CN109678562B - Method for metallizing ceramic - Google Patents
Method for metallizing ceramic Download PDFInfo
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- CN109678562B CN109678562B CN201910167439.6A CN201910167439A CN109678562B CN 109678562 B CN109678562 B CN 109678562B CN 201910167439 A CN201910167439 A CN 201910167439A CN 109678562 B CN109678562 B CN 109678562B
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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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- 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
- C04B41/45—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
- C04B41/5144—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal with a composition mainly composed of one or more of the metals of the iron group
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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
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
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Abstract
A method of ceramic metallization comprising the steps of: s1: preparing a metal paste, uniformly mixing molybdenum powder, manganese powder, titanium dioxide powder and a binder, and wet-grinding to obtain a metal paste S2: printing the metal paste obtained in the step S1 on two planes of a ceramic substrate, baking and sintering; s3: and (4) nickel coating. The metallization method provided by the invention can obviously enhance the air tightness of subsequent end sealing.
Description
Technical Field
The invention relates to the field of ceramic material processing, in particular to a method for metallizing ceramic.
Background
The sealing of ceramic connecting material is a multi-purpose comprehensive technology, which has wide application in the national economic fields of aerospace, aviation, electric power, electronics, machinery, chemical engineering, petroleum, mining, automobiles and the like and the national defense and military fields, and is a key technology for ensuring the high quality of various complete machines and components. The ceramic connecting material of the battery connector is used as a key component material in the connection technology of batteries and batteries of electric vehicles, has excellent flexural strength and extremely high tensile strength, and has great application value in the field of electric vehicles. At present, the ceramic has better thermal shock resistance and high insulation which are incomparable with other materials, so that the ceramic connecting material prepared into the power battery sealing connector has great market prospect.
However, ceramics have the problems of high brittleness, low breaking strength and tensile strength, and the like; in addition, pores are left in the conventional ceramic connecting material in the sintering process, so that the air tightness of the ceramic connecting material is reduced; the traditional material can generate cracks in the preparation process, and the cracks can be expanded along with the time; the time required by the traditional method is long, so that the time and the energy are wasted; the traditional granulation process can cause the breakage of particles, and has larger brittleness and hardness.
Therefore, a ceramic connecting material that can effectively solve the above technical problems is to be developed in the art.
Disclosure of Invention
In order to solve the above technical problem, a first aspect of the present invention provides a method for ceramic metallization, comprising the steps of:
s1: preparing a metal paste
Uniformly mixing molybdenum powder, manganese powder, titanium dioxide powder and a binder, and wet-grinding to obtain a metal paste;
s2: printing the metal paste obtained in the step S1 on two planes of a ceramic substrate, baking and sintering;
s3: and (4) nickel coating.
As a preferred embodiment, the weight ratio of the molybdenum powder to the manganese powder is (45-75): (5-22).
In a preferred embodiment, the weight ratio of the titanium dioxide powder to the ceramic matrix is (10-15): (10-23).
In a preferred embodiment, the weight ratio of the titanium dioxide powder, the ceramic matrix, the molybdenum powder and the manganese powder is (10-15): (10-23): (45-75): (5-22).
As a preferred embodiment, the metal paste has a particle size of 1.3 to 1.8 μm.
As a preferred embodiment, the ceramic matrix comprises Al2O3、ZrO2、TiO2、SiO2MgO, CaO and SrO.
As a preferred embodiment, the ceramic matrix comprises Al2O3、TiO2、SiO2CaO and SrO.
As a preferred embodiment, the Al2O3、TiO2、SiO2The weight ratio of CaO to SrO is (30-35): 1: (3-5): (0.2-0.5): (0.2-0.5).
In a preferred embodiment, the nickel is applied by one of electroplating nickel, chemically applying nickel after electroplating, and chemically applying nickel after electroplating.
In a preferred embodiment, the printing in step S2 uses a welding jig, and the shape of the welding jig is determined by the ceramic substrate.
Detailed Description
For purposes of the following detailed description, it is to be understood that the invention may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
Moreover, it should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of "1 to 10" is intended to include all sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, i.e., having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.
