CN115732117B - 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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- CN115732117B CN115732117B CN202210220815.5A CN202210220815A CN115732117B CN 115732117 B CN115732117 B CN 115732117B CN 202210220815 A CN202210220815 A CN 202210220815A CN 115732117 B CN115732117 B CN 115732117B
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- 238000007639 printing Methods 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 67
- 239000000843 powder Substances 0.000 claims abstract description 59
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- 239000000292 calcium oxide Substances 0.000 claims description 43
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- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 43
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- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 4
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- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 abstract description 21
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- Conductive Materials (AREA)
Abstract
The invention belongs to the technical field of 3D printing, and particularly relates to conductive silver paste for ceramic surface circuit printing and a preparation method and application thereof. The invention provides a 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 nano graphene oxide; 10-15% of a solvent; 0.5-3% of surfactant; 0.2-2% of binder; 0.5-2% of diluent; 0.5-5% of thixotropic agent. According to the invention, through the matching of the components and the adjustment of the materials, the obtained conductive silver paste ensures that the silver structure of the 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 thermal stress of a ceramic and silver interface is effectively reduced, the falling 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 ceramic surface circuit printing 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 called additive manufacturing, which is a technology for constructing objects by using powdery metal or plastic and other bondable materials in a layer-by-layer printing mode based on digital model files.
In 3D printing, the forming means of silver paste is carried out by multi-purpose screen printing, and the prior art discloses a conductive silver paste and a preparation method thereof, wherein the conductive silver paste comprises conductive silver powder, glass powder and an organic carrier, 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 castor oil derivative, the thickening agent is ethyl cellulose, the coupling agent is silane coupling agent or 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 molding precision, high thermal strain in a high-temperature state and easy falling off from a substrate in a high-temperature use process.
Disclosure of Invention
Therefore, the invention aims to overcome the defects of lower static viscosity, higher fluidity, lower molding precision, higher thermal strain in a high-temperature state and the like of the conductive silver paste in the prior art, thereby providing the conductive silver paste for ceramic surface circuit printing, and the preparation method and the application thereof.
Therefore, the invention provides the following technical proposal,
the invention provides a 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;
0.5-3% of surfactant;
0.2-2% of binder;
0.5-2% of diluent;
0.5-5% 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) - (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 conductive silver paste for ceramic surface circuit printing, which comprises the following steps:
(1) Mixing the solvent with the surfactant, adding the binder, stirring, adding the diluent and the thixotropic agent, and uniformly mixing to obtain an organic colloid;
(2) Mixing silver powder with ceramic powder, and 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 temperature of the stirring is 50-100 ℃ and the time is 1-5h;
and/or the mixing is under 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 mu m.
The ball milling time is 5-12h;
the ball milling is wet ball milling or dry ball milling,
the mass ratio of the powder to the liquid in the wet ball milling process is 1: (5-20);
when the ball milling is wet ball milling, the ball milling in the step (2) is further performed with drying and grinding to obtain powder;
the drying temperature is 50-100 ℃, and the grinding time is 1-5h.
The invention also provides an application of the conductive silver paste for ceramic surface circuit printing or the conductive silver paste for ceramic surface circuit printing prepared by the preparation method in 3D printing.
Optionally, at least one of (1) - (9) is satisfied:
(1) The 3D printing is direct-write 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 mu m;
(4) The direct-writing 3D printing air pressure is 10-120Psi;
(5) The line width overlapping rate of direct-writing 3D printing is 5% -15%;
(6) The jet 3D printing speed is 0.5-100mm/s;
(7) The jet 3D printing interval is 1-10mm;
(8) The jet 3D printing air pressure is 10-100Psi;
(9) The difference in jetting 3D printing voltage is 50-100V.
Optionally, the printing step further comprises drying, adhesive discharging and sintering treatment.
Optionally, at least one of the following (1) - (5) is satisfied:
(1) Drying at 50-100deg.C for 30-300min;
(2) Discharging glue at 300-500 ℃;
(3) Heating to the glue discharging temperature at a 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.
