CN113782250A - High-thixotropy low-temperature co-fired ceramic inner electrode silver paste and preparation method and application thereof - Google Patents
High-thixotropy low-temperature co-fired ceramic inner electrode silver paste and preparation method and application thereof Download PDFInfo
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- CN113782250A CN113782250A CN202110987348.4A CN202110987348A CN113782250A CN 113782250 A CN113782250 A CN 113782250A CN 202110987348 A CN202110987348 A CN 202110987348A CN 113782250 A CN113782250 A CN 113782250A
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 77
- 239000004332 silver Substances 0.000 title claims abstract description 77
- 239000000919 ceramic Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011521 glass Substances 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000969 carrier Substances 0.000 claims abstract description 6
- 238000000498 ball milling Methods 0.000 claims description 20
- 239000002002 slurry Substances 0.000 claims description 13
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- 235000019438 castor oil Nutrition 0.000 claims description 11
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- 238000005303 weighing Methods 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 230000009974 thixotropic effect Effects 0.000 claims description 6
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- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 5
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- 239000013008 thixotropic agent Substances 0.000 claims description 5
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 4
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- BAECOWNUKCLBPZ-HIUWNOOHSA-N Triolein Natural products O([C@H](OCC(=O)CCCCCCC/C=C\CCCCCCCC)COC(=O)CCCCCCC/C=C\CCCCCCCC)C(=O)CCCCCCC/C=C\CCCCCCCC BAECOWNUKCLBPZ-HIUWNOOHSA-N 0.000 claims description 4
- PHYFQTYBJUILEZ-UHFFFAOYSA-N Trioleoylglycerol Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(OC(=O)CCCCCCCC=CCCCCCCCC)COC(=O)CCCCCCCC=CCCCCCCCC PHYFQTYBJUILEZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical group CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 4
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 4
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 claims description 4
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- 235000021314 Palmitic acid Nutrition 0.000 claims description 3
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- 235000005687 corn oil Nutrition 0.000 claims description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000003981 vehicle Substances 0.000 claims description 3
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 claims description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 2
- 239000001856 Ethyl cellulose Substances 0.000 claims description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical group CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 2
- 229960000541 cetyl alcohol Drugs 0.000 claims description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920001249 ethyl cellulose Polymers 0.000 claims description 2
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 2
- -1 ketone compounds Chemical class 0.000 claims description 2
- 229940116411 terpineol Drugs 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims 1
- 238000010344 co-firing Methods 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 4
- 238000005245 sintering Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000011084 recovery Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 229910000838 Al alloy Inorganic materials 0.000 description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000010431 corundum Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
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- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0016—Apparatus or processes specially adapted for manufacturing conductors or cables for heat treatment
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Inorganic Chemistry (AREA)
- Thermal Sciences (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses a high-thixotropy low-temperature co-fired ceramic inner electrode silver paste and a preparation method and application thereof, wherein the electrode silver paste comprises the following components in percentage by mass: 75-82% of silver powder; 1-3.5% of glass powder; 0.3 to 1 percent of alumina; the balance of organic carriers; the silver powder consists of spherical silver powder and flake silver powder; the thickness of the flake silver powder is 100-200 nanometers, and the diameter is 3-5 micrometers; the diameter of the spherical silver powder is 0.5-1.3 microns; the mass ratio of the spherical silver powder to the flake silver powder is 79-81: 19-21. The electric high thixotropy low-temperature co-fired ceramic inner electrode silver paste has the advantages of good co-firing matching property and printability with the LTCC green ceramic substrate, excellent conductivity, simple preparation process and the like.
Description
Technical Field
The invention relates to the field of preparation of silver conductive paste, in particular to high-thixotropy low-temperature co-fired ceramic inner electrode silver paste and a preparation method and application thereof.
