CN116352075B - Composite copper powder and preparation method and application thereof - Google Patents
Composite copper powder and preparation method and application thereof Download PDFInfo
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- CN116352075B CN116352075B CN202310344324.6A CN202310344324A CN116352075B CN 116352075 B CN116352075 B CN 116352075B CN 202310344324 A CN202310344324 A CN 202310344324A CN 116352075 B CN116352075 B CN 116352075B
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 239000002131 composite material Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 125
- 239000002184 metal Substances 0.000 claims abstract description 96
- 229910052751 metal Inorganic materials 0.000 claims abstract description 96
- 239000010949 copper Substances 0.000 claims abstract description 32
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical group [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 24
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011701 zinc Substances 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000003985 ceramic capacitor Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 239000012803 melt mixture Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 28
- 230000003647 oxidation Effects 0.000 abstract description 22
- 238000007254 oxidation reaction Methods 0.000 abstract description 22
- 238000007747 plating Methods 0.000 abstract description 20
- 238000005245 sintering Methods 0.000 abstract description 18
- 229910052725 zinc Inorganic materials 0.000 abstract description 13
- 238000009713 electroplating Methods 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 20
- 230000000694 effects Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910000365 copper sulfate Inorganic materials 0.000 description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000012797 qualification Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 150000001879 copper Chemical class 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229960005070 ascorbic acid Drugs 0.000 description 3
- 235000010323 ascorbic acid Nutrition 0.000 description 3
- 239000011668 ascorbic acid Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000013008 thixotropic agent Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229940116411 terpineol Drugs 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/09—Mixtures of metallic powders
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/04—Alloys based on copper with zinc as the next major constituent
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/005—Electrodes
- H01G4/008—Selection of materials
- H01G4/0085—Fried electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/107—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing organic material comprising solvents, e.g. for slip casting
-
- 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
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
- B22F7/04—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention relates to composite copper powder, a preparation method and application thereof, and belongs to the field of multilayer ceramic capacitors. The composite copper powder comprises the following components in percentage by mass: 40-80% of first metal powder and 20-60% of second metal powder; the first metal powder is pure copper powder; the second metal powder is copper zinc powder, and the chemical formula of the copper zinc powder is Cu x Zn y Wherein: x is more than or equal to 1.25 and less than or equal to 1.53,0.03, y is more than or equal to 0.31; the average particle size of the first metal powder is less than or equal to the average particle size of the second metal powder. By adopting the copper zinc powder with the specific chemical formula, zinc with specific mass is introduced into copper and compounded with copper powder with specific mass, so that the oxidation resistance of the copper powder can be effectively improved, the sintering temperature of a copper layer of the terminal electrode is reduced, the compactness of the terminal electrode is improved, and the copper zinc powder can be corroded by an acidic electroplating solution to obtain rugged holes, so that the binding force between an external plating layer and the copper electrode is increased.
Description
Technical Field
The invention belongs to the field of multilayer ceramic capacitors, and particularly relates to composite copper powder and a preparation method and application thereof.
Background
The multilayer ceramic capacitor (Multi-layers Ceramic Capacitor, MLCC) has the advantages of high capacity, strong reliability, small volume, low price and the like, is widely applied to the fields of automobiles, aviation, portable electronic equipment, intelligent instrument automation and the like, and with the high-speed development of scientific technology, the performance requirements on the MLCC in the market are increasingly improved, and the aim of obtaining a thin-layer and miniaturized capacitor can be achieved, and meanwhile, the reliability and the durability of the MLCC can be further improved.
