CN114394828B - Electronic ceramic material with medium dielectric constant and preparation method thereof - Google Patents

Electronic ceramic material with medium dielectric constant and preparation method thereof Download PDF

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CN114394828B
CN114394828B CN202210019481.5A CN202210019481A CN114394828B CN 114394828 B CN114394828 B CN 114394828B CN 202210019481 A CN202210019481 A CN 202210019481A CN 114394828 B CN114394828 B CN 114394828B
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ceramic material
electronic ceramic
composite powder
dielectric constant
sintering aid
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CN114394828A (en
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方豪杰
贺亦文
张晓云
曾雄
张斗
黄荣厦
龙莹
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Hunan Meicheng Ceramic Technology Co ltd
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Abstract

The invention relates to the field of electronic ceramic materials, in particular to an electronic ceramic material with a medium dielectric constant and a preparation method thereof, wherein the electronic ceramic material consists of a main crystal phase, a sintering aid and composite powder; the main crystal phase is BaSm 2 Ti 4 O 12 (ii) a The sintering aid is CuTa 2 O 6 、Eu 2 O 3 And fluoride; the composite powder is porous Al 2 O 3 Adsorption of nano SnO 2 And nano CeO 2 The dielectric constant of the electronic ceramic material prepared by the invention is 45.20-45.37, the stability is high, the dielectric loss is small, the quality factor is high, the temperature coefficient of the resonant frequency is infinitely close to zero, the drift degree is small, the working stability can be ensured, and the requirement of 5G communication base station construction can be met.

Description

Electronic ceramic material with medium dielectric constant and preparation method thereof
Technical Field
The invention relates to the field of electronic ceramic materials, in particular to an electronic ceramic material with a medium dielectric constant and a preparation method thereof.
Background
Electronic ceramics (electronic ceramics) refers to ceramics having electrical and magnetic properties that can be used in the electronics industry. The method is to finally obtain the ceramic with new functions by precisely controlling the surface, the crystal boundary and the size structure, is also an important component and an indispensable material basis of high and new technologies such as aerospace, new energy, new materials, microelectronics, laser, ocean engineering, bioengineering and the like at present, and is one of hot spots of current high-technology competition.
One of the keys to the development of 5G communication is the construction of communication base stations. The development of 5G communication puts forward the requirements of high integration level, high frequency, high speed, high temperature stability and ultra-low power consumption on novel microwave components. Electronic ceramic material (30) with medium dielectric constant<ε r <70 Is an important material in the aspect of microwave components for communication base stations, and has higher requirements on the dielectric property of electronic ceramic materials.
In order to meet the requirements of electronic ceramic materials in the field of communication base station construction, it is important to prepare an electronic ceramic material with a medium dielectric constant.
Disclosure of Invention
The purpose of the invention is as follows: in view of the above-mentioned drawbacks and needs of the prior art, the present invention provides a medium-dielectric-constant electronic ceramic material and a method for preparing the same.
The technical scheme adopted by the invention is as follows:
an electronic ceramic material with a medium dielectric constant is characterized by comprising a main crystal phase, a sintering aid and composite powder;
the main crystal phase is BaSm 2 Ti 4 O 12 ；
The sintering aid is CuTa 2 O 6 、Eu 2 O 3 And fluoride;
the composite powder is porous Al 2 O 3 Adsorption of nano SnO 2 And nano CeO 2 。
Further, the fluoride is LF or MF 2 Or ReF 3 Wherein L is alkali metal, M is Ca or Mg, and Re is Y, la, gd, dy, tm and Yb.
Furthermore, the addition amount of the sintering aid is 4-9% of the mass of the main crystal phase.
