CN115732117A - Conductive silver paste for ceramic surface circuit printing and preparation method and application thereof - Google Patents
Conductive silver paste for ceramic surface circuit printing and preparation method and application thereof Download PDFInfo
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- CN115732117A CN115732117A CN202210220815.5A CN202210220815A CN115732117A CN 115732117 A CN115732117 A CN 115732117A CN 202210220815 A CN202210220815 A CN 202210220815A CN 115732117 A CN115732117 A CN 115732117A
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- 238000002156 mixing Methods 0.000 claims description 69
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Images
Abstract
The invention belongs to the technical field of 3D printing, and particularly relates to conductive silver paste for printing a ceramic surface circuit, and a preparation method and application thereof. The invention provides conductive silver paste for printing a ceramic surface circuit, which comprises the following components in percentage by mass: 50-87.8% of silver powder; 0-15% of ceramic powder; 0.5-9% of nano graphene oxide; 10-15% of a solvent; 0.5 to 3 percent of surfactant; 0.2 to 2 percent of binder; 0.5 to 2 percent of diluent; 0.5 to 5 percent of thixotropic agent. According to the invention, through the matching of the components and the adjustment of materials, the obtained conductive silver paste ensures that the silver structure printed by 3D has smaller thermal strain in a high-temperature environment, and the thermal strain is only 0.6% at the high temperature of 800 ℃, so that the thermal stress of the ceramic and silver interface is effectively reduced, the shedding of the silver conductive structure at the high temperature is avoided, and the high-temperature stability of the material is improved.
Description
Technical Field
The invention belongs to the technical field of 3D printing, and particularly relates to conductive silver paste for printing a ceramic surface circuit, and a preparation method and application thereof.
Background
The conductive silver paste is a mixed paste composed of high-purity metal silver particles, an adhesive, a solvent and an auxiliary agent. 3D printing is a rapid prototyping technology, also known as additive manufacturing, which is a technology that uses a digital model file as a basis, uses a bondable material such as powdered metal or plastic, and constructs an object by layer-by-layer printing.
In 3D printing, a forming means of a silver paste is performed by using screen printing, and a conductive silver paste and a preparation method thereof are disclosed in the prior art, wherein the conductive silver paste comprises conductive silver powder, glass powder and an organic carrier, wherein the conductive silver powder is spherical, the organic carrier comprises an organic solvent, a surfactant, a defoaming agent, an anti-settling agent, a thickening agent, a coupling agent and a plasticizer, the organic solvent is tributyl citrate or dibutyl phthalate, the surfactant is xylene or lecithin, the defoaming agent is n-butyl alcohol or methyl silicone oil, the anti-settling agent is a castor oil derivative, the thickening agent is ethyl cellulose, the coupling agent is a silane coupling agent or a titanate coupling agent, and the plasticizer is dioctyl phthalate or diethylene glycol butyl ether acetate.
However, the conductive silver paste in the prior art generally has the problems of low static viscosity, high fluidity, low forming precision, high thermal strain at a high temperature state and easy shedding with a substrate in a high-temperature use process.
Disclosure of Invention
Therefore, the invention aims to overcome the defects of low static viscosity, high fluidity, low forming precision, high thermal strain at a high temperature and the like of conductive silver paste in the prior art, and provides conductive silver paste for ceramic surface circuit printing, and a preparation method and application thereof.
Therefore, the invention provides the following technical scheme,
the invention provides conductive silver paste for ceramic surface circuit printing, which comprises the following components in percentage by mass:
50-87.8% of silver powder;
0-15% of ceramic powder;
0.5-9% of graphene oxide;
10-15% of a solvent;
0.5 to 3 percent of surfactant;
0.2 to 2 percent of binder;
0.5 to 2 percent of diluent;
0.5 to 5 percent of thixotropic agent.
Optionally, the ceramic powder comprises silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide;
optionally, the mass ratio of the silicon oxide, the boron oxide, the aluminum oxide, the zinc oxide, the sodium oxide and the calcium oxide is (1-8): (2-4): (1-6): (0.5-2): (0.5-1): (0.5-1).
Optionally, at least one of (1) to (5) is satisfied:
(1) The solvent is one of terpineol, butanol and isopropanol;
(2) The surfactant is one of triton and sodium dodecyl benzene sulfonate;
(3) The binder is one or more of ethyl cellulose, polyvinyl alcohol and polyvinyl butyral;
(4) The diluent is one or more of polyvinylpyrrolidone and polyacrylic acid;
(5) The thixotropic agent is one or more of nano montmorillonite, castor oil, hydroxyethyl cellulose or gas-phase nano silicon dioxide.
The invention provides a preparation method of the conductive silver paste for printing the ceramic surface circuit, which comprises the following steps:
(1) Mixing a solvent and a surfactant, adding a binder, stirring, adding a diluent and a thixotropic agent, and uniformly mixing to obtain an organic colloid;
(2) Mixing silver powder and ceramic powder, and performing ball milling to obtain powder;
(3) Carrying out ultrasonic dispersion and drying on graphene oxide;
(4) And mixing the obtained organic colloid with powder, and adding the dried graphene oxide to obtain the conductive silver paste.
Optionally, the stirring temperature is 50-100 ℃, and the stirring time is 1-5h;
and/or, the mixing is carried out under the vacuum condition, and the vacuum degree is 20-100Kpa.
Optionally, the particle size of the graphene oxide is 0.05-50 μm;
and/or the ultrasonic dispersion time is 0.5-5h, and the drying temperature is 50-100 ℃.