The drugs or components used in the present invention are all commercially available.
In order to solve the above technical problems, a first aspect of the present invention provides a method of ceramic metallization.
In a specific embodiment, the method of ceramic metallization comprises the steps of:
s1: preparing a metal paste
Uniformly mixing molybdenum powder, manganese powder, titanium dioxide powder and a binder, and wet-grinding to obtain a metal paste;
s2: printing the metal paste obtained in the step S1 on two planes of a ceramic substrate, baking and sintering;
s3: and (4) nickel coating.
In a specific embodiment, the weight ratio of the molybdenum powder to the manganese powder is (45-75): (5-22).
In a preferred embodiment, the weight ratio of molybdenum powder to manganese powder is 60: 17.
in a specific embodiment, the weight ratio of the titanium dioxide powder to the ceramic matrix is (10-15): (10-23).
In a preferred embodiment, the weight ratio of titanium dioxide dust to ceramic matrix is 12: 17.
in a specific embodiment, the weight ratio of the titanium dioxide powder, the ceramic matrix, the molybdenum powder and the manganese powder is (10-15): (10-23): (45-75): (5-22).
The applicant finds that when the weight ratio of the titanium dioxide powder, the ceramic matrix, the molybdenum powder and the manganese powder is controlled to be (10-15): (10-23): (45-75): (5-22), the subsequent sealing airtightness can be obviously enhanced. The reason is probably that when such a ratio is controlled, the surface energy can be increased, the grain rearrangement and the grain growth are promoted, and the flexural strength is effectively increased.
In a preferred embodiment, the weight ratio of the titanium dioxide powder, the ceramic matrix, the molybdenum powder and the manganese powder is 12: 17: 60: 17.
in a specific embodiment, the metal paste has a particle size of 1.3 to 1.8 μm.
In a preferred embodiment, the metal paste has a particle size of 1.5 μm.
In a specific embodiment, the ceramic matrix comprises Al2O3、ZrO2、TiO2、SiO2MgO, CaO and SrO.
In a preferred embodiment, the ceramic matrix comprises Al2O3、TiO2、SiO2CaO and SrO.
In particular toIn an embodiment, the Al2O3、TiO2、SiO2The weight ratio of CaO to SrO is (30-35): 1: (3-5): (0.2-0.5): (0.2-0.5).
In a preferred embodiment, the Al is2O3、TiO2、SiO2And the weight ratio of CaO to SrO is 32: 1: 4: 0.35: 0.35.
in a specific embodiment, the sintering is vacuum sintering, the sintering temperature is 1500-1600 ℃, and the sintering time is 4-6 h.
In a preferred embodiment, the sintering is vacuum sintering, the sintering temperature is 1550 ℃, and the sintering time is 4.5 h.
When the manganese powder is added into the ceramic powder, the temperature is controlled to 1550-.
In particular embodiments, the binder is terpineol and/or ethyl cellulose.
In a preferred embodiment, the binder is terpineol and ethyl cellulose in a weight ratio of 3: and 7, combining.
In a specific embodiment, the nickel plating method is one of nickel plating, chemical nickel plating and chemical nickel plating, and chemical nickel plating and nickel plating.
In a preferred embodiment, the nickel is plated by a method of plating nickel.
In a specific embodiment, in step S2, a welding jig is used for printing, and the shape of the welding jig is determined by the ceramic substrate. This is because the heat dissipation problem of the ceramic part on the ceramic-to-metal welding surface must be considered in the welding jig designed for various products, so as to avoid the generation of ceramic microcracks due to stress concentration, which causes the subsequent ceramic to generate random leakage, and the vacuum degree gradually decreases until the failure. Therefore, the ceramic end of the welding fixture close to the welding surface is added with the radiating ring or the radiating block according to different shapes of ceramics.
In order to solve the above technical problems, a second aspect of the present invention provides a method for preparing a ceramic substrate.
