CN101550570A - Non-cyanide electro cooper plating bath of EDTA system and use method thereof - Google Patents
Non-cyanide electro cooper plating bath of EDTA system and use method thereof Download PDFInfo
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- CN101550570A CN101550570A CNA2009100943527A CN200910094352A CN101550570A CN 101550570 A CN101550570 A CN 101550570A CN A2009100943527 A CNA2009100943527 A CN A2009100943527A CN 200910094352 A CN200910094352 A CN 200910094352A CN 101550570 A CN101550570 A CN 101550570A
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- copper
- cyanide
- edta
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- 238000007747 plating Methods 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 16
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 title claims abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052802 copper Inorganic materials 0.000 claims abstract description 44
- 239000010949 copper Substances 0.000 claims abstract description 44
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims abstract description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 15
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004323 potassium nitrate Substances 0.000 claims abstract description 8
- 235000010333 potassium nitrate Nutrition 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 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 claims abstract description 7
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims abstract description 7
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims abstract description 6
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 6
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims abstract description 6
- 239000001509 sodium citrate Substances 0.000 claims abstract description 5
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 5
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 5
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims abstract description 5
- 229940038773 trisodium citrate Drugs 0.000 claims abstract description 5
- QLBHNVFOQLIYTH-UHFFFAOYSA-L dipotassium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [K+].[K+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O QLBHNVFOQLIYTH-UHFFFAOYSA-L 0.000 claims abstract description 4
- 238000009713 electroplating Methods 0.000 claims description 20
- LEKPFOXEZRZPGW-UHFFFAOYSA-N copper;dicyanide Chemical compound [Cu+2].N#[C-].N#[C-] LEKPFOXEZRZPGW-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 238000009423 ventilation Methods 0.000 claims description 5
- 229940001516 sodium nitrate Drugs 0.000 claims description 4
- GPSAAQWVJOVCBK-UHFFFAOYSA-N [K].[K].[K].OC(=O)CC(O)(C(O)=O)CC(O)=O Chemical compound [K].[K].[K].OC(=O)CC(O)(C(O)=O)CC(O)=O GPSAAQWVJOVCBK-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000008139 complexing agent Substances 0.000 claims description 2
- 230000003750 conditioning effect Effects 0.000 claims description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 abstract description 14
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- 239000001508 potassium citrate Substances 0.000 abstract description 3
- 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 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 229940116318 copper carbonate Drugs 0.000 abstract 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 abstract 1
- 229940058180 edetate dipotassium anhydrous Drugs 0.000 abstract 1
- 229960002635 potassium citrate Drugs 0.000 abstract 1
- 235000011082 potassium citrates Nutrition 0.000 abstract 1
- 235000011118 potassium hydroxide Nutrition 0.000 abstract 1
- 229940074439 potassium sodium tartrate Drugs 0.000 abstract 1
- 235000019263 trisodium citrate Nutrition 0.000 abstract 1
- IPDWABJNXLNLRA-UHFFFAOYSA-N 2,3-dihydroxybutanedioic acid;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound OC(=O)C(O)C(O)C(O)=O.OC(=O)CC(O)(C(O)=O)CC(O)=O IPDWABJNXLNLRA-UHFFFAOYSA-N 0.000 description 12
- 238000004062 sedimentation Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- XRBURMNBUVEAKD-UHFFFAOYSA-N chromium copper nickel Chemical compound [Cr].[Ni].[Cu] XRBURMNBUVEAKD-UHFFFAOYSA-N 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012669 liquid formulation Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 235000015870 tripotassium citrate Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The present invention provides a new non-cyanide electro cooper plating bath of EDTA system and use method thereof. In the electro copper plating bath, using disodium EDTA or dipotassium EDTA as main complexant, using copper sulfate or basic copper carbonate as main salt, using trisodium citrate, potassium citrate or potassium sodium tartrate as auxiliary complexant, using sodium nitrate or potassium nitrate as conductive salt, using sodium hydroxide or potassium hydrate as pH value regulator. The invention also provides a use method of the non-cyanide electro cooper plating bath. The invention has advantages: simple plating bath formula, easy control and operation, wide temperature range of plating bath using, high current efficiency, fine crystallization coating, good appearance color, stable plating bath, strong uniform plating and covering ability, low cost, easy wastewater treatment. The invention can be used for pre copper plating or direct electro-coppering instead of virulent cyaniding electro-coppering process.
Description
Technical field
The present invention relates to a kind of electroplate liquid, particularly relate to non-cyanide copper electroplating liquid, belong to the electroplating technology field.