Optionally, the silver powder is one of flake silver powder or spherical silver powder;
the particle size of the silver powder is 30nm-20 μm.
The ball milling time is 5-12h;
the ball milling is wet ball milling or dry ball milling,
the mass ratio of powder to liquid in the wet ball milling process is 1: (5-20);
when the ball milling is wet ball milling, drying and grinding are carried out after the ball milling in the step (2) to obtain powder;
the drying temperature is 50-100 ℃, and the grinding time is 1-5h.
The invention also provides application of the conductive silver paste for ceramic surface circuit printing or the conductive silver paste prepared by the preparation method in 3D printing.
Optionally, at least one of (1) - (9) is satisfied:
(1) The 3D printing is direct-writing 3D printing or jet 3D printing;
(2) The direct-writing 3D printing speed is 0.1-150mm/s;
(3) The diameter of the direct-writing 3D printing head is 20-800 μm;
(4) The direct-writing 3D printing air pressure is 10-120Psi;
(5) The overlap rate of the line widths of the direct-writing 3D printing is 5% -15%;
(6) The spraying 3D printing speed is 0.5-100mm/s;
(7) The jet 3D printing distance is 1-10mm;
(8) The jetting 3D printing air pressure is 10-100Psi;
(9) The difference of the ejection 3D printing voltage is 50-100V.
Optionally, the printing step further comprises drying, binder removal and sintering.
Optionally, at least one of the following (1) to (5) is satisfied:
(1) Drying at 50-100 deg.C for 30-300min;
(2) Removing glue at 300-500 deg.C;
(3) Heating to the glue discharging temperature at the heating rate of 1-5 ℃/min;
(4) Sintering at 600-900 deg.C for 15-90min;
(5) Heating to the sintering temperature at a heating rate of 1-10 ℃/min.
Optionally, before adding the graphene oxide, the graphene oxide needs to be subjected to ultrasonic dispersion, drying and grinding.
Satisfies at least one of (1) to (4);
(1) The number of graphene oxide sheets is 1-20;
(2) The sheet diameter of the graphene oxide is 10-50 μm;
(3) The ultrasonic time is 20-60min;
(4) In the ultrasonic process, the mass ratio of the graphene oxide to the solution is 1: (20-100), wherein the solution is one of deionized water, absolute ethyl alcohol or N, N-dimethylformamide.
The technical scheme provided by the invention has the following advantages,
1. the invention provides conductive silver paste for printing a ceramic surface circuit, which comprises the following components in percentage by mass: 50-87.8% of silver powder; 0-15% of ceramic powder; 0.5-9% of graphene oxide; 10-15% of a solvent; 0.5 to 3 percent of surfactant; 0.2 to 2 percent of binder; 0.5 to 2 percent of diluent; 0.5 to 5 percent of thixotropic agent. According to the conductive silver paste disclosed by the invention, through the matching of the components and the adjustment of materials, the obtained conductive silver paste ensures that the silver structure for 3D printing has smaller thermal strain in a high-temperature environment, and the thermal strain is only 0.6% at the high temperature of 800 ℃, so that the conductive silver paste is effectiveThe thermal stress of the ceramic and silver interface is reduced, the silver conductive structure is prevented from falling off at high temperature, the high-temperature stability of the material is improved, the high-temperature use temperature reaches 900 ℃, the error of the line width forming precision is less than 10 microns, the error of the line spacing forming is less than 10 microns, and the conductivity reaches 2 multiplied by 10 7 s/m. Specifically, the conductive silver paste disclosed by the invention uses the thixotropic agent such as castor oil, the thixotropic agent has high viscosity at a low shear rate, and the use of the nano graphene oxide can effectively increase the steric hindrance effect of the nano graphene oxide in the paste, greatly improve the static viscosity of the paste, reduce the fluidity of the paste and further improve the forming precision. According to the invention, after the nano graphene oxide is subjected to high-temperature treatment, the nano graphene oxide is completely oxidized, but the conductivity characteristic of the silver material is not sacrificed, so that the high conductivity characteristic of the slurry is realized, and moreover, due to the fact that the nano graphene oxide can generate a certain proportion of micro-nano pores in the high-temperature treatment process, the pores can provide a certain deformation space for the expansion of the silver material in a high-temperature environment, so that the overall thermal strain of the material is effectively inhibited, and the stability of the electrode material in a high-temperature use state is improved. In addition, in the invention, the rheological property of the silver paste can be greatly modified by using a small amount of nano graphene oxide, and the preparation cost of the paste can be effectively reduced.
2. The conductive silver paste for printing the ceramic surface circuit provided by the invention can further comprise ceramic powder, wherein the ceramic powder is softened into a liquid phase under the action of high temperature and is deposited on the interface of the conductive paste and the ceramic substrate, so that the combination of the interface is promoted, and the problem of falling off of the conductive silver paste and the substrate can be further avoided.
3. The invention provides a preparation method of conductive silver paste for printing a circuit on a ceramic surface, which comprises the following steps: (1) Mixing a solvent and a surfactant, adding a binder, stirring and mixing, and adding a diluent and a thixotropic agent to obtain an organic colloid; (2) mixing the silver powder and the ceramic powder, and carrying out ball milling to obtain powder; (3) And mixing the obtained organic colloid with powder, and adding nano graphene oxide to obtain the conductive silver paste. The method provided by the invention ensures that the rheological property of the silver paste is improved on the premise of extremely small using amount of the graphene oxide, and the printing precision of the silver paste is improved.