In a specific embodiment, the method for preparing the ceramic matrix comprises the following steps:
weighing ceramic matrix raw materials according to the formula amount, uniformly mixing, putting into an oven for baking at the baking temperature of 140-160 ℃ for 10-20 h, putting into a ball mill for ball milling for 20-28 h to obtain uniformly refined mixed raw materials, wherein the granularity reaches 3-3.5 mu m, heating to 1100-1200 ℃ at 3-5 ℃ per minute in air, preserving heat and presintering for 2h, cooling along with the furnace, crushing the obtained mixed raw materials, carrying out secondary ball milling, sieving with an 80-mesh sieve and then drying to obtain mixed powder, adding 10% of polyvinyl alcohol into the mixed powder, granulating by using a granulator, and carrying out dry pressing molding by using a press machine under 6MPa to obtain a ceramic blank; sintering the ceramic blank, controlling the temperature to be 37-300 ℃ for 200 minutes, controlling the temperature to be 300-850 ℃ for 300 minutes, controlling the temperature to be 850-1250 ℃ for 150 minutes, controlling the temperature to be 1250-1600 ℃ for 150 minutes, and finally controlling the temperature to be 1600 ℃ for 150 minutes to obtain the ceramic matrix.
In a preferred embodiment, the method for preparing the ceramic matrix comprises the following steps:
weighing ceramic matrix raw materials according to the formula amount, uniformly mixing, placing into an oven for baking at the baking temperature of 150 ℃ for 15h, placing into a ball mill for ball milling for 24h to obtain uniformly refined mixed raw materials, wherein the granularity reaches 3.2 mu m, heating to 1150 ℃ at 4 ℃ per minute in air, preserving heat and presintering for 2h, cooling along with the furnace, crushing the obtained mixed raw materials, carrying out secondary ball milling, sieving with an 80-mesh sieve and drying to obtain mixed powder, adding 10% of polyvinyl alcohol into the mixed powder, granulating by using a granulator, and carrying out dry pressing molding by using a press machine under 6MPa to obtain a ceramic blank; sintering the ceramic blank, heating the temperature from 37 ℃ to 300 ℃, maintaining the temperature at 300 ℃ for 30min, heating the temperature from 300 ℃ to 850 ℃, heating the temperature from 850 ℃ to 1250 ℃, maintaining the temperature at 1250 ℃ for 40min, heating the temperature from 1250 ℃ to 1600 ℃, and finally controlling the temperature at 1600 ℃ and preserving the temperature for 150 min to obtain the ceramic matrix.
Electroplating is an electrochemical process and also an oxidation-reduction process, and the basic process of electroplating is to immerse a part in a solution of metal salt as a cathode, a metal plate as an anode and then to deposit a required coating on the part after a direct current power supply is connected.
Adopt the nickel of electroplating, easy operation, safety to can effectually prevent the subsidence of other impurity on ceramic matrix surface, make the later stage not have the dissociation of impurity and lead to the decline of gas tightness.
Thereby effectively improving the air tightness of the surface of the ceramic matrix.
In a specific embodiment, during nickel plating, the cathode is a ceramic substrate to be plated, the anode is a pure nickel plate, and the following reactions respectively occur at the cathode and the anode:
cathode (plated): ni2++2e → Ni (main reaction)
2H++2e→H2↓ (side reaction)
Anode (nickel plate): ni-2 e → Ni2+(main reaction)
4OH-－4e→2H2O+O2(side reaction)
The following description will be given by way of specific examples.
Examples
Example 1
A first aspect of example 1 provides a method of ceramic metallization comprising the steps of:
s1: preparing a metal paste
Uniformly mixing molybdenum powder, manganese powder, titanium dioxide powder and a binder, and wet-grinding to obtain a metal paste;
s2: printing the metal paste obtained in the step S1 on two planes of a ceramic substrate, baking and sintering;
s3: electroplating nickel;
the weight ratio of the titanium dioxide powder, the ceramic matrix, the molybdenum powder and the manganese powder is 12: 17: 60: 17, the sintering is vacuum sintering, the sintering temperature is 1550 ℃, the sintering time is 5h, and the binder is terpineol and ethyl cellulose according to a weight ratio of 3: and 7, combining.
