CN101104918A - Method for modifying copper-aluminum metallurgy combination interface by auxiliary coating agent - Google Patents
Method for modifying copper-aluminum metallurgy combination interface by auxiliary coating agent Download PDFInfo
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- CN101104918A CN101104918A CNA2007100124343A CN200710012434A CN101104918A CN 101104918 A CN101104918 A CN 101104918A CN A2007100124343 A CNA2007100124343 A CN A2007100124343A CN 200710012434 A CN200710012434 A CN 200710012434A CN 101104918 A CN101104918 A CN 101104918A
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- Prior art keywords
- copper
- assistant agent
- aqueous solution
- plating assistant
- plating
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 25
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 title claims description 7
- 239000011248 coating agent Substances 0.000 title claims description 6
- 238000005272 metallurgy Methods 0.000 title claims description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 47
- 239000010949 copper Substances 0.000 claims abstract description 47
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000007747 plating Methods 0.000 claims abstract description 29
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 23
- 239000004411 aluminium Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002131 composite material Substances 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 238000005269 aluminizing Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000011282 treatment Methods 0.000 abstract description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 abstract 1
- 229910017767 Cu—Al Inorganic materials 0.000 abstract 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract 1
- 235000019270 ammonium chloride Nutrition 0.000 abstract 1
- 239000011701 zinc Substances 0.000 abstract 1
- 229910052725 zinc Inorganic materials 0.000 abstract 1
- 239000003513 alkali Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 238000005554 pickling Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000748 compression moulding Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 238000007431 microscopic evaluation Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 239000011157 advanced composite material Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000009867 copper metallurgy Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- ALKZAGKDWUSJED-UHFFFAOYSA-N dinuclear copper ion Chemical compound [Cu].[Cu] ALKZAGKDWUSJED-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Landscapes
- Coating With Molten Metal (AREA)
Abstract
The invention belongs to the cross field of material surface science and physical chemistry and relates to copper surface pretreatment, particularly a process of hot dip aluminizing and a method of selecting plating assistant agent. The invention is characterized in that the copper work piece is subjected to base washing, water washing, acid washing and water washing treatments and then dipped in a premixed aqueous solution of plating assistant agent; the copper work piece coated with the assistant agent is taken out and oven-dried to remove moisture and crystal water; the aqueous solution of plating assistant agent is an 1-15 percent aqueous solution of KF or a mixture of 1-10 percent aqueous solution of KF and 2-10 percent aqueous solution of NH4Cl. The invention has the advantages that the plating assistant agent helps to efficiently prevent the copper work piece from air oxidation and simultaneously increase the surface activity of copper, so that the molten zinc can rapid wet the copper surface and react therewith, thereby ensuring good metallurgical bonding layer. The plating assistant agent is widely used in the industrial production of Cu-Al composite wire and bus.
Description
Technical field
The invention belongs to material surface science and physicochemical interleaving techniques field, relate to the surface treatment of copper, specially refer to the selection of hot dip aluminum plating process and plating assistant agent.
Background technology
Copper-clad aluminum conductor is the advanced composite material of 21 century, is to coat the copper layer with one heart and make the copper bed interface form the bimetallic wire of metallurgical binding on the aluminium core.It can replace copper cash manufacturing transmission signal cable and carry the copper bus-bar of big electric current.The processing method of industrial production copper aluminum composite material adopts compression moulding method mostly and coats the weldering method at present.Though compression moulding method has good product quality, production efficiency height and environmental issue wait a bit less, and the rolling equipment investment is bigger, the production cost height.In addition, compression moulding method is difficult to produce the copper aluminum composite material with complex section.Coat the weldering rule and be the copper material slit that to be coated on aluminium rod surface with argon arc welding or ratio-frequency welding method, thereby coat the weldering method production of omnibus bar is had limitation its seam.Above-mentioned two kinds of methods can not guarantee that all 100% obtains copper metallurgy of aluminium key coat, especially coat the weldering method and are difficult to obtain the excellent metallurgical key coat more.In order to obtain the excellent metallurgical key coat, the present invention adopts the hot dip process method, selects 1%~15%KF aqueous solution and 1%~10%KF and 2%~10%NH for use
4The compound aqueous solution plating assistant agent of Cl.Plating assistant agent makes copper have maximum surfactivity when entering aluminium liquid, prevents copper aluminium simultaneously in conjunction with oxidation by air before, makes copper fitting and aluminium liquid quick humidification and reaction, obtains the excellent metallurgical key coat.
Summary of the invention
1%~15%KF aqueous solution and 1%~10%KF and 2%~10%NH have been the purpose of this invention is to provide
4The compound aqueous solution plating assistant agent of Cl can effectively improve copper aluminium bonding interface, guarantees to obtain the excellent metallurgical key coat.
Technical scheme of the present invention is as follows:
One, copper surface preparation
The copper matrix surface all can leave greasy dirt and zone of oxidation in making and transportation, must fully clean before its surface heat dip calorizing.
1.1 alkali cleaning is handled
Copper fitting is immersed 30 ℃~70 ℃ 5%~15% alkaline wash 25~30 minutes,, can adopt steel brush to wash surface or supersound process by rubbing with the hands in order to accelerate alkali cleaning speed.The purpose of alkali cleaning is in order to remove the greasy dirt on copper fitting surface.
1.2 washing
Copper fitting is washed in clear water through after the oil removal treatment.Washing is in order to remove remaining alkaline wash.
1.3 cleanup acid treatment
Carry out acid pickling and rust removing in the sulphuric acid soln with the immersion of the copper fitting after the washing 5%~25%.The time of pickling can be decided the pickling time according to the temperature of pickle solution, at room temperature soaked 3~10 minutes.Pickling is for the rusty scale of removing the copper fitting surface and the remaining alkaline wash of neutralization.
1.4 washing
Copper fitting after rust cleaning cleans its surface to remove residual acid solution and other salts, in order to avoid influence the quality of hot dip process with clear water again.
Two, the use of plating assistant agent
Adopt 1%~15%KF aqueous solution or 1%~10%KF and 2%~10%NH
4The compound aqueous solution plating assistant agent of Cl soaks product, up to copper fitting top layer complete wetting and covered the complete plating assistant agent film of one deck.Its effect is to prevent that copper fitting again be oxidized before hot dip process, and when hot dip process the activated copper matrix surface, to improve the wetting and expansion capability of aluminium liquid to the copper matrix.
Three, oven dry
Product after plating assistant agent solution takes out is put into drying oven and was carried out drying 1~3 hour, and drying temperature is 110 ℃~140 ℃.The purpose of oven dry is water and the crystal water of removing in the plating assistant agent, prevents that copper fitting from entering hot dip aluminum plating process generation reoxidation.
Four, hot dip aluminum plating
The copper fitting of thorough drying is put into 670 ℃~730 ℃ aluminium liquid, and by mobile product the gas of copper aluminium interface generation and impurity are floated, the abundant wetting copper spare of aluminium liquid is to form good copper aluminium bonding interface; In addition, obtain uniform and stable temperature of aluminum liquid field, guarantee that the temperature on copper top layer is even, cover uniform product thereby obtain coating by mobile copper fitting.After the immersion plating 2 seconds~30 seconds, take out product then and cool off.
Five, end properties detects
Carry out macroanalysis after aluminizing earlier, then the metallurgical binding layer is done microscopic analysis.Macroanalysis is to observe the surface whether to have plating leakage, color and luster etc., and microscopic analysis then is the thickness, solidity to corrosion of analysis and observation key coat etc.
Effect of the present invention and benefit be, can prevent the copper fitting oxidation by air effectively after adopting plating assistant agent, and can effectively improve the activity on copper surface, makes copper aluminium quick humidification and reaction, obtains the excellent metallurgical key coat.The use of this plating assistant agent has improved the quality and the yield rate of copper aluminium composite bed greatly, can be widely used in the industrial production of copper copper/aluminum composite wire and omnibus bar.
Embodiment
Be described in detail specific embodiments of the invention below in conjunction with technical scheme.
One, the surface preparation of copper
1.1 alkali cleaning is handled
60 ℃ of alkaline washs copper fitting being put into following prescription soaked 30 minutes, washed the top layer by rubbing with the hands with steel brush simultaneously and removed greasy dirt.
Composition | Concentration (g/L) |
NaOH | 10 |
Na 2CO 3 | 25 |
Na 3PO 4·12H 2O | 55 |
Na 2SiO 3 | 10 |
1.2 washing
To wash in the alkali cleaning product immersion clear water later.
1.3 cleanup acid treatment
Product immersed soaked in 15% dilute sulphuric acid 3~4 minutes, remove residual alkali lye as much as possible.
1.4 washing
Pickling is carried out rinsing with copper fitting with an amount of clear water later, removes residual unnecessary acid, in order to avoid influence the follow-up plating that helps.
Two, the use of plating assistant agent
With copper fitting immerse that concentration is 4%, temperature is that the time is 3~5 minutes in 40 ℃ the KF aqueous solution.
Three, oven dry
To put into the stoving oven inner drying from the copper fitting that quickening liquid takes out, temperature is controlled at 120 ℃~140 ℃, continues 2 hours.
Four, hot dip aluminum plating
With drying completely copper fitting immerse 680 ℃ aluminium liquid 3 seconds, and keep copper fitting moving in aluminium liquid, after 3 seconds product is taken out to be analyzed.
Five, end properties detects
5.1 visual examination
The tectal continuity of hot aluminizing, color and luster are all tested by GB/T 6462-2005 standard, all reach requirement.
5.2 microcosmic detects
The coat thickness of hot dipping aluminium lamination, intensity, erosion resistance detect by GB/T 6462-2005, and the requirement that all is up to state standards, particularly thickness reach ideal 30~100 μ m.
Claims (3)
1. method with modifying copper-aluminum metallurgy combination interface by auxiliary coating agent is characterized in that: copper fitting is through surface preparation, after helping plating lid layer plating assistant agent and drying, is immersed in 670 ℃~730 ℃ the aluminium liquid and carries out hot dip aluminum plating.
2. a kind of method with modifying copper-aluminum metallurgy combination interface by auxiliary coating agent according to claim 1, its feature comprises: the plating assistant agent of employing is 1%~15%KF aqueous solution or 1%~10%KF and 2%~10%NH
4The Cl compound aqueous solution.
3. a kind of method according to claim 1 with modifying copper-aluminum metallurgy combination interface by auxiliary coating agent, its feature also comprises: after helping plating, must finish-drying before the copper fitting hot dip process.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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CNA2007100124343A CN101104918A (en) | 2007-08-07 | 2007-08-07 | Method for modifying copper-aluminum metallurgy combination interface by auxiliary coating agent |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNA2007100124343A CN101104918A (en) | 2007-08-07 | 2007-08-07 | Method for modifying copper-aluminum metallurgy combination interface by auxiliary coating agent |
Publications (1)
Publication Number | Publication Date |
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CN101104918A true CN101104918A (en) | 2008-01-16 |
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CNA2007100124343A Pending CN101104918A (en) | 2007-08-07 | 2007-08-07 | Method for modifying copper-aluminum metallurgy combination interface by auxiliary coating agent |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103952742A (en) * | 2014-04-22 | 2014-07-30 | 上海理工大学 | Copper lead with insulating layer and preparation method thereof |
CN106676447A (en) * | 2016-12-28 | 2017-05-17 | 蚌埠南实科技有限公司 | Copper bar aluminizing process |
CN110952104A (en) * | 2019-08-19 | 2020-04-03 | 西南交通大学 | Method for preparing deep narrow gap consumable electrode gas shielded welding contact tip |
CN114934189A (en) * | 2022-06-21 | 2022-08-23 | 北京奥邦新材料有限公司 | Plasma heating refining furnace capable of continuously refining precious metals |
CN115161647A (en) * | 2022-07-13 | 2022-10-11 | 江苏富乐华半导体科技股份有限公司 | Method for improving copper surface oxidation after copper-clad ceramic substrate welding |
CN115958183A (en) * | 2022-12-27 | 2023-04-14 | 东北大学 | Foamed aluminum filled metal tube with metallurgical bonding interface and preparation method thereof |
-
2007
- 2007-08-07 CN CNA2007100124343A patent/CN101104918A/en active Pending
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103952742A (en) * | 2014-04-22 | 2014-07-30 | 上海理工大学 | Copper lead with insulating layer and preparation method thereof |
CN103952742B (en) * | 2014-04-22 | 2016-06-08 | 上海理工大学 | Copper conductor with insulating barrier and preparation method thereof |
CN106676447A (en) * | 2016-12-28 | 2017-05-17 | 蚌埠南实科技有限公司 | Copper bar aluminizing process |
CN110952104A (en) * | 2019-08-19 | 2020-04-03 | 西南交通大学 | Method for preparing deep narrow gap consumable electrode gas shielded welding contact tip |
CN114934189A (en) * | 2022-06-21 | 2022-08-23 | 北京奥邦新材料有限公司 | Plasma heating refining furnace capable of continuously refining precious metals |
CN115161647A (en) * | 2022-07-13 | 2022-10-11 | 江苏富乐华半导体科技股份有限公司 | Method for improving copper surface oxidation after copper-clad ceramic substrate welding |
CN115161647B (en) * | 2022-07-13 | 2023-07-21 | 江苏富乐华半导体科技股份有限公司 | Method for improving oxidation of copper surface of copper-clad ceramic substrate after welding |
CN115958183A (en) * | 2022-12-27 | 2023-04-14 | 东北大学 | Foamed aluminum filled metal tube with metallurgical bonding interface and preparation method thereof |
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