4. The preparation method of the conductive silver paste for printing the ceramic surface circuit, provided by the invention, needs to perform ultrasonic dispersion on the graphene oxide. Carrying out ultrasonic dispersion to graphite oxide can effectually avoid graphite oxide to reunite, ensure graphite oxide's two-dimensional sheet structure, reduce multilayer structure and pile up and lead to graphite oxide thickness increase, improve graphite oxide slenderness ratio, increase specific surface area to effectively improve its steric hindrance effect in the thick liquids, can ensure to realize the improvement of silver thick liquids rheological property under the minimum prerequisite of graphite oxide quantity, improve its printing accuracy.
5. The preparation method of the conductive silver paste for ceramic surface circuit printing provided by the invention has the advantages that the vacuum uniform mixing is carried out in the step (1), so that the gas in the paste can be effectively removed, the dispersibility of the paste is promoted, and the stability of the paste is improved. In addition, the ball milling in the step (2) can disperse the agglomerated parts in the powder so as to realize better dispersion of the powder.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a view showing the molding accuracy of test example 1 of the present invention;
FIG. 2 is a schematic diagram of the conductivity change of a 3D printed silver paste in test example 3 of the present invention after high temperature use;
fig. 3 is a schematic diagram of thermal strain at high temperature after sintering of 3D printed silver paste in test example 3 of the present invention.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are conventional reagent products which are commercially available, and manufacturers are not indicated.
Example 1
The embodiment provides conductive silver paste for ceramic surface circuit printing, which comprises the following components in percentage by mass:
silver powder 80g, a mixture of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide (mass ratio of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide 1.
The embodiment also provides a preparation method of the conductive silver paste for ceramic surface circuit printing, which comprises the following steps:
1. 10g of terpineol and 0.5g of triton are mixed and stirred uniformly, then 0.5g of a mixture of ethyl cellulose and polyvinyl butyral (the mass ratio of the ethyl cellulose to the polyvinyl butyral is 1:1) is added, and stirring is carried out for 4.5 hours at a temperature of 90 ℃. Then, uniformly mixing the mixture by using a vacuum defoaming stirrer, then adding 0.5g of a mixture of polyvinylpyrrolidone and polyacrylic acid (the mass ratio of the polyvinylpyrrolidone to the polyacrylic acid is 1:1), 1.5g of a mixture of nano-montmorillonite and gas-phase nano-silica (the mass ratio of the nano-montmorillonite to the gas-phase nano-silica is 2:1), and uniformly mixing the mixture by using the vacuum defoaming stirrer (the vacuum degree is 20Kpa, and the stirring time is 300 s) to obtain the organic colloid.
2. Mixing 80g of flake silver powder (with the particle size of 5 μm) and 4g of a mixture of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide (the mass ratio of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide is 1.
3. Ultrasonically dispersing 3g of nano graphene oxide (single layer, sheet diameter of 30 mu m) in 60g of absolute ethyl alcohol for 2h, and then drying at 80 ℃;
4. adding the powder into the organic colloid, uniformly mixing by using a vacuum defoaming stirrer (the vacuum degree is 20Kpa, and the stirring time is 300 s), then adding 3g of dried nano graphene oxide, and uniformly mixing by using the vacuum defoaming stirrer (the vacuum degree is 20Kpa, and the stirring time is 300 s) to obtain the conductive silver paste.
Example 2 (different adhesive and thixotropic agent compared to example 1)
The embodiment provides conductive silver paste for ceramic surface circuit printing, which comprises the following components in percentage by mass:
silver powder 80g, a mixture of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide (mass ratio of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide 1.
The embodiment also provides a preparation method of the conductive silver paste for ceramic surface circuit printing, which comprises the following steps:
1. 10g of terpineol and 0.5g of triton were mixed and stirred uniformly, and then 0.5g of a mixture of ethyl cellulose, polyvinyl alcohol and polyvinyl butyral (mass ratio of ethyl cellulose, polyvinyl alcohol and polyvinyl butyral 1: 1) was added and stirred at 90 ℃ for 4.5 hours. Then, the mixture was mixed uniformly by a vacuum defoaming mixer, and then 0.5g of a mixture of polyvinylpyrrolidone and polyacrylic acid (the mass ratio of polyvinylpyrrolidone to polyacrylic acid is 1:1) and 1.5g of nano-montmorillonite were added and mixed uniformly by a vacuum defoaming mixer (the vacuum degree is 20Kpa, and the mixing time is 300 s) to obtain an organic colloid.
2. Mixing 80g of flake silver powder (with the particle size of 5 μm) and 4g of a mixture of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide (the mass ratio of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide is 1.
3. Ultrasonically dispersing 3g of nano graphene oxide (single layer, sheet diameter of 30 mu m) in 60g of absolute ethyl alcohol for 2h, and then drying at 80 ℃;
4. adding the powder into the organic colloid, uniformly mixing by using a vacuum defoaming stirrer (the vacuum degree is 20Kpa, and the stirring time is 300 s), then adding 3g of dried nano graphene oxide, and uniformly mixing by using the vacuum defoaming stirrer (the vacuum degree is 20Kpa, and the stirring time is 300 s) to obtain the conductive silver paste.
Example 3 (in comparison with example 1, the silver powder was spherical silver powder having a particle size of 100 nm)
The embodiment provides conductive silver paste for ceramic surface circuit printing, which comprises the following components in percentage by mass:
silver powder 80g, a mixture of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide (mass ratio of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide 1.
