CN114808050B - Nano nickel plating liquid medicine and nickel plating method - Google Patents
Nano nickel plating liquid medicine and nickel plating method Download PDFInfo
- Publication number
- CN114808050B CN114808050B CN202210382610.7A CN202210382610A CN114808050B CN 114808050 B CN114808050 B CN 114808050B CN 202210382610 A CN202210382610 A CN 202210382610A CN 114808050 B CN114808050 B CN 114808050B
- Authority
- CN
- China
- Prior art keywords
- nickel plating
- plating
- parts
- nickel
- liquid medicine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 375
- 238000007747 plating Methods 0.000 title claims abstract description 305
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 160
- 239000007788 liquid Substances 0.000 title claims abstract description 87
- 239000003814 drug Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract description 35
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 27
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 18
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 claims abstract description 12
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 9
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims abstract description 9
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 82
- 229910052802 copper Inorganic materials 0.000 claims description 82
- 239000010949 copper Substances 0.000 claims description 82
- 238000005406 washing Methods 0.000 claims description 52
- 239000002253 acid Substances 0.000 claims description 43
- 238000005238 degreasing Methods 0.000 claims description 42
- 238000009713 electroplating Methods 0.000 claims description 31
- 230000004913 activation Effects 0.000 claims description 26
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 19
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 15
- 235000011180 diphosphates Nutrition 0.000 claims description 15
- 230000037452 priming Effects 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000005868 electrolysis reaction Methods 0.000 claims description 8
- 238000004512 die casting Methods 0.000 claims description 7
- CHLCPTJLUJHDBO-UHFFFAOYSA-M sodium;benzenesulfinate Chemical compound [Na+].[O-]S(=O)C1=CC=CC=C1 CHLCPTJLUJHDBO-UHFFFAOYSA-M 0.000 claims description 7
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 claims description 7
- LDYUIVOAQFHBIO-UHFFFAOYSA-N n,n-dimethylprop-1-yn-1-amine Chemical compound CC#CN(C)C LDYUIVOAQFHBIO-UHFFFAOYSA-N 0.000 claims description 6
- DGSDBJMBHCQYGN-UHFFFAOYSA-M sodium;2-ethylhexyl sulfate Chemical compound [Na+].CCCCC(CC)COS([O-])(=O)=O DGSDBJMBHCQYGN-UHFFFAOYSA-M 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 63
- 230000007797 corrosion Effects 0.000 abstract description 47
- 238000005260 corrosion Methods 0.000 abstract description 47
- 230000007547 defect Effects 0.000 abstract description 17
- 238000012423 maintenance Methods 0.000 abstract description 16
- 238000004140 cleaning Methods 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 description 39
- 230000008569 process Effects 0.000 description 25
- 230000008901 benefit Effects 0.000 description 24
- 239000000047 product Substances 0.000 description 21
- 238000004519 manufacturing process Methods 0.000 description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 17
- 230000008021 deposition Effects 0.000 description 17
- 239000013040 bath agent Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 15
- 239000013527 degreasing agent Substances 0.000 description 15
- 238000005237 degreasing agent Methods 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 14
- 239000000080 wetting agent Substances 0.000 description 13
- 239000003153 chemical reaction reagent Substances 0.000 description 12
- 230000032683 aging Effects 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 230000009467 reduction Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 230000002269 spontaneous effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 241000080590 Niso Species 0.000 description 7
- 230000002427 irreversible effect Effects 0.000 description 7
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 7
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 6
- 230000009471 action Effects 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000013589 supplement Substances 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000004381 surface treatment Methods 0.000 description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- 239000004519 grease Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 239000004902 Softening Agent Substances 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000003788 bath preparation Substances 0.000 description 3
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 3
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 3
- 238000009499 grossing Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QDYWDMCTLACQCS-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCC([Na])CC Chemical compound OS(O)(=O)=O.CCCCCC([Na])CC QDYWDMCTLACQCS-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000005282 brightening Methods 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000005536 corrosion prevention Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910001229 Pot metal Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- LEKPFOXEZRZPGW-UHFFFAOYSA-N copper;dicyanide Chemical compound [Cu+2].N#[C-].N#[C-] LEKPFOXEZRZPGW-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- -1 dimethyl propyne amine Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- 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
- C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention relates to a nano nickel plating liquid medicine and a nickel plating method. The preparation raw materials of the nano nickel plating liquid medicine comprise nickel sulfamate, ammonium citrate, potassium pyrophosphate, potassium carbonate, sodium phosphite, potassium hydroxide and water. The nano nickel plating liquid can replace chemical nickel plating liquid, has 100 percent dispersibility same as chemical nickel plating, can ensure that deep holes or low-current areas of zinc alloy products can be completely covered with nickel plating layers, improves the corrosion resistance of plating layers of the low-current areas, has the characteristic of only needing regular cleaning treatment and maintenance like the chemical nickel plating liquid, has no problem of needing to update plating liquid after the plating liquid is aged, and overcomes the defects of the chemical nickel plating liquid.
Description
Technical Field
The invention belongs to the technical field of zinc alloy surface treatment, and particularly relates to a nano nickel plating liquid medicine and a nickel plating method.
Background
The zinc alloy is generally composed of aluminum, copper, magnesium and zinc according to a certain proportion, is an important and cheap metal material, can be used for manufacturing various industrial products, parts and the like with small tolerance and complex shape by a die casting molding method, and is commonly used for replacing copper, copper alloy and steel materials to manufacture structural members and decorating parts with smaller tolerance and complex shape. Because of the negative potential of the zinc alloy electrode and poor chemical stability, the surface treatment needs to be carried out for corrosion prevention, wherein, the copper/nickel/chromium multi-layer corrosion prevention decorative coating is a widely and effectively applied mode. After the zinc alloy product is subjected to electroplating surface treatment, the full-bright mirror surface appearance can be obtained, the decorative effect is excellent, the surface hardness, the wear resistance and the corrosion resistance can be improved, and the zinc alloy product is widely applied to industries such as building hardware, bathroom, electronic parts, case fittings, automobile fittings and the like.
The general appearance of zinc alloy die castings is relatively complex, particularly zinc alloy die castings containing deep holes or blind holes often generate component segregation phenomenon in the die casting process, and aluminum-rich phases or zinc-rich phases are formed on the surface, and are soluble in acid and alkali. In the treatment process of the electroplating surface, the deep hole or the blind hole of the zinc alloy die casting is blocked or shielded, the current density of the cathode is relatively small, the deposited coating is insufficient in thickness or can not be coated, so that the base material of the deep hole or the blind hole is easily corroded by strong acid or strong oxidizing plating solution (such as sulfate copper plating, hexavalent chromium plating and the like), and the adverse phenomena of blackening, foaming and the like of the coating are caused, so that the corrosion resistance is reduced, the yield is reduced, and the production cost is increased.
