CN114653942A - Composite carrier capable of generating reducing atmosphere in sintering process and preparation method and application thereof - Google Patents
Composite carrier capable of generating reducing atmosphere in sintering process and preparation method and application thereof Download PDFInfo
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- CN114653942A CN114653942A CN202210020873.3A CN202210020873A CN114653942A CN 114653942 A CN114653942 A CN 114653942A CN 202210020873 A CN202210020873 A CN 202210020873A CN 114653942 A CN114653942 A CN 114653942A
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- reducing atmosphere
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- 238000005245 sintering Methods 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 40
- 230000008569 process Effects 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000010410 layer Substances 0.000 claims abstract description 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000012792 core layer Substances 0.000 claims abstract description 33
- 239000002002 slurry Substances 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims description 64
- 238000002156 mixing Methods 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 17
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 12
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims description 12
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 12
- 238000007873 sieving Methods 0.000 claims description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims description 7
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 claims description 6
- 108010010803 Gelatin Proteins 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 229920000159 gelatin Polymers 0.000 claims description 6
- 239000008273 gelatin Substances 0.000 claims description 6
- 235000019322 gelatine Nutrition 0.000 claims description 6
- 235000011852 gelatine desserts Nutrition 0.000 claims description 6
- 229960003512 nicotinic acid Drugs 0.000 claims description 6
- 235000001968 nicotinic acid Nutrition 0.000 claims description 6
- 239000011664 nicotinic acid Substances 0.000 claims description 6
- 229960005323 phenoxyethanol Drugs 0.000 claims description 6
- 229920002401 polyacrylamide Polymers 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 229940068984 polyvinyl alcohol Drugs 0.000 claims description 6
- 229940037312 stearamide Drugs 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 5
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 5
- 239000004642 Polyimide Substances 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims description 3
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- 235000020778 linoleic acid Nutrition 0.000 claims description 3
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 claims description 3
- 229960004488 linolenic acid Drugs 0.000 claims description 3
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 claims description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 2
- 239000000969 carrier Substances 0.000 claims 1
- 238000009472 formulation Methods 0.000 claims 1
- 239000004020 conductor Substances 0.000 abstract description 11
- 239000010953 base metal Substances 0.000 abstract description 9
- 230000001681 protective effect Effects 0.000 abstract description 4
- 239000000843 powder Substances 0.000 description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical compound [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Powder Metallurgy (AREA)
- Conductive Materials (AREA)
Abstract
The invention relates to a composite carrier generating reducing atmosphere in the sintering process and a preparation method and application thereof, belonging to the technical field of electronic slurry, wherein the carrier comprises a core layer, an intermediate layer and a buffer layer which are sequentially wrapped from the inside to the outside, the core layer contains graphite powder or carbon powder, the core layer generates reducing gas in the sintering process, the intermediate layer can control the release speed of the reducing gas, and the buffer layer can enable the composite carrier to be more effectively dispersed in the electronic slurry; the composite carrier prepared by the invention does not react with other components of the electronic paste; in the sintering process, the conductive phase can be prevented from being oxidized, the conductive phase can be reduced to generate oxides in the preparation process of the slurry and the electrode, and no residue is left. The invention has the characteristics of simple preparation method and convenient use; meanwhile, the technical index of sintering the electronic paste in air or protective atmosphere can be met, and a carrier for ensuring excellent electrode performance is provided for sintering base metal conductor paste.
Description
Technical Field
The invention belongs to the technical field of electronic paste, and particularly relates to a composite carrier generating a reducing atmosphere in a sintering process, and a preparation method and application thereof.
Background
For the conductive paste, the conductive phase is mostly noble metal powder such as platinum, palladium, gold and silver, and the silver conductive paste is most widely used. In recent years, the cost of slurry has increased due to the surge in the price of precious metals; on the other hand, the silver paste itself has silver migration, which makes it unable to meet the requirements of high-performance electronic components. Therefore, the development direction of electronic paste is about to reduce the cost, search for novel conductive powder with excellent performance and replace precious metals with base metals to prepare electronic paste.
At present, nickel paste, copper paste, aluminum paste and zinc paste are gradually used on electrodes of different electronic components instead of silver paste, but in the processes of preparing base metal paste and preparing electrodes, even if sintering is carried out in protective atmosphere, the problems that conductive phase metal powder is oxidized and conductive phase metal is oxidized are avoided, the conductive characteristic of the conductive phase metal powder is seriously damaged, the weldability is poor, the adhesive force is reduced and the like are also solved. How to reduce or avoid the oxidation of base metals in the sintering process has been one of the main directions of efforts of researchers.
