CN102324276B - Production process of copper coated aluminum-magnesium bimetallic conductor - Google Patents
Production process of copper coated aluminum-magnesium bimetallic conductor Download PDFInfo
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- CN102324276B CN102324276B CN201110149485.7A CN201110149485A CN102324276B CN 102324276 B CN102324276 B CN 102324276B CN 201110149485 A CN201110149485 A CN 201110149485A CN 102324276 B CN102324276 B CN 102324276B
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Abstract
The invention relates to the technical field of metal conductor processing, in particular to a production process of a copper coated aluminum-magnesium bimetallic conductor, solving the technical problems of unreasonable prior art and the like. The production process comprises the following steps of: A, surface preprocessing; B, zinc deposit preprocessing; C, cyanogens-free nickel preplating; D, silicate copper plating; and E, postprocessing. The production process of the copper coated aluminum-magnesium bimetallic conductor has the advantages that: 1, the surface activity of an aluminum-magnesium alloy is better regulated, operation quality in a subsequence electroplating process and stability in a drawing process are ensured; 2, the problem of broken wires of electroplating intermediate products in a subsequent drawing process is solved, yield of final products is increased; and 3, electroplating is carried out by adopting a pulse modulation power supply, a microstructure of electrocrystallization copper is improved, compactness of a copper coating is improved, and hydrogen evolution side reaction is inhibited.
Description
Technical field
The present invention relates to plain conductor processing technique field, especially relate to a kind of copper coated aluminum-magnesium bimetallic conductor and produce work
Skill.
Background technology
The development of wires and cables industry, the conductive material such as too busy to get away copper, aluminium.Copper has good electric property, is tradition
Conductive material, electric wire copper consumption accounts for the 60～70% of national copper consumption figure, but the scarcity of copper resource and the market price
Continuous improvement, promote cable industry actively to seek substitute material.Copper coated aluminum-magnesium bimetallic conductor is a kind of in Al-Mg alloy core
The bimetallic conductor of one layer of certain thickness fine copper is coated with one heart on line.On the premise of ensureing serviceability, both there is the excellent of copper
Good electric conductivity, have again the light weight of aluminium, soft the features such as, be the optimal material substituting pure copper wire as conductor.Copper-clad aluminum conductor
Advantage be mainly shown as：1. conduct electricity very well, its dc resistivity is 1.5 times of pure copper wire, when resistance is identical, copper-clad aluminum conductor
Weight is about the 1/2 of pure copper wire.Calculated according to " Kelvin effect ", in more than 5MHZ high frequency, resistivity is identical with pure copper wire.②
Good weldability, because copper-clad aluminum conductor surface has coated one layer of fine copper with one heart, therefore has the solderability as pure copper wire.
3. light weight, its proportion is only the 30%～32% of pure copper wire, and in the case that line footpath, quality are equal, its length is pure copper wire
2.5 times, thus greatly reduce production cost.4. due to lightweight, sag degree is little, more suitable for physical blowing high frequency cable
Production technology is it is ensured that concentricity.5. bending property is better than pure copper wire, it is possible to reduce the impedance causing because bending radius is little becomes
Change.6. can overcome make outer conductor with aluminum pipe, pure copper wire makees the cable of inner wire in the case of temperature change is too big, due to both
The cable core " core pulling " that linear expansion coefficient difference causes and the phenomenon of connector " uncoupling ".
Galvanoplastic are traditional bimetallic composite wire rod production technologies, because aluminum-magnesium alloy wire surface easily forms oxidation
Film, copper plate is of poor quality, and adhesion, loosely it is impossible to meet the demand of wires and cables industry, cannot form industrialization always.In recent years
Come, sharp rise with copper material price, step up in the world to study the method more saving copper resource.The beginning of this century, Germany
Develop hydrochlorate electrocoppering new technology, copperizing continuously on aluminum-magnesium alloy wire, then through drawing skill of exchanging work to obtain required line footpath
Copper cladding aluminum conductor.It is low, not fine and close, in uneven thickness etc. that this technique solves the coating adhesion that usual copper-plating technique exists
Deficiency, copper material consumption declines 20% than machinery cladding process, and energy consumption declines 25%, and electric property is more excellent.This technology
Substantially reach a standard at present, starting industrialized production.But the hydrochlorate copper-plating method new technology of Germany uses Full-automatic machine
Electrical integrated production line, its technical equipment is very expensive, and a production line price is up to more than 150 ten thousand Euros, production cost
Also higher.
