CN219951208U - Plating layer structure of non-cyanide cadmium-plating silane passivation - Google Patents
Plating layer structure of non-cyanide cadmium-plating silane passivation Download PDFInfo
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- 238000007747 plating Methods 0.000 title claims abstract description 157
- 238000002161 passivation Methods 0.000 title claims abstract description 73
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 50
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 title claims description 7
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 51
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 50
- 239000011701 zinc Substances 0.000 claims abstract description 50
- 238000007789 sealing Methods 0.000 claims abstract description 39
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052802 copper Inorganic materials 0.000 claims abstract description 38
- 239000010949 copper Substances 0.000 claims abstract description 38
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 33
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 32
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000011159 matrix material Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 35
- BQVVSSAWECGTRN-UHFFFAOYSA-L copper;dithiocyanate Chemical compound [Cu+2].[S-]C#N.[S-]C#N BQVVSSAWECGTRN-UHFFFAOYSA-L 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000000758 substrate Substances 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 6
- 238000010998 test method Methods 0.000 abstract description 3
- 238000005234 chemical deposition Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 118
- 239000000126 substance Substances 0.000 description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 238000005406 washing Methods 0.000 description 16
- 238000001556 precipitation Methods 0.000 description 14
- 229910052759 nickel Inorganic materials 0.000 description 13
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 12
- 238000000151 deposition Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 238000005282 brightening Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 230000032683 aging Effects 0.000 description 7
- 239000008139 complexing agent Substances 0.000 description 7
- 230000008021 deposition Effects 0.000 description 7
- 238000009713 electroplating Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 6
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 6
- LEKPFOXEZRZPGW-UHFFFAOYSA-N copper;dicyanide Chemical compound [Cu+2].N#[C-].N#[C-] LEKPFOXEZRZPGW-UHFFFAOYSA-N 0.000 description 6
- 235000011164 potassium chloride Nutrition 0.000 description 6
- 239000001103 potassium chloride Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- NHMJUOSYSOOPDM-UHFFFAOYSA-N cadmium cyanide Chemical compound [Cd+2].N#[C-].N#[C-] NHMJUOSYSOOPDM-UHFFFAOYSA-N 0.000 description 5
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 4
- -1 hydroxyl graphene Chemical compound 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000011550 stock solution Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 3
- 229940074439 potassium sodium tartrate Drugs 0.000 description 3
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 3
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- FJMNNXLGOUYVHO-UHFFFAOYSA-N aluminum zinc Chemical compound [Al].[Zn] FJMNNXLGOUYVHO-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound 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 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- BIABJQLRIVAXSJ-UHFFFAOYSA-N aluminum;tricyanide Chemical compound [Al+3].N#[C-].N#[C-].N#[C-] BIABJQLRIVAXSJ-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000012224 working solution Substances 0.000 description 1
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- Chemically Coating (AREA)
Abstract
The utility model discloses a plating layer structure of cyanide-free cadmium plating silane passivation, which comprises an aluminum alloy matrix, and an electroless zinc plating layer, a cyanide-free copper plating layer, a cyanide-free cadmium plating layer, a silane passivation layer and a graphene sealing layer which are sequentially prepared on the aluminum alloy matrix from inside to outside. The plating layer structure of the cyanide-free cadmium-plating silane passivation disclosed by the utility model has excellent corrosion resistance, and the binding force of the plating layer meets the requirements of GB/T5270-2005 standard of test method comment on the adhesion strength of a metal covering layer and a chemical deposition layer on a metal substrate. The preparation process is environment-friendly and has good application prospect.
Description
Technical Field
The utility model belongs to the field of metal electroplating, and particularly relates to a plating layer structure for passivation of cyanide-free cadmium plating silane.
Background
The traditional process of electroplating the aluminum alloy part comprises the steps of sequentially preparing plating layers such as a electroless zinc plating layer, a cyanide copper plating layer and the like on an aluminum alloy substrate. With cyanide being tightly regulated, the industry has developed a new process that replaces cyanide copper plating with electroless nickel.
The utility model patent with the publication number of CN 204918772U discloses a plating layer structure of non-cyanide cadmium plating for aerospace parts, which comprises an aluminum alloy matrix, and an electroless zinc plating layer, an electroless nickel plating layer, a non-cyanide cadmium plating layer and a hexavalent chromium passivation layer which are sequentially prepared on the aluminum alloy matrix. Currently, aerospace enterprises typically use this process to prepare cadmium-plated layers on aluminum alloy parts.