Disclosure of Invention
In order to overcome the problems of the background art, a first object of the present invention is to provide a composite support for creating a reducing atmosphere during sintering, which can create a reducing atmosphere during sintering of an electronic slurry, prevent oxidation of a conductive phase metal, and at the same time completely volatilize or decompose without any residue. (ii) a A second object of the present invention is to provide a method for preparing a composite carrier that generates a reducing atmosphere during sintering; the third purpose of the invention is to provide the application of the composite carrier which generates the reducing atmosphere in the sintering process, wherein the composite carrier is used as one of the components of the slurry formula, is added with the organic carrier simultaneously in the slurry rolling process, and is uniformly dispersed in the slurry.
The first purpose of the invention is realized by the following technical scheme:
the composite carrier generating reducing atmosphere in the sintering process comprises a core layer and an intermediate layer; the middle layer is wrapped outside the core layer; the core layer contains a material that creates a reducing atmosphere during sintering.
Further, the intermediate layer contains a material capable of controlling gradual release of the reducing gas generated from the core layer.
Further, the material capable of generating the reducing atmosphere in the core layer is graphite or carbon.
Further, the core layer material is formed by mixing one or more of graphite, carbon, ethyl acetoacetate, gelatin, methyl acrylate, polyacrylamide, polyvinyl alcohol, phenoxyethanol, nicotinic acid and isoamylol, wherein the graphite or the carbon is an essential component.
Furthermore, the material of the middle layer is formed by mixing one or two or more than two of bismaleimide, polyamide, polyimide, polytetrafluoroethylene and polyurethane.
Further, the buffer layer is also included; the core layer, the middle layer and the buffer layer are sequentially wrapped from inside to outside; the buffer layer contains a material having oleophilic properties which enhances the dispersibility of the carrier in the slurry.
Furthermore, the buffer layer material is formed by mixing one or two or more of materials of vinyl bis stearamide, oleic acid acyl, ethylene-vinyl acetate copolymer, linear alkyl polyoxyethylene ether, block polyether, linolenic acid and linoleic acid.
The second purpose of the invention is realized by the following technical scheme:
the preparation method of the composite carrier generating the reducing atmosphere in the sintering process comprises the following steps:
(1) preparing a core layer: mixing graphite powder or carbon powder with one or more of acetoacetic ester, gelatin, methyl acrylate, polyacrylamide, polyvinyl alcohol, phenoxyethanol, nicotinic acid and isoamylol, grinding and sieving; wherein, the mass ratio of the graphite powder or the carbon powder is 70-100%, and the mass ratio of the mixed material is 0-30%;
(2) intermediate layer wrapping: mixing the core layer material and the intermediate layer material, and curing at 200-300 deg.C to coat the core layer material with the intermediate layer material
Further, the method also comprises a buffer layer wrapping step, which specifically comprises the following steps:
mixing the material prepared in the step (2) with a buffer layer material, and ultrasonically stirring to form a buffer layer package; and screening the prepared material, wherein the screened material is a composite carrier generating a reducing atmosphere in the sintering process.
The third purpose of the invention is realized by the following technical scheme:
the composite carrier generating reducing atmosphere in the sintering process is applied to electronic slurry, and particularly, the composite carrier is used as one of electronic slurry formula components and is added with an organic carrier simultaneously in the rolling process of the electronic slurry. The composite carrier is uniformly dispersed in the slurry, the slurry can generate a reducing atmosphere in the sintering process, the base metal conductive phase is protected from being oxidized, base metal oxide can be reduced, and meanwhile, the composite carrier does not react with other components of the slurry, can be completely volatilized or decomposed, and does not have any residue.
The invention has the beneficial effects that:
the composite carrier which generates the reducing atmosphere in the sintering process is added with the organic carrier simultaneously in the slurry rolling process and is uniformly dispersed in the slurry; the reduction atmosphere is generated in the sintering process (sintering in air and protective atmosphere), the conductive phase can be prevented from being oxidized, and the oxide is generated in the preparation process of the slurry and the electrode by reducing the conductive phase, so that the composite carrier which ensures the excellent performance of the electrode is provided for the sintering of the base metal conductor slurry.
The composite carrier which generates the reducing atmosphere in the sintering process of the invention is completely volatilized or decomposed, and has no residue; the preparation method is simple and the use is convenient; meanwhile, the technical index of sintering the electronic paste in air or protective atmosphere is met.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, preferred embodiments of the present invention will be described in detail below to facilitate understanding of the skilled person.