Background technology
The crystallization of cyanide electroplating copper layer is careful, bonding force good, all platings of plating bath, leveling property, stability are also very good, can be on iron and steel, zinc and zinc alloy matrix part Direct Electroplating.But contain cyanide ion in the cyanide electroplating copper liquid, toxicity is big, and waste water and waste liquid are difficult, and contaminate environment is serious, and is detrimental to health.Therefore, people are seeking the cyanide-free copper electroplating technology that can substitute cyanide copper always.Existing cyanide-free copper electroplating technology mainly contains pyrophosphate method of electro-plating copper, vitriol electro-coppering, quadrol electro-coppering, fluoroborate plating copper, citric acid-tartrate electro-coppering, HEDP electro-coppering and thionamic acid electro-coppering system etc.Wherein, pyrophosphate copper plating system large-scale application is handled but generally also need to carry out cyanide pre-plating copper in production, and the plating solution maintenance complexity, and cost is higher.Citric acid-tartrate electro-coppering system also has and is used on a small quantity producing, but bonding force is not ideal enough, and the plating bath cost is also higher, and long-term the placement is easy to mildew.Bonding force extreme difference during vitriol electro-coppering system Direct Electroplating.HEDP electro-coppering system almost can compare favourably with cyanide electroplating, but the sewage disposal expense is still higher.Other several technologies are to rest on the experimental study stage also because of all there being different defectives basically, also are not used for industrial production fully.
Summary of the invention
Purpose of the present invention is exactly at the prior art above shortcomings, and a kind of new EDTA system non-cyanide copper electroplating liquid and using method thereof are provided.
The major advantage of non-cyanide copper electroplating liquid of the present invention is that electroplate liquid formulation is simple, is easy to control and operation, plating bath use temperature wide ranges, and the current efficiency height, the coating crystallization is careful, and appearance luster is good, bath stability, all plating and hiding power are strong, and cost is low, and wastewater treatment is easy.Can replace containing the cyanide electroplating process for copper of severe toxicity, use as pre-copper facing or Direct Electroplating copper.
The feature of non-cyanide copper electroplating liquid provided by the invention is: the prescription of said electrolytic copper plating solution is:
Main complexing agent: disodium ethylene diamine tetraacetate or EDTA-2K 120～170g/;
Auxiliary complex-former: trisodium citrate or citric acid tri potassium 25～40g/L, or Seignette salt 20～40g/L;
Main salt: copper sulfate 25～45g/L or ventilation breather 12～18g/L;
Conducting salt: SODIUMNITRATE or saltpetre 4～8g/L;
PH value conditioning agent: sodium hydroxide or potassium hydroxide 20～40g/L.
Non-cyanide copper electroplating liquid of the present invention has also been applied for a kind of using method, it is characterized in that: the cathode current density of electrolytic copper plating solution is 0.5～3.0A/dm during plating
2, pH is controlled between 12～13, and temperature is 50～70 ℃.
Compared with prior art, the present invention has following advantage or positively effect:
1, electrolytic copper plating solution is a cyanide-free plating bath, and composition is simple, and easy operation and maintenance is applicable to the Direct Electroplating on steel-iron components surface.
2, the electrolytic copper plating solution polarization performance is good.When not adding saltpetre in the plating bath, cathode efficiency is higher, generally all more than 80%.When current density at 1A/dm
2During the left and right sides, current efficiency is about 90%.
3, the electrolytic copper plating solution that is added with saltpetre has higher limit cathode current density, the current density range broad in coating light district, and the upper limit of current density can reach 3A/dm
2
4, the covering power of electrolytic copper plating solution is better than citric acid-tartrate electro-coppering and cyanide copper system.After adding Tripotassium Citrate and saltpetre, the covering power of electrolytic copper plating solution obviously improves, and can reach 100%.
When 5, thickness of coating was the same, the copper plate porosity that obtains with the electrolytic copper plating solution that does not contain Seignette salt was far below citric acid-tartrate system; The copper plate porosity that electrolytic copper plating solution when containing saltpetre-Tripotassium Citrate obtains is lower than or approaches the cyanide copper system.
6, binding force of cladding material can be satisfied the demand, and the pre-plating layer that can be used as copper-nickel-chromium protecting decorative coating uses.Bonding force intensity is a little less than the cyaniding system, but is higher than citric acid-tartrate system.
7, the stability of electrolytic copper plating solution is high, works continuously through 170h, and plating bath still can use.