Further, the CuTa 2 O 6 、Eu 2 O 3 The mass ratio of the fluoride is 10-12:3-5:1.
further, the preparation method of the composite powder comprises the following steps:
SnCl 4 ·5H 2 O、Ce(NO 3 ) 3 ·6H 2 Adding O into water, dropwise adding dilute HCl while stirring, stopping dropwise adding after the system is dissolved, and adding porous Al 2 O 3 Slowly dropwise adding ammonia water under ice bath, adjusting pH of the reaction solution to 8-10, removing ice bath, heating to 40-50 deg.C, stirring for 5-8h, filtering, washing solid with water until no Cl is formed - 、NO 3 - Adding into saturated ammonia water, stirring for 5-10h, filtering, washing with water and ethanol, vacuum drying at 60-80 deg.C for 6-10h, heating to 650-680 deg.C, and calcining for 3-5h.
Further, the porous Al 2 O 3 The particle diameter of (A) is 8-20 μm.
Further, the mass concentration of the dilute HCl is 1-2%, and the mass concentration of the ammonia water is 15-25%.
Further, the temperature rise rate during the calcination is 3-10 ℃/min.
The preparation method of the medium dielectric constant electronic ceramic material comprises the following steps:
weighing BaCO according to stoichiometric ratio 3 、Sm 2 O 3 、TiO 2 Ball milling for 8-10h by a wet method after mixing, presintering for 2-5h at 1000-1150 ℃ after drying and sieving, mixing with sintering aids and composite powder, ball milling for 15-20h by the wet method, adding binders for granulation after drying and sieving, tabletting, and heating to 1200-1280 ℃ for sintering for 4-6 h.
Further, the binder is a polyvinyl alcohol solution with the mass concentration of 10-15%.
The invention has the beneficial effects that:
the invention provides an electronic ceramic material with medium dielectric constant, the dielectric constant of the prepared electronic ceramic material is 45.20-45.37, and the main crystal phase of the electronic ceramic material is BaSm 2 Ti 4 O 12 ，BaCO 3 -Sm 2 O 3 -TiO 2 The system is one of the main materials of wet medium dielectric constant microwave dielectric ceramic, but the system is easy to generate oxygen vacancy at high temperature to increase the dielectric loss, and if the temperature is not well controlled in the high-temperature firing process, the floating range of the dielectric constant is increased and the stability is poor, so the inventor adds CuTa 2 O 6 、Eu 2 O 3 A sintering aid composed of fluoride and capable of accelerating BaCO 3 -Sm 2 O 3 -TiO 2 The composite powder is composed of micron and nanometer particles, the micron and nanometer particles with high surface energy can occupy the lowest free energy position, the generated melt can pull the crystal particles together to minimize the free energy, promote the ordered growth of the crystal particles, and further improve the dielectric property.
Drawings
Fig. 1 is an SEM image of the medium dielectric constant electronic ceramic material prepared in example 1 of the present invention, and it can be seen that the inter-granular continuity is good, the density is high, and the number of pores is small.
Detailed Description
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.
Example 1:
an electronic ceramic material with medium dielectric constant is prepared from BaSm as main crystal phase 2 Ti 4 O 12 From CuTa 2 O 6 、Eu 2 O 3 、YF 3 Sintering aid and porous Al of composition 2 O 3 Adsorption of nano SnO 2 And nano CeO 2 Composite powder;
wherein, the addition amount of the sintering aid is 6 percent of the mass of the main crystal phase.
CuTa 2 O 6 、Eu 2 O 3 The mass ratio of the fluoride is 10:4:1.
the preparation method of the composite powder comprises the following steps:
the mass ratio of the materials is 1:1 SnCl 4 ·5H 2 O、Ce(NO 3 ) 3 ·6H 2 Adding O into water, dropwise adding 1.5% diluted HCl while stirring, stopping dropwise adding after the system is dissolved, and adding porous Al with particle size of 8-20 μm 2 O 3 Slowly dropwise adding ammonia water with the mass concentration of 18% under ice bath, adjusting the pH of the reaction solution to 9, removing the ice bath, heating to 45 ℃, stirring for 5h, filtering, washing the solid with water until no Cl exists - 、NO 3 - Then adding saturated ammonia water, stirring for 10h, filtering, washing with water and ethanol, vacuum drying at 80 ℃ for 6h, heating to 680 ℃ at a speed of 3 ℃/min, and roasting for 5h.