A preparation method of a composite carrier generating a reducing atmosphere in a sintering process comprises the following steps:
(1) preparation of the core layer
Mixing graphite powder or carbon powder with one or more of acetoacetic ester, gelatin, methyl acrylate, polyacrylamide, polyvinyl alcohol, phenoxyethanol, nicotinic acid and isoamylol, grinding and sieving; wherein, the mass ratio of the graphite powder or the carbon powder is 70-100%, and the mass ratio of the mixed material is 0-30%;
the core layer contains graphite powder or carbon powder, the graphite powder or the carbon powder is one or a mixture of more of scaly graphite, earthy graphite and amorphous carbon, and the graphite powder or the carbon powder generates carbon monoxide in the sintering process to provide a reducing atmosphere, prevent the conductive phase metal from being oxidized in the sintering process of the electronic slurry, and reduce the oxide generated in the preparation process of the slurry and the electrode of the conductive phase.
As a preferred technical scheme, besides graphite powder or carbon powder, the core layer material also contains one or more derivative additional materials of ethyl acetoacetate, gelatin, methyl acrylate, polyacrylamide, polyvinyl alcohol, phenoxyethanol, nicotinic acid and isoamylol, wherein the mass percentage of the graphite powder or the carbon powder is 70-90%, and the balance is the additional material.
(2) Intermediate layer wrapping
And (3) mixing the core layer material and the middle layer material in a ratio of 20-80: 1, and curing at 200-300 ℃ to ensure that the core layer material is wrapped by the middle layer material. The curing time is 30-90 minutes, and the materials can be stirred in the curing process.
The middle layer material is formed by mixing one or two or more than two of bismaleimide, polyamide, polyimide, polytetrafluoroethylene and polyurethane. The function of the middle layer material is to control the gradual release of the reducing gas generated by the core layer, thereby forming controllability to the reducing atmosphere. The intermediate layer material is large in molecular weight, the core layer material can be tightly combined in the coating process, and large-area contact is formed between the intermediate layer material and the core layer material, so that the core layer material can be shrunk and wrapped in the heating process, the intermediate layer is decomposed and volatilized along with the continuation of heating, the core layer gas is released, the coating powder is decomposed from outside to inside, the reducing gas is also gradually released, and the controllable release of the reducing gas is realized.
(3) Buffer layer wrapping
Mixing the carrier and the buffer layer material in the step (2) according to a mass ratio of 80-90: 1, stirring under an ultrasonic condition, and wrapping the buffer layer outside the material obtained in the step (2).
The buffer layer material is formed by mixing one or two or more than two of materials of vinyl bis stearamide, oleic acid acyl, ethylene-vinyl acetate copolymer, linear alkyl polyoxyethylene ether, block polyether, linolenic acid and linoleic acid. These materials have lipophilic properties and improve the dispersibility of the carrier in the slurry.
Stirring under ultrasonic condition, wherein the ultrasonic can uniformly disperse the powder produced in the previous step, thereby avoiding powder agglomeration and laying a foundation for good coating of the buffer layer.
The composite carrier which generates the reducing atmosphere in the sintering process and is prepared without wrapping the buffer layer can also generate good reducing atmosphere for the sintering process of the electronic slurry; by adding the buffer layer, the prepared composite carrier generating the reducing atmosphere in the sintering process has better dispersibility in the electronic slurry, and by virtue of good dispersibility, the use amount of the composite carrier can be saved by 10-30%, and the reducing atmosphere is further strengthened.
(4) Sieving
And (4) sieving the material in the step (3) by a 250-mesh sieve, wherein the sieved material is the composite carrier generating the reducing atmosphere in the sintering process. The composite carrier can be mixed into electronic slurry to be used as a carrier, the composite carrier and an organic carrier are added into the electronic slurry at the same time, the composite carrier is uniformly dispersed in the slurry, the composite carrier does not react with other components of the slurry in the sintering process, and can generate reducing gas with controllable release speed to protect base metals from being oxidized and reduce surrounding base metal oxides, and the composite carrier can be completely volatilized or decomposed in the sintering process without any residue.
Example 1
Preparation method of composite carrier capable of generating reducing atmosphere in sintering process
(1) Weighing 70% of graphite powder and 30% of isoamylol according to the mass ratio, mixing the graphite powder and the isoamylol, putting the mixture into a stainless steel ball milling tank, ball milling for 2 hours according to the ball-to-material ratio of 10:1, taking out, and sieving by using a 250-mesh sample sieve.
(2) Stirring and mixing 250-mesh undersize powder and bismaleimide according to a mass ratio of 50:1 for 2 hours; and (3) putting the mixed powder into an oven to be cured for 1 hour at 200 ℃, and stirring for at least 1 time during curing to finally form the intermediate layer.
