:
s1, Synthesis of Mg2-3xCaxTiO4-2x: putting magnesium hydroxide, calcium carbonate and titanium dioxide into a ball mill according to a ratio, adding water, uniformly mixing, carrying out wet ball milling, calcining at the temperature of 1050-1300 ℃ for 2-4 hours in air atmosphere to obtain Mg2-3xCaxTiO4-2x(ii) a The specific surface area of the magnesium hydroxide is more than 7.0m2The specific surface area of the titanium dioxide is more than 5.0m2/g；
S2, Synthesis of CaSiO3: proportionally placing calcium carbonate and silicon dioxide in a ball mill, adding water, uniformly mixing, carrying out wet ball milling, calcining at 1050-1100 ℃ for 1-2 hours in air atmosphere to obtain CaSiO3；
S3, mixing the Mg obtained in the step S12-3xCaxTiO4-2xCaSiO obtained in step S23And the modified additives are put into a ball mill together according to the formula requirements, water is added for wet ball milling, homogenization treatment is carried out, and then the ball-milled materials are dried to obtain the microwave dielectric ceramic material in a powder state.
5. The preparation method according to claim 4, wherein in step S3, the particle size of the ball-milled material is 0.4-1.0 um.
6. The method of claim 4, further comprising the steps of:
s4, adding an adhesive, a plasticizer, a dispersing agent and the like into the microwave dielectric ceramic material in a powder state, performing ball milling for 1-2 hours to obtain slurry, drying to obtain powder, and pressing the powder into a green body;
s5, removing glue: placing the green body in a temperature range of 500-650 ℃, and preserving heat for 16-32 hours to obtain a green body;
s6, sintering: keeping the blank subjected to the binder removal at 1300-1380 ℃ for 3-5 hours in an air atmosphere;
s7, annealing: and after sintering, keeping the temperature for 1-2 hours at 950-1050 ℃ to obtain the formed microwave dielectric ceramic material.
7. The method according to claim 6, wherein the binder is polyvinyl alcohol, the plasticizer is polyethylene glycol, and the dispersant is ammonium carboxylate.
8. The method according to claim 6, wherein in the step S5, the temperature rising rate is less than 10 ℃/hr.
9. The method according to claim 6, wherein the sintering process of step S6 has a temperature rise rate of 150 ℃ to 200 ℃/hr.
10. The preparation method of claim 6, wherein the formed microwave dielectric ceramic material is obtained, and has a warm dielectric constant of 18-23 and a temperature coefficient τ f (-40-85 ℃): +/-10 ppm/deg.C, and Qf value greater than or equal to 40000 GHz.
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CN112939595A (en) * 2021-04-06 2021-06-11 厦门松元电子有限公司 Microwave dielectric ceramic material with near-zero temperature coefficient at high temperature and preparation method thereof
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CN115925401A (en) * 2022-11-10 2023-04-07 华中科技大学 Low-dielectric silicate microwave dielectric ceramic material and preparation method thereof

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