CN113929440A - Complex phase ceramic material and preparation method thereof - Google Patents

Complex phase ceramic material and preparation method thereof Download PDF

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CN113929440A
CN113929440A CN202111337549.6A CN202111337549A CN113929440A CN 113929440 A CN113929440 A CN 113929440A CN 202111337549 A CN202111337549 A CN 202111337549A CN 113929440 A CN113929440 A CN 113929440A
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ceramic material
powder
temperature
weight
oxide
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CN113929440B (en
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张昕
孙正斌
宋运运
裴亚星
刘勋
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Zhengzhou Research Institute for Abrasives and Grinding Co Ltd
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Zhengzhou Research Institute for Abrasives and Grinding Co Ltd
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Abstract

The invention relates to a complex phase conductive ceramic material which is mainly prepared from the following raw materials in percentage by weight: 50-75% of calcined alumina, 5-40% of tin dioxide, 5-10% of silicon dioxide, 3-6% of magnesium oxide, 2-5% of calcium oxide, 0.05-0.6% of antimony trioxide, 0.01-0.1% of zinc oxide and 0.01-0.1% of copper oxide. The ceramic material has good electrical conductivity, small density, high strength and small thermal expansion coefficient, is an excellent choice for manufacturing a base of a workbench of scribing equipment, simplifies the manufacturing process by the whole body electrical conductivity, and also prolongs the service life of the workbench; the ceramic material can also be suitable for electric spark machining and applied to other fields of electric conduction and static prevention.

Description

Complex phase ceramic material and preparation method thereof
Technical Field
The invention belongs to the technical field of functional ceramic materials, and particularly relates to a complex phase conductive ceramic material and a preparation method thereof.
Background
Dicing saws are important processing equipment in the field of semiconductor processing. Before scribing a wafer and a packaging workpiece, the main shaft drives the scribing knife to move downwards to enable the scribing knife to be in contact with the workbench, a reference zero position is measured by a conductive loop formed by the workbench and the scribing knife, and therefore the working height of the scribing knife is adjusted, and therefore the workbench and the scribing knife are required to be provided with conductive parts. The worktable of the dicing saw consists of a vacuum adsorption part and a conductive base, wherein the vacuum adsorption part mainly adopts porous ceramic materials at present, and the base part mainly adopts stainless steel materials at present because of good conductivity and mechanical strength. However, the stainless steel material has high density, large thermal expansion coefficient, large burden on equipment and influence on use precision, and the defects of the stainless steel substrate become more obvious along with the increase of the size of the wafer.
In recent years, the semiconductor industry tries to replace stainless steel materials with alumina ceramic materials with low density and low thermal expansion coefficient to manufacture a workbench base, and in order to endow alumina materials with conductivity, the current common method is to coat a conductive coating on the surface of the alumina ceramic, but the preparation process of the method is complicated, the coating is easy to fall off, the coating cannot be repaired after being damaged, and the service life of the workbench is seriously shortened.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a complex phase conductive ceramic material which has good conductivity, small density, high strength and small thermal expansion coefficient, is an excellent choice for manufacturing a base of a workbench of scribing equipment, simplifies the manufacturing process by the whole conductive performance and also prolongs the service life of the workbench; the ceramic material can also be suitable for electric spark machining and applied to other fields of electric conduction and static prevention.
The invention also provides a preparation method of the complex phase conductive ceramic material, which has a simple preparation process, can be fired at a lower temperature of 1400-1500 ℃ in an atmospheric atmosphere, greatly reduces the manufacturing cost, is low-carbon and environment-friendly, and is suitable for large-scale industrial production.
In order to achieve the above purpose, the invention provides the following technical scheme:
a multiphase conductive ceramic material is mainly prepared from the following raw materials in percentage by weight: 50-75% of calcined alumina, 5-40% of tin dioxide, 5-10% of silicon dioxide, 3-6% of magnesium oxide, 2-5% of calcium oxide, 0.05-0.6% of antimony trioxide, 0.01-0.1% of zinc oxide and 0.01-0.1% of copper oxide.
Further, the purity of the calcined alumina is not less than 99.5%, and the particle size ranges from 0.3 μm to 1.8. mu.m.
Furthermore, tin dioxide, silicon dioxide, magnesium oxide, calcium oxide, antimony trioxide, zinc oxide and copper oxide are all industrial grade 99% full-screened micropowder of 325 meshes.