For the problem of corrosion of deep holes or blind holes in zinc alloy electroplating surface treatment, the current solution method is as follows: after the zinc alloy is pretreated, a cyanide-free copper plating bottoming and chemical nickel plating process is adopted, the characteristic that chemical nickel plating does not need to be electrified and spontaneously reduced and deposited is utilized, the zinc alloy has the advantages of 100% dispersibility, very uniform and compact plating thickness and few pores, deep hole parts or low current areas of zinc alloy products can be completely covered with a nickel plating layer, the corrosion resistance is excellent, the follow-up corrosion is avoided during copper plating by sulfuric acid, and the yield can be ensured while the product performance is improved. Although the method solves the deep hole corrosion problem of zinc alloy products, the chemical nickel plating process has the problems of large dosage, short service life, complex management and maintenance and high use cost.
Disclosure of Invention
The present invention aims to solve at least one of the above technical problems in the prior art. Therefore, the invention provides a nano nickel plating liquid medicine which is used for replacing chemical nickel plating liquid medicine, not only has 100 percent dispersibility which is the same as that of chemical nickel plating, can ensure that deep holes or low-current areas of zinc alloy products can be completely covered with nickel plating layers, improves the corrosion resistance of the plating layers of the low-current areas, but also has the characteristic of only needing periodical cleaning treatment and maintenance like the chemical nickel plating liquid medicine, has no aging problem and needs to be updated, and overcomes the defects of the chemical nickel plating liquid medicine.
The invention also provides a nickel plating method.
The first aspect of the invention provides a nano nickel plating liquid medicine, which is prepared from the raw materials of nickel sulfamate, ammonium citrate, potassium pyrophosphate, potassium carbonate, sodium phosphite, potassium hydroxide and water.
The invention relates to a technical scheme of nano nickel plating liquid medicine, which has at least the following beneficial effects:
In the surface electroplating treatment process of the zinc alloy product, the corrosion resistance problem of deep holes or blind holes of the zinc alloy product is usually solved by adopting a combination mode of cyanide-free copper plating bottoming and chemical nickel plating, but in practical production and application, the following defects exist in the chemical nickel plating process: (1) The chemical nickel plating liquid medicine is consumed and replenished, irreversible aging can occur, all the liquid medicine must be scrapped and updated periodically, the usage amount is large, and the cost is high; (2) The chemical nickel plating scrapped liquid is large in liquid amount, high in nickel content, high in wastewater treatment difficulty and extremely high in comprehensive treatment cost; (3) The chemical nickel plating has the advantages that various performances are reduced along with the aging of the liquid medicine, the stability is also poor, the management and the maintenance are complex, and the requirement is high; (4) The chemical nickel plating is spontaneous reduction deposition, the deposition speed is slow, the plating time is long, and the production efficiency is low. Therefore, the conventional combination method of cyanide-free copper plating bottoming and chemical nickel plating cannot be widely popularized and applied because the comprehensive cost is too high and the method is only applied to a few markets with high-end requirements.
The nano nickel plating liquid can replace chemical nickel plating liquid, has 100 percent dispersibility same as chemical nickel plating, can ensure that deep holes or low-current areas of zinc alloy products can be completely covered with nickel plating layers, improves the corrosion resistance of plating layers of the low-current areas, has the characteristic of only needing regular cleaning treatment and maintenance like the chemical nickel plating liquid, has no problem of needing to update plating liquid after the plating liquid is aged, and overcomes the defects of the chemical nickel plating liquid.
The nano nickel plating liquid of the invention, through reasonable design of components and combined action of external current and spontaneous reduction, enables the nickel plating layer to be deposited on any surface of zinc alloy rapidly and uniformly, has the advantage of high nickel plating deposition speed and the advantage of 100% dispersibility of chemical nickel plating, thereby improving the corrosion resistance of a low current area. In addition, the nano nickel plating liquid medicine has the advantage of nickel plating, irreversible aging does not occur, so that the liquid medicine does not need to be scrapped and updated regularly, the waste water amount is small, the nickel content is low, the comprehensive treatment is relatively simple, the cost is low, the management and maintenance are simple, and the performance is more stable. The nano nickel plating liquid of the invention can not only improve the corrosion resistance of a low current area, but also improve the production efficiency, overcomes the defects of the existing chemical nickel plating liquid, greatly reduces the use cost, and is suitable for general popularization and application.
The nano nickel plating liquid medicine disclosed by the invention is simple in management and maintenance, stable in liquid medicine performance, low in key use cost and easy for large-scale application.
Specifically, in the preparation raw materials, the functions of the components are as follows:
nickel sulfamate is used as the main metal salt component to provide the cathodically reduced nickel metal.
Ammonium citrate is used as a main complexing agent for complexing nickel metal, so as to ensure the stability of the liquid medicine.
Potassium pyrophosphate is used as an auxiliary complexing agent to refine crystallization in a high-current area and prevent the plating layer from being rough.
The potassium carbonate is used as a conductive salt and a pH value buffer agent for increasing the conductive performance of the liquid medicine and stabilizing the pH value of the liquid medicine.
Sodium phosphite is used as a reducing agent, so that the deep holes or blind holes can be spontaneously reduced and deposited with a nickel metal coating due to no current.
Potassium hydroxide is used as a pH regulator to raise the pH value of the liquid medicine to the application range.
Water is the carrier of the liquid medicine.
According to some embodiments of the invention, the preparation raw materials comprise the following components in parts by weight:
nickel sulfamate: 2 to 5 parts of the components in parts by weight,
Ammonium citrate: 2 to 5 parts of the components in parts by weight,
Potassium pyrophosphate: 1.5 to 5 parts of the total weight of the composition,
Potassium carbonate: 2 to 5 parts of the components in parts by weight,
Sodium phosphite: 0.5 to 2 parts of the total weight of the composition,
Potassium hydroxide: 1 to 4 parts of the components,
Water: 60-100 parts.
According to some embodiments of the invention, the preparation raw materials comprise the following components in parts by weight:
Nickel sulfamate: 3 to 4 parts of the components,
Ammonium citrate: 3 to 4 parts of the components,
Potassium pyrophosphate: 2.5 to 3.5 parts of a compound,
Potassium carbonate: 3 to 4 parts of the components,
Sodium phosphite: 1 to 1.5 parts of the components,
Potassium hydroxide: 2 to 3 parts of the components in total,
Water: 70-100 parts.
According to some embodiments of the invention, the composition further comprises 0.01 to 0.1 parts by weight of sodium benzene sulfinate.
According to some embodiments of the invention, the composition further comprises 0.03 to 0.05 parts by weight of sodium benzene sulfinate.
Sodium benzene sulfinate is used as a low-current area locating agent, so that the coating coverage performance of a low-current area can be improved, and the corrosion resistance of the low area can be improved.
According to some embodiments of the invention, the composition further comprises 0.05 parts to 0.2 parts by weight of p-toluenesulfonamide.
According to some embodiments of the invention, the composition further comprises 0.1 to 0.15 parts by weight of p-toluenesulfonamide.
The p-toluenesulfonamide is used as a crystallization refiner, so that the nickel coating is crystallized more finely, and the dispersion performance of the coating is improved.
According to some embodiments of the invention, the composition further comprises 0.01 to 0.05 parts by weight of dimethyl propynylamine.
According to some embodiments of the invention, the composition further comprises 0.02-0.03 parts by weight of dimethyl propynylamine.
The dimethyl propyne amine is used as a brightening agent, so that the coating achieves the effect of uniform brightening.
According to some embodiments of the invention, the composition further comprises 0.01 to 0.05 parts by weight of sodium ethylhexyl sulfate.
