CN114717614A - Electroplating solution and surface treatment method for improving corrosion resistance of stainless steel by using same - Google Patents
Electroplating solution and surface treatment method for improving corrosion resistance of stainless steel by using same Download PDFInfo
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- CN114717614A CN114717614A CN202210588606.6A CN202210588606A CN114717614A CN 114717614 A CN114717614 A CN 114717614A CN 202210588606 A CN202210588606 A CN 202210588606A CN 114717614 A CN114717614 A CN 114717614A
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- 239000010935 stainless steel Substances 0.000 title claims abstract description 62
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 62
- 238000009713 electroplating Methods 0.000 title claims abstract description 46
- 230000007797 corrosion Effects 0.000 title claims abstract description 39
- 238000005260 corrosion Methods 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000004381 surface treatment Methods 0.000 title claims abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000007747 plating Methods 0.000 claims abstract description 36
- 239000000758 substrate Substances 0.000 claims abstract description 33
- 229910001096 P alloy Inorganic materials 0.000 claims abstract description 27
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 23
- 238000002161 passivation Methods 0.000 claims abstract description 14
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims abstract description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004327 boric acid Substances 0.000 claims abstract description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 6
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 238000004140 cleaning Methods 0.000 claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- 229910000808 amorphous metal alloy Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000005238 degreasing Methods 0.000 claims 1
- 238000007598 dipping method Methods 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 10
- 230000007547 defect Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
- C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Automation & Control Theory (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention provides an electroplating solution, which comprises the following components: 150-240 g/L of nickel sulfate, 25-40 g/L of sodium sulfate, 30-50 g/L of sodium hypophosphite, 5-35 g/L of phosphorous acid, 10-50 g/L of boric acid and the balance of water. The invention also provides a surface treatment method for improving the corrosion resistance of the stainless steel, which comprises the steps of taking the stainless steel with the passivation layer removed as a substrate, immersing the substrate into a pre-plating solution for pre-nickel plating, and then putting the substrate into an electroplating solution for electroplating the nickel-phosphorus alloy. The stainless steel obtained by the invention has bright surface, compact crystallization of the plating layer, good binding force between the corrosion-resistant layer and the matrix, good corrosion resistance and longer service life in marine environment.
Description
Technical Field
The invention belongs to the technical field of electrochemical surface treatment, and particularly relates to an electroplating solution and a surface treatment method for improving the corrosion resistance of stainless steel by using the same.
Background
The 21 st century is that of the ocean and mankind has entered a new era of ocean development. Under the general open war background, the dependence of China on ocean is continuously increasing, the method is embodied in various fields of marine transportation, ocean resource development, ecological environment protection and the like, and the global ocean strategy has great strategic significance for maintaining national safety, promoting economic and environmental sustainable development and seeking new ocean management ways.
Ocean engineering materials are the basis for the development and utilization of the ocean. In recent years, with the development and use of marine resources, the demand for materials for marine engineering has been increasing. At present, the most widely applied materials in the marine environment are various carbon steel and stainless steel materials. The stainless steel has good corrosion resistance and is widely applied in various fields. However, in the marine environment containing chloride ions, the corrosion resistance of the stainless steel is reduced, and the application of the stainless steel material in the marine environment is restricted.
The structure of the amorphous material has no crystal boundary inside, the corrosion resistance is extremely high, and the electroplating of the amorphous alloy on the surface of the stainless steel is an effective means for improving the corrosion resistance of the stainless steel material. The nickel-phosphorus alloy containing more than 8wt% of phosphorus is single-phase amorphous alloy, and the nickel-phosphorus alloy is dispersed in the nickel substrate by intermetallic compounds with structures of Ni2P, Ni3P and the like, so that the obtained plating layer is compact and bright, the porosity is low, and the corrosion resistance of the matrix material can be effectively improved.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide an electroplating solution and a surface treatment method for improving the corrosion resistance of stainless steel by using the electroplating solution, and the stainless steel treated by the method has better corrosion resistance.
The invention provides an electroplating solution, which comprises the following components: 150-240 g/L of nickel sulfate, 25-40 g/L of sodium sulfate, 30-50 g/L of sodium hypophosphite, 5-35 g/L of phosphorous acid, 10-50 g/L of boric acid and the balance of water.