MLCCs are typically composed of ceramic dielectric layers, inner electrodes, and outer (terminal) electrodes from a structural perspective. The external electrode is generally divided into three layers from inside to outside, namely a copper layer directly contacted with the internal electrode, a nickel layer used for resisting welding erosion and a tin layer convenient for welding. At present, the copper layer is basically in a form of being sintered after being coated with copper paste, and the nickel layer and the tin layer are in a form of being electroplated, but still have a plurality of problems: copper powder for preparing copper slurry is easily oxidized by air to lose conductivity, copper powder sintering activity is low, poor compactness caused by poor sintering is easy to occur, and poor binding force between a copper end and a plating layer affects the performance and service life of the MLCC.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the composite copper powder which can enhance the bonding performance and compactness of an electroplated layer of an MLCC terminal electrode and has excellent oxidation resistance.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the invention provides composite copper powder, which comprises the following components in percentage by mass: 40-80% of first metal powder and 20-60% of second metal powder;
the first metal powder is pure copper powder; the second metal powder is copper zinc powder, and the chemical formula of the copper zinc powder is Cu x Zn y Wherein: x is more than or equal to 1.25 and less than or equal to 1.53,0.03, y is more than or equal to 0.31;
the average particle size of the first metal powder is less than or equal to the average particle size of the second metal powder.
The average particle size of the invention is obtained by measuring by a laser particle size analyzer.
The inventor researches find that by adopting the copper zinc powder with the specific chemical formula, zinc with specific mass is introduced into copper and compounded with pure copper powder with specific mass, the sintering temperature of a copper layer of an MLCC terminal electrode can be effectively reduced, low-temperature sintering is facilitated, the prepared MLCC has better compactness, and the copper zinc powder can be corroded by an acid electroplating solution to obtain rugged holes, so that the bonding force between a plating layer and an electrode is increased.
In addition, the inventor of the invention conducts a great deal of experimental study on the addition amount of the copper zinc powder and the pure copper powder, and discovers that the composite copper powder prepared by adopting the method can ensure that the comprehensive performance of the MLCC is optimal within the mass percentage range of the copper zinc powder and the copper powder. And compared with the average particle size of the second metal powder, the composite copper powder prepared by compounding the first metal powder with the same or smaller average particle size is favorable for improving the sintering activity of copper slurry, and the first metal powder with larger average particle size and the first metal powder are compounded, so that more gaps exist among copper powder and zinc powder, the sintering activity of the composite copper powder is reduced, and the sintering temperature is required to be improved.
As a preferred embodiment of the composite copper powder according to the present invention, the crystal structure of the second metal powder is a face-centered cubic structure.
The inventor of the invention researches and discovers that the copper zinc powder with the crystal structure of face-centered cubic structure can improve the oxidation initiation temperature of copper powder and enhance the oxidation resistance of composite copper powder.
As a preferred embodiment of the composite copper powder according to the present invention, the x satisfies the following conditions: x is more than or equal to 1.42 and less than or equal to 1.50; the y satisfies the following conditions: y is more than or equal to 0.06 and less than or equal to 0.20.
The inventor researches find that the zinc addition is added into copper powder, and is compounded with specific pure copper powder, so that the bonding force between the copper end of the MLCC end electrode prepared from the composite copper powder and a coating can be enhanced, the porosity is lower, and the MLCC end electrode has better compactness. In addition, when the content of zinc in the copper zinc powder is low, the oxidation resistance of the composite copper powder is reduced, and meanwhile, the binding force between a copper end and a plating layer is reduced; when the zinc content in the copper zinc powder is large, on one hand, the composite copper powder generates more holes due to the corrosion of zinc in the plating solution, so that the compactness of the MLCC is reduced, and on the other hand, the excessive zinc is added, so that the melting point of the composite copper powder is lower, the melting phenomenon of metal powder occurs in the sintering process, and the performance of the MLCC is reduced.
In a preferred embodiment of the composite copper powder according to the present invention, the first metal powder has a spherical shape, the average particle diameter of the first metal powder is 1 to 3 μm, and the average particle diameter of the second metal powder is 2 to 4 μm.
The inventor of the invention conducts a great deal of experimental study on the average particle sizes of the first metal powder and the second metal powder, and discovers that the adoption of the first metal powder and the second metal powder which are limited in the average particle size range can well fill the pores among the powder, effectively improve the compactness of the MLCC after sintering, and simultaneously enhance the binding force between a copper end and a plating layer. When the average particle size of the first metal powder is smaller, the sintering activity of the composite copper powder is reduced, and the sintering is not facilitated; when the average grain diameter of the first metal powder is larger, the binding force between the copper end and the coating is reduced due to the increase of pores among the powder, and meanwhile, the porosity is higher, and the compactness of the MLCC is poorer.