The embodiment also provides a preparation method of the conductive silver paste for ceramic surface circuit printing, which comprises the following steps:
1. 10g of terpineol and 0.5g of triton are mixed and stirred uniformly, then 0.5g of a mixture of ethyl cellulose and polyvinyl butyral (mass ratio of ethyl cellulose to polyvinyl butyral 1:1) is added, and stirring is carried out at a temperature of 90 ℃ for 4.5 hours. Then, uniformly mixing the mixture by using a vacuum defoaming stirrer, then adding 0.5g of a mixture of polyvinylpyrrolidone and polyacrylic acid (the mass ratio of the polyvinylpyrrolidone to the polyacrylic acid is 1:1) and 1.5g of a mixture of nano-montmorillonite and gas-phase nano-silica (the mass ratio of the nano-montmorillonite to the gas-phase nano-silica is 2:1), and uniformly mixing the mixture by using the vacuum defoaming stirrer (the vacuum degree is 20Kpa, and the stirring time is 300 s) to obtain the organic colloid.
2. After mixing 80g of spherical silver powder (particle size of 100 nm) and 4g of a mixture of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide (mass ratio of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide 1.
3. Ultrasonically dispersing 3g of nano graphene oxide (single layer, sheet diameter of 30 mu m) in 60g of absolute ethyl alcohol for 2h, and then drying at 80 ℃;
4. adding the powder into the organic colloid, uniformly mixing by using a vacuum defoaming stirrer (the vacuum degree is 20Kpa, and the stirring time is 300 s), then adding 3g of dried nano graphene oxide, and uniformly mixing by using the vacuum defoaming stirrer (the vacuum degree is 20Kpa, and the stirring time is 300 s) to obtain the conductive silver paste.
Example 4 (sheet diameter of graphene oxide is 50 μm compared with example 1)
The embodiment provides conductive silver paste for ceramic surface circuit printing, which comprises the following components in percentage by mass:
silver powder 80g, a mixture of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide (mass ratio of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide 1.
The embodiment also provides a preparation method of the conductive silver paste for ceramic surface circuit printing, which comprises the following steps:
1. 10g of isopropanol and 0.5g of triton were mixed and stirred uniformly, and then 0.5g of a mixture of ethyl cellulose and polyvinyl butyral (mass ratio of ethyl cellulose to polyvinyl butyral 1:1) was added and stirred at 90 ℃ for 4.5 hours. Then, uniformly mixing the mixture by using a vacuum defoaming stirrer, then adding 0.5g of a mixture of polyvinylpyrrolidone and polyacrylic acid (the mass ratio of the polyvinylpyrrolidone to the polyacrylic acid is 1:1) and 1.5g of a mixture of nano-montmorillonite and gas-phase nano-silica (the mass ratio of the nano-montmorillonite to the gas-phase nano-silica is 2:1), and uniformly mixing the mixture by using the vacuum defoaming stirrer (the vacuum degree is 50Kpa, and the stirring time is 200 s) to obtain the organic colloid.
2. Mixing 80g of flake silver powder (with the particle size of 5 μm) and 4g of a mixture of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide (the mass ratio of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide is 1.
3. Ultrasonically dispersing 3g of nano graphene oxide (single layer, sheet diameter of 50 mu m) in 60g of absolute ethyl alcohol for 2h, and then drying at 80 ℃;
4. adding the powder into the organic colloid, uniformly mixing by using a vacuum defoaming stirrer (the vacuum degree is 50Kpa, and the stirring time is 200 s), then adding 3g of dried nano graphene oxide, and uniformly mixing by using a vacuum defoaming stirrer (the vacuum degree is 50Kpa, and the stirring time is 200 s) to obtain the conductive silver paste.
Example 5 (end point values of the Range data compared to example 1)
The embodiment provides a conductive silver paste for ceramic surface circuit printing, which comprises the following components in percentage by mass:
87.8g of silver powder, 4g of a mixture of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide (mass ratio of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide 1.
The embodiment also provides a preparation method of the conductive silver paste for ceramic surface circuit printing, which comprises the following steps:
1. 15g of isopropanol and 3g of triton were mixed and stirred uniformly, then 2g of a mixture of ethyl cellulose and polyvinyl butyral (mass ratio of ethyl cellulose to polyvinyl butyral 1:1) were added and stirred at 90 ℃ for 4.5h. Then, uniformly mixing the mixture by using a vacuum defoaming stirrer, then adding 2g of a mixture of polyvinylpyrrolidone and polyacrylic acid (the mass ratio of the polyvinylpyrrolidone to the polyacrylic acid is 1:1), 5g of a mixture of nano-montmorillonite and gas-phase nano-silica (the mass ratio of the nano-montmorillonite to the gas-phase nano-silica is 2:1), and uniformly mixing the mixture by using a vacuum defoaming stirrer (the vacuum degree is 20Kpa, and the stirring time is 200 s) to obtain the organic colloid.
2. After 87.8g of flake silver powder (particle size of 5 μm) and 15g of a mixture of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide (mass ratio of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide 1.
3. Ultrasonically dispersing 9g of nano graphene oxide (single layer, sheet diameter of 30 mu m) in 900g of absolute ethyl alcohol for 2h, and then drying at 80 ℃;
4. adding the powder into the organic colloid, uniformly mixing by using a vacuum defoaming stirrer (the vacuum degree is 20Kpa, and the stirring time is 300 s), then adding 9g of dried nano graphene oxide, and uniformly mixing by using the vacuum defoaming stirrer (the vacuum degree is 20Kpa, and the stirring time is 300 s) to obtain the conductive silver paste.