The invention also provides a surface treatment method for improving the corrosion resistance of stainless steel by using the electroplating solution, which comprises the following steps:
s1, preparing an electroplating solution capable of obtaining the nickel-phosphorus alloy on the surface of the stainless steel, and stirring for more than 24 hours; controlling the pH value of the electroplating solution to be 1.5-3.5;
s2, removing the passivation layer, namely, removing oil, removing rust and cleaning the stainless steel substrate, and immersing the stainless steel substrate into a hydrochloric acid solution to remove the passivation layer;
s3 pre-plating nickel, namely, immersing the stainless steel substrate without the passivation layer into a pre-plating solution for pre-plating nickel;
s4 nickel plating, namely immersing the stainless steel substrate subjected to nickel pre-plating in the electroplating solution obtained in the step S1, electroplating a nickel-phosphorus alloy corrosion-resistant layer on the stainless steel substrate, controlling the temperature of the electroplating solution to be 60-90 ℃, controlling the cathode current density to be 10-30A/dm 2, and maintaining the uniformity and stability of the electroplating solution on the cathode surface by adopting a cathode movement or air stirring mode;
and S5, taking and cleaning, namely taking out the workpiece, cleaning and drying the workpiece when the nickel-phosphorus alloy corrosion-resistant layer electroplated on the stainless steel substrate reaches the required thickness.
Optionally, the pH value of the electroplating solution in the step S1 is controlled to be 2-3.
Optionally, the concentration of the hydrochloric acid solution in step S2 is 10% to 20%, and the treatment time is 30 ± 10 seconds.
Optionally, the pre-plating solution in step S3 consists of: 150-250 g/L of nickel chloride, 150-200 ml/L of hydrochloric acid, 5-10A/dm 2 of current density, and electroplating for 30-60 seconds at room temperature, wherein the thickness of the nickel preplating layer is 0.2-1 μm.
Optionally, in step S4, the temperature of the electroplating solution is controlled to 70-80 ℃, and the cathode current density is 15-25A/dm 2.
Optionally, the thickness of the nickel-phosphorus alloy corrosion-resistant layer in step S5 is 30-100 μm.
Optionally, in step S5, the corrosion-resistant layer of the nickel-phosphorus alloy contains more than 8wt% of phosphorus, and the nickel-phosphorus alloy is a single-phase amorphous alloy.
The design idea of the invention is as follows:
the surface of the stainless steel is provided with a stable passive film, and the existence of the passive film can influence the binding force of the nickel-phosphorus alloy layer and the stainless steel matrix and the performance of a plating layer. The passivation layer is thoroughly removed before the nickel-phosphorus alloy is electroplated on the surface of the stainless steel, and a nickel layer is pre-plated between the stainless steel substrate and the nickel-phosphorus alloy layer, so that the binding force between the nickel-phosphorus alloy layer and the stainless steel substrate is improved.
The structure of the nickel-phosphorus alloy coating is related to the phosphorus content in the coating, and the single-phase amorphous alloy with better corrosion resistance can be obtained when the phosphorus content is more than 8 wt%. The pH value is a key parameter of the electroplating nickel-phosphorus alloy, and when the pH value exceeds 3.5, the content of phosphorus in the plating layer is reduced, and the corrosion resistance of the plating layer is reduced. The electroplating solution adopted by the invention comprises nickel sulfate which is used for providing a source of nickel in the plating layer, hypophosphite and phosphorous acid which are used for providing a source of phosphorus in the plating layer, the pH value of the solution is adjusted by compounding the hypophosphite and the phosphorous acid, and boric acid is used for buffering agent.
The invention has the advantages and beneficial effects that:
the nickel-phosphorus alloy corrosion-resistant layer is electroplated on the stainless steel substrate, the plating layer is compact and bright, the porosity is low, and the occurrence of cavitation erosion of the stainless steel substrate material can be effectively reduced; the coating contains more than 8wt% of phosphorus, is a single-phase amorphous alloy, has no defects such as crystal boundary and the like, and has extremely high corrosion resistance. Therefore, the corrosion resistance of the stainless steel material is greatly improved, and the service life of the stainless steel material in the marine environment is prolonged.
Drawings
FIG. 1 is a flow chart of a surface treatment method for improving corrosion resistance of stainless steel according to the present invention.
Detailed Description
The present invention is further illustrated by the following examples.
Example 1
In this embodiment, a surface treatment method for improving corrosion resistance of stainless steel includes the following steps:
s1 preparation, preparing an electroplating solution capable of obtaining the nickel-phosphorus alloy on the surface of the stainless steel, wherein the components of the electroplating solution are as follows: 180g/L of nickel sulfate, 35g/L of sodium sulfate, 32g/L of sodium hypophosphite, 8g/L of phosphorous acid, 20g/L of boric acid and the balance of water. The substances are uniformly mixed and stirred for 24 hours to prepare an electroplating solution, and the pH value of the solution is 2.5.