According to some embodiments of the invention, the composition further comprises 0.02 to 0.03 parts by weight of sodium ethylhexyl sulfate.
And the sodium ethylhexyl sulfate is used as a wetting agent to wet the surface of the workpiece, so that the surface coating is uniform, and the problem of pinholes is avoided.
A second aspect of the present invention provides a nickel plating method comprising the steps of:
S1: immersing the pretreated workpiece into the nano nickel plating liquid medicine for electroplating treatment to obtain a nickel plating workpiece;
S2: and carrying out copper plating and post-treatment on the nickel-plated piece.
In the surface electroplating treatment process of the zinc alloy product, the corrosion resistance problem of deep holes or blind holes of the zinc alloy product is usually solved by adopting a combination mode of cyanide-free copper plating bottoming and chemical nickel plating, but in practical production and application, the following defects exist in the chemical nickel plating process: (1) The chemical nickel plating liquid medicine is consumed and replenished, irreversible aging can occur, all the liquid medicine must be scrapped and updated periodically, the usage amount is large, and the cost is high; (2) The chemical nickel plating scrapped liquid is large in liquid amount, high in nickel content, high in wastewater treatment difficulty and extremely high in comprehensive treatment cost; (3) The chemical nickel plating has the advantages that various performances are reduced along with the aging of the liquid medicine, the stability is also poor, the management and the maintenance are complex, and the requirement is high; (4) The chemical nickel plating is spontaneous reduction deposition, the deposition speed is slow, the plating time is long, and the production efficiency is low. Therefore, the conventional combination method of cyanide-free copper plating bottoming and chemical nickel plating cannot be widely popularized and applied because the comprehensive cost is too high and the method is only applied to a few markets with high-end requirements.
The nickel plating method adopts the nano nickel plating process to replace the traditional chemical nickel plating process, so that the advantages of the chemical nickel plating process are maintained, the nano nickel plating process is electrified and supported, the deposition speed is higher, the nickel plating time can be shortened, the production benefit is improved, and the use cost is greatly reduced.
The nickel plating method is used for replacing a combination method of cyanide-free copper plating bottoming and chemical nickel plating in the existing process flow, can improve the corrosion resistance of deep holes or low-current areas of zinc alloy products, shortens the time of nickel plating, improves the production benefit, can overcome the defects of the existing chemical nickel plating, and meets the environmental protection trend requirements of energy conservation and consumption reduction.
The nickel plating method adopts the combination of cyanide-free copper plating bottoming and nano nickel plating, wherein the nano nickel plating liquid medicine is used for enabling a nickel plating layer to be rapidly and uniformly deposited on any surface of zinc alloy under the combined action of external current and spontaneous reduction, has the advantage of high nickel plating deposition speed and the advantage of 100% dispersibility of chemical nickel plating, and thus has the advantage of improving the corrosion resistance of a low current area. However, the nano nickel plating liquid medicine has the advantage of nickel plating, and irreversible aging does not occur, so that periodic scrapping and updating are not needed, the waste water amount is small, the nickel content is low, the comprehensive treatment is relatively simple, the cost is low, the management and maintenance are simple, and the performance is more stable. Not only can improve the corrosion resistance of a low-current area, but also can improve the production efficiency, overcome the defects of the existing chemical nickel plating liquid medicine, greatly reduce the use cost, and is suitable for general popularization and application.
The nickel plating method adopts the combination of cyanide-free copper plating bottoming and nano nickel plating, on one hand, by utilizing the combined action of externally applied current and spontaneous reduction, not only the corrosion resistance of a plating layer in a low current area is improved, but also the deposition speed of nickel is improved, and the defects of low chemical nickel plating deposition speed, long plating time and low production efficiency are overcome. On the other hand, due to the characteristic of the nickel electroplating liquid, scrapping and updating are not needed, the waste water amount is small, and the treatment is relatively simple. Furthermore, the management and maintenance are simple, the liquid medicine performance is stable, the key use cost is low, and the large-scale application is easy.
According to some embodiments of the invention, the temperature of the nano nickel plating solution is 40 ℃ to 50 ℃.
According to some embodiments of the invention, the pH of the nano nickel plating solution is 7.0-9.0.
According to some embodiments of the invention, the pH of the nano nickel plating solution is 7.5-9.0.
According to some embodiments of the invention, the pH of the nano nickel plating solution is 8.0-9.0.
According to some embodiments of the invention, the cathodic current density of the electroplating treatment is 1.0A/dm 2～5.0A/dm2.
According to some embodiments of the invention, the cathodic current density of the electroplating treatment is 2.0A/dm 2～5.0A/dm2.
According to some embodiments of the invention, the cathodic current density of the electroplating treatment is 3.0A/dm 2～5.0A/dm2.
According to some embodiments of the invention, the electroplating treatment is for a period of time ranging from 5 minutes to 20 minutes.
According to some embodiments of the invention, the electroplating treatment is for a time period of 10min to 20min.
According to some embodiments of the invention, the nano nickel plated anode plate is a stainless steel plate.
In the step S1, the pretreatment comprises hot dip degreasing, ultrasonic degreasing, cathodic electrolytic degreasing, acid activation and cyanide-free copper plating priming.
The hot dip degreasing function is to clean grease and dirt on the surface of the material.
The agent for hot dip degreasing is RS-15B degreasing agent with the concentration of about 60g/L.
The temperature of hot dip degreasing is 50-60 ℃ and the time is about 10min.
The ultrasonic degreasing function is to clean grease and dirt in the deep hole of the material.
The agent for ultrasonic degreasing is RS-15B degreasing agent with the concentration of about 30g/L.
The temperature of ultrasonic degreasing is 50-60 ℃ and the time is about 3min.
The cathode electrolysis degreasing function is to utilize hydrogen generated by cathode electrolysis to promote the surface to be cleaner.
The agent for cathodic electrolytic degreasing is RH-368 electrolytic degreasing agent with the concentration of about 55g/L.
The temperature of the cathode electrolysis degreasing is 20-35 ℃ and the time is about 1min. The cathode current density is about 2.0A/dm 2, and the anode plate is a stainless steel plate.
The acid activation is used for activating surface metal or plating layers, so that the bonding force between the plating layers is better.
The acid activation is prepared by 98% concentrated sulfuric acid according to the proportion of 80mL/L, the temperature of the acid activation is 25-35 ℃ and the time is about 10s.
The cyanide-free copper plating bottoming is used for bottoming a plating layer of a zinc alloy material, and good binding force between the base material and the plating layer is ensured.
The bath preparation for cyanide-free copper plating priming is 500mL/L RP-9964Mu.
The supplement for cyanide-free copper plating priming was 80mL/L RP-9964A.
The temperature of the cyanide-free copper plating bottoming is 50-60 ℃. The pH value is 9.0-9.5, the time is about 20min, and the cathode current density is 2.0-2.5A/dm 2. The thickness of the copper layer is 6-7 mu m.
In step S2, copper plating includes pyrophosphate copper plating and acid copper plating.
The effect of the pyrophosphate copper plating is to increase the thickness of the plating layer at the deep hole.