Example 6 (using another endpoint value of the range data compared to example 1)
The embodiment provides conductive silver paste for ceramic surface circuit printing, which comprises the following components in percentage by mass:
50g of silver powder, 4g of a mixture of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide (mass ratio of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide 1.
The embodiment also provides a preparation method of the conductive silver paste for ceramic surface circuit printing, which comprises the following steps:
1. 10g of terpineol and 0.5g of triton are mixed and stirred uniformly, then 0.2g of a mixture of ethyl cellulose and polyvinyl butyral (mass ratio of ethyl cellulose to polyvinyl butyral 1:1) is added, and stirring is carried out at a temperature of 90 ℃ for 4.5 hours. Then, uniformly mixing the mixture by using a vacuum defoaming stirrer, then adding 0.5g of a mixture of polyvinylpyrrolidone and polyacrylic acid (the mass ratio of the polyvinylpyrrolidone to the polyacrylic acid is 1:1) and 0.5g of a mixture of nano-montmorillonite and gas-phase nano-silica (the mass ratio of the nano-montmorillonite to the gas-phase nano-silica is 2:1), and uniformly mixing the mixture by using the vacuum defoaming stirrer (the vacuum degree is 20Kpa, and the stirring time is 300 s) to obtain the organic colloid.
2. After mixing 50g of flake silver powder (particle size 5 μm) and 4g of a mixture of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide (mass ratio of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide 1.
3. Ultrasonically dispersing 0.5g of nano graphene oxide (single layer, sheet diameter of 30 mu m) in 50g of absolute ethyl alcohol for 2h, and then drying at 80 ℃;
4. adding the powder into the organic colloid, uniformly mixing by using a vacuum defoaming stirrer (the vacuum degree is 20Kpa, and the stirring time is 300 s), then adding 0.5g of dried nano graphene oxide, and uniformly mixing by using the vacuum defoaming stirrer (the vacuum degree is 20Kpa, and the stirring time is 300 s) to obtain the conductive silver paste.
Example 7 (comparison with example 1, using different substances as claimed)
The embodiment provides conductive silver paste for ceramic surface circuit printing, which comprises the following components in percentage by mass:
silver powder 80g, mixture of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide (mass ratio of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide 1.
The embodiment also provides a preparation method of the conductive silver paste for ceramic surface circuit printing, which comprises the following steps:
1. 10g of isopropanol and 0.5g of triton are mixed and stirred uniformly, then 0.5g of ethyl cellulose is added and stirring is carried out for 4.5h at the temperature of 90 ℃. Then, the mixture was mixed uniformly by a vacuum defoaming mixer, and then a mixture of 0.5g of polyvinylpyrrolidone, 1.5g of nano-montmorillonite and fumed nano-silica was added thereto, and the mixture was mixed uniformly by a vacuum defoaming mixer (vacuum degree 20Kpa, mixing time 300 s) to obtain an organic colloid.
2. Mixing 80g of silver powder and a mixture of 4g of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide, performing ball milling dispersion by using 420g of absolute ethyl alcohol solution, performing ball milling for 5 hours at a ball milling rotation speed of 200r/min, filtering mixed liquid after ball milling, drying at 80 ℃, and grinding the dried powder for 3 hours to obtain powder.
3. Ultrasonically dispersing 3g of nano graphene oxide (single layer, sheet diameter of 30 mu m) in 60g of absolute ethyl alcohol for 2h, and then drying at 80 ℃;
4. adding the powder into the organic colloid, uniformly mixing by using a vacuum defoaming stirrer (the vacuum degree is 20Kpa, and the stirring time is 300 s), then adding 3g of dried nano graphene oxide, and uniformly mixing by using the vacuum defoaming stirrer (the vacuum degree is 20Kpa, and the stirring time is 300 s) to obtain the conductive silver paste.
Example 8 (No ceramic powder, compare with example 1)
The embodiment provides conductive silver paste for ceramic surface circuit printing, which comprises the following components in percentage by mass:
80g of silver powder, 3g of nano graphene oxide, 10g of terpineol, 0.5g of triton, 0.5g of a mixture of ethyl cellulose and polyvinyl butyral (the mass ratio of the ethyl cellulose to the polyvinyl alcohol is 1:1), 0.5g of a mixture of polyvinylpyrrolidone and polyacrylic acid (the mass ratio of the polyvinylpyrrolidone to the polyacrylic acid is 1:1), and 1.5g of a mixture of nano montmorillonite and gas-phase nano silica (the mass ratio of the nano montmorillonite to the gas-phase nano silica is 2:1).
The embodiment also provides a preparation method of the conductive silver paste for ceramic surface circuit printing, which comprises the following steps:
1. 10g of terpineol and 0.5g of triton are mixed and stirred uniformly, then 0.5g of a mixture of ethyl cellulose and polyvinyl butyral (the mass ratio of the ethyl cellulose to the polyvinyl butyral is 1:1) is added, and stirring is carried out for 4.5 hours at a temperature of 90 ℃. Then, uniformly mixing the mixture by using a vacuum defoaming stirrer, then adding 0.5g of a mixture of polyvinylpyrrolidone and polyacrylic acid (the mass ratio of the polyvinylpyrrolidone to the polyacrylic acid is 1:1) and 1.5g of a mixture of nano-montmorillonite and gas-phase nano-silica (the mass ratio of the nano-montmorillonite to the gas-phase nano-silica is 2:1), and uniformly mixing the mixture by using the vacuum defoaming stirrer (the vacuum degree is 20Kpa, and the stirring time is 300 s) to obtain the organic colloid.