Embodiment
The invention will be further described with embodiment below.
Embodiment 1
The prescription of electrolytic copper plating solution is:
Disodium ethylene diamine tetraacetate 120g/L
Ventilation breather 12g/L
Potassium hydroxide 30g/L
Citric acid tri potassium 30g/L
Saltpetre 6g/L;
Processing condition during plating are: the pH value 12 of electrolytic copper plating solution, 50 ℃ of temperature, current density 0.5A/dm
2
Embodiment 1 compares with citric acid-tartrate electro-coppering system with prussiate, and covering power and leveling property are good, and covering power is suitable.Maximum current efficient and sedimentation velocity are more lower slightly.Can satisfy the demand of strike copper plating technique.
Embodiment 2
The prescription of electrolytic copper plating solution is:
EDTA-2K 145g/L
Ventilation breather 14g/L
Trisodium citrate 25g/L
SODIUMNITRATE 5g/L
Sodium hydroxide 20g/L;
Processing condition during plating are: the pH value 12.5 of electrolytic copper plating solution, 60 ℃ of temperature, current density 1.0A/dm
2
Embodiment 2 compares with citric acid-tartrate electro-coppering system with prussiate, and covering power and leveling property are good, maximum current efficient height.Covering power and sedimentation velocity are more lower slightly.Can satisfy the needs of strike copper plating technique.
Embodiment 3
The prescription of electrolytic copper plating solution is:
Disodium ethylene diamine tetraacetate 155g/L
Ventilation breather 18g/L
Seignette salt 30g/L
SODIUMNITRATE 5g/L
Potassium hydroxide 40g/L;
Processing condition during plating are: the pH value 13 of electrolytic copper plating solution, 70 ℃ of temperature, current density 2.5A/dm
2.
Embodiment 3 compares with citric acid-tartrate electro-coppering system with prussiate, and covering power is good, maximum current efficient height.Covering power and sedimentation velocity are more lower slightly, and leveling property is relatively poor relatively.Substantially can satisfy the needs of strike copper plating technique.
Embodiment 4
The prescription of electrolytic copper plating solution is:
Disodium ethylene diamine tetraacetate 170g/L
Copper sulfate 25g/L
Sodium hydroxide 40g/L
Seignette salt 20g/L
Saltpetre 4g/L;
Processing condition during plating are: the pH value 12.5 of electrolytic copper plating solution, 65 ℃ of temperature, current density 3.0A/dm
2
Embodiment 4 compares with citric acid-tartrate electro-coppering system with prussiate, and covering power is good.But covering power, maximum current efficient, leveling property and sedimentation velocity are slightly weaker.Substantially can satisfy the needs of strike copper plating technique.
Embodiment 5
The prescription of electrolytic copper plating solution is the same basically with embodiment 1, and just auxiliary complex-former wherein is trisodium citrate 40g/L, and main salt is copper sulfate 35g/L, and other composition is identical with embodiment 1; Processing condition during plating are also identical with embodiment 1.
Embodiment 5 compares with citric acid-tartrate electro-coppering system with prussiate, and covering power is good, and maximum current efficient is higher.Covering power and sedimentation velocity are more lower slightly, and leveling property is better relatively.Substantially can satisfy the needs of strike copper plating technique.
Embodiment 6
The prescription of electrolytic copper plating solution is the same basically with embodiment 2, and just auxiliary complex-former wherein is Seignette salt 40g/L, and main salt is copper sulfate 45g/L, and other composition is identical with embodiment 2; Processing condition during plating are also identical with enforcement 2.
Embodiment 6 compares with citric acid-tartrate electro-coppering system with prussiate, and covering power is good, and maximum current efficient is higher.Covering power and sedimentation velocity are more lower slightly, and leveling property is better relatively, can satisfy the needs of strike copper plating technique substantially.
The performance of embodiments of the invention and cyanide copper and citric acid-tartrate electro-coppering relatively sees Table 1.