Satisfying at least one of (1) to (4);
(1) The number of the graphene oxide sheets is 1-20;
(2) The sheet diameter of the graphene oxide is 10-50 mu m;
(3) The ultrasonic time is 20-60min;
(4) In the ultrasonic process, the mass ratio of graphene oxide to solution is 1: (20-100), wherein the solution is one of deionized water, absolute ethyl alcohol or N, N-dimethylformamide.
The technical proposal provided by the invention has the following advantages,
1. the invention provides a 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; 0.5-3% of surfactant; 0.2-2% of binder; 0.5-2% of diluent; 0.5-5% of thixotropic agent. The invention ensures that the silver structure of the 3D printing has smaller thermal strain in a high-temperature environment by matching the components and adjusting the materials, the thermal strain is only 0.6 percent at the high temperature of 800 ℃, the thermal stress of a ceramic and silver interface is effectively reduced, the falling of the silver conductive structure at the high temperature is avoided, the high-temperature stability of the material is improved, the high-temperature use temperature reaches 900 ℃, the line width forming precision error is less than 10 microns, the line spacing forming error is less than 10 microns, and the conductivity reaches 2 multiplied by 10 7 s/m. Specifically, the conductive silver paste of the invention uses thixotropic agents such as castor oil and the like, the thixotropic agents have high viscosity at low shear rate, and the conductive silver paste is combined with the use of nano graphene oxide,the steric hindrance effect of the nano graphene oxide in the slurry can be effectively increased, the static viscosity of the slurry is greatly improved, the fluidity of the slurry is reduced, and the forming precision is further improved. 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 a certain proportion of micro-nano pores are generated in the high-temperature treatment process by the nano graphene oxide, and the pores can provide a certain deformation space for the expansion of the silver material in a high-temperature environment, so that the integral thermal strain of the material is effectively restrained, 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 few nano graphene oxide, so that the preparation cost of the paste can be effectively reduced.
2. The conductive silver paste for ceramic surface circuit printing 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 at the interface of the conductive paste and a ceramic substrate, so that the bonding of the interface is promoted, and the problem of falling off with the substrate can be further avoided.
3. The invention provides a preparation method of conductive silver paste for ceramic surface circuit printing, which comprises the following steps: (1) Mixing a solvent with a surfactant, adding a binder, stirring and mixing, and adding a diluent and a thixotropic agent to obtain an organic colloid; (2) mixing silver powder with ceramic powder, and ball milling to obtain powder; (3) 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 graphene oxide consumption, and the printing precision of the silver paste is improved.
4. The preparation method of the conductive silver paste for ceramic surface circuit printing provided by the invention also needs to carry out ultrasonic dispersion on graphene oxide. The ultrasonic dispersion of the graphene oxide can effectively avoid graphene oxide agglomeration, ensure a two-dimensional lamellar structure of the graphene oxide, reduce the thickness increase of the graphene oxide caused by stacking of a multilayer structure, improve the length-diameter ratio of the graphene oxide and increase the specific surface area, thereby effectively improving the steric hindrance effect of the graphene oxide in the slurry, ensuring the improvement of the rheological property of the silver slurry on the premise of extremely small dosage of the graphene oxide, and improving the printing precision of the silver slurry.
