CN101387000A - Non-cyanogen strike copper plating technique - Google Patents
Non-cyanogen strike copper plating technique Download PDFInfo
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- CN101387000A CN101387000A CNA2008101431466A CN200810143146A CN101387000A CN 101387000 A CN101387000 A CN 101387000A CN A2008101431466 A CNA2008101431466 A CN A2008101431466A CN 200810143146 A CN200810143146 A CN 200810143146A CN 101387000 A CN101387000 A CN 101387000A
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- normal temperature
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- copper
- temperature washing
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000010949 copper Substances 0.000 title claims abstract description 72
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 72
- 238000007747 plating Methods 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 37
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 67
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011701 zinc Substances 0.000 claims abstract description 36
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 230000004913 activation Effects 0.000 claims abstract description 26
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000010936 titanium Substances 0.000 claims abstract description 20
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 20
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 19
- 239000011777 magnesium Substances 0.000 claims abstract description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000003486 chemical etching Methods 0.000 claims abstract description 15
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 12
- 239000010959 steel Substances 0.000 claims abstract description 12
- 150000002739 metals Chemical class 0.000 claims abstract description 5
- 238000009713 electroplating Methods 0.000 claims description 73
- 238000005406 washing Methods 0.000 claims description 70
- 239000007788 liquid Substances 0.000 claims description 49
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 31
- 238000005238 degreasing Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 229910000838 Al alloy Inorganic materials 0.000 claims description 22
- 229910052742 iron Inorganic materials 0.000 claims description 20
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 20
- 239000004411 aluminium Substances 0.000 claims description 17
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 16
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 15
- 238000011084 recovery Methods 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 10
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- -1 phospho Chemical class 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 5
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims 3
- 230000001105 regulatory effect Effects 0.000 claims 2
- 238000004140 cleaning Methods 0.000 abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 abstract description 8
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 abstract description 7
- 229910045601 alloy Inorganic materials 0.000 abstract description 4
- 239000000956 alloy Substances 0.000 abstract description 4
- 238000012423 maintenance Methods 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 2
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract 1
- 238000004381 surface treatment Methods 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 18
- 238000000576 coating method Methods 0.000 description 18
- 238000005516 engineering process Methods 0.000 description 11
- 238000001311 chemical methods and process Methods 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- UPLPHRJJTCUQAY-WIRWPRASSA-N 2,3-thioepoxy madol Chemical compound C([C@@H]1CC2)[C@@H]3S[C@@H]3C[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@](C)(O)[C@@]2(C)CC1 UPLPHRJJTCUQAY-WIRWPRASSA-N 0.000 description 1
- JJJOZVFVARQUJV-UHFFFAOYSA-N 2-ethylhexylphosphonic acid Chemical compound CCCCC(CC)CP(O)(O)=O JJJOZVFVARQUJV-UHFFFAOYSA-N 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical group [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229940120146 EDTMP Drugs 0.000 description 1
- JBSWPCUWUNTVKK-UHFFFAOYSA-N OC(C)=C(C(CC)(CC)P(O)(O)=O)CCCC Chemical class OC(C)=C(C(CC)(CC)P(O)(O)=O)CCCC JBSWPCUWUNTVKK-UHFFFAOYSA-N 0.000 description 1
- 150000008431 aliphatic amides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- LGAWFGCTQRLGQE-UHFFFAOYSA-N octan-3-ylphosphonic acid Chemical class CCCCCC(CC)P(O)(O)=O LGAWFGCTQRLGQE-UHFFFAOYSA-N 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 230000035935 pregnancy Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 235000015870 tripotassium citrate Nutrition 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
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- Electroplating Methods And Accessories (AREA)
Abstract
The invention relates to a process method for preplating copper without cyanide, which belongs to the technical field of surface treatment plating, and can be widely applied to the preplating of bottom copper when steel, aluminum, magnesium, zinc, titanium and alloy thereof and other metals are plated. The method comprises cleaning before preplating, preplating copper and preplating post-treatment. The method is technically characterized in that the pH value of non-cyanide plating solution is controlled in a range of between 9 and 10.5; the temperature is controlled at between 15 and 45 DEG C; a part to be plated is electrified to be fed into a tank; when the part is fed in the tank, current density of the part is more than one third to one half of the prior plating current density (0.3 to 2.0 ampere/decimeter<2>) for 1 to 2 minutes of strike plating so as to improve the surface active potential of the part to be plated; the part to be plated is subjected to chemical etching before preplating, and is subjected to activation with 10 percent of sulfuric acid after preplating. The method has the advantages of simple process, convenient maintenance, flexible plating coat, corrosion resistance, low porosity, fine crystallization, reliable combination and the like.
