CN107502934B - One kind copper coating on aluminium and aluminum alloy coiled materials - Google Patents
One kind copper coating on aluminium and aluminum alloy coiled materials Download PDFInfo
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- CN107502934B CN107502934B CN201710667388.4A CN201710667388A CN107502934B CN 107502934 B CN107502934 B CN 107502934B CN 201710667388 A CN201710667388 A CN 201710667388A CN 107502934 B CN107502934 B CN 107502934B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/42—Pretreatment of metallic surfaces to be electroplated of light metals
- C25D5/44—Aluminium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention discloses one kind copper coatings on aluminium and aluminum alloy coiled materials, after coiled material is unfolded, are successively carried out continuously following key step: (1) coiled material surface degreasing degreasing, pickling;(2) coiled material surface secondary soaking zinc;(3) it the outer nickel coating of zinc layers and activates;(4) nickel layer outer copper plate, microetch post-passivation;(5) layers of copper surface micropore is blocked using organic matter;(6) coiled material blowing, drying and processing.The present invention realizes the continuous plating process of aluminium and aluminum alloy coiled materials, that is aluminium and the technique of aluminum alloy coiled materials electro-coppering, product after plating it is conductive it is good, solderability is strong, rapid heat dissipation, light-weight, easy punching press, it is at low cost the features such as, aluminium after plating has the property of copper material, can reach the purpose of substitution copper material.
Description
Technical field
The present invention relates to a kind of copper coatings on metal base, and in particular to one kind is plated on aluminium and aluminum alloy coiled materials
The method of copper belongs to metal surface working process technical field.
Background technique
Electroplating technology is exactly the process for plating the other metal or alloy of a thin layer on the metal surface using electrolysis principle, is
The technique of the surface of metal or other materials product attachment layer of metal film is set to prevent metal oxygen to play using electrolysis
The effects of changing (as corroded), improving wearability, electric conductivity, reflective, corrosion resistance and having improved aesthetic appearance.
Traditional plating production method is: buying material commercially available from Xian Zhao material factory, then goes punch forming, then carries out electricity again
Plating, finally returns user on hand.This mode adds additional intermediate link, transportation cost, time cost etc..With electricity
Sub- product processes it is more and more mature, the requirement to supplier also more come it is also high, when product needs to weld, monolithic weight more
Gently, speed of production faster when, traditional production method has been unable to meet the requirement of client.
Traditional plating mode cannot capture the technique of coiled material continuous electroplating, although having there is continuous electroplating currently on the market
Production technology, but it is still immature in the technique of aluminum alloy coiled materials electroplated on top copper, so to realize coiled material quantity-produced
Electroplating technology also needs to overcome technical difficulty.
Summary of the invention
The technical problem to be solved by the present invention is the copperizing continuously on aluminium and aluminum alloy coiled materials.
In order to solve the above-mentioned technical problems, the present invention provides one kind copper coatings on aluminium and aluminum alloy coiled materials, will
After coiled material expansion, successively it is carried out continuously following steps and completes copper facing:
Step 1: coiled material surface degreasing degreasing;
Step 2: coiled material surface pickling;
Step 3: coiled material surface soaks zinc for the first time;
Step 4: moving back zinc;
Step 5: coiled material surface soaks zinc for the second time;
Step 6: completing nickel coating outside the zinc layers after second of leaching zinc;
Step 7: activation procedure: removing the remaining nickel oxide of coiled material surface;
Step 8: copper-plating technique: the copper plate outside nickel layer;
Step 9: microetch technique: the copper powder on cleaning layers of copper surface;
Step 10: passivation technology: protection layers of copper;
Step 11: epithelium is handled: blocking the micropore on layers of copper surface using organic matter;
Step 12: to coiled material blowing, drying and processing.
Further, step 1 uses ultrasonic degreasing oil removing, detailed step are as follows: under conditions of temperature is 40-60 DEG C,
After coiled material is impregnated 7-12 seconds in the alkaline degreasing agent solution that concentration is 30-60g/L, water cleans 1 time or more;
Further, the detailed step of step 2 are as follows: under conditions of temperature is 10-30 DEG C, by coiled material in 15wt%-
After being impregnated 7-12 seconds in the nitric acid solution of 30wt%, wash with water 3 times or more.