The pyrophosphate copper plating reagent includes: about 85g/L copper pyrophosphate, about 310g/L potassium pyrophosphate, about 3mL/L ammonia (28%) and about 2mL/L of a gloss agent RP-951.
The temperature of the pyrophosphate copper plating is 55-60 ℃. The pH value is 8.5-9.0, the time is about 20min, and the cathode current density is about 5A/dm 2.
The acid copper plating is used for obtaining high-filling and high-gloss appearance texture on the surface and reducing surface defects of a plating layer.
The acid copper plating reagent includes: about 200g/L copper sulfate (CuSO 4·5H2 O), about 70g/L sulfuric acid (H 2SO4) (98%), about 100mg/L chloride ion, about 8mL/L bath agent RP-9811Mu, about 0.4mL/L gloss agent RP-9811A, about 0.4mL/L leveler RP-9811B.
The temperature of the acid copper plating is 24-26 ℃ and the time is about 20min, and the cathode current density is about 4.0A/dm 2. The thickness of the copper layer is 20-25 mu m.
In step S2, the post-treatment comprises semi-gloss nickel plating, full-gloss nickel plating, decorative chrome plating, hot water washing and drying.
The semi-gloss nickel plating has the function of forming potential difference with the full gloss nickel layer, and can obviously improve the overall corrosion resistance.
The semi-gloss nickel plating reagent includes: about 280g/L nickel sulfate (NiSO 4·6H2 O), about 50g/L nickel chloride (NiCl 2·6H2 O), about 50g/L boric acid (H 3BO3), about 6.0mL/L bath agent RN-3110Mu, about 0.7mL/L gloss agent RN-3110A, about 0.4mL/L wetting agent RN-664.
The semi-gloss nickel plating temperature is 50-60 ℃, the pH is 3.5-4.2, the time is about 20min, and the cathode current density is about 4.0A/dm 2. The thickness of the nickel layer is 18-25 mu m.
The full gloss nickel plating is used for achieving the appearance effect of high brightness and high filling texture on the surface.
The full gloss nickel plating reagent includes: about 280g/L nickel sulfate (NiSO 4·6H2 O), about 50g/L nickel chloride (NiCl 2·6H2 O), about 50g/L boric acid (H 3BO3), about 6.0mL/L gloss agent RN-8605, about 0.4mL/L softener RN-6702PT, about 0.6mL/L wetting agent RN-7625.
The full gloss nickel plating temperature is 50-60 ℃, the pH is 4.4-4.8, the time is about 20min, and the cathode current density is about 4.0A/dm 2. The thickness of the nickel layer is 18-25 mu m.
The function of decorative chrome plating is to make the surface obtain the appearance effect of silver and white band blue, and improve the wear resistance and corrosion resistance of the surface.
The agent for decorating chrome plating comprises: about 200g/L chromic acid, about 0.5g/L sulfuric acid (H2 SO 4) (98%), about 15mL/L additive RM-88B.
The temperature of the decorative chrome plating is 30-40 ℃, the time is about 3min, and the cathode current density is about 8.0A/dm 2. The thickness of the chromium layer is 0.15-0.25 mu m.
The hot water washing function is to clean the surface more cleanly. The temperature of hot water washing is 25-35 ℃ and the time is 10-15 s.
The effect of the drying is to make the surface coating sufficiently dry. The temperature of the drying is 100-110 ℃ and the time is 15-20 min.
The above-mentioned RS-15B degreasing agent, RH-368 electrolytic degreasing agent, RP-9964Mu (bath agent), RP-9964A (supplement), RP-9811Mu (bath agent), RP-9811A (gloss agent), RP-9811B (smoothing agent), RN-3110Mu (bath agent), RN-3110A (gloss agent), RN-664 (wetting agent), RN-8605 (gloss agent), RN-6702PT (softening agent), RN-7625H (wetting agent) and RM-88B (additive) are commercially available, and they can be purchased from Jiang Menshi Rayleigh engineering Co.
Detailed Description
The following are specific embodiments of the present invention, and the technical solutions of the present invention will be further described with reference to the embodiments, but the present invention is not limited to these embodiments.
In some embodiments of the present invention, there is provided a nickel plating method including the steps of:
S1: immersing the pretreated workpiece into nano nickel plating liquid to carry out electroplating treatment, so as to obtain a nickel plating piece;
S2: and carrying out copper plating and post-treatment on the nickel-plated piece.
Wherein the temperature of the nano nickel plating liquid medicine is 40-50 ℃.
The pH value of the nano nickel plating liquid medicine is 7.0-9.0.
The pH of the nano nickel plating solution is 7.5-9.0, preferably 8.0-9.0.
The cathode current density of the plating treatment is 1.0A/dm 2～5.0A/dm2, preferably 2.0A/dm 2～5.0A/dm2, and more preferably 3.0A/dm 2～5.0A/dm2.
The time of the electroplating treatment is 5 min-20 min, preferably 10 min-20 min.
The anode plate treated by nano nickel plating electroplating is a stainless steel plate.
Specifically, in step S1, the pretreatment includes hot dip degreasing, ultrasonic degreasing, cathodic degreasing, acid activation, and cyanide-free copper plating priming.
Among them, it is understood that the hot dip degreasing functions to clean grease and dirt on the surface of the material.
The agent for hot dip degreasing is RS-15B degreasing agent with the concentration of about 60g/L.
The temperature of hot dip degreasing is 50-60 ℃ and the time is about 10min.
It is understood that the ultrasonic degreasing function is to clean grease and dirt in the deep hole of the material.
The agent for ultrasonic degreasing is RS-15B degreasing agent with the concentration of about 30g/L.
The temperature of ultrasonic degreasing is 50-60 ℃ and the time is about 3min.
It is understood that the cathode electrolysis degreasing function is to utilize hydrogen generated by cathode electrolysis to promote the surface to be cleaner.
The agent for cathodic electrolytic degreasing is RH-368 electrolytic degreasing agent with the concentration of about 55g/L.
The temperature of the cathode electrolysis degreasing is 20-35 ℃ and the time is about 1min.
The cathode current density is about 2.0A/dm 2, and the anode plate is a stainless steel plate.
It is understood that the acid activation serves to activate the surface metal or coating to provide better adhesion between the coatings.
The acid activation is prepared by 98% concentrated sulfuric acid according to the proportion of 80mL/L, the temperature of the acid activation is 25-35 ℃ and the time is about 10s.
It can be understood that the cyanide-free copper plating bottoming is used for the zinc alloy material bottoming coating, and good binding force between the base material and the coating is ensured.
The bath preparation for cyanide-free copper plating priming is 500mL/L RP-9964Mu.
The supplement for cyanide-free copper plating priming was 80mL/L RP-9964A.
The temperature of the cyanide-free copper plating bottoming is 50-60 ℃.
The pH value is 9.0-9.5, the time is about 20min, and the cathode current density is 2.0-2.5A/dm 2.
The thickness of the copper layer of the cyanide-free copper plating is 6-7 mu m.
Specifically, in step S2, copper plating includes pyrophosphate copper plating and acid copper plating.
It is understood that the effect of pyrophosphate copper plating is to increase the thickness of the plating layer at the deep hole site.
The pyrophosphate copper plating reagent includes: about 85g/L copper pyrophosphate, about 310g/L potassium pyrophosphate, about 3mL/L ammonia (28%) and about 2mL/L of a gloss agent RP-951.