Description
Technical field
The present invention relates to a kind of non-cyanogen strike copper plating technique method, metal surface is handled the electroplating technology field, the preplating of bottom copper when it can be widely used in Metal plating such as iron and steel, aluminium and aluminium alloy, magnesium and magnesium alloy, zinc and zinc alloy, titanium or titanium alloy.
Background technology
Domestic electroplating industry extensively adopts cyaniding electrolytic solution that matrix metal (iron and steel, aluminium, magnesium, zinc, titanium and alloy thereof etc.) is carried out pre-copper facing at present, though the cyaniding bath composition is simple, easy to maintenance and binding force of cladding material is good, but cyaniding electrolytic solution can produce hypertoxic prussiate under hot environment, big to human body harm, the havoc ecotope.Country's " promotion law on cleaner production " clearly stipulates to want time limit to eliminate " containing cyanogen electroplates ", tries to explore and study new cyanogenless electroplating technology.In the background technology, domestic electroplating industry progressively begins to adopt the non-cyanide pre-plating copper method, but have all at present that processing performance is relatively poor, processing range is narrower, Operation and Maintenance is loaded down with trivial details, coating is in conjunction with shortcoming such as unreliable.For overcoming above defective, substitute cyaniding electrolytic solution with cyanideless electro-plating liquid, the non-cyanogen strike copper plating technique method that is common to matrix metals such as iron and steel, aluminium, magnesium, zinc, titanium and alloy thereof is studied.
Summary of the invention
Technical problem to be solved by this invention provides a kind of non-cyanogen strike copper plating technique method, it substitutes cyaniding electrolytic solution with cyanideless electro-plating liquid, pH value by control cyanideless electro-plating liquid, temperature, current density etc., make organic phosphine in the cyanideless electro-plating liquid and bivalent cupric ion form the chelating ion of high stability, form pliable and tough in base metal surface, anti-corrosion, porosity is low, crystallization is careful, the copper plate that bonding force is strong, this processing method can be common to iron and steel, aluminium and aluminium alloy, magnesium and magnesium alloy, zinc and zinc alloy, the preplating of bottom copper when matrix metals such as titanium or titanium alloy are electroplated.