Traditional galvanoplastic manufacture in aluminium in copper magnesium bimetallic conductor technology has obvious weak point, and showing of having is raw
Produce environment aspect, such as create the red cigarette of more nitrogen oxides in almag bar scale removal pre-treating technology, coating is beaten after heavy zinc
Employ cyanide pre-plating copper method in bottom technique and create serious cyanogen pollution.Have shows product inherent quality index
On, the finished product composite wire hydrogen embrittlement fracture that such as in aluminium substrate, the copper coating fault-layer-phenomenon of appearance, cathode hydrogen evolution side reaction cause is existing
As.Have is also manifested by production run efficiency, and in the arrangement quantity of almag bar such as in electrolytic cell, continuous electroplating, magnalium closes
Walking speed setting of golden bar etc..Totally see, mainly just like lower section surface technology problem in current conventional plating process：2nd, copper, aluminium interface
Structure is difficult to control to；1st, the environmental hazard that the technique such as cyanide copper pre-plating is brought；3rd, product hydrogen embrittlement problem；4th, miscellaneous in process medium
The recycled problem of plating solution after the removing of matter metal ion and process.
Content of the invention
The purpose of the present invention is for the problems referred to above, provides a kind of easy to implement, low in the pollution of the environment, high copper of product quality
Alclad magnesium bimetallic conductor production technology.
For reaching above-mentioned purpose, present invention employs following technical proposal：This production process of copper coated aluminum-magnesium bimetallic conductor,
It is characterized in that, this technique comprises the steps：
A, surface preparation：Hydronalium is carried out oil removing dirty removing processing, thus removing hydronalium surface
Oxide-film；
B, heavy zinc pretreatment：The hydronalium removing surface film oxide is carried out heavy zinc process, make almag material
Material surface forms one layer of densification and the uniform many intermediate metals of zinc-base；
C, non-cyanide pre-plating nickel：Non-cyanide plating nickel is passed through on the hydronalium surface having the many intermediate metals of zinc-base on surface
Mode electroplates one layer of nickel dam；
D, hydrochlorate copper facing：The hydronalium being coated with nickel dam is carried out hydrochlorate copper facing, thus forming densification on surface
Oxygen-free copper layer；
E, post processing：The hydronalium being coated with layers of copper is post-processed, thus aluminium in copper magnesium bimetallic is obtained leading
Line.
In above-mentioned production process of copper coated aluminum-magnesium bimetallic conductor, in above-mentioned step A, first adopt degreaser to aluminium
Magnesium alloy materials surface degreasing, then uses acid etching dirty removing processing liquid to remove hydronalium surface film oxide.
In above-mentioned production process of copper coated aluminum-magnesium bimetallic conductor, in above-mentioned step A, at described acid etching scale removal
Reason liquid includes following components：Concentration is 68% HNO3Solution：500-600ml/L；H3PO4：300-350ml/L；Inorganic ammonium salt：
10-15g/L；Organic amino-contained compound 15-25g/L；Surfactant：5-10g/L；Balance of water.
In above-mentioned production process of copper coated aluminum-magnesium bimetallic conductor, in above-mentioned step B, using Zinc-based multi-element alloy
Deposition liquid is sunk zinc pretreatment at least one times, and described Zinc-based multi-element alloy deposition liquid includes following components：NaOH：
100-150g/L；Zinc oxide：10-30g/L；Sodium potassium tartrate tetrahydrate：8-10g/L；Nickel salt：10-50g/L；Cobalt salt：8-20g/L；Tin
Salt：5-15g/L；Iron chloride：2-3g/L；Surfactant：1-5g/L；Balance of water.
In above-mentioned production process of copper coated aluminum-magnesium bimetallic conductor, in above-mentioned step D, add liberation of hydrogen in the plating solution
The high APES class liberation of hydrogen inhibitor of overpotential.
In above-mentioned production process of copper coated aluminum-magnesium bimetallic conductor, in above-mentioned step D, adopt pulse in plating
Modulation power source is electroplated, and that is, in certain time period, electrode will carry out the negative electrode electro-deposition under higher current density, when one section
Between after, electrode will enter reverse anodic solution stage.