In a more preferred embodiment of the composite copper powder according to the present invention, the average particle diameter of the first metal powder is 2 to 3 μm, and the average particle diameter of the second metal powder is 3 to 4 μm.
The inventor of the invention researches and discovers that the MLCC prepared by adopting the first metal powder and the second metal powder which are defined in the average particle size range can have better compactness and higher binding force between a copper end and a plating layer.
As a preferred embodiment of the composite copper powder of the present invention, the mass ratio of the first metal powder to the second metal powder is (2 to 4): (2-3).
The inventor of the present invention has found that the composite copper powder prepared by the present invention has the best combination property of the MLCC, wherein the mass ratio of the first metal powder to the second metal powder is in the above range. When the content of the copper zinc powder is low, the improvement effect on the overall oxidation resistance of the composite copper powder is not obvious, and the improvement effect on the combination performance of a plating layer, a copper end and an external electrode is not obvious; when the content of copper zinc powder is higher, the corrosion effect of the plating solution on zinc is obvious, the plating solution is led to permeate into the MLCC, the reliability of the MLCC is reduced, the binding force of copper and nickel is reduced, and the tensile property of the product is influenced.
As a more preferable embodiment of the composite copper powder of the present invention, the mass ratio of the first metal powder to the second metal powder is (3 to 4): (2-2.7).
The inventor of the present invention has found that the mass ratio of the first metal powder to the second metal powder in the above range can not only optimize the oxidation resistance of the composite copper powder, but also provide the MLCC prepared from the composite copper powder with the best compactness and the highest bonding force between the copper end and the plating layer.
As a preferred embodiment of the composite copper powder of the present invention, the method for preparing the second metal powder comprises the steps of:
s1, weighing first metal powder and zinc powder, and heating and melting until the first metal powder and the zinc powder are uniformly mixed to obtain a single-phase liquid melt mixture;
s2, carrying out reduction treatment on the molten mixture in the step S1 in a reducing atmosphere, cooling to obtain metal blocks, and carrying out crushing and granulating under the protection of carbon dioxide gas to obtain the second metal powder;
in the step S1, the temperature of the heating and melting is 1100-1200 ℃, and the time of the heating and melting is 3-4 hours.
The inventor researches and discovers that by adopting the heating and melting process disclosed by the invention, the first metal powder and the zinc powder can be fully mixed in a molten state to form single-phase molten liquid, and the crystal structure of the copper zinc powder obtained after cooling treatment is of a face-centered cubic structure, so that the oxidation starting temperature of the copper powder can be increased, the oxidation resistance of the composite copper powder is enhanced, and the preservation of the composite copper powder and the maximization of a window of a drying process are facilitated.
In a preferred embodiment of the composite copper powder according to the present invention, in the step S2, the reduction temperature is 650 to 900 ℃, and the reduction time is 6 to 8 hours.
As a preferred embodiment of the composite copper powder according to the present invention, in the step S2, the reducing atmosphere includes hydrogen or ammonia.
In a second aspect, the invention also provides a preparation method of the composite copper powder, which comprises the following steps: and weighing the first metal powder and the second metal powder, uniformly mixing, and sieving to obtain the composite copper powder.
As a preferred embodiment of the method for preparing composite copper powder according to the present invention, the method for preparing the first metal powder comprises the steps of: and (3) weighing copper salt and solvent, uniformly mixing until the copper salt is completely dissolved, adding a reducing agent, uniformly mixing, preserving heat for 1-2 hours at 70-85 ℃, and then washing, drying and sieving to obtain the first metal powder.
As a preferred embodiment of the method for producing a composite copper powder according to the present invention, the copper salt includes at least one of copper sulfate, copper nitrate, and copper chloride.
As a preferred embodiment of the preparation method of the composite copper powder, the reducing agent comprises at least one of hydrazine hydrate, ascorbic acid, citric acid and glycerin.
As a preferred embodiment of the preparation method of the composite copper powder, the molar ratio of the copper salt to the reducing agent is as follows: reducing agent= (1.1-1.3): 1.
as a preferred embodiment of the method for producing a composite copper powder according to the present invention, the solvent may include any one of diethylene glycol, ammonium hydroxide, and ethylene glycol.