5. According to the preparation method of the conductive silver paste for ceramic surface circuit printing, disclosed by the invention, in the step (1), the vacuum mixing is carried out, 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 part 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 that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a diagram showing molding accuracy of test example 1 of the present invention;
FIG. 2 is a graph showing the change in conductivity of 3D printed silver paste after use at high temperature in test example 3 according to the present invention;
fig. 3 is a schematic view 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 for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
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, 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 1:3:1:0.5:1:0.5), 3g of nano graphene oxide, 10g of terpineol, 0.5g of triton, 0.5g of a mixture of ethylcellulose and polyvinyl butyral (the mass ratio of ethylcellulose and polyvinyl alcohol is 1:1), 0.5g of a mixture of polyvinylpyrrolidone and polyacrylic acid (the mass ratio of polyvinylpyrrolidone and polyacrylic acid is 1:1), and 1.5g of a mixture of nano montmorillonite and gas phase nano silica (the mass ratio of nano montmorillonite and 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 triamcinolone are mixed and stirred uniformly, then 0.5g of a mixture of ethylcellulose and polyvinyl butyral (the mass ratio of ethylcellulose to polyvinyl butyral is 1:1) is added, and stirring is carried out at a temperature of 90 ℃ for 4.5 hours. Then uniformly mixing by using a vacuum defoaming stirrer, adding 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 a mixture of nano montmorillonite and gas-phase nano silica (the mass ratio of nano montmorillonite to gas-phase nano silica is 2:1), and uniformly mixing by using a 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 (particle size of 5 μm) with 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 of 1:3:1:0.5:1:0.5), performing ball milling and dispersing by using 420g of absolute ethanol solution for 5h at a ball milling 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. 3g of nano graphene oxide (single-layer, sheet diameter 30 μm) is ultrasonically dispersed in 60g of absolute ethyl alcohol for 2 hours, and then dried at 80 ℃;
4. adding 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 (compared to example 1, the binder and thixotropic agent are different)
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, 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 1:3:1:0.5:1:0.5), 3g of nano graphene oxide, 10g of terpineol, 0.5g of triton, 0.5g of a mixture of ethylcellulose, polyvinyl alcohol and polyvinyl butyral (the mass ratio of ethylcellulose, polyvinyl alcohol and polyvinyl butyral is 1:1:1), 0.5g of a mixture of polyvinylpyrrolidone and polyacrylic acid (the mass ratio of polyvinylpyrrolidone and polyacrylic acid is 1:1), and 1.5g of nano montmorillonite.
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 triamcinolone are mixed and stirred uniformly, then 0.5g of a mixture of ethylcellulose, polyvinyl alcohol and polyvinyl butyral (the mass ratio of ethylcellulose, polyvinyl alcohol and polyvinyl butyral is 1:1:1) is added, and stirring is carried out for 4.5 hours at a temperature of 90 ℃. Then uniformly mixing by using a vacuum defoaming stirrer, adding 0.5g of mixture of polyvinylpyrrolidone and polyacrylic acid (the mass ratio of polyvinylpyrrolidone to polyacrylic acid is 1:1) and 1.5g of nano montmorillonite, and uniformly mixing 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 (particle size of 5 μm) with 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 of 1:3:1:0.5:1:0.5), performing ball milling and dispersing by using 420g of absolute ethanol solution for 5h at a ball milling 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. 3g of nano graphene oxide (single-layer, sheet diameter 30 μm) is ultrasonically dispersed in 60g of absolute ethyl alcohol for 2 hours, and then dried at 80 ℃;
4. adding 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 (As compared with example 1, the silver powder was spherical silver powder having a particle size of 100 nm)
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, 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 1:3:1:0.5:1:0.5), 3g of nano graphene oxide, 10g of terpineol, 0.5g of triton, 0.5g of a mixture of ethylcellulose and polyvinyl butyral (the mass ratio of ethylcellulose and polyvinyl alcohol is 1:1), 0.5g of a mixture of polyvinylpyrrolidone and polyacrylic acid (the mass ratio of polyvinylpyrrolidone and polyacrylic acid is 1:1), and 1.5g of a mixture of nano montmorillonite and gas phase nano silica (the mass ratio of nano montmorillonite and 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 triamcinolone are mixed and stirred uniformly, then 0.5g of a mixture of ethylcellulose and polyvinyl butyral (the mass ratio of ethylcellulose to polyvinyl butyral is 1:1) is added, and stirring is carried out at a temperature of 90 ℃ for 4.5 hours. Then uniformly mixing by using a vacuum defoaming stirrer, adding 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 a mixture of nano montmorillonite and gas-phase nano silica (the mass ratio of nano montmorillonite to gas-phase nano silica is 2:1), and uniformly mixing by using a vacuum defoaming stirrer (the vacuum degree is 20Kpa and the stirring time is 300 s) to obtain the organic colloid.