Background
With the rapid development of modern microelectronic information technology, people demand electronic components in the aspects of portability, miniaturization, digitalization, multifunction, high performance and high reliability, so that the requirements of integration, miniaturization and modularization of electronic components are increasingly urgent. Low temperature co-fired ceramic (LTCC) is a multi-disciplinary cross integrated assembly technology emerging in recent decades and becomes a research hotspot of people in recent years, and due to good thermodynamics, electronics and corresponding mechanical properties, LTCC technology has become a preferential development direction in the fields of electronic component integrated devices and microwave technology in the future, and has a good application prospect.
The conductive silver paste is a key functional material required by electronic components, integrated circuits and solar cell industries, and has huge market demand and technical progress potential. In the field of the existing electronic paste, the silver paste has the characteristics of high conductivity, stable performance, high bonding strength with a substrate and the like, and is widely applied to the production of electronic components such as integrated circuits, multi-chip components, thin-film switches and the like. However, the conductive silver paste has more requirements on the performance of the silver paste, such as conductivity, printability, tensile strength, acid and alkali resistance, weather resistance and thixotropy, wherein the silver paste is required to have good thixotropy and recovery property in the screen printing process of the conductive silver paste, and if the thixotropy of the silver paste is low, a breakpoint phenomenon occurs in the printing process of the silver paste, so that the normal use of the silver paste is influenced; if the recovery of silver paste is poor, the silver paste can not recover the viscosity in time after the extrusion of the acting force of the scraper, so that the electrodes are crossed, and the service performance of the final silver conductive product is influenced. Therefore, a conductive silver paste having high thixotropy and recovery is urgently needed.
Disclosure of Invention
The invention aims to provide high-thixotropy low-temperature co-fired ceramic inner electrode silver paste.
The second purpose of the invention is to provide a preparation method of the high thixotropy low temperature co-fired ceramic inner electrode silver paste.
The third purpose of the invention is to provide application of the high thixotropy low temperature co-fired ceramic inner electrode silver paste.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a high thixotropy low temperature co-fired ceramic inner electrode silver paste, which comprises the following components in percentage by mass:
75-82% of silver powder;
1-3.5% of glass powder;
0.3 to 1 percent of alumina;
the balance of organic carriers;
the silver powder consists of spherical silver powder and flake silver powder; the thickness of the flake silver powder is 100-200 nanometers, and the diameter is 3-5 micrometers; the diameter of the spherical silver powder is 0.5-1.5 microns; the mass ratio of the spherical silver powder to the flake silver powder is 79-81: 19-21; the mass ratio of the spherical silver powder to the flake silver powder is in the range, the sheet resistance is small after the electrode silver paste is sintered, and the silver layer is compact; more preferably, the mass ratio of the spherical silver powder to the flake silver powder is 80:20, and the electrode silver paste prepared according to the ratio is optimal in sheet resistance and compactness after being sintered.
The invention finds that the agglomeration of the electrode silver paste can be avoided, the screen printing performance can be improved, the resistance can be reduced, and the conductivity of the electrode silver paste can be improved by controlling the shape and the size of the silver powder. In addition, the invention also discovers that the traditional electrode silver paste enhances the thixotropy by using a thixotropic auxiliary agent and other modes, so that the conductivity of the electrode silver paste is improved, and the original performances of the electrode silver paste, such as poor viscosity, poor sintering property and the like, can be reduced more or less, and the actual production requirements cannot be met. The invention can achieve the effect of obviously enhancing the thixotropy and the recovery of the silver paste of the electrode on the basis of not influencing the original performance by reasonably controlling the appearance, the size and the proportion of other components of the silver paste of the electrode.
Further, the glass powder comprises the following components in percentage by mass:
Li2o is 0.1-1.5%.
Further, the organic carrier comprises the following components in parts by weight:
further, in the organic carrier, the solvent is one or more of terpineol, butyl carbitol acetate, butyl carbitol and ethylene glycol ethyl ether acetate.
The plasticizer is dibutyl phthalate and/or dioctyl phthalate.
The dispersant is one or more of castor oil, span 85, tributyl phosphate and polymethacrylic acid amine.
The adhesive is ethyl cellulose and/or cetyl alcohol.
The additive is one or more of ketone compounds.
The thixotropic agent is one or more of hydrogenated castor oil, polyamide, palmitic acid, furoic acid, octadecylamine, acrylic resin, corn oil and triolein.
