CN113264763A - Wide-temperature-stability barium titanate-based dielectric ceramic material and preparation method thereof - Google Patents
Wide-temperature-stability barium titanate-based dielectric ceramic material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of ceramic materials, and discloses a wide-temperature-stable barium titanate-based dielectric ceramic material and a preparation method thereof, wherein the chemical formula of the ceramic material is 0.9BaTiO3‑0.1Bi(ZnxMg0.5‑ xY0.5)O0.275X is more than or equal to 0.1 and less than or equal to 0.3; the preparation method comprises mixing BaTiO3、Bi2O3、ZnO、MgO、Y2O3Mixing and ball milling are carried out after the materials are mixed; drying and sieving the raw materials obtained after ball milling, presintering for 2 hours at 900 ℃, and mixing and ball milling the presintered powder; and drying and sieving the raw materials obtained after ball milling, adding a binder into the obtained powder for granulation, sieving and pressing the powder into a blank, sintering the blank at 1250 ℃, and preserving heat for 2 hours to obtain a final sample. The invention passes through donor ions Bi3+Substituted in the A position with an acceptor ion Mg2+SubstitutionB site, generating defect dipole to restrict the migration of free carriers in crystal grains, thereby achieving the purpose of improving the dielectric property of the material; meanwhile, the core-shell distribution of the crystal grains is influenced by different diffusion rates of ions in the crystal grains, the temperature change curve is smoothed, and the wide temperature stability of the material is realized.
Description
Technical Field
The invention belongs to the technical field of ceramic materials, and particularly relates to a barium titanate-based dielectric ceramic material and a preparation method thereof.
Technical Field
The rapid development of 5G communication technology and automotive electronics has increasingly demanded ceramic capacitor products with small size, large capacity and wide temperature stability. The temperature stable dielectric material has the excellent characteristics of high dielectric constant and wide working temperature range, and can be used for preparing a temperature stable capacitor.
With the development of electronic components, the working temperature range of the temperature-stable dielectric material needs to be extended continuously. For example, the temperature of the working environment of a control unit in an automobile engine is far beyond 125 ℃, and the capacitor devices applied to the fields of national defense and military industry, oil exploration, aerospace and the like need to adapt to more extreme environmental temperature. Therefore, the temperature-stable dielectric material needs to be developed in a wider operating temperature range while ensuring high dielectric constant and high stability.
Disclosure of Invention
The invention provides a barium titanate-based dielectric ceramic material with wide temperature stability and a preparation method thereof, and aims to solve the problem of BaTiO3Related technical problem of base dielectric materials, by donor ions Bi3+Substituted in the A position with an acceptor ion Mg2+The B site is replaced, and a defect dipole is generated to restrict the migration of free carriers in the crystal grains, so that the purpose of improving the dielectric property of the material is achieved; meanwhile, the core-shell distribution of the crystal grains is influenced by different diffusion rates of ions in the crystal grains, the temperature change curve is smoothed, and the wide temperature stability of the material is realized.
The invention is realized by the following technical scheme:
according to one aspect of the invention, the barium titanate-based dielectric ceramic material with wide temperature stability is characterized in that the chemical formula is 0.9BaTiO3-0.1Bi(ZnxMg0.5-xY0.5)O0.275，0.1≤x≤0.3。
According to another aspect of the present invention, there is provided the above broad temperature stable BaTiO3The preparation method of the base dielectric ceramic material is characterized by comprising the following steps of:
(1) mixing BaTiO3、Bi2O3、ZnO、MgO、Y2O3In a stoichiometric ratio of 0.9BaTiO3-0.1Bi(ZnxMg0.5-xY0.5)O0.275X is more than or equal to 0.1 and less than or equal to 0.3; mixing the ingredients and ball-milling;
(2) performing infrared drying and screening on the raw materials obtained after ball milling in the step (1) to obtain powder with uniform particles;
(3) pre-burning the powder obtained in the step (2) at 900 ℃ for 2 h;
(4) mixing the powder subjected to the pre-sintering in the step (3) for secondary ball milling;
(5) performing infrared drying and sieving on the raw materials obtained after the mixing and ball milling in the step (4) to obtain powder with uniform particles;
(6) adding a binder into the powder obtained in the step (5), granulating, sieving and pressing into a blank;
(7) and sintering the blank at 1250 ℃, and preserving heat for 2 hours to obtain a final sample.
Further, in the step (1) and the step (4), deionized water, zirconium balls and powder are mixed and ball-milled according to the mass ratio of 2:1: 1.