In a third aspect, the invention also provides an application of the composite copper powder in preparing a chip type multilayer ceramic capacitor terminal electrode.
The copper paste of the MLCC terminal electrode prepared by adopting the composite copper powder can improve the binding force between a plating layer and the electrode and can also enable the MLCC to have better compactness.
Compared with the prior art, the invention has the beneficial effects that:
(1) By adopting the copper zinc powder with the specific chemical formula, zinc with specific mass is introduced into copper and compounded with copper powder with specific mass, the sintering temperature of a copper layer can be effectively reduced, the MLCC (metal-insulator-metal) has excellent compactness, and the copper zinc powder can be corroded by an acidic electroplating solution to obtain rugged holes, so that the binding force between a plating layer and an electrode is increased;
(2) The invention adopts the copper zinc powder with a face-centered cubic structure, can improve the oxidation starting temperature of copper powder and enhance the oxidation resistance of composite copper powder.
Detailed Description
The technical scheme of the invention is further described below by referring to examples. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The methods or operations used in the examples, unless specifically indicated, are conventional methods or conventional operations in the art.
Examples 1 to 8 and comparative examples 1 to 6
Examples 1 to 8 and comparative examples 1 to 6 are composite copper powders according to the present invention. The composite copper powder of examples 1 to 8 and comparative examples 1 to 6 comprises a first metal powder and a second metal powder, wherein the first metal powder is spherical copper powder, the second metal powder is copper zinc powder, and the copper zinc powder has a chemical formula of Cu x Zn y The specific parameters and mass percentages of the components are shown in the following table 1.
TABLE 1
The preparation method of the composite copper powder of the embodiments 1 to 8 and the comparative examples 1 to 6 comprises the following steps: and weighing the first metal powder and the second metal powder, uniformly mixing, and sieving to obtain the composite copper powder.
The preparation method of the first metal powder of examples 1 to 8 and comparative examples 1 to 6 of the present invention comprises the steps of: weighing copper sulfate and ethylene glycol, uniformly mixing until the copper sulfate is completely dissolved, adding the ascorbic acid into the copper sulfate solution at a uniform speed according to the mass ratio of the copper sulfate to the ascorbic acid being 1:1, uniformly mixing, preserving the heat for 2 hours at 80 ℃, and then washing, drying and sieving to obtain the first metal powder.
The preparation method of the second metal powder of examples 1 to 8 and comparative examples 1 to 5 of the present invention comprises the steps of:
s1, weighing first metal powder and zinc powder, stirring for 2 hours, and heating and melting at 1150 ℃ for 4 hours until the mixture is uniformly mixed to obtain a molten mixture;
s2, carrying out reduction treatment on the molten mixture in the step S1 in a hydrogen atmosphere, wherein the reduction temperature is 800 ℃, the reduction time is 7 hours, cooling to obtain metal blocks, and carrying out crushing and granulating under the protection of carbon dioxide gas to obtain the second metal powder.
In step S1 of the preparation method of the second metal powder, the mass percentages of the first metal powder and the zinc powder are shown in the following table 2.
TABLE 2
The preparation method of the second metal powder of the comparative example 6 of the present invention comprises the following steps:
s1, weighing first metal powder and zinc powder, and stirring for 2 hours to obtain a mixture;
s2, carrying out reduction treatment on the mixture in the step S1 in a hydrogen atmosphere, wherein the reduction temperature is 800 ℃, the reduction time is 7 hours, cooling to obtain metal blocks, and carrying out crushing and granulating under the protection of carbon dioxide gas to obtain the second metal powder.