The technical solution adopted for the present invention to solve the technical problems is:
1, steel-iron components
Chemical degreasing → normal temperature washing → electrolytic degreasing → hot water wash → pre-copper facing → the recovery of normal temperature washing → 10% sulfuric acid activation → normal temperature washing → normal temperature washing → cyanideless electro-plating liquid → normal temperature washing → 10% other metal level of sulfuric acid activation → plating;
2, zinc and zinc alloy part
Chemical degreasing → normal temperature washing → go up the hanger → pre-copper facing → recovery of normal temperature washing → 6% sulfuric acid activation → twice normal temperature washing → cyanideless electro-plating liquid → normal temperature to wash → 10% other metal level of sulfuric acid activation → plating;
3, aluminium and aluminum alloy part
Last hanger → chemical degreasing → hot water wash → normal temperature washing → 50% nitric acid → twice normal temperature soaks zinc → twice normal temperature washing → first time and washes → 10% sulfuric acid and move back zinc → twice normal temperature and soak zinc → twice pre-copper facing → recovery of normal temperature washing → cyanideless electro-plating liquid → normal temperature the washing → second time and wash → 10% other metal level of sulfuric acid activation → plating;
4, magnesium and magnesium alloy parts
Zinc → twice pre-copper facing → recovery of normal temperature washing → cyanideless electro-plating liquid → normal temperature washing → 10% other metal level of sulfuric acid activation → plating is washed → soaked to last hanger → chemical degreasing → hot water wash → normal temperature washing → chemical etching (15%～20% chromic anhydride) → twice normal temperature washing → activation (160～250g/L phosphoric acid, 70～80g/L ammonium bifluoride) → twice normal temperature;
5, titanium or titanium alloy part
Chemical degreasing → hot water wash → normal temperature washing → chemical etching (200g/L potassium bichromate solution, 20～30 ml concns are 60% hydrofluoric acid) → twice pre-copper facing → recovery of normal temperature washing → cyanideless electro-plating liquid → normal temperature washing → 10% other metal level of sulfuric acid activation → plating.
Described cyanideless electro-plating liquid is by following composition:
A, copper sulfate, ventilation breather or cupric nitrate 30～60g/L
B, methene di 2 ethylhexyl phosphonic acid, 1-hydroxy ethylidene 1.1 di 2 ethylhexyl phosphonic acids, 1-hydroxyl fourth are pitched a kind of or two kinds of mixture 120～160g/L in 1.1 di 2 ethylhexyl phosphonic acids
A kind of or two kinds of mixture 2～5g/L in c, first ammonia two methene phosphonic acids, pregnancy fork diamines tetramethyl fork phosphonic acids, the ethylene diamine tetra methylene phosphonic acid
A kind of 6～12g/L in d, Tripotassium Citrate, lemon acid amide or the Seignette salt
The volumetric concentration of e, polymine alkyl salt or aliphatic amide oxyethyl group sulfonated bodies 0.02～0.05g/L is formed.
The present invention compares the beneficial effect that is produced with background technology:
1. adopt the compound cyanideless electro-plating liquid of organic phosphine to replace cyaniding electrolytic solution fully, eliminated prussiate to the harm of human body with to the severe contamination of environment.
2. it is common to matrix metals such as iron and steel, aluminium, magnesium, zinc, titanium and alloy thereof is carried out non-cyanide pre-plating copper, both can thickly plate, but also flash plating both has been applicable to simple part, also is applicable to complicated difficult plating part.
3. because can utilize traditional cyanide electroplating equipment fully, do not need to carry out improvement of manufacturing line, even new production line does not have particular requirement yet, cost is low, less investment.
4. technology is simple, easy to maintenance, the coating combination is reliable.
Embodiment
Mode one (steel-iron components):
Chemical degreasing → normal temperature washing → electrolytic degreasing → hot water wash → pre-copper facing → the recovery of normal temperature washing → 10% sulfuric acid activation → twice normal temperature washing → cyanideless electro-plating liquid → normal temperature washing → 10% other metal level of sulfuric acid activation → plating.
1, cleans before the preplating
At first steel-iron components to be plated is carried out degreasing with chemical process, clean with normal-temperature water after the degreasing, after the washing steel-iron components to be plated is carried out electrolytic degreasing, clean with 60 ℃ of hot water earlier then and use the normal-temperature water cleaning components again, cleaning the back is that 10% sulfuric acid carries out surface active to steel-iron components with concentration, again the steel-iron components that passes through surface active is carried out twice washing on this basis.
