CN112725852A - Alkaline zinc-nickel alloy electroplating solution and preparation method and electroplating process thereof - Google Patents
Alkaline zinc-nickel alloy electroplating solution and preparation method and electroplating process thereof Download PDFInfo
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- CN112725852A CN112725852A CN202011549939.5A CN202011549939A CN112725852A CN 112725852 A CN112725852 A CN 112725852A CN 202011549939 A CN202011549939 A CN 202011549939A CN 112725852 A CN112725852 A CN 112725852A
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- nickel alloy
- zinc
- polyoxyethylene ether
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- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 229910000990 Ni alloy Inorganic materials 0.000 title claims abstract description 91
- 238000009713 electroplating Methods 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 96
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 82
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 62
- 239000008139 complexing agent Substances 0.000 claims abstract description 54
- 238000002156 mixing Methods 0.000 claims abstract description 46
- 238000005282 brightening Methods 0.000 claims abstract description 45
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 40
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 40
- 239000011787 zinc oxide Substances 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 82
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 82
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 claims description 80
- 238000007747 plating Methods 0.000 claims description 52
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 32
- -1 alkyl quaternary ammonium salt Chemical class 0.000 claims description 31
- 229920002873 Polyethylenimine Polymers 0.000 claims description 18
- 150000002191 fatty alcohols Chemical class 0.000 claims description 18
- 239000012535 impurity Substances 0.000 claims description 18
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 18
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 17
- PNEBXWLVOMLIPS-UHFFFAOYSA-N benzyl pyridine-2-carboxylate Chemical compound C=1C=CC=NC=1C(=O)OCC1=CC=CC=C1 PNEBXWLVOMLIPS-UHFFFAOYSA-N 0.000 claims description 17
- AVTYONGGKAJVTE-OLXYHTOASA-L potassium L-tartrate Chemical compound [K+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O AVTYONGGKAJVTE-OLXYHTOASA-L 0.000 claims description 17
- 239000001472 potassium tartrate Substances 0.000 claims description 17
- 229940111695 potassium tartrate Drugs 0.000 claims description 17
- 235000011005 potassium tartrates Nutrition 0.000 claims description 17
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 16
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 16
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 16
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 16
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000080 wetting agent Substances 0.000 claims description 9
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 8
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 8
- 229920000858 Cyclodextrin Polymers 0.000 claims description 7
- 150000003983 crown ethers Chemical class 0.000 claims description 7
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 claims description 7
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- 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 description 5
- 229940074439 potassium sodium tartrate Drugs 0.000 claims description 5
- 239000001632 sodium acetate Substances 0.000 claims description 5
- 235000017281 sodium acetate Nutrition 0.000 claims description 5
- 229960004249 sodium acetate Drugs 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
- 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 claims description 5
- 229960001790 sodium citrate Drugs 0.000 claims description 5
- 235000011083 sodium citrates Nutrition 0.000 claims description 5
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 5
- 229960001124 trientine Drugs 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229960004418 trolamine Drugs 0.000 claims description 3
- 229910007567 Zn-Ni Inorganic materials 0.000 claims 1
- 229910007614 Zn—Ni Inorganic materials 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 claims 1
- 239000000956 alloy Substances 0.000 claims 1
- 238000005246 galvanizing Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract 2
- 238000003756 stirring Methods 0.000 description 49
- 239000011248 coating agent Substances 0.000 description 29
- 238000000576 coating method Methods 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 25
- 239000000203 mixture Substances 0.000 description 19
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 14
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 14
- 150000003457 sulfones Chemical class 0.000 description 10
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 8
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910001453 nickel ion Inorganic materials 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000003381 solubilizing effect Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical group [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 125000000373 fatty alcohol group Chemical group 0.000 description 1
- ZWGTVKDEOPDFGW-UHFFFAOYSA-N hexadecylazanium;chloride Chemical group [Cl-].CCCCCCCCCCCCCCCC[NH3+] ZWGTVKDEOPDFGW-UHFFFAOYSA-N 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ONKVOPHWLJLAIK-UHFFFAOYSA-N octan-1-ol;sodium Chemical group [Na].CCCCCCCCO ONKVOPHWLJLAIK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- HVTHJRMZXBWFNE-UHFFFAOYSA-J sodium zincate Chemical compound [OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Zn+2] HVTHJRMZXBWFNE-UHFFFAOYSA-J 0.000 description 1
- LGORLCOUTMVEAC-UHFFFAOYSA-M sodium;2-nonylphenolate Chemical group [Na+].CCCCCCCCCC1=CC=CC=C1[O-] LGORLCOUTMVEAC-UHFFFAOYSA-M 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical group COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or 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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
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 application relates to the technical field of galvanizing electroplating liquid, and particularly discloses alkaline zinc-nickel alloy electroplating liquid and a preparation method and an electroplating process thereof. An alkaline zinc-nickel alloy electroplating solution, wherein each liter of the electroplating solution mainly comprises the following raw materials: 10-20g of zinc oxide, 150g of sodium hydroxide, 15-40g of nickel sulfate, 20-50g of complexing agent, 8-15g of brightening agent and the balance of water; the preparation method comprises the following steps: 1) uniformly mixing zinc oxide, sodium hydroxide and part of water to prepare a solution A; 2) uniformly mixing a coordination agent, nickel sulfate and part of water to prepare a solution B; 3) and adding the solution B into the solution A, uniformly mixing, adding the rest water and the brightening agent, and uniformly mixing to obtain the brightening agent. The alkaline zinc-nickel alloy electroplating solution can be used for zinc-nickel alloy electroplating and has the advantage of good thermal stability.
Description
Technical Field
The application relates to the technical field of galvanizing electroplating solution, in particular to alkaline zinc-nickel alloy electroplating solution and a preparation method and an electroplating process thereof.
Background
The zinc-nickel alloy plating layer has excellent corrosion resistance which is 3-6 times that of a zinc plating layer, has excellent performances of good brightness, strong tarnish resistance, high hardness, convenient machining and the like, and is widely applied to industries such as automobiles, machining, aviation industry, instruments, electronics and the like. At present, the electroplating solution in the zinc-nickel alloy electroplating process is mainly divided into an acidic system and an alkaline system, wherein the acidic system such as a potassium chloride type electroplating solution has the advantages of stable electroplating solution, high cathode efficiency and convenient operation, but the change of current density has great influence on the formation of the plating layer, and the formed zinc-nickel alloy plating layer has poor performance in a corrosion resistance test. The plating solution of the alkaline system has good dispersibility, and the formed zinc-nickel alloy plating layer is fine and has excellent corrosion resistance. In order to increase the crystal grain density of the zinc-nickel coating and increase the brightness of the zinc-nickel alloy coating, brighteners are typically added to the electroplating bath to improve the brightness of the zinc-nickel coating. Chinese patent with application publication number CN104878418A discloses a high-stability cyanide-free alkaline zinc plating solution, which is characterized by comprising the following components: 6-14g/L of zinc ions; 90-150g/L of sodium hydroxide; 0.5-1.5mL/L of brightener; 6-20mL/L of auxiliary agent. By re-selecting and combining the main brightener, the auxiliary brightener and the carrier brightener, the coating has the effects of uniform distribution and bright surface.
In view of the above, the inventors of the present invention have considered that the cyanide-free alkaline zinc plating solution has a low cloud point of the brightener, and thus tends to cause turbidity of the plating solution, resulting in poor thermal stability of the plating solution.
Disclosure of Invention
In order to solve the problem of poor thermal stability of the electroplating solution, the application provides the alkaline zinc-nickel alloy electroplating solution and the preparation method and the electroplating process thereof.
In a first aspect, the present application provides an alkaline zinc-nickel alloy electroplating solution, which adopts the following technical scheme:
an alkaline zinc-nickel alloy electroplating solution, wherein each liter of the electroplating solution mainly comprises the following raw materials: 10-20g of zinc oxide, 150g of sodium hydroxide, 15-40g of nickel sulfate, 20-50g of complexing agent, 8-15g of brightening agent and the balance of water; the complexing agent is at least one of triethanolamine, triethylene tetramine, potassium tartrate, potassium sodium tartrate, sodium citrate and sodium acetate; the brightener consists of a main brightener, a carrier and an auxiliary brightener in a mass ratio of (0.4-0.6) to (0.2-0.3) to (0.1-0.4); the main brightening agent is at least one of furfural, pyridine, imidazole, methylimidazole and guazine; the auxiliary brightening agent is at least one of polyethyleneimine quaternary ammonium salt, benzyl pyridine carboxylate and alkyl quaternary ammonium salt; the carrier comprises polyoxyethylene ether sulfonate.
By adopting the technical scheme, the basic zinc-nickel alloy electroplating solution adopts the polyoxyethylene ether sulfonate as a brightener carrier, and the polyoxyethylene ether sulfonate can play a role in solubilizing the main brightener after being dissolved in the electrolyte, so that the dispersing capacity, the covering capacity and the penetrating capacity of the electroplating solution are improved, and the addition amount and the electrolytic consumption amount of the main brightener can be reduced; in addition, the polyoxyethylene ether sulfonate has higher cloud point, is not easy to precipitate at higher temperature, and can enlarge the working temperature range of the electroplating solution; in addition, the polyethyleneimine quaternary ammonium salt and polyoxyethylene ether sulfonate generate a compounding synergistic effect, the bright current density range of the zinc-nickel alloy coating is expanded, the uniform plating and deep plating capability of the coating is better, and the zinc-nickel alloy coating obtains a better brightness effect.
Preferably, the polyoxyethylene ether sulfonate consists of fatty alcohol polyoxyethylene ether sulfonate, alkylphenol polyoxyethylene sulfonate and phenol polyoxyethylene ether sulfonate according to the mass ratio of (0.3-0.6): (0.1-0.2): (0.05-0.1).
By adopting the technical scheme, the hydrophilic and lipophilic balance values of the fatty alcohol-polyoxyethylene ether sulfonate, the alkylphenol polyoxyethylene ether sulfonate and the phenol polyoxyethylene sulfonate are very close, and a complex synergistic effect is achieved, so that the interfacial activity of the electroplating solution can be improved, the interfacial tension of the electroplating solution is reduced, and the dispersibility and the homogeneity of the zinc-nickel alloy electroplating solution are further improved.
Preferably, the molecular number of the added ethylene oxide in the molecular chain of the polyoxyethylene ether sulfonate is 8-15.
By adopting the technical scheme, when the number of ethylene oxide molecules added on the molecular chain of the polyoxyethylene ether sulfonate is small, the critical micelle concentration of the polyoxyethylene ether sulfonate is high, and the required addition amount of the carrier is excessive, so that the unbalance of an electroplating solution system is easily caused; when the number of the ethylene oxide molecules added on the molecular chain of the polyoxyethylene ether sulfonate is more, the stability of the polyoxyethylene ether sulfonate is weakened, and when the number of the ethylene oxide molecules added on the molecular chain of the polyoxyethylene ether sulfonate is 8-15, the polyethylene oxide sulfonate has good wetting, penetrating, dispersing and solubilizing capabilities, so that the dispersion degree of the brightener in the electroplating solution is increased, and the thermal stability of the zinc-nickel alloy electroplating solution is further improved.
Preferably, the carbon chain length of the fatty alcohol in the fatty alcohol polyoxyethylene ether sulfonate is C1-C8.
By adopting the technical scheme, the fatty alcohol polyoxyethylene ether sulfonate with the carbon chain length of the fatty alcohol of C1-C8 has smaller molecular steric hindrance, is easy to arrange to form a tightly arranged oil-water interface film, effectively reduces the interfacial tension of the electroplating solution, and can be more easily dispersed in the electroplating solution.
Preferably, the carrier also comprises 1, 3-propane sultone, and the mass ratio of the 1, 3-propane sultone to the polyoxyethylene ether sulfonate is (7-8.5) to (1.5-3).
By adopting the technical scheme, the 1, 3-propane sultone forms a layer of compact resistance passive film on the surface of the electrode, the deposition rate of zinc ions and nickel ions is delayed, the crystallization of a zinc-nickel coating is refined, the brightness and the leveling capability of the coating are improved, in addition, the 1, 3-propane sultone also has certain wetting and impurity resistance capabilities, the impurity content in a zinc-nickel alloy is reduced, the corrosion resistance of the zinc-nickel alloy coating is improved, meanwhile, the 1, 3-propane sultone has better thermal stability, and generates a synergistic effect with polyoxyethylene ether sulfonate, so that the thermal stability of the electroplating solution is further improved.
Preferably, the raw materials also comprise (1.5-3) g/L of wetting agent; the wetting agent is sodium dodecyl sulfate.
By adopting the technical scheme, the sodium dodecyl sulfate can effectively reduce the surface tension of the electroplating solution, increase the wettability of the electroplating solution, quickly dissipate and discharge bubbles formed by gas generated by the cathode, effectively reduce the phenomenon of pinholes on the surface of the zinc-nickel coating and improve the flatness of the surface of the zinc-nickel coating.
Preferably, the raw materials also comprise (0.5-2) g/L of impurity removing agent, wherein the impurity removing agent is thiourea, thiosemicarbazide, cyclodextrin and crown ether which consist of (0.5-0.7) to (0.1-0.15) to (0.05-0.1) to (0.02-0.05) by mass ratio
By adopting the technical scheme, the thiourea, the thiosemicarbazide, the cyclodextrin and the crown ether have stronger metal ion affinity, the lone electron pair on the thiourea can be coordinated on an empty track of metal ions to form a complex with impurity metal ions in electroplating solution, the deposition amount of the impurity metal ions on the zinc-nickel alloy coating is reduced, and the purity of the zinc-nickel alloy coating is improved.
In a second aspect, the present application provides a method for preparing an alkaline zinc-nickel alloy electroplating solution, which adopts the following technical scheme: a preparation method of alkaline zinc-nickel alloy electroplating solution comprises the following steps:
1) uniformly mixing zinc oxide, sodium hydroxide and part of water to prepare a solution A;
2) uniformly mixing a coordination agent, nickel sulfate and part of water to prepare a solution B;
3) and adding the solution B into the solution A, uniformly mixing, adding the rest water and the brightening agent, and uniformly mixing to obtain the brightening agent.
By adopting the technical scheme, zinc oxide, sodium hydroxide and part of water are mixed to obtain a relatively uniform sodium zincate solution, the complexing agent, nickel sulfate and part of water are uniformly mixed to enable the complexing agent and nickel ions to form effective coordination, then the solution B is added into the solution A to enable the nickel ions to be uniformly dispersed in a solution system, and the solution B is uniformly mixed after the brightener and the rest water are added, so that the dispersion degree of each raw material is further improved, and the system stability of the zinc-nickel alloy electroplating solution is improved.
In a third aspect, the present application provides an electroplating process of an alkaline zinc-nickel alloy electroplating solution, which adopts the following technical scheme:
an electroplating process of alkaline zinc-nickel alloy electroplating solution, which comprises the following steps: setting the current density at 20-40 deg.c and current density of 2-3.5A/dm, anode insoluble nickel plate and cathode to be plated for 15-45 min.
By adopting the technical scheme, under the conditions that the current density is 2-3.5A/dm and the temperature is 20-40 ℃, the mass fraction of nickel in the zinc-nickel alloy coating can be maintained at about 12-15%, the zinc-nickel alloy coating has a lower self-corrosion potential, the corrosion resistance of the zinc-nickel alloy coating is better, and the content of nickel ions in the electroplating solution can be more stable due to the fact that the anode is made of the insoluble nickel plate.
In summary, the present application has the following beneficial effects:
1. adopt polyoxyethylene ether sulphonate as the brightener carrier in the alkaline zinc-nickel alloy plating solution of this application, the main brightener of cooperation can improve dispersion degree, cover ability and the infiltration ability of plating solution to improve the cloud point of brightener, enlarged the operating temperature scope of plating solution, made the zinc-nickel alloy obtain the good effect of luminance, also strengthened the thermal stability of alkaline zinc-nickel alloy plating solution simultaneously.
2. The carrier in the application is also added with 1, 3-propane sultone, so that the crystallization of the zinc-nickel alloy coating can be refined, and the brightness and leveling capability of the zinc-nickel alloy coating are further improved.
3. The sodium dodecyl sulfate is added into the alkaline zinc-nickel alloy electroplating solution, the surface tension of the electroplating solution is reduced through the sodium dodecyl sulfate, the wettability of the electroplating solution is increased, the phenomenon of pinholes on the surface of a zinc-nickel alloy coating is reduced, and the flatness of the zinc-nickel alloy coating is further improved.
Detailed Description
The present application will be described in further detail with reference to examples.
The application provides a zinc-nickel alloy plating solution, every liter plating solution mainly contains following each component raw materials: 10-20g of zinc oxide, 150g of sodium hydroxide, 15-40g of nickel sulfate, 20-50g of complexing agent, 8-15g of brightening agent and the balance of water; the complexing agent is at least one of triethanolamine, triethylene tetramine, potassium tartrate, potassium sodium tartrate, sodium citrate and sodium acetate; the brightener consists of a main brightener, a carrier and an auxiliary brightener in a mass ratio of (0.4-0.6) to (0.2-0.3) to (0.1-0.4); the main brightening agent is at least one of furfural, pyridine, imidazole, methylimidazole and guazine; the auxiliary brightening agent is at least one of polyethyleneimine quaternary ammonium salt, benzyl pyridine carboxylate and alkyl quaternary ammonium salt; the carrier comprises polyoxyethylene ether sulfonate.
Preferably, the complexing agent is composed of any one of triethanolamine and triethylene tetramine and any one of potassium tartrate, potassium sodium tartrate, sodium citrate and sodium acetate according to the mass ratio of (1-2) to (2-5). More preferably, the complexing agent is composed of any one of triethanolamine and triethylene tetramine and any one of potassium tartrate, potassium sodium tartrate, sodium citrate and sodium acetate according to the mass ratio of 1.5: 3. More preferably, the complexing agent is composed of triethanolamine and potassium tartrate according to the mass ratio of 1.5: 3.
Preferably, the main brightener is at least one of furfural, pyridine, imidazole, methylimidazole and guazine. Further preferably, the main brightener is composed of pyridine and methylimidazole according to the mass ratio of (2-5) to (1-3). Further preferably, the main brightener is composed of pyridine and methylimidazole according to the mass ratio of 3.5: 2.
Preferably, the auxiliary brightening agent is at least one of polyethyleneimine quaternary ammonium salt, benzyl pyridine carboxylate and alkyl quaternary ammonium salt. Further preferably, the anion in the polyethyleneimine quaternary ammonium salt, benzyl pyridine carboxylate and alkyl quaternary ammonium salt is chloride ion. Further preferably, the alkyl carbon chain length in the alkyl quaternary ammonium salt is C12-C18. Further preferably, the quaternary alkylammonium salt is cetylammonium chloride. Further preferably, the auxiliary brightening agent is composed of polyethyleneimine quaternary ammonium salt, benzyl pyridine carboxylate and alkyl quaternary ammonium salt according to the mass ratio of (1-2) to (2-5) to (2-3) to (1-3). Further preferably, the auxiliary brightening agent is composed of polyethyleneimine quaternary ammonium salt, benzyl pyridine carboxylate and alkyl quaternary ammonium salt according to the mass ratio of 1.5:4:2: 2.
Preferably, the polyoxyethylene ether sulfonate is fatty alcohol polyoxyethylene ether sulfonate, alkylphenol polyoxyethylene sulfonate and phenol polyoxyethylene ether sulfonate according to the mass ratio of (0.3-0.6) to (0.1-0.2) to (0.05-0.1). Preferably, the polyoxyethylene ether sulfonate is composed of fatty alcohol polyoxyethylene ether sulfonate, alkylphenol polyoxyethylene ether sulfonate and phenol polyoxyethylene ether sulfonate according to a mass ratio of 0.5:0.15: 0.07.
Further preferably, the fatty alcohol polyoxyethylene ether sulfonate, the alkylphenol polyoxyethylene ether sulfonate and the phenol polyoxyethylene ether sulfonate are sodium salts or potassium salts. Preferably, the fatty alcohol-polyoxyethylene ether is sodium n-octanol polyoxyethylene ether sulfonate, the alkylphenol polyoxyethylene ether is sodium nonylphenol polyoxyethylene ether sulfonate, and the phenol polyoxyethylene ether sulfonate is sodium phenolpolyoxyethylene ether sulfonate.
Preferably, the carrier consists of polyoxyethylene sulfonate, condensed urea and polyamine sulfone derivatives according to the mass ratio of (0.7-0.8) to (0.2-0.5) to (0.3-0.5). More preferably, the biuret is biuret. More preferably, the polyamine sulfone derivative is a polyimine sulfone. Further preferably, the polyoxyethylene sulfonate is sodium polyoxyethylene sulfonate.
Preferably, the molecular number of the ethylene oxide added in the molecular chain of the polyoxyethylene ether sulfonate is 12.
Preferably, the mass ratio of the 1, 3-propane sultone to the polyoxyethylene ether sulfonate is 2: 8.
Preferably, the wetting agent is sodium dodecyl sulfate. Further preferably, the raw material also comprises 2g/L of wetting agent.
Preferably, the impurity removing agent is thiourea, thiosemicarbazide, cyclodextrin and crown ether according to the mass ratio of (0.5-0.7): (0.1-0.15): (0.05-0.1): 0.02-0.05). More preferably, the impurity removing agent is thiourea, thiosemicarbazide, cyclodextrin and crown ether according to the mass ratio of 0.5:0.12:0.08: 0.05.
The preparation method of the alkaline zinc-nickel alloy electroplating solution comprises the following steps:
1) uniformly mixing zinc oxide, sodium hydroxide and part of water to prepare a solution A;
2) uniformly mixing a coordination agent, nickel sulfate and part of water to prepare a solution B;
3) and adding the solution B into the solution A, uniformly mixing, adding the rest water and the brightening agent, and uniformly mixing to obtain the brightening agent.
Preferably, the step 1) of uniformly mixing the zinc oxide, the sodium hydroxide and the part of water to prepare the solution A is to stir the zinc oxide and the part of water at the rotating speed of 800-; stirring sodium hydroxide and part of water at the rotation speed of 1000-.
Preferably, the step 2) of uniformly mixing the complexing agent, the nickel sulfate and the part of water to prepare the solution B is to stir the complexing agent, the nickel sulfate and the part of water at the rotation speed of 600-800rpm for 30 min.
Preferably, the step 3) of adding the solution B into the solution A and uniformly mixing, and then adding the residual water and the brightener to uniformly mix, namely adding the solution B into the solution A and then stirring at the rotation speed of 1200-1500rpm for 10min to obtain the alkaline zinc-nickel alloy electroplating solution.
The information on the main raw materials of the examples and comparative examples of the present application is shown in table 1.
TABLE 1 information on main raw materials of examples and comparative examples of the present application
Examples
Example 1
The zinc-nickel alloy electroplating solution of the embodiment is prepared from the following raw materials in parts by weight: 1kg of zinc oxide, 1.2kg of sodium hydroxide, 1.5kg of nickel sulfate, 2kg of complexing agent, 800g of brightening agent and 100kg of water.
Wherein the complexing agent consists of triethanolamine and potassium tartrate according to the mass ratio of 1.5: 3. The brightener consists of a main brightener, a carrier and an auxiliary brightener in a mass ratio of 0.4:0.2: 0.05. The main brightener is composed of pyridine and methylimidazole according to the mass ratio of 3.5: 2. The auxiliary brightening agent is composed of polyethyleneimine quaternary ammonium salt, benzyl pyridine carboxylate and alkyl quaternary ammonium salt according to the mass ratio of 1.5:4:2: 2. The carrier consists of fatty alcohol polyoxyethylene ether sulfonate, alkylphenol polyoxyethylene ether sulfonate and phenol polyoxyethylene ether sulfonate according to the mass ratio of 0.5:0.15: 0.07.
The preparation method of the alkaline zinc-nickel electroplating solution of the embodiment comprises the following steps:
1) stirring zinc oxide and part of water at the rotating speed of 800rpm for 5min to prepare a mixture C; stirring sodium hydroxide and part of water at the rotating speed of 1000rpm for 10min, cooling, adding the mixture C, and stirring at the rotating speed of 800rpm for 20 min;
2) uniformly mixing the complexing agent, the nickel sulfate and part of water to prepare a solution B, namely stirring the complexing agent, the nickel sulfate and the part of water at the rotating speed of 600rpm for 30 min;
3) adding the solution B into the solution A, uniformly mixing, then adding the residual water and the brightening agent, and uniformly mixing, namely adding the solution B into the solution A and stirring at the rotating speed of 1200rpm for 10min to obtain the composite material.
The electroplating process of the alkaline zinc-nickel alloy electroplating solution of the embodiment specifically comprises the following steps:
setting the current density at 35 deg.c and 35 deg.c, anode insoluble nickel plate, cathode to be plated and electroplating time of 30 min.
Example 2
The zinc-nickel alloy electroplating solution of the embodiment is prepared from the following raw materials in parts by weight: 2kg of zinc oxide, 1.5kg of sodium hydroxide, 4kg of nickel sulfate, 5kg of complexing agent, 1.5g of brightening agent and 100kg of water.
Wherein the complexing agent consists of triethanolamine and potassium tartrate according to the mass ratio of 1.5: 3. The brightener is prepared from a main brightener, a carrier and an auxiliary brightener in a mass ratio of 0.6: 0.3: 0.1. The main brightener is composed of pyridine and methylimidazole according to the mass ratio of 3.5: 2. The auxiliary brightening agent is composed of polyethyleneimine quaternary ammonium salt, benzyl pyridine carboxylate and alkyl quaternary ammonium salt according to the mass ratio of 1.5:4:2: 2. The carrier consists of fatty alcohol polyoxyethylene ether sulfonate, alkylphenol polyoxyethylene ether sulfonate and phenol polyoxyethylene ether sulfonate according to the mass ratio of 0.5:0.15: 0.07.
The preparation method of the alkaline zinc-nickel electroplating solution of the embodiment comprises the following steps:
1) stirring zinc oxide and part of water at the rotating speed of 1000rpm for 5min to obtain a mixture C; stirring sodium hydroxide and part of water at the rotating speed of 1500rpm for 10min, cooling, adding the mixture C, and stirring at the rotating speed of 1000rpm for 20 min;
2) uniformly mixing the complexing agent, the nickel sulfate and part of water to prepare a solution B, namely stirring the complexing agent, the nickel sulfate and the part of water at the rotating speed of 800rpm for 30 min;
3) adding the solution B into the solution A, uniformly mixing, then adding the residual water and the brightener, and uniformly mixing, namely adding the solution B into the solution A and stirring at the rotating speed of 1500rpm for 10min to obtain the water-soluble brightener.
The electroplating process of the alkaline zinc-nickel alloy electroplating solution of the embodiment specifically comprises the following steps:
setting the current density at 35 deg.c and 35 deg.c, anode insoluble nickel plate, cathode to be plated and electroplating time of 30 min.
Example 3
The zinc-nickel alloy electroplating solution of the embodiment is prepared from the following raw materials in parts by weight: 1.5kg of zinc oxide, 1.4kg of sodium hydroxide, 3kg of nickel sulfate, 3.5kg of complexing agent, 1.2kg of brightening agent and 100kg of water.
Wherein the complexing agent consists of triethanolamine and potassium tartrate according to the mass ratio of 1.5: 3. The brightener is prepared from a main brightener, a carrier and an auxiliary brightener in a mass ratio of 0.5: 0.25: 0.08 (wt. percent). The main brightener is composed of pyridine and methylimidazole according to the mass ratio of 3.5: 2. The auxiliary brightening agent is composed of polyethyleneimine quaternary ammonium salt, benzyl pyridine carboxylate and alkyl quaternary ammonium salt according to the mass ratio of 1.5:4:2: 2. The carrier is prepared from polyoxyethylene sulfonate, biuret and polyimine sulfone derivatives according to the mass ratio of 0.7: 0.2: 0.3. The polyoxyethylene ether sulfonate is composed of fatty alcohol polyoxyethylene ether sulfonate, alkylphenol polyoxyethylene ether sulfonate and phenol polyoxyethylene ether sulfonate according to the mass ratio of 0.5:0.15: 0.07.
The preparation method of the alkaline zinc-nickel electroplating solution of the embodiment comprises the following steps:
1) stirring zinc oxide and part of water at the rotation speed of 900rpm for 5min to obtain a mixture C; stirring sodium hydroxide and part of water at the rotating speed of 1200rpm for 10min, cooling, adding the mixture C, and stirring at the rotating speed of 900rpm for 20 min;
2) uniformly mixing the complexing agent, the nickel sulfate and part of water to prepare a solution B, namely stirring the complexing agent, the nickel sulfate and the part of water at the rotating speed of 600rpm for 30 min;
3) adding the solution B into the solution A, uniformly mixing, then adding the residual water and the brightener, and uniformly mixing, namely adding the solution B into the solution A and stirring at the rotating speed of 1300rpm for 10min to obtain the finished product.
The plating process of the alkaline zinc-nickel alloy plating solution of this example was the same as that of example 1.
Example 4
The zinc-nickel alloy electroplating solution of the embodiment is prepared from the following raw materials in parts by weight: 1.5kg of zinc oxide, 1.4kg of sodium hydroxide, 3kg of nickel sulfate, 3.5kg of complexing agent, 1.2kg of brightening agent and 100kg of water.
Wherein the complexing agent consists of triethanolamine and potassium tartrate according to the mass ratio of 1.5: 3. The brightener is prepared from a main brightener, a carrier and an auxiliary brightener in a mass ratio of 0.5: 0.25: 0.08 (wt. percent). The main brightener is composed of pyridine and methylimidazole according to the mass ratio of 3.5: 2. The auxiliary brightening agent is composed of polyethyleneimine quaternary ammonium salt, benzyl pyridine carboxylate and alkyl quaternary ammonium salt according to the mass ratio of 1.5:4:2: 2. The carrier is prepared from polyoxyethylene sulfonate, biuret and polyimine sulfone derivatives according to the mass ratio of 0.8: 0.5: 0.5. The polyoxyethylene ether sulfonate is composed of fatty alcohol polyoxyethylene ether sulfonate, alkylphenol polyoxyethylene ether sulfonate and phenol polyoxyethylene ether sulfonate according to the mass ratio of 0.5:0.15: 0.07.
The preparation method of the alkaline zinc-nickel electroplating solution of the embodiment comprises the following steps:
1) stirring zinc oxide and part of water at the rotation speed of 900rpm for 5min to obtain a mixture C; stirring sodium hydroxide and part of water at the rotating speed of 1200rpm for 10min, cooling, adding the mixture C, and stirring at the rotating speed of 900rpm for 20 min;
2) uniformly mixing the complexing agent, the nickel sulfate and part of water to prepare a solution B, namely stirring the complexing agent, the nickel sulfate and the part of water at the rotating speed of 600rpm for 30 min;
3) adding the solution B into the solution A, uniformly mixing, then adding the residual water and the brightener, and uniformly mixing, namely adding the solution B into the solution A and stirring at the rotating speed of 1300rpm for 10min to obtain the finished product.
The plating process of the alkaline zinc-nickel alloy plating solution of this example was the same as that of example 1.
Example 5
The zinc-nickel alloy electroplating solution of the embodiment is prepared from the following raw materials in parts by weight: 1.5kg of zinc oxide, 1.4kg of sodium hydroxide, 3kg of nickel sulfate, 3.5kg of complexing agent, 1.2kg of brightening agent and 100kg of water.
Wherein the complexing agent consists of triethanolamine and potassium tartrate according to the mass ratio of 1.5: 3. The brightener is prepared from a main brightener, a carrier and an auxiliary brightener in a mass ratio of 0.5: 0.25: 0.08 (wt. percent). The main brightener is composed of pyridine and methylimidazole according to the mass ratio of 3.5: 2. The auxiliary brightening agent is composed of polyethyleneimine quaternary ammonium salt, benzyl pyridine carboxylate and alkyl quaternary ammonium salt according to the mass ratio of 1.5:4:2: 2. The carrier is prepared from polyoxyethylene sulfonate, biuret and polyimine sulfone derivatives according to the mass ratio of 0.7: 0.2: 0.3. The polyoxyethylene ether sulfonate is composed of fatty alcohol polyoxyethylene ether sulfonate, alkylphenol polyoxyethylene ether sulfonate and phenol polyoxyethylene ether sulfonate according to the mass ratio of 0.5:0.15: 0.07.
The preparation method of the alkaline zinc-nickel electroplating solution of the embodiment comprises the following steps:
1) stirring zinc oxide and part of water at the rotation speed of 900rpm for 5min to obtain a mixture C; stirring sodium hydroxide and part of water at the rotating speed of 1200rpm for 10min, cooling, adding the mixture C, and stirring at the rotating speed of 900rpm for 20 min;
2) uniformly mixing the complexing agent, the nickel sulfate and part of water to prepare a solution B, namely stirring the complexing agent, the nickel sulfate and the part of water at the rotating speed of 600rpm for 30 min;
3) adding the solution B into the solution A, uniformly mixing, then adding the residual water and the brightener, and uniformly mixing, namely adding the solution B into the solution A and stirring at the rotating speed of 1300rpm for 10min to obtain the finished product.
The plating process of the alkaline zinc-nickel alloy plating solution of this example was the same as that of example 1.
Example 6
The zinc-nickel alloy electroplating solution of the embodiment is prepared from the following raw materials in parts by weight: 1.5kg of zinc oxide, 1.4kg of sodium hydroxide, 3kg of nickel sulfate, 3.5kg of complexing agent, 1.2kg of brightening agent and 100kg of water.
Wherein the complexing agent consists of triethanolamine and potassium tartrate according to the mass ratio of 1.5: 3. The brightener is prepared from a main brightener, a carrier and an auxiliary brightener in a mass ratio of 0.5: 0.25: 0.08 (wt. percent). The main brightener is composed of pyridine and methylimidazole according to the mass ratio of 3.5: 2. The auxiliary brightening agent is composed of polyethyleneimine quaternary ammonium salt, benzyl pyridine carboxylate and alkyl quaternary ammonium salt according to the mass ratio of 1.5:4:2: 2. The carrier is prepared from polyoxyethylene sulfonate, biuret and polyimine sulfone derivatives according to the mass ratio of 0.75: 0.35: 0.4. The polyoxyethylene ether sulfonate is composed of fatty alcohol polyoxyethylene ether sulfonate, alkylphenol polyoxyethylene ether sulfonate and phenol polyoxyethylene ether sulfonate according to the mass ratio of 0.5:0.15: 0.07.
The preparation method of the alkaline zinc-nickel electroplating solution of the embodiment comprises the following steps:
1) stirring zinc oxide and part of water at the rotation speed of 900rpm for 5min to obtain a mixture C; stirring sodium hydroxide and part of water at the rotating speed of 1200rpm for 10min, cooling, adding the mixture C, and stirring at the rotating speed of 900rpm for 20 min;
2) uniformly mixing the complexing agent, the nickel sulfate and part of water to prepare a solution B, namely stirring the complexing agent, the nickel sulfate and the part of water at the rotating speed of 600rpm for 30 min;
3) adding the solution B into the solution A, uniformly mixing, then adding the residual water and the brightener, and uniformly mixing, namely adding the solution B into the solution A and stirring at the rotating speed of 1300rpm for 10min to obtain the finished product.
The plating process of the alkaline zinc-nickel alloy plating solution of this example was the same as that of example 1.
Example 7
The zinc-nickel alloy electroplating solution of the embodiment is prepared from the following raw materials in parts by weight: 1.5kg of zinc oxide, 1.4kg of sodium hydroxide, 3kg of nickel sulfate, 3.5kg of complexing agent, 1.2kg of brightening agent and 100kg of water.
Wherein the complexing agent consists of triethanolamine and potassium tartrate according to the mass ratio of 1.5: 3. The brightener is prepared from a main brightener, a carrier and an auxiliary brightener in a mass ratio of 0.5: 0.25: 0.08 (wt. percent). The main brightener is composed of pyridine and methylimidazole according to the mass ratio of 3.5: 2. The auxiliary brightening agent is composed of polyethyleneimine quaternary ammonium salt, benzyl pyridine carboxylate and alkyl quaternary ammonium salt according to the mass ratio of 1.5:4:2: 2. The carrier is prepared from polyoxyethylene sulfonate, biuret, polyimine sulfone derivative and 1, 3-propane sultone according to the mass ratio of 0.75: 0.35: 0.4: 0.2. The polyoxyethylene ether sulfonate is composed of fatty alcohol polyoxyethylene ether sulfonate, alkylphenol polyoxyethylene ether sulfonate and phenol polyoxyethylene ether sulfonate according to the mass ratio of 0.5:0.15: 0.07.
The preparation method of the alkaline zinc-nickel electroplating solution of the embodiment comprises the following steps:
1) stirring zinc oxide and part of water at the rotation speed of 900rpm for 5min to obtain a mixture C; stirring sodium hydroxide and part of water at the rotating speed of 1200rpm for 10min, cooling, adding the mixture C, and stirring at the rotating speed of 900rpm for 20 min;
2) uniformly mixing the complexing agent, the nickel sulfate and part of water to prepare a solution B, namely stirring the complexing agent, the nickel sulfate and the part of water at the rotating speed of 600rpm for 30 min;
3) adding the solution B into the solution A, uniformly mixing, then adding the residual water and the brightener, and uniformly mixing, namely adding the solution B into the solution A and stirring at the rotating speed of 1300rpm for 10min to obtain the finished product.
The plating process of the alkaline zinc-nickel alloy plating solution of this example was the same as that of example 1.
Example 8
The zinc-nickel alloy electroplating solution of the embodiment is prepared from the following raw materials in parts by weight: 1.5kg of zinc oxide, 1.4kg of sodium hydroxide, 3kg of nickel sulfate, 3.5kg of complexing agent, 1.2kg of brightening agent, 150g of impurity removing agent and 100kg of water.
Wherein the complexing agent consists of triethanolamine and potassium tartrate according to the mass ratio of 1.5: 3. The brightener is prepared from a main brightener, a carrier and an auxiliary brightener in a mass ratio of 0.5: 0.25: 0.08 (wt. percent). The main brightener is composed of pyridine and methylimidazole according to the mass ratio of 3.5: 2. The auxiliary brightening agent is composed of polyethyleneimine quaternary ammonium salt, benzyl pyridine carboxylate and alkyl quaternary ammonium salt according to the mass ratio of 1.5:4:2: 2. The carrier is prepared from polyoxyethylene sulfonate, biuret, polyimine sulfone derivative and 1, 3-propane sultone according to the mass ratio of 0.75: 0.35: 0.4: 0.2. The polyoxyethylene ether sulfonate is composed of fatty alcohol polyoxyethylene ether sulfonate, alkylphenol polyoxyethylene ether sulfonate and phenol polyoxyethylene ether sulfonate according to the mass ratio of 0.5:0.15: 0.07. The impurity removing agent is thiourea, thiosemicarbazide, cyclodextrin and crown ether according to the mass ratio of 0.5:0.12:0.08: 0.05.
The preparation method of the alkaline zinc-nickel electroplating solution of the embodiment comprises the following steps:
1) stirring zinc oxide and part of water at the rotation speed of 900rpm for 5min to obtain a mixture C; stirring sodium hydroxide and part of water at the rotating speed of 1200rpm for 10min, cooling, adding the mixture C, and stirring at the rotating speed of 900rpm for 20 min;
2) uniformly mixing the complexing agent, the nickel sulfate and part of water to prepare a solution B, namely stirring the complexing agent, the nickel sulfate and the part of water at the rotating speed of 600rpm for 30 min;
3) adding the solution B into the solution A, uniformly mixing, then adding the residual water, the brightening agent and the impurity removing agent, and uniformly mixing, namely adding the solution B into the solution A and then stirring at the rotating speed of 1300rpm for 10min to obtain the product.
The plating process of the alkaline zinc-nickel alloy plating solution of this example was the same as that of example 1.
Example 9
The zinc-nickel alloy electroplating solution of the embodiment is prepared from the following raw materials in parts by weight: 1.5kg of zinc oxide, 1.4kg of sodium hydroxide, 3kg of nickel sulfate, 3.5kg of complexing agent, 1.2kg of brightening agent, 150g of impurity removing agent, 200g of wetting agent and 100kg of water.
Wherein the complexing agent consists of triethanolamine and potassium tartrate according to the mass ratio of 1.5: 3. The brightener is prepared from a main brightener, a carrier and an auxiliary brightener in a mass ratio of 0.5: 0.25: 0.08 (wt. percent). The main brightener is composed of pyridine and methylimidazole according to the mass ratio of 3.5: 2. The auxiliary brightening agent is composed of polyethyleneimine quaternary ammonium salt, benzyl pyridine carboxylate and alkyl quaternary ammonium salt according to the mass ratio of 1.5:4:2: 2. The carrier is prepared from polyoxyethylene sulfonate, biuret, polyimine sulfone derivative and 1, 3-propane sultone according to the mass ratio of 0.75: 0.35: 0.4: 0.2. The polyoxyethylene ether sulfonate is composed of fatty alcohol polyoxyethylene ether sulfonate, alkylphenol polyoxyethylene ether sulfonate and phenol polyoxyethylene ether sulfonate according to the mass ratio of 0.5:0.15: 0.07. The impurity removing agent is thiourea, thiosemicarbazide, cyclodextrin and crown ether according to the mass ratio of 0.5:0.12:0.08: 0.05. The wetting agent is sodium dodecyl sulfate.
The preparation method of the alkaline zinc-nickel electroplating solution of the embodiment comprises the following steps:
1) stirring zinc oxide and part of water at the rotation speed of 900rpm for 5min to obtain a mixture C; stirring sodium hydroxide and part of water at the rotating speed of 1200rpm for 10min, cooling, adding the mixture C, and stirring at the rotating speed of 900rpm for 20 min;
2) uniformly mixing the complexing agent, the nickel sulfate and part of water to prepare a solution B, namely stirring the complexing agent, the nickel sulfate and the part of water at the rotating speed of 600rpm for 30 min;
3) adding the solution B into the solution A, uniformly mixing, then adding the residual water, the brightening agent, the impurity removing agent and the wetting agent, and uniformly mixing, namely adding the solution B into the solution A and then stirring at the rotating speed of 1300rpm for 10min to obtain the product.
The plating process of the alkaline zinc-nickel alloy plating solution of this example was the same as that of example 1.
Comparative example
Comparative example 1
The alkaline zinc-nickel alloy plating bath of the comparative example was prepared from the following raw materials by weight: 1.5kg of zinc oxide, 1.4kg of sodium hydroxide, 3kg of nickel sulfate, 3.5kg of complexing agent, 1.2kg of brightening agent and 100kg of water.
Wherein the complexing agent consists of triethanolamine and potassium tartrate according to the mass ratio of 1.5: 3. The brightener is 3-methoxy-4-hydroxybenzaldehyde.
The method of preparing the alkaline zinc-nickel alloy plating bath of this comparative example was the same as example 1.
The plating process of the alkaline zinc-nickel alloy plating bath of this comparative example was the same as that of example 1.
Comparative example 2
The alkaline zinc-nickel alloy plating bath of the comparative example was prepared from the following raw materials by weight: 1kg of zinc oxide, 1.2kg of sodium hydroxide, 1.5kg of nickel sulfate, 2kg of complexing agent, 800g of brightening agent and 100kg of water.
Wherein the complexing agent consists of triethanolamine and potassium tartrate according to the mass ratio of 1.5: 3. The brightener consists of a main brightener and an auxiliary brightener in a mass ratio of 0.4: 0.05. The main brightener is composed of pyridine and methylimidazole according to the mass ratio of 3.5: 2. The auxiliary brightening agent is composed of polyethyleneimine quaternary ammonium salt, benzyl pyridine carboxylate and alkyl quaternary ammonium salt according to the mass ratio of 1.5:4:2: 2.
The method of preparing the alkaline zinc-nickel alloy plating bath of this comparative example was the same as example 1.
The plating process of the alkaline zinc-nickel alloy plating bath of this comparative example was the same as that of example 1.
Performance test
(1) The alkaline zinc-nickel alloy plating solutions of examples 1 to 9 and comparative examples 1 to 2 were subjected to a temperature stability test by measuring turbidity at different temperatures of the alkaline zinc-nickel alloy plating solutions of examples 1 to 9 and comparative examples 1 to 2 in accordance with the GB 13200-1991 standard, and the results are shown in Table 2.
TABLE 2 results of turbidity test of alkaline zinc-nickel alloy plating baths of examples 1 to 9 and comparative examples 1 to 2
(2) The alkaline zinc-nickel alloy plating solutions of examples 1 to 9 and comparative examples 1 to 2 were used to plate the article to be plated according to the above-mentioned plating process, and the brightness of the plated layer was visually examined for the article to be plated, and the examination results are shown in table 3.
TABLE 3 comparison of Brightness data for electroplated work pieces of examples 1-9 and comparative examples 1-2
| Lightness of light | |
| Example 1 | Three-stage |
| Example 2 | Three-stage |
| Example 3 | Second stage |
| Example 4 | Second stage |
| Example 5 | Second stage |
| Example 6 | First stage |
| Example 7 | First stage |
| Example 8 | First stage |
| Example 9 | First stage |
| Comparative example 1 | Four stages |
| Comparative example 2 | Four stages |
(3) The alkaline zinc-nickel alloy plating solutions of examples 1 to 9 and comparative examples 1 to 2 were used to plate the article to be plated according to the above-mentioned plating process, and the article was tested according to the GB6458-86 standard for testing neutral salt spray of metal coating, and the test results are shown in Table 4.
TABLE 4 neutral salt spray test results for plated parts
| Time h | |
| Example 1 | 256 |
| Example 2 | 271 |
| Example 3 | 321 |
| Example 4 | 523 |
| Example 5 | 536 |
| Example 6 | 548 |
| Example 7 | 563 |
| Example 8 | 577 |
| Example 9 | 583 |
| Comparative example 1 | 205 |
| Comparative example 2 | 235 |
It can be seen from comparison of examples 1-2 and comparative examples 1-2 with Table 2 that polyoxyethylene ether sulfonate has a high cloud point and good stability, and the working temperature range of the zinc-nickel alloy electroplating solution is enlarged.
Comparing example 3, example 4, example 5, example 6, example 7 and comparative examples 1-2 with tables 3 and 4, it can be seen that 1, 3-propane sultone can improve the crystal fine density of the zinc-nickel alloy, improve the brightness and leveling ability of the zinc-nickel alloy coating, and increase the corrosion resistance of the zinc-nickel alloy coating.
Comparing examples 1-7, example 8 and comparative examples 1-2 with table 4, it can be seen that the impurity removing agent can reduce the content of impurity metal ions in the zinc-nickel alloy coating, improve the purity of the zinc-nickel alloy and further increase the corrosion resistance of the zinc-nickel alloy coating.
By comparing the examples 8 and 9 with the comparative examples 1 to 2 and combining the table 3, it can be seen that the sodium dodecyl sulfate can further improve the brightness and the flatness of the zinc-nickel alloy coating, and the uniformity of the zinc-nickel alloy coating is better.
In summary, the alkaline zinc-nickel alloy electroplating solution has the advantages of large working temperature range, good thermal stability, high crystalline density of the zinc-nickel alloy coating, good brightness and high corrosion resistance.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (9)
1. The alkaline zinc-nickel alloy electroplating solution is characterized in that each liter of electroplating solution mainly comprises the following raw materials: 10-20g of zinc oxide, 150g of sodium hydroxide, 15-40g of nickel sulfate, 20-50g of complexing agent, 8-15g of brightening agent and the balance of water; the complexing agent is at least one of triethanolamine, triethylene tetramine, potassium tartrate, potassium sodium tartrate, sodium citrate and sodium acetate; the brightener consists of a main brightener, a carrier and an auxiliary brightener in a mass ratio of (0.4-0.6) to (0.2-0.3) to (0.1-0.4); the main brightening agent is at least one of furfural, pyridine, imidazole, methylimidazole and guazine; the auxiliary brightening agent is at least one of polyethyleneimine quaternary ammonium salt, benzyl pyridine carboxylate and alkyl quaternary ammonium salt; the carrier comprises polyoxyethylene ether sulfonate.
2. The alkaline zinc-nickel alloy electroplating bath as claimed in claim 1, wherein the polyoxyethylene ether sulfonate is composed of (0.3-0.6) of fatty alcohol polyoxyethylene ether sulfonate, (0.1-0.2) of alkylphenol polyoxyethylene ether sulfonate and (0.05-0.1) of phenol polyoxyethylene ether sulfonate.
3. The alkaline zinc-nickel alloy plating solution as set forth in claim 2, wherein the molecular weight of the ethylene oxide added to the molecular chain of said polyoxyethylene ether sulfonate is 8 to 15.
4. The alkaline zinc-nickel alloy electroplating bath as claimed in claim 2, wherein the fatty alcohol-polyoxyethylene ether sulfonate contains fatty alcohol with carbon chain length of C1-C8.
5. The alkaline zinc-nickel alloy plating bath according to any of the claims 1-4, wherein the carrier further comprises 1, 3-propane sultone, and the mass ratio of 1, 3-propane sultone to polyoxyethylene ether sulfonate is (7-8.5): (1.5-3).
6. The alkaline zinc-nickel alloy electroplating bath according to claim 1, wherein the raw materials further comprise (1.5-3) g/L of a wetting agent; the wetting agent is sodium dodecyl sulfate.
7. The alkaline Zn-Ni alloy electroplating bath as claimed in claim 1, wherein the raw materials further include 0.5-2g/L of an impurity removing agent, and the impurity removing agent is thiourea, thiosemicarbazide, cyclodextrin, and crown ether in a mass ratio of (0.5-0.7), (0.1-0.15), (0.05-0.1), (0.02-0.05).
8. The method for preparing an alkaline zinc-nickel alloy plating bath according to claim 1, comprising the steps of:
1) uniformly mixing zinc oxide, sodium hydroxide and part of water to prepare a solution A;
2) uniformly mixing a coordination agent, nickel sulfate and part of water to prepare a solution B;
3) and adding the solution B into the solution A, uniformly mixing, adding the rest water and the brightening agent, and uniformly mixing to obtain the brightening agent.
9. The plating process of an alkaline zinc-nickel alloy plating solution according to claim 1, wherein: the specific electroplating process is as follows: setting the current density at 20-40 deg.c and current density of 2-3.5A/dm, anode insoluble nickel plate and cathode to be plated for 15-45 min.
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| CN113862503A (en) * | 2021-09-09 | 2021-12-31 | 兴发铝业（成都）有限公司 | Corrosion-resistant and oxidation-resistant aluminum and preparation method thereof |
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Denomination of invention: An alkaline zinc nickel alloy electroplating solution, its preparation method and electroplating process Effective date of registration: 20221024 Granted publication date: 20220325 Pledgee: Zhejiang Fuyang Rural Commercial Bank Co.,Ltd. Chang'an Sub branch Pledgor: Hangzhou Jiaxing galvanizing Co.,Ltd. Registration number: Y2022980019390 |
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