CN101565842B - Manufacturing method of copper cladding aluminum conductor using rolling electrodeposition method - Google Patents

Manufacturing method of copper cladding aluminum conductor using rolling electrodeposition method Download PDF

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Publication number
CN101565842B
CN101565842B CN2009101038753A CN200910103875A CN101565842B CN 101565842 B CN101565842 B CN 101565842B CN 2009101038753 A CN2009101038753 A CN 2009101038753A CN 200910103875 A CN200910103875 A CN 200910103875A CN 101565842 B CN101565842 B CN 101565842B
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copper
aluminium conductor
metallic cylinder
power supply
voltage power
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CN101565842A (en
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孙智富
罗静
王春欢
张微
詹捷
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Chongqing University of Technology
Chongqing Institute of Technology
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Chongqing University of Technology
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Abstract

The invention discloses a copper cladding aluminum conductor manufacturing method using rolling electrodeposition method, comprising the following steps: performing the deoiling treatment, connecting the aluminum conductor on the cathode of a low-voltage power supply and connecting a metal cylinder with the anode of the low-voltage power supply, spraying the electro-hydrostatic liquid on the metalcylinder during moving; performing the surface activating treatment, connecting the aluminum conductor on anode of the low-voltage power supply and connecting the metal cylinder with the cathode of t he low-voltage power supply; spraying the acid activate fluid on the metal cylinder during moving; performing the copper plating treatment, connecting the aluminum conductor on the cathode of a low-voltage power supply and connecting the metal cylinder with the anode of the low-voltage power supply; spraying the electrodeposite plating fluid on the metal cylinder during moving; performing the heattreatment at the thermal treatment temperature, annealing treatment time according to the technological requirements; finally producing the eligible copper cladding aluminum conductor after performin g the rolling treatment. The method has features of high copper aluminum bond strength, greatly increased transmission performance of the high frequency current, nod harm substance discharge, increased mutual diffusion between the copper and aluminum and improved interface bonding performance.

Description

Make the method for copper cladding aluminum conductor with the rolling electrodeposition method
Technical field
The present invention relates to the manufacture method of the used copper cladding aluminum conductor of a kind of carry high frequency current domain, especially make the processing method of copper cladding aluminum conductor with the rolling electrodeposition method.
Background technology
With copper cladding aluminum conductor carry high frequency electric current, have more advantage than traditional copper conductor or aluminium conductor.Because it is electric current when flowing through conductor that high-frequency current has " surface action ", current concentration is in the transmission of surface of conductors layer, and therefore, the aluminium conductor that adopts copper-clad to wrap up in can significantly improve the transmission performance of high-frequency current.Copper-clad aluminum conductor also can replace all kinds of electric currents, cable in the medium and low frequency transmission range, and a large amount of valuable strategic materials copper is saved in weight reduction; Copper cladding aluminum conductor is widely used in industries such as Aeronautics and Astronautics, electrical equipment, instrument, instrument, computer.In the prior art, the method for producing copper cladding aluminum conductor both at home and abroad mainly contains:
1. quiet liquid extrusion process: with suit aluminium bar in the major diameter red copper pipe, adopt quiet liquid extruding then, strengthen deformation rate and combine closely for its copper, aluminium.
2. core-filled and continuously casted method: this method is to adopt core-filled and continuously casted method, at first produces the copper-clad aluminium bar, thereby obtains copper-clad aluminum conductor through drawing and thermal treatment then.
3. clad welded method: be with the aluminium plug appearance copper clad after cleaning, the vertical employing argon arc welding method with copper welds then, then obtains through technologies such as drawing thermal treatments again.
More than the shortcoming of each method be copper, aluminium lamination in conjunction with being mechanical bond after testing, reason is the very easily oxidation of outside surface of copper and aluminium, has particularly more aggravated oxidation in the heat-processed afterwards.This bonding strength is not high, easily contains hole at the interface, is mingled with, and is discontinuous etc., influenced intensity and conductivity.And weld, structural constituent that method such as casting causes is inhomogeneous also can influence conductivity.
Summary of the invention
The present invention is directed to the above-mentioned deficiency of the production of copper alclad wire method of prior art, the method that a kind of copper aluminium bonding strength height is provided, can increases substantially the transmission performance of high-frequency current, not discharge environmentally harmful material when making copper clad aluminum conductor with rolling electrodeposition method manufacturing copper cladding aluminum conductor.
Technical scheme of the present invention is: the method with rolling electrodeposition method manufacturing copper cladding aluminum conductor is characterized in that comprising the steps:
(1), aluminium conductor is carried out oil removal treatment, to remove aluminium conductor surface and oil contaminant and other impurity; To treat the aluminium conductor of oil removal treatment, be connected on the negative pole of low-voltage power supply, the other end inserts in the metallic cylinder of liner absorbent cotton, and this metallic cylinder is connected with the positive pole of this low-voltage power supply; The aluminium conductor for the treatment of oil removal treatment when mobile, sprays electric quiet liquid according to processing requirement to metallic cylinder with certain control speed in the absorbent cotton of metallic cylinder;
(2), to the aluminium conductor after the oil removal treatment, carry out surface activation process, to remove the zone of oxidation on aluminium conductor surface; With the aluminium conductor of processing to be activated, be connected on the positive pole of low-voltage power supply, the other end inserts in the metallic cylinder of liner absorbent cotton, and this metallic cylinder is connected with the negative pole of this low-voltage power supply; The aluminium conductor of processing to be activated during from the absorbent cotton of metallic cylinder interior mobile, sprays the tart activation solution according to processing requirement to metallic cylinder with certain control speed;
(3), to the aluminium conductor after the surface activation process, carry out copper plating treatment, form copper alloy layer on aluminium conductor surface; With the aluminium conductor of processing to be activated, be connected on the negative pole of low-voltage power supply, the other end inserts the metallic cylinder internal surface of liner absorbent cotton, and this metallic cylinder is connected with the positive pole of this low-voltage power supply; Treat aluminium conductor that copper facing handles with certain control speed in the absorbent cotton of metallic cylinder when mobile, spray the galvanic deposit plating bath according to processing requirement to metallic cylinder, under galvanic action, make the copper alloy plating be attached to the aluminium conductor surface, form certain thickness copper alloy layer on the aluminium conductor surface;
(4), the aluminium conductor after the copper plating treatment is carried out anneal; Aluminium conductor after the copper plating treatment is placed on the process furnace internal heating to the thermal treatment temp of processing requirement, according to the anneal time of processing requirement, heat-treats;
(5), after roller process, just produce satisfactory copper clad aluminum conductor.
Further feature is: described galvanic deposit electroplate liquid formulation is: CuSO 45H 2O, 26g/L; H 2SO 4, 50mg/L; Quadrol, 50mg/L; The nanometer fine copper, and 5g/L (degree<200nm); Rare earth La, 2g/L.
Described thermal treatment temp is 280 ℃~420 ℃, 2~4 minutes anneal time.
Method with rolling electrodeposition method manufacturing copper cladding aluminum conductor of the present invention has following advantage:
1, the present invention adopts nanosized copper and rare earth, and the electricity consumption brush plating is deposited on the aluminium conductor (line, row, rod etc.), subsequently low-temperature annealing.Because nano level copper is owing to have small-size effect, surface effects, and photon effect greatly improve the effect of its transmission current, and the adding of rare earth and 300 ℃~400 ℃ annealing have subsequently then improved makes copper, aluminium mutual diffusion improve interfacial combined function.
2, copper aluminium bonding strength height can increase substantially the transmission performance of high-frequency current
3, technology of the present invention is not discharged environmentally harmful material when making copper clad aluminum conductor.
Description of drawings
The present invention is further illustrated below in conjunction with accompanying drawing:
Fig. 1 is a process principle figure of making copper cladding aluminum conductor with the rolling electrodeposition method.
In Fig. 1,1-aluminium conductor to be plated, 2-low-voltage power supply, 3-liner absorbent cotton stainless steel cylinder, 4-deposit fluid shower nozzle, 5-pick up liquid dish, 6-recycle pump.
Embodiment
Embodiment of the present invention are as follows: the method with rolling electrodeposition method manufacturing copper cladding aluminum conductor comprises the steps:
1, aluminium conductor is carried out oil removal treatment, to remove aluminium conductor surface and oil contaminant and other impurity; The aluminium conductor of oil removal treatment will be treated, be connected on the negative pole of low-voltage power supply (as 6V~8V, 8V~10V, 6V~10V, 6V~12V or the like), the other end inserts porous surface and water-absorbent is strong, the internal surface of liner absorbent cotton metallic cylinder (or in interior bone), and this metallic cylinder is connected with the positive pole of aforementioned low-voltage power supply; When the aluminium conductor for the treatment of oil removal treatment is moved by the internal surface with the absorbent cotton of certain control speed in metallic cylinder, according to processing requirement, above metallic cylinder or other positions spray electric quiet liquid to metallic cylinder, reach the purpose of surface degreasing.Except the clean liquid of the electricity of prior art, the invention provides a kind of concrete prescription (main oil removing): NaOH 25g/L; Na3PO4 50g/L; NaCL 2.3g/L, the buffer reagent trace, all the other are water, add water to an amount of (about one liter).
2,, carry out surface activation process, to remove the zone of oxidation on aluminium conductor surface to the aluminium conductor after the oil removal treatment; To the aluminium conductor after the oil removal treatment, at first flushing; Then with the aluminium conductor of processing to be activated, be connected on the positive pole of low-voltage power supply (as 6V~8V, 8V~10V, 6V~10V, 6V~12V or the like), the other end inserts porous surface and water-absorbent is strong, the internal surface of liner absorbent cotton metallic cylinder (or in interior bone), and this metallic cylinder is connected with the negative pole of aforementioned low-voltage power supply; When the aluminium conductor of processing to be activated moves with the internal surface of the absorbent cotton of certain control speed in metallic cylinder, spray the tart activation solution to metallic cylinder, reach surface activation process, remove the purpose of the zone of oxidation on surface according to processing requirement.Except the activation solution of prior art, the invention provides a kind of concrete prescription (mainly removing pellumina): organic acid (as citric acid) 90g/L, Trisodium Citrate 150g/L, all the other are water, add water to an amount of (about one liter).
3, to the aluminium conductor after the surface activation process, carry out copper plating treatment, form copper alloy layer on the aluminium conductor surface; To the aluminium conductor after the surface activation process, at first flushing; To the aluminium conductor of activation treatment then, be connected on the negative pole of low-voltage power supply (as 6V~8V, 8V~10V, 6V~10V, 5V~10V, 6V~12V or the like), the other end inserts porous surface and water-absorbent is strong, the internal surface of liner absorbent cotton metallic cylinder (or in interior bone), and this metallic cylinder is connected with the positive pole of aforementioned low-voltage power supply; When treating that aluminium conductor that copper facing handles moves with the internal surface of the absorbent cotton of certain control speed in metallic cylinder, spray the galvanic deposit plating bath according to processing requirement to metallic cylinder, under galvanic action, make the copper alloy plating be attached to the aluminium conductor surface, form certain thickness copper alloy layer on the aluminium conductor surface; Adopt the method (positive and negative electrode relative movement when promptly electroplating) of brush plating, more help copper electrodeposition forming the uniform copper plate of thickness on the aluminum steel surface.Except the galvanic deposit plating bath of prior art, the invention provides a kind of concrete galvanic deposit electroplate liquid formulation: CuSO 45H 2O, 26g/L; H 2SO 4, 50mg/L; Quadrol, 50mg/L; The nanometer fine copper, and 5g/L (degree>200nm); Rare earth La, 2g/L mixes.
4, the aluminium conductor after the copper plating treatment is carried out anneal; Aluminium conductor after the copper plating treatment is placed on the process furnace internal heating to the thermal treatment temp of processing requirement, according to the anneal time of processing requirement, heat-treats; According to the different requirements of the use properties of aluminium conductor, thermal treatment should have respective change; Common thermal treatment temp is (280 ℃~420 ℃), 2~4 minutes anneal time about 350 ℃.
5, after roller process, just produce satisfactory copper clad aluminum conductor.
Below in conjunction with Fig. 1 the inventive method is further described:
Embodiment of the present invention are as shown in Figure 1: with the quiet oil removing of aluminium conductor 1 surface electrical to be plated, its method is to treat the aluminium wire of oil removal treatment, connect low-voltage power supply 2 (6~8V) negative pole, the other end inserts porous surface and the internal surface of bibulous liner absorbent cotton stainless steel cylinder 3 is arranged, the top is sprayed electric quiet liquid by deposit fluid shower nozzle 4 to liner absorbent cotton stainless steel cylinder 3 then, picks up liquid dish 5 and prevents electric quiet liquid outflow.It is injected in, and liquid can be returned by pump 6 in the dish, and the liquid circulation of collecting in the ten liquid dishes 5 is used.The quiet liquid of electricity is gone in the absorbent cotton by the orifice flow on the stainless steel cylinder 3.
Pull out from the internal surface of liner absorbent cotton 3 with certain control speed by the other end when aluminium conductor 1 to be plated, reach the purpose of surface degreasing.
Aluminium conductor to be plated 1 after the quiet oil removing of electricity is after the tap water flushing, enter when activating in the activator identical with Fig. 1 structure, the electric current reversal connection is that aluminium conductor 1 to be plated is (+) utmost point, liner absorbent cotton stainless steel cylinder 3 is (-) utmost point, what spray in stainless steel tube is the tart activation solution, its objective is the zone of oxidation of removing aluminum alloy surface; Activation solution is gone in the absorbent cotton by the orifice flow on the stainless steel cylinder 3.Enter in the device of the identical acid copper of structure after the water flushing through aluminium conductor to be plated 1 surface of surface active then, aluminium conductor 1 to be plated is (-) utmost point, liner absorbent cotton stainless steel cylinder 3 is (+) utmost point, spray the galvanic deposit plating bath according to processing requirement to stainless steel cylinder 3, the galvanic deposit plating bath is gone into absorbent cotton by the orifice flow of metallic cylinder; Enter 350 ℃ adding in the tubular oven through water flushing then, can produce copper clad aluminum conductor through roll-in again through 2~3 minutes anneal.
Principle of the present invention is to use the high frequency surface action: when promptly electric current flows through conductor, most of electric current all concentrates on the surface of conductors transmission, inside then seldom even does not have the physical phenomenon of electric current process, and the degree of depth δ that its electric current of copper conductor is penetrated can calculate with following formula:
δ=66~69/f1/2
Wherein: δ be electric current when flowing through conductor penetration depth (μ m) f be the frequency (Hz) of signal.

Claims (2)

1. make the method for copper cladding aluminum conductor with the rolling electrodeposition method, it is characterized in that comprising the steps:
(1), aluminium conductor is carried out oil removal treatment, to remove aluminium conductor surface and oil contaminant and other impurity: the aluminium conductor that will treat oil removal treatment, be connected on the negative pole of low-voltage power supply, the other end inserts in the metallic cylinder of liner absorbent cotton, and this metallic cylinder is connected with the positive pole of this low-voltage power supply; The aluminium conductor for the treatment of oil removal treatment when mobile, sprays electric quiet liquid according to processing requirement to metallic cylinder with certain control speed in the absorbent cotton of metallic cylinder; The quiet liquid of electricity is gone into absorbent cotton by the orifice flow of metallic cylinder;
(2), to the aluminium conductor after the oil removal treatment, carry out surface activation process, to remove the zone of oxidation on aluminium conductor surface:, be connected on the positive pole of low-voltage power supply with the aluminium conductor of processing to be activated, the other end inserts in the metallic cylinder of liner absorbent cotton, and this metallic cylinder is connected with the negative pole of this low-voltage power supply; The aluminium conductor of processing to be activated during from the absorbent cotton of metallic cylinder interior mobile, sprays the tart activation solution according to processing requirement to metallic cylinder with certain control speed; Activation solution is gone into absorbent cotton by the orifice flow of metallic cylinder;
(3), to the aluminium conductor after the surface activation process, carry out copper plating treatment, form copper alloy layer on the aluminium conductor surface: incite somebody to action the aluminium conductor of activation treatment, be connected on the negative pole of low-voltage power supply, the other end inserts the metallic cylinder internal surface of liner absorbent cotton, and this metallic cylinder is connected with the positive pole of this low-voltage power supply; Treat aluminium conductor that copper facing handles with certain control speed in the absorbent cotton of metallic cylinder when mobile, spray the galvanic deposit plating bath according to processing requirement to metallic cylinder, the galvanic deposit plating bath is gone into absorbent cotton by the orifice flow of metallic cylinder, under galvanic action, make the copper alloy plating be attached to the aluminium conductor surface, form certain thickness copper alloy layer on the aluminium conductor surface;
(4), the aluminium conductor after the copper plating treatment is carried out anneal: the aluminium conductor after the copper plating treatment is placed on the process furnace internal heating to the thermal treatment temp of processing requirement, according to the anneal time of processing requirement, heat-treats;
Described thermal treatment temp is 280 ℃~420 ℃, 2~4 minutes anneal time;
(5), after roller process, just produce satisfactory copper clad aluminum conductor.
2. the method with rolling electrodeposition method manufacturing copper cladding aluminum conductor according to claim 1, it is characterized in that: described galvanic deposit electroplate liquid formulation is: CuSO 45H 2O, 26g/L; H 2SO 4, 50mg/L; Quadrol, 50mg/L; The nanometer fine copper, 5g/L, a degree<200nm; Rare earth La, 2g/L.
CN2009101038753A 2009-05-15 2009-05-15 Manufacturing method of copper cladding aluminum conductor using rolling electrodeposition method Expired - Fee Related CN101565842B (en)

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CN102231293B (en) * 2011-06-20 2012-10-03 徐志峰 Copper-coated rear earth aluminum alloy flat wire or flat cable and manufacturing method thereof
CN104451804B (en) * 2014-12-11 2017-01-25 重庆材料研究院有限公司 Processing process for plating gold on insoluble metal wire
JP6788550B2 (en) * 2017-06-16 2020-11-25 株式会社神戸製鋼所 Arc welding method and solid wire
CN107267967B (en) * 2017-07-06 2019-07-12 中国石油大学(华东) A method of super-hydrophobic copper coating is prepared in aluminum alloy surface
CN107502945A (en) * 2017-08-22 2017-12-22 成都新柯力化工科技有限公司 A kind of graphene aluminium alloy conductor and preparation method
CN107858726A (en) * 2017-11-29 2018-03-30 铜陵市东方矿冶机械有限责任公司 The copper-plating technique of aluminum wire rod
CN108878063A (en) * 2018-07-02 2018-11-23 孟静 The preparation method of copper clad aluminum cable
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CN116536739A (en) * 2023-07-05 2023-08-04 江苏台祥自动化科技有限公司 Hardware electroplating equipment

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