The temperature of the pyrophosphate copper plating is 55-60 ℃. The pH value is 8.5-9.0, the time is about 20min, and the cathode current density is about 5A/dm 2.
It is understood that the effect of acidic copper plating is to achieve a high level and high gloss appearance of the surface while reducing surface defects in the plating.
The acid copper plating reagent includes: about 200g/L copper sulfate (CuSO 4·5H2 O), about 70g/L sulfuric acid (H 2SO4) (98%), about 100mg/L chloride ion, about 8mL/L bath agent RP-9811Mu, about 0.4mL/L gloss agent RP-9811A, about 0.4mL/L leveler RP-9811B.
The temperature of the acid copper plating is 24-26 ℃ and the time is about 20min, and the cathode current density is about 4.0A/dm 2.
The thickness of the copper layer of the acid copper plating is 20-25 mu m.
Specifically, in step S2, the post-treatment includes semi-gloss nickel plating, full-gloss nickel plating, decorative chrome plating, hot water washing, and drying.
It can be understood that the semi-gloss nickel plating has the function of forming potential difference with the full gloss nickel layer, and the overall corrosion resistance can be obviously improved.
The semi-gloss nickel plating reagent includes: about 280g/L nickel sulfate (NiSO 4·6H2 O), about 50g/L nickel chloride (NiCl 2·6H2 O), about 50g/L boric acid (H 3BO3), about 6.0mL/L bath agent RN-3110Mu, about 0.7mL/L gloss agent RN-3110A, about 0.4mL/L wetting agent RN-664.
The semi-gloss nickel plating temperature is 50-60 ℃, the pH is 3.5-4.2, the time is about 20min, and the cathode current density is about 4.0A/dm 2.
The thickness of the nickel layer of the semi-gloss nickel plating is 18-25 mu m.
It is understood that the effect of full gloss nickel plating is to give the surface an appearance effect of high brightness and high fill-in texture.
The full gloss nickel plating reagent includes:
About 280g/L of nickel sulfate (NiSO 4·6H2 O),
About 50g/L nickel chloride (NiCl 2·6H2 O),
About 50g/L boric acid (H 3BO3),
About 6.0mL/L of gloss agent RN-8605,
About 0.4mL/L of softener RN-6702PT,
About 0.6mL/L of wetting agent RN-7625.
The full gloss nickel plating temperature is 50-60 ℃, the pH is 4.4-4.8, the time is about 20min, and the cathode current density is about 4.0A/dm 2.
The thickness of the nickel layer of the full gloss nickel plating is 18-25 mu m.
It is understood that the decorative chrome plating has the function of enabling the surface to obtain the appearance effect of silver and white bands and improving the wear resistance and corrosion resistance of the surface.
The agent for decorating chrome plating comprises:
About 200g/L of chromic acid,
About 0.5g/L sulfuric acid (H 2SO4) (98%),
About 15mL/L of additive RM-88B.
The temperature of the decorative chrome plating is 30-40 ℃, the time is about 3min, and the cathode current density is about 8.0A/dm 2.
The thickness of the chromium layer for decorative chrome plating is 0.15-0.25 mu m.
It will be appreciated that the effect of hot water washing is to make the surface cleaner. The temperature of hot water washing is 25-35 ℃ and the time is 10-15 s.
It will be appreciated that the effect of the drying is to dry the surface coating sufficiently.
The temperature of the drying is 100-110 ℃ and the time is 15-20 min.
The above-mentioned RS-15B degreasing agent, RH-368 electrolytic degreasing agent, RP-9964Mu (bath agent), RP-9964A (supplement), RP-9811Mu (bath agent), RP-9811A (gloss agent), RP-9811B (smoothing agent), RN-3110Mu (bath agent), RN-3110A (gloss agent), RN-664 (wetting agent), RN-8605 (gloss agent), RN-6702PT (softening agent), RN-7625H (wetting agent) and RM-88B (additive) are commercially available, and they can be purchased from Jiang Menshi Rayleigh engineering Co.
The substrate of this example is a die-cast zinc alloy product, grade 925, 200mm long by 50mm wide by 70mm deep. The sample is a body of a brand tap of a high-end bathroom, the appearance is relatively complex, two large deep holes (the aperture is 30mm, the depth is 50 mm) are formed, an internal connection small hole (the aperture is 15mm, the depth is 30 mm) is additionally arranged, and a plating layer is difficult to plate on the deep hole position by an electroplating method without using an auxiliary anode.
The electroplating surface treatment is carried out according to the following process flow:
Hot dip degreasing, water washing, ultrasonic degreasing, water washing, cathodic electrolytic degreasing, water washing, acid activation, water washing, cyanide-free copper plating priming, water washing, nano nickel plating, water washing, acid activation, water washing, pyrophosphate copper plating, water washing, acid activation, water washing, acid copper plating, water washing, acid activation, water washing, semi-gloss nickel plating, full gloss nickel plating, water washing, acid activation, water washing, decorative chromium plating, water washing, hot water washing, drying, and performance detection (binding force and deep hole corrosion).
The above process flows, operating conditions and use of the drugs were carried out according to standard product specifications provided by the rayleigh fine chemical engineering company.
In example 1, the formula and content of the nano nickel plating liquid medicine are as follows:
the content of nickel sulfamate is 2%,
The content of ammonium citrate is 2%,
The content of potassium pyrophosphate is 1.5%,
The content of potassium carbonate is 2%,
The content of sodium phosphite is 2%,
The content of sodium benzene sulfinate is 0.03%,
The content of p-toluenesulfonamide was 0.1%,
The content of the dimethyl propynylamine is 0.02 percent,
The content of sodium ethylhexyl sulfate is 0.02%,
The content of potassium hydroxide is 1%,
The balance being water.
The conditions for electroplating treatment in the nano nickel plating liquid medicine are as follows: the temperature is 40 ℃, the time is 10min, the pH value is 8.5, the cathode current density is 3.0A/dm 2, and the anode plate is a stainless steel plate.
In example 2, the formula and content of the nano nickel plating liquid medicine are as follows:
The content of nickel sulfamate is 3.5 percent,
The content of ammonium citrate is 3.5%,
The content of potassium pyrophosphate is 3 percent,
The content of potassium carbonate is 3.5%,
The content of sodium phosphite is 1.0%,
The content of sodium benzene sulfinate is 0.035%,
The content of p-toluenesulfonamide was 0.15%,
The content of the dimethyl propynylamine is 0.025 percent,
The content of ethylhexyl sodium sulfate is 0.025%,
The content of potassium hydroxide is 2.5%,
The balance being water.
The conditions for electroplating treatment in the nano nickel plating liquid medicine are as follows: the temperature is 45 ℃, the time is 10min, the pH value is 8.0, the cathode current density is 3.0A/dm 2, and the anode plate is a stainless steel plate.
In example 3, the formulation and content of the nano nickel plating solution are as follows:
The content of nickel sulfamate is 5 percent,
The content of ammonium citrate is 5%,
The content of potassium pyrophosphate is 5 percent,
The content of potassium carbonate is 5%,
The content of sodium phosphite is 0.5%,
The content of sodium benzene sulfinate is 0.1 percent,
The content of p-toluenesulfonamide was 0.2%,
The content of the dimethyl propynylamine is 0.04 percent,
The content of ethylhexyl sodium sulfate is 0.04%,
The content of potassium hydroxide is 4%,
The balance being water.