2. Mixing 80g of spherical silver powder (with the particle size of 100 nm) 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 to calcium oxide is 1:3:1:0.5:1:0.5), performing ball milling and dispersing by using 420g of absolute ethanol solution for 5h at the ball milling speed of 200r/min, filtering the mixture after ball milling, drying at 80 ℃, and grinding the dried powder for 3h to obtain powder.
3. 3g of nano graphene oxide (single-layer, sheet diameter 30 μm) is ultrasonically dispersed in 60g of absolute ethyl alcohol for 2 hours, and then dried at 80 ℃;
4. adding 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 (compared to example 1, graphene oxide has a sheet diameter of 50 μm)
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, 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 1:3:1:0.5:1:0.5), 3g of nano graphene oxide, 10g of terpineol, 0.5g of triton, 0.5g of a mixture of ethylcellulose and polyvinyl butyral (the mass ratio of ethylcellulose and polyvinyl alcohol is 1:1), 0.5g of a mixture of polyvinylpyrrolidone and polyacrylic acid (the mass ratio of polyvinylpyrrolidone and polyacrylic acid is 1:1), and 1.5g of a mixture of nano montmorillonite and gas phase nano silica (the mass ratio of nano montmorillonite and 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 isopropanol and 0.5g of triton were mixed and stirred uniformly, then 0.5g of a mixture of ethylcellulose and polyvinyl butyral (the mass ratio of ethylcellulose to polyvinyl butyral is 1:1) was added, and stirring was carried out at a temperature of 90℃for 4.5 hours. Then uniformly mixing by using a vacuum defoaming stirrer, adding 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 a mixture of nano montmorillonite and gas-phase nano silica (the mass ratio of nano montmorillonite to gas-phase nano silica is 2:1), and uniformly mixing by using a 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 (particle size of 5 μm) with 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 is 1:3:1:0.5:1:0.5), performing ball milling and dispersing by using 420g of absolute ethanol solution for 5h at a ball milling speed of 200r/min, filtering the mixed solution after ball milling, drying at 50 ℃, and grinding the dried powder for 1.5h to obtain the powder.
3. 3g of nano graphene oxide (single layer, sheet diameter 50 μm) is ultrasonically dispersed in 60g of absolute ethyl alcohol for 2 hours, and then dried at 80 ℃;
4. adding 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 the vacuum defoaming stirrer (the vacuum degree is 50Kpa and the stirring time is 200 s) to obtain the conductive silver paste.
Example 5 (As compared to example 1, the end point values of the range data are used)
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 (the mass ratio of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide is 1:3:1:0.5:1:0.5), 9g of nano graphene oxide, 15g of isopropanol, 3g of triton, 2g of a mixture of ethylcellulose and polyvinyl butyral (the mass ratio of ethylcellulose and polyvinyl alcohol is 1:1), 2g of a mixture of polyvinylpyrrolidone and polyacrylic acid (the mass ratio of polyvinylpyrrolidone and polyacrylic acid is 1:1), and 5g of a mixture of nano montmorillonite and gaseous nano silica (the mass ratio of nano montmorillonite and gaseous 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. 15g of isopropyl alcohol and 3g of triton are mixed and stirred uniformly, then 2g of a mixture of ethyl cellulose and polyvinyl butyral (mass ratio of ethyl cellulose to polyvinyl butyral is 1:1) is added, and stirring is carried out at 90 ℃ for 4.5h. Then uniformly mixing by using a vacuum defoaming stirrer, adding 2g of a mixture of polyvinylpyrrolidone and polyacrylic acid (the mass ratio of polyvinylpyrrolidone to polyacrylic acid is 1:1) and 5g of a mixture of nano montmorillonite and gas phase nano silicon dioxide (the mass ratio of nano montmorillonite to gas phase nano silicon dioxide is 2:1), and uniformly mixing by using the vacuum defoaming stirrer (the vacuum degree is 20Kpa and the stirring time is 200 s) to obtain the organic colloid.