In a second aspect, the invention provides a preparation method of a high thixotropy low temperature co-fired ceramic inner electrode silver paste, which comprises the following steps:
weighing the components in proportion, dissolving the organic carrier at 70-80 ℃, then adding silver powder, glass powder and alumina, uniformly mixing to obtain slurry, and then ball-milling the obtained slurry by using a ball mill until the fineness is less than 5 micrometers to obtain the nano-silver/aluminum/silver/aluminum/silver/aluminum.
Preferably, the preparation method further comprises adding a certain amount of dispersant after adding other components, wherein the dispersant is one or more of castor oil, span 85, tributyl phosphate and polymethacrylic acid amine.
In a third aspect, the invention provides an application of high thixotropy low temperature co-fired ceramic inner electrode silver paste in preparing a silver conductive film layer.
According to the specific embodiment of the invention, the preparation of the silver conductive film layer by using the high thixotropy low temperature co-fired ceramic inner electrode silver paste specifically comprises the following steps:
printing the electric high thixotropy low-temperature co-fired ceramic inner electrode silver paste on a substrate by a screen printing process, drying at 100 ℃ for 10-15 minutes, and then sintering in a high-temperature sintering furnace for 120 minutes, wherein the peak temperature is 800-900 ℃ and the peak time is 10-15 minutes.
The invention has the following beneficial effects:
the high-thixotropy low-temperature co-fired ceramic inner electrode silver paste has the advantages of high thixotropy and high recovery, and has good co-firing matching property, printability, excellent conductivity and the like with an LTCC green ceramic substrate.
The preparation method of the electric high thixotropy low-temperature co-fired ceramic inner electrode silver paste has simple steps and is easy to realize industrialization.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 shows a comparative graph of rheological curves of different high thixotropy low temperature co-fired ceramic inner electrode silver pastes prepared in examples 1-8.
FIG. 2 is a graph showing the comparison of the viscosity change curves of different high thixotropy low temperature co-fired ceramic inner electrode silver pastes prepared in examples 9-12 with time.
Fig. 3 shows a schematic diagram of the printed patterns when testing the printing performance of different electrode silver pastes.
Detailed Description
In order to make the technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
Example 1
The high-thixotropy low-temperature co-fired ceramic inner electrode silver paste comprises the following components in percentage by mass:
76% of silver powder (wherein the silver powder consists of spherical silver powder and flake silver powder, the thickness of the flake silver powder is 100-200 nm, the diameter is 5 microns, the diameter of the spherical silver powder is 0.5-1.5 microns, and the mass ratio of the spherical silver powder to the flake silver powder is 80: 20);
3.5% of glass powder;
0.5 percent of alumina;
the balance of organic carriers;
the preparation method comprises the following steps:
(1) preparing glass powder: weighing the components according to the proportion shown in the table 1, putting the components into a corundum crucible, and fully and uniformly stirring the components by using a glass rod; then putting the mixture into a high-temperature sintering furnace, and preheating the mixture at 400 ℃ for 10 minutes; then, the temperature of the high-temperature sintering furnace is increased to 1400 ℃ at the speed of 10 ℃/min, and the temperature is kept for 30 minutes; filling 1.4L of aluminum alloy lunch box with deionized water, and placing the lunch box near a high-temperature sintering furnace; taking out the molten glass powder by using a sampling clamp, and then quickly pouring the molten glass powder into an aluminum alloy lunch box filled with deionized water for water quenching; and then cooling to room temperature, putting the cooled glass powder into a ball milling tank, adding zirconium balls (the zirconium balls are 8cm, 5cm and 3cm in a mass ratio of 5:3: 2) according to a ball material mass ratio of 5:3, adding alcohol serving as a ball milling medium according to a solid-liquid mass ratio of 3:2, carrying out ball milling for 30 hours, drying, grinding and sieving to obtain the glass powder.
(2) Preparing an organic carrier: weighing the components according to the proportion shown in the table 2, mixing in a glass beaker, putting the glass beaker into a constant-temperature oil bath magnetic stirrer at 70 ℃ and uniformly stirring until all indissolvable substances are completely dissolved, and storing the mixture at room temperature and ambient temperature to obtain the product.
(3) Preparing electrode silver paste: accurately weighing the components according to the proportion of 20g in total; and (2) pre-stirring for 5 hours by using a magnetic stirrer to obtain slurry, and then carrying out ball milling on the obtained slurry, wherein the ball milling speed is 500rad/min, the ball milling time is 15 hours, and the fineness of the ball-milled slurry is less than 5 micrometers, so that the high-performance magnetic material is obtained.
TABLE 1
| Composition (I) | SiO2 | Al2O3 | B2O3 | CaO | Li2O |
| Content (wt%) | 38 | 15 | 8 | 38 | 1 |
TABLE 2
Examples 2 to 8
The same as example 1, except that the hydrogenated castor oil in the organic vehicle was replaced with equal amounts of: triolein, acrylic, corn, octadecylamine, furoic, palmitic and polyamide.
Examples 9 to 12
The same as example 1, except that the dispersant (the sum of castor oil and tributyl phosphate) in the organic vehicle was replaced with: tributyl phosphate, castor oil, span 8 and polymethacrylic acid amine.
Example 13
The high-thixotropy low-temperature co-fired ceramic inner electrode silver paste comprises the following components in percentage by mass:
80% of silver powder (wherein the silver powder consists of spherical silver powder and flake silver powder, the thickness of the flake silver powder is 100-200 nanometers, the diameter of the flake silver powder is 5 micrometers, the diameter of the spherical silver powder is 0.5-1.5 micrometers, and the mass ratio of the spherical silver powder to the flake silver powder is 80: 20);
1.5 percent of glass powder;
0.3 percent of alumina;
the balance of organic carriers;
the preparation method comprises the following steps:
(1) preparing glass powder: weighing the components according to the proportion shown in the table 3, putting the components into a corundum crucible, and fully and uniformly stirring the components by using a glass rod; then putting the mixture into a high-temperature sintering furnace, and preheating the mixture at 400 ℃ for 10 minutes; then, the temperature of the high-temperature sintering furnace is increased to 1400 ℃ at the speed of 10 ℃/min, and the temperature is kept for 30 minutes; filling 1.4L of aluminum alloy lunch box with deionized water, and placing the lunch box near a high-temperature sintering furnace; taking out the molten glass powder by using a sampling clamp, and then quickly pouring the molten glass powder into an aluminum alloy lunch box filled with deionized water for water quenching; and then cooling to room temperature, putting the cooled glass powder into a ball milling tank, adding zirconium balls (the zirconium balls are 8cm, 5cm and 3cm in a mass ratio of 5:3: 2) according to a ball material mass ratio of 5:3, adding alcohol serving as a ball milling medium according to a solid-liquid mass ratio of 3:2, carrying out ball milling for 30 hours, drying, grinding and sieving to obtain the glass powder.
(2) Preparing an organic carrier: weighing the components according to the proportion shown in Table 4, mixing in a glass beaker, putting into a constant-temperature oil bath magnetic stirrer at 70 ℃, uniformly stirring until all indissolvable substances are completely dissolved, and storing at room temperature to obtain the product.
(3) Preparing electrode silver paste: accurately weighing the components according to the proportion of 20g in total; and (2) pre-stirring for 5 hours by using a magnetic stirrer to obtain slurry, and then carrying out ball milling on the obtained slurry, wherein the ball milling speed is 500rad/min, the ball milling time is 15 hours, and the fineness of the ball-milled slurry is less than 5 micrometers, so that the high-performance magnetic material is obtained.
TABLE 3
| Composition (I) | SiO2 | Al2O3 | B2O3 | Ca O | Li2O |
| Content (wt%) | 36 | 13 | 10 | 39.5 | 1.5 |
TABLE 4
Example 14
The high-thixotropy low-temperature co-fired ceramic inner electrode silver paste comprises the following components in percentage by mass:
78% of silver powder (wherein the silver powder consists of spherical silver powder and flake silver powder, the thickness of the flake silver powder is 100-200 nanometers, the diameter of the flake silver powder is 5 micrometers, the diameter of the spherical silver powder is 0.5-1.5 micrometers, and the mass ratio of the spherical silver powder to the flake silver powder is 80: 20);
2.5 percent of glass powder;
1.0% of alumina;
the balance of organic carriers;
the preparation method comprises the following steps:
(1) preparing glass powder: weighing the components according to the proportion shown in the table 5, putting the components into a corundum crucible, and fully and uniformly stirring the components by using a glass rod; then putting the mixture into a high-temperature sintering furnace, and preheating the mixture at 400 ℃ for 10 minutes; then, the temperature of the high-temperature sintering furnace is increased to 1400 ℃ at the speed of 10 ℃/min, and the temperature is kept for 30 minutes; filling 1.4L of aluminum alloy lunch box with deionized water, and placing the lunch box near a high-temperature sintering furnace; taking out the molten glass powder by using a sampling clamp, and then quickly pouring the molten glass powder into an aluminum alloy lunch box filled with deionized water for water quenching; and then cooling to room temperature, putting the cooled glass powder into a ball milling tank, adding zirconium balls (the zirconium balls are 8cm, 5cm and 3cm in a mass ratio of 5:3: 2) according to a ball material mass ratio of 5:3, adding alcohol serving as a ball milling medium according to a solid-liquid mass ratio of 3:2, carrying out ball milling for 30 hours, drying, grinding and sieving to obtain the glass powder.
(2) Preparing an organic carrier: the components were weighed in the proportions shown in table 6, mixed in a glass beaker, placed in a 75 ℃ constant temperature oil bath magnetic stirrer and stirred until all the insoluble substances were completely dissolved, and stored at room temperature.
(3) Preparing electrode silver paste: accurately weighing the components according to the proportion of 20g in total; and (2) pre-stirring for 5 hours by using a magnetic stirrer to obtain slurry, and then carrying out ball milling on the obtained slurry, wherein the ball milling speed is 500rad/min, the ball milling time is 15 hours, and the fineness of the ball-milled slurry is less than 5 micrometers, so that the high-performance magnetic material is obtained.
TABLE 5
| Composition (I) | SiO2 | Al2O3 | B2O3 | Ca O | Li2O |
| Content (wt%) | 39 | 17.5 | 7 | 36 | 0.5 |
TABLE 6
Comparative example 1
The only difference from example 1 was that the thickness of the plate-like silver powder in the silver powder was 500 nm.
Comparative example 2
The only difference from example 1 is that the thickness of the plate-like silver powder in the silver powder was 50 nm.
Comparative example 3
The difference from example 1 is only that the plate-like silver powder in the silver powder has a diameter of 10 μm.
Comparative example 4
The only difference from example 1 is that the silver powder is a spherical silver powder.
Comparative example 5
The only difference from example 1 is that the silver powder is a plate-like silver powder.
Performance testing
The rheological properties of the high thixotropic low temperature co-fired ceramic inner electrode silver paste of comparative examples 1 to 8 are shown in fig. 1.
The viscosity of the high thixotropic low temperature co-fired ceramic inner electrode silver paste of comparative examples 9-12 was plotted with time, and the results are shown in fig. 2.
The high thixotropic low temperature co-fired ceramic inner electrode silver pastes of comparative examples 1, 13, 14 and comparative examples 1 to 5 have the properties of conductivity, thixotropic index, co-firing matching with ceramic, shrinkage (the shrinkage refers to shrinkage after co-firing, determined by comparing the distance between two points on a printed pattern with the same distance between two points after firing), printability at a line width of 400 μm and a line pitch of 100 μm (as shown in fig. 3), and the like, and the test results are shown in table 8.