Effect example
In order to explore the performance of the composite copper powder in preparing the MLCC terminal electrode, the composite copper powder of the invention in examples 1 to 8 and comparative examples 1 to 6 is used for preparing the MLCC, and the preparation method of the MLCC comprises the following steps:
s1, weighing 40-70% of BaO and 40-70% of Al according to mass percentage 2 O 3 5～15％、B 2 O 3 10～30％、SiO 2 3～10％、ZnO 5～20％、CaO 3～8％、Na 2 Oxide raw materials with O of 0-3 percent are evenly mixed and sieved, the mixed batch is added into a quartz crucible, the temperature is kept at 1100 ℃ for 1h, the rapid cooling treatment is carried out for 2s to reduce the temperature to 25 ℃, and the cooled glass is crushed and sieved to obtain the glass with the average grain size of 1 mu m and the bulk density of 0.8g/cm 3 Is prepared for later use; in particular BaO 60%, al 2 O 3 15％、B 2 O 3 10％、SiO 2 3％、ZnO 5％、CaO 5％、Na 2 O 2％；
S2, mixing the organic solvent terpineol with acrylic resin according to the proportion of 7:3, mixing and adding the mixture into a stirring tank, heating and stirring at the constant temperature of 80 ℃ and the stirring frequency of 20Hz, and keeping stirring until the resin is completely dissolved;
s3, weighing 60-75% of the composite copper powder prepared by the method, stirring 5-15% of the glass powder in the step S1 in a mixing cylinder until the glass powder is uniform, adding 14-24% of the glue in the step S2 after preliminary mixing, and adding 0.5-3% of the thixotropic agent polyamide wax in the stirring process; fully mixing the dispersed slurry by using a three-roller mill to prepare the required slurry; 67% of composite copper powder, 15% of glass powder, 15% of glue and 3% of thixotropic agent;
and S4, terminating the MLCC by using the slurry in the step S3, and sintering the opposite electrode after terminating, wherein the sintering temperature is 800 ℃ and the sintering time is 10min.
The performance test method comprises the following steps:
(1) Tensile Property test
The instrument used is as follows: a tensile tester.
The testing method comprises the following steps: and (3) respectively welding soldering wires with the diameter of 0.50-0.56 mm at two ends of the end electrode, performing a tensile test on the product by using a tensile tester, and recording a test value when the broken end falls off, namely the bonding strength measured by stretching.
The qualification index is as follows: the resin with the bonding strength is not less than 1.5Kgf, so as to meet the qualification requirement.
(2) Oxidation resistance test
The instrument used is as follows: thermogravimetric analyzer.
The testing method comprises the following steps: and (3) testing the sample by using a thermogravimetric analyzer, and detecting the initial temperature of the composite copper powder for starting oxidation under the test conditions that the test atmosphere is mixed air and the temperature rising rate is 1 ℃/min.
The qualification index is as follows: the measured initial temperature of the oxidation resistance of the composite copper powder is within the temperature range of 220-350 ℃, and the composite copper powder meets the qualification requirement.
(3) Compact performance test
The instrument used is as follows: scanning Electron Microscopy (SEM).
The testing method comprises the following steps: and placing the sintered product under SEM for test and observation, observing whether the surface of the copper electrode is compact, and calculating to obtain the porosity of the surface of the sintered and molded rear-end electrode.
The qualification index is as follows: the porosity is not higher than 15%, and the compactness is good.
The test results are shown in table 3 below.
TABLE 3 Table 3
As can be seen from Table 3, the composite copper powders prepared in examples 1 to 8 of the present invention have good oxidation resistance, and the MLCC prepared by using the composite copper powder of the present invention has low porosity and high bonding strength. Wherein, the composite copper powder of the embodiment 2-2 has the best oxidation resistance, the copper end and the plating layer of the MLCC end electrode prepared by the composite copper powder of the embodiment 2-2 have the binding force of 3.5Kgf, and the porosity of the MLCC is only 4 percent, thus having better compactness.
As can be seen from comparative examples 2-2 and comparative example 1, when the average particle size of the first metal powder is higher than that of the second metal powder, the pores between the powder bodies of the composite copper powder are increased, and the prepared MLCC has higher porosity and poorer compactness.
As can be seen from comparison of examples 2-1 and comparative example 2, the copper zinc powder prepared by incorporating zinc powder of a specific quality into copper powder can provide MLCC with better compactability and plating layer bonding performance. While the composite copper powder of the comparative example 2-1 has higher oxidation resistance when the doping amount of zinc is more, the porosity of the MLCC is greatly increased and the compactness is worse due to more corrosion of the plating solution to zinc, and the combination property of the plating layer of the MLCC terminal electrode is not obviously improved; when the zinc doping amount is small, the oxidation resistance of the composite copper powder of the comparative example 2-2 is poor, the preservation and sintering of the composite copper powder are not facilitated, the compactness of the MLCC is reduced, and the improvement of the bonding performance of the electroplated layer of the MLCC terminal electrode is not obvious.
As can be seen from the comparison of example 1 and comparative example 3, when the amount of the second metal powder is small, the composite copper powder of comparative example 3-1 has poor oxidation resistance and has no remarkable effect on improving the bonding properties of the plating layer and copper terminal with the external electrode; when the content of copper zinc powder is higher, the composite copper powder of the comparative examples 3-2 and 3-3 has higher oxidation resistance, but the porosity of the MLCC is higher due to the obvious corrosion effect of the plating solution on zinc, and the plating layer bonding performance of the MLCC terminal electrode is also reduced.
As can be seen from the comparison of examples 2-2 and comparative examples 4-5, when the average particle size of the first metal powder is smaller, the sintering activity of the composite copper powder prepared in comparative example 4 is reduced, which is unfavorable for sintering, and the oxidation resistance of the composite copper powder is reduced, so that the porosity of the prepared MLCC is higher and the bonding performance of the electroplated layer of the terminal electrode is reduced; when the average particle diameter of the first metal powder is larger, the composite copper powder of comparative example 5 not only can reduce the bonding performance of the electroplated layer of the MLCC terminal electrode, but also can lead to higher porosity and poorer compactness of the MLCC.
As can be seen from comparative examples 2-2 and 6, the copper zinc powder with the face-centered cubic structure, which is prepared by adopting the method disclosed by the invention, can not only enhance the oxidation resistance of the composite copper powder, but also improve the binding force between the copper end and the coating when the composite copper powder is used for preparing the MLCC end electrode and reduce the porosity of the MLCC.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (8)
1. The composite copper powder is characterized by comprising the following components in percentage by mass: 40-80% of first metal powder and 20-60% of second metal powder;
the first metal powder is pure copper powder; the second metal powder is copper zinc powder, and the chemical formula of the copper zinc powder is Cu x Zn y Wherein: x is more than or equal to 1.25 and less than or equal to 1.53,0.03, y is more than or equal to 0.31;
the average particle size of the first metal powder is less than or equal to the average particle size of the second metal powder;
the crystal structure of the second metal powder is a face-centered cubic structure; the average grain diameter of the first metal powder is 1-3 mu m, and the average grain diameter of the second metal powder is 2-4 mu m;
the preparation method of the second metal powder comprises the following steps:
s1, weighing first metal powder and zinc powder, and heating and melting until the first metal powder and the zinc powder are uniformly mixed to obtain a single-phase liquid melt mixture;
s2, carrying out reduction treatment on the molten mixture in the step S1 in a reducing atmosphere, cooling to obtain metal blocks, and carrying out crushing and granulating under the protection of carbon dioxide gas to obtain the second metal powder;
in the step S1, the temperature of the heating and melting is 1100-1200 ℃, and the time of the heating and melting is 3-4 hours.
2. The composite copper powder of claim 1, wherein x satisfies: x is more than or equal to 1.42 and less than or equal to 1.50; the y satisfies the following conditions: y is more than or equal to 0.06 and less than or equal to 0.20.
3. The composite copper powder of claim 1, wherein the first metal powder is spherical.
4. A composite copper powder according to claim 3, wherein the average particle size of the first metal powder is 2 to 3 μm and the average particle size of the second metal powder is 3 to 4 μm.
5. The composite copper powder of claim 1, wherein the mass ratio of the first metal powder to the second metal powder is (2-4): (2-3).
6. The composite copper powder of claim 5, wherein the mass ratio of the first metal powder to the second metal powder is (3-4): (2-2.7).
7. The method for producing a composite copper powder according to any one of claims 1 to 6, comprising the steps of: and weighing the first metal powder and the second metal powder, uniformly mixing, and sieving to obtain the composite copper powder.
8. Use of the composite copper powder according to any one of claims 1 to 6 for the production of chip multilayer ceramic capacitor termination electrodes.
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