2. And (2) performing ball milling dispersion on 80g of flake silver powder (with the particle size of 5 mu m) by using 420g of absolute ethanol solution for 5h at the ball milling rotation speed of 200r/min, filtering the mixed solution after ball milling, drying at 80 ℃, and grinding the dried powder for 3h to obtain powder.
3. Ultrasonically dispersing 3g of nano graphene oxide (single layer, sheet diameter of 30 mu m) in 60g of absolute ethyl alcohol for 2h, and then drying at 80 ℃;
4. adding the powder into the organic colloid, uniformly mixing by using a vacuum defoaming stirrer (the vacuum degree is 20Kpa, and the stirring time is 300 s), then adding 3g of dried nano graphene oxide, and uniformly mixing by using the vacuum defoaming stirrer (the vacuum degree is 20Kpa, and the stirring time is 300 s) to obtain the conductive silver paste.
Example 9 (No vacuum mixing compared to example 1)
The embodiment provides a conductive silver paste for ceramic surface circuit printing, which comprises the following components in percentage by mass:
80g of silver powder, 3g of nano graphene oxide, 10g of terpineol, 0.5g of triton, 0.5g of a mixture of ethyl cellulose and polyvinyl butyral (the mass ratio of the ethyl cellulose to the polyvinyl alcohol is 1:1), 0.5g of a mixture of polyvinylpyrrolidone and polyacrylic acid (the mass ratio of the polyvinylpyrrolidone to the polyacrylic acid is 1:1), and 1.5g of a mixture of nano montmorillonite and gas-phase nano silica (the mass ratio of the nano montmorillonite to the gas-phase nano silica is 2:1).
The embodiment also provides a preparation method of the conductive silver paste for ceramic surface circuit printing, which comprises the following steps:
1. 10g of terpineol and 0.5g of triton are mixed and stirred uniformly, then 0.5g of a mixture of ethyl cellulose and polyvinyl butyral (mass ratio of ethyl cellulose to polyvinyl butyral 1:1) is added, and stirring is carried out at a temperature of 90 ℃ for 4.5 hours. Then, uniformly mixing the mixture by using a vacuum defoaming stirrer, then adding 0.5g of a mixture of polyvinylpyrrolidone and polyacrylic acid (the mass ratio of the polyvinylpyrrolidone to the polyacrylic acid is 1:1) and 1.5g of a mixture of nano-montmorillonite and fumed nano-silica (the mass ratio of the nano-montmorillonite to the fumed nano-silica is 2:1), and uniformly mixing the mixture by using a stirrer (the stirring time is 300 s) to obtain the organic colloid.
2. And (2) performing ball milling dispersion on 80g of flake silver powder (with the particle size of 5 mu m) by using 420g of absolute ethanol solution for 5h at the ball milling rotation speed of 200r/min, filtering the mixed solution after ball milling, drying at 80 ℃, and grinding the dried powder for 3h to obtain powder.
3. Ultrasonically dispersing 3g of nano graphene oxide (single layer, sheet diameter of 30 mu m) in 60g of absolute ethyl alcohol for 2h, and then drying at 80 ℃;
4. adding the powder into the organic colloid, uniformly mixing by using a vacuum defoaming stirrer (the vacuum degree is 20Kpa, and the stirring time is 300 s), then adding 3g of dried nano graphene oxide, and uniformly mixing by using the vacuum defoaming stirrer (the vacuum degree is 20Kpa, and the stirring time is 300 s) to obtain the conductive silver paste.
Example 10 (No ultrasonic dispersion of graphene oxide compared to example 1)
The embodiment provides conductive silver paste for ceramic surface circuit printing, which comprises the following components in percentage by mass:
silver powder 80g, a mixture of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide (mass ratio of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide 1.
The embodiment also provides a preparation method of the conductive silver paste for ceramic surface circuit printing, which comprises the following steps:
1. 10g of terpineol and 0.5g of triton are mixed and stirred uniformly, then 0.5g of a mixture of ethyl cellulose and polyvinyl butyral (the mass ratio of the ethyl cellulose to the polyvinyl butyral is 1:1) is added, and stirring is carried out for 4.5 hours at a temperature of 90 ℃. Then, uniformly mixing the mixture by using a vacuum defoaming stirrer, then adding 0.5g of a mixture of polyvinylpyrrolidone and polyacrylic acid (the mass ratio of the polyvinylpyrrolidone to the polyacrylic acid is 1:1) and 1.5g of a mixture of nano-montmorillonite and gas-phase nano-silica (the mass ratio of the nano-montmorillonite to the gas-phase nano-silica is 2:1), and uniformly mixing the mixture by using the vacuum defoaming stirrer (the vacuum degree is 20Kpa, and the stirring time is 300 s) to obtain the organic colloid.
2. Mixing 80g of flake silver powder (with the particle size of 5 μm) and 4g of a mixture of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide (the mass ratio of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide is 1.
3. Adding the powder into the organic colloid, uniformly mixing by using a vacuum defoaming stirrer (the vacuum degree is 20Kpa, and the stirring time is 300 s), then adding 3g of nano graphene oxide (the single layer and the sheet diameter are 30 mu m), and uniformly mixing by using the vacuum defoaming stirrer (the vacuum degree is 20Kpa, and the stirring time is 300 s) to obtain the conductive silver paste.