In the formula of the composite conductive ceramic material, tin dioxide is used as a conductive agent, antimony trioxide is used as a conductive doping agent, and antimony ions replace the position of Sn in the tin dioxide and are dissolved in the tin dioxide in a solid manner to increase the density of current carriers, so that the resistivity of the material is reduced. The magnesium oxide and calcium oxide function as sintering aids. Zinc oxide and copper oxide function as conductivity promoters.
The preparation method of the complex phase conductive ceramic material comprises the following steps:
1) preparing materials: taking the raw materials according to the weight percentage to prepare powder;
2) ball milling: putting the powder into a ball mill, adding a ball milling medium accounting for 150-200% of the weight of the powder, pure water accounting for 50-80% of the weight of the powder and a dispersing agent accounting for 0.1-0.5% of the weight of the powder, ball milling for 20-40h, adding a binder accounting for 0.5-10% of the weight of the powder and a lubricating agent accounting for 0.5-10% of the weight of the powder, and ball milling for 0.5-1h to obtain slurry;
3) aging: placing the slurry in an environment with the temperature of 20-35 ℃ and the humidity of 45-65%, and aging for 24-36 h;
4) and (3) granulating and forming: spraying and granulating the aged slurry, then putting the slurry into a rubber mold, sealing the rubber mold, placing the rubber mold into a cold isostatic press for molding, and releasing the pressure and demolding to obtain a complex-phase conductive ceramic blank (plate or strip);
5) and (3) sintering: normal pressure sintering is adopted, the temperature is raised to 500-fold sand 600 ℃ within 48 hours, the temperature is kept for 3-6 hours, then the temperature is raised to 1400-fold sand 1500 ℃ within 24 hours, the temperature is kept for 3-5 hours, and the temperature is lowered to room temperature within 48 hours, so that the composite conductive ceramic material is obtained. The purpose of the 500-600 ℃ heat preservation is to fully discharge organic matters. The sintering temperature is 1400 ℃ and 1500 ℃, the temperature is not suitable to be too high, and the sublimation of the tin dioxide is avoided.
The normal temperature resistivity of the multiphase conductive ceramic material prepared by the invention is 10-108Omega cm, density lower than 4.5g/cm3Flexural strength higher than 200MPa and thermal expansion coefficient lower than 6.5X 10-6/℃（25-400℃）。
Specifically, in the step 2), the ball milling medium is alumina ceramic balls with the purity of more than 95%; the dispersant may be polyvinyl carboxylic acid or triethanolamine, etc.
Specifically, in the step 2), the binder may be a polyvinyl alcohol (PVA) aqueous solution, a carboxymethyl cellulose (CMC) aqueous solution, a phenolic resin solution, or the like, with a mass concentration of 5 to 15%; the lubricant may be oleic acid, emulsified paraffin or glycerol.
Further, in the step 4), the aged slurry is sent to a spray granulation tower for spray granulation, the rotation speed of a centrifugal spray disk in the tower is 8000-15000rpm, the negative pressure is maintained at 120-200Pa, the inlet temperature is set to 170-200 Pa, and the outlet temperature is set to 60-80 ℃.
Further, in the step 4), oil or water and the like are selected as pressure transmission media of the cold isostatic press; the technological parameters of cold isostatic pressing are as follows: the molding pressure is 100-180MPa, and the pressure maintaining time is 5-15 min.
Compared with the prior art, the invention has the following beneficial effects:
1) the invention provides a light high-strength composite conductive ceramic material, the normal temperature resistivity of which is 10-108Omega cm, density lower than 4.5g/cm3Flexural strength higher than 200MPa and thermal expansion coefficient lower than 6.5X 10-6/. degree.C. (25-400 ℃ C.). The material has the advantages of excellent conductivity and low expansion coefficient of the conductive ceramic, mechanical strength superior to that of common conductive ceramic and density far lower than that of stainless steel materials, and can be applied to the conductive field and antistatic field of LED, semiconductor, automobile, tool and other industries. The material is suitable for electric spark machining, and has the advantages of conductive whole body and simple machining process.
2) The preparation method of the multiphase conductive ceramic material has the advantages of simple process, low cost and low sintering temperature, and is suitable for large-scale industrial production.
Drawings
FIG. 1 is an SEM image of a composite conductive ceramic material prepared in example 1;
FIG. 2 is an SEM image of the complex phase conductive ceramic material prepared in example 2;
FIG. 3 is an SEM image of the complex phase conductive ceramic material prepared in example 3;
FIG. 4 is an XRD pattern of the complex phase conductive ceramic material prepared in example 1;
FIG. 5 is an XRD pattern of the complex phase conductive ceramic material prepared in example 2;
fig. 6 is an XRD pattern of the complex phase conductive ceramic material prepared in example 3.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following examples, but the scope of the present invention is not limited thereto.