The temperature of the electroless nickel plating working solution is generally higher than 80 ℃, and the electroless nickel plating is carried out after the electroless zinc plating of the aluminum alloy part, and the electroless nickel plating solution or the alkaline electroless nickel plating solution has different degrees of damage to the electroless zinc plating layer, so that the bonding force between the electroless nickel plating layer and the aluminum alloy substrate is not as high as that between the electroless nickel plating layer and the cyanide copper plating layer. In addition, the price of the metal nickel is 2-3 times higher than that of the metal copper, and the cost of chemical nickel plating is higher.
Due to the special technical requirements in the aerospace field, hexavalent chromium passivation technology is always adopted by aerospace enterprises to passivate cadmium plating layers, but hexavalent chromium passivation has the problem of high pollution.
The substitution of chromium-free passivation for hexavalent and trivalent chromium passivation represents a trend in modern passivation techniques. With the continuous enhancement of environmental protection requirements, development of chromium-free passivation technology for cadmium plating has attracted attention to aerospace enterprises.
Laboratory experiments show that the silane passivation layer prepared by the solvent type silane passivation agent has good corrosion resistance and self-repairing property [1] The passivation technology is used for preparing a high corrosion resistance protective layer of the metal part, and good environmental benefit and social benefit are obtained. However, outdoor tests show that the aging resistance of the passivation layer is not high, white powdery substances are generated on the surface of the passivation layer after the passivation layer is placed for 1 year in the open air, and the aging phenomenon occurs. The corrosion resistance of the passivation layer gradually decreases after aging, which results in shortened service life of the device and parts.
Preparation of pre-copper plating on metal surfaces such as steel by cyanide-free copper plating instead of cyanide copper plating has been studied for many years, butThe binding force problem between the coating and the matrix can not be solved well [2] . The latest developed copper plating process of the polymeric thiocyanate uses cuprous salt as main salt and sodium polymeric thiocyanate as complexing agent, the process performance of the copper plating process is close to that of cyanide copper plating, and the copper plating process is a cyanide-free copper plating process which is hopeful to replace cyanide copper plating.
Reference is made to: [1] laimen, guo Chongwu, high performance chromium-free passivation technique [ J ], electroplating and environmental protection, 2012, 32 (6): 35-37. [2] Qin Zuzu, li Jiansan, xu Jinlai, national and international advances in cyanide-free copper plating process research [ J ], electroplating and finishing, 2015, 34 (3): 149-152.
Disclosure of Invention
In order to solve the high pollution problem of hexavalent chromium passivation of a cadmium plating layer and overcome the technical defect of poor ageing resistance of a silane passivation layer, the utility model provides a plating layer structure of non-cyanide cadmium plating silane passivation. In order to achieve the above purpose, the utility model adopts the following technical scheme:
the plating layer structure comprises an aluminum alloy matrix, and an electroless zinc plating layer, a cyanide-free copper plating layer, a cyanide-free cadmium plating layer, a silane passivation layer and a graphene sealing layer which are sequentially prepared on the aluminum alloy matrix from inside to outside;
the silane passivation layer is prepared by adopting a solvent type silane passivating agent;
the thickness of the silane passivation layer is 0.3-1.2 mu m.
Preferably, the cyanide-free copper plating layer is prepared by adopting a polymerized thiocyanate copper plating process, and the thickness of the plating layer is 3-10 mu m.
Preferably, the thickness of the cyanide-free cadmium plating layer is 8-25 μm.
Preferably, the thickness of the graphene sealing layer is 0.5-2.5 μm.
Compared with the prior art, the utility model has the following beneficial effects:
1. the plating layer structure of the cyanide-free cadmium plating silane passivation disclosed by the utility model adopts a silane passivating agent to replace the existing hexavalent chromium passivating agent with high toxicity, so that the problem of high pollution caused by using hexavalent chromium passivation is solved;
2. the hydroxyl graphene modified sealing agent is adopted to seal the silane passivation layer, so that the technical defect of poor ageing resistance of the silane passivation layer is overcome;
3. the utility model uses the polymerized thiocyanate copper plating to replace chemical nickel plating to prepare the pre-copper plating layer on the surface of the aluminum alloy, thereby reducing the production cost.
Drawings
The accompanying drawings, which are included to provide a further understanding of the utility model and constitute a part of this specification, are incorporated in and constitute a part of this specification and do not limit the utility model in any way, and in which:
fig. 1 is a schematic diagram of the plating structure of examples 1 and 2 of the present utility model.
Description of the embodiments
The present utility model will now be described in detail with reference to the drawings and the specific embodiments thereof, wherein the exemplary embodiments and descriptions of the present utility model are provided for illustration of the utility model and are not intended to be limiting.
A plating layer structure of cyanide-free cadmium plating silane passivation comprises an aluminum alloy matrix, and an electroless zinc plating layer, a cyanide-free copper plating layer, a cyanide-free cadmium plating layer, a silane passivation layer and a graphene sealing layer which are sequentially prepared on the aluminum alloy matrix from inside to outside.
The prior pretreatment process is adopted to remove wax, oil, scale and activate the aluminum alloy workpiece.
And preparing a chemical zinc-depositing layer by adopting the existing chemical zinc-depositing process after the pretreatment of the aluminum alloy workpiece.
Preferably, the chemical zinc precipitation layer is prepared by adopting an AZIN-113 acidic aluminum upper zinc precipitation process in the super-bonding chemical industry: 50-250 mL/L of AZIN-113 acidic aluminum zinc precipitation agent, the working temperature is 15-30 ℃, the pH range of zinc precipitation solution is 3.4-4.2, and the zinc precipitation time is 20-80 s. The prepared electroless zinc plating layer contains two components of zinc and nickel.
Preferably, the electroless zinc plating layer is prepared by adopting an ALBUME AS-699 cyanide-free aluminum electroless zinc plating process of the super-bonding chemical industry: 160-220 mL/L of ALBUME AS-699 cyanide-free aluminum zinc-plating agent, and the working temperature is 20-30 ℃ and the zinc-plating time is 60-120 s. The electroless zinc plating layer comprises two components of zinc and copper.
And preparing the cyanide-free copper plating layer by adopting a polymeric thiocyanate copper plating process after chemically depositing zinc on the aluminum alloy workpiece.
Preferably, the thickness of the cyanide-free copper plating layer is 3 to 10 μm.
Preferably, the cyanide-free copper plating layer is prepared by adopting an HT-810 polymerized thiocyanate copper plating process of Zunyi electroplating materials limited company: 100-160 g/L of polymeric sodium thiocyanate complexing agent, 17-23 g/L of polymeric cuprous thiocyanate, 8-12 g/L of potassium sodium tartrate, 1-2 mL/L of HT-810 brightening agent, 2-4 mL/L of HT-810 plating solution, 45-55 ℃ of plating bath temperature, 12-13 pH ranges of plating solution and 0.5-1.0A/dm of cathode current density 2 The cathode moves for 5-7 m/min, and the anode current density is less than or equal to 0.5A/dm 2 Oxygen-free electrolytic copper corners (or copper particles) are used as anodes.
After cyanide-free copper plating of the aluminum alloy workpiece, preparing a cyanide-free cadmium plating layer by adopting the current cyanide-free cadmium plating process.
Preferably, the thickness of the cyanide-free cadmium plating layer is 8-25 μm.
Preferably, the cyanide-free cadmium plating layer is prepared by adopting a potassium chloride cyanide-free cadmium plating process of super-bonding chemical industry: 25-35 g/L of cadmium chloride, 100-140 g/L of PULIZIER NCC-617 complexing agent, 100-140 g/L of potassium chloride, 1.5-2.5 mL/L of PULIZIER NCC-617 brightening agent, 20-30 mL/L of PULIZIER NCC-617 auxiliary agent, 8-12 mL/L of PULIZIER NCC-617 high-area brightening agent, 7-9 pH range of plating solution, 20-35 ℃ of working temperature and 0.5-1.5A/dm of cathode current density 2 The cathode moves 2-4 m/min.
After the aluminum alloy workpiece is subjected to cyanide-free cadmium plating, a silane passivation layer is prepared by adopting the current silane chromium-free passivation technology.
Preferably, the thickness of the silane passivation layer is 0.3-1.2 μm.
Preferably, the silane passivation layer is prepared from a super-bonding zinc-coated PRODICO Z-Caot 888 FL chromium-free passivating agent, and the passivation process is as follows:
passivating agent: the zinc kest PRODICO Z-Caot 888 FL is solvent, and the stock solution is used;
operating temperature: room temperature;
passivation time: 30-90 s;
and (3) drying: baking at 80-100 deg.c for 18-25 min.
Preferably, the silane passivation layer is prepared from a super-bonding zinc-cobalt-825 chromium-free passivation agent, and the passivation process is as follows:
passivating agent: the zinc-specific ZECCOAT-825 chromium-free passivating agent is solvent type, and the stock solution is used;
operating temperature: room temperature;
passivation time: 30-90 s;
and (3) drying: baking at 70-90 deg.c for 20-25 min.
And preparing a graphene sealing layer by adopting a graphene sealing process after the aluminum alloy workpiece is subjected to silane passivation.
Preferably, the thickness of the graphene blocking layer is 0.5-2.5 μm.
Preferably, the graphene sealing layer is prepared by adopting a PRODICO 480 graphene sealing process in the super-bonding chemical industry:
diluting a PRODICO 480 hydroxyl graphene modified sealing agent with water to 3 times to prepare sealing liquid;
preparing a graphene sealing layer by a dip-coating method for the aluminum alloy workpiece after silane passivation;
and (3) after the aluminum alloy workpiece is sealed, baking for 20-35 min at 70-100 ℃ to solidify the graphene sealing layer.
Examples
As shown in fig. 1, the plating structure of the cyanide-free cadmium-plating silane passivation comprises an aluminum alloy substrate 1, and an electroless zinc plating layer 2, a cyanide-free copper plating layer 3, a cyanide-free cadmium-plating layer 4, a silane passivation layer 5 and a graphene sealing layer 6 which are sequentially prepared on the aluminum alloy substrate 1 from inside to outside.
The chemical zinc precipitation layer 2 is prepared by adopting an AZIN-113 acidic aluminum upper zinc precipitation agent: 150mL/L of AZIN-113 acid aluminum zinc precipitation agent, the working temperature is 25 ℃, the pH value of zinc precipitation solution is 3.8, and the zinc precipitation time is 50s. The prepared electroless zinc plating layer contains two components of zinc and nickel.
The cyanide-free copper plating layer 3 is prepared by adopting an HT-810 polymerized thiocyanate copper plating process of Zunyi electroplating materials limited company, and the thickness of the plating layer is 6 mu m.
120g/L of polymeric sodium thiocyanate complexing agent, 19g/L of polymeric cuprous thiocyanate, 10g/L of potassium sodium tartrate, 1.5mL/L of HT-810 brightening agent, 3mL/L of HT-810 locating agent, 53 ℃ of plating bath temperature, 12.8 pH of plating solution and 0.8A/dm of cathode current density 2 The cathode was moved 5m/min and the anode current density was 0.3A/dm 2 An oxygen-free electrolytic copper corner was used as the anode.
The cyanide-free cadmium plating layer 4 is prepared by adopting a PULIZIER NCC-617 potassium chloride cyanide-free cadmium plating process in the super-bonding chemical industry, and the thickness of the plating layer is 12 mu m.
30g/L cadmium chloride, 130g/L PULIZIER NCC-617 complexing agent, 120g/L potassium chloride, 2mL/L PULIZIER NCC-617 brightening agent, 25mL/L PULIZIER NCC-617 auxiliary agent, 10mL/L PULIZIER NCC-617 high-area brightening agent, pH of plating solution of 8, working temperature of 25 ℃ and cathode current density of 1A/dm 2 The cathode was moved 3m/min.
The silane passivation layer 5 is prepared from a super-bonding zinc-coated PRODICO Z-Caot 888 FL chromium-free passivating agent, the thickness of the passivation layer is 0.8 mu m, and the passivation process is as follows:
passivating agent: the zinc kest PRODICO Z-Caot 888 FL is solvent, and the stock solution is used;
operating temperature: room temperature;
passivation time: 60s;
and (3) drying: baking at 90deg.C for 22min.
The graphene sealing layer 6 is prepared by adopting a PRODICO 480 graphene sealing process in the super-bonding chemical industry, and the thickness of the sealing layer is 1 mu m.
Diluting a PRODICO 480 hydroxyl graphene modified sealing agent with water to 3 times to prepare sealing liquid;
preparing a graphene sealing layer by a dip-coating method for the aluminum alloy workpiece after silane passivation;
and (3) baking the aluminum alloy workpiece for 30min at 80 ℃ after sealing, so that the graphene sealing layer is solidified.
The specific operation of this embodiment is divided into the following steps:
1. pretreatment: the method comprises the steps of 'chemical paraffin removal, water washing, ultrasonic paraffin removal, water washing, chemical oil removal, water washing, descaling by an aluminum alloy descaling agent, water washing, sulfuric acid activation and water washing' of an aluminum alloy workpiece substrate 1.
2. And (3) chemical zinc precipitation: the chemical zinc deposition layer 2 is prepared by carrying out 'first chemical zinc deposition, water washing, zinc removal, water washing, second chemical zinc deposition and water washing' after the pretreatment of the aluminum alloy workpiece.
3. Cyanide-free copper plating: and (3) performing copper plating with polymerized thiocyanate after chemical zinc precipitation on the aluminum alloy workpiece to prepare the cyanide-free copper plating layer 3.
4. Cadmium plating without cyanide: after cyanide-free copper plating of the aluminum alloy workpiece, "cyanide-free cadmium plating- & gt water washing- & gt light-emitting 4s in 2% nitric acid by mass fraction- & gt water washing- & gt oxidation film 10s in 5% sulfuric acid by mass fraction- & gt water washing- & gt drying" to prepare the cyanide-free cadmium plating layer 4.
5. And (3) silane passivation: the silane passivation layer 5 is prepared by performing ' silane chromium-free passivation ' after the aluminum alloy workpiece is subjected to cyanide-free cadmium plating, blowing off residual liquid drops at the bottom of the aluminum alloy workpiece by high-pressure air, and drying and curing '.
6. And (3) graphene sealing: and (3) after the silane passivation of the aluminum alloy workpiece, preparing the graphene sealing layer 6 by dipping the graphene sealing liquid, discharging from a groove, blowing off liquid drops remained at the bottom of the aluminum alloy workpiece by high-pressure air, and drying and curing.
Examples
As shown in fig. 1, the plating structure of the cyanide-free cadmium-plating silane passivation comprises an aluminum alloy substrate 1, and an electroless zinc plating layer 2, a cyanide-free copper plating layer 3, a cyanide-free cadmium-plating layer 4, a silane passivation layer 5 and a graphene sealing layer 6 which are sequentially prepared on the aluminum alloy substrate 1 from inside to outside.
The electroless zinc plating layer 2 is prepared by adopting ALBUME AS-699 non-cyanide aluminum upper zinc plating agent: ALBUME AS-699 cyanide-free aluminum zinc-depositing agent 200mL/L, working temperature 28 ℃ and zinc-depositing time 80s. The electroless zinc plating layer comprises two components of zinc and copper.
The cyanide-free copper plating layer 3 is prepared by adopting an HT-810 polymerized thiocyanate copper plating process of Zunyi electroplating materials limited company, and the thickness of the plating layer is 8 mu m.
140g/L of polymeric sodium thiocyanate complexing agent, 21g/L of polymeric cuprous thiocyanate, 10g/L of potassium sodium tartrate, 1.5mL/L of HT-810 brightening agent, 3mL/L of HT-810 locating agent, 50 ℃ of plating bath temperature, 12.8 pH of plating solution and 0.8A/dm of cathode current density 2 Cathode, cathodeMoving for 5m/min, the anode current density is 0.3A/dm 2 Oxygen-free electrolytic copper particles are used as anode.
The cyanide-free cadmium plating layer 4 is prepared by adopting a PULIZIER NCC-617 potassium chloride cyanide-free cadmium plating process in the super-bonding chemical industry, and the thickness of the plating layer is 14 mu m.
25g/L of cadmium chloride, 120g/L of NCC-617 complexing agent, 120g/L of potassium chloride, 2mL/L of NCC-617 brightening agent, 25mL/L of NCC-617 auxiliary agent, 10mL/L of PULIZIER NCC-617 high-area brightening agent, pH of plating solution of 8.5, working temperature of 30 ℃ and cathode current density of 0.8A/dm 2 The cathode was moved 4m/min.
The silane passivation layer 4 is prepared by adopting a super-bonding zinc-cobalt-825 chromium-free passivation agent, the thickness of the passivation layer is 0.8 mu m, and the passivation process is as follows:
passivating agent: the zinc-specific ZECCOAT-825 chromium-free passivating agent is solvent type, and the stock solution is used;
operating temperature: room temperature;
passivation time: 60s;
and (3) drying: baking at 80deg.C for 25min.
The graphene sealing layer 5 is prepared by adopting a PRODICO 480 graphene sealing process in the super-bonding chemical industry, and the thickness of the sealing layer is 1 mu m.
Diluting a PRODICO 480 hydroxyl graphene modified sealing agent with water to 3 times to prepare sealing liquid;
preparing a graphene sealing layer by a dip-coating method for the aluminum alloy workpiece after silane passivation;
and (3) baking the aluminum alloy workpiece for 30min at 80 ℃ after sealing, so that the graphene sealing layer is solidified.
The specific operation of this embodiment is divided into the following steps:
1. pretreatment: the method comprises the steps of 'chemical paraffin removal, water washing, ultrasonic paraffin removal, water washing, chemical oil removal, water washing, descaling by an aluminum alloy descaling agent, water washing, sulfuric acid activation and water washing' of an aluminum alloy workpiece substrate 1.
2. And (3) chemical zinc precipitation: the chemical zinc deposition layer 2 is prepared by carrying out 'first chemical zinc deposition, water washing, zinc removal, water washing, second chemical zinc deposition and water washing' after the pretreatment of the aluminum alloy workpiece.
3. Cyanide-free copper plating: and (3) performing copper plating with polymerized thiocyanate after chemical zinc precipitation on the aluminum alloy workpiece to prepare the cyanide-free copper plating layer 3.
4. Cadmium plating without cyanide: after cyanide-free copper plating of the aluminum alloy workpiece, "cyanide-free cadmium plating- & gt water washing- & gt light-emitting 4s in 2% nitric acid by mass fraction- & gt water washing- & gt oxidation film 10s in 5% sulfuric acid by mass fraction- & gt water washing- & gt drying" to prepare the cyanide-free cadmium plating layer 4.
5. And (3) silane passivation: the silane passivation layer 5 is prepared by performing ' silane chromium-free passivation ' after the aluminum alloy workpiece is subjected to cyanide-free cadmium plating, blowing off residual liquid drops at the bottom of the aluminum alloy workpiece by high-pressure air, and drying and curing '.
6. And (3) graphene sealing: and (3) after the silane passivation of the aluminum alloy workpiece, preparing the graphene sealing layer 6 by dipping the graphene sealing liquid, discharging from a groove, blowing off liquid drops remained at the bottom of the aluminum alloy workpiece by high-pressure air, and drying and curing.
Test example 1:
the non-cyanide cadmium-plated silane passivated coating structures prepared in the example 1 and the example 2 are subjected to a neutral salt spray test for 4000 hours according to GB/T10125-2021 salt spray test for artificial atmosphere corrosion test, and white corrosions are not generated on the surface of a coated part.
Test example 2:
the non-cyanide cadmium silane-passivated plating pieces prepared in example 1 and example 2 were evaluated according to GB/T5270-2005 test methods for adhesion strength of metal coating electrodeposit and chemical deposition layer on Metal substrate, and the binding force of the plating was measured by the thermal shock test method. And (3) placing the plating part in a heating furnace, heating to 220 ℃, preserving heat for 30min, taking out, placing in water at room temperature, cooling suddenly, and ensuring that the plating layer does not foam or fall off and has good bonding force.
Test example 3:
the non-cyanide cadmium silane-passivated plating pieces prepared in the examples 1 and 2 are placed in the outdoor natural environment for 2 years, and the surface of the plating layer has no aging phenomenon.
Comparative example 1:
the chemical zinc deposition layer, the cyanide-free copper plating layer, the cyanide-free cadmium plating layer and the silane passivation layer are sequentially prepared after the pretreatment of the aluminum alloy piece, the plating piece is placed in an outdoor natural environment for 1 year, white powder is generated on the surface of the plating layer, and the aging phenomenon occurs.
The foregoing has outlined the detailed description of the embodiments of the present utility model, and the detailed description of the embodiments and the embodiments of the present utility model has been provided herein by way of illustration of specific examples, which are intended to be merely illustrative of the principles of the embodiments of the present utility model. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the utility model, which are all within the scope of the utility model.
Claims (4)
1. The plating layer structure of non-cyanide cadmium-plating silane passivation is characterized in that: comprises an aluminum alloy matrix, and an electroless zinc plating layer, a cyanide-free copper plating layer, a cyanide-free cadmium plating layer, a silane passivation layer and a graphene sealing layer which are sequentially prepared on the aluminum alloy matrix from inside to outside;
the silane passivation layer is prepared by adopting a solvent type silane passivating agent;
the thickness of the silane passivation layer is 0.3-1.2 mu m.
2. The cyanide-free cadmium-plated silane-passivated plating structure of claim 1, wherein: the cyanide-free copper plating layer is prepared by adopting a polymerized thiocyanate copper plating process, and the thickness of the plating layer is 3-10 mu m.
3. The cyanide-free cadmium-plated silane-passivated plating structure of claim 1, wherein: the thickness of the cyanide-free cadmium plating layer is 8-25 mu m.
4. The cyanide-free cadmium-plated silane-passivated plating structure of claim 1, wherein: the thickness of the graphene sealing layer is 0.5-2.5 mu m.
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