CN113620702A - Yb (Yb)3+Doped giant dielectric constant low-loss ceramic and preparation method thereof - Google Patents

Yb (Yb)3+Doped giant dielectric constant low-loss ceramic and preparation method thereof Download PDF

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CN113620702A
CN113620702A CN202110811666.5A CN202110811666A CN113620702A CN 113620702 A CN113620702 A CN 113620702A CN 202110811666 A CN202110811666 A CN 202110811666A CN 113620702 A CN113620702 A CN 113620702A
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dielectric constant
powder
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成鹏飞
王丹
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Xian Polytechnic University
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Abstract

The invention discloses a Yb3+A doped giant dielectric constant low-loss ceramic and a preparation method thereof belong to the field of ceramic molding products and preparation methods thereof. The giant dielectric constant low-loss ceramic is made of CaCu3Ti4O12And Yb2O3And (4) forming. The preparation method comprises the following steps: under air atmosphere with CaCO3CuO and TiO2As a raw material, Yb2O3The giant dielectric constant low-loss ceramic is prepared by adopting a solid-phase reaction process as an additive. The invention fully utilizes the advantages of simple preparation process, high repeatability, high yield and the like of the solid phase method, and paves the way for large-scale industrial production.

Description

Yb (Yb)3+Doped giant dielectric constant low-loss ceramic and preparation method thereof
Technical Field
The invention belongs to the field of ceramic molded products and preparation methods thereof.
Background
In 1979, CaCu was prepared by a solid-phase reaction method from Bochu subject group3Ti4O12(abbreviated as CCTO) ceramic materials. Further research on M.A. Subramanian shows that the CCTO ceramic material with the perovskite structure has the dielectric constant of more than 10000 at normal temperature, has little temperature dependence and hardly changes the dielectric constant within the temperature range of 100K to 600K. The excellent performances not only can well meet the development requirements of high energy storage, green and stable performance,and lays an important foundation for the development of important electronic devices such as capacitors, memories, nonlinear devices and the like to miniaturization, integration and intellectualization.
Although CCTO ceramic materials have a high dielectric constant, the high dielectric constant is often accompanied by high dielectric loss, and the high dielectric loss causes problems of heat generation, unstable operation or signal attenuation of devices or circuits in practical applications, thereby severely limiting the application of CCTO ceramics. Therefore, the dielectric loss reasonably reduced while ensuring the giant dielectric constant of the CCTO ceramic is a problem to be solved urgently in order to ensure that the material can be applied to engineering. Li Jie et al in Chinese patent CN 100494117C adopts a cold isostatic pressing process to reduce the dielectric loss of CCTO ceramics to 0.026 under the condition of room temperature of 1KHz, but the dielectric constant is also reduced to about 3000; KIM et al prepared BaTiO by sol-gel process3Coated CCTO ceramics (Kim H E, Lee S Y, Yoo S I. improved electric Properties of BaTiO3-coated CaCu3Ti4O12Dielectrics[C]MRS proceedings. cambridge University Press,2012,1454:75-80), the dielectric loss is significantly reduced compared to pure CCTO, 0.02(100KHz), but at the same time the dielectric constant is also reduced by an order of magnitude, only 4075; LI et al prepared Eu by conventional solid phase reaction method2O3Added CCTO ceramics (Li M, Liu Q, Li C X. study of the dielectric stresses of Eu-bonded CaCu)3Ti4O12[J]Journal of Alloys and Compounds,2017,699, 278-; zhao Yan Hui (Zhao Yan Hui. coprecipitation method for preparing calcium copper titanate and dielectric property research [ D)]2013,39-48) of China ocean university, the dielectric loss is reduced compared with pure CCTO in a wider frequency range at normal temperature, and the dielectric constant can still reach 9775. The above experiments resulted in a large reduction in dielectric constant while suppressing dielectric loss, or difficulty in industrial mass production due to an excessively complicated process. The CCTO ceramic prepared by the traditional solid phase method not only maintains the giant dielectric constant, but also obviously reduces the dielectric constantThe dielectric loss and the preparation process are simple, the mass production is easy, the process repeatability and the performance stability of the prepared sample are high, and the industrial mass production is easy.
Disclosure of Invention
To solve the problems of the prior art, embodiments of the present invention provide a Yb3+Doped giant dielectric constant low-loss ceramic and a preparation method thereof. The technical scheme is as follows:
in one aspect, there is provided Yb3+Doped giant dielectric constant low loss ceramic made from CaCu3Ti4O12And Yb2O3And (4) forming.
Preferably, the chemical formula is CaCu3Ti4O12+xYb2O3Wherein x is less than or equal to 0.01.
More preferably, x is 0.01, 0.04 or 0.07.
In another aspect, there is provided Yb3+The preparation method of the doped giant dielectric constant low-loss ceramic comprises the following steps: under air atmosphere with CaCO3CuO and TiO2As a raw material, Yb2O3As an additive, adopts a solid-phase reaction process to prepare CaCu3Ti4O12+xYb2O3。
Preferably, the solid-phase reaction process comprises mixing, presintering, molding, binder removal and sintering, wherein the presintering is carried out by heating from room temperature to 950 ℃ at a heating rate of 10 ℃/3min and then carrying out heat preservation for 15 h.
More preferably, the sintering condition is that the temperature is increased from room temperature to 1000 ℃ at the heating rate of 10 ℃/3min, the temperature is increased to 1100-1120 ℃ at the heating rate of 10 ℃/min, the temperature is kept for 20h, and then the furnace cooling is carried out.
In the above or more preferred embodiment, the mixture is: CaCO with a purity of 99.0%3Powder, CuO powder, TiO2Powder of Yb2O3Mixing the powder to obtain mixed powder, putting the mixed powder into an agate ball milling tank for wet ball milling, taking absolute ethyl alcohol as a ball milling medium, wherein the mass ratio of the mixed powder to agate balls to the absolute ethyl alcohol is 1: 1-3: 0.8-1.2, and then grinding the mixed powder to obtain the composite powder in a planetary ball mill by 37Ball milling is carried out for 10h at the rotating speed of 0r/min, and the obtained slurry is dried at the temperature of 60 ℃.
In the above or more preferred embodiment, the molding is: weighing the pre-sintered powder, adding 2 wt% of PVA adhesive with the same mass for granulation, ageing the particles with the particle size between 60 meshes and 100 meshes for 24 hours, and then dry-pressing the particles into cylindrical green bodies with the diameter of 12mm and the thickness of 2mm by using a powder tablet machine under the pressure of 10 MPa. In the above or more preferred embodiment, the binder removal is: and (3) placing the molded green body into a muffle furnace, heating to 150 ℃ from room temperature at a heating rate of 6.5 ℃/min, heating to 350 ℃ at a heating rate of 10 ℃/3min, heating to 600 ℃ at a heating rate of 0.5 ℃/min, preserving heat for 1h, then cooling to 370 ℃ at a cooling rate of 1 ℃/min, and finally cooling along with the furnace.
The technical scheme provided by the embodiment of the invention has the following beneficial effects:
the invention provides a method for reducing dielectric loss on the basis of keeping the giant dielectric constant of a CCTO ceramic material, namely, Yb is added into the formula2O3The ceramic material with huge dielectric constant and low loss is obtained by solid phase sintering in the process, and the dielectric constant epsilon is within a wider frequency range of 1000-90000 Hzr16000-19000, and the dielectric loss tan delta is less than or equal to 0.1; and ε is measured when the test frequency is 16700Hzr17566, tan δ 0.07. Therefore, the CCTO ceramic material with huge dielectric constant and low dielectric loss is prepared by the method, and the dielectric property of the CCTO ceramic material is improved. The invention fully utilizes the advantages of simple preparation process, high repeatability, high yield and the like of the solid phase method, and paves the way for large-scale industrial production.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a graph of dielectric constant versus frequency for CCTO ceramics made in accordance with the first and second embodiments of the present invention;
FIG. 2 is a graph of dielectric loss versus frequency for CCTO ceramics made in accordance with the first and second embodiments of the present invention;
FIG. 3 is a graph of dielectric constant versus frequency for CCTO ceramics prepared in the third and fourth embodiments of the present invention;
FIG. 4 is a graph of dielectric loss as a function of frequency for CCTO ceramics prepared in the third and fourth embodiments of the present invention;
FIG. 5 is a graph of dielectric constant versus frequency for CCTO ceramics prepared in accordance with the fifth and sixth embodiments of the present invention;
fig. 6 is a graph of dielectric loss versus frequency for CCTO ceramics prepared in fifth and sixth examples of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
The first embodiment is as follows: preparing CaCu by solid-phase reaction at 1100 deg.C for 20h3Ti4O12+0.01 Yb2O3Of a ceramic material
CaCO with a purity of 99.0%3Powder, CuO powder, TiO2Powder of Yb2O3Weighing and mixing the powder according to a certain molar ratio (Ca + Yb) and Cu: Ti of 1:3:4 to obtain a raw material, putting the raw material into an agate ball milling tank for wet ball milling, and taking absolute ethyl alcohol as a ball milling medium, wherein the mass ratio of the raw material to agate balls to the absolute ethyl alcohol is 1: 1-3: 0.8-1.2. Ball milling is carried out for 10 hours at 370r/min by using a planetary ball mill, the ball milled slurry is dried in an oven at 60 ℃, and then the dried powder is put in a sintering furnace for presintering at 950 ℃. And (3) performing secondary ball milling and drying on the calcined briquette, adding PVA (polyvinyl alcohol) adhesive (2 wt%) with equal mass, granulating and grinding. The granules with the grain size between 60 meshes and 100 meshes are aged for 24h, and the aged granules are dry pressed into a cylindrical green body with the diameter of about 12mm and the thickness of about 2mm by using a powder tablet press under the pressure of about 10 MPa. And placing the green body in a sintering furnace for glue discharging treatment at 600 ℃. Placing the green body after the rubber discharge treatment into a sintering furnace to be sintered for 20 hours at 1100 ℃ to obtainA CCTO ceramic body. And (3) polishing the surface of the CCTO ceramic body, sputtering a gold electrode, and testing the dielectric property. Epsilon at room temperature at a test frequency of 12000Hzr69800, tan δ is 0.19. As shown in the graphs of fig. 1(a) and 2 (a).
Example 2: preparing CaCu by solid-phase reaction at 1120 ℃ for 20h3Ti4O12+0.01 Yb2O3Of a ceramic material
CaCO with a purity of 99.0%3Powder, CuO powder, TiO2Powder of Yb2O3Weighing and mixing the powder according to a certain molar ratio (Ca + Yb) and Cu: Ti of 1:3:4 to obtain a raw material, putting the raw material into an agate ball milling tank for wet ball milling, and taking absolute ethyl alcohol as a ball milling medium, wherein the mass ratio of the raw material to agate balls to the absolute ethyl alcohol is 1: 1-3: 0.8-1.2. Ball milling is carried out for 10 hours at 370r/min by using a planetary ball mill, the ball milled slurry is dried in an oven at 60 ℃, and then the dried powder is put in a sintering furnace for presintering at 950 ℃. And (3) performing secondary ball milling and drying on the calcined briquette, adding PVA (polyvinyl alcohol) adhesive (2 wt%) with equal mass, granulating and grinding. The granules with the grain size between 60 meshes and 100 meshes are aged for 24h, and the aged granules are dry pressed into a cylindrical green body with the diameter of about 12mm and the thickness of about 2mm by using a powder tablet press under the pressure of about 10 MPa. And placing the green body in a sintering furnace for glue discharging treatment at 600 ℃. And placing the green body subjected to the binder removal treatment into a sintering furnace, and sintering for 20 hours at 1120 ℃ to obtain the CCTO ceramic body. And (3) polishing the surface of the CCTO ceramic body, sputtering a gold electrode, and testing the dielectric property. Epsilon at room temperature at a test frequency of 12000Hzr54000, tan δ 0.12. As shown in the graphs of fig. 1(b) and 2 (b).
Example 3: preparing CaCu by solid-phase reaction at 1100 deg.C for 20h3Ti4O12+0.04 Yb2O3Of a ceramic material
Weighing and mixing 99.0% purity CaCO3 powder, CuO powder, TiO2 powder and Yb2O3 powder according to a certain molar ratio, namely (Ca + Yb) Cu and Ti are 1:3:4 to obtain raw materials, putting the raw materials into an agate ball milling tank for wet ball milling, and taking absolute ethyl alcohol as a ball milling medium, wherein the mass ratio of the raw materials to agate balls to the absolute ethyl alcohol is 1: 1-3: 0.8-1.2. Make itBall-milling for 10h at 370r/min by using a planetary ball mill, drying the ball-milled slurry in an oven at 60 ℃, and then putting the dried powder in a sintering furnace for presintering at 950 ℃. And (3) performing secondary ball milling and drying on the calcined briquette, adding PVA (polyvinyl alcohol) adhesive (2 wt%) with equal mass, granulating and grinding. The granules with the grain size between 60 meshes and 100 meshes are aged for 24h, and the aged granules are dry pressed into a cylindrical green body with the diameter of about 12mm and the thickness of about 2mm by using a powder tablet press under the pressure of about 10 MPa. And placing the green body in a sintering furnace for glue discharging treatment at 600 ℃. And placing the green body subjected to the binder removal treatment into a sintering furnace to be sintered for 20 hours at 1100 ℃ to obtain the CCTO ceramic body. And (3) polishing the surface of the CCTO ceramic body, sputtering a gold electrode, and testing the dielectric property. At room temperature, when the test frequency is 8500Hz,. epsilonr150076, tan δ is 0.13. As shown in the graphs of fig. 3(c) and 4 (c).
Example 4: preparing CaCu by solid-phase reaction at 1120 ℃ for 20h3Ti4O12+0.04 Yb2O3Of a ceramic material
Weighing and mixing 99.0% purity CaCO3 powder, CuO powder, TiO2 powder and Yb2O3 powder according to a certain molar ratio, namely (Ca + Yb) Cu and Ti are 1:3:4 to obtain raw materials, putting the raw materials into an agate ball milling tank for wet ball milling, and taking absolute ethyl alcohol as a ball milling medium, wherein the mass ratio of the raw materials to agate balls to the absolute ethyl alcohol is 1: 1-3: 0.8-1.2. Ball milling is carried out for 10 hours at 370r/min by using a planetary ball mill, the ball milled slurry is dried in an oven at 60 ℃, and then the dried powder is put in a sintering furnace for presintering at 950 ℃. And (3) performing secondary ball milling and drying on the calcined briquette, adding PVA (polyvinyl alcohol) adhesive (2 wt%) with equal mass, granulating and grinding. The granules with the grain size between 60 meshes and 100 meshes are aged for 24h, and the aged granules are dry pressed into a cylindrical green body with the diameter of about 12mm and the thickness of about 2mm by using a powder tablet press under the pressure of about 10 MPa. And placing the green body in a sintering furnace for glue discharging treatment at 600 ℃. And placing the green body subjected to the binder removal treatment into a sintering furnace, and sintering for 20 hours at 1120 ℃ to obtain the CCTO ceramic body. And (3) polishing the surface of the CCTO ceramic body, sputtering a gold electrode, and testing the dielectric property. At room temperature, when the test frequency is 8500Hz,. epsilonr43000 and tan δ 0.11. As shown in the graphs of fig. 3(d) and 4 (d).
Example 5: preparing CaCu by solid-phase reaction at 1100 deg.C for 20h3Ti4O12+0.07 Yb2O3Of a ceramic material
CaCO with a purity of 99.0%3Powder, CuO powder, TiO2Powder of Yb2O3Weighing and mixing the powder according to a certain molar ratio (Ca + Yb) and Cu: Ti of 1:3:4 to obtain a raw material, putting the raw material into an agate ball milling tank for wet ball milling, and taking absolute ethyl alcohol as a ball milling medium, wherein the mass ratio of the raw material to agate balls to the absolute ethyl alcohol is 1: 1-3: 0.8-1.2. Ball milling is carried out for 10 hours at 370r/min by using a planetary ball mill, the ball milled slurry is dried in an oven at 60 ℃, and then the dried powder is put in a sintering furnace for presintering at 950 ℃. And (3) performing secondary ball milling and drying on the calcined briquette, adding PVA (polyvinyl alcohol) adhesive (2 wt%) with equal mass, granulating and grinding. The granules with the grain size between 60 meshes and 100 meshes are aged for 24h, and the aged granules are dry pressed into a cylindrical green body with the diameter of about 12mm and the thickness of about 2mm by using a powder tablet press under the pressure of about 10 MPa. And placing the green body in a sintering furnace for glue discharging treatment at 600 ℃. And placing the green body subjected to the binder removal treatment into a sintering furnace to be sintered for 20 hours at 1100 ℃ to obtain the CCTO ceramic body. And (3) polishing the surface of the CCTO ceramic body, sputtering a gold electrode, and testing the dielectric property. At room temperature, when the test frequency is 16700Hz,. epsilonr73288, tan δ is 0.09. As shown in the graphs of fig. 5(e) and 6 (e).