2. Mixing 87.8g of flake silver powder (particle size of 5 μm) with 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 of 1:3:1:0.5:1:0.5), performing ball milling and dispersing by using 300g of absolute ethanol solution for 5 hours at the ball milling speed of 200r/min, filtering the mixture after ball milling, drying at 50 ℃, and grinding the dried powder for 5 hours to obtain powder.
3. Dispersing 9g of nano graphene oxide (single-layer, sheet diameter 30 μm) in 900g of absolute ethyl alcohol for 2 hours by ultrasonic, and then drying at 80 ℃;
4. adding 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 (as compared to example 1, another endpoint value for the range data is used)
The embodiment provides a 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 (the mass ratio of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide is 1:3:1:0.5:1:0.5), 0.5g of nano graphene oxide, 10g of terpineol, 0.5g of triton, 0.2g of a mixture of ethylcellulose and polyvinyl butyral (the mass ratio of ethylcellulose and polyvinyl alcohol is 1:1), 0.5g of a mixture of polyvinylpyrrolidone and polyacrylic acid (the mass ratio of polyvinylpyrrolidone and polyacrylic acid is 1:1), and 0.5g of a mixture of nano montmorillonite and gas phase nano silica (the mass ratio of nano montmorillonite and 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 triamcinolone are mixed and stirred uniformly, then 0.2g of a mixture of ethylcellulose and polyvinyl butyral (the mass ratio of ethylcellulose to polyvinyl butyral is 1:1) is added, and stirring is carried out at a temperature of 90 ℃ for 4.5 hours. Then uniformly mixing by using a vacuum defoaming stirrer, adding 0.5g of a mixture of polyvinylpyrrolidone and polyacrylic acid (the mass ratio of polyvinylpyrrolidone to polyacrylic acid is 1:1) and 0.5g of a mixture of nano montmorillonite and gas-phase nano silica (the mass ratio of nano montmorillonite to gas-phase nano silica is 2:1), and uniformly mixing by using a vacuum defoaming stirrer (the vacuum degree is 20Kpa and the stirring time is 300 s) to obtain the organic colloid.
2. 50g of flake silver powder (particle size of 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: 1:3:1:0.5:1:0.5) were mixed, and then ball-milled and dispersed by using 300g of an absolute ethanol solution for 5 hours at a ball-milling speed of 200r/min, and then the mixture after ball milling was filtered, dried at 80 ℃ and the dried powder was milled for 3 hours to obtain a powder.
3. Dispersing 0.5g of nano graphene oxide (single layer, sheet diameter 30 μm) in 50g of absolute ethyl alcohol for 2 hours by ultrasonic, and then drying at 80 ℃;
4. adding 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 (use of a different substance as claimed 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, 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 1:3:1:0.5:1:0.5), 3g of nano graphene oxide, 10g of isopropanol, 0.5g of triton, 0.5g of ethylcellulose, 0.5g of polyvinylpyrrolidone and 1.5g of a mixture of nano montmorillonite and gas-phase nano silicon dioxide (the mass ratio of nano montmorillonite to gas-phase nano silicon dioxide 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 isopropanol and 0.5g of triton were mixed and stirred uniformly, then 0.5g of ethylcellulose was added, and stirring was carried out at a temperature of 90℃for 4.5 hours. Then uniformly mixing by using a vacuum defoaming stirrer, adding 0.5g of polyvinylpyrrolidone, 1.5g of nano montmorillonite and gas phase nano silicon dioxide mixture, and uniformly mixing 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 silver powder with 4g of a mixture of silicon oxide, boron oxide, aluminum oxide, zinc oxide, sodium oxide and calcium oxide, performing ball milling and dispersing by using 420g of absolute ethanol solution for 5h at a ball milling speed of 200r/min, filtering the ball-milled mixed solution, drying at 80 ℃, and grinding the dried powder for 3h to obtain powder.
