CN108689708B - Bismuth-doped copper titanium tantalate giant dielectric ceramic material and preparation method thereof - Google Patents
Bismuth-doped copper titanium tantalate giant dielectric ceramic material and preparation method thereof Download PDFInfo
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 33
- IUYOGGFTLHZHEG-UHFFFAOYSA-N copper titanium Chemical compound [Ti].[Cu] IUYOGGFTLHZHEG-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000010949 copper Substances 0.000 claims abstract description 18
- 238000005245 sintering Methods 0.000 claims abstract description 16
- 239000010936 titanium Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 3
- 238000000227 grinding Methods 0.000 claims description 61
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 46
- 239000002994 raw material Substances 0.000 claims description 36
- 238000000498 ball milling Methods 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 25
- 239000011268 mixed slurry Substances 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 20
- 239000000919 ceramic Substances 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 15
- 229910052709 silver Inorganic materials 0.000 claims description 15
- 239000004332 silver Substances 0.000 claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000007873 sieving Methods 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 10
- 238000005498 polishing Methods 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- 239000004570 mortar (masonry) Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 239000012798 spherical particle Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 238000000265 homogenisation Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 2
- 239000003990 capacitor Substances 0.000 abstract description 3
- 238000013500 data storage Methods 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 244000137852 Petrea volubilis Species 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
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Abstract
The invention relates to a bismuth-doped copper titanium tantalate giant dielectric ceramic material, which has the chemical composition conforming to the general formula: bi2x/3Cu3‑ xTa2Ti2O12Wherein, the value range of x is 0<x is less than or equal to 1, and the preferable value of x is 0.5. The preparation method can be used for preparing the high-dielectric solid capacitor and the data storage, and has the advantages of low sintering temperature, simple preparation process, high dielectric constant, good temperature stability and the like.
Description
Technical Field
The invention belongs to the technical field of ceramic materials, and relates to a bismuth-doped copper titanium tantalate giant dielectric ceramic material and a preparation method thereof.
Background
The giant dielectric material is an electronic material with wide application, and can be prepared into electronic devices such as filters, oscillators, memories, phase converters and the like. Perovskite-like structure AB3C4O12The ceramic material has high dielectric constant in a wide frequency range (100-100 kHz) at room temperature (25 ℃), has stable dielectric properties in a certain temperature range (20-400 ℃), and is of great interest. There are findings for AB3C4O12Ceramic material of the type whose dielectric properties are mainly determined by three factors: the giant dielectric property source of the C bit element bonding type, the B bit element quantity and the A bit element type mainly comprises two parts: (1) internal barrier effect (IBLC) of the material microstructure, but does not explain the giant dielectric origin of the single crystal; (2) the polarization effect of carriers in the material, but the critical polarized ion species and the space-occupying mechanism are still unclear. The inventors' group produced perovskite-like (AB) in a preliminary study3C4O12Type) structure Cu3Ta2Ti2O12The ceramic material is a ceramic material, and the dielectric constant of the ceramic material is relatively low and the temperature stability is not high through experiments; by regulating the C bit element bonding type and changing the Ta/Ti ratio, the dielectric constant is obviously improved, but the loss is increased, and the effect is not ideal enough.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the bismuth-doped titanium copper tantalate giant dielectric ceramic material and the preparation method thereof, which can be used for preparing high-dielectric solid capacitors and data storages and have the advantages of low sintering temperature, simple preparation process, high dielectric constant, good temperature stability and the like.
The technical scheme adopted by the invention for solving the technical problems is as follows: a bismuth-doped copper titanium tantalate giant dielectric ceramic material has a chemical composition conforming to the general formula: bi2x/3Cu3-xTa2Ti2O12Wherein, the value range of x is 0<x is less than or equal to 1, and the preferable value of x is 0.5.
A preparation method of a bismuth-doped copper titanium tantalate giant dielectric ceramic material comprises the following preparation steps:
(1) raw material weighing and proportioning
According to the formula Bi2x/3Cu3-xTa2Ti2O12Wherein 0 is<x is less than or equal to 1, and the raw material Bi is accurately weighed according to the stoichiometry2O3、CuO、TiO2、Ta2O5Mixing, namely filling the raw material mixture into a polytetrafluoroethylene tank;
(2) ball milling and drying
Uniformly mixing the raw materials selected in the step (1) to form a raw material mixture, taking zirconia grinding balls and absolute ethyl alcohol as grinding media, wherein the mass ratio of the raw material mixture to the zirconia grinding balls to the absolute ethyl alcohol is 1:3: 1.2-1.5, performing ball milling for 8-12 hours, sorting out the zirconia grinding balls, and drying the mixed slurry subjected to ball milling in a drying oven at the temperature of 60-110 ℃ for 12-20 hours;
(3) pre-firing
Fully grinding the mixed raw materials dried in the step (2), sieving the ground raw materials by a 100-mesh sieve, placing the ground raw materials into an alumina circular crucible, covering the alumina circular crucible, placing the alumina circular crucible into a muffle furnace for presintering for 3 to 8 hours at 900 to 950 ℃, and naturally cooling the crucible to room temperature;
(4) secondary ball milling granulation
Grinding the powder block subjected to pre-sintering in the step (3) and sieving with a 100-mesh sieve, filling the powder block into a polytetrafluoroethylene tank, taking zirconium oxide grinding balls and absolute ethyl alcohol as grinding media, continuously carrying out ball milling on the ball mill for 2-4 hours, separating the zirconium oxide grinding balls, putting mixed slurry subjected to ball milling into a drying oven, drying the mixed slurry at 70-100 ℃ for 4-8 hours, grinding the mixed slurry and putting the mixed slurry into an agate mortar, dropwise adding a polyvinyl alcohol aqueous solution with the mass fraction of 6% and the mass percentage of 20-30%, fully stirring and grinding the mixed slurry, sieving with a 120-mesh sieve, preparing spherical particles, bagging and sealing the particles for homogenization;
(5) tabletting
Placing the homogenized powder into a stainless steel grinding tool with the diameter of 10mm, and pressing the powder into a cylindrical green body under the pressure of 100-120 MPa;
(6) binder removal sintering
Placing the cylindrical green body in an alumina boat-type crucible, heating to 600 ℃ at a heating rate of 2-3 ℃/min, preserving heat for 1-3 hours, heating to 980-1040 ℃ at a heating rate of 4-6 ℃/min, sintering for 4-12 hours, cooling to 600 ℃ at a cooling rate of 3 ℃/min, and naturally cooling to room temperature along with a furnace;
(7) silver electrode coating
And (3) sequentially polishing the sintered ceramic surface by using 1000-mesh and 2000-mesh abrasive paper, polishing to a thickness of 0.6-0.8 mm, washing for 15 minutes by using ultrasonic waves, wiping by using alcohol, coating silver paste on the upper surface and the lower surface of the ceramic, placing the ceramic in a resistance furnace, preserving the heat for 40 minutes at 550 ℃, naturally cooling to room temperature to form a silver electrode, and preparing the bismuth-doped copper titanium tantalate giant dielectric ceramic material.
Bi selected in the step (1)2O3Has a purity of 99.5%, CuO and Ta2O5All with a purity of 99%, TiO2The purity of (2) was 99.99%.
The invention has the positive effects that: the prepared ceramic material has the characteristics of low sintering temperature, simple preparation process, excellent dielectric property and the like. When the value of x is 0.5, under the room temperature condition of 100-100 kHz test frequency, the dielectric constant is high (> 19000), the dielectric loss is low, and the dielectric frequency stability range is wide; the dielectric constant of the high-dielectric-constant-temperature-resistant material is good in stability within the temperature range of-70-250 ℃ at 1kHz, and the high-dielectric-constant-temperature-resistant material can be used for preparing a high-dielectric-constant solid capacitor and a data storage.
Drawings
FIG. 1 is an XRD pattern of copper tantalate titanate giant dielectric ceramic materials with different Bi contents.
FIG. 2 is a graph showing the dielectric constant and dielectric loss of the copper titanium tantalate giant dielectric ceramic material at 1kHz as a function of the Bi content.
FIG. 3 is a graph showing the change of dielectric constant of Bi1/6Cu2.75Ta2Ti2O12 dielectric ceramic material with temperature.
FIG. 4 is a graph showing the change of dielectric constant of the Bi1/3Cu2.5Ta2Ti2O12 dielectric ceramic material with temperature.
FIG. 5 is a graph showing the change of dielectric constant with temperature of a Bi2/3Cu2Ta2Ti2O12 dielectric ceramic material.
Detailed Description
The invention is further explained below with reference to the drawings and the embodiments.
Example 1
Preparation of Bi of the general formula1/6Cu2.75Ta2Ti2O12The giant dielectric ceramic material comprises the following raw materials in parts by weight:
(1) raw material weighing and proportioning
According to Bi1/6Cu2.75Ta2Ti2O12Accurately weighing raw material Bi in stoichiometric mode2O30.3883g、CuO2.1876g、TiO21.5976g、Ta2O54.4189g, and the raw material mixture was charged into a polytetrafluoroethylene can, in which Bi was contained2O3Has a purity of 99.5%, CuO and Ta2O5All with a purity of 99%, TiO2The purity of (2) is 99.99%;
(2) ball milling and drying
The raw materials are uniformly mixed, and zirconia grinding balls and absolute ethyl alcohol are used as grinding media, wherein the mass ratio of the zirconia grinding balls to the absolute ethyl alcohol is 1:3:1.4, and the mass ratio of the zirconia grinding balls to the absolute ethyl alcohol is 25.78g and 12.02 g. Ball milling for 10 hours, separating out zirconia grinding balls, and drying the mixed slurry after ball milling in a drying oven at 80 ℃ for 15 hours;
(3) pre-firing
Placing the mixed raw materials which are ground and sieved by a 100-mesh sieve into an alumina circular crucible, covering the alumina circular crucible, placing the alumina circular crucible into a muffle furnace for presintering for 6 hours at 950 ℃, and naturally cooling to room temperature along with the furnace;
(4) secondary ball milling granulation
Grinding the pre-sintered powder blocks, sieving the powder blocks by a 100-mesh sieve, loading the powder blocks into a polytetrafluoroethylene tank, continuously carrying out ball milling on the powder blocks for 4 hours on a ball mill by taking zirconia grinding balls and absolute ethyl alcohol as grinding media, separating the zirconia grinding balls, drying the mixed slurry subjected to ball milling in a drying oven for 6 hours at 90 ℃, placing the mixed slurry into an agate mortar after grinding, dropwise adding 2.24g of polyvinyl alcohol aqueous solution with the mass fraction of 6%, fully stirring and grinding the mixed slurry, sieving the mixed slurry by a 120-mesh sieve to prepare spherical particles, bagging, sealing and homogenizing the particles;
(5) tabletting
Putting the granulated powder into a stainless steel grinding tool with the diameter of 10mm, and pressing the granulated powder into a cylindrical green body by using the pressure of 120 MPa;
(6) binder removal sintering
Placing the cylindrical green body in an alumina boat-shaped crucible, heating to 600 ℃ at the speed of 2 ℃/min, preserving heat for 1 hour, heating to 1000 ℃ at the heating rate of 6 ℃/min, sintering for 8 hours, cooling to 600 ℃ at the cooling rate of 3 ℃/min, and naturally cooling to room temperature along with the furnace;
(7) silver electrode coating
And (3) sequentially polishing the sintered ceramic surface by using 1000-2000-mesh sand paper, polishing to a thickness of 0.6-0.8 mm, washing for 15 minutes by using ultrasonic waves, wiping by using alcohol, coating silver paste on the upper surface and the lower surface of the ceramic, placing the ceramic in a resistance furnace, preserving the heat for 40 minutes at 550 ℃, naturally cooling to room temperature to form a silver electrode, and preparing the bismuth-doped copper titanium tantalate giant dielectric ceramic material.
Example 2
Preparation of Bi of the general formula1/3Cu2.5Ta2Ti2O12The giant dielectric ceramic material comprises the following raw materials in parts by weight:
(1) raw material weighing and proportioning
According to Bi1/3Cu2.5Ta2Ti2O12Accurately weighing raw material Bi in stoichiometric mode2O30.7766g、CuO1.9888g、TiO21.5976g、Ta2O54.4189g, and the raw material mixture was charged into a polytetrafluoroethylene can, in which Bi was contained2O3Has a purity of 99.5%, CuO and Ta2O5All with a purity of 99%, TiO2The purity of (2) is 99.99%;
(2) ball milling and drying
Uniformly mixing the raw materials, taking zirconia grinding balls and absolute ethyl alcohol as grinding media, wherein the mass ratio of the zirconia grinding balls to the absolute ethyl alcohol is 1:3:1.2, grinding for 8 hours, sorting out the zirconia grinding balls, and drying the mixed slurry subjected to ball grinding in a drying oven at 80 ℃ for 12 hours;
(3) pre-firing
Placing the mixed raw materials which are ground and sieved by a 100-mesh sieve into an alumina circular crucible, covering the alumina circular crucible, placing the alumina circular crucible into a muffle furnace for presintering for 4 hours at 950 ℃, and naturally cooling to room temperature along with the furnace;
(4) secondary ball milling granulation
Grinding the pre-sintered powder blocks, sieving the powder blocks by a 100-mesh sieve, loading the powder blocks into a polytetrafluoroethylene tank, continuously carrying out ball milling on the powder blocks for 2 hours on a ball mill by taking zirconia grinding balls and absolute ethyl alcohol as grinding media, separating the zirconia grinding balls, drying the mixed slurry subjected to ball milling in a drying oven at 80 ℃ for 6 hours, grinding the mixed slurry, placing the mixed slurry into an agate mortar, dropwise adding 1.76g of polyvinyl alcohol aqueous solution with the mass fraction of 6%, fully stirring and grinding the mixed slurry, sieving the mixed slurry by a 120-mesh sieve to prepare spherical particles, bagging the particles, sealing and homogenizing the particles;
(5) tabletting
Putting the granulated powder into a stainless steel grinding tool with the diameter of 10mm, and pressing the granulated powder into a cylindrical green body by using the pressure of 120 MPa;
(6) binder removal sintering
Placing the cylindrical green body in an alumina boat-shaped crucible, heating to 600 ℃ at a rate of 3 ℃/min, preserving heat for 1 hour, heating to 1000 ℃ at a heating rate of 4 ℃/min, sintering for 6 hours, cooling to 600 ℃ at a cooling rate of 3 ℃/min, and naturally cooling to room temperature along with the furnace;
(7) silver electrode coating
And (3) sequentially polishing the sintered ceramic surface by using 1000-2000-mesh sand paper, polishing to a thickness of 0.6-0.8 mm, washing for 15 minutes by using ultrasonic waves, wiping by using alcohol, coating silver paste on the upper surface and the lower surface of the ceramic, placing the ceramic in a resistance furnace, preserving the heat for 40 minutes at 550 ℃, naturally cooling to room temperature to form a silver electrode, and preparing the bismuth-doped copper titanium tantalate giant dielectric ceramic material.
Example 3
Preparation of Bi of the general formula2/3Cu2Ta2Ti2O12The giant dielectric ceramic material comprises the following raw materials in parts by weight:
(1) raw material weighing and proportioning
According to Bi2/3Cu2Ta2Ti2O12Accurately weighing raw material Bi in stoichiometric mode2O31.5532g、CuO1.5910g、TiO21.5976g、Ta2O54.4189g, and the raw material mixture was charged into a polytetrafluoroethylene can, in which Bi was contained2O3Has a purity of 99.5%, CuO and Ta2O5All with a purity of 99%, TiO2The purity of (2) is 99.99%;
(2) ball milling and drying
Uniformly mixing the raw materials, and taking a zirconia grinding ball and absolute ethyl alcohol as grinding media, wherein the mass ratio of the zirconia grinding ball to the absolute ethyl alcohol is 1:3:1.5, and the mass ratio of the zirconia grinding ball to the absolute ethyl alcohol is 27.48g and 13.74 g. Ball milling for 12 hours, separating out zirconia grinding balls, and drying the mixed slurry after ball milling in a drying oven at 100 ℃ for 18 hours;
(3) pre-firing
Placing the mixed raw materials which are ground and sieved by a 100-mesh sieve into an alumina circular crucible, covering the alumina circular crucible, placing the alumina circular crucible into a muffle furnace for presintering for 8 hours at 900 ℃, and naturally cooling to room temperature along with the furnace;
(4) secondary ball milling granulation
Grinding the pre-sintered powder blocks, sieving with a 100-mesh sieve, loading into a polytetrafluoroethylene tank, continuously ball-milling for 4 hours on a ball mill by using zirconia grinding balls and absolute ethyl alcohol as grinding media, separating out the zirconia grinding balls, drying the mixed slurry after ball milling in a drying oven at 100 ℃ for 8 hours, grinding, placing in an agate mortar, dropwise adding 2.75g of polyvinyl alcohol aqueous solution with the mass fraction of 6%, fully stirring and grinding, sieving with a 120-mesh sieve, preparing into spherical particles, bagging, sealing and homogenizing;
(5) tabletting
The granulated powder was put into a stainless steel mold having a diameter of 10mm, and pressed into a cylindrical green compact under a pressure of 120 MPa.
(6) Binder removal sintering
Placing the cylindrical green body in an alumina boat-shaped crucible, heating to 600 ℃ at the speed of 2 ℃/min, preserving heat for 2.5 hours, heating to 1040 ℃ at the heating rate of 5 ℃/min, sintering for 10 hours, cooling to 600 ℃ at the cooling rate of 3 ℃/min, and naturally cooling to room temperature along with the furnace;
(7) silver electrode coating
Sequentially grinding the sintered ceramic surface by using 1000-2000-mesh abrasive paper, polishing to a thickness of 0.6-0.8 mm, washing for 15 minutes by using ultrasonic waves, wiping by using alcohol, coating silver paste on the upper surface and the lower surface of the ceramic, placing the ceramic in a resistance furnace, preserving heat for 40 minutes at 550 ℃, naturally cooling to room temperature to form a silver electrode, and preparing the bismuth-doped copper titanium tantalate giant dielectric ceramic material;
then the dielectric property of the prepared bismuth-doped copper titanium tantalate giant dielectric ceramic material is tested, and the specific test is carried out
The situation is as follows:
testing an instrument: x-ray diffractometer model D8 ADVANCE manufactured by Bruker, Germany; a broadband dielectric temperature spectrometer, model Concept80, manufactured by Novocontrol, Germany.
After testing, the results obtained were:
(1) from FIG. 1, it can be seen that the ceramic materials obtained all exhibited main diffraction peaks of perovskite structure phase when sintered at 1040 ℃.
(2) As can be seen from FIG. 2, Bi was found to be present at 1040 ℃ sintering under 1kHz test1/3Cu2.5Ta2Ti2O12The ceramic has the highest dielectric properties and the lowest dielectric losses.
FIGS. 3 to 5 show Bi2x/3Cu3-xTa2Ti2O12(x =0.25, 0.5, 1) graph of dielectric constant versus temperature for the giant dielectric ceramic material at different frequencies. As can be seen, Bi is present at 1kHz1/3Cu2.5Ta2Ti2O12The giant dielectric ceramic has a dielectric constant with good temperature stability within the range of-70 to 250 ℃.
Claims (3)
1. A bismuth-doped copper titanium tantalate giant dielectric ceramic material is characterized in that the chemical composition conforms to the general formula: bi2x/3Cu3- xTa2Ti2O12Wherein, the value range of x is 0<x≤1。
2. A method for preparing the bismuth-doped copper titanotatate giant dielectric ceramic material as claimed in claim 1, characterized in that the preparation steps are:
(1) raw material weighing and proportioning
According to the formula Bi2x/3Cu3-xTa2Ti2O12Wherein 0 is<x is less than or equal to 1, and the raw material Bi is accurately weighed according to the stoichiometry2O3、CuO、TiO2、Ta2O5Mixing, namely filling the raw material mixture into a polytetrafluoroethylene tank;
(2) ball milling and drying
Uniformly mixing the raw materials selected in the step (1) to form a raw material mixture, taking zirconia grinding balls and absolute ethyl alcohol as grinding media, wherein the mass ratio of the raw material mixture to the zirconia grinding balls to the absolute ethyl alcohol is 1:3: 1.2-1.5, performing ball milling for 8-12 hours, sorting out the zirconia grinding balls, and drying the mixed slurry subjected to ball milling in a drying oven at the temperature of 60-110 ℃ for 12-20 hours;
(3) pre-firing
Fully grinding the mixed raw materials dried in the step (2), sieving the ground raw materials by a 100-mesh sieve, placing the ground raw materials into an alumina circular crucible, covering the alumina circular crucible, placing the alumina circular crucible into a muffle furnace for presintering for 3 to 8 hours at 900 to 950 ℃, and naturally cooling the crucible to room temperature;
(4) secondary ball milling granulation
Grinding the powder block subjected to pre-sintering in the step (3) and sieving with a 100-mesh sieve, filling the powder block into a polytetrafluoroethylene tank, taking zirconium oxide grinding balls and absolute ethyl alcohol as grinding media, continuously carrying out ball milling on the ball mill for 2-4 hours, separating the zirconium oxide grinding balls, putting mixed slurry subjected to ball milling into a drying oven, drying the mixed slurry at 70-100 ℃ for 4-8 hours, grinding the mixed slurry and putting the mixed slurry into an agate mortar, dropwise adding a polyvinyl alcohol aqueous solution with the mass fraction of 6% and the mass percentage of 20-30%, fully stirring and grinding the mixed slurry, sieving with a 120-mesh sieve, preparing spherical particles, bagging and sealing the particles for homogenization;
(5) tabletting
Placing the homogenized powder into a stainless steel grinding tool with the diameter of 10mm, and pressing the powder into a cylindrical green body under the pressure of 100-120 MPa;
(6) binder removal sintering
Placing the cylindrical green body in an alumina boat-type crucible, heating to 600 ℃ at a heating rate of 2-3 ℃/min, preserving heat for 1-3 hours, heating to 980-1040 ℃ at a heating rate of 4-6 ℃/min, sintering for 4-12 hours, cooling to 600 ℃ at a cooling rate of 3 ℃/min, and naturally cooling to room temperature along with a furnace;
(7) silver electrode coating
And (3) sequentially polishing the sintered ceramic surface by using 1000-mesh and 2000-mesh abrasive paper, polishing to a thickness of 0.6-0.8 mm, washing for 15 minutes by using ultrasonic waves, wiping by using alcohol, coating silver paste on the upper surface and the lower surface of the ceramic, placing the ceramic in a resistance furnace, preserving the heat for 40 minutes at 550 ℃, naturally cooling to room temperature to form a silver electrode, and preparing the bismuth-doped copper titanium tantalate giant dielectric ceramic material.
3. The method of preparing a bismuth-doped copper titantantalate giant dielectric ceramic material of claim 2, wherein: bi selected in the step (1)2O3Has a purity of 99.5%, CuO and Ta2O5All with a purity of 99%, TiO2The purity of (2) was 99.99%.
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