High-performance dielectric ceramic material and preparation method thereof

Abstract

The invention discloses a dielectric ceramic material with high performance, which belongs to the technical field of ceramic materials and is prepared from the following raw materials in parts by weight: 95.5810 to 99.9448 parts of BaTiO3, 0.4221 to 0.7885 parts of ZnO, 0.5567 to 1.2344 parts of CuO, 3.9105 to 4.1435 parts of BaCO3, 8.1000 to 8.8300 parts of SnO2, 3.3938 to 3.7653 parts of CaCO3, 0.0500 part of La2O3 and 0.0400 part of Li2CO3. The dielectric ceramic material is used for solving the technical problems that a dielectric ceramic material is not stable enough, the dielectric loss is relatively large and the insulation resistance is not high.

Description

Technical Field

[0001] The invention belongs to the technical field of ceramic materials, and in particular relates to a high-performance dielectric ceramic material and a preparation method thereof. Background Art

[0002] Dielectric ceramic materials, also known as dielectric ceramics or dielectric ceramics, are a type of functional ceramics that have polarization ability under the action of an electric field and can establish an electric field in the body for a long time. Dielectric ceramic materials are also a type of ceramic material that is used as a dielectric material in microwave and radio frequency circuits and performs one or more functions.

[0003] With the continuous development of electronic devices and communication technology, dielectric ceramic materials are widely used in various communication and electronic fields, resulting in an increasing demand for materials. For example, ceramic capacitors require dielectric ceramics to have advantages such as high dielectric constant, low dielectric loss, and high insulation resistance. The existing capacitor dielectric ceramics are not stable enough, have large losses, and low insulation resistance, so they cannot meet the market's requirements for comprehensive material properties. Summary of the invention

[0004] The present invention provides a high-performance dielectric ceramic material and a preparation method thereof, which are used to solve the technical problems that the existing dielectric ceramic material is not stable enough, has large dielectric loss and low insulation resistance.

[0005] In view of this, the present invention provides a high-performance dielectric ceramic material, which includes the following raw materials in parts by weight: 95.5810-99.9448 parts of BaTiO 3 , 0.4221-0.7885 parts of ZnO, 0.5567-1.2344 parts of CuO, 3.9105-4.1435 parts of BaCO 3 8.1000-8.8300 parts of SnO 2 , 3.3938-3.7653 parts of CaCO 3 , 0.0500 parts of La 2 O 3 , 0.0400 parts of Li 2 CO 3 .

[0006] A method for preparing a high-performance dielectric ceramic material comprises the following steps:

[0007] S1: adding zirconium balls and deionized water to the raw materials for primary ball milling, followed by drying, crushing, and sieving to obtain a mixed material;

[0008] S2: pre-calcining the mixed material to obtain an intermediate material;

[0009] S3: adding zirconium balls and deionized water to the intermediate material for secondary ball milling, followed by drying, crushing, sieving, and manual granulation to obtain granulated material;

[0010] S4: pressurizing the granulated material to take out the green pellet;

[0011] S5: Sintering the green body to obtain a dielectric ceramic material.

[0012] Furthermore, a method for preparing a high-performance dielectric ceramic material comprises the following steps:

[0013] S1: Add zirconium balls and deionized water to the raw materials, perform primary ball milling in a multi-axis ball mill lined with a polyurethane tank, and then dry at a temperature of 100-140° C., crush, and pass through an 80-mesh sieve to obtain a mixed material;

[0014] S2: pre-calcining the mixed material to obtain an intermediate material;

[0015] S3: Add zirconium balls and deionized water to the intermediate material, perform secondary ball milling in a multi-axis ball mill lined with a polyurethane tank, and then dry at a temperature of 100-140° C., crush, pass through an 80-mesh sieve, and granulate manually to obtain a granulated material;

[0016] S4: pressurizing the granulated material to take out the green pellet;

[0017] S5: sintering the green body to obtain a ceramic material;

[0018] The drying temperature for both times is preferably 120°C.

[0019] Optionally, the diameter of the zirconium balls used in the initial ball milling in step S1 is 6 mm, the ball milling speed is 320-360 rpm, and the ball milling time is 5-7 h.

[0020] Optionally, in step S1, the weight ratio of the raw material, zirconium balls and deionized water is 2.5:1:1.2.

