CN1300868A - Hot-dip technology for producing steel-in-copper wires by flux activating method and its apparatus - Google Patents
Hot-dip technology for producing steel-in-copper wires by flux activating method and its apparatus Download PDFInfo
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- CN1300868A CN1300868A CN 99120443 CN99120443A CN1300868A CN 1300868 A CN1300868 A CN 1300868A CN 99120443 CN99120443 CN 99120443 CN 99120443 A CN99120443 A CN 99120443A CN 1300868 A CN1300868 A CN 1300868A
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Abstract
A hot-dip technology for producing steel-in-copper wires by flux activating method includes pre-treating the surface of steel wire with the coating assistant prepared from borax, anhydrous sodium carbonate, NaCl, Na3AlF6, CuCl2 and NaF, deoxidizing and refining molten copper, adding rare-earth, Zn, Sn, Zr and Si, and hot dipping in electric furnace with inverse crystallizer. Its advantages are high adhesion, uniform, compact and thick coated layer, no pollution.
Description
The present invention relates to the bimetallic wire technology of preparing of the good copper clad steel wire of a kind of high strength and conductivity, be specially adapted to need the cable of high strength, self-supporting and good connection function.
Producing steel-in-copper wires be with steel wire as core body, coat layer of copper thereon by methods such as metallurgical, machinery or electrochemistry, be a kind of metal matrix core copper-clad matrix material.Since the sixties, the external copper sheathed steel production technologies such as electrochemical plating, casting, copper strips crimping method, welding coating method, sleeve pipe coating method of successively developing.At present, domestic production producer adopts electrochemical plating more, and power consumption is big, coating is relatively poor with combining of matrix, be difficult to obtain deficiencies, particularly electroplating effluent such as thickness coating, productivity is low, the utilization of area rate is low that environment is had pollution but electrochemical plating exist, and easily causes public hazards.The eighties, developed countries such as Japan, Germany, the U.S. successively develop the Hot Dipping Method producing steel-in-copper wires, and it has overcome galvanized " three wastes " pollutes, the copper clad bed thickness, and productivity and utilization of area rate are all very high.But because gas reduction technology is all adopted in the copper sheathed steel hot dip process, it exists facility investment big, and the deficiency that production cost is high is unfavorable for using at medium and small business enterprise expand.
After the present invention seeks to develop a kind of pollution-free, short flow process, coating, low-cost, high efficiency hot-dip technology for producing steel-in-copper wires and device thereof.
After flux activation method hot dipping copper facing of the present invention is the steel wire dip-coating plating assistant agent aqueous solution that will purify, drying, remove moisture after, introduce the electric mantle heater that has reverse crystallizer more from bottom to top, copper liquid adheres to the or immersion process of solidifying on steel wire.Because the fusing point higher (1083 ℃) of copper, thereby need to select dystectic plating assistant agent, otherwise plating assistant agent can melt in advance, decompose, not have due provide protection, Steel Wire Surface is again by oxidation again.This plating assistant agent has been selected materials with high melting point for use, is main component with borax and anhydrous sodium carbonate, and adds muriate and fluorochemical.Plating assistant agent composition and proportioning are respectively: 45%～50% borax, 6%～8%NaCl, 2%～4%Na
3AlF
6, 4%～7%CuCl
2, 1%～3%NaF, all the other are anhydrous sodium carbonate.Borax and anhydrous sodium carbonate are protected the Steel Wire Surface that has purified before hot dip process, fusing when hot dip process, volatilization are decomposed, and float to liquid level.NaCl, Na
3AlF
6, CuCl
2Fusing point lower, in plating assistant agent, mainly play activation and promote solvolysis, make the decomposition of melting rapidly at short notice and volatilize of borax and anhydrous sodium carbonate, guarantee that Steel Wire Surface cleans, flux decomposes fully, increase the activity of Steel Wire Surface simultaneously.NaF is a tensio-active agent, and it can reduce the surface tension of steel wire and copper liquid, improves the wettability of copper liquid, thereby improves the bonding force of copper coating and core body.Plating assistant agent is founded into blocks of solid, and it is last to pulverize again, and the plating assistant agent aqueous solution of preparation 4～10wt.% is as copper sheathed steel used for hot dip galvanizing plating assistant agent.
The Steel Wire Surface pre-treatment comprises technologies such as alkali cleaning, pickling, washing among the present invention, and alkali cleaning can be removed greasy dirt, and pickling can be removed iron rust, and residual alkali lye and acid solution are then removed in washing.
Red copper is when melting, and very easily oxygen uptake produces the Red copper oxide that is dissolved in copper liquid in a large number, and this can cause the reduction significantly of copper coating conductivity.For improving the purity of copper liquid, need carry out deoxidation and refining.The phosphorus of reductor employing 0.005%～0.01%, 0.003%～0.007% lithium and 0.01%～0.015% rich Ce rare earth.Refining agent is a basic salt, forms low-melting double salt because basic salt and acidic oxide are mingled with, and these double salt not only fusing point are low, and proportion is little, is easy to assemble and come-up, and is excluded.The component of basic salt and proportioning are 30%～50% soda, 25%～40% lime carbonate, all the other are fluorite.
Copper liquid for the crystal grain of refinement coating copper, improves the crystal boundary structure of copper coating after deoxidation and refining, reduce the surface tension of copper liquid, and improve producing steel-in-copper wires conductivity and coating and basal body binding force, has added trace element.The trace element that adds is zinc, tin, zirconium, silicon and micro-cerium-rich rare earth, the total amount of adding element is about 0.1%, and addition is 0.01%～0.02% zinc, 0.01%～0.015% tin, 0.005%～0.01% zirconium, 0.005%～0.01% silicon, 0.02%～0.03% cerium-rich rare earth.
The steel wire that purifies is behind the plating assistant agent aqueous solution of dip-coating 4～10wt.%, drying is removed the moisture in the flux layer, forms the flux layer of one deck densification on the surface, it can prevent the steel wire oxidation again that purified, and can further remove the molysite remaining after the pickling and the residue of pickling reaction product.When hot dip process, this flux layer is heated and volatilizees or the dissolving come-up, thereby fresh Steel Wire Surface is directly contacted with molten metal, and diffusion reaction takes place, thereby realizes the plating of copper liquid to steel wire.
Vertically upward by copper liquid, copper liquid adheres on steel wire and solidifies steel wire from the downside of the reverse crystallizer that keeps molten copper liquid.This technology shortens the duration of contact of steel wire and copper liquid greatly, and production efficiency and quality of coating increase substantially.Oppositely the crystallizer liner adopts graphite material, and copper liquid is very low to its wetting property.The selection of or immersion parameter plays a crucial role to the adjusting of thickness of coating.Immerse the increase of time with steel wire, initial copper coating adheres to than increasing sharply, reach maximum value after, adhere to than reducing on the contrary with the increase of the time of immersion, thereby the immersion time is generally between 0.05～1.0 second.Copper liquid temperature of superheat raises, and adheres to than the curve that changes with the immersion time to descend, and promptly adheres to than reduction.The copper liquid temperature difference, but adhering to than the prolongation with the time of immersion of copper coating increases the back reduction earlier.Copper liquid temperature is high more, and the time that remelting takes place is short more, thereby copper liquid temperature is generally between 1130～1280 ℃, and insulating process is in order to guarantee that copper liquid is in constant temp, and the temperature of copper liquid directly influences the thickness of coating of producing steel-in-copper wires.The preheating meeting of steel wire reduces copper and adheres to ratio, and coating surface is smooth, the minimizing plating leakage but can make, and the steel wire preheating temperature is between 550～800 ℃.Steel wire after the hot dip process needs cooling fast, otherwise the copper sheathed steel surface can form a large amount of oxide skin, and influences the conductivity of wire rod.
With reference to the accompanying drawings the present invention is described in detail below.Fig. 1 provides hot-dip technology for producing steel-in-copper wires and device synoptic diagram.1 is pay off rack, and 2 is steel wire, and 3 is alkaline bath, 4 is washing bath, and 5 is pickling tank, and 6 is washing bath, 7 for helping coating bath, and 8 is drying baker, and 9 are the induction preheating, 10 is reverse crystallizer, 11 temperature control instruments, and 12 is electric mantle heater, 13 is the copper smelting furnace, 14 is water cooler, and 15 is the copper sheathed steel composite wire, and 16 is take-up stand.The steel wire pre-processing device comprises pay off rack, alkaline bath, washing bath, pickling tank, helps coating bath, drying baker, and they take linear pattern to be arranged in order; Copper smelter and electric mantle heater will be placed nearby, and connect by running channel; Induction primary heater unit, the reverse crystallizer of used for hot dip galvanizing and water cooler adopt vertical arrangement from bottom to top; What temperature control instrument was measured is the interior copper liquid temperature of reverse crystallizer; Take-up equipment then can make full use of the space, makes it rationally distributed, compact.The producing steel-in-copper wires production process is: steel wire at first enters alkaline bath, washes then, pickling, washes, helps that plating is handled, oven dry; After the copper fusing, in smelting furnace, carry out deoxidation, refining, interpolation trace element successively, after this copper liquid is poured in the holding furnace, oppositely crystallizer is communicated with holding furnace, and when the thermopair displays temperature in the crystallizer reached requirement, steel wire was after the high-frequency induction preheating, enter copper liquid from the bottom vertical of reverse crystallizer, pass copper liquid with the very short time, draw from the top of crystallizer immediately, after high speed cold obtains producing steel-in-copper wires after but.
The copper sheathed steel composite wire obtains to use widely in industries such as communication, the energy, traffic, electronics, it can be used as the substitute material of copper, saved the consumption of copper greatly, and it combines the premium properties of copper and two kinds of metals of steel, has the high-intensity performance of corrosion resisting property, conductivity and the steel of the excellence of copper concurrently.The present invention proposes the flux activation method of copper sheathed steel hot dip process first, and develops a kind of novel hot dipping copper facing plating assistant agent.The producing steel-in-copper wires over-all properties of utilizing this technology to produce far surpasses the product of producing with electrochemical plating.This technology is a kind of pollution-free, short flow process, low cost, high efficiency producing steel-in-copper wires production method, and it will help applying of producing steel-in-copper wires.
Embodiment: Φ 6.0mm steel wire immerses in the plating assistant agent aqueous solution of 5～6wt.% behind alkali cleaning, acid-scrubbing cleaning.The prescription of plating assistant agent is: 45%～50% borax, 6%～8%NaCl, 2%～4%Na
3AlF
6, 4%～7%CuCl
2, 1%～3%NaF, all the other are anhydrous sodium carbonate.Behind the dip-coating plating assistant agent, oven dry.Red copper is when melting, and the method that adopts 0.005% phosphorus, 0.003% lithium to combine with 0.01% rich Ce rare earth is carried out deoxidation; Adopt 35%～40% soda, 30%～35% lime carbonate, all the other carry out refining for fluorite; The trace element that adds is 0.01%～0.02% zinc, 0.01%～0.015% tin, 0.005%～0.01% zirconium, 0.005%～0.01% silicon, 0.02%～0.03% cerium-rich rare earth.Steel wire immerses in 1175 ± 5 ℃ the copper liquid after 650 ± 10 ℃ of preheatings, and the immersion time is 0.3 second, after cooling fast, obtains the copper sheathed steel composite wire.Its performance index are: copper coating thickness 1.05mm, electric conductivity is 49%IACS.
Claims (5)
1. flux activation method copper sheathed steel or immersion comprises alkali cleaning, pickling, washes, helps plating, stoving process, in the copper smelting furnace, add reductor, refining agent and trace additives respectively, the copper smelting furnace is connected with electric mantle heater with reverse crystallizer by running channel, it is characterized in that pretreated steel wire is through the high-frequency induction preheating, vertically enter reverse crystallizer from bottom to top, cold soon by water cooler again after drawing; The composition of plating assistant agent and proportioning (weight percent) are: 45%～50% borax, 6%～8%NaCl, 2%～4%Na
3AlF
6, 4%～7%CuCl
2, 1%～3%NaF, all the other are anhydrous sodium carbonate, and plating assistant agent is founded into blocks of solid, it is last to pulverize again, the plating assistant agent aqueous solution of preparation 4～10wt.%.
2. hot-dip technology for producing steel-in-copper wires by flux activating method according to claim 1 is characterized in that the composition of described reductor and proportioning (weight percent) are: 0.005%～0.01% phosphorus, 0.003%～0.007% lithium and 0.01%～0.015% cerium-rich rare earth.
3. hot-dip technology for producing steel-in-copper wires by flux activating method according to claim 1 is characterized in that the composition of described refining agent and proportioning (weight percent) are: 30%～50% soda, 25%～40% lime carbonate, all the other are fluorite.
4. hot-dip technology for producing steel-in-copper wires by flux activating method according to claim 1, it is characterized in that copper liquid after deoxidation, refining, add following trace element again: 0.01%～0.02% zinc, 0.01%～0.015% tin, 0.005%～0.01% zirconium, 0.005%～0.01% silicon, 0.02%～0.03% cerium-rich rare earth.
5. hot-dip technology for producing steel-in-copper wires by flux activating method according to claim 1 is characterized in that described reverse crystallizer liner adopts graphite material; Copper liquid temperature is 1130～1280 ℃ in the electric mantle heater; Steel wire by reverse crystallizer the immersion time be 0.05～1.0 second.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991204433A CN1152974C (en) | 1999-12-23 | 1999-12-23 | Hot-dip technology for producing steel-in-copper wires by flux activating method and its apparatus |
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|---|---|---|---|
| CNB991204433A CN1152974C (en) | 1999-12-23 | 1999-12-23 | Hot-dip technology for producing steel-in-copper wires by flux activating method and its apparatus |
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| CN1152974C CN1152974C (en) | 2004-06-09 |
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Cited By (11)
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| CN100386159C (en) * | 2006-04-26 | 2008-05-07 | 玉溪玉杯金属制品有限公司 | No-acid-cleaning synchronous same-speed continuous on-line production method for steel wire |
| CN101629274B (en) * | 2009-08-19 | 2011-10-12 | 曹佩荣 | Upward forming method of thermal dip-coating copper covered steel and upward forming device thereof |
| CN102810358A (en) * | 2011-05-31 | 2012-12-05 | 常州市金利特种焊丝有限公司 | Production method of copper covered steel wire for electronic product connecting line |
| CN103194706A (en) * | 2012-01-10 | 2013-07-10 | 伍开南 | Method and device for silver-copper wire production |
| CN103320737A (en) * | 2013-06-26 | 2013-09-25 | 上海大学 | Method for preparing high-silicon silicon steel ribbon by hot dipping silicon method and continuous preparation device of silicon steel ribbon |
| CN104451505A (en) * | 2014-10-30 | 2015-03-25 | 江苏兴达钢帘线股份有限公司 | Brass-plating process of pearlite steel wires |
| CN105861970A (en) * | 2016-05-30 | 2016-08-17 | 浙江慧钢技术发展有限公司 | High-efficiency hot dip galvanizing production line |
| CN106367767A (en) * | 2016-11-17 | 2017-02-01 | 常州朗锐铸造有限公司 | Steel shell preprocessing system and steel shell preprocessing method |
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| CN111094828A (en) * | 2017-09-26 | 2020-05-01 | 日立金属株式会社 | Method for producing black-cored malleable cast iron member formed by plating, and black-cored malleable cast iron member and pipe joint formed by plating |
| CN113174554A (en) * | 2021-04-02 | 2021-07-27 | 酒泉钢铁(集团)有限责任公司 | Iron-based amorphous nanocrystalline composite poly magnetic medium rod and preparation method thereof |
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- 1999-12-23 CN CNB991204433A patent/CN1152974C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100386159C (en) * | 2006-04-26 | 2008-05-07 | 玉溪玉杯金属制品有限公司 | No-acid-cleaning synchronous same-speed continuous on-line production method for steel wire |
| CN101629274B (en) * | 2009-08-19 | 2011-10-12 | 曹佩荣 | Upward forming method of thermal dip-coating copper covered steel and upward forming device thereof |
| CN102810358A (en) * | 2011-05-31 | 2012-12-05 | 常州市金利特种焊丝有限公司 | Production method of copper covered steel wire for electronic product connecting line |
| CN103194706A (en) * | 2012-01-10 | 2013-07-10 | 伍开南 | Method and device for silver-copper wire production |
| CN103320737B (en) * | 2013-06-26 | 2016-01-13 | 上海大学 | Hot dip process silicon process prepares method and the silicon strip continuous preparation device of high-silicon steel thin strip |
| CN103320737A (en) * | 2013-06-26 | 2013-09-25 | 上海大学 | Method for preparing high-silicon silicon steel ribbon by hot dipping silicon method and continuous preparation device of silicon steel ribbon |
| CN104451505A (en) * | 2014-10-30 | 2015-03-25 | 江苏兴达钢帘线股份有限公司 | Brass-plating process of pearlite steel wires |
| CN105861970A (en) * | 2016-05-30 | 2016-08-17 | 浙江慧钢技术发展有限公司 | High-efficiency hot dip galvanizing production line |
| CN105861970B (en) * | 2016-05-30 | 2018-08-03 | 浙江慧钢技术发展有限公司 | A kind of efficient hot-dip galvanizing line |
| CN106367767A (en) * | 2016-11-17 | 2017-02-01 | 常州朗锐铸造有限公司 | Steel shell preprocessing system and steel shell preprocessing method |
| CN111094828A (en) * | 2017-09-26 | 2020-05-01 | 日立金属株式会社 | Method for producing black-cored malleable cast iron member formed by plating, and black-cored malleable cast iron member and pipe joint formed by plating |
| CN111094828B (en) * | 2017-09-26 | 2022-02-08 | 日立金属株式会社 | Method for producing black-cored malleable cast iron member formed by plating, and black-cored malleable cast iron member and pipe joint formed by plating |
| CN110923599A (en) * | 2019-12-04 | 2020-03-27 | 马鞍山市凯敏钢缆有限责任公司 | Steel wire galvanizing method and galvanizing device used by same |
| CN110923599B (en) * | 2019-12-04 | 2024-03-19 | 马鞍山市凯敏钢缆有限责任公司 | Steel wire galvanization method and galvanization device used by same |
| CN113174554A (en) * | 2021-04-02 | 2021-07-27 | 酒泉钢铁(集团)有限责任公司 | Iron-based amorphous nanocrystalline composite poly magnetic medium rod and preparation method thereof |
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| CN1152974C (en) | 2004-06-09 |
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