The preparation method of the medium-dielectric-constant electronic ceramic material comprises the following steps:
weighing BaCO according to stoichiometric ratio 3 、Sm 2 O 3 、TiO 2 And performing wet ball milling for 10h after mixing, pre-sintering for 5h at 1050 ℃ after drying and sieving, mixing with a sintering aid and composite powder, performing wet ball milling for 20h, adding a polyvinyl alcohol solution with the mass concentration of 10% as a binder for granulation after drying and sieving, heating to 1240 ℃ after tabletting, and sintering for 6h to obtain the powder, wherein the density of the powder is 98.5%.
Example 2:
an electronic ceramic material with medium dielectric constant is prepared from BaSm as main crystal phase 2 Ti 4 O 12 From CuTa 2 O 6 、Eu 2 O 3 、YF 3 Sintering aid and porous Al of composition 2 O 3 Adsorption of nano SnO 2 And nano CeO 2 Composite powder;
wherein, the addition amount of the sintering aid is 4 percent of the mass of the main crystal phase.
CuTa 2 O 6 、Eu 2 O 3 The mass ratio of the fluoride is 10:5:1.
the preparation method of the composite powder comprises the following steps:
the mass ratio of the materials is 1:1SnCl of 4 ·5H 2 O、Ce(NO 3 ) 3 ·6H 2 Adding O into water, dropwise adding 1% diluted HCl while stirring, stopping dropwise adding after the system is dissolved, and adding porous Al with particle size of 8-20 μm 2 O 3 Slowly dropwise adding ammonia water with the mass concentration of 15% under ice bath, adjusting the pH of the reaction solution to 10, removing the ice bath, heating to 50 ℃, stirring for 6h, filtering, washing the solid with water until no Cl exists - 、NO 3 - Adding saturated ammonia water, stirring for 10h, filtering, washing with water and ethanol, vacuum drying at 70 deg.C for 10h, heating to 680 deg.C at 5 deg.C/min, and calcining for 5h.
The preparation method of the medium-dielectric-constant electronic ceramic material comprises the following steps:
weighing BaCO according to stoichiometric ratio 3 、Sm 2 O 3 、TiO 2 The powder is subjected to wet ball milling for 10 hours after mixing, is dried and sieved, is presintered for 5 hours at 1100 ℃, is mixed with a sintering aid and composite powder, is subjected to wet ball milling for 18 hours, is dried and sieved, is added with a polyvinyl alcohol solution with the mass concentration of 12 percent as a binder for granulation, is tableted and is heated to 1280 ℃ for sintering for 5 hours, and the compactness is 98.3 percent.
Example 3:
an electronic ceramic material with medium dielectric constant is prepared from BaSm as main crystal phase 2 Ti 4 O 12 From CuTa 2 O 6 、Eu 2 O 3 、YF 3 Sintering aid and porous Al of composition 2 O 3 Adsorption of nano SnO 2 And nano CeO 2 Composite powder;
wherein, the addition amount of the sintering aid is 4 percent of the mass of the main crystal phase.
CuTa 2 O 6 、Eu 2 O 3 The mass ratio of the fluoride is 10:3:1.
the preparation method of the composite powder comprises the following steps:
the mass ratio of the materials is 1:1 SnCl 4 ·5H 2 O、Ce(NO 3 ) 3 ·6H 2 Adding O into water, dropwise adding 1% diluted HCl while stirring, stopping dropwise adding after the system is dissolved, and adding porous Al with particle size of 8-20 μm 2 O 3 Slowly dropwise adding ammonia water with the mass concentration of 15% under ice bath, adjusting the pH of the reaction solution to 8, removing the ice bath, heating to 40 ℃, stirring for 5h, filtering, washing the solid with water until no Cl exists - 、NO 3 - Then adding saturated ammonia water, stirring for 5h, filtering, washing with water and ethanol, vacuum drying at 60 ℃ for 6h, heating to 650 ℃ at the speed of 3 ℃/min, and roasting for 3h.