A second aspect of example 1 provides a method of preparing a ceramic substrate comprising the steps of:
weighing ceramic matrix raw materials according to the formula amount, uniformly mixing, placing into an oven for baking at the baking temperature of 150 ℃ for 15h, placing into a ball mill for ball milling for 24h to obtain uniformly refined mixed raw materials, wherein the granularity reaches 3.2 mu m, heating to 1150 ℃ at 4 ℃ per minute in air, preserving heat and presintering for 2h, cooling along with the furnace, crushing the obtained mixed raw materials, carrying out secondary ball milling, sieving with an 80-mesh sieve and drying to obtain mixed powder, adding 10% of polyvinyl alcohol into the mixed powder, granulating by using a granulator, and carrying out dry pressing molding by using a press machine under 6MPa to obtain a ceramic blank; sintering the ceramic blank, heating the temperature from 37 ℃ to 300 ℃, maintaining the temperature at 300 ℃ for 30min, heating the temperature from 300 ℃ to 850 ℃, heating the temperature from 850 ℃ to 1250 ℃, maintaining the temperature at 1250 ℃ for 40min, heating the temperature from 1250 ℃ to 1600 ℃, and finally controlling the temperature at 1600 ℃ and preserving the temperature for 150 min to obtain a ceramic matrix;
the Al is2O3、TiO2、SiO2And the weight ratio of CaO to SrO is 32: 1: 4: 0.35: 0.35.
example 2
A first aspect of example 2 provides a method of ceramic metallization comprising the steps of:
s1: preparing a metal paste
Uniformly mixing molybdenum powder, manganese powder, titanium dioxide powder and a binder, and wet-grinding to obtain a metal paste;
s2: printing the metal paste obtained in the step S1 on two planes of a ceramic substrate, baking and sintering;
s3: electroplating nickel;
the weight ratio of the titanium dioxide powder, the ceramic matrix, the molybdenum powder and the manganese powder is 10: 10: 45: 5, sintering is vacuum sintering, the sintering temperature is 1500 ℃, the sintering time is 4h, and the binder is terpineol and ethyl cellulose according to a weight ratio of 3: and 7, combining.
A second aspect of example 2 provides a method of preparing a ceramic substrate comprising the steps of:
weighing ceramic matrix raw materials according to the formula amount, uniformly mixing, placing into an oven for baking at the baking temperature of 150 ℃ for 15h, placing into a ball mill for ball milling for 24h to obtain uniformly refined mixed raw materials, wherein the granularity reaches 3.2 mu m, heating to 1150 ℃ at 4 ℃ per minute in air, preserving heat and presintering for 2h, cooling along with the furnace, crushing the obtained mixed raw materials, carrying out secondary ball milling, sieving with an 80-mesh sieve and drying to obtain mixed powder, adding 10% of polyvinyl alcohol into the mixed powder, granulating by using a granulator, and carrying out dry pressing molding by using a press machine under 6MPa to obtain a ceramic blank; sintering the ceramic blank, heating the temperature from 37 ℃ to 300 ℃, maintaining the temperature at 300 ℃ for 30min, heating the temperature from 300 ℃ to 850 ℃, heating the temperature from 850 ℃ to 1250 ℃, maintaining the temperature at 1250 ℃ for 40min, heating the temperature from 1250 ℃ to 1600 ℃, and finally controlling the temperature at 1600 ℃ and preserving the temperature for 150 min to obtain a ceramic matrix;
the Al is2O3、TiO2、SiO2And the weight ratio of CaO to SrO is 30: 1: 3: 0.2: 0.2.
example 3
A first aspect of example 3 provides a method of ceramic metallization comprising the steps of:
s1: preparing a metal paste
Uniformly mixing molybdenum powder, manganese powder, titanium dioxide powder and a binder, and wet-grinding to obtain a metal paste;
s2: printing the metal paste obtained in the step S1 on two planes of a ceramic substrate, baking and sintering;
s3: electroplating nickel;
the weight ratio of the titanium dioxide powder, the ceramic matrix, the molybdenum powder and the manganese powder is 15: 23: 75: 22, the sintering is vacuum sintering, the sintering temperature is 1600 ℃, the sintering time is 6h, and the binder is terpineol and ethyl cellulose according to a weight ratio of 3: and 7, combining.