Comparative example 1 (No thixotropic agent compared to example 1)
The comparative example provides conductive silver paste for printing a ceramic surface circuit, which comprises the following components in percentage by mass:
silver powder 80g, a mixture of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide (mass ratio of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide 1.
The comparative example also provides a preparation method of the conductive silver paste for printing the circuit on the ceramic surface, which comprises the following steps:
1. 10g of terpineol and 0.5g of triton are mixed and stirred uniformly, then 0.5g of a mixture of ethyl cellulose and polyvinyl butyral (mass ratio of ethyl cellulose to polyvinyl butyral 1:1) is added, and stirring is carried out at a temperature of 90 ℃ for 4.5 hours. Then, the mixture was mixed uniformly by a vacuum defoaming mixer, and then 0.5g of a mixture of polyvinylpyrrolidone and polyacrylic acid (mass ratio of polyvinylpyrrolidone to polyacrylic acid is 1:1) was added thereto, and the mixture was mixed uniformly by a vacuum defoaming mixer (vacuum degree 20Kpa, mixing time 300 s) to obtain an organic colloid.
2. Mixing 80g of flake silver powder (with the particle size of 5 μm) and 4g of a mixture of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide (the mass ratio of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide is 1.
3. Ultrasonically dispersing 3g of nano graphene oxide (single layer, sheet diameter of 30 mu m) in 60g of absolute ethyl alcohol for 2h, and then drying at 80 ℃;
4. adding the powder into the organic colloid, uniformly mixing by using a vacuum defoaming stirrer (the vacuum degree is 20Kpa, and the stirring time is 300 s), then adding 3g of dried nano graphene oxide, and uniformly mixing by using the vacuum defoaming stirrer (the vacuum degree is 20Kpa, and the stirring time is 300 s) to obtain the conductive silver paste.
Comparative example 2 (comparing with example 1, without using nano graphene oxide)
The comparative example provides conductive silver paste for printing a ceramic surface circuit, which comprises the following components in percentage by mass:
silver powder 80g, a mixture of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide (mass ratio of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide 1.
The comparative example also provides a preparation method of the conductive silver paste for printing the ceramic surface circuit, which comprises the following steps:
1. 10g of terpineol and 0.5g of triton are mixed and stirred uniformly, then 0.5g of a mixture of ethyl cellulose and polyvinyl butyral (mass ratio of ethyl cellulose to polyvinyl butyral 1:1) is added, and stirring is carried out at a temperature of 90 ℃ for 4.5 hours. Then, uniformly mixing the mixture by using a vacuum defoaming stirrer, then adding 0.5g of a mixture of polyvinylpyrrolidone and polyacrylic acid (the mass ratio of the polyvinylpyrrolidone to the polyacrylic acid is 1:1) and 1.5g of a mixture of nano-montmorillonite and gas-phase nano-silica (the mass ratio of the nano-montmorillonite to the gas-phase nano-silica is 2:1), and uniformly mixing the mixture by using the vacuum defoaming stirrer (the vacuum degree is 20Kpa, and the stirring time is 300 s) to obtain the organic colloid.
2. Mixing 80g of flake silver powder (with the particle size of 5 μm) and 4g of a mixture of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide (the mass ratio of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide is 1.
3. Adding the powder into the organic colloid, and uniformly mixing by using a vacuum defoaming stirrer (the vacuum degree is 20Kpa, and the stirring time is 300 s) to obtain the conductive silver paste.
Test example
Test example 1
The conductive silver paste for printing the ceramic surface circuit prepared in example 1 was subjected to 3D printing, and the specific printing method was as follows:
1. and (3) respectively filling the conductive silver paste prepared in the embodiment 1 into a printing head, connecting a 3D printer, setting a printing model and 3D printing parameters, and then carrying out 3D printing on the surface of the ceramic substrate subjected to surface treatment. The printing mode is direct-writing 3D printing; the direct-writing 3D printing speed is 10mm/s; the diameter of the direct-writing 3D printing head is 50 mu m; the direct-writing 3D printing air pressure is 30Psi; the line width overlapping rate of the direct-writing 3D printing is 12%; the ceramic surface treatment mode is sulfuric acid treatment for 30min.
2. And placing the 3D printed ceramic-based circuit structure in a vacuum drying oven for drying treatment, and then placing the ceramic-based circuit structure in an air atmosphere furnace for glue removal treatment and sintering. The drying temperature in the drying process is 50 ℃; the drying time is 300min; the heating speed in the glue discharging process is 1 ℃/min; the glue discharging temperature is 500 ℃; the temperature rise speed in the sintering process is 1 ℃/min; the sintering temperature is 900 ℃ during sintering; the sintering time was 30min.
The test results are shown in fig. 1.
As can be seen from fig. 1, the paste has excellent forming accuracy and forming quality, and the formed line width and the line interval are uniform.
Test example 2
The silver pastes prepared in examples 1 to 10 and comparative examples 1 to 3 were subjected to performance tests including static viscosity, precision of formed line width, error of formed line pitch, thermal strain at 800 c and high temperature resistance.
The static viscosity was measured as follows: the test was performed using a rotational rheometer.
The testing method of the forming line width precision comprises the following steps: and (5) high-precision measurement microscope testing.
The testing method of the forming line spacing error comprises the following steps: and (5) high-precision measurement microscope testing.
The test method of the thermal strain at 800 ℃ comprises the following steps: and testing by a high-temperature visual deformation analyzer.