In above-mentioned production process of copper coated aluminum-magnesium bimetallic conductor, in above-mentioned step E, it is blunt that post processing includes surface
Change, dry, wind and wire drawing.
Compared with prior art, the advantage of this production process of copper coated aluminum-magnesium bimetallic conductor is：1st, pass through zinc-base many
Microstructure integrality in gained superficial layer after first alloy deposition liquid process, obtains on high chemically active almag matrix
Even compact, conductive excellent Zinc-based multi-element alloy transition zone, have adjusted the surface-active of almag well it is ensured that
The running quality of following electroplating process and the stability drawing group processing procedure.2nd, add the high alkyl of overpotential of hydrogen evolution in the plating solution
Phenol polyethenoxy ethers liberation of hydrogen inhibitor, drastically reduce the area the liberation of hydrogen side reaction in copper ion cathodic electrodeposition process, significantly
Reduce the degree that copper-clad electroplated aluminum intermediate products occur hydrogen embrittlement, solve plating intermediate products disconnected in follow-up drawing process
Silk phenomenon, improves the yield rate of final products.3rd, select impulse modulation power supply to electroplate, improve the microcosmic knot of electrocrystallization copper
Structure, improves the packing of copper coating it is suppressed that liberation of hydrogen side reaction.4th, the acid etching dirty removing processing liquid of fluoride-free, in formula
Add surfactant and the inhibitor of organic nitrogen oxides containing amino, make the almag surface can during acid etching, scale removal
Effectively remove surface film oxide, can effectively suppress the excessive corrosion of matrix, nitrogen oxides pollution thing amount compared with traditional handicraft again
Decrease more than 90%, significantly improve production operation environment.
Specific embodiment
This production process of copper coated aluminum-magnesium bimetallic conductor comprises the steps：
A, surface preparation：Hydronalium is carried out oil removing dirty removing processing, thus removing hydronalium surface
Oxide-film.First adopt degreaser to hydronalium surface degreasing, then use acid etching dirty removing processing liquid to remove almag material
Material surface film oxide.Acid etching dirty removing processing liquid includes following components：Concentration is 68% HNO3Solution：500-600ml/L；
H3PO4：300-350ml/L；Inorganic ammonium salt：10-15g/L；Organic amino-contained compound 15-25g/L；Surfactant：5-10g/
L；Balance of water.
B, heavy zinc pretreatment：The hydronalium removing surface film oxide is carried out heavy zinc process, make almag material
Material surface forms one layer of densification and the uniform many intermediate metals of zinc-base.Carried out at least one times using Zinc-based multi-element alloy deposition liquid
Heavy zinc pretreatment, described Zinc-based multi-element alloy deposition liquid includes following components：NaOH：100-150g/L；Zinc oxide：
10-30g/L；Sodium potassium tartrate tetrahydrate：8-10g/L；Nickel salt：10-50g/L；Cobalt salt：8-20g/L；Pink salt：5-15g/L；Iron chloride：2-
3g/L；Surfactant：1-5g/L；Balance of water.
C, non-cyanide pre-plating nickel：Non-cyanide plating nickel is passed through on the hydronalium surface having the many intermediate metals of zinc-base on surface
Mode electroplates one layer of nickel dam.
D, hydrochlorate copper facing：The hydronalium being coated with nickel dam is carried out hydrochlorate copper facing, thus forming densification on surface
Oxygen-free copper layer.Add the high APES class liberation of hydrogen inhibitor of overpotential of hydrogen evolution in the plating solution.Adopt in plating
Impulse modulation power supply is electroplated, and that is, in certain time period, electrode will carry out the negative electrode electro-deposition under higher current density, and one
After the section time, electrode will enter the reverse anodic solution stage.
E, post processing：The hydronalium being coated with layers of copper is post-processed, thus aluminium in copper magnesium bimetallic is obtained leading
Line.Post processing includes surface passivation, drying, winding and wire drawing.
In step A, in acid etching dirty removing processing liquid, do not contain high concentration fluorine ion, add suitable surfactant, promote
Acid corrosion process.Additionally, containing the release that organic amino-contained compound can be greatly reduced nitrogen oxides.With traditional handicraft phase
Decrease more than 90% than nitrogen oxides pollution thing amount, significantly improve production operation environment.
