CN107365171B - Ceramic metallization paste and preparation method and application thereof - Google Patents
Ceramic metallization paste and preparation method and application thereof Download PDFInfo
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- CN107365171B CN107365171B CN201710749235.4A CN201710749235A CN107365171B CN 107365171 B CN107365171 B CN 107365171B CN 201710749235 A CN201710749235 A CN 201710749235A CN 107365171 B CN107365171 B CN 107365171B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
- C04B41/5138—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal with a composition mainly composed of Mn and Mo, e.g. for the Moly-manganese method
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/88—Metals
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Abstract
The invention relates toThe ceramic metallization paste comprises the following components in percentage by mass: 71-73% of Mo powder; 8-13% of Mn powder; al (Al)2O39-11% of powder; SiO 227-9% of powder; 1.1 to 3 percent of CaO powder. The invention mixes the powder in the formula, grinds the powder to the granularity of 0.5-1.3 μm, and then adopts the rolling process to prepare the paste, thus obtaining the paste with fine and smooth components and small granularity. The obtained ceramic metallization paste can realize good mutual permeation with ceramic after metallization sintering at 1330-1350 ℃, and energy consumption is reduced. The ceramic metallization paste prepared by the invention is coated on the ceramic end face, the metallization layer formed after sintering is continuous and compact, the sealing strength reaches more than 300MPa and is far greater than the industrial standard, the air tightness of the welded junction meets the requirement, and the ceramic metallization paste has good economic benefit and wide application prospect.
Description
Technical Field
The invention relates to the technical field of vacuum arc-extinguishing chambers, in particular to a ceramic metallization paste and a preparation method and application thereof.
Background
The vacuum arc-extinguishing chamber is the heart of the vacuum switch and is also the main functional element of the vacuum switch. The quality of the ceramic metallization is critical to the performance of the vacuum interrupter. In the existing ceramic metallization technology, powders of molybdenum, manganese and the like are prepared into paste to be coated on the surface of sealing between ceramics and metal, then the powders are sintered into a whole through high-temperature sintering, and the powders permeate into the surface of alumina ceramics, so that a metal layer and the ceramics are sintered together, and meanwhile, the metal layer with moderate thickness, compactness and no cavity is obtained, so as to achieve the conditions of tensile strength, airtightness and the like required by sealing. However, the particles of the metalized paste such as molybdenum and manganese are thick, high temperature of about 1500 ℃ is required during sintering, the temperature is high, the energy consumption is large, and the requirement on equipment is high. Moreover, the metalized layer is not compact and can not meet the requirements of strength and air tightness after sealing,
CN1887814A discloses powder for ceramic metallization paste and a preparation method thereof, belonging to the technical field of ceramic metallization material application. The composite material is prepared from the following raw materials in parts by weight: 60-80 parts of molybdenum powder and 20-40 parts of glass phase component. The invention improves the tensile strength by 60 percent compared with the original tensile strength, and simultaneously reduces the sintering temperature of metallization to 1400-1450 ℃.
CN103172408A discloses a high-strength alumina ceramic metallization paste and a preparation method thereof, wherein the metallization paste comprises the following substances in percentage by weight: 70-85% of molybdenum powder, 5-15% of manganese powder and 5-15% of Al2O3Powder, 5-10% of silicon dioxide powder, 0.2-1.2% of calcium oxide and 0.2 to 1.5 percent of magnesium oxide, 0.2 to 1.5 percent of zirconia powder and 0.2 to 1.0 percent of titanium dioxide powder; the preparation method comprises the following steps: proportionally placing the substances into an oven respectively, and drying for 1-2 hours at the temperature of 100-110 ℃; putting the molybdenum powder into a ball mill, adding absolute ethyl alcohol, grinding for 24-48 hours, and drying at the temperature of 100-110 ℃; mixing manganese powder and Al2O3Putting the powder, silicon dioxide powder, calcium oxide, magnesium oxide, zirconium oxide powder and titanium dioxide powder into a ball mill, grinding for 4-6 hours, adding the ground molybdenum powder, and continuously grinding for 36-48 hours to obtain mixed powder of the materials; and adding a binder into the mixed powder, and grinding for 24-48 hours to obtain the metallization paste. The method widens the sintering temperature range, and the three-point average tensile strength of the metal film reaches more than 300MPa after secondary metallization.