Table 1
| The contrast index | Covering power (%) | Covering power (%) | Maximum current efficient (%) | Leveling property (%) | Sedimentation velocity (μ m/min) |
| Cyanide copper | 75 | 100 | 80 | 90 | 0.27 |
| Citric acid-tartrate electro-coppering | 73 | 100 | 93 | 36 | 0.18 |
| Embodiment 1 | 85 | 100 | 70 | 94 | 0.13 |
| Embodiment 2 | 79 | 80 | 93 | 96 | 0.19 |
| Embodiment 3 | 79 | 80 | 92 | 33 | 0.19 |
| Embodiment 4 | 91 | 85 | 58 | 60 | 0.12 |
| Embodiment 5 | 83 | 92 | 88 | 91 | 0.16 |
| Embodiment 6 | 80 | 89 | 91 | 92 | 0.18 |
。
Claims (2)
1, a kind of EDTA system non-cyanide copper electroplating liquid, it is characterized in that: the prescription of said electrolytic copper plating solution is:
Main complexing agent: disodium ethylene diamine tetraacetate or EDTA-2K 120～170g/L;
Auxiliary complex-former: trisodium citrate or citric acid tri potassium 25～40g/L, or Seignette salt 20～40g/L;
Main salt: copper sulfate 25～45g/L or ventilation breather 12～18g/L;
Conducting salt: SODIUMNITRATE or saltpetre 4～8g/L;
PH value conditioning agent: sodium hydroxide or potassium hydroxide 20～40g/L.
2, the using method of the non-cyanide copper electroplating liquid of claim 1 is characterized in that: the cathode current density of electrolytic copper plating solution is 0.5～3.0A/dm during plating
2, pH is controlled between 12～13, and temperature is 50～70 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100943527A CN101550570A (en) | 2009-04-15 | 2009-04-15 | Non-cyanide electro cooper plating bath of EDTA system and use method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100943527A CN101550570A (en) | 2009-04-15 | 2009-04-15 | Non-cyanide electro cooper plating bath of EDTA system and use method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101550570A true CN101550570A (en) | 2009-10-07 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2009100943527A Pending CN101550570A (en) | 2009-04-15 | 2009-04-15 | Non-cyanide electro cooper plating bath of EDTA system and use method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101550570A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102978669A (en) * | 2012-10-30 | 2013-03-20 | 南通汇丰电子科技有限公司 | Environment-friendly electro-coppering liquid |
| US20130264214A1 (en) * | 2012-04-04 | 2013-10-10 | Rohm And Haas Electronic Materials Llc | Metal plating for ph sensitive applications |
| CN103668357A (en) * | 2013-12-19 | 2014-03-26 | 株洲永盛电池材料有限公司 | Alkaline cyanide-free high-speed copper plating solution |
| CN106319581A (en) * | 2016-10-21 | 2017-01-11 | 昆明理工大学 | Method for green copper plating of stainless steel filaments under catalysis of metals |
| CN106367782A (en) * | 2016-08-26 | 2017-02-01 | 湖北吉和昌化工科技有限公司 | Electroplating liquid of sub-acid system electroplated bright copper as well as preparation method and electroplating process of electroplating liquid |
| CN109706487A (en) * | 2017-10-26 | 2019-05-03 | 丹阳市金长汽车部件有限公司 | A kind of anti-oxidant electroplate liquid of copper facing |
-
2009
- 2009-04-15 CN CNA2009100943527A patent/CN101550570A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 周卫铭: "无氰碱性镀铜工艺研究", 中国优秀硕士学位论文全文数据库工程科技I辑 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130264214A1 (en) * | 2012-04-04 | 2013-10-10 | Rohm And Haas Electronic Materials Llc | Metal plating for ph sensitive applications |
| CN102978669A (en) * | 2012-10-30 | 2013-03-20 | 南通汇丰电子科技有限公司 | Environment-friendly electro-coppering liquid |
| CN103668357A (en) * | 2013-12-19 | 2014-03-26 | 株洲永盛电池材料有限公司 | Alkaline cyanide-free high-speed copper plating solution |
| CN103668357B (en) * | 2013-12-19 | 2016-08-17 | 湖南永盛新材料股份有限公司 | A kind of alkaline non-cyanide high-speed plating copper electrolyte |
| CN106367782A (en) * | 2016-08-26 | 2017-02-01 | 湖北吉和昌化工科技有限公司 | Electroplating liquid of sub-acid system electroplated bright copper as well as preparation method and electroplating process of electroplating liquid |
| CN106367782B (en) * | 2016-08-26 | 2018-12-14 | 湖北吉和昌化工科技有限公司 | Electroplate liquid of subacidity system electroplating bright copper and preparation method thereof and electroplating technology |
| CN106319581A (en) * | 2016-10-21 | 2017-01-11 | 昆明理工大学 | Method for green copper plating of stainless steel filaments under catalysis of metals |
| CN109706487A (en) * | 2017-10-26 | 2019-05-03 | 丹阳市金长汽车部件有限公司 | A kind of anti-oxidant electroplate liquid of copper facing |
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