The conditions for electroplating treatment in the nano nickel plating liquid medicine are as follows: the temperature is 50 ℃, the time is 10min, the pH value is 9.0, the cathode current density is 3.0A/dm 2, and the anode plate is a stainless steel plate.
In examples 1 to 3, the conditions of pretreatment, copper plating and post-treatment were the same.
Specifically, in step S1, the agent for the pretreatment of hot dip degreasing is RS-15B degreasing agent, and the concentration is about 60g/L.
The temperature of the hot dip degreasing is 55 ℃ and the time is about 10min.
The agent for ultrasonic degreasing is RS-15B degreasing agent with the concentration of about 30g/L.
The temperature of ultrasonic degreasing is 55 ℃ and the time is about 3min.
The agent for cathodic electrolytic degreasing is RH-368 electrolytic degreasing agent with the concentration of about 55g/L.
The temperature of the cathode electrolysis degreasing is 25 ℃ and the time is about 1min. The cathode current density is about 2.0A/dm 2, and the anode plate is a stainless steel plate.
The acid activation is prepared by adopting 98% concentrated sulfuric acid according to the proportion of 80mL/L, the temperature of the acid activation is 30 ℃, and the time is about 10s.
The bath preparation for cyanide-free copper plating priming is 500mL/L RP-9964Mu.
The supplement for cyanide-free copper plating priming was 80mL/L RP-9964A.
The temperature of the cyanide-free copper plating bottoming is 55 ℃. The pH value was 9.0, the time was about 20 minutes, and the cathode current density was 2.0A/dm 2. The copper layer thickness of the cyanide-free copper plating was 6. Mu.m.
In step S2, the pyrophosphate copper plating reagent includes: about 85g/L copper pyrophosphate, about 310g/L potassium pyrophosphate, about 3mL/L ammonia (28%) and about 2mL/L of a gloss agent RP-951.
The temperature of the pyrophosphate copper plating was 55 ℃. The pH value is 8.5, the time is about 20min, and the cathode current density is about 5A/dm 2.
The acid copper plating reagent includes: about 200g/L copper sulfate (CuSO 4·5H2 O), about 70g/L sulfuric acid (H 2SO4) (98%), about 100mg/L chloride ion, about 8mL/L bath agent RP-9811Mu, about 0.4mL/L gloss agent RP-9811A, about 0.4mL/L leveler RP-9811B.
The temperature of the acid copper plating is about 25 ℃ and the time is about 20min, and the cathode current density is about 4.0A/dm 2.
The copper layer thickness of the acid copper plating was 22. Mu.m.
In step S2, the post-treated semi-gloss nickel plating reagent includes: about 280g/L nickel sulfate (NiSO 4·6H2 O), about 50g/L nickel chloride (NiCl 2·6H2 O), about 50g/L boric acid (H 3BO3), about 6.0mL/L bath agent RN-3110Mu, about 0.7mL/L gloss agent RN-3110A, about 0.4mL/L wetting agent RN-664.
The semi-gloss nickel plating temperature was 55deg.C, pH about 3.5, time about 20min, and cathodic current density about 4.0A/dm 2. The thickness of the nickel layer of the semi-gloss nickel plating was 20. Mu.m.
The full gloss nickel plating reagent includes: about 280g/L nickel sulfate (NiSO 4·6H2 O), about 50g/L nickel chloride (NiCl 2·6H2 O), about 50g/L boric acid (H 3BO3), about 6.0mL/L gloss agent RN-8605, about 0.4mL/L softener RN-6702PT, about 0.6mL/L wetting agent RN-7625.
The full gloss nickel plating was carried out at a temperature of 55℃and a pH of 4.6 for about 20 minutes at a cathode current density of about 4.0A/dm 2. The nickel layer had a thickness of 22 μm.
The agent for decorating chrome plating comprises: about 200g/L chromic acid, about 0.5g/L sulfuric acid (H2 SO 4) (98%), about 15mL/L additive RM-88B.
The temperature of the decorative chrome plating is 35 ℃, the time is about 3min, and the cathode current density is about 8.0A/dm 2. The chromium layer had a thickness of 0.2. Mu.m.
The temperature of the hot water washing is 30 ℃ and the time is 12s.
The temperature of the drying is 100 ℃ and the time is 15min.
The above-mentioned RS-15B degreasing agent, RH-368 electrolytic degreasing agent, RP-9964Mu (bath agent), RP-9964A (supplement), RP-9811Mu (bath agent), RP-9811A (gloss agent), RP-9811B (smoothing agent), RN-3110Mu (bath agent), RN-3110A (gloss agent), RN-664 (wetting agent), RN-8605 (gloss agent), RN-6702PT (softening agent), RN-7625H (wetting agent) and RM-88B (additive) are commercially available, and they can be purchased from Jiang Menshi Rayleigh engineering Co.
Blank is directly subjected to pyrophosphate copper plating after cyanide-free copper plating bottoming. The test process flow is as follows:
Hot dip degreasing, water washing, ultrasonic degreasing, water washing, cathodic electrolytic degreasing, water washing, acid activation, water washing, cyanide-free copper plating priming, water washing, acid activation, water washing, pyrophosphate copper plating, water washing, acid activation, water washing, acid copper plating, water washing, acid activation, water washing, semi-gloss nickel plating, full gloss nickel plating, water washing, acid activation, water washing, decorative chrome plating, water washing, hot water washing, drying and performance detection (binding force and deep hole corrosion).
Comparative example 1 was conducted by using a combination of cyanide-free copper plating bottoming and electroless nickel plating, and the test process flow was:
Hot dip degreasing, water washing, ultrasonic degreasing, water washing, cathodic electrolytic degreasing, water washing, acid activation, water washing, cyanide-free copper plating priming, water washing, chemical nickel plating, water washing, acid activation, water washing, pyrophosphate copper plating, water washing, acid activation, water washing, acid copper plating, water washing, acid activation, water washing, semi-gloss nickel plating, full gloss nickel plating, water washing, acid activation, water washing, decorative chromium plating, water washing, hot water washing, drying, and performance detection (binding force and deep hole corrosion).
Wherein, the chemical nickel plating comprises the following components and operation conditions:
The liquid medicine comprises the following components:
nickel sulfate (NiSO 4·6H2 O): 20g/L;
sodium hypophosphite: 20g/L;
Sodium citrate: 50g/L;
lactic acid: 5g/L;
thiourea: 0.01g/L.
Operating conditions:
temperature: 45 ℃;
pH value: 8.0;
Time: and 10min.
At the beginning of electroless nickel plating, the sample must be plated with iron sheet, so that the electroless nickel plating can be performed normally.
Comparative example 2 is identical to comparative example 1 except that the electroless nickel plating is performed for 20 minutes, which is used to increase the thickness for comparison.
Samples prepared in examples and comparative examples were tested for binding force and corrosion resistance.