CN103172408A discloses a powder for alumina ceramic nano-metallization paste and a preparation method thereof, which comprises the following components in parts by weight: 65-80 parts of Mo powder, 12-14 parts of Mn powder and Al2O38-12 parts of powder and SiO22.5-7.0 parts of powder, 0.5-3 parts of MgO powder, 1-5 parts of CaO powder and ZrO21-2 parts of powder, wherein Al2O3The powder is composed of nanoscale Al2O3Powder, submicron grade Al2O3Powder and micron-sized Al2O3And (3) powder composition. The sintering temperature of the powder for the paste provided by the invention is 1400-year-old 1450 ℃/60min, and the sealing tensile strength is more than or equal to 125 MPa.
Although the method can reduce the sintering temperature of the ceramic metallization paste to a certain extent and improve the sealing tensile strength, the sintering temperature is still higher than 1400 ℃, the sealing tensile strength is insufficient, and a space for continuous improvement is still provided.
Disclosure of Invention
In order to solve the technical problems, the invention provides a ceramic metallization paste and a preparation method and application thereof, the ceramic metallization paste which is fine and smooth, has uniform components and small granularity is prepared, the sintering temperature is 1330-1350 ℃, the energy consumption is reduced, the sealing strength reaches more than 300MPa, the air tightness meets the requirements of a vacuum arc-extinguishing chamber, and the ceramic metallization paste is suitable for industrial application.
In a first aspect, the invention provides a ceramic metallization paste, which comprises the following components in percentage by mass:
according to the invention, the content of Mo powder in the ceramic metallization paste is 71-73% by mass, and may be, for example, 71%, 71.2%, 71.5%, 71.8%, 72%, 72.3%, 72.5%, 72.7% or 73%, and the specific values between the above values are not exhaustive for reasons of space and simplicity.
According to the invention, the content of Mn powder in the ceramic metallization paste is 8-13% by mass, and may be, for example, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5% or 13%, and the specific values between the above values are not exhaustive for reasons of space and simplicity.
According to the invention, the ceramic metallization paste contains Al in percentage by mass2O3The amount of powder is 9-11%, for example, 9%, 9.3%, 9.5%, 9.7%, 10%, 10.3%, 10.5%, 10.7% or 11%, and the specific values between the above values, are not exhaustive for reasons of brevity and clarity.
According to the invention, the ceramic metallization paste contains SiO in percentage by mass2The amount of flour is 7-9%, for example, 7%, 7.3%, 7.5%, 7.8%, 8%, 8.2%, 8.5%, 8.8% or 9%, and the specific values between the above values, are not exhaustive for reasons of brevity and clarity.
According to the invention, the content of CaO powder in the ceramic metallization paste is 1.1-3% by mass, and may be, for example, 1.1%, 1.3%, 1.5%, 1.8%, 2%, 2.3%, 2.5%, 2.8% or 3%, and the specific values between the above values, which are not exhaustive for reasons of space and simplicity.
As a preferable technical scheme, the ceramic metallization paste comprises the following components in percentage by mass:
according to the invention, the particle size of the Mo powder is: d10 is less than 1.2 μm, D50 is less than 2.5 μm, and D90 is less than 7.0 μm; the granularity of the Mn powder is D10 less than 4.0 mu m, D50 less than 12 mu m and D90 less than 25 mu m; the Al is2O3The particle size of the powder is D10 less than 1.5 μm, D50 less than 5.0 μm, and D90 less than 40 μm; the SiO2The particle size of the powder is D10 less than 1.5 μm, D50 less than 5.0 μm, and D90 less than 40 μm; the granularity of the CaO powder is D10 less than 3 μm, D50 less than 10 μm and D90 less than 40 μm.
According to the invention, the ceramic metallization paste also contains a binder; the mass ratio of the binder to the total amount of the metal powder is (5.0-6.0):1, and may be, for example, 5.1:1, 5.2:1, 5.3:1, 5.4:1, 5.5:1, 5.6:1, 5.7:1, 5.8:1, 5.9:1 or 6.0:1, and the specific values therebetween are not intended to be exhaustive for reasons of space and simplicity.