(3) And (3) stirring and mixing the material obtained in the step (2) and the vinyl bis stearamide under the ultrasonic condition according to the mass ratio of 90:1, wherein the stirring and mixing time is 0.5 hour.
(4) Sieving the powder prepared in the step (3) by using a 250-mesh sample sieve, wherein the powder below the sieve is the powder which is reduced in the sintering process: an atmospheric composite carrier (hereinafter referred to as a composite carrier).
This example uses for the preparation of composite Carrier
The application conditions are as follows: 1. when the electronic paste is rolled, the composite carrier is added according to 5 percent of the weight of the copper powder, and the electronic paste and the organic carrier are rolled together to prepare the copper paste. 2. Printing thickness: 5 to 15 μm. 3. Screen material and mesh number: and (5) polyester silk screen of 200-280 meshes. 4. Drying conditions are as follows: and after printing, placing the mixture in an oven or a drying tunnel road at 150-280 ℃ for 2-5 minutes. 5. The sintering process comprises the following steps: sintering in a tunnel furnace, wherein the sintering peak temperature is 600 ℃, the peak heat preservation time is 10 minutes, and the sintering period is 60 minutes.
Under the same conditions, the copper conductor paste (1#) for the piezoresistor produced by adding the composite carrier of the embodiment is compared with the copper conductor paste (2#) for the piezoresistor produced without adding the composite carrier of the embodiment, and the results are shown in table 1.
TABLE 1 comparison of copper conductor paste properties
Example 2
Preparation method of composite carrier generating reducing atmosphere in sintering process
(1) Weighing 70% of a graphite powder and carbon powder mixture (the ratio of the graphite powder to the carbon is 1:1) according to the weight percentage; and 30% of ethyl acetoacetate, mixing the two, putting the mixture into a stainless steel ball milling tank, ball milling for 2 hours according to the ball-to-material ratio of 10:1, taking out, and sieving by using a 250-mesh sample sieve.
(2) Stirring and mixing the undersize powder in the step (1) and polyimide for 2 hours according to the weight percentage of 70: 30; and (3) putting the mixed powder into an oven to be cured for 1 hour at 200 ℃, and stirring for at least 1 time during curing to finally form the intermediate layer.
(3) And (3) ultrasonically stirring and mixing the powder obtained in the step (2) and the vinyl bis-stearamide according to the mass ratio of 50:1, wherein the stirring and mixing time is 0.5 hour.
(4) And (4) sieving the powder obtained after stirring and mixing in the step (3) by using a 250-mesh sample sieve, wherein the powder under the sieve is a qualified composite carrier.
This example uses for the preparation of composite Carrier
The experimental conditions were applied: 1. when the electronic paste is rolled, the composite carrier is added according to 3 percent of the weight of the nickel powder, and the electronic paste and the organic carrier are rolled together to prepare the nickel paste. 2. Printing thickness: 5 to 15 μm. 3. Screen material and mesh number: and (5) polyester silk screen of 200-280 meshes. 4. Drying conditions are as follows: and after printing, placing the mixture in an oven or a drying tunnel road at 150-280 ℃ for 2-5 minutes. 5. The sintering process comprises the following steps: sintering in a tunnel furnace, wherein the sintering peak temperature is 850 ℃, the peak heat preservation time is 10 minutes, and the sintering period is 60 minutes.
Under the same conditions, the nickel conductor paste (3#) produced by adding the composite carrier in the embodiment and the nickel conductor paste (4#) produced by not adding the composite carrier are added, the performance parameters of the nickel electrode prepared by printing on the alumina substrate are compared, and the comparison result is shown in table 2.
TABLE 2 comparison of Nickel conductor paste Properties
Example 3
Preparation method of composite carrier generating reducing atmosphere in sintering process
(1) Weighing 70% of graphite and 30% of isoamyl alcohol according to weight percentage, mixing the graphite and the isoamyl alcohol, putting the mixture into a stainless steel ball milling tank, ball milling for 2 hours according to the ball-to-material ratio of 10:1, taking out, and sieving by using a 250-mesh sample sieve.
(2) Stirring and mixing the undersize powder obtained in the step (1) and bismaleimide according to a mass ratio of 70:30 for 2 hours; and placing the mixed powder into an oven to be cured for 1 hour at 200 ℃, and stirring for at least 1 time during curing to form the middle layer.
(3) And (3) ultrasonically stirring, mixing and mixing the powder obtained in the step (2) and the vinyl bis-stearamide according to the mass ratio of 40:1, wherein the stirring and mixing time is 0.5 hour.
(4) And (4) sieving the powder prepared in the step (3) by using a 250-mesh sample sieve, wherein the sieved powder is a qualified composite carrier.