In the following examples, the raw materials used were all common commercial products that were directly available. The purity of the calcined alumina (a common commercially available product) is not less than 99.5%, and the particle size ranges from 0.3 μm to 1.8. mu.m. Tin dioxide, silicon dioxide, magnesium oxide, calcium oxide, antimony trioxide, zinc oxide and copper oxide are all technical grade 99% content 325 mesh full-screened micropowder. Emulsified paraffin (common commercial product).
Example 1
A multiphase conductive ceramic material is mainly prepared from the following raw materials in percentage by weight: 75% of calcined alumina, 5% of tin dioxide, 9.9% of silicon dioxide, 5% of magnesium oxide, 5% of calcium oxide, 0.07% of antimony trioxide, 0.015% of zinc oxide and 0.015% of copper oxide.
The preparation method of the complex phase conductive ceramic material comprises the following steps:
1) preparing materials: taking the raw materials according to the weight percentage to prepare powder;
2) ball milling: putting the powder into a ball mill, adding a ball milling medium (alumina ceramic balls with the purity of more than 95%) accounting for 200% of the weight of the powder, pure water accounting for 80% of the weight of the powder and dispersant polyvinyl carboxylic acid accounting for 0.1% of the weight of the powder, carrying out ball milling for 20 hours, adding a binder polyvinyl alcohol aqueous solution (the mass concentration is 15 wt%) accounting for 0.5% of the weight of the powder and lubricant emulsified paraffin accounting for 0.5% of the weight of the powder, and carrying out ball milling for 1 hour to obtain slurry;
3) aging: placing the slurry in an environment with the temperature of 20 ℃ and the humidity of 45%, and aging for 36 h;
4) and (3) granulation: feeding the aged slurry into a spray granulation tower for spray granulation, wherein the rotating speed of a centrifugal spray disc in the tower is 15000rpm, the negative pressure is kept at 120Pa, the inlet temperature is set to be 170 ℃, and the outlet temperature is set to be 80 ℃ to obtain granulated powder;
5) molding: placing the granulated powder into a rubber mold, sealing, placing the rubber mold into a cold isostatic press for molding (the pressure of the cold isostatic press is 150MPa, and the pressure maintaining time is 10 min), and releasing the pressure and demolding to obtain a complex phase conductive ceramic blank;
6) and (3) sintering: and (3) placing the blank in a high-temperature furnace, sintering at normal pressure, heating to 600 ℃ within 48 hours, preserving heat for 5 hours, heating to 1500 ℃ within 24 hours, preserving heat for 5 hours, and cooling to room temperature within 48 hours to obtain the complex-phase conductive ceramic material.
FIG. 1 shows an SEM image of the complex phase conductive ceramic material prepared in example 1; it can be seen in the figure that: the ceramic crystal grains are in an elliptical plate shape and are combined tightly, and the size of the crystal grains is 1.5-15 mu m. FIG. 4 shows an XRD pattern of the complex phase conductive ceramic material prepared in example 1; it can be seen in the figure that: the main crystal phases are tin oxide and aluminum oxide.
The complex phase conductive ceramic material is tested for relative performance, and the normal temperature resistivity of the complex phase conductive ceramic material is 5 multiplied by 10 through detection7Omega cm, density 3.92g/cm3Flexural strength of 300MPa and thermal expansion coefficient of 6.2X 10-6The material can be used as antistatic material at 25-400 deg.C.
The normal temperature resistivity detection method refers to the GB/T1410-2006 material volume resistivity and surface resistivity experimental method; the density detection method refers to the GB/T25995-2010 fine ceramic density and apparent porosity test method; the flexural strength detection method refers to the GB/T6569-2006 fine ceramic flexural strength test method; the thermal expansion coefficient detection method refers to the GB/T16535-2008 fine ceramic linear expansion coefficient test method.
Example 2
A multiphase conductive ceramic material is mainly prepared from the following raw materials in percentage by weight: 50% of calcined alumina powder, 39% of tin dioxide, 5.2% of silicon dioxide, 3% of magnesium oxide, 2% of calcium oxide, 0.6% of antimony trioxide, 0.1% of zinc oxide and 0.1% of copper oxide.