A second aspect of example 3 provides a method of preparing a ceramic substrate comprising the steps of:
weighing ceramic matrix raw materials according to the formula amount, uniformly mixing, placing into an oven for baking at the baking temperature of 150 ℃ for 15h, placing into a ball mill for ball milling for 24h to obtain uniformly refined mixed raw materials, wherein the granularity reaches 3.2 mu m, heating to 1150 ℃ at 4 ℃ per minute in air, preserving heat and presintering for 2h, cooling along with the furnace, crushing the obtained mixed raw materials, carrying out secondary ball milling, sieving with an 80-mesh sieve and drying to obtain mixed powder, adding 10% of polyvinyl alcohol into the mixed powder, granulating by using a granulator, and carrying out dry pressing molding by using a press machine under 6MPa to obtain a ceramic blank; sintering the ceramic blank, heating the temperature from 37 ℃ to 300 ℃, maintaining the temperature at 300 ℃ for 30min, heating the temperature from 300 ℃ to 850 ℃, heating the temperature from 850 ℃ to 1250 ℃, maintaining the temperature at 1250 ℃ for 40min, heating the temperature from 1250 ℃ to 1600 ℃, and finally controlling the temperature at 1600 ℃ and preserving the temperature for 150 min to obtain a ceramic matrix;
the Al is2O3、TiO2、SiO2And the weight ratio of CaO to SrO is 35: 1: 5: 0.5: 0.5.
example 4
A first aspect of example 4 provides a method of ceramic metallization comprising the steps of:
s1: preparing a metal paste
Uniformly mixing molybdenum powder, manganese powder, titanium dioxide powder and a binder, and wet-grinding to obtain a metal paste;
s2: printing the metal paste obtained in the step S1 on two planes of a ceramic substrate, baking and sintering;
s3: electroplating nickel;
the weight ratio of the titanium dioxide powder, the ceramic matrix, the molybdenum powder and the manganese powder is 18: 7: 60: 17, the sintering is vacuum sintering, the sintering temperature is 1550 ℃, the sintering time is 5h, and the binder is terpineol and ethyl cellulose according to a weight ratio of 3: and 7, combining.
A second aspect of example 4 provides a method of preparing a ceramic substrate comprising the steps of:
weighing ceramic matrix raw materials according to the formula amount, uniformly mixing, placing into an oven for baking at the baking temperature of 150 ℃ for 15h, placing into a ball mill for ball milling for 24h to obtain uniformly refined mixed raw materials, wherein the granularity reaches 3.2 mu m, heating to 1150 ℃ at 4 ℃ per minute in air, preserving heat and presintering for 2h, cooling along with the furnace, crushing the obtained mixed raw materials, carrying out secondary ball milling, sieving with an 80-mesh sieve and drying to obtain mixed powder, adding 10% of polyvinyl alcohol into the mixed powder, granulating by using a granulator, and carrying out dry pressing molding by using a press machine under 6MPa to obtain a ceramic blank; sintering the ceramic blank, heating the temperature from 37 ℃ to 300 ℃, maintaining the temperature at 300 ℃ for 30min, heating the temperature from 300 ℃ to 850 ℃, heating the temperature from 850 ℃ to 1250 ℃, maintaining the temperature at 1250 ℃ for 40min, heating the temperature from 1250 ℃ to 1600 ℃, and finally controlling the temperature at 1600 ℃ and preserving the temperature for 150 min to obtain a ceramic matrix;
the Al is2O3、TiO2、SiO2And the weight ratio of CaO to SrO is 32: 1: 4: 0.35: 0.35.
example 5
A first aspect of example 5 provides a method of ceramic metallization comprising the steps of:
s1: preparing a metal paste
Uniformly mixing molybdenum powder, manganese powder, titanium dioxide powder and a binder, and wet-grinding to obtain a metal paste;
s2: printing the metal paste obtained in the step S1 on two planes of a ceramic substrate, baking and sintering;
s3: electroplating nickel;
the weight ratio of the titanium dioxide powder, the ceramic matrix, the molybdenum powder and the manganese powder is 12: 17: 85: 2, the sintering is vacuum sintering, the sintering temperature is 1550 ℃, the sintering time is 5h, and the binder is terpineol and ethyl cellulose according to a weight ratio of 3: and 7, combining.