3. 3g of nano graphene oxide (single-layer, sheet diameter 30 μm) is ultrasonically dispersed in 60g of absolute ethyl alcohol for 2 hours, and then dried at 80 ℃;
4. adding 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 (compared with example 1, no ceramic powder was contained)
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 silicon dioxide (the mass ratio of the nano montmorillonite to the gas-phase nano silicon dioxide 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 triamcinolone are mixed and stirred uniformly, then 0.5g of a mixture of ethylcellulose and polyvinyl butyral (the mass ratio of ethylcellulose to polyvinyl butyral is 1:1) is added, and stirring is carried out at a temperature of 90 ℃ for 4.5 hours. Then uniformly mixing by using a vacuum defoaming stirrer, adding 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 a mixture of nano montmorillonite and gas-phase nano silica (the mass ratio of nano montmorillonite to gas-phase nano silica is 2:1), and uniformly mixing by using a vacuum defoaming stirrer (the vacuum degree is 20Kpa and the stirring time is 300 s) to obtain the organic colloid.
2. 80g of flake silver powder (particle size of 5 μm) is subjected to ball milling and dispersion by using 420g of absolute ethanol solution, wherein the ball milling time is 5h, the ball milling rotating speed is 200r/min, then the mixed liquid after ball milling is filtered, the mixed liquid is dried at 80 ℃, and the dried powder is ground for 3h, so that powder is obtained.
3. 3g of nano graphene oxide (single-layer, sheet diameter 30 μm) is ultrasonically dispersed in 60g of absolute ethyl alcohol for 2 hours, and then dried at 80 ℃;
4. adding 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 (compared to example 1, no vacuum mixing was performed)
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 silicon dioxide (the mass ratio of the nano montmorillonite to the gas-phase nano silicon dioxide 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 triamcinolone are mixed and stirred uniformly, then 0.5g of a mixture of ethylcellulose and polyvinyl butyral (the mass ratio of ethylcellulose to polyvinyl butyral is 1:1) is added, and stirring is carried out at a temperature of 90 ℃ for 4.5 hours. Then uniformly mixing by using a vacuum defoaming stirrer, adding 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 a mixture of nano montmorillonite and gas-phase nano silica (the mass ratio of nano montmorillonite to gas-phase nano silica is 2:1), and uniformly mixing by using a stirrer (the stirring time is 300 s) to obtain the organic colloid.
2. 80g of flake silver powder (particle size of 5 μm) is subjected to ball milling and dispersion by using 420g of absolute ethanol solution, wherein the ball milling time is 5h, the ball milling rotating speed is 200r/min, then the mixed liquid after ball milling is filtered, the mixed liquid is dried at 80 ℃, and the dried powder is ground for 3h, so that powder is obtained.
3. 3g of nano graphene oxide (single-layer, sheet diameter 30 μm) is ultrasonically dispersed in 60g of absolute ethyl alcohol for 2 hours, and then dried at 80 ℃;
4. Adding 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 (compared to example 1, graphene oxide was not ultrasonically dispersed)
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, 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 1:3:1:0.5:1:0.5), 3g of nano graphene oxide, 10g of terpineol, 0.5g of triton, 0.5g of a mixture of ethylcellulose and polyvinyl butyral (the mass ratio of ethylcellulose and polyvinyl alcohol is 1:1), 0.5g of a mixture of polyvinylpyrrolidone and polyacrylic acid (the mass ratio of polyvinylpyrrolidone and polyacrylic acid is 1:1), and 1.5g of a mixture of nano montmorillonite and gas phase nano silica (the mass ratio of nano montmorillonite and 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 triamcinolone are mixed and stirred uniformly, then 0.5g of a mixture of ethylcellulose and polyvinyl butyral (the mass ratio of ethylcellulose to polyvinyl butyral is 1:1) is added, and stirring is carried out at a temperature of 90 ℃ for 4.5 hours. Then uniformly mixing by using a vacuum defoaming stirrer, adding 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 a mixture of nano montmorillonite and gas-phase nano silica (the mass ratio of nano montmorillonite to gas-phase nano silica is 2:1), and uniformly mixing by using a 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 (particle size of 5 μm) with 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 of 1:3:1:0.5:1:0.5), performing ball milling and dispersing by using 420g of absolute ethanol solution for 5h at a ball milling 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. Adding 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 is 30 mu m), and uniformly mixing by using the vacuum defoaming stirrer (the vacuum degree is 20Kpa and the stirring time is 300 s), thus obtaining the conductive silver paste.