This example uses for the preparation of composite Carrier
Experimental conditions applied: 1. when the electronic paste is rolled, the composite carrier is added according to 8 percent of the weight of the zinc powder, and the electronic paste and the organic carrier are rolled together to prepare the zinc paste. 2. Printing thickness: 5 to 15 μm. 3. Screen material and mesh number: and (5) polyester silk screen of 200-280 meshes. 4. Drying conditions are as follows: and after printing, placing the mixture in an oven or a drying tunnel road at 150-280 ℃ for 2-5 minutes. 5. The sintering process comprises the following steps: sintering in a tunnel furnace, wherein the sintering peak temperature is 600 ℃, the peak heat preservation time is 10 minutes, and the sintering period is 60 minutes.
Under the same conditions, the zinc conductor paste (No. 5) produced by adding the composite carrier in the embodiment and the zinc conductor paste (No. 6) produced by not adding the composite carrier are added, the performance parameters of the zinc electrode prepared by printing on the alumina substrate are compared, and the comparison result is shown in Table 3.
TABLE 3 comparison of Performance of Zinc conductor pastes
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (10)
1. A composite carrier generating a reducing atmosphere in a sintering process is characterized in that: comprises a core layer and an intermediate layer; the middle layer is wrapped outside the core layer; the core layer contains a material which generates a reducing atmosphere in the sintering process.
2. The composite carrier for generating a reducing atmosphere during sintering according to claim 1, wherein: the intermediate layer contains a material capable of controlling the gradual release of the reducing gas generated from the core layer.
3. The composite carrier for generating a reducing atmosphere during sintering according to claim 1, wherein: the material in the core layer capable of generating reducing atmosphere is graphite or carbon.
4. The composite carrier for generating a reducing atmosphere during sintering according to claim 3, wherein: the core layer material is prepared by mixing one or more of graphite, carbon, ethyl acetoacetate, gelatin, methyl acrylate, polyacrylamide, polyvinyl alcohol, phenoxyethanol, nicotinic acid and isoamylol, wherein the graphite or the carbon is an essential component.
5. The composite carrier for generating a reducing atmosphere during sintering according to claim 2, wherein: the middle layer material is formed by mixing one or two or more than two of bismaleimide, polyamide, polyimide, polytetrafluoroethylene and polyurethane.
6. The composite carrier for generating a reducing atmosphere during sintering according to any one of claims 1 to 5, characterized in that: the buffer layer is also included; the core layer, the middle layer and the buffer layer are sequentially wrapped from inside to outside; the buffer layer contains a material having oleophilic properties and capable of improving the dispersibility of the composite carrier in the slurry.
7. The composite carrier for generating a reducing atmosphere during sintering according to claim 6, wherein: the buffer layer material is formed by mixing one or two or more than two of materials of vinyl bis stearamide, oleic acid acyl, ethylene-vinyl acetate copolymer, linear alkyl polyoxyethylene ether, block polyether, linolenic acid and linoleic acid.
8. The composite carrier for generating a reducing atmosphere during sintering according to any one of claims 1 to 7, which is prepared by a method comprising the steps of:
(1) preparing a core layer: mixing graphite powder or carbon powder with one or more of acetoacetic ester, gelatin, methyl acrylate, polyacrylamide, polyvinyl alcohol, phenoxyethanol, nicotinic acid and isoamylol, grinding and sieving; wherein, the mass ratio of the graphite powder or the carbon powder is 70-100%, and the mass ratio of the mixed material is 0-30%;
(2) intermediate layer wrapping: the core layer material and the middle layer material are mixed and cured at 200-300 ℃ to ensure that the core layer material is wrapped by the middle layer material.
9. The composite carrier for generating a reducing atmosphere during sintering according to claim 8, wherein the preparation method further comprises a buffer layer wrapping step, specifically:
mixing the material prepared in the step (2) with a buffer layer material, and ultrasonically stirring to form a buffer layer package; and screening the prepared materials, wherein the screened materials are composite carriers generating reducing atmosphere in the sintering process.
10. The composite carrier for generating a reducing atmosphere during sintering according to any one of claims 1 to 7, for use in an electronic paste, in particular as one of the components of an electronic paste formulation, to be added simultaneously with an organic carrier during rolling of an electronic paste.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210020873.3A CN114653942B (en) | 2022-01-10 | Composite carrier generating reducing atmosphere in sintering process and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210020873.3A CN114653942B (en) | 2022-01-10 | Composite carrier generating reducing atmosphere in sintering process and preparation method and application thereof |
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| CN114653942B CN114653942B (en) | 2024-06-21 |
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