Further, the detailed step of step 3 are as follows: under conditions of temperature is 10-30 DEG C, by coiled material in 15wt%-
After being impregnated 7-12 seconds in the zinc dipping solution of 30wt%, wash with water 3 times or more;
Further, the detailed step of step 4 are as follows: under conditions of temperature is 10-30 DEG C, by coiled material in 15wt%-
After being impregnated 7-12 seconds in the nitric acid solution of 30wt%, wash with water 3 times or more;
Further, the detailed step of step 5 are as follows: under conditions of temperature is 10-30 DEG C, by coiled material in 15wt%-
After being impregnated 7-12 seconds in the zinc dipping solution of 30wt%, wash with water 3 times or more.
Further, the detailed step of step 6 are as follows: under conditions of temperature is 50-60 DEG C, using coiled material as cathode, with nickel
Ball is anode, cathode-current density 5-10A/dm2, after coiled material impregnates 7-12 seconds in nickeliferous mixed solution, water clean 1 time with
On;The concentration proportioning of nickeliferous mixed solution each component are as follows: 500-700g/L nickel sulfamic acid, 10-25g/L nickel chloride, 35-55g/
L boric acid, 0.12-0.2g/L nickel softening agent, 0.1-0.25g/L nickel brightener, the pH value of nickeliferous mixed solution are adjusted to 3.0-
4.5;
Further, the detailed step of step 7 are as follows: under conditions of temperature is 10-30 DEG C, the coiled material of nickel plating will be completed
After being impregnated 7-12 seconds in the sulfuric acid solution of 10wt%-20wt%, wash with water 3 times or more.
Further, the detailed step of step 8 are as follows: under conditions of temperature is 30-45 DEG C, using coiled material as cathode, with copper
Ball is anode, cathode-current density 5-10A/dm2, after coiled material impregnates 7-12 seconds in cupric mixed solution, water clean 1 time with
On;The concentration proportioning of cupric mixed solution each component are as follows: 150-180g/L copper sulphate, 30-50g/L sulfuric acid, 0.12-0.2g/L copper
Additive, 0.1-0.25g/L copper brightener;The pH value of cupric mixed solution is adjusted to 1.5-3.Wherein, copper brightener be sulfuric acid,
The aqueous solution of Salzburg vitriol.
Further, the detailed step of step 9 are as follows: under conditions of 10-30 DEG C of temperature, by coiled material be placed in containing
After being impregnated 7-12 seconds in 25wt%-35wt% copper microetch agent solution, wash with water 1 time or more;Copper micro-etching agent selects sulfuric acid.
Further, the detailed step of step 10 are as follows: under conditions of 25-60 DEG C of temperature, will complete copper-plated coiled material in
After being impregnated 7-12 seconds in copper protective agent solution, water cleans 1 time or more;The concentration of copper protective agent solution is 15wt%-25wt%;Copper
The pH value for protecting agent solution is 11-14.
Further, the detailed step of step 11 are as follows: under conditions of 40-60 DEG C of temperature, by weight ratio 3wt%-
After being impregnated 7-12 seconds in water-soluble closed dose of 8wt% and the solution of water composition, wash with water 1 time or more;Water-soluble closed dose
Select rosin.
Further, the detailed step of step 12 are as follows: under the conditions of 40-60 DEG C of temperature of hot wind, by coiled material in hot wind
It is lower continuously to be dried, then dried with 70-90 DEG C of baking oven, it dries, time for drying is respectively 7-12 seconds.
Beneficial effects of the present invention: the continuous plating process of aluminium and aluminum alloy coiled materials, i.e. aluminium and aluminum alloy coiled materials are realized
The technique of electro-coppering.Product after plating it is conductive it is good, solderability is strong, rapid heat dissipation, light-weight, easy punching press, at low cost etc.
Feature, the aluminium after plating have the property of copper material, can reach the purpose of substitution copper material.
Specific embodiment
The prior art is to carry out the electro-coppering of monolithic shaped article after raw material to be carried out to punching press again.
The present invention is that metallic copper plating is formed on the surface of aluminium alloy and combined in aluminium material surface by special electroplating technology
Securely, sub- bright, fine and close, uniform, continuous coating.Aluminium material surface after making plating has the characteristic of copper, while having aluminium again
The advantages of, it can be widely used for the electronic product modules such as mobile phone, dataphone.