A second aspect of example 5 provides a method of preparing a ceramic substrate comprising the steps of:
weighing ceramic matrix raw materials according to the formula amount, uniformly mixing, placing into an oven for baking at the baking temperature of 150 ℃ for 15h, placing into a ball mill for ball milling for 24h to obtain uniformly refined mixed raw materials, wherein the granularity reaches 3.2 mu m, heating to 1150 ℃ at 4 ℃ per minute in air, preserving heat and presintering for 2h, cooling along with the furnace, crushing the obtained mixed raw materials, carrying out secondary ball milling, sieving with an 80-mesh sieve and drying to obtain mixed powder, adding 10% of polyvinyl alcohol into the mixed powder, granulating by using a granulator, and carrying out dry pressing molding by using a press machine under 6MPa to obtain a ceramic blank; sintering the ceramic blank, heating the temperature from 37 ℃ to 300 ℃, maintaining the temperature at 300 ℃ for 30min, heating the temperature from 300 ℃ to 850 ℃, heating the temperature from 850 ℃ to 1250 ℃, maintaining the temperature at 1250 ℃ for 40min, heating the temperature from 1250 ℃ to 1600 ℃, and finally controlling the temperature at 1600 ℃ and preserving the temperature for 150 min to obtain a ceramic matrix;
the Al is2O3、TiO2、SiO2And the weight ratio of CaO to SrO is 32: 1: 4: 0.35: 0.35.
example 6
A first aspect of example 6 provides a method of ceramic metallization comprising the steps of:
s1: preparing a metal paste
Uniformly mixing molybdenum powder, manganese powder, titanium dioxide powder and a binder, and wet-grinding to obtain a metal paste;
s2: printing the metal paste obtained in the step S1 on two planes of a ceramic substrate, baking and sintering;
s3: electroplating nickel;
the weight ratio of the titanium dioxide powder, the ceramic matrix, the molybdenum powder and the manganese powder is 18: 7: 90: 3, the sintering is vacuum sintering, the sintering temperature is 1550 ℃, the sintering time is 5h, and the binder is terpineol and ethyl cellulose according to a weight ratio of 3: and 7, combining.
A second aspect of example 6 provides a method of preparing a ceramic substrate comprising the steps of:
weighing ceramic matrix raw materials according to the formula amount, uniformly mixing, placing into an oven for baking at the baking temperature of 150 ℃ for 15h, placing into a ball mill for ball milling for 24h to obtain uniformly refined mixed raw materials, wherein the granularity reaches 3.2 mu m, heating to 1150 ℃ at 4 ℃ per minute in air, preserving heat and presintering for 2h, cooling along with the furnace, crushing the obtained mixed raw materials, carrying out secondary ball milling, sieving with an 80-mesh sieve and drying to obtain mixed powder, adding 10% of polyvinyl alcohol into the mixed powder, granulating by using a granulator, and carrying out dry pressing molding by using a press machine under 6MPa to obtain a ceramic blank; sintering the ceramic blank, heating the temperature from 37 ℃ to 300 ℃, maintaining the temperature at 300 ℃ for 30min, heating the temperature from 300 ℃ to 850 ℃, heating the temperature from 850 ℃ to 1250 ℃, maintaining the temperature at 1250 ℃ for 40min, heating the temperature from 1250 ℃ to 1600 ℃, and finally controlling the temperature at 1600 ℃ and preserving the temperature for 150 min to obtain a ceramic matrix;
the Al is2O3、TiO2、SiO2And the weight ratio of CaO to SrO is 32: 1: 4: 0.35: 0.35.
example 7
A first aspect of example 7 provides a method of ceramic metallization comprising the steps of:
s1: preparing a metal paste
Uniformly mixing molybdenum powder, manganese powder, titanium dioxide powder and a binder, and wet-grinding to obtain a metal paste;
s2: printing the metal paste obtained in the step S1 on two planes of a ceramic substrate, baking and sintering;
s3: electroplating nickel;
the weight ratio of the titanium dioxide powder, the ceramic matrix, the molybdenum powder and the manganese powder is 12: 17: 60: 17, the sintering is vacuum sintering, the sintering temperature is 1550 ℃, the sintering time is 5h, and the binder is terpineol and ethyl cellulose according to a weight ratio of 3: and 7, combining.