Further, the ball milling time in the step (1) and the step (4) is 4 h.
Further, the drying temperature in the step (2) and the step (5) is 80-120 ℃.
Further, the sieving in the step (2) and the step (5) is 40-mesh sieving.
Further, the temperature rise curve of the pre-firing in the step (2) is to raise the temperature to 900 ℃ at 5 ℃/min.
Further, the binder in the step (6) was 7 wt% paraffin wax.
Further, the sieving in the step (6) is 80-mesh sieving.
Further, the temperature rise curve of the sintering in the step (7) is room temperature → 200 ℃, heat preservation 60min → 550 ℃, heat preservation 150min → 1250 ℃, heat preservation 233min → 1250 ℃, heat preservation 120min → 300 ℃, heat preservation 233min
The invention has the beneficial effects that:
the invention prepares a barium titanate-based dielectric material for a wide temperature stable capacitor by a simple solid phase synthesis methodAfter doping ions into the barium titanate system, Mg2+Ti substituted for barium titanate lattice4+And Bi3+Ba substituted for barium titanate lattice2+Synthesizing a defective dipole to generate short-range hopping polarization and inhibit the long-range migration of carriers; meanwhile, the proportion of the crystal grain core-shell structure is changed, the volume ratio of the crystal grain shell is increased, the dielectric temperature curve of the material in a low-temperature area is gradually gentle, and the low-temperature application prospect of the capacitor is enlarged. The sample has better comprehensive performance: dielectric constant ε25℃More than 1000, and the temperature tolerance change rate of the material is within +/-15% within-55-145 ℃, thereby realizing the wide temperature stability characteristic.
Detailed Description
The invention is described in further detail below by means of specific examples and comparative examples:
example 1
Firstly, BaTiO is mixed3、Bi2O3、MgO、Y2O3In a stoichiometric ratio of 0.9BaTiO3-0.1Bi(ZnxMg0.5-xY0.5)O0.275(x is 0), and mixing the following materials in percentage by mass with deionized water: zirconium ball: after the powder materials are mixed in a ratio of 2:1:1, a planetary ball mill is adopted for ball milling for 4 hours, and the rotating speed of the ball mill is 400 r/m; putting the ball-milled raw materials into an infrared oven, drying at 80-120 ℃, and sieving with a 40-mesh sieve; drying and sieving the powder, putting the dried and sieved powder into a sintering furnace, pre-sintering the powder for 2 hours at the temperature rising rate of 5 ℃/min to 900 ℃, and synthesizing the main crystalline phase of the system; the pre-sintered powder is prepared by the following steps of (1) deionized water: zirconium ball: after the powder materials are mixed in a ratio of 2:1:1, a planetary ball mill is adopted for ball milling for 4 hours, and the rotating speed of the ball mill is 400 r/m; putting the ball-milled raw materials into an infrared oven, drying at 80-120 ℃, and sieving with a 40-mesh sieve; adding paraffin with the mass percent of 7%, and sieving by a 80-mesh sieve sample separating sieve for granulation;
the granulated powder is pressed into a disc green body with phi 10 multiplied by 1mm under 4MPa, and the disc green body is sintered in a sintering furnace according to a sintering curve of room temperature → 200 ℃ (1h) → 550 ℃ (150min) → 1250 ℃ (233min) → 1250 ℃ (120min) → 300 ℃ (233min), so as to obtain the wide temperature stable capacitor dielectric material.
And uniformly coating silver paste on the upper surface and the lower surface of the obtained product, and preparing an electrode by sintering and infiltrating at 840 ℃ to obtain a sample to be detected. The obtained samples were tested for capacity temperature change rate by an LCR digital bridge and a high-low temperature circulating incubator, and the results are shown in Table 1.
TABLE 1
Example 2
First, BaTiO3、Bi2O3、ZnO、MgO、Y2O3In a stoichiometric ratio of 0.9BaTiO3-0.1Bi(ZnxMg0.5-xY0.5)O0.275(x is 0.1), and mixing the following materials in percentage by mass with deionized water: zirconium ball: after the powder materials are mixed in a ratio of 2:1:1, a planetary ball mill is adopted for ball milling for 4 hours, and the rotating speed of the ball mill is 400 r/m; putting the ball-milled raw materials into an infrared oven, drying at 80-120 ℃, and sieving with a 40-mesh sieve; drying and sieving the powder, putting the dried and sieved powder into a sintering furnace, pre-sintering the powder for 2 hours at the temperature rising rate of 5 ℃/min to 900 ℃, and synthesizing the main crystalline phase of the system; the pre-sintered powder is prepared by the following steps of (1) deionized water: zirconium ball: after the powder materials are mixed in a ratio of 2:1:1, a planetary ball mill is adopted for ball milling for 4 hours, and the rotating speed of the ball mill is 400 r/m; putting the ball-milled raw materials into an infrared oven, drying at 80-120 ℃, and sieving with a 40-mesh sieve; adding paraffin with the mass percent of 7%, and sieving by a 80-mesh sieve sample separating sieve for granulation;
the granulated powder is pressed into a disc green body with phi 10 multiplied by 1mm under 4MPa, and the disc green body is sintered in a sintering furnace according to a sintering curve of room temperature → 200 ℃ (1h) → 550 ℃ (150min) → 1250 ℃ (233min) → 1250 ℃ (120min) → 300 ℃ (233min), so as to obtain the wide temperature stable capacitor dielectric material.
And uniformly coating silver paste on the upper surface and the lower surface of the obtained product, and preparing an electrode by sintering and infiltrating at 840 ℃ to obtain a sample to be detected. The obtained samples were tested for capacity temperature change rate by an LCR digital bridge and a high-low temperature circulating incubator, and the results are shown in Table 2.
TABLE 2
Example 3
First, BaTiO3、Bi2O3、ZnO、MgO、Y2O3In a stoichiometric ratio of 0.9BaTiO3-0.1Bi(ZnxMg0.5-xY0.5)O0.275(x is 0.2), and mixing the following materials in percentage by mass with deionized water: zirconium ball: after the powder materials are mixed in a ratio of 2:1:1, a planetary ball mill is adopted for ball milling for 4 hours, and the rotating speed of the ball mill is 400 r/m; putting the ball-milled raw materials into an infrared oven, drying at 80-120 ℃, and sieving with a 40-mesh sieve; drying and sieving the powder, putting the dried and sieved powder into a sintering furnace, pre-sintering the powder for 2 hours at the temperature rising rate of 5 ℃/min to 900 ℃, and synthesizing the main crystalline phase of the system; the pre-sintered powder is prepared by the following steps of (1) deionized water: zirconium ball: after the powder materials are mixed in a ratio of 2:1:1, a planetary ball mill is adopted for ball milling for 4 hours, and the rotating speed of the ball mill is 400 r/m; putting the ball-milled raw materials into an infrared oven, drying at 80-120 ℃, and sieving with a 40-mesh sieve; adding paraffin with the mass percent of 7%, and sieving by a 80-mesh sieve sample separating sieve for granulation;
the granulated powder is pressed into a disc green body with phi 10 multiplied by 1mm under 4MPa, and the disc green body is sintered in a sintering furnace according to a sintering curve of room temperature → 200 ℃ (1h) → 550 ℃ (150min) → 1250 ℃ (233min) → 1250 ℃ (120min) → 300 ℃ (233min), so as to obtain the wide temperature stable capacitor dielectric material.
And uniformly coating silver paste on the upper surface and the lower surface of the obtained product, and preparing an electrode by sintering and infiltrating at 840 ℃ to obtain a sample to be detected. The obtained samples were tested for capacity temperature change rate by an LCR digital bridge and a high-low temperature circulating incubator, and the results are shown in Table 3.
TABLE 3
Example 4
First, BaTiO3、Bi2O3、ZnO、MgO、Y2O3In stoichiometric ratio0.9BaTiO3-0.1Bi(ZnxMg0.5-xY0.5)O0.275(x is 0.3), and mixing the following materials in percentage by mass with deionized water: zirconium ball: after the powder materials are mixed in a ratio of 2:1:1, a planetary ball mill is adopted for ball milling for 4 hours, and the rotating speed of the ball mill is 400 r/m; putting the ball-milled raw materials into an infrared oven, drying at 80-120 ℃, and sieving with a 40-mesh sieve; drying and sieving the powder, putting the dried and sieved powder into a sintering furnace, pre-sintering the powder for 2 hours at the temperature rising rate of 5 ℃/min to 900 ℃, and synthesizing the main crystalline phase of the system; the pre-sintered powder is prepared by the following steps of (1) deionized water: zirconium ball: after the powder materials are mixed in a ratio of 2:1:1, a planetary ball mill is adopted for ball milling for 4 hours, and the rotating speed of the ball mill is 400 r/m; putting the ball-milled raw materials into an infrared oven, drying at 80-120 ℃, and sieving with a 40-mesh sieve; adding paraffin with the mass percent of 7%, and sieving by a 80-mesh sieve sample separating sieve for granulation;
the granulated powder is pressed into a disc green body with phi 10 multiplied by 1mm under 4MPa, and the disc green body is sintered in a sintering furnace according to a sintering curve of room temperature → 200 ℃ (1h) → 550 ℃ (150min) → 1250 ℃ (233min) → 1250 ℃ (120min) → 300 ℃ (233min), so as to obtain the wide temperature stable capacitor dielectric material.
And uniformly coating silver paste on the upper surface and the lower surface of the obtained product, and preparing an electrode by sintering and infiltrating at 840 ℃ to obtain a sample to be detected. The obtained samples were tested for capacity temperature change rate by an LCR digital bridge and a high-low temperature circulating incubator, and the results are shown in Table 4.
TABLE 4
Example 5
First, BaTiO3、Bi2O3、ZnO、MgO、Y2O3In a stoichiometric ratio of 0.9BaTiO3-0.1Bi(ZnxMg0.5-xY0.5)O0.275(x is 0.4), and mixing the following materials in percentage by mass with deionized water: zirconium ball: after the powder materials are mixed in a ratio of 2:1:1, a planetary ball mill is adopted for ball milling for 4 hours, and the rotating speed of the ball mill is 400 r/m; putting the ball-milled raw materials into an infrared oven, drying at 80-120 ℃, and passing through40 mesh sieve; drying and sieving the powder, putting the dried and sieved powder into a sintering furnace, pre-sintering the powder for 2 hours at the temperature rising rate of 5 ℃/min to 900 ℃, and synthesizing the main crystalline phase of the system; the pre-sintered powder is prepared by the following steps of (1) deionized water: zirconium ball: after the powder materials are mixed in a ratio of 2:1:1, a planetary ball mill is adopted for ball milling for 4 hours, and the rotating speed of the ball mill is 400 r/m; putting the ball-milled raw materials into an infrared oven, drying at 80-120 ℃, and sieving with a 40-mesh sieve; adding paraffin with the mass percent of 7%, and sieving by a 80-mesh sieve sample separating sieve for granulation;
the granulated powder is pressed into a disc green body with phi 10 multiplied by 1mm under 4MPa, and the disc green body is sintered in a sintering furnace according to a sintering curve of room temperature → 200 ℃ (1h) → 550 ℃ (150min) → 1250 ℃ (233min) → 1250 ℃ (120min) → 300 ℃ (233min), so as to obtain the wide temperature stable capacitor dielectric material.
And uniformly coating silver paste on the upper surface and the lower surface of the obtained product, and preparing an electrode by sintering and infiltrating at 840 ℃ to obtain a sample to be detected. The obtained samples were tested for capacity temperature change rate by an LCR digital bridge and a high-low temperature circulating incubator, and the results are shown in Table 5.
TABLE 5
Example 6
First, BaTiO3、Bi2O3、ZnO、MgO、Y2O3In a stoichiometric ratio of 0.9BaTiO3-0.1Bi(ZnxMg0.5-xY0.5)O0.275(x is 0.5), and mixing the following materials in percentage by mass with deionized water: zirconium ball: after the powder materials are mixed in a ratio of 2:1:1, a planetary ball mill is adopted for ball milling for 4 hours, and the rotating speed of the ball mill is 400 r/m; putting the ball-milled raw materials into an infrared oven, drying at 80-120 ℃, and sieving with a 40-mesh sieve; drying and sieving the powder, putting the dried and sieved powder into a sintering furnace, pre-sintering the powder for 2 hours at the temperature rising rate of 5 ℃/min to 900 ℃, and synthesizing the main crystalline phase of the system; preparation ofThe sintered powder is prepared by the following steps of (1) deionized water: zirconium ball: after the powder materials are mixed in a ratio of 2:1:1, a planetary ball mill is adopted for ball milling for 4 hours, and the rotating speed of the ball mill is 400 r/m; putting the ball-milled raw materials into an infrared oven, drying at 80-120 ℃, and sieving with a 40-mesh sieve; adding paraffin with the mass percent of 7%, and sieving by a 80-mesh sieve sample separating sieve for granulation;
the granulated powder is pressed into a disc green body with phi 10 multiplied by 1mm under 4MPa, and the disc green body is sintered in a sintering furnace according to a sintering curve of room temperature → 200 ℃ (1h) → 550 ℃ (150min) → 1250 ℃ (233min) → 1250 ℃ (120min) → 300 ℃ (233min), so as to obtain the wide temperature stable capacitor dielectric material.
And uniformly coating silver paste on the upper surface and the lower surface of the obtained product, and preparing an electrode by sintering and infiltrating at 840 ℃ to obtain a sample to be detected. The obtained samples were tested for the capacity temperature change rate by an LCR digital bridge and a high-low temperature circulating incubator, and the results are shown in Table 6.
TABLE 6
The test results show that: 0.9BaTiO obtained within the range of x is more than or equal to 0.1 and less than or equal to 0.33-0.1Bi(ZnxMg0.5- xY0.5)O0.275Dielectric ceramic material of MgO in BaTiO with low diffusivity3BaTiO used as additive for regulating shell-core structure3In the system, thereby increasing the temperature application range of the material. Meanwhile, Mg doping can also affect the diffusion of other ions, in the system, the Mg doping prevents Bi, Zn, Y and other elements from diffusing to the core layer at the same time, and a shell-core structure is formed, so that the low-temperature dielectric peak is enhanced, the high-temperature dielectric peak is weakened, and the temperature holding curve of the material is flattened and slowed. In addition, the rare earth element Y can also form a chemical non-uniform structure in the ceramic modification, and BaTiO can be effectively improved3Temperature capacity characteristic of base porcelain. Wherein the optimal value of x is 0.1.
Although the preferred embodiments of the present invention have been described, the present invention is not limited to the above-mentioned embodiments, which are only illustrative and not restrictive, and those skilled in the art can make various modifications without departing from the spirit and scope of the present invention, which falls within the protection scope of the present invention.
Claims (10)
1. The wide temperature stable barium titanate-based dielectric ceramic material is characterized in that the chemical formula is 0.9BaTiO3-0.1Bi(ZnxMg0.5-xY0.5)O0.275，0.1≤x≤0.3。
2. A method for preparing a wide temperature stable barium titanate based dielectric ceramic material as claimed in claim 1, wherein said method comprises the steps of:
(1) mixing BaTiO3、Bi2O3、ZnO、MgO、Y2O3In a stoichiometric ratio of 0.9BaTiO3-0.1Bi(ZnxMg0.5-xY0.5)O0.275X is more than or equal to 0.1 and less than or equal to 0.3; mixing the ingredients and ball-milling;
(2) performing infrared drying and screening on the raw materials obtained after ball milling in the step (1) to obtain powder with uniform particles;
(3) pre-burning the powder obtained in the step (2) at 900 ℃ for 2 h;
(4) mixing the powder subjected to the pre-sintering in the step (3) for secondary ball milling;
(5) performing infrared drying and sieving on the raw materials obtained after the mixing and ball milling in the step (4) to obtain powder with uniform particles;
(6) adding a binder into the powder obtained in the step (5), granulating, sieving and pressing into a blank;
(7) and sintering the blank at 1250 ℃, and preserving heat for 2 hours to obtain a final sample.
3. The method for preparing a barium titanate-based dielectric ceramic material with wide temperature stability according to claim 2, wherein in the step (1) and the step (4), deionized water, zirconium balls and powder are mixed and ball-milled according to a mass ratio of 2:1: 1.
4. The method for preparing a wide temperature stability type barium titanate-based dielectric ceramic material according to claim 2, wherein the ball milling time in step (1) and step (4) is 4 h.
5. The method for preparing a barium titanate-based dielectric ceramic material with wide temperature stability according to claim 2, wherein the drying temperature in the step (2) and the step (5) is 80-120 ℃.
6. The method for preparing a wide temperature stable barium titanate-based dielectric ceramic material as claimed in claim 2, wherein the sieving in step (2) and step (5) is a 40 mesh sieve.
7. The method for preparing a wide temperature stable barium titanate-based dielectric ceramic material as claimed in claim 2, wherein the pre-firing in step (2) is performed with a temperature rise profile of 5 ℃/min to 900 ℃.
8. The method for preparing a barium titanate-based dielectric ceramic material with wide temperature stability according to claim 2, wherein the binder in step (6) is 7 wt% paraffin wax.
9. The method for preparing a barium titanate-based dielectric ceramic material with wide temperature stability according to claim 2, wherein the sieving in step (6) is 80 mesh sieving.
10. The method for preparing a wide temperature stable barium titanate-based dielectric ceramic material as claimed in claim 2, wherein the temperature rise curve of the sintering in step (7) is room temperature → 200 ℃, 60min → 550 ℃, 150min → 1250 ℃, 233min → 1250 ℃, 120min → 300 ℃ and 233 min.
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