2, the pre-copper facing of steel-iron components
PH value with KOH or organic phospho acid adjusting cyanideless electro-plating liquid, the pH value of cyanideless electro-plating liquid is remained in 9～10.5 scopes, the anode of electrolyzer adopts fine copper plate or electrolysis copper coin, negative electrode is a steel-iron components to be plated, the temperature of cyanideless electro-plating liquid is controlled at 15～45 ℃ of scopes, to insert in the cyanideless electro-plating liquid electrolyzer through the steel-iron components that cleans, this moment, part to be plated should be charged be gone into groove (not allowing part to go into long-time no power behind the groove), and the current density when part is gone into groove should be greater than conventional electroplating current density (0.3～2.0A/dm
2) 1/3～1/2, carry out 1～2 minute strike plating, to improve the surface active current potential of part to be plated, simultaneously, must stir electroplate liquid with pressurized air in the electroplating process, make electroplate liquid fully mobile, help improving current density upper range and sedimentation velocity like this, reduce concentration polarization.After carrying out 1～2 minute strike plating, return to conventional electroplating current density,,, electroplate until finishing copper coating according to definite electroplating times such as quantity, shape, size and thickness of coating of part to be plated according to conventional electroplating technology flow process.
3, preplating aftertreatment
After steel-iron components has plated copper coating, part being taken out from electrolyzer, it is carried out the washing of normal temperature, is that 10% sulfuric acid activates its surface with concentration then, and the strike copper plating preface is finished.Can carry out the plating of other metal level this moment to steel-iron components.
Mode two (zinc and zinc alloy part):
Chemical degreasing → normal temperature washing → go up the hanger → pre-copper facing → recovery of normal temperature washing → 6%～10% sulfuric acid activation → twice normal temperature washing → cyanideless electro-plating liquid → normal temperature to wash other each layer of metal of → 10% sulfuric acid activation → plating
1, cleans before the preplating
At first zinc to be plated and zinc alloy part are carried out degreasing with chemical process, normal temperature washing after the degreasing, after the washing part to be plated is hung on the hanger, on hanger, use the normal-temperature water cleaning components, with 6%～10% sulfuric acid part is carried out surface active again, again the part through surface active is carried out twice normal temperature washing on this basis.
2, zinc and the pre-copper facing of zinc alloy part
PH value with KOH or organic phospho acid adjusting cyanideless electro-plating liquid, the pH value of the pH value that makes cyanideless electro-plating liquid during a little less than steel plating iron part, remain in 9～10 scopes, the anode of electrolyzer adopts fine copper plate or electrolysis copper coin, negative electrode is for treating zinc-plated and the zinc alloy part, to insert in the cyanideless electro-plating liquid electrolyzer through cleaning the zinc and the zinc alloy part that hang on the hanger, this moment, part to be plated should be charged be gone into groove (not allowing part to go into long-time no power behind the groove), current density when part is gone into groove should be greater than conventional electroplating current density 1/3～1/2, carry out 1～2 minute strike plating, to improve the surface active current potential of part to be plated, simultaneously, necessary continuous mobile hanger in the electroplating process makes to keep mobile relatively between electroplate liquid and the part to be plated, help improving current density upper range and sedimentation velocity like this, reduce concentration polarization.After carrying out 1～2 minute strike plating, return to conventional electroplating current density,,, electroplate until finishing copper coating according to definite electroplating times such as quantity, shape, size and thickness of coating of part to be plated according to conventional electroplating technology flow process.
3, preplating aftertreatment
After zinc and zinc alloy part have plated copper coating, part being taken out from electrolyzer, it is carried out the washing of normal temperature, is that 10% sulfuric acid activates its surface with concentration then, and the strike copper plating preface is finished.Can carry out the plating of other metal level this moment to zinc and zinc alloy part.
Mode three (aluminium and aluminum alloy part):
Last hanger → chemical degreasing → hot water wash → normal temperature washing → chemical etching (50% nitric acid) → twice normal temperature soaks zinc → twice normal temperature washing → 10% sulfuric acid the washing → first time and moves back zinc → twice normal temperature and soak zinc → twice pre-copper facing → recovery of normal temperature washing → cyanideless electro-plating liquid → normal temperature the washing → second time and wash → 10% other metal level of sulfuric acid activation → plating.