The total amount of the metal powder in the invention refers to the Mo powder, the Mn powder and the Al powder2O3Powder, SiO2The sum of the total mass of the powder and the CaO powder.
According to the invention, the binder comprises the following components in percentage by mass:
according to the invention, the content of terpineol in the binder is 90-97% by mass, and may be, for example, 90%, 91%, 92%, 93%, 94%, 95%, 96% or 97%, and the specific values between the above values, which are not exhaustive for reasons of space and simplicity.
According to the invention, the binder contains 3 to 8% by weight of ethylcellulose, for example 3%, 4%, 5%, 6%, 7% or 8%, and the particular values between the above values, limited to space and for the sake of brevity, are not exhaustive.
According to the invention, the content of diethanol dibutyl ether in the binder is 1-3% by mass, and may be, for example, 1%, 1.5%, 2%, 2.5% or 3%, and the specific values between the above values, limited to space and for the sake of brevity, are not exhaustive.
According to the invention, the content of castor oil in the binder is 0-1% by mass, and may be, for example, 0%, 0.2%, 0.4%, 0.6%, 0.8% or 1%, and the specific values between the above values, which are limited to space and for the sake of brevity, are not exhaustive.
In a second aspect, the present invention provides a method of making a ceramic metallization paste according to the first aspect, the method comprising the steps of:
(1) according to the formula amount, Mo powder, Mn powder and Al powder2O3Mixing the powder and CaO powder, adding absolute ethyl alcohol, and grinding until the particle size of the metal mixed powder is 0.5-1.3 mu m;
(2) drying the ground slurry;
(3) and mixing the dried material and the binder according to the formula amount, stirring, and binding and pressing after stirring to obtain the ceramic metallization paste.
According to the invention, the particle size of the metal mixed powder obtained after grinding in step (1) is 0.5-1.3 μm, and may be, for example, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1.0 μm, 1.1 μm, 1.2 μm or 1.3 μm, and the specific values therebetween are not intended to be exhaustive for reasons of space and simplicity.
According to the invention, anhydrous ethanol is added to the metal mixed powder before grinding in the step (1), the mass ratio of the metal mixed powder to the anhydrous ethanol is (0.9-1):1, for example, 0.9:1, 0.92:1, 0.94:1, 0.96:1, 0.98:1 or 1:1, and the specific values between the above values are limited to space and for the sake of brevity, and the invention is not exhaustive.
According to the invention, the grinding in step (1) is carried out using ZrO2And (5) carrying out ball milling on the grinding balls.
According to the invention, the ZrO2The grinding balls have a diameter of 8-15mm, preferably 10mm, and may be, for example, 8mm, 9mm, 10mm, 11mm, 12mm, 13mm, 14mm or 15mm, and the specific values therebetween are not exhaustive for the sake of brevity and simplicity.
According to the invention, the ZrO2The mass ratio of the grinding balls to the metal mixed powder is (2-3):1, and may be, for example, 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1 or 3:1, and the specific values between the above values are limited to space and are not exhaustive for the sake of brevity.
According to the invention, the grinding time in step (1) is 48-72h, for example 48h, 52h, 56h, 60h, 64h, 68h or 72h, and the specific values therebetween are not exhaustive for reasons of space and simplicity.
According to the present invention, the temperature of the drying in the step (2) is 85-90 ℃, for example, 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃ or 90 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the present invention is not exhaustive.
According to the present invention, the drying time in the step (2) is 20-30h, for example, 20h, 22h, 24h, 26h, 28h or 30h, and the specific values between the above values are limited to space and for brevity, and the present invention is not exhaustive.
According to the invention, the stirring in step (3) is carried out using a stirrer.
According to the invention, the stirring time in step (3) is 30-60min, such as 30min, 35min, 40min, 45min, 50min, 55min or 60min, and the specific values therebetween are limited to space and for the sake of brevity, and the present invention is not exhaustive.
According to the invention, the rolling in the step (3) is carried out by using a three-roll grinder, and when the rolling is carried out, the gap between the rolls of the three-roll grinder is adjusted to be 3-5 μm.
According to the invention, the number of times of the rolling in step (3) is 4 to 6, for example, 4, 5 or 6.