TABLE 8
As can be seen from fig. 1, in examples 1 to 8, when hydrogenated castor oil, triolein, acrylic resin, corn oil, octadecylamine, furoic acid, palmitic acid and polyamide are respectively used as thixotropic agents to prepare electrode silver pastes, the thixotropy of each finally obtained electrode silver paste is in a reasonable range. In comparison, however, the thixotropy of the electrode silver paste prepared in example 1 is the most moderate, and the thixotropy of the electrode silver pastes in examples 3 and 4 is larger, so that the electrode silver paste is more suitable for being used as a pore filling paste compared with the electrode silver paste.
As can be seen from fig. 2, in examples 9 to 12, when tributyl phosphate, castor oil, span 85, and polymethacrylic acid amine were used as dispersants to prepare electrode silver pastes, the recovery time of each finally obtained electrode silver paste was within a reasonable range. However, in comparison, the recovery time of the electrode silver paste prepared in example 12 is too fast, which may be unfavorable for the leveling property of the electrode silver paste, and the recovery time of the inner electrode silver paste prepared in example 11 is most suitable.
The combination of the test results of fig. 1 and fig. 2 shows that the internal electrode silver paste prepared by using the hydrogenated castor oil as the thixotropic agent and the span 85 as the dispersing agent has better combination properties.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (10)
1. The high-thixotropy low-temperature co-fired ceramic inner electrode silver paste is characterized by comprising the following components in percentage by mass:
75-82% of silver powder;
1-3.5% of glass powder;
0.3 to 1 percent of alumina;
the balance of organic carriers;
the silver powder consists of spherical silver powder and flake silver powder; the thickness of the flake silver powder is 100-200 nanometers, and the diameter is 3-5 micrometers; the diameter of the spherical silver powder is 0.5-1.5 microns; the mass ratio of the spherical silver powder to the flake silver powder is 79-81: 19-21.
2. The high thixotropy low temperature co-fired ceramic inner electrode silver paste of claim 1, wherein said glass frit comprises the following components in mass percent:
SiO2 35-40％；
Al2O3 12-18％
B2O3 7-10％；
CaO 35-40％；
Li2O 0.1-1.5％。
3. the high thixotropy low temperature co-fired ceramic inner electrode silver paste of claim 1, wherein said organic vehicle comprises the following components in parts by weight:
59-65 parts of a solvent;
9-11 parts of a plasticizer;
9-13 parts of an adhesive;
8-15 parts of a dispersing agent;
0-15 parts of an additive;
0.5-1.5 parts of thixotropic agent.
4. The high thixotropy low temperature co-fired ceramic inner electrode silver paste according to claim 3, wherein said solvent is one or more of terpineol, butyl carbitol acetate, butyl carbitol and ethylene glycol ethyl ether acetate.
5. The high thixotropy low temperature co-fired ceramic inner electrode silver paste according to claim 3, wherein said plasticizer is dibutyl phthalate and/or dioctyl phthalate.
6. The high thixotropy low temperature co-fired ceramic inner electrode silver paste according to claim 3, wherein said dispersant is one or more of castor oil, span 85, tributyl phosphate and polymethacrylic acid amine.
7. The high thixotropy low temperature co-fired ceramic inner electrode silver paste of claim 3, wherein said binder is ethyl cellulose and/or cetyl alcohol;
preferably, the additive is one or more of ketone compounds.
8. The high thixotropy low temperature co-fired ceramic inner electrode silver paste according to claim 3, wherein said thixotropic agent is one or more of hydrogenated castor oil, polyamide, palmitic acid, furoic acid, octadecylamine, acrylic resin, corn oil and triolein.
9. The preparation method of the high thixotropy low temperature co-fired ceramic inner electrode silver paste according to any one of claims 1 to 8, characterized by comprising the following steps:
weighing the components in proportion, dissolving the organic carrier at 70-80 ℃, then adding silver powder, glass powder and alumina, uniformly mixing to obtain slurry, and then ball-milling the obtained slurry by using a ball mill until the fineness is less than 5 micrometers to obtain the nano-silver/aluminum/silver/aluminum/silver/aluminum.
10. Use of the high thixotropic low temperature co-fired ceramic inner electrode silver paste according to any one of claims 1 to 8 in preparing a silver conductive film layer.
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