Wherein, the binding force detection adopts a thermal shock test method in GB 5270-85: baking the electroplated workpiece at 150 ℃ for 30min, taking out, immediately putting into water at room temperature for quenching, and repeatedly testing for 3 times. The plating layer was observed for bubbling or flaking.
Evaluation mode:
"goodbinding force, no bubbling;
"Deltay" represents a local bubble, and the binding force is general;
"×" indicates severe foaming and poor bonding force.
The corrosion resistance detection adopts Neutral Salt Spray (NSS) resistant time to evaluate the corrosion resistance of the whole part in the sample, and particularly, the corrosion condition of the deep hole or blind hole part after the test is observed.
The evaluation index is as follows: after the same test time, simultaneously observing the corrosion conditions of the appearance surface of the sample and the deep hole or blind hole part, and judging the corrosion severity according to the standard, wherein the higher the grade is, the better the corrosion resistance is; conversely, the lower the level, the worse the corrosion resistance, and the level value is 0 to 10.
Neutral salt spray test (NSS) was performed according to ASTM-B117.
The test solution is 50g/L NaCl solution, the pH value is 7.0-7.1, the continuous spraying is carried out, the test temperature is 35+/-1 ℃, and the spraying amount is 1-2 ml/(80 cm 2/hr).
The test piece was placed at an angle of 30 °.
The effective spray area was 0.6dm 2/pcs.
Each set of experiments tested 4pcs and the data obtained were averaged.
In order to more accurately evaluate the corrosion resistance of the deep hole or the blind hole of the sample, the deep hole or the blind hole of the sample is observed and judged by half-line cutting, and meanwhile, the front and rear comparison of neutral salt fog is also carried out. The results data were averaged for each set of 4 pcs.
The results are shown in Table 1.
Table 1 results of the test for bonding force and corrosion resistance of the samples
As can be seen from the table, the deep hole or blind hole part of the zinc alloy product has slight corrosion phenomenon after electroplating under the condition of only cyanide copper plating bottoming process, and the corrosion resistance is obviously improved after chemical nickel plating or nano nickel is added, and the appearance is slightly corroded after salt spray test, so that the zinc alloy product has very good performance. As can be seen from the comparison of the examples and the comparative examples 1 and 2, the nano nickel has a deposition rate which is obviously faster than that of the chemical nickel at the same time, and the corrosion resistance is obviously improved. The effect of the embodiment 2 of the invention is relatively optimal in view of the comprehensive production efficiency and corrosion resistance.
In the surface electroplating treatment process of the zinc alloy product, the corrosion resistance problem of deep holes or blind holes of the zinc alloy product is usually solved by adopting a combination mode of cyanide-free copper plating bottoming and chemical nickel plating, but in practical production and application, the following defects exist in the chemical nickel plating process: (1) The chemical nickel plating liquid medicine is consumed and replenished, irreversible aging can occur, all the liquid medicine must be scrapped and updated periodically, the usage amount is large, and the cost is high; (2) The chemical nickel plating scrapped liquid is large in liquid amount, high in nickel content, high in wastewater treatment difficulty and extremely high in comprehensive treatment cost; (3) The chemical nickel plating has the advantages that various performances are reduced along with the aging of the liquid medicine, the stability is also poor, the management and the maintenance are complex, and the requirement is high; (4) The chemical nickel plating is spontaneous reduction deposition, the deposition speed is slow, the plating time is long, and the production efficiency is low. Therefore, the conventional combination method of cyanide-free copper plating bottoming and chemical nickel plating cannot be widely popularized and applied because the comprehensive cost is too high and the method is only applied to a few markets with high-end requirements.
The nickel plating method adopts the nano nickel plating process to replace the traditional chemical nickel plating process, so that the advantages of the chemical nickel plating process are maintained, the nano nickel plating process is electrified and supported, the deposition speed is higher, the nickel plating time can be shortened, the production benefit is improved, and the use cost is greatly reduced.
The nickel plating method is used for replacing a combination method of cyanide-free copper plating bottoming and chemical nickel plating in the existing process flow, can improve the corrosion resistance of deep holes or low-current areas of zinc alloy products, shortens the time of nickel plating, improves the production benefit, can overcome the defects of the existing chemical nickel plating, and meets the environmental protection trend requirements of energy conservation and consumption reduction.
The nickel plating method adopts the combination of cyanide-free copper plating bottoming and nano nickel plating, wherein the nano nickel plating liquid medicine is used for enabling a nickel plating layer to be rapidly and uniformly deposited on any surface of zinc alloy under the combined action of external current and spontaneous reduction, has the advantage of high nickel plating deposition speed and the advantage of 100% dispersibility of chemical nickel plating, and thus has the advantage of improving the corrosion resistance of a low current area. However, the nano nickel plating liquid medicine has the advantage of nickel plating, and irreversible aging does not occur, so that periodic scrapping and updating are not needed, the waste water amount is small, the nickel content is low, the comprehensive treatment is relatively simple, the cost is low, the management and maintenance are simple, and the performance is more stable. Not only can improve the corrosion resistance of a low-current area, but also can improve the production efficiency, overcome the defects of the existing chemical nickel plating liquid medicine, greatly reduce the use cost, and is suitable for general popularization and application.
The nickel plating method adopts the combination of cyanide-free copper plating bottoming and nano nickel plating, on one hand, by utilizing the combined action of externally applied current and spontaneous reduction, not only the corrosion resistance of a plating layer in a low current area is improved, but also the deposition speed of nickel is improved, and the defects of low chemical nickel plating deposition speed, long plating time and low production efficiency are overcome. On the other hand, due to the characteristic of the nickel electroplating liquid, scrapping and updating are not needed, the waste water amount is small, and the treatment is relatively simple. Furthermore, the management and maintenance are simple, the liquid medicine performance is stable, the key use cost is low, and the large-scale application is easy.
The nano nickel plating liquid can replace chemical nickel plating liquid, has 100 percent dispersibility same as chemical nickel plating, can ensure that deep holes or low-current areas of zinc alloy products can be completely covered with nickel plating layers, improves the corrosion resistance of plating layers of the low-current areas, has the characteristic of only needing regular cleaning treatment and maintenance like the chemical nickel plating liquid, has no problem of needing to update plating liquid after the plating liquid is aged, and overcomes the defects of the chemical nickel plating liquid.
The nano nickel plating liquid of the invention, through reasonable design of components and combined action of external current and spontaneous reduction, enables the nickel plating layer to be deposited on any surface of zinc alloy rapidly and uniformly, has the advantage of high nickel plating deposition speed and the advantage of 100% dispersibility of chemical nickel plating, thereby improving the corrosion resistance of a low current area.
In addition, the nano nickel plating liquid medicine has the advantage of nickel plating, irreversible aging does not occur, so that the liquid medicine does not need to be scrapped and updated regularly, the waste water amount is small, the nickel content is low, the comprehensive treatment is relatively simple, the cost is low, the management and maintenance are simple, and the performance is more stable. The nano nickel plating liquid of the invention can not only improve the corrosion resistance of a low current area, but also improve the production efficiency, overcomes the defects of the existing chemical nickel plating liquid, greatly reduces the use cost, and is suitable for general popularization and application.
The nano nickel plating liquid medicine disclosed by the invention is simple in management and maintenance, stable in liquid medicine performance, low in key use cost and easy for large-scale application.