In step B, Zinc-based multi-element alloy deposition liquid can be many in hydronalium surface formation zinc-base nickel, cobalt, tin, iron
First alloy-layer.Microstructure integrality in gained superficial layer after heavy zinc process, obtains on high chemically active almag matrix
Obtained even compact, conductive excellent Zinc-based multi-element alloy transition zone, have adjusted the surface-active of almag well it is ensured that
The running quality of following electroplating process and draw the stability dialling processing procedure.By chemical replacement on hydronalium surface
Deposition multiple zinc-base alloy, the microstructure substantially improving the zinc-containing alloy layer replacing formation on hydronalium is complete
Property, also refine the size separating out kirsite crystal grain simultaneously, improve the adhesion between Zinc alloy film and almag matrix.This
Aluminium in high chemical activity in subsequent handling, magnesium surface are formed with to be tightly combined copper plate extremely important.Additionally, adding appropriate
Surfactant can be obviously improved the stability for the treatment of fluid.Here surfactant refers to there is fixing hydrophilic and oleophilic base
Group, aligns in the surface energy of solution, and can make the material that surface tension is remarkably decreased.The molecular structure tool of surfactant
Have amphipathic：One end is hydrophilic radical, and the other end is hydrophobic group；Hydrophilic radical is often the group of polarity, such as carboxylic acid, sulfonic acid,
Sulfuric acid, amino or amido and its salt, may also be hydroxyl, amide groups, ehter bond etc.；And hydrophobic group is often nonpolar hydrocarbon chain, such as 8
The above hydrocarbon chain of carbon atom.Surfactant is divided into ionic surfactant and nonionic surface active agent etc..
In step C, for improving the bond strength of Zinc-based multi-element alloy layer and copper plate further, in Zinc-based multi-element alloy layer
Upper pre-nickel plating it is ensured that newly separate out electrodeposited coating and original chemical replacement deposition Zinc-based multi-element alloy layer and between good knot
Close, played nickel in Zinc-based multi-element alloy layer, the effect of cobalt composition, significantly improved Mechanics of Machinery and the electric property of coating.
In step D, during traditional hydrochlorate electro-coppering, it is that improve production efficiency employs higher current density, typically
For 500A/m2 or higher.In the case, when the mass transfer in liquid phase of reaction mass copper ion in electrolyte is under-supply, liberation of hydrogen
Side reaction necessarily aggravates, thus leading to electroplate amount of hydrogen infiltration increase in copper cover aluminum product, and causes hydrogen embrittlement problem further, that is, rear
There is fracture of wire phenomenon in continuous drawing process, have a strong impact on quality and the yield rate of product, sometimes or even at all cannot produce.Hydrogen embrittlement
Problem is quality problems that are most important and must solving for galvanoplastic copper-clad aluminum conductor manufacturer.The side that the present invention adopts
Method is to address on the source of cathode reaction dynamic analysis from hydrochlorate electroplating process.According to principle of electrochemical reaction, solve
The certainly liberation of hydrogen side reaction having its source in suppression electrochemical cathode course of reaction of hydrogen embrittlement problem.The present invention is swept using linear potential
Retouch and electrochemical AC impedance achievement in research, liberation of hydrogen in salt cathodic electrodeposition process is secondary anti-to copper to test more than 20 additive
The inhibition answered, has therefrom filtered out the APES class additive with excellent inhibitory action.By in plating
A certain amount of APES class additive is added, success is in inhibiting the liberation of hydrogen in cathode electrodeposition process in liquid
Side reaction, preferably solves the amount of hydrogen infiltration in plating copper cover aluminum product, thus solving the problems, such as hydrogen embrittlement.
The conventional current mode adopting in Domestic Plating copper cover aluminum production at present is conventional DC power supply, the applicant
On the basis of the employing conventional DC power supply plating test of long period, find that Traditional DC current system is easily subject to reaction mass
Mass transfer impact and produce concentration polarization effect, and then affect the surface quality of coating, such as produce coating coarse grains, loose many
Hole, inadequate even compact etc..For solving this technical barrier, applicants have discovered that adopting modulation power source pulse plating techniques, can
Improve the packing of copper coating.Knowable to plating basic theories, the technological factor of impact compactness of electroplating mainly includes：(1) plate
Liquid composition；(2) cathode-current density；(3) concentration of reaction mass and mass transfer in liquid phase situation in electrolyte；(4) current system.?