A second aspect of example 7 provides a method of preparing a ceramic substrate comprising the steps of:
weighing ceramic matrix raw materials according to the formula amount, uniformly mixing, placing into an oven for baking at the baking temperature of 150 ℃ for 15h, placing into a ball mill for ball milling for 24h to obtain uniformly refined mixed raw materials, wherein the granularity reaches 3.2 mu m, heating to 1150 ℃ at 4 ℃ per minute in air, preserving heat and presintering for 2h, cooling along with the furnace, crushing the obtained mixed raw materials, carrying out secondary ball milling, sieving with an 80-mesh sieve and drying to obtain mixed powder, adding 10% of polyvinyl alcohol into the mixed powder, granulating by using a granulator, and carrying out dry pressing molding by using a press machine under 6MPa to obtain a ceramic blank; sintering the ceramic blank, heating the temperature from 37 ℃ to 300 ℃, maintaining the temperature at 300 ℃ for 30min, heating the temperature from 300 ℃ to 850 ℃, heating the temperature from 850 ℃ to 1250 ℃, maintaining the temperature at 1250 ℃ for 40min, heating the temperature from 1250 ℃ to 1600 ℃, and finally controlling the temperature at 1600 ℃ and preserving the temperature for 150 min to obtain a ceramic matrix;
the Al is2O3、TiO2、SiO2And the weight ratio of CaO to SrO is 12: 1: 14: 0.1: 1.35.
example 8
A first aspect of example 8 provides a method of ceramic metallization comprising the steps of:
s1: preparing a metal paste
Uniformly mixing molybdenum powder, manganese powder, titanium dioxide powder and a binder, and wet-grinding to obtain a metal paste;
s2: printing the metal paste obtained in the step S1 on two planes of a ceramic substrate, baking and sintering;
s3: electroplating nickel;
the weight ratio of the titanium dioxide powder, the ceramic matrix, the molybdenum powder and the manganese powder is 12: 17: 60: 17, the sintering is vacuum sintering, the sintering temperature is 1250 ℃, the sintering time is 15h, and the binder is terpineol and ethyl cellulose in a weight ratio of 3: and 7, combining.
A second aspect of example 8 provides a method of preparing a ceramic substrate comprising the steps of:
weighing ceramic matrix raw materials according to the formula amount, uniformly mixing, placing into an oven for baking at the baking temperature of 150 ℃ for 15h, placing into a ball mill for ball milling for 24h to obtain uniformly refined mixed raw materials, wherein the granularity reaches 3.2 mu m, heating to 1150 ℃ at 4 ℃ per minute in air, preserving heat and presintering for 2h, cooling along with the furnace, crushing the obtained mixed raw materials, carrying out secondary ball milling, sieving with an 80-mesh sieve and drying to obtain mixed powder, adding 10% of polyvinyl alcohol into the mixed powder, granulating by using a granulator, and carrying out dry pressing molding by using a press machine under 6MPa to obtain a ceramic blank; sintering the ceramic blank, heating the temperature from 37 ℃ to 300 ℃, maintaining the temperature at 300 ℃ for 30min, heating the temperature from 300 ℃ to 850 ℃, heating the temperature from 850 ℃ to 1250 ℃, maintaining the temperature at 1250 ℃ for 40min, heating the temperature from 1250 ℃ to 1600 ℃, and finally controlling the temperature at 1600 ℃ and preserving the temperature for 150 min to obtain a ceramic matrix;
the Al is2O3、TiO2、SiO2And the weight ratio of CaO to SrO is 32: 1: 4: 0.35: 0.35.
example 9
A first aspect of example 9 provides a method of ceramic metallization comprising the steps of:
s1: preparing a metal paste
Uniformly mixing molybdenum powder, manganese powder, titanium dioxide powder and a binder, and wet-grinding to obtain a metal paste;
s2: printing the metal paste obtained in the step S1 on two planes of a ceramic substrate, baking and sintering;
s3: electroplating nickel;
the weight ratio of the titanium dioxide powder, the ceramic matrix, the molybdenum powder and the manganese powder is 18: 7: 90: 3, the sintering is vacuum sintering, the sintering temperature is 1200 ℃, the sintering time is 15h, and the binder is terpineol and ethyl cellulose according to the weight ratio of 3: and 7, combining.