The preparation method of the medium-dielectric-constant electronic ceramic material comprises the following steps:
weighing BaCO according to stoichiometric ratio 3 、Sm 2 O 3 、TiO 2 And performing wet ball milling for 8h after mixing, pre-sintering for 2h at 1000 ℃ after drying and sieving, mixing with a sintering aid and composite powder, performing wet ball milling for 15h, adding a polyvinyl alcohol solution with the mass concentration of 10% as a binder for granulation after drying and sieving, heating to 1200 ℃ after tabletting, and sintering for 4h, wherein the density is 98.1%.
Example 4:
an electronic ceramic material with medium dielectric constant is prepared from BaSm as main crystal phase 2 Ti 4 O 12 From CuTa 2 O 6 、Eu 2 O 3 、YF 3 Sintering aid and porous Al of composition 2 O 3 Adsorption of nano SnO 2 And nano CeO 2 Composite powder;
wherein, the addition amount of the sintering aid is 9 percent of the mass of the main crystal phase.
CuTa 2 O 6 、Eu 2 O 3 And the mass ratio of the fluoride is 12:5:1.
the preparation method of the composite powder comprises the following steps:
the mass ratio of the materials is 1:1 SnCl 4 ·5H 2 O、Ce(NO 3 ) 3 ·6H 2 Adding O into water, dropwise adding diluted HCl with mass concentration of 2% while stirring, stopping dropwise adding after the system is dissolved, and adding porous Al with particle size of 8-20 μm 2 O 3 Slowly dropwise adding 25% ammonia water under ice bath, adjusting pH of the reaction solution to 10, removing ice bath, heating to 50 deg.C, stirring for 8h, filtering, and washing the solid with water until no Cl is formed - 、NO 3 - Adding saturated ammonia water, stirring for 10 hr, and filteringWashing with water, washing with ethanol, vacuum drying at 80 deg.C for 10 hr, heating to 680 deg.C at a speed of 10 deg.C/min, and calcining for 5 hr.
The preparation method of the medium-dielectric-constant electronic ceramic material comprises the following steps:
weighing BaCO according to stoichiometric ratio 3 、Sm 2 O 3 、TiO 2 The powder is subjected to wet ball milling for 10 hours after mixing, is subjected to drying and sieving, is presintered at 1150 ℃ for 5 hours, is mixed with a sintering aid and composite powder, is subjected to wet ball milling for 20 hours, is subjected to drying and sieving, is added with 15 mass percent polyvinyl alcohol solution serving as a binder for granulation, is subjected to tabletting, is heated to 1280 ℃ and is sintered for 6 hours, and the compactness is 98.3 percent.
Example 5:
an electronic ceramic material with medium dielectric constant is prepared from BaSm as main crystal phase 2 Ti 4 O 12 From CuTa 2 O 6 、Eu 2 O 3 、YF 3 Sintering aid and porous Al of composition 2 O 3 Adsorption of nano SnO 2 And nano CeO 2 Composite powder;
wherein, the addition amount of the sintering aid is 4 percent of the mass of the main crystal phase.
CuTa 2 O 6 、Eu 2 O 3 And the mass ratio of the fluoride is 12:3:1.
the preparation method of the composite powder comprises the following steps:
the mass ratio of the materials is 1:1 SnCl 4 ·5H 2 O、Ce(NO 3 ) 3 ·6H 2 Adding O into water, dropwise adding diluted HCl with mass concentration of 2% while stirring, stopping dropwise adding after the system is dissolved, and adding porous Al with particle size of 8-20 μm 2 O 3 Slowly dropwise adding ammonia water with the mass concentration of 15% under ice bath, adjusting the pH of the reaction solution to 10, removing the ice bath, heating to 40 ℃, stirring for 8h, filtering, washing the solid with water until no Cl exists - 、NO 3 - Then adding saturated ammonia water, stirring for 5h, filtering, washing with water and ethanol, vacuum drying at 80 ℃ for 6h, heating to 650 ℃ at the speed of 10 ℃/min, and roasting for 5h.