The present embodiment the specific technical proposal is: the copper coating on aluminium and aluminum alloy coiled materials, includes the following steps:
Step 1: ultrasonic degreasing oil removing process:, will be with aluminum alloy coiled materials in dense under conditions of temperature is 40-60 DEG C
After being impregnated 7-12 seconds in the alkaline degreasing agent solution that degree is 30-60g/L, water cleans 1 time or more.
Step 2: pickling process: under conditions of temperature is 10-30 DEG C, by aluminum alloy coiled materials in 15wt%-30wt%'s
After being impregnated 7-12 seconds in nitric acid solution, wash with water 3 times or more.
Step 3: leaching zinc process: under conditions of temperature is 10-30 DEG C, by aluminum alloy coiled materials in 15wt%-30wt%'s
After being impregnated 7-12 seconds in zinc dipping solution, wash with water 3 times or more.
Step 4: moving back zinc process: under conditions of temperature is 10-30 DEG C, by aluminum alloy coiled materials in 15wt%-30wt%'s
After being impregnated 7-12 seconds in nitric acid solution, wash with water 3 times or more.
Step 5: secondary soaking zinc process: under conditions of temperature is 10-30 DEG C, by aluminum alloy coiled materials in 15wt%-
After being impregnated 7-12 seconds in the zinc dipping solution of 30wt%, wash with water 3 times or more.
Step 6: electronickelling process: in 50-60 DEG C of temperature, cathode-current density 5-10A/dm2Under conditions of, with volume
Material is cathode, and nickel ball is anode, is impregnated in pH value 3.0-4.5, and nickel sulfamic acid containing 500-700g/L, 10-25g/L chlorine from
Son, 35-55g/L boric acid, the commercially available nickel additive of 0.12-0.2g/L, 0.1-0.25g/L nickel brightener solution in impregnate 7-12 seconds
(corresponding electroplating bath can be increased according to the difference of thickness requirement), then with pure water cleaning 1 time or more.
Step 7: activation procedure: under conditions of temperature is 10-30 DEG C, by aluminum alloy coiled materials in 10wt%-20wt%'s
After being impregnated 7-12 seconds in sulfuric acid solution, wash with water 3 times or more.Activating process is used to remove the nickel oxide on nickel layer surface.
Step 8: plating copper process: in 30-45 DEG C of temperature, cathode-current density 5-10A/dm2Under conditions of, with volume
Material is cathode, and copper ball is anode, is impregnated in pH value 1.5-3, and commercial sulfuric acid copper (the copper sulphate rate of deposition containing 150-180g/L
Comparatively fast, to reach the purpose of high speed electrodeposition), 30-50g/L sulfuric acid (increasing the activity of copper sulphate, promote to increase rate of deposition),
The commercially available copper additives of 0.12-0.2g/L (increasing the limpness of product surface, to promote the ductility of coating), 0.1-0.25g/L
Impregnate 7-12 seconds in the solution of copper brightener (brightness for increasing product surface) (can increase accordingly according to the difference of thickness requirement
Electroplating bath), then with pure water cleaning 1 time or more.Copper additives: sulfuric acid, Salzburg vitriol, water complex.Electro-coppering is common
Cyanide copper, and electroplating temperature is generally 40-60 DEG C, although effect is good, raw material has severe toxicity.The present invention needs for environmental protection,
Using copper-bath, and under than usually lower electroplating temperature, plating can be completed.
Step 9: copper microetch technique: under conditions of 10-30 DEG C of temperature, coiled material being placed in containing the city 25wt%-35wt%
It sells after being impregnated 7-12 seconds in copper microetch agent solution, washs with water and (clean the copper powder of electroplated copper surface more than once, prevent and the external world
Air contacts and causes surface oxidation).Copper micro-etching agent selects sulfuric acid.
Step 10: passivation procedure: under conditions of 25-60 DEG C of temperature, by coiled material in pH value 11-14, and containing 15wt%-
After being impregnated 7-12 seconds in the solution of the commercially available copper protective agent of 25wt%, wash with water 1 time or more.The just copper coating in plating, character
It is more active, it is contacted with air easy to oxidize.This step is to prevent the oxidation of copper.
Step 11: epithelium is handled: under conditions of 40-60 DEG C of temperature, being sealed by the water solubility of weight ratio 3wt%-8wt%
It closes in the solution of agent and water composition after impregnating 7-12 seconds, washs with water 1 time or more.Because being fast continuous electric plating, copper coating is very
It is thin, some atomic small holes (1nm or several nm) are inevitably left, rosin is used to block these holes as sealer.
Step 12: blowing, drying and processing: under the conditions of 40-60 DEG C of temperature of hot wind, by aluminum alloy coiled materials under hot wind
It is continuously dried, then is dried with 70-90 DEG C of baking oven, dried, time for drying is 7-12 seconds.
With liquid medicine directly by being bought in the market, the liquid medicine of special technique is carried out by special liquid medicine supplier for plating
The formulation section liquid medicine supplier of especially production, liquid medicine carries out patent protection.Applicant is for degreasing degreasing, pickling, leaching zinc, work
Change, be passivated, epithelium treatment process is diluted processing according to a certain percentage and reaches technique requirement;It needs for electroplating bath according to not
Same liquid medicine is matched and (is analyzed each chemical concentration in a manner of titration).
The present invention combines the special process of the technique of aluminium alloy electric copper facing and continuous electroplating, realizes entire volume aluminium alloy
The technique of material continuous copper electroplating significantly improves the efficiency of production, saves intermediate link production time, transport etc.
Cost, the direct punch forming of this materials'use is i.e. solderable to be used.
The preferred embodiment of the present invention has been described in detail above.It should be appreciated that those skilled in the art without
It needs creative work according to the present invention can conceive and makes many modifications and variations.Therefore, all technologies in the art
Personnel are available by logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea
Technical solution, all should be within the scope of protection determined by the claims.
Claims (7)
1. a kind of copper coating on aluminium and aluminum alloy coiled materials, which is characterized in that after coiled material expansion, successively continuously into
Row following steps complete copper facing:
Step 1: the coiled material surface degreasing degreasing;
Step 2: the coiled material surface pickling;
Step 3: the coiled material surface soaks zinc for the first time;
Step 4: moving back zinc;
Step 5: the coiled material surface soaks zinc for the second time;
Step 6: completing nickel coating outside the zinc layers after second of leaching zinc;
Step 7: activation procedure: removing the remaining nickel oxide of the coiled material surface;
Step 8: copper-plating technique: the copper plate outside the nickel layer;
Step 9: microetch technique: cleaning the copper powder on the layers of copper surface;
The detailed step of the step 9 are as follows: under conditions of 10-30 DEG C of temperature, the coiled material is placed in containing 25wt%-
After being impregnated 7-12 seconds in 35wt% copper microetch agent solution, wash with water 1 time or more;The copper micro-etching agent selects sulfuric acid;
Step 10: passivation technology: protecting the layers of copper;
The detailed step of the step 10 are as follows: under conditions of 25-60 DEG C of temperature, the copper-plated coiled material will be completed and protected in copper
After being impregnated 7-12 seconds in agent solution, water cleans 1 time or more;The concentration of the copper protective agent solution is 15wt%-25wt%;It is described
The pH value of copper protective agent solution is 11-14;
Step 11: epithelium is handled: blocking the micropore on the layers of copper surface using organic matter;
The detailed step of the step 11 are as follows: under conditions of 40-60 DEG C of temperature, by the water-soluble of weight ratio 3wt%-8wt%
Property sealer and water composition solution in impregnate 7-12 seconds after, wash with water 1 time or more;The water-soluble closed dose of selection rosin
Water;
Step 12: to coiled material blowing, drying and processing.
2. one kind copper coating on aluminium and aluminum alloy coiled materials according to claim 1, which is characterized in that
The step 1 uses ultrasonic degreasing oil removing, detailed step are as follows: under conditions of temperature is 40-60 DEG C, by the volume
After material impregnates 7-12 seconds in the alkaline degreasing agent solution that concentration is 30-60g/L, water cleans 1 time or more;
The detailed step of the step 2 are as follows: under conditions of temperature is 10-30 DEG C, by the coiled material in 15wt%-30wt%
Nitric acid solution in impregnate 7-12 seconds after, wash with water 3 times or more.
3. one kind copper coating on aluminium and aluminum alloy coiled materials according to claim 1, which is characterized in that
The detailed step of the step 3 are as follows: under conditions of temperature is 10-30 DEG C, by the coiled material in 15wt%-30wt%
Zinc dipping solution in impregnate 7-12 seconds after, wash with water 3 times or more;
The detailed step of the step 4 are as follows: under conditions of temperature is 10-30 DEG C, by the coiled material in 15wt%-30wt%
Nitric acid solution in impregnate 7-12 seconds after, wash with water 3 times or more;
The detailed step of the step 5 are as follows: under conditions of temperature is 10-30 DEG C, by the coiled material in 15wt%-30wt%
Zinc dipping solution in impregnate 7-12 seconds after, wash with water 3 times or more.
4. one kind copper coating on aluminium and aluminum alloy coiled materials according to claim 1, which is characterized in that the step
Six detailed step are as follows: under conditions of temperature is 50-60 DEG C, using the coiled material as cathode, using nickel ball as anode, cathode current
Density is 5-10A/dm2, after the coiled material impregnates 7-12 seconds in nickeliferous mixed solution, water cleans 1 time or more;It is described nickeliferous mixed
Close solution each component concentration proportioning are as follows: 500-700g/L nickel sulfamic acid, 10-25g/L nickel chloride, 35-55g/L boric acid,
0.12-0.2g/L nickel softening agent, 0.1-0.25g/L nickel brightener;The pH value of the nickeliferous mixed solution is adjusted to 3.0-4.5;
The detailed step of the step 7 are as follows: under conditions of temperature is 10-30 DEG C, will complete the coiled material of nickel plating in
After being impregnated 7-12 seconds in the sulfuric acid solution of 10wt%-20wt%, wash with water 3 times or more.
5. one kind copper coating on aluminium and aluminum alloy coiled materials according to claim 1, which is characterized in that the step
Eight detailed step are as follows: under conditions of temperature is 30-45 DEG C, using the coiled material as cathode, using copper ball as anode, cathode current
Density is 5-10A/dm2, after the coiled material impregnates 7-12 seconds in cupric mixed solution, water cleans 1 time or more;The cupric is mixed
Close solution each component concentration proportioning are as follows: 150-180g/L copper sulphate, 30-50g/L sulfuric acid, 0.12-0.2g/L copper additives,
0.1-0.25g/L copper brightener;The pH value of the cupric mixed solution is adjusted to 1.5-3.
6. one kind copper coating on aluminium and aluminum alloy coiled materials according to claim 5, which is characterized in that the bronzing
Bright dose for sulfuric acid, Salzburg vitriol aqueous solution.
7. one kind copper coating on aluminium and aluminum alloy coiled materials according to claim 1, which is characterized in that the step
12 detailed step are as follows: under the conditions of 40-60 DEG C of temperature of hot wind, the coiled material is continuously dried under hot wind,
It is dried, is dried, time for drying is respectively 7-12 seconds with 70-90 DEG C of baking oven again.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101250733A (en) * | 2008-04-16 | 2008-08-27 | 丹阳利华电子有限公司 | Technique for producing aluminum magnesium plating copper wire copper-coating |
CN101368285A (en) * | 2008-08-28 | 2009-02-18 | 尼尔金属(苏州)有限公司 | Technique for plating copper on aluminum and aluminum alloy base material and products produced thereby |
CN101928940A (en) * | 2009-06-22 | 2010-12-29 | 尼尔金属(苏州)有限公司 | Process method of plating copper on aluminum and aluminum alloy substrate |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101250733A (en) * | 2008-04-16 | 2008-08-27 | 丹阳利华电子有限公司 | Technique for producing aluminum magnesium plating copper wire copper-coating |
CN101368285A (en) * | 2008-08-28 | 2009-02-18 | 尼尔金属(苏州)有限公司 | Technique for plating copper on aluminum and aluminum alloy base material and products produced thereby |
CN101928940A (en) * | 2009-06-22 | 2010-12-29 | 尼尔金属(苏州)有限公司 | Process method of plating copper on aluminum and aluminum alloy substrate |
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