A second aspect of example 9 provides a method of preparing a ceramic substrate comprising the steps of:
weighing ceramic matrix raw materials according to the formula amount, uniformly mixing, placing into an oven for baking at the baking temperature of 150 ℃ for 15h, placing into a ball mill for ball milling for 24h to obtain uniformly refined mixed raw materials, wherein the granularity reaches 3.2 mu m, heating to 1150 ℃ at 4 ℃ per minute in air, preserving heat and presintering for 2h, cooling along with the furnace, crushing the obtained mixed raw materials, carrying out secondary ball milling, sieving with an 80-mesh sieve and drying to obtain mixed powder, adding 10% of polyvinyl alcohol into the mixed powder, granulating by using a granulator, and carrying out dry pressing molding by using a press machine under 6MPa to obtain a ceramic blank; sintering the ceramic blank, heating the temperature from 37 ℃ to 300 ℃, maintaining the temperature at 300 ℃ for 30min, heating the temperature from 300 ℃ to 850 ℃, heating the temperature from 850 ℃ to 1250 ℃, maintaining the temperature at 1250 ℃ for 40min, heating the temperature from 1250 ℃ to 1600 ℃, and finally controlling the temperature at 1600 ℃ and preserving the temperature for 150 min to obtain a ceramic matrix;
the Al is2O3、TiO2、SiO2And the weight ratio of CaO to SrO is 12: 1: 14: 0.1: 1.35.
evaluation of Performance test
1) Performance testing
The flexural strength of the power battery sealing connectors prepared in examples 1 to 9 was tested by the method provided in GB/T3001-2007, and the tensile strength of the power battery sealing connectors prepared in examples 1 to 10 was tested by the method provided in GB/T228-1987, with the results shown in table 1.
TABLE 1
| Examples | Flexural strength/MPa | Tensile strengthstrength/MPa | Porosity/% |
| 1 | 82.9 | 421 | 0.002 |
| 2 | 81.5 | 412 | 0.009 |
| 3 | 80.6 | 416 | 0.008 |
| 4 | 69.4 | 380 | 0.371 |
| 5 | 71.1 | 379 | 0.361 |
| 6 | 65.8 | 309 | 0.386 |
| 7 | 65.9 | 311 | 0.201 |
| 8 | 68.2 | 339 | 0.231 |
| 9 | 42.5 | 205 | 0.392 |
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (4)
1. A method of ceramic metallization, comprising the steps of:
s1: preparing a metal paste;
uniformly mixing molybdenum powder, manganese powder, titanium dioxide powder and a binder, and wet-grinding to obtain a metal paste;
s2: printing the metal paste obtained in the step S1 on two planes of a ceramic substrate, baking and sintering;
s3: nickel is coated;
the weight ratio of the titanium dioxide powder, the ceramic matrix, the molybdenum powder and the manganese powder is 12: 17: 60: 17;
the ceramic matrix comprises Al2O3、TiO2、SiO2CaO and SrO;
the Al is2O3、TiO2、SiO2The weight ratio of CaO to SrO is (30-35): 1: (3-5): (0.2-0.5): (0.2-0.5).
2. The method of claim 1, wherein the metal paste has a particle size of 1.3-1.8 μm.
3. The method of claim 2, wherein the nickel is applied by one of electroplating nickel, chemically applying nickel after electroplating, and chemically applying nickel after electroplating.
4. The method according to any one of claims 2 to 3, wherein the printing in step S2 uses a welding jig, and the shape of the welding jig is determined by the shape of the ceramic substrate.
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