Comparative example 1 (in comparison with example 1, no thixotropic agent is used)
The comparative example provides a conductive silver paste for ceramic surface circuit printing, which comprises the following components in percentage by mass:
80g of silver powder, 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 1:3:1:0.5:1:0.5), 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 ethyl cellulose and polyvinyl alcohol is 1:1), and 0.5g of a mixture of polyvinylpyrrolidone and polyacrylic acid (the mass ratio of polyvinylpyrrolidone and polyacrylic acid is 1:1).
The comparative example 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 triamcinolone are mixed and stirred uniformly, then 0.5g of a mixture of ethylcellulose and polyvinyl butyral (the mass ratio of ethylcellulose to polyvinyl butyral is 1:1) is added, and stirring is carried out at a temperature of 90 ℃ for 4.5 hours. Then, the mixture was uniformly mixed by using a vacuum degassing stirrer, and then 0.5g of a mixture of polyvinylpyrrolidone and polyacrylic acid (the mass ratio of polyvinylpyrrolidone to polyacrylic acid is 1:1) was added, and the mixture was uniformly mixed by using a vacuum degassing stirrer (the vacuum degree was 20Kpa, and the stirring time was 300 s), to obtain an organic colloid.
2. Mixing 80g of flake silver powder (particle size of 5 μm) with 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 of 1:3:1:0.5:1:0.5), performing ball milling and dispersing by using 420g of absolute ethanol solution for 5h at a ball milling 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. 3g of nano graphene oxide (single-layer, sheet diameter 30 μm) is ultrasonically dispersed in 60g of absolute ethyl alcohol for 2 hours, and then dried at 80 ℃;
4. Adding 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 (compared to example 1, no nano graphene oxide was used)
The comparative example provides a conductive silver paste for ceramic surface circuit printing, which comprises the following components in percentage by mass:
80g of silver powder, 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 1:3:1:0.5:1:0.5), 10g of terpineol, 0.5g of triton, 0.5g of a mixture of ethylcellulose and polyvinyl butyral (the mass ratio of ethylcellulose and polyvinyl alcohol is 1:1), 0.5g of a mixture of polyvinylpyrrolidone and polyacrylic acid (the mass ratio of polyvinylpyrrolidone and polyacrylic acid is 1:1), and 1.5g of a mixture of nano montmorillonite and gaseous nano silica (the mass ratio of nano montmorillonite and gaseous nano silica is 2:1).
The comparative example 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 triamcinolone are mixed and stirred uniformly, then 0.5g of a mixture of ethylcellulose and polyvinyl butyral (the mass ratio of ethylcellulose to polyvinyl butyral is 1:1) is added, and stirring is carried out at a temperature of 90 ℃ for 4.5 hours. Then uniformly mixing by using a vacuum defoaming stirrer, adding 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 a mixture of nano montmorillonite and gas-phase nano silica (the mass ratio of nano montmorillonite to gas-phase nano silica is 2:1), and uniformly mixing by using a 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 (particle size of 5 μm) with 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 of 1:3:1:0.5:1:0.5), performing ball milling and dispersing by using 420g of absolute ethanol solution for 5h at a ball milling 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. Adding 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 case
Test example 1
Conducting silver paste for ceramic surface circuit printing prepared in example 1 is subjected to 3D printing, and the specific printing method is as follows:
1. the conductive silver paste prepared in example 1 was respectively loaded into a printhead, connected to a 3D printer, and 3D printed on the surface of the surface-treated ceramic substrate after setting a printing model and 3D printing parameters. 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 direct-writing 3D printing is 12%; the ceramic surface treatment mode is sulfuric acid treatment for 30min.