In a third aspect, the present invention provides a use of the ceramic metallization paste of the first aspect, the use being: the prepared ceramic metallization paste is coated on the ceramic end face of the vacuum arc-extinguishing chamber and then sintered for 40-60min in a hydrogen furnace at the temperature of 1330-1350 ℃.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the invention selects the raw materials with specific components and particle size range, obtains powder particles with the particle size of 0.5-1.3 mu m by grinding the powder in the formula, and simultaneously prepares paste by adopting a rolling process; the raw materials are selected and matched with the preparation process to obtain the paste which is fine and smooth, has uniform components and small granularity.
(2) The ceramic metallization paste obtained by the invention can realize good mutual permeation with ceramic after metallization sintering at 1330-1350 ℃, thereby greatly reducing energy consumption and production cost.
(3) The ceramic metallization paste prepared by the invention is coated on the ceramic end face, the metallization layer formed after sintering is continuous and compact, and the sealing strength reaches more than 300MPa, which is far greater than the technical index that the three-point method (rivet) sealing tensile strength is more than or equal to 130MPa in the ceramic tube shell for the vacuum switch tube in the national electronic industry standard of China (SJ/T11246-2014).
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
(1) Weighing 71 percent of Mo powder, 8 percent of Mn powder and 11 percent of Al according to the mass percentage3O2Powder, SiO2Mixing 8% of CaO powder and 2% of CaO powder, placing the mixture into a ball milling pot, and adding absolute ethyl alcohol and ZrO into the ball milling pot2Grinding balls, and placing the balls on a ball mill for ball milling; the weight ratio of the metal mixed powder to the absolute ethyl alcohol is 1: 1; ZrO (ZrO)2The diameter of the grinding ball is 10 mm; the weight ratio of the grinding balls to the metal mixed powder is 2:1, and the average particle size of the metal mixed powder obtained after ball milling for 72 hours is 1 micron;
(2) taking out the slurry obtained after ball milling, putting the slurry into an oven, and drying the slurry for 24 hours at 90 ℃;
(3) weighing 95% of terpineol, 3% of ethyl cellulose, 1.5% of diethanol dibutyl ether and 0.5% of castor oil as binders according to the mass percentage, mixing the dried material in the step (2) with the binders according to the mass ratio of 5.3:1, and stirring for 30min by using a stirrer; and (3) rolling by using a three-roll grinding machine after stirring is finished, adjusting the gap between the rolls to be 3 mu m during rolling, and rolling for 5 times to obtain the ceramic metallization paste.
The obtained ceramic metallization paste is coated on the ceramic end face of the vacuum arc-extinguishing chamber and then sintered in a hydrogen furnace at a temperature of 1340 ℃ for 40 min.
The sealing performance of the sintered ceramic is tested by a three-point method (blind rivet), five groups of experiments are carried out, and the sealing tensile strength is respectively as follows: 1. 302 MPa; 2. 330 MPa; 3. 312 MPa; 4. 320 MPa; 5. 318 MPa. The results show that the gas tightness of the seal crater is all qualified under the above seal tensile strength.
Example 2
(1) Weighing 73 percent of Mo powder, 9 percent of Mn powder and 9 percent of Al according to the mass percentage3O2Powder, 7% SiO2Mixing the powder and 2% CaO powder, placing the mixture in a ball milling pot, and adding absolute ethyl alcohol and ZrO in the ball milling pot2Grinding balls, and placing the balls on a ball mill for ball milling; the weight ratio of the metal mixed powder to the absolute ethyl alcohol is 0.9: 1; ZrO (ZrO)2The diameter of the grinding ball is 11 mm; the weight ratio of the grinding balls to the metal mixed powder is 2.51, the average grain diameter of the metal mixed powder obtained after ball milling for 60 hours is 0.8 mu m;
(2) taking out the slurry obtained after ball milling, putting the slurry into an oven, and drying the slurry for 30 hours at 85 ℃;
(3) weighing 93% of terpineol, 5% of ethyl cellulose, 1% of diethanol dibutyl ether and 1% of castor oil as binders according to the mass percentage, mixing the dried material in the step (2) with the binders according to the mass ratio of 5.8:1, and stirring for 40min by using a stirrer; and (3) rolling by using a three-roll grinding machine after stirring is finished, adjusting the gap between the rolls to be 3 mu m during rolling, and rolling for 5 times to obtain the ceramic metallization paste.