And S2, removing the passivation layer, namely, removing oil and rust from the stainless steel substrate, cleaning the stainless steel substrate, immersing the stainless steel substrate into dilute hydrochloric acid with the concentration of 20 percent (mass fraction) for activation treatment, and removing the surface passivation layer for 20 seconds.
S3 pre-plating nickel, namely, immersing the stainless steel substrate with the passivation layer removed into the solution for pre-plating nickel; the solution composition is: 200g/L of nickel chloride, 150ml/L of hydrochloric acid, 5A/dm2 of current density, 30 seconds of electroplating at room temperature, and the thickness of the nickel preplating layer is 0.3 mu m.
S4 nickel plating, namely immersing the stainless steel substrate subjected to nickel preplating in the electroplating solution obtained in the step S1, electroplating a nickel-phosphorus alloy corrosion-resistant layer on the stainless steel substrate, wherein the temperature of the electroplating solution is 70 ℃, the cathode current density is 15A/dm2, and the cathode surface electroplating solution is maintained to be uniform and stable by adopting a cathode movement or air stirring mode;
s5 workpiece taking and cleaning, when the thickness of the plating layer is 30 μm, the workpiece is taken out, cleaned and dried. The prepared plating layer contains 14wt% of phosphorus, and the nickel-phosphorus alloy is single-phase amorphous alloy and has no crystallization defect.
Example 2
In this embodiment, a surface treatment method for improving corrosion resistance of stainless steel includes the following steps:
s1 preparation, preparing an electroplating solution capable of obtaining the nickel-phosphorus alloy on the surface of the stainless steel, wherein the components of the electroplating solution are as follows: 210g/L of nickel sulfate, 35g/L of sodium sulfate, 16g/L of sodium hypophosphite, 12g/L of phosphorous acid, 30g/L of boric acid and the balance of water. The substances are uniformly mixed and stirred for 24 hours to prepare electroplating solution, and the pH value of the solution is 2.0.
And S2, removing the passivation layer, namely, removing oil and rust from the stainless steel substrate, cleaning the stainless steel substrate, immersing the stainless steel substrate into dilute hydrochloric acid with the concentration of 20 percent (mass fraction) for activation treatment, and removing the surface passivation layer for 20 seconds.
S3, pre-plating nickel, namely immersing the stainless steel substrate with the passivation layer removed into solution to carry out pre-plating nickel treatment; the solution composition is: 200g/L of nickel chloride, 150ml/L of hydrochloric acid, 5A/dm2 of current density, 30 seconds of electroplating at room temperature and 0.3 mu m of nickel plating layer thickness.
S4 nickel plating, namely immersing the stainless steel substrate subjected to nickel preplating in the electroplating solution obtained in the step S1, electroplating a nickel-phosphorus alloy corrosion-resistant layer on the stainless steel substrate, wherein the temperature of the electroplating solution is 70 ℃, the cathode current density is 25A/dm2, and the cathode surface electroplating solution is maintained to be uniform and stable by adopting a cathode movement or air stirring mode;
s5 taking out the workpiece for cleaning, taking out the workpiece when the thickness of the plating layer is 50 mu m, cleaning and drying. The prepared plating layer contains 9wt% of phosphorus, and the nickel-phosphorus alloy is single-phase amorphous alloy and has no crystallization defect.
The present invention has been described in relation to the above embodiments, which are only exemplary of the implementation of the present invention. It should be noted that the disclosed embodiments do not limit the scope of the invention. Rather, it is intended that the invention be covered by the appended claims without departing from the spirit and scope of the invention.
Claims (8)
1. An electroplating solution, comprising the following components: 150-240 g/L of nickel sulfate, 25-40 g/L of sodium sulfate, 30-50 g/L of sodium hypophosphite, 5-35 g/L of phosphorous acid, 10-50 g/L of boric acid and the balance of water.
2. A surface treatment method for improving corrosion resistance of stainless steel using the plating solution of claim 1, comprising the steps of:
s1, preparing an electroplating solution, stirring for more than 24 hours, and controlling the pH value of the electroplating solution to be 1.5-3.5;
s2, removing the passivation layer, namely, degreasing, derusting and cleaning the stainless steel substrate, and immersing the stainless steel substrate into a hydrochloric acid solution to remove the passivation layer of the stainless steel substrate;
s3 pre-plating nickel, namely, immersing the stainless steel substrate without the passivation layer into a pre-plating solution for pre-plating nickel;
s4 nickel plating, namely immersing the stainless steel substrate subjected to nickel pre-plating in the electroplating solution obtained in the step S1, electroplating a nickel-