Example 6: preparing CaCu by solid-phase reaction at 1120 ℃ for 20h3Ti4O12+0.07 Yb2O3Of a ceramic material
CaCO with a purity of 99.0%3Powder, CuO powder, TiO2Powder of Yb2O3Weighing and mixing the powder according to a certain molar ratio (Ca + Yb) and Cu: Ti of 1:3:4 to obtain a raw material, putting the raw material into an agate ball milling tank for wet ball milling, and taking absolute ethyl alcohol as a ball milling medium, wherein the mass ratio of the raw material to agate balls to the absolute ethyl alcohol is 1: 1-3: 0.8-1.2. Ball milling is carried out for 10 hours at 370r/min by using a planetary ball mill, the ball milled slurry is dried in an oven at 60 ℃, and then the dried powder is put in a sintering furnace for presintering at 950 ℃. Firing after preburningAnd (3) performing secondary ball milling on the blocks, drying, adding PVA (polyvinyl acetate) adhesive (2 wt%) with equal mass, granulating and grinding. The granules with the grain size between 60 meshes and 100 meshes are aged for 24h, and the aged granules are dry pressed into a cylindrical green body with the diameter of about 12mm and the thickness of about 2mm by using a powder tablet press under the pressure of about 10 MPa. And placing the green body in a sintering furnace for glue discharging treatment at 600 ℃. And placing the green body subjected to the binder removal treatment into a sintering furnace, and sintering for 20 hours at 1120 ℃ to obtain the CCTO ceramic body. At room temperature, when the test frequency is from 1000 to 90000Hz, epsilonr16000-19000, tan delta is less than or equal to 0.1; and ε is measured when the test frequency is 16700Hzr17566, tan δ 0.07. As shown in the graphs of fig. 5(f) and 6 (f).
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (9)

1. Yb (Yb)3+Doped giant dielectric constant low loss ceramic characterized by being made of CaCu3Ti4O12And Yb2O3And (4) forming.
2. Yb according to claim 13+A doped giant dielectric constant low loss ceramic characterized by the chemical formula CaCu3Ti4O12+xYb2O3Wherein x is less than or equal to 0.01.
3. Yb according to claim 23+A doped giant dielectric constant low loss ceramic characterized by x of 0.01, 0.04 or 0.07.
4. Yb according to claim 1, 2 or 33+The preparation method of the doped giant dielectric constant low-loss ceramic is characterized by comprising the following steps of: under air atmosphere with CaCO3CuO and TiO2As a raw material, Yb2O3As an additive, adopts a solid-phase reaction process to prepare CaCu3Ti4O12+x Yb2O3。
5. Yb according to claim 43+The preparation method of the doped giant dielectric constant low-loss ceramic is characterized in that the solid phase reaction process comprises the steps of mixing, presintering, forming, binder removal and sintering, wherein the presintering is carried out by heating from room temperature to 950 ℃ at the heating rate of 10 ℃/3min and then carrying out heat preservation for 15 h.
6. Yb according to claim 53+The preparation method of the doped giant dielectric constant low-loss ceramic is characterized in that the sintering condition is that the temperature is increased from room temperature to 1000 ℃ at the heating rate of 10 ℃/3min, the temperature is increased to 1100-1120 ℃ at the heating rate of 10 ℃/min, the temperature is kept for 20h, and then the ceramic is cooled along with a furnace.
7. An Yb as claimed in claim 5 or 63+The preparation method of the doped giant dielectric constant low-loss ceramic is characterized in that the mixed material is as follows: CaCO with a purity of 99.0%3Powder, CuO powder, TiO2Powder of Yb2O3Mixing the powder to obtain mixed powder, putting the mixed powder into an agate ball milling tank for wet ball milling, taking absolute ethyl alcohol as a ball milling medium, wherein the mass ratio of the mixed powder to agate balls to the absolute ethyl alcohol is 1: 1-3: 0.8-1.2, then carrying out ball milling in a planetary ball mill at the rotating speed of 370r/min for 10 hours, and drying the obtained slurry at the temperature of 60 ℃.
8. An Yb as claimed in claim 5 or 63+A method for preparing a doped giant dielectric constant low loss ceramic, characterized in that the molding is: weighing the pre-sintered powder, adding 2 wt% of PVA adhesive with the same mass for granulation, ageing the particles with the particle size between 60 meshes and 100 meshes for 24 hours, and then dry-pressing the particles into cylindrical green bodies with the diameter of 12mm and the thickness of 2mm by using a powder tablet machine under the pressure of 10 MPa.
9. An Yb as claimed in claim 5 or 63+The preparation method of the doped giant dielectric constant low-loss ceramic is characterized in that the binder removal is: and (3) placing the molded green body into a muffle furnace, heating to 150 ℃ from room temperature at a heating rate of 6.5 ℃/min, heating to 350 ℃ at a heating rate of 10 ℃/3min, heating to 600 ℃ at a heating rate of 0.5 ℃/min, preserving heat for 1h, then cooling to 370 ℃ at a cooling rate of 1 ℃/min, and finally cooling along with the furnace.
CN202110811666.5A 2021-07-19 2021-07-19 Yb (Yb)3+Doped giant dielectric constant low-loss ceramic and preparation method thereof Pending CN113620702A (en)

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