The preparation method of the medium-dielectric-constant electronic ceramic material comprises the following steps:
according toStoichiometric weighing of BaCO 3 、Sm 2 O 3 、TiO 2 And performing wet ball milling for 8h after mixing, pre-burning for 2h at 1150 ℃ after drying and sieving, mixing with a sintering aid and composite powder, performing wet ball milling for 20h, adding a polyvinyl alcohol solution with the mass concentration of 10% as a binder for granulation after drying and sieving, heating to 1280 ℃ after tabletting, and sintering for 4h, wherein the density is 97.9%.
Example 6:
an electronic ceramic material with medium dielectric constant is prepared from BaSm as main crystal phase 2 Ti 4 O 12 From CuTa 2 O 6 、Eu 2 O 3 、YF 3 Sintering aid and porous Al of composition 2 O 3 Adsorption of nano SnO 2 And nano CeO 2 Composite powder;
wherein, the addition amount of the sintering aid is 9 percent of the mass of the main crystal phase.
CuTa 2 O 6 、Eu 2 O 3 The mass ratio of the fluoride is 10:5:1.
the preparation method of the composite powder comprises the following steps:
the mass ratio of the materials is 1:1 SnCl 4 ·5H 2 O、Ce(NO 3 ) 3 ·6H 2 Adding O into water, dropwise adding 1% diluted HCl while stirring, stopping dropwise adding after the system is dissolved, and adding porous Al with particle size of 8-20 μm 2 O 3 Slowly dropwise adding 25% ammonia water under ice bath, adjusting pH of the reaction solution to 8, removing ice bath, heating to 50 deg.C, stirring for 5h, filtering, and washing the solid with water until no Cl is formed - 、NO 3 - Then adding saturated ammonia water, stirring for 10h, filtering, washing with water and ethanol, vacuum drying at 60 ℃ for 10h, heating to 680 ℃ at the speed of 3 ℃/min, and roasting for 3h.
The preparation method of the medium-dielectric-constant electronic ceramic material comprises the following steps:
weighing BaCO according to stoichiometric ratio 3 、Sm 2 O 3 、TiO 2 Wet ball milling for 10 hr after mixing, pre-sintering at 1000 deg.c for 5 hr after stoving and sieving, mixing with sintering assistant and composite powder, wet ball milling for 15 hr, stoving and sieving, adding the mixture in certain weightAnd (3) granulating by taking 15% polyvinyl alcohol solution as a binder, tabletting, heating to 1200 ℃ and sintering for 6 hours, wherein the density is 98.3%.
Comparative example 1:
comparative example 1 is substantially the same as example 1 except that the compactness of 64.2% is not achieved without adding a sintering aid.
Comparative example 2:
comparative example 2 is substantially the same as example 1 except that CuTa is not added to the sintering aid 2 O 6 The compactness is 70.8 percent, and the use requirement cannot be met.
Comparative example 3:
comparative example 3 is substantially the same as example 1 except that Eu is not added to the sintering aid 2 O 3 The compactness is 76.1 percent, and the use requirement cannot be met.
Comparative example 4:
comparative example 4 is substantially the same as example 1 except that YF is not added to the sintering aid 3 The compactness is 82.6 percent, and the use requirement cannot be met.
Comparative example 5:
comparative example 5 is substantially the same as example 1 except that the compactness thereof is 95.3% without adding the composite powder.
Comparative example 6:
comparative example 6 is substantially the same as example 1 except that porous Al is used 2 O 3 Nano SnO 2 CeO, ceO nanoparticles 2 The mixture is added separately, and the compactness is 96.6 percent.