The preparation method of the complex phase conductive ceramic material comprises the following steps:
1) preparing materials: taking the raw materials according to the weight percentage to prepare powder;
2) ball milling: putting the powder into a ball mill, adding a ball milling medium (alumina ceramic balls with the purity of more than 95%) accounting for 150% of the weight of the powder, pure water accounting for 50% of the weight of the powder and dispersant triethanolamine accounting for 0.5% of the weight of the powder, performing ball milling for 40 hours, adding a binder carboxymethyl cellulose aqueous solution (with the mass concentration of 5 wt%) accounting for 10% of the weight of the powder and lubricant oleic acid accounting for 1% of the weight of the powder, and performing ball milling for 0.5 hour to obtain slurry;
3) aging: placing the slurry in an environment with the temperature of 35 ℃ and the humidity of 65 percent, and aging for 24 hours;
4) and (3) granulation: feeding the aged slurry into a spray granulation tower for spray granulation, wherein the rotating speed of a centrifugal spray disc in the tower is 8000rpm, the negative pressure is kept at 200Pa, the inlet temperature is set to be 200 ℃, and the outlet temperature is set to be 60 ℃ to obtain granulated powder;
5) molding: placing the granulated powder into a rubber mold, sealing, placing the rubber mold into a cold isostatic press for molding (the pressure of the cold isostatic press is 180MPa, and the pressure maintaining time is 15 min), and releasing the pressure and demolding to obtain a complex phase conductive ceramic blank;
6) and (3) sintering: and (3) placing the blank in a high-temperature furnace, sintering at normal pressure, heating to 500 ℃ for 40h, preserving heat for 3h, heating to 1400 ℃ for 20h, preserving heat for 3h, and cooling to room temperature for 40h to obtain the complex-phase conductive ceramic material.
FIG. 2 is a SEM image of the complex phase conductive ceramic material prepared in example 2; it can be seen in the figure that: the ceramic crystal grains are in short column shape and are tightly combined, and the grain size is 1.2-8 μm. FIG. 5 shows an XRD pattern of the complex phase conductive ceramic material prepared in example 2; it can be seen in the figure that: the main crystalline phases are tin oxide and cordierite.
The detection shows that the normal temperature resistivity of the multiphase conductive ceramic material is 85 omega cm, and the density is 4.3g/cm3A flexural strength of 265MPa and a thermal expansion coefficient of 5.9X 10-6The material can be used as conductive material at 25-400 deg.C, and can be processed by electric spark.
Example 3
A multiphase conductive ceramic material is mainly prepared from the following raw materials in percentage by weight: calcined alumina 64%, tin dioxide 19%, silicon dioxide 7.6%, magnesium oxide 5%, calcium oxide 4%, antimony trioxide 0.3%, zinc oxide 0.05%, copper oxide 0.05%.
The preparation method of the complex phase conductive ceramic material comprises the following steps:
1) preparing materials: taking the raw materials according to the weight percentage to prepare powder;
2) ball milling: putting the powder into a ball mill, adding a ball milling medium (alumina ceramic balls with the purity of more than 95%) accounting for 180% of the weight of the powder, pure water accounting for 70% of the weight of the powder and dispersant polyvinyl carboxylic acid accounting for 0.3% of the weight of the powder, ball milling for 24 hours, adding a binder phenolic resin liquid (with the mass concentration of 5 wt%) accounting for 5% of the weight of the powder and lubricant glycerin accounting for 5% of the weight of the powder, and ball milling for 1 hour to obtain slurry;
3) aging: placing the slurry in an environment with the temperature of 25 ℃ and the humidity of 50%, and aging for 30 h;
4) and (3) granulation: feeding the aged slurry into a spray granulation tower for spray granulation, wherein the rotating speed of a centrifugal spray disc in the tower is 12000rpm, the negative pressure is kept at 160Pa, the inlet temperature is set to be 180 ℃, and the outlet temperature is set to be 70 ℃ to obtain granulated powder;
5) molding: placing the granulated powder into a rubber mold, sealing, placing the rubber mold into a cold isostatic press for molding (the pressure of the cold isostatic press is 160MPa, and the pressure maintaining time is 10 min), and releasing the pressure and demolding to obtain a complex phase conductive ceramic blank;
6) and (3) sintering: and (3) placing the blank in a high-temperature furnace, sintering at normal pressure, heating to 550 ℃ within 45h, preserving heat for 4h, heating to 1450 ℃ within 24h, preserving heat for 4h, and cooling to room temperature within 48h to obtain the complex-phase conductive ceramic material.