The ceramic metallization paste obtained is applied to the ceramic end face of the vacuum interrupter and then sintered in a hydrogen furnace at a temperature of 1330 ℃ for 50 min.
The sealing performance of the sintered ceramic is tested by a three-point method (blind rivet), five groups of experiments are carried out, and the sealing tensile strength is respectively as follows: 1. 317 MPa; 2. 323 MPa; 3. 325 MPa; 4. 324 MPa; 5. 330 Mpa. The results show that the gas tightness of the seal crater is all qualified under the above seal tensile strength.
Example 3
(1) Weighing 71 percent of Mo powder, 9 percent of Mn powder and 11 percent of Al according to the mass percentage3O2Powder, 7% SiO2Mixing the powder and 2% CaO powder, placing the mixture in a ball milling pot, and adding absolute ethyl alcohol and ZrO in the ball milling pot2Grinding balls, and placing the balls on a ball mill for ball milling; the weight ratio of the metal mixed powder to the absolute ethyl alcohol is 1: 1; ZrO (ZrO)2The diameter of the grinding ball is 10 mm; the weight ratio of the grinding balls to the metal mixed powder is 3:1, and the average particle size of the metal mixed powder obtained after ball milling for 68 hours is 0.6 mu m;
(2) taking out the slurry obtained after ball milling, putting the slurry into an oven, and drying the slurry for 27 hours at 88 ℃;
(3) weighing 96% of terpineol, 3% of ethyl cellulose and 1% of diethanol dibutyl ether as binders according to the mass percentage, mixing the dried material in the step (2) with the binders according to the mass ratio of 6.0:1, and stirring for 40min by using a stirrer; and (3) rolling by using a three-roll grinder after stirring, adjusting the gap between the rolls to be 3.5 mu m during rolling, and rolling for 4 times to obtain the ceramic metallization paste.
The ceramic metallization paste obtained is applied to the ceramic end face of the vacuum interrupter and then sintered in a hydrogen furnace at a temperature of 1330 ℃ for 60 min.
The sealing performance of the sintered ceramic is tested by a three-point method (blind rivet), five groups of experiments are carried out, and the sealing tensile strength is respectively as follows: 1. 345 MPa; 2. 355 MPa; 3. 348 MPa; 4. 353 MPa; 5. 340 MPa. The results show that the gas tightness of the seal crater is all qualified under the above seal tensile strength.
Comparative example 1
Compared with the example 1, except that the rolling process in the step (3) is replaced by the ordinary ball milling, the other conditions are completely the same as the example 1, namely, the materials stirred by the stirrer in the step (3) are subjected to the ordinary ball milling to obtain the ceramic metallization paste.
The ceramic metallization paste obtained in the comparative example is coated on the ceramic end face of the vacuum arc-extinguishing chamber, and the metallization sintering is difficult to complete at 1340 ℃, and the metallization is completed by increasing the temperature to 1380 ℃ and sintering for 40 min.
The sealing performance of the sintered ceramic is tested by a three-point method (blind rivet), five groups of experiments are carried out, and the sealing tensile strength is respectively as follows: 1. 302 MPa; 2. 270 MPa; 3. 250 MPa; 4. 230 MPa; 5. 170 MPa. The results show that, under the sealing tensile strength, the airtightness of the sealing craters of 1-4 groups does not meet the requirement except the airtightness of the experimental sealing craters of the 5 th group.
Comparative example 2
The conditions were the same as in example 1 except that the diameter of the milling balls in step (1) and other milling parameters were adjusted so that the average particle diameter of the metal mixed powder obtained after ball milling was 2 μm, as compared with example 1.
The ceramic metallization paste obtained in the comparative example is coated on the ceramic end face of the vacuum arc-extinguishing chamber, and the metallization sintering is difficult to complete at 1340 ℃, and the metallization is completed by increasing the temperature to 1450 ℃ and sintering for 40 min.
The sealing performance of the sintered ceramic is tested by a three-point method (blind rivet), five groups of experiments are carried out, and the sealing tensile strength is respectively as follows: 1. 302 MPa; 2. 270 MPa; 3. 250 MPa; 4. 230 MPa; 5. 170 MPa. The result shows that the air tightness of the experimental sealing craters of the 3 rd to 5 th groups is qualified, and the air tightness of the sealing craters of the 1 st and 2 th groups is not qualified under the sealing tensile strength.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (19)
1. The ceramic metallization paste with the sintering temperature of 1330-1350 ℃ is characterized by comprising the following components in percentage by mass:
the granularity of the Mo powder is as follows: d10 is less than 1.2 μm, D50 is less than 2.5 μm, and D90 is less than 7.0 μm; the granularity of the Mn powder is D10 less than 4.0 mu m, D50 less than 12 mu m and D90 less than 25 mu m; the Al is2O3The particle size of the powder is D10 less than 1.5 μm, D50 less than 5.0 μm, and D90 less than 40 μm; the SiO2The particle size of the powder is D10 less than 1.5 μm, D50 less than 5.0 μm, and D90 less than 40 μm; the granularity of the CaO powder is D10 less than 3 μm, D50 less than 10 μm and D90 less than 40 μm;
the preparation method of the ceramic metallization paste comprises the following steps:
(1) according to the formula amount, Mo powder, Mn powder and Al powder2O3Powder, SiO2Mixing the powder and CaO powder, and grinding the mixture until the particle size of the metal mixed powder is 0.5-1.3 mu m;
(2) drying the ground slurry;
(3) and mixing the dried material and the binder according to the formula amount, stirring, and binding and pressing after stirring to obtain the ceramic metallization paste.
2. The ceramic metallization paste according to claim 1, having a sintering temperature of 1330-1350 ℃, wherein the ceramic metallization paste comprises the following components in percentage by mass:
3. the ceramic metallization paste according to claim 1, wherein the mass ratio of the binder to the total amount of the metal powder is 1 (5.0-6.0);
the metal powder comprises Mo powder, Mn powder and Al2O3Powder, SiO2Powder and CaO powder.
4. The ceramic metallization paste according to claim 1, wherein the binder comprises the following components in percentage by mass:
the sum of the above components is 100%.
5. The method for preparing a ceramic metallization paste according to any of claims 1 to 4, wherein the sintering temperature is 1330-1350 ℃, the method comprising the steps of:
(1) according to the formula amount, Mo powder, Mn powder and Al powder2O3Powder, SiO2Mixing the powder and CaO powder, and grinding the mixture until the particle size of the metal mixed powder is 0.5-1.3 mu m;
(2) drying the ground slurry;
(3) and mixing the dried material and the binder according to the formula amount, stirring, and binding and pressing after stirring to obtain the ceramic metallization paste.
6. The method of claim 5, wherein absolute ethanol is added to the metal mixed powder before grinding in step (1).
7. The method according to claim 6, wherein the mass ratio of the metal mixed powder to the absolute ethyl alcohol is (0.9-1): 1.
8. The method of claim 5, wherein the grinding of step (1) is with ZrO2And (5) carrying out ball milling on the grinding balls.
9. The method according to claim 8, wherein the ZrO-Si-O-is2The diameter of the grinding ball is 8-15 mm.
10. The method according to claim 8, wherein the ZrO-Si-O-is2The mass ratio of the grinding balls to the metal mixed powder is (2-3) to 1.
11. The method of claim 5, wherein the milling time of step (1) is 48 to 72 hours.
12. The method of claim 5, wherein the temperature of the drying in step (2) is 85-90 ℃.
13. The method of claim 5, wherein the drying time in step (2) is 20-30 h.
14. The method of claim 5, wherein said agitating of step (3) is performed using an agitator.
15. The method of claim 5, wherein the stirring time of step (3) is 30-60 min.
16. The method of claim 5, wherein said rolling of step (3) is performed using a three-roll mill.
17. The method of claim 16, wherein the gap between the rolls of the three roll mill is 3-5 μm.
18. The method according to claim 5, wherein the number of the pressing in the step (3) is 4 to 6.
19. The use of a ceramic metallization paste according to any of the claims 1-4 with a sintering temperature of 1330-1350 ℃, wherein the use is: the prepared ceramic metallization paste is coated on the ceramic end face of the vacuum arc-extinguishing chamber and then sintered for 40-60min in a hydrogen furnace at the temperature of 1330-1350 ℃.
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| CN201710749235.4A CN107365171B (en) | 2017-08-28 | 2017-08-28 | Ceramic metallization paste and preparation method and application thereof |
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