In Electrochemical Engineering, current density indicates the speed of electrochemical reaction.Manufacture in copper cover aluminum production in galvanoplastic, for carrying
High efficiency is general to adopt higher current density, but the raising of current density is it is necessary to need the good liquid of reaction mass
Phase mass transfer is ensureing.If mass transfer in liquid phase cannot be guaranteed while improving current density, electro-deposition grain coarsening, coating will be led to
Not fine and close, and between coating and matrix, adhesion is deteriorated, the more dangerous generation significantly being aggravated evolving hydrogen reaction, and then product
The hydrogen embrittlement of raw electroplated product.Both can guarantee that production efficiency for smooth solution, and quality of coating can have been improved, the applicant is innovatively again
Propose to modulate the electroplating technology of the pulse power.The modulation pulse power is that a kind of periodicity adjusts the polarity of electric current, amplitude
Extraordinary electric current, its parameter includes pulsewidth, dutycycle.The concept of impulse modulation power supply is quick in copper electrolyzing refining and battery
It is used in charging technique, but not yet adopt in copper-clad cromalin produces.Theoretically analyze, using impulse modulation power supply
Technology, in certain time period, electrode will carry out the negative electrode electro-deposition under higher current density, but after a period of time, electrode will
Enter the reverse anodic solution stage, through the reverse dissolving in this stage, positive half cycle electro-deposition both can have been made to separate out bad crystalline substance
Grain occurs again to dissolve, but also can alleviate the concentration of copper ion in electrode surface liquid layer, eliminates concentration polarization effect.And
And, by this technology, liberation of hydrogen side reaction can be eliminated.
The technology of the copper coated aluminum-magnesium bimetallic conductor being processed by the present invention is as follows with performance indications：
(1) outward appearance：Layers of copper uniformly continuous cladding almag heart yearn on, smooth surface rounding, must not have indenture, crackle,
The dew defect such as aluminium and obvious rust staining；
(2) nominal diameter：0.1～2.77mm (also can be produced the aluminium in copper magnesium line of other sizes) by user's requirement；Diameter
Aluminium in copper magnesium line less than 0.3mm, deviation is less than +/- 0.003mm；Aluminium in copper magnesium line with diameter greater than 0.3mm, deviation does not surpass
Cross 1%.
(3) resistivity：＜=0.029 (mm2/ m, 20 DEG C)
(4) tensile strength and percentage elongation
(5) copper layer thickness：=＞ 3.5% (line footpath), for the CCAM copper layer thickness of high frequency signal transmission,
Also need the skin depth more than signal；
(6) density：＜=3.32 (g/cm3)
(7) layers of copper density：Intercept the sample of suitable length, it is clamped and draw in the interval of 15 times of nominal diameter
Tightly, 3 circles are reversed in the same direction, then turn-back 3 is enclosed again.Should any destructive, successional crackle in layers of copper.
(8) copper aluminium cohesive：Alternating bending is carried out to sample, up to sample fracture, the copper aluminium on fracture should flush, both
Very close to each other.
Specific embodiment described herein is only explanation for example to present invention spirit.The affiliated technology of the present invention is led
The technical staff in domain can be made various modifications or supplement or replaced using similar mode to described specific embodiment
Generation, but the spirit without departing from the present invention or surmount scope defined in appended claims.
Although more employing term herein, it is not precluded from the possibility using other terms.Using these terms
Just for the sake of more easily describing and explaining the essence of the present invention；Be construed as any additional restriction be all with
Spirit of the present invention is contrary.
Claims (1)
1. a kind of production process of copper coated aluminum-magnesium bimetallic conductor is it is characterised in that this technique comprises the steps：
A, surface preparation：Hydronalium is carried out oil removing dirty removing processing, thus removing hydronalium surface oxidation
Film；
B, heavy zinc pretreatment：The hydronalium removing surface film oxide is carried out heavy zinc process, make hydronalium table
Face forms one layer of densification and the uniform many intermediate metals of zinc-base；
C, non-cyanide pre-plating nickel：There is the hydronalium surface of the many intermediate metals of zinc-base by non-cyanide plating nickel mode on surface
One layer of nickel dam of plating；
D, hydrochlorate copper facing：The hydronalium being coated with nickel dam is carried out hydrochlorate copper facing, thus form the anaerobic of densification on surface
Layers of copper；
E, post processing：The hydronalium being coated with layers of copper is post-processed, thus copper coated aluminum-magnesium bimetallic conductor is obtained；
In above-mentioned step A, first adopt degreaser to hydronalium surface degreasing, then gone with acid etching dirty removing processing liquid
Except hydronalium surface film oxide；Described acid etching dirty removing processing liquid includes following components：Concentration is 68% HNO3Molten
Liquid：500-600ml/L；H3PO4：300-350ml/L；Inorganic ammonium salt：10-15g/L；Organic amino-contained compound 15-25g/L；Table
Face activating agent：5-10g/L；Balance of water；
In above-mentioned step B, zinc pretreatment is sunk at least one times using Zinc-based multi-element alloy deposition liquid, described zinc-base is many
First alloy deposition liquid includes following components：NaOH：100-150g/L；Zinc oxide：10-30g/L；Sodium potassium tartrate tetrahydrate：8-
10g/L；Nickel salt：10-50g/L；Cobalt salt：8-20g/L；Pink salt：5-15g/L；Iron chloride：2-3g/L；Surfactant：1-5g/
L；Balance of water；
In above-mentioned step D, add the high APES class liberation of hydrogen inhibitor of overpotential of hydrogen evolution in the plating solution；?
In above-mentioned step D, plating when electroplated using impulse modulation power supply, that is, in certain time period electrode will carry out higher
Negative electrode electro-deposition under current density, after a period of time, electrode will enter the reverse anodic solution stage；In above-mentioned step E
In, post processing includes surface passivation, drying, winding and wire drawing.
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| CN201110149485.7A CN102324276B (en) | 2011-06-02 | 2011-06-02 | Production process of copper coated aluminum-magnesium bimetallic conductor |
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| CN201110149485.7A CN102324276B (en) | 2011-06-02 | 2011-06-02 | Production process of copper coated aluminum-magnesium bimetallic conductor |
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| CN102324276B true CN102324276B (en) | 2017-02-22 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20160065959A (en) * | 2013-12-02 | 2016-06-09 | 가부시키가이샤후지쿠라 | High-frequency electrical wire and coil |
| CN108221018A (en) * | 2017-12-28 | 2018-06-29 | 中宥(平原)科技有限公司 | A kind of high-efficiency copper based on secondary heavy zinc covers aluminium technique |
| CN114045476B (en) * | 2021-11-11 | 2023-10-20 | 重庆大学 | Copper-magnesium composite material and preparation method and application thereof |
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| CN1069079A (en) * | 1991-07-30 | 1993-02-17 | 韩允志 | The compound method of aluminum heat exchanger restrainer |
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| JP2008524436A (en) * | 2004-12-20 | 2008-07-10 | アトテック・ドイチュラント・ゲーエムベーハー | Continuous operation of acidic or alkaline zinc or zinc alloy bath |
| CN101307454A (en) * | 2008-05-29 | 2008-11-19 | 杭州金利多实业有限公司 | Production process of acid salt cyanideless electro-plating copper dural alclad magnesium alloy wire |
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| US3651868A (en) * | 1970-07-29 | 1972-03-28 | Continental Oil Co | Removal of calcium sulfate deposits |
| CN1069079A (en) * | 1991-07-30 | 1993-02-17 | 韩允志 | The compound method of aluminum heat exchanger restrainer |
| JP2008524436A (en) * | 2004-12-20 | 2008-07-10 | アトテック・ドイチュラント・ゲーエムベーハー | Continuous operation of acidic or alkaline zinc or zinc alloy bath |
| CN1970839A (en) * | 2005-11-23 | 2007-05-30 | 熊映明 | Bright levelling technology for aluminium alloy |
| CN101307454A (en) * | 2008-05-29 | 2008-11-19 | 杭州金利多实业有限公司 | Production process of acid salt cyanideless electro-plating copper dural alclad magnesium alloy wire |
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