Comparative example 7:
comparative example 7 is substantially the same as example 1 except that the composite powder does not contain nano CeO 2 The compactness thereof is 96.9 percent.
Comparative example 8:
comparative example 8 is substantially the same as example 1 except that the composite powder does not contain nano SnO 2 The compactness thereof is 97.4%.
And (4) performance testing:
after the electronic ceramic materials prepared in examples 1 to 6 of the present invention and comparative examples 5 to 8 were double-side polished, dielectric properties thereof were measured using a Hakki vector network analyzer of angiont corporation, usa, and dielectric constants, dielectric losses, quality factors, and resonant frequency temperature coefficients were measured using a TEo11 resonant mode, and the results are shown in table 1.
Table 1:
Figure BDA0003461856820000091
as can be seen from the above table 1, the dielectric constant of the electronic ceramic material prepared by the invention is 45.20-45.37, the electronic ceramic material has high stability, small dielectric loss, high quality factor, infinite resonant frequency temperature coefficient close to zero, small drift degree, and can ensure the working stability and meet the requirements of 5G communication base station construction.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (8)

1. An electronic ceramic material with a medium dielectric constant is characterized by comprising a main crystal phase, a sintering aid and composite powder;
the main crystal phase is BaSm 2 Ti 4 O 12 ；
The sintering aid is CuTa 2 O 6 、Eu 2 O 3 And fluoride;
the composite powder is porous Al 2 O 3 Adsorption of nano SnO 2 And nano CeO 2 ；
The addition amount of the sintering aid is 4-9% of the mass of the main crystal phase;
the CuTa 2 O 6 、Eu 2 O 3 Mass of fluorideThe ratio is 10-12:3-5:1.
2. a dielectric constant electron ceramic material according to claim 1 wherein said fluoride is LF, MF 2 Or ReF 3 Wherein L is alkali metal, M is Ca or Mg, and Re is Y, la, gd, dy, tm and Yb.
3. A dielectric constant electronic ceramic material as claimed in claim 1, wherein said composite powder is prepared by the following steps:
SnCl 4 ·5H 2 O、Ce(NO 3 ) 3 ·6H 2 Adding O into water, dropwise adding dilute HCl while stirring, stopping dropwise adding after the system is dissolved, and adding porous Al 2 O 3 Slowly dropwise adding ammonia water under ice bath, adjusting pH of the reaction solution to 8-10, removing ice bath, heating to 40-50 deg.C, stirring for 5-8h, filtering, washing solid with water until no Cl is formed - 、NO 3 - Adding into saturated ammonia water, stirring for 5-10h, filtering, washing with water and ethanol, vacuum drying at 60-80 deg.C for 6-10h, heating to 650-680 deg.C, and calcining for 3-5h.
4. A medium-dielectric-constant electronic ceramic material according to claim 3, wherein the porous Al is 2 O 3 The particle diameter of (A) is 8-20 μm.
5. A dielectric constant electronic ceramic material as claimed in claim 3, wherein the dilute HCl is 1-2% by mass and the ammonia water is 15-25% by mass.
6. A medium-dielectric-constant electronic ceramic material as claimed in claim 3, wherein the temperature rise rate at the time of firing is 3 to 10 ℃/min.
7. A process for the preparation of a medium-dielectric-constant electronic ceramic material according to any one of claims 1 to 6, characterized in that the BaCO is weighed in stoichiometric proportions 3 、Sm 2 O 3 、TiO 2 Wet after mixingBall-milling for 8-10h, drying, sieving, pre-sintering at 1000-1150 deg.C for 2-5h, mixing with sintering aid and composite powder, ball-milling for 15-20h, drying, sieving, adding binder, granulating, tabletting, and heating to 1200-1280 deg.C for sintering for 4-6 h.
8. The method of claim 7, wherein the binder is a polyvinyl alcohol solution with a mass concentration of 10-15%.
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