1, cleans before the preplating
At first aluminium to be plated and aluminum alloy part are hung on the hanger, carry out degreasing with chemical process, after the degreasing earlier with behind the hot water with normal-temperature water cleaning components twice, with 50% nitric acid part to be plated is carried out chemical etching again, after normal temperature is washed twice of part, carry out soaking the first time zinc, washing twice again after soaking zinc, is that 10% sulfuric acid moves back zinc with concentration afterwards, moves back the zinc after washing twice, carry out soaking the second time zinc, wash part again twice.
2, the pre-copper facing of aluminium and aluminum alloy part
PH value with KOH or organic phospho acid adjusting cyanideless electro-plating liquid, the pH value of the pH value that makes cyanideless electro-plating liquid during a little less than steel plating iron part, remain in 9～10 scopes, the anode of electrolyzer adopts fine copper plate or electrolysis copper coin, negative electrode is aluminized and aluminum alloy part for waiting, to insert in the cyanideless electro-plating liquid electrolyzer through cleaning the aluminium and the aluminum alloy part that hang on the hanger, this moment, part to be plated should be charged be gone into groove (not allowing part to go into long-time no power behind the groove), current density when part is gone into groove should be greater than conventional electroplating current density 1/3～1/2, carry out 1～2 minute strike plating, to improve the surface active current potential of part to be plated, simultaneously, necessary continuous mobile hanger in the electroplating process makes to keep mobile relatively between electroplate liquid and the part to be plated, help improving current density upper range and sedimentation velocity like this, reduce concentration polarization.After carrying out 1～2 minute strike plating, return to conventional electroplating current density,,, electroplate until finishing copper coating according to definite electroplating times such as quantity, shape, size and thickness of coating of part to be plated according to conventional electroplating technology flow process.
3, preplating aftertreatment
After aluminium and aluminum alloy part have plated copper coating, part being taken out from electrolyzer, it is carried out the washing of normal temperature, is that 10% sulfuric acid activates its surface with concentration then, and the strike copper plating preface is finished.Can carry out the plating of other metal level this moment to aluminium and aluminum alloy part.
Mode four (magnesium and magnesium alloy parts):
Zinc → twice pre-copper facing → recovery of normal temperature washing → cyanideless electro-plating liquid → normal temperature washing → 10% other metal level of sulfuric acid activation → plating is washed → soaked to last hanger → chemical degreasing → hot water wash → normal temperature washing → chemical etching (15%～20% chromic anhydride) → twice normal temperature washing → activation (160～250g/L phosphoric acid, 70～80g/L ammonium bifluoride) → twice normal temperature.
1, cleans before the preplating
At first magnesium to be plated and magnesium alloy parts are hung on the hanger, carry out degreasing with chemical process, elder generation is with using twice of normal-temperature water cleaning components behind the hot water after the degreasing, with 15%～20% chromic anhydride part to be plated is carried out chemical etching again, behind twice of the normal-temperature water cleaning components, activate twice of normal temperature washing again after the activation with 160～250g/L phosphoric acid and 70～80g/L ammonium bifluoride, soak zinc afterwards, wash part again twice after soaking zinc.
2, the pre-copper facing of magnesium and magnesium alloy parts
PH value with KOH or organic phospho acid adjusting cyanideless electro-plating liquid, the pH value of the pH value that makes cyanideless electro-plating liquid during a little less than steel plating iron part, remain in 9～10 scopes, the anode of electrolyzer adopts fine copper plate or electrolysis copper coin, negative electrode is magnesium to be plated and magnesium alloy parts, to insert in the cyanideless electro-plating liquid electrolyzer through cleaning the magnesium and the magnesium alloy parts that hang on the hanger, this moment, part to be plated should be charged be gone into groove (not allowing part to go into long-time no power behind the groove), current density when part is gone into groove should be greater than conventional electroplating current density 1/3～1/2, carry out 1～2 minute strike plating, to improve the surface active current potential of part to be plated, simultaneously, necessary continuous mobile hanger in the electroplating process makes to keep mobile relatively between electroplate liquid and the part to be plated, help improving current density upper range and sedimentation velocity like this, reduce concentration polarization.After carrying out 1～2 minute strike plating, return to conventional electroplating current density,,, electroplate until finishing copper coating according to definite electroplating times such as quantity, shape, size and thickness of coating of part to be plated according to conventional electroplating technology flow process.