The high temperature resistant test method comprises the following steps: and analyzing and comparing the line width and the surface appearance change of the conducting circuit before and after the muffle furnace is subjected to high-temperature treatment by using a scanning electron microscope.
The test results are shown in the following table:
from the above table it can be seen that: the combined action of the thixotropic agent and the graphene oxide effectively improves the static viscosity of the slurry, increases the shape retention capacity of the slurry, reduces the forming precision error of the slurry and improves the forming precision of the slurry.
Test example 3
The conductive silver paste prepared in example 1 was subjected to a performance test, the test contents include conductivity change of the 3D printed silver paste after high temperature use and thermal strain of the 3D printed silver paste after sintering at high temperature.
The method for testing the conductivity change of the 3D printing silver paste after high-temperature use comprises the following steps: the four-probe method.
The method for testing the thermal strain at high temperature after sintering of the 3D printing silver paste comprises the following steps: and testing by using a high-temperature visual deformation analyzer.
The test results are shown in fig. 2 and 3.
From fig. 2 and 3, it can be derived that: the slurry has excellent conductive property and high-temperature use stability after being sintered, and the conductivity is not obviously reduced after being used at high temperature and still has extremely high conductivity. And the thermal strain of the material at high temperature is extremely small, and at the high temperature of 900 ℃, the thermal strain is less than 0.6 percent, so that the material has good high-temperature stability.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. The conductive silver paste for printing the ceramic surface circuit is characterized by comprising the following components in percentage by mass:
50-87.8% of silver powder;
0-15% of ceramic powder;
0.5-9% of graphene oxide;
10-15% of a solvent;
0.5 to 3 percent of surfactant;
0.2 to 2 percent of binder;
0.5 to 2 percent of diluent;
0.5 to 5 percent of thixotropic agent.
2. The conductive silver paste for ceramic surface circuit printing according to claim 1, wherein the ceramic powder comprises silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide;
and/or the mass ratio of the silicon oxide, the boron oxide, the aluminum oxide, the zinc oxide, the sodium oxide and the calcium oxide is (1-8): (2-4): (1-6): (0.5-2): (0.5-1): (0.5-1).
3. The conductive silver paste for ceramic surface circuit printing according to claim 1 or 2, wherein at least one of (1) to (5) is satisfied:
(1) The solvent is one of terpineol, butanol and isopropanol;
(2) The surfactant is one of triton and sodium dodecyl benzene sulfonate;
(3) The binder is one or more of ethyl cellulose, polyvinyl alcohol and polyvinyl butyral;
(4) The diluent is one or more of polyvinylpyrrolidone and polyacrylic acid;
(5) The thixotropic agent is one or more of nano montmorillonite, castor oil, hydroxyethyl cellulose or gas-phase nano silicon dioxide.
4. A method for preparing the conductive silver paste for ceramic surface circuit printing according to any one of claims 1 to 3, comprising the steps of,
(1) Mixing a solvent and a surfactant, adding a binder, stirring, adding a diluent and a thixotropic agent, and uniformly mixing to obtain an organic colloid;
(2) Mixing silver powder and ceramic powder, and performing ball milling to obtain powder;
(3) Carrying out ultrasonic dispersion and drying on graphene oxide;
(4) And mixing the obtained organic colloid with powder, and adding the dried graphene oxide to obtain the conductive silver paste.
5. The preparation method of the conductive silver paste for ceramic surface circuit printing according to claim 4, wherein the stirring temperature is 50-100 ℃ and the stirring time is 1-5h;
and/or, the mixing is carried out under the vacuum condition, and the vacuum degree is 20-100Kpa.
6. The method for preparing the conductive silver paste for ceramic surface circuit printing according to claim 4, wherein the particle size of the graphene oxide is 0.05-50 μm;
and/or the ultrasonic dispersion time is 0.5-5h, and the drying temperature is 50-100 ℃.
7. Use of the conductive silver paste for ceramic surface circuit printing according to any one of claims 1 to 3 or the conductive silver paste for ceramic surface circuit printing prepared by the preparation method according to any one of claims 4 to 6 in 3D printing.
8. The use of the conductive silver paste for ceramic surface circuit printing according to claim 7 in 3D printing, characterized in that at least one of (1) to (9):
(1) The 3D printing is direct-writing 3D printing or jet 3D printing;
(2) The direct-writing 3D printing speed is 0.1-150mm/s;
(3) The diameter of the direct-writing 3D printing head is 20-800 μm;
(4) The direct-writing 3D printing air pressure is 10-120Psi;
(5) The overlap rate of the line widths of the direct-writing 3D printing is 5% -15%;
(6) The spraying 3D printing speed is 0.5-100mm/s;
(7) The jet 3D printing interval is 1-10mm;
(8) The jetting 3D printing air pressure is 10-100Psi;
(9) The difference of the ejection 3D printing voltage is 50-100V.
9. The use of the conductive silver paste for ceramic surface circuit printing according to claim 7 or 8 in 3D printing, wherein the printing step further comprises drying, binder removal and sintering treatments.
10. The use of the conductive silver paste for ceramic surface circuit printing according to claim 9 in 3D printing, characterized in that at least one of the following (1) to (5) is satisfied:
(1) Drying at 50-100 deg.C for 30-300min;
(2) Removing glue at 300-500 deg.C;
(3) Heating to the glue discharging temperature at the heating rate of 1-5 ℃/min;
(4) Sintering at 600-900 deg.C for 15-90min;
(5) Heating to the sintering temperature at the heating rate of 1-10 ℃/min.
Priority Applications (1)
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