2. And (3) 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 discharging treatment and sintering. The drying temperature in the drying process is 50 ℃; the drying time is 300min; the temperature rising speed in the glue discharging process is 1 ℃/min; the glue discharging temperature is 500 ℃; the temperature rising speed in the sintering process is 1 ℃/min; the sintering temperature in the sintering process is 900 ℃; the sintering time was 30min.
The test results are shown in FIG. 1.
As can be seen from fig. 1, the paste has excellent molding accuracy and molding quality, and the molded line width and line spacing 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, accuracy of molded line width, error in molded line spacing, thermal strain at 800 c and high temperature resistance.
The static viscosity test method comprises the following steps: the test was performed using a rotarheometer.
The method for testing the precision of the formed line width comprises the following steps: high precision measurement microscopy.
The testing method of the forming line spacing error comprises the following steps: high precision measurement microscopy.
The testing method of the 800 ℃ thermal strain comprises the following steps: and (5) testing by a high-temperature visual deformation analyzer.
The high temperature resistance testing method comprises the following steps: and analyzing the line width and the surface morphology change of the conductive circuit before and after the high-temperature treatment of the contrast muffle furnace by using a scanning electron microscope.
The test results are shown in the following table:
from the table above, 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
Performance tests were performed on the conductive silver paste prepared in example 1, and the test contents include conductivity change of the 3D printing silver paste after high-temperature use and thermal strain of the 3D printing silver paste at high temperature after sintering.
The method for testing the conductivity change of the 3D printing silver paste after high-temperature use comprises the following steps: four probe method.
The testing method of the thermal strain of the 3D printing silver paste at high temperature after sintering comprises the following steps: and (5) testing by 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 sintering, and the conductivity is not obviously reduced after high-temperature use, and the slurry still has extremely high conductivity. And the thermal strain of the material is extremely small at high temperature, and is less than 0.6% at 900 ℃, so that the material has good high-temperature stability.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (10)
1. The conductive silver paste for ceramic surface circuit printing 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;
0.5-3% of surfactant;
0.2-2% of binder;
0.5-2% of diluent;
0.5-5% 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 a conductive silver paste for ceramic surface circuit printing according to any one of claim 1 to 3, comprising the steps of,
(1) Mixing the solvent with the surfactant, adding the binder, stirring, adding the diluent and the thixotropic agent, and uniformly mixing to obtain an organic colloid;
(2) Mixing silver powder with ceramic powder, and 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 method for preparing a conductive silver paste for ceramic surface circuit printing according to claim 4, wherein the stirring temperature is 50-100 ℃ for 1-5 hours;
and/or the mixing is under vacuum condition, and the vacuum degree is 20-100Kpa.
6. The method for preparing a 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 a conductive silver paste for ceramic surface circuit printing according to claim 7, wherein at least one of (1) to (9) is satisfied:
(1) The 3D printing is direct-write 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 mu m;
(4) The direct-writing 3D printing air pressure is 10-120Psi;
(5) The line width overlapping rate of direct-writing 3D printing is 5% -15%;
(6) The jet 3D printing speed is 0.5-100mm/s;
(7) The jet 3D printing interval is 1-10mm;
(8) The jet 3D printing air pressure is 10-100Psi;
(9) The difference in jetting 3D printing voltage is 50-100V.
9. The use of a conductive silver paste for ceramic surface circuit printing according to claim 7 or 8 in 3D printing, further comprising drying, paste discharging and sintering treatment after the printing step.
10. The use of the conductive silver paste for ceramic surface circuit printing according to claim 9, wherein at least one of the following (1) to (5) is satisfied:
(1) Drying at 50-100deg.C for 30-300min;
(2) Discharging glue at 300-500 ℃;
(3) Heating to the glue discharging temperature at a 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.
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