3, preplating aftertreatment
After magnesium and magnesium alloy parts have plated copper coating, part being taken out from electrolyzer, it is carried out the washing of normal temperature, is that 10% sulfuric acid activates its surface with concentration then, and the strike copper plating preface is finished.Can carry out the plating of other metal level this moment to magnesium and magnesium alloy parts.
Mode five (titanium or titanium alloy part):
Chemical degreasing → hot water wash → normal temperature washing → chemical etching (200g/L potassium bichromate solution, 20～30 ml concns are 60% hydrofluoric acid) → twice pre-copper facing → recovery of normal temperature washing → cyanideless electro-plating liquid → normal temperature washing → 10% other metal level of sulfuric acid activation → plating.
1, cleans before the preplating
At first titanium or titanium alloy part to be plated is carried out degreasing with chemical process, clean with 60 ℃ of hot water earlier after the degreasing of titanium or titanium alloy part, clean with normal-temperature water then, be that 60% hydrofluoric acid carries out chemical etching with 200g/L potassium bichromate solution and 20～30 ml concns again, the normal temperature washing is twice after the chemical etching.
2, the pre-copper facing of titanium or titanium alloy part
PH value with KOH or organic phospho acid adjusting cyanideless electro-plating liquid, the pH value of the pH value that makes cyanideless electro-plating liquid during a little less than steel plating iron part, remain in 9～10 scopes, the anode of electrolyzer adopts fine copper plate or electrolysis copper coin, negative electrode is a titanium or titanium alloy part to be plated, to insert in the cyanideless electro-plating liquid electrolyzer through the titanium or titanium alloy part that cleans, this moment, part to be plated should be charged be gone into groove (not allowing part to go into long-time no power behind the groove), current density when part is gone into groove should be greater than conventional electroplating current density 1/3～1/2, carry out 1～2 minute strike plating, to improve the surface active current potential of part to be plated, simultaneously, must stir electroplate liquid with pressurized air in the electroplating process, make electroplate liquid fully mobile, help all even formation good bonding force of overlay coating of part to be plated like this.After carrying out 1～2 minute strike plating, return to conventional electroplating current density,,, electroplate until finishing copper coating according to definite electroplating times such as quantity, shape, size and thickness of coating of part to be plated according to conventional electroplating technology flow process.
3, preplating aftertreatment
After the titanium or titanium alloy part has plated copper coating, part being taken out from electrolyzer, it is carried out the washing of normal temperature, is that 10% sulfuric acid activates its surface with concentration then, and the strike copper plating preface is finished.Can carry out the plating of other metal level this moment to the titanium or titanium alloy part.
Claims (5)
1, a kind of non-cyanogen strike copper plating technique method, the preplating of bottom copper when it can be common to matrix metals such as iron and steel, zinc and zinc alloy, aluminium and aluminium alloy, magnesium and magnesium alloy, titanium or titanium alloy are electroplated, it comprise before the preplating clean, pre-copper facing, three processes of preplating aftertreatment, it is characterized in that it realizes in the following manner:
Mode one (steel-iron components):
Chemical degreasing → normal temperature washing → electrolytic degreasing → hot water wash → pre-copper facing → the recovery of normal temperature washing → 10% sulfuric acid activation → twice normal temperature washing → cyanideless electro-plating liquid → normal temperature washing → 10% other metal level of sulfuric acid activation → plating;
Mode two (zinc and zinc alloy part):
Chemical degreasing → normal temperature washing → go up the hanger → pre-copper facing → recovery of normal temperature washing → 6% sulfuric acid activation → twice normal temperature washing → cyanideless electro-plating liquid → normal temperature to wash → 10% other metal level of sulfuric acid activation → plating.