[0021] Optionally, the specific steps of pre-burning in step S2 are:

[0022] S2.1: Raise the temperature from room temperature to 985-1015℃ for 8h;

[0023] S2.2: Keep at 985-1015°C for 5h;

[0024] S2.3: Cool down to room temperature at a rate of 2°C / min.

[0025] More preferably, the heating temperature is 1000°C.

[0026] Optionally, the diameter of the zirconium balls used in the secondary ball milling in step S3 is 6 mm, the ball milling speed is 320-360 rpm, and the ball milling time is 6-10 h.

[0027] Optionally, in step S3, the weight ratio of the intermediate material, zirconium balls and deionized water is 2.5:1:0.8.

[0028] Optionally, 2-6 wt % PVA of the sieved material is added during granulation in step S3.

[0029] Optionally, in step S4, the granulated material is placed into a mold with a diameter of 21 mm, and the mold groove depth is adjusted to 16-18 mm, and the pressurization pressure is 6-10 MPa.

[0030] Optionally, the specific steps of sintering in step S5 are:

[0031] S5.1: Heat from room temperature to 1235-1265℃, heating time 10h;

[0032] S5.2: Keep at 1235-1265°C for 6 hours;

[0033] S5.3: Cool down to room temperature at a rate of 1.5°C / min.

[0034] More preferably, the heating temperature is 1250°C.

[0035] It can be seen from the above technical solutions that the embodiments of the present invention have the following advantages:

[0036] 1. The dielectric ceramic material of the present application has the advantages of high dielectric constant, low dielectric loss, high insulation resistance, etc., which makes the ceramic material have better comprehensive performance and more stable performance, meeting the comprehensive performance requirements of the electronic component market for dielectric materials. The preparation process cost is low, mainly by changing the components and the content of the components, sintering temperature, holding time and heating and cooling curve, and the process has good stability.

[0037] Among them, BaTiO 3 -BaCO 3 -CaCO 3 -Li 2 CO 3 Used to realize dielectric ceramic materials with high dielectric constants, ZnO doping can effectively regulate the dielectric properties of the material; CuO, as a common sintering aid, can reduce the sintering temperature of ceramics by promoting the formation of liquid phase and improve microwave dielectric properties; SnO 2 The doping of La can adjust the dielectric constant, dielectric loss and other properties of microwave dielectric materials; 2 O 3Doping in microwave dielectric ceramics can effectively improve the dielectric properties of the material, optimize the microstructure, and thus optimize the insulation resistance. DETAILED DESCRIPTION

[0038] In order to make the technical scheme of the present invention better understood by the personnel of the technical field, the technical scheme in the embodiment of the present invention is clearly and completely described below. Obviously, the described embodiment is only a part of the embodiment of the present invention, rather than all the embodiments. Based on the embodiment in the present invention, all other embodiments obtained by ordinary technicians in the field without making creative work are within the scope of protection of the present invention. Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or can be prepared by existing methods.

[0039] Example

[0040] Example 1

[0041] A high-performance dielectric ceramic material, the raw material ratio of which is shown in Table 1.

[0042] A method for preparing a high-performance dielectric ceramic material comprises the following steps:

[0043] S1: Add zirconium balls with a diameter of 6 mm and deionized water to the raw materials, perform primary ball milling in a multi-axis ball mill lined with a polyurethane tank, the ball milling speed is 340 rpm, the ball milling time is 6 h, and then dry at a temperature of 120° C., crush, and pass through an 80-mesh sieve to obtain a mixed material;

[0044] S2: pre-sintering the mixed material, first heating it from room temperature to 1000°C for 8 hours, and keeping it at 1000°C for 5 hours, and finally cooling it to room temperature at a rate of 2°C / min to obtain an intermediate material;

[0045] S3: Add zirconium balls with a diameter of 6 mm and deionized water to the intermediate material, perform secondary ball milling in a multi-axis ball mill lined with a polyurethane tank, the ball milling speed is 340 rpm, the ball milling time is 8 hours, and then dry at a temperature of 120° C., crush, pass through an 80-mesh sieve, and then add 4 wt% of PVA to the sieved material for manual granulation to obtain a granulated material;

[0046] S4: putting the granulated material into a mold with a diameter of 21 mm, adjusting the mold groove depth to 17 mm, applying pressure of 8 MPa to take out the green billet;

[0047] S5: sintering the green body, first heating from room temperature to 1250° C., the heating time is 10 hours, and keeping at 1250° C. for 6 hours, and finally cooling to room temperature at a rate of 1.5° C. / min to obtain a dielectric ceramic material;

[0048] Among them, the weight ratio of raw materials, zirconium balls and deionized water in step S1 is 2.5:1:1.2, and the added amounts of raw materials, zirconium balls and deionized water in step S1 of this embodiment are 116.2287 grams, 46.4915 grams and 55.7898 grams respectively; the weight ratio of intermediate materials, zirconium balls and deionized water in step S3 is 2.5:1:0.8, and the added amounts of intermediate materials, zirconium balls and deionized water in step S3 of this embodiment are 116.2287 grams, 46.4915 grams and 37.1932 grams respectively.

[0049] Embodiment 2-4

[0050] A high-performance dielectric ceramic material, which differs from Example 1 in that the raw material ratio of the ceramic material is different, and the raw material ratio is shown in Table 1.

[0051] In addition, the amounts of raw material, zirconium ball, and deionized water added in step S1 of Example 2 are 117.8197 g, 47.1279 g, and 56.5536 g, respectively; the amounts of intermediate material, zirconium ball, and deionized water added in step S3 are 117.8197 g, 47.1279 g, and 37.7383 g, respectively; the amounts of raw material, zirconium ball, and deionized water added in step S1 of Example 3 are 112.4943 g, 44.9977 g, and 53.997 2 grams, the added amounts of the intermediate material, zirconium balls and deionized water in step S3 are 112.4943 grams, 44.9977 grams and 35.9982 grams respectively; the added amounts of the raw material, zirconium balls and deionized water in step S1 of Example 4 are 116.2427 grams, 46.4971 grams and 55.7965 grams respectively, and the added amounts of the intermediate material, zirconium balls and deionized water in step S3 are 116.2427 grams, 46.4971 grams and 37.1977 grams respectively.

[0052] Table 1 Weight of each raw material (g)

[0053]

[0054]

[0055] Comparative Example

[0056] Comparative Example 1-2

[0057] A high-performance dielectric ceramic material, which differs from Example 1 in that the raw material ratio of the ceramic material is different, and the raw material ratio is shown in Table 2.

[0058] Table 2 Weight of each raw material (g)

[0059] raw material Comparative Example 1 Comparative Example 2 <![CDATA[BaTiO 3 ]]> 99.3087 99.9448 ZnO 0.8000 0.0000 CuO 0.9000 0.0000 <![CDATA[BaCO 3 ]]> 4.0305 4.1435 <![CDATA[SnO 2 ]]> 10.2500 0.0000 <![CDATA[CaCO 3 ]]> 3.4361 3.7653 <![CDATA[La 2 THE 3 ]]> 0.1000 0.0000 <![CDATA[Li 2 CO 3 ]]> 0.0400 0.0400

[0060] Performance testing

[0061] The following performance tests were performed on the dielectric ceramic materials in Examples 1-4 and Comparative Examples 1-2:

[0062] Dielectric constant: The dielectric constant of ceramic materials was measured according to GB / T 23260-2009. The test results are shown in Table 3.

[0063] Dielectric loss: The dielectric loss of ceramic materials was measured according to GB / T 23260-2009. The test results are shown in Table 3.

[0064] Temperature characteristics: The temperature characteristics of ceramic materials were measured according to GB / T 23260-2009. The test results are shown in Table 3.

[0065] Insulation resistance: The insulation resistance of ceramic materials was measured according to GB / T 23260-2009. The test results are shown in Table 3.

[0066] Table 3 Test results

[0067] project Dielectric constant Dielectric loss Temperature characteristics (%) <![CDATA[Insulation resistance (×10 4 MΩ)]]> Example 1 3915 0.0002 1.5 9.9 Example 2 3931 0.0001 1.3 9.8 Example 3 4130 0.0002 1.4 9.8 Example 4 4021 0.0003 1.2 9.7 Comparative Example 1 3927 0.4 30 0.12 Comparative Example 2 3965 0.3 35 0.13

[0068] As can be seen from Table 1, the present application obtains better material performance through the synergy between the raw materials and by adjusting the formula and preparation process of the dielectric ceramic material. The preparation process cost is low. It mainly changes the components and the content of each component, the sintering temperature, the holding time and the heating and cooling curve. The process has good stability, so that the ceramic material has better comprehensive performance and more stable performance, which meets the comprehensive performance requirements of the electronic components market for dielectric materials.