FIG. 3 is a SEM image of the complex phase conductive ceramic material prepared in example 3; it can be seen in the figure that: the ceramic crystal grains are in an ellipsoidal shape and are tightly combined, and the size of the crystal grains is 1.2-9.2 mu m. FIG. 6 shows an XRD pattern of the complex phase conductive ceramic material prepared in example 3; it can be seen in the figure that: the main crystalline phases are tin oxide and cordierite.
After the detection, the detection result shows that,the normal temperature resistivity of the multiphase conductive ceramic material is 6 multiplied by 103Omega cm, density 3.92g/cm3Flexural strength of 300MPa and thermal expansion coefficient of 6.1X 10-6The conductive material can be used at 25-400 deg.C.
In summary, it can be seen that: the ceramic material has good electrical conductivity, small density, high strength and small thermal expansion coefficient, is an excellent choice for manufacturing a base of a workbench of scribing equipment, simplifies the manufacturing process due to the whole body electrical conductivity, and also prolongs the service life of the workbench.

Claims (8)

1. The composite ceramic material is characterized by being mainly prepared from the following raw materials in percentage by weight: 50-75% of calcined alumina, 5-40% of tin dioxide, 5-10% of silicon dioxide, 3-6% of magnesium oxide, 2-5% of calcium oxide, 0.05-0.6% of antimony trioxide, 0.01-0.1% of zinc oxide and 0.01-0.1% of copper oxide.
2. The composite phase ceramic material according to claim 1, wherein the calcined alumina has a purity of not less than 99.5% and a particle size in the range of 0.3 μm to 1.8 μm.
3. The composite ceramic material as claimed in claim 1 or 2, wherein tin dioxide, silicon dioxide, magnesium oxide, calcium oxide, antimony trioxide, zinc oxide and copper oxide are all prepared by using 325 mesh full-screened micropowder with 99% content of industrial grade.
4. A process for the preparation of a composite ceramic material according to any one of claims 1 to 3, comprising the steps of:
1) preparing materials: taking the raw materials according to the weight percentage to prepare powder;
2) ball milling: putting the powder into a ball mill, adding a ball milling medium accounting for 150-200% of the weight of the powder, pure water accounting for 50-80% of the weight of the powder and a dispersing agent accounting for 0.1-0.5% of the weight of the powder, ball milling for 20-40h, adding a binder accounting for 0.5-10% of the weight of the powder and a lubricating agent accounting for 0.5-10% of the weight of the powder, and ball milling for 0.5-1h to obtain slurry;
3) aging: placing the slurry in an environment with the temperature of 20-35 ℃ and the humidity of 45-65%, and aging for 24-36 h;
4) and (3) granulating and forming: spraying and granulating the aged slurry, then placing the slurry into a rubber mold, sealing the rubber mold, placing the rubber mold into a cold isostatic press for molding, and releasing pressure and demolding to obtain a complex-phase conductive ceramic blank;
5) and (3) sintering: normal pressure sintering is adopted, the temperature is raised to 500-fold sand 600 ℃ within 48 hours, the temperature is kept for 3-6 hours, then the temperature is raised to 1400-fold sand 1500 ℃ within 24 hours, the temperature is kept for 3-5 hours, and the temperature is lowered to room temperature within 48 hours, so that the composite conductive ceramic material is obtained.
5. The method for preparing the composite ceramic material according to claim 4, wherein in the step 2), the ball milling media are alumina ceramic balls with purity of more than 95%; the dispersant is polyvinyl carboxylic acid or triethanolamine.
6. The preparation method of the composite ceramic material as claimed in claim 4, wherein in the step 2), the binder is a polyvinyl alcohol aqueous solution, a carboxymethyl cellulose aqueous solution or a phenolic resin solution with a mass concentration of 5-15%; the lubricant is oleic acid, emulsified paraffin or glycerol.
7. The method for preparing the composite ceramic material as claimed in claim 4, wherein in the step 4), the aged slurry is sent to a spray granulation tower for spray granulation, the rotation speed of a centrifugal spray disk in the tower is 8000-15000rpm, the negative pressure is maintained at 120-200Pa, the inlet temperature is set at 170-200 ℃, and the outlet temperature is set at 60-80 ℃.
8. The method for preparing the composite ceramic material according to claim 4, wherein in the step 4), the pressure transmission medium of the cold isostatic press is selected from oil or water; the technological parameters of cold isostatic pressing are as follows: the molding pressure is 100-180MPa, and the pressure maintaining time is 5-15 min.
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