Mode three (aluminium and aluminum alloy part):
Last hanger → chemical degreasing → hot water wash → normal temperature washing → 50% nitric acid → twice normal temperature soaks zinc → twice normal temperature washing → first time and washes → 10% sulfuric acid and move back zinc → twice normal temperature and soak zinc → twice pre-copper facing → recovery of normal temperature washing → cyanideless electro-plating liquid → normal temperature the washing → second time and wash → 10% other metal level of sulfuric acid activation → plating;
Mode four (magnesium and magnesium alloy parts):
Zinc → twice pre-copper facing → recovery of normal temperature washing → cyanideless electro-plating liquid → normal temperature washing → 10% other metal level of sulfuric acid activation → plating is washed → soaked to last hanger → chemical degreasing → hot water wash → normal temperature washing → chemical etching (15%～20% chromic anhydride) → twice normal temperature washing → activation (160～250g/L phosphoric acid, 70～80g/L ammonium bifluoride) → twice normal temperature;
Mode five (titanium or titanium alloy part):
Chemical degreasing → hot water wash → normal temperature washing → chemical etching (200g/L potassium bichromate solution, 20～30 ml concns are 60% hydrofluoric acid) → twice pre-copper facing → recovery of normal temperature washing → cyanideless electro-plating liquid → normal temperature washing → 10% other metal level of sulfuric acid activation → plating.
2, non-cyanogen strike copper plating technique method according to claim 1, when it is characterized in that the pre-copper facing of described steel-iron components, the pH value with KOH or organic phospho acid are regulated cyanideless electro-plating liquid remains in 9～10.5 scopes pH value of cyanideless electro-plating liquid; During the pre-copper facing of described zinc and zinc alloy, aluminium and aluminium alloy, magnesium and magnesium alloy, titanium or titanium alloy part, the pH value with KOH or organic phospho acid are regulated cyanideless electro-plating liquid remains in 9～10 scopes pH value of cyanideless electro-plating liquid.
3, non-cyanogen strike copper plating technique method according to claim 1, the temperature that it is characterized in that described cyanideless electro-plating liquid is controlled at 15～45 ℃, part to be plated must be charged be gone into groove, and the current density when going into groove should be greater than conventional electroplating current density (0.3～2.0A/dm
2) 1/3～1/2, carry out 1～2 minute strike plating, to improve the surface active current potential of part to be plated.
4, non-cyanogen strike copper plating technique method according to claim 1 is characterized in that the preceding nitric acid with 50% of the pre-copper facing of described aluminium and aluminum alloy part carries out chemical etching; Chromic anhydride with 15%～20% before the pre-copper facing of described magnesium and magnesium alloy parts carries out chemical etching; Be that 60% hydrofluoric acid carries out chemical etching before the pre-copper facing of described titanium or titanium alloy part with 200g/L potassium bichromate solution and 20～30 ml concns.
5, non-cyanogen strike copper plating technique method according to claim 1 is characterized in that after described iron and steel, zinc and zinc alloy, aluminium and aluminium alloy, magnesium and magnesium alloy, the pre-copper facing of titanium or titanium alloy with concentration being that 10% sulfuric acid activates.
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| CN102286763A (en) * | 2011-08-25 | 2011-12-21 | 西北工业大学 | Process method for electroplating copper on TC4 titanium alloy surface |
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| CN111519224A (en) * | 2020-06-01 | 2020-08-11 | 合肥浩凌机械设计制造有限公司 | Post-processing method for electroplating molding in copper-clad wire manufacturing |
| CN113186572A (en) * | 2021-04-30 | 2021-07-30 | 东莞市环侨金属制品有限公司 | Rhodium ruthenium alloy electroplating process |
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