The present invention has been described in detail with reference to the embodiments, but the present invention is not limited to the embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.
Claims (2)
1. The nano nickel electroplating liquid medicine for die casting zinc alloy is characterized in that the preparation raw materials are as follows:
nickel sulfamate: 2 to 5 parts of the components,
Ammonium citrate: 2 to 5 parts of the components,
Potassium pyrophosphate: 1.5 to 5 parts of the components,
Potassium carbonate: 2 to 5 parts of the components,
Sodium phosphite: 0.5 to 2 parts of the components,
Potassium hydroxide: 1 to 4 parts of the components,
Sodium benzene sulfinate: 0.01 to 0.1 parts,
Para-toluene sulfonamide: 0.05 to 0.2 parts,
Dimethyl propynylamine: 0.01 to 0.05 parts,
Sodium ethylhexyl sulfate: 0.01 to 0.05 parts,
Water: 60-100 parts of a compound, wherein the compound comprises,
The pH value of the nano nickel electroplating liquid medicine is 7.0-9.0.
2. An electroplating method of die-casting zinc alloy is characterized by comprising the following steps:
S1: immersing the pretreated workpiece into the nano nickel electroplating liquid according to claim 1 for electroplating treatment to obtain a nickel-plated workpiece;
S2: copper plating and post-treatment are carried out on the nickel plating piece;
The temperature of the nano nickel electroplating liquid medicine is 40-50 ℃;
The cathode current density of the electroplating treatment is 1.0A/dm 2~5.0 A/dm2;
The time of the electroplating treatment is 5 min-20 min,
In the step S1, the pretreatment comprises hot dip degreasing, ultrasonic degreasing, cathodic electrolysis degreasing, acid activation and cyanide-free copper plating priming;
in step S2, the copper plating includes pyrophosphate copper plating and acid copper plating;
in the step S2, the post-treatment comprises semi-gloss nickel plating, full-gloss nickel plating, decorative chrome plating, hot water washing and drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210382610.7A CN114808050B (en) | 2022-04-13 | 2022-04-13 | Nano nickel plating liquid medicine and nickel plating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210382610.7A CN114808050B (en) | 2022-04-13 | 2022-04-13 | Nano nickel plating liquid medicine and nickel plating method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114808050A CN114808050A (en) | 2022-07-29 |
| CN114808050B true CN114808050B (en) | 2024-05-10 |
Family
ID=82534874
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210382610.7A Active CN114808050B (en) | 2022-04-13 | 2022-04-13 | Nano nickel plating liquid medicine and nickel plating method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114808050B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105483783A (en) * | 2015-10-30 | 2016-04-13 | 姜少群 | Chromium electroplating method of aluminum alloy hub |
| CN105483765A (en) * | 2015-12-16 | 2016-04-13 | 张颖 | Production method for zinc alloy zipper |
| CN105506690A (en) * | 2015-12-24 | 2016-04-20 | 张颖 | Method for plating decorative chromium by die-cast zinc alloy part |
| CN107345308A (en) * | 2017-07-08 | 2017-11-14 | 安徽雪雨洁具有限公司 | A kind of electroplating technology that made tap casting is processed by gravitation casting method |
| CN110344088A (en) * | 2019-08-26 | 2019-10-18 | 钢铁研究总院 | A kind of Deep hole electroplating nickel plating bath and preparation method thereof |
| CN110670098A (en) * | 2019-11-15 | 2020-01-10 | 贵州振华华联电子有限公司 | Method for improving quality of silicon-aluminum alloy electroplated nickel |
-
2022
- 2022-04-13 CN CN202210382610.7A patent/CN114808050B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105483783A (en) * | 2015-10-30 | 2016-04-13 | 姜少群 | Chromium electroplating method of aluminum alloy hub |
| CN105483765A (en) * | 2015-12-16 | 2016-04-13 | 张颖 | Production method for zinc alloy zipper |
| CN105506690A (en) * | 2015-12-24 | 2016-04-20 | 张颖 | Method for plating decorative chromium by die-cast zinc alloy part |
| CN107345308A (en) * | 2017-07-08 | 2017-11-14 | 安徽雪雨洁具有限公司 | A kind of electroplating technology that made tap casting is processed by gravitation casting method |
| CN110344088A (en) * | 2019-08-26 | 2019-10-18 | 钢铁研究总院 | A kind of Deep hole electroplating nickel plating bath and preparation method thereof |
| CN110670098A (en) * | 2019-11-15 | 2020-01-10 | 贵州振华华联电子有限公司 | Method for improving quality of silicon-aluminum alloy electroplated nickel |
Non-Patent Citations (1)
| Title |
|---|
| 方景礼等.《电镀添加剂理论与应用》.国防工业出版社,2006,(第1版),第121-125页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114808050A (en) | 2022-07-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10006135B2 (en) | Electroplating bath and method for producing dark chromium layers | |
| CN103132114B (en) | Wear-resistant workpiece and manufacturing method of wear-resistant coating thereof | |
| CN104775142B (en) | Super-corrosion-resistant nickel-chromium plated part and manufacturing method thereof | |
| CN102363884B (en) | Surface treatment process for zinc alloy die casting | |
| CN102691081A (en) | A kind of electroplating silver solution and electroplating method | |
| CN110592626A (en) | Cyanide-free electroplating brass liquid and use method thereof | |
| CN204589340U (en) | A kind of super anti-corrosion nickel plating-chromium parts | |
| US2658032A (en) | Electrodeposition of bright copper-tin alloy | |
| CN103806032A (en) | Cyanide-free one-step rapid copper plating process for steel wire surface | |
| CN100588750C (en) | Pyrophosphate copper plating used as grounding electroplate liquid for cyanogen-free copper plating | |
| CN114808050B (en) | Nano nickel plating liquid medicine and nickel plating method | |
| CN204585986U (en) | Nickel plating-chromium parts | |
| CN110592627B (en) | Cyanide-free imitation gold electroplating solution and magnesium alloy electroplating process thereof | |
| CN204589342U (en) | Nickel plating parts | |
| CN104775143B (en) | Multilayer super corrosion resistant nickel-chromium plated component and method of making same | |
| KR100402730B1 (en) | Method process for forming copper and nickel-plated of electrolytic plating in magnesium compound | |
| CN102644097A (en) | Preparation method of electric co-depositing zinc magnesium alloy plating layer in aqueous solution | |
| JPH10251870A (en) | Chrome plate products | |
| CN106521574A (en) | Cyanide-free copper-plated electroplating solution suitable for wide pH range and wide current density range and preparation method for cyanide-free copper-plated electroplating solution | |
| JP2678834B2 (en) | Chrome plating method for resin products | |
| JPH06240490A (en) | Corrosion resistant chromium plating | |
| CN102206840B (en) | Alkaline chloride copper-plating treatment agent and preparation method thereof | |
| CN100362141C (en) | Propanetriol non-cyanide bright copper plating liquid | |
| US3514380A (en) | Chromium plating from a fluosilicate type bath containing sodium,ammonium and/or magnesium ions | |
| CN105112949A (en) | Method for improving glossiness of aluminum alloy plated parts, aluminum alloy plated parts, and electronic device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |