CN110041069B - Microwave dielectric ceramic material and preparation method thereof - Google Patents
Microwave dielectric ceramic material and preparation method thereof Download PDFInfo
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Abstract
The present invention belongs toIn the technical field of ceramic processing, in particular to a microwave dielectric ceramic material and a preparation method thereof. The preparation method of the microwave dielectric ceramic material comprises the following steps: (1) mixing barium source, titanium source, Ba2Ti9O20Mixing with solvent to obtain premix; the barium source is at least one of barium hydroxide, barium chloride, barium acetate and barium nitrate; the titanium source is at least one of titanium dioxide and titanate; the mass of the solvent used is Ba2Ti9O206-20% of the mass; (2) maintaining the pressure and the heat of the premix for 1-120 min at the temperature of 180-190 ℃ under the pressure of 430-450 MPa to obtain a precursor; (3) and (3) preserving the heat of the precursor for 3-5 h at 700-900 ℃. The preparation method has simple process, the maximum heat treatment temperature is only 900 ℃, which is far lower than the heat treatment temperature of the conventional process, and the relative density of the prepared microwave dielectric ceramic material can reach Ba prepared by the conventional process2Ti9O20Relative density of microwave dielectric ceramic.
Description
Technical Field
The invention belongs to the technical field of ceramic processing, and particularly relates to a microwave dielectric ceramic material and a preparation method thereof.
Background
High frequency dielectric materials have been widely used in a variety of applications such as electronic packaging, substrates, and functionsComponents, and the like. Ba2Ti9O20Has excellent microwave dielectric property and high dielectric constant (epsilon)r39.8), low temperature coefficient of resonance frequency (τ)f2ppm/° c) and a high quality factor (Q × f 8000), is a microwave dielectric ceramic material that can be used in resonators and filters. Ba2Ti9O20Along the [001 ] in its structural arrangement]The axes present an O-Ba-vacancy-Ba-O sequence, the structure being such that Ba is present2+The Ba moves between the vacancy and the normal position in a jumping manner under the left and right action of the external electric field, and the Ba is limited by the geometric space2+Can move only within a limited range, and therefore, Ba2Ti9O20Has better microwave dielectric property.
The melting point of common ceramic materials is very high, and the temperature of traditional sintering needs to reach 50-75% of the melting point. Therefore, for most ceramic materials, the sintering temperature during preparation is above 1000 ℃. For example, the Chinese patent application with publication number CN1420102A discloses a quasi-nano grade barium nonatitanium oxide microwave ceramic and a preparation method thereof. Quasi-nano grade Ba2Ti9O20The microwave ceramic comprises main components Ba (OH)2·8H2O and TiO2And a trace amount of additive Al2O3、SiO2And Bi2O3The preparation method comprises the following steps: carrying out hydrothermal reaction on the main component in a high-pressure reaction kettle, adding a trace additive into a product, and then carrying out heat preservation at 1250-1300 ℃ to obtain the catalyst. Higher sintering temperatures result in energy waste, and high temperatures require complex equipment; if the raw materials contain high-temperature volatile substances, the stoichiometric ratio is not correct, so that the final product is far from the ideal product. Higher sintering temperature makes Ba2Ti9O20The inability to co-fire with other metals, such as Ag, to produce multilayer capacitors limits Ba2Ti9O20Application of microwave dielectric ceramic material.
The Chinese patent application with application publication number CN103342383A discloses a preparation method of microwave dielectric ceramic, which comprises the following steps: preparing a first solution by using barium nitrate, tetrabutyl titanate and citric acid as raw materials; preparing a second solution by taking barium nitrate, tetrabutyl titanate and citric acid as raw materials, adding ammonia water to adjust the pH value to 5 to prepare sol, drying to prepare gel, calcining at 1100 ℃ to obtain barium-titanium-based micron powder, and adding ethanol to prepare a suspension; mixing the suspension with the first solution to prepare sol, drying and calcining at 700 ℃ to obtain a precursor; then the barium titanium base microwave dielectric ceramic is sintered in a high temperature furnace at 1200 ℃ to obtain the barium titanium base microwave dielectric ceramic. The method has more complex steps, the barium-titanium-based micron powder is prepared into suspension, then the suspension is mixed with the first solution, the powder is obtained by adopting a sol-gel method, and then the powder is obtained by two-stage sintering, and the sintering temperature of the second stage is higher.
Disclosure of Invention
The invention aims to provide a preparation method of a microwave dielectric ceramic material with simple process.
The invention also aims to provide the microwave dielectric ceramic material prepared by the preparation method, and the microwave dielectric ceramic material has higher density.
In order to realize the aim, the preparation method of the microwave dielectric ceramic material adopts the technical scheme that:
a preparation method of a microwave dielectric ceramic material comprises the following steps:
(1) mixing barium source, titanium source, Ba2Ti9O20Mixing with solvent to obtain premix; the barium source is at least one of barium hydroxide, barium chloride, barium acetate and barium nitrate; the titanium source is at least one of titanium oxide and titanate; the mass of the solvent used is Ba2Ti9O206-20% of the mass;
(2) maintaining the pressure and the heat of the premix obtained in the step (1) at 430-450 MPa and 180-190 ℃ for 1-120 min to obtain a precursor;
(3) and (3) preserving the heat of the precursor obtained in the step (2) for 3-5 hours at 700-900 ℃ to obtain the material.
Ba2Ti9O20Barium source, titanium sourceAfter mixing with solvent, Ba2Ti9O20The particles are wetted with a liquid containing a barium source and a titanium source, and a layer of the liquid is attached to the surface. And (3) accurately controlling the pressure and the temperature during pressure maintaining and heat preservation in the step (2) to avoid cracking of the microwave dielectric ceramic material. In the process of pressure and heat preservation, the Ba is acted by pressure and temperature and simultaneously under the action of capillary force of liquid phase2Ti9O20Slipping and rearrangement of the particles, Ba2Ti9O20Point contact between particles, capillary force causing Ba2Ti9O20Increased particle solubility, Ba2Ti9O20The phase migrates from the high solubility region to the low solubility region, causing the particles in the contact region to gradually flatten and approach each other, shrinking the ceramic matrix and achieving densification. Meanwhile, the barium source and the titanium source are dissolved and reacted in a natural mineralizing mode to precipitate an amorphous substance (the Ba/Ti ratio in the amorphous substance is close to 2/9), and the precipitated amorphous substance is filled in Ba2Ti9O20The internal holes are reduced and the density of the material is increased at the periphery and the clearance of the particles. The amorphous material crystallizes during the subsequent heat treatment to further crystallize Ba2Ti9O20The particles gradually change from spherical to polygonal, eventually forming a densified polycrystalline structure.
The invention uses liquid phase solvent as medium, the flowing of liquid phase causes Ba2Ti9O20The particles rearrange at temperatures much lower than the migration temperature (1150 c) and therefore the manufacturing process of the present invention enables highly densified materials to be obtained at lower temperatures. The preparation method of the invention leads the inorganic solid particles to be a compact polycrystalline structure through the action of heat energy and pressure, which is a very critical step for processing bulk ceramics. Furthermore, the properties of the material, such as dielectric properties, dielectric breakdown strength, electrical conductivity, etc., are related to the degree of densification.
The preparation method has the advantages of short sintering time, simple equipment, energy consumption saving and simple operation, the maximum heat treatment temperature is only 900 ℃, the temperature is far lower than that of the conventional process, and the preparation method is expected to realize the co-sintering with the Ag/Cu electrode material. According to the inventionBa prepared by preparation method2Ti9O20The relative density of the microwave dielectric ceramic can reach Ba prepared by the traditional process2Ti9O20Relative density of microwave dielectric ceramic.
In the step (1), a barium source, a titanium source and Ba are added2Ti9O20Mixing with a solvent as follows: firstly, mixing barium source, titanium source and solvent to prepare suspension, then mixing the suspension with Ba2Ti9O20And (4) uniformly mixing.
The nano material has fine particles, large specific surface area and high possibility of agglomeration, so that the particle size of the nano particles added in the conventional sense is dozens of microns on a Malvern laser particle size analyzer, which shows that the agglomerated nano particles reach the micron-level particle size in appearance and are difficult to play the role of the nano particles. The invention combines the suspension with Ba2Ti9O20And (3) mixing, namely uniformly dispersing the particles in the suspension by utilizing the interaction force of the particles in a liquid medium, and ensuring that the particles are not easy to agglomerate.
Said Ba in step (1)2Ti9O20Has an average particle diameter of 50 to 100 nm. When Ba is present2Ti9O20When the average grain diameter of the ceramic sheet is 50-100 nm, the prepared ceramic sheet has high density. When the particle size is larger than 100nm, Ba2Ti9O20The size of pores formed by the particles in the pressure and heat preservation process is large, so that the density of the final ceramic material is reduced; when the particle size is less than 50nm, Ba is completely wetted2Ti9O20The particles need more solvent, and the volume occupied by the solvent in the pressure and heat preservation process forms more pores, so that the density of the final ceramic material is reduced.
The total mass of the barium source, the titanium source and the solvent in the step (1) is Ba2Ti9O2010-30% of the mass. When the amount of the solvent is too large during mixing, the premix becomes too thin and is difficult to mold; if the amount is too small, it becomes difficult to uniformly wet Ba2Ti9O20The surface of the particles.
The molar ratio of barium in the barium source to titanium in the titanium source in the step (1) is (0.47-0.72): (1.1-1.8). The use of the above molar ratio of barium source to titanium source facilitates the formation of an amorphous material having a Ba/Ti ratio of approximately 2/9.
In the step (2), before pressure and heat preservation, the temperature is kept at 430-450 MPa and normal temperature for 10-15 min, and then the temperature is increased to 180-190 ℃. Keeping the temperature at 430-450 MPa for 10-15 min at normal temperature to promote Ba2Ti9O2The particles are rearranged, which is beneficial to improving the density.
The heating rate is 9-15 ℃/min, the temperature of the sample is rapidly increased to 180-190 ℃, and evaporation loss of the solvent in the heating process is reduced.
In order to ensure that the water is fully evaporated, in the step (3), before the heat preservation at 700-900 ℃, the heat preservation is carried out for 11-12 hours at 150-250 ℃, and then the temperature is raised to 700-900 ℃.
The temperature rising rate is 3-5 ℃/min. The temperature increase at a slower rate facilitates the removal of residual solvent.
The microwave dielectric ceramic material adopts the technical scheme that:
a microwave dielectric ceramic material prepared by the preparation method of the microwave dielectric ceramic material.
The microwave dielectric ceramic material of the invention has relative density reaching Ba prepared by the traditional process2Ti9O20Relative density and dielectric constant epsilon of microwave dielectric ceramicr35-40, quality factor Qxf 33800-33950 GHz, and temperature coefficient of resonance frequency tauf＝1.25～1.68ppm/℃。
Detailed Description
The preparation method of the microwave dielectric ceramic material comprises the following steps:
(1) mixing barium source, titanium source, Ba2Ti9O20Mixing with solvent to obtain premix; the barium source is at least one of barium hydroxide, barium chloride, barium acetate and barium nitrate; the titanium source is at least one of titanium dioxide and titanate; the mass of the solvent used is Ba2Ti9O206-20% of the mass;
(2) maintaining the pressure and the heat of the premix obtained in the step (1) at 430-450 MPa and 180-190 ℃ for 1-120 min to obtain a precursor;
(3) and (3) preserving the heat of the precursor obtained in the step (2) for 3-5 h at 700-900 ℃.
Preferably, TiO2Is amorphous TiO2。
The titanate is at least one of ethyl titanate and tetrabutyl titanate.
The solvent is water.
Preferably, a barium source, a titanium source, Ba2Ti9O20Mixing with a solvent as follows: firstly, mixing barium source, titanium source and solvent to prepare suspension, then mixing the suspension with Ba2Ti9O20And (4) uniformly mixing.
Preferably, the suspension is mixed with Ba2Ti9O20The mixing is grinding mixing. The abrasive mixing comprises: adding the suspension to Ba2Ti9O20And stirring and grinding for 1-2 min.
Preferably, the barium source is Ba (OH)2。
The present invention will be further described with reference to the following specific examples.
Example 1 of the preparation method of microwave dielectric ceramic material
Microwave dielectric ceramic Ba of the present embodiment2Ti9O20The preparation method comprises the following steps:
(1) 3.1547g of Ba (OH)2·8H2O, 2.1031g amorphous TiO2And 20mL of deionized water to prepare a suspension;
(2) 1.4179g of Ba having an average particle diameter of 50nm2Ti9O20Nano powder and mass is Ba2Ti9O20Grinding and mixing the suspension with the mass of 30 percent of the nano powder in a quick grinder for 2min to obtain premix, and putting the premix into a mold;
(3) pressurizing the mold to 430MPa on a single shaft at normal temperature, preserving heat for 10min, then heating to 180 ℃ at the heating rate of 9 ℃/min, keeping the pressure unchanged, then preserving heat for 1min at 180 ℃, and removing the pressure to obtain a precursor;
(4) and (3) preserving the heat of the precursor for 12h at 200 ℃, then heating to 700 ℃ at the heating rate of 5 ℃/min, and preserving the heat for 3h to obtain the material.
Example 2 of the preparation method of microwave dielectric ceramic material
Microwave dielectric ceramic Ba of the present embodiment2Ti9O20The preparation method comprises the following steps:
(1) 3.1547g of Ba (OH)2·8H2O, 1.9717g amorphous TiO2And 20mL of deionized water to prepare a suspension;
(2) 1.5124g of Ba having an average particle diameter of 100nm2Ti9O20Nano powder and mass is Ba2Ti9O20Grinding and mixing the suspension with the mass of 20 percent of the nano powder in a quick grinder for 1min to obtain premix, and putting the premix into a mold;
(3) pressurizing the mould to 435MPa in a single shaft at normal temperature, preserving heat for 12min, then heating to 190 ℃ at the heating rate of 10 ℃/min, keeping the pressure unchanged, then preserving heat for 15min at 190 ℃, and removing the pressure to obtain a precursor;
(4) and (3) preserving the heat of the precursor for 12h at 200 ℃, then increasing the temperature to 750 ℃ at the heating rate of 5 ℃/min, and preserving the heat for 3.5h to obtain the composite material.
Example 3 of the preparation method of microwave dielectric ceramic material
Microwave dielectric ceramic Ba of the present embodiment2Ti9O20The preparation method comprises the following steps:
(1) 3.1547g of Ba (OH)2·8H2O, 2.0222g amorphous TiO2And 20mL of deionized water to prepare a suspension;
(2) 1.3234g of Ba with an average particle size of 100nm2Ti9O20Nano powder and mass is Ba2Ti9O20Grinding and mixing a suspension of which the mass is 30% of that of the nano powder in a quick grinder for 1min to obtain a premix, and putting the premix into a mold;
(3) pressurizing the mold to 450MPa in a single shaft at normal temperature, preserving heat for 10min, heating to 185 ℃ at the heating rate of 15 ℃/min, keeping the pressure unchanged, preserving heat at 185 ℃ for 30min, and removing the pressure to obtain a precursor;
(4) and (3) preserving the heat of the precursor for 12h at 200 ℃, then heating to 800 ℃ at the heating rate of 5 ℃/min, and preserving the heat for 3.2h to obtain the material.
Example 4 of the preparation method of microwave dielectric ceramic material
Microwave dielectric ceramic Ba of the present embodiment2Ti9O20The preparation method comprises the following steps:
(1) 3.1547g of Ba (OH)2·8H2O, 2.1031g amorphous TiO2And 20mL of deionized water to prepare a suspension;
(2) 1.4179g of Ba having an average particle diameter of 50nm2Ti9O20Nano powder and mass is Ba2Ti9O20Grinding and mixing the suspension with the mass of 10 percent of the nano powder in a quick grinder for 2min to obtain premix, and putting the premix into a mold;
(3) pressurizing the mold to 440MPa in a single shaft at normal temperature, preserving heat for 10min, then heating to 185 ℃ at the heating rate of 10 ℃/min, keeping the pressure unchanged, then preserving heat for 60min at 185 ℃, and removing the pressure to obtain a precursor;
(4) and (3) keeping the temperature of the precursor at 200 ℃ for 12h, then heating to 850 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 3h to obtain the catalyst.
Example 5 of the preparation method of microwave dielectric ceramic Material
Microwave dielectric ceramic Ba of the present embodiment2Ti9O20The preparation method comprises the following steps:
(1) 3.1547g of Ba (OH)2·8H2O, 2.1031g amorphous TiO2And 20mL of deionized water to make a suspension, wherein Ba (OH)2·8H2O, amorphous TiO2The weight ratio of the two is 1.5: 1, the molar ratio is 0.48: 1.2;
(2) 1.4179g of Ba having an average particle diameter of 50nm2Ti9O20Nano powder and mass is Ba2Ti9O20Grinding and mixing the suspension liquid with the mass of 25 percent of the nano powder in a quick grinder for 2min to obtain premix, and putting the premix into a mold;
(3) pressurizing the mold to 445MPa in a single shaft at normal temperature, preserving heat for 15min, then heating to 182 ℃ at the heating rate of 12 ℃/min, keeping the pressure unchanged, then preserving heat for 120min at 182 ℃, and removing the pressure to obtain a precursor;
(4) and (3) preserving the heat of the precursor for 12h at 200 ℃, then heating to 900 ℃ at the heating rate of 5 ℃/min, and preserving the heat for 3.5h to obtain the material.
Example 1 of microwave dielectric ceramic Material
The microwave dielectric ceramic material of the present example was prepared by the preparation method of example 1 of the preparation method of the microwave dielectric ceramic material.
Example 2 of microwave dielectric ceramic Material
The microwave dielectric ceramic material of the present example was prepared by the preparation method of example 2 of the preparation method of the microwave dielectric ceramic material.
Example 3 of microwave dielectric ceramic Material
The microwave dielectric ceramic material of the present example was prepared by the preparation method of example 3 of the preparation method of the microwave dielectric ceramic material.
Example 4 of microwave dielectric ceramic Material
The microwave dielectric ceramic material of the present example was prepared by the preparation method of example 4 of the preparation method of the microwave dielectric ceramic material.
Example 5 of microwave dielectric ceramic Material
The microwave dielectric ceramic material of the present example was prepared by the preparation method of example 5 of the preparation method of the microwave dielectric ceramic material.
Test examples
The microwave dielectric ceramics of examples 1 to 5 of the microwave dielectric ceramic material of the present invention were subjected to a performance test by a shielded cavity resonance method, and the test results are shown in table 1.
Table 1 results of performance testing
As can be seen from Table 1, Ba was prepared by the process of the present invention2Ti9O20The relative density and microwave dielectric property of the microwave dielectric ceramic sample can be compared with those of the traditional process, such as the dielectric constant epsilonr35-40, quality factor Qxf 33800-33950 GHz, and temperature coefficient of resonance frequency tauf1.25 to 1.68 ppm/DEG C, but Ba is present in the invention2Ti9O20The maximum heat treatment temperature of the microwave dielectric ceramic sample is only 900 ℃, which is far lower than the heat treatment temperature of the conventional process.
Claims (4)
1. The preparation method of the microwave dielectric ceramic material is characterized by comprising the following steps of:
(1) mixing barium source, titanium source, Ba2Ti9O20Mixing with solvent to obtain premix; the barium source is at least one of barium hydroxide, barium chloride, barium acetate and barium nitrate; the titanium source is at least one of titanium dioxide and titanate; the mass of the solvent used is Ba2Ti9O206-20% of the mass; said Ba2Ti9O20The average particle diameter of (A) is 50 to 100 nm; the total mass of the barium source, the titanium source and the solvent is Ba2Ti9O2010-30% of the mass; the barium source, the titanium source and the Ba2Ti9O20Mixing with a solvent as follows: firstly, mixing barium source, titanium source and solvent to prepare suspension, then mixing the suspension with Ba2Ti9O20Mixing uniformly; the molar ratio of barium in the barium source to titanium in the titanium source is (0.47-0.72): (1.1-1.8);
(2) maintaining the pressure and the heat of the premix obtained in the step (1) at 430-450 MPa and 180-190 ℃ for 1-120 min to obtain a precursor; before pressure maintaining and heat preservation, keeping the temperature at the normal temperature of 430-450 MPa for 10-15 min, and then heating to 180-190 ℃;
(3) preserving the heat of the precursor obtained in the step (2) at 700-900 ℃ for 3-5 h to obtain the precursor; in the step (3), before heat preservation at 700-900 ℃, heat preservation is carried out for 11-12 hours at 150-250 ℃, and then the temperature is raised to 700-900 ℃.
2. The preparation method of the microwave dielectric ceramic material as claimed in claim 1, wherein the temperature rise rate in the step (2) is 9-15 ℃/min.
3. The preparation method of the microwave dielectric ceramic material as claimed in claim 1, wherein the temperature rise rate in the step (3) is 3-5 ℃/min.
4. A microwave dielectric ceramic material prepared by the method for preparing a microwave dielectric ceramic material according to claim 1.
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Application publication date: 20190723 Assignee: Zhongshan Lvgao Building Materials Co.,Ltd. Assignor: HENAN University OF SCIENCE AND TECHNOLOGY Contract record no.: X2023980035142 Denomination of invention: A microwave dielectric ceramic material and its preparation method Granted publication date: 20211130 License type: Common License Record date: 20230428 |