[0069] Combining Example 1 and Comparative Examples 1-2, it can be seen that the addition amount of each raw material in Example 1 is more appropriate. ZnO, CuO, SnO are added to the basic raw materials of the ceramic material. 2 ,La 2 O 3 After that, the comprehensive performance of ceramic materials was further improved. Specifically, ZnO doping can effectively regulate the dielectric properties of materials; CuO, as a common sintering aid, can reduce the sintering temperature of ceramics by promoting the formation of liquid phase and improve microwave dielectric properties; SnO 2 The doping of La can adjust the dielectric constant, dielectric loss and other properties of microwave dielectric materials; 2 O 3 Doping in microwave dielectric ceramics can effectively improve the dielectric properties of the material, optimize the microstructure, and thus optimize the insulation resistance.

[0070] As described above, the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features thereof may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A high-performance dielectric ceramic material, characterized in that: It includes the following raw materials in parts by weight: 95.5810-99.9448 parts of BaTiO3, 0.4221-0.7885 parts of ZnO, 0.5567-1.2344 parts of CuO, 3.9105-4.1435 parts of BaCO3, 8.1000-8.8300 parts of SnO2, 3.3938-3.7653 parts of CaCO3, 0.0500 parts of La2O3, and 0.0400 parts of Li2CO3.

2. A method for preparing a high-performance dielectric ceramic material as claimed in claim 1, characterized in that: The steps include: S1: adding zirconium balls and deionized water to the raw materials for primary ball milling, followed by drying, crushing, and sieving to obtain a mixed material; S2: pre-calcining the mixed material to obtain an intermediate material; S3: adding zirconium balls and deionized water to the intermediate material for secondary ball milling, followed by drying, crushing, sieving, and manual granulation to obtain granulated material; S4: pressurizing the granulated material to take out the green pellet; S5: Sintering the green body to obtain a dielectric ceramic material.

3. The method for preparing a high-performance dielectric ceramic material according to claim 2, characterized in that: The diameter of the zirconium balls used in the initial ball milling in step S1 is 6 mm, the ball milling speed is 320-360 rpm, and the ball milling time is 5-7 h.

4. The method for preparing a high-performance dielectric ceramic material according to claim 2, characterized in that: In step S1, the weight ratio of the raw material, zirconium balls and deionized water is 2.5:1:1.

2.

5. The method for preparing a high-performance dielectric ceramic material according to claim 2, characterized in that: The specific steps of pre-burning in step S2 are: S2.1: Raise the temperature from room temperature to 985-1015℃ for 8h; S2.2: Keep at 985-1015°C for 5h; S2.3: Cool down to room temperature at a rate of 2°C / min.

6. The method for preparing a high-performance dielectric ceramic material according to claim 2, characterized in that: The diameter of the zirconium balls used in the secondary ball milling in step S3 is 6 mm, the ball milling speed is 320-360 rpm, and the ball milling time is 6-10 h.

7. The method for preparing a high-performance dielectric ceramic material according to claim 2, characterized in that: In step S3, the weight ratio of the intermediate material, zirconium balls and deionized water is 2.5:1:0.

8.

8. The method for preparing a high-performance dielectric ceramic material according to claim 2, characterized in that: During granulation in step S3, 2-6 wt % PVA of the sieved material is added.

9. The method for preparing a high-performance dielectric ceramic material according to claim 2, characterized in that: In step S4, the granulated material is placed into a mold with a diameter of 21 mm, and the mold groove depth is adjusted to 16-18 mm and the pressurization pressure is 6-10 MPa.

10. The method for preparing a high-performance dielectric ceramic material according to claim 2, characterized in that: The specific steps of sintering in step S5 are: S5.1: Heat from room temperature to 1235-1265℃, heating time 10h; S5.2: Keep at 1235-1265°C for 6 hours; S5.3: Cool down to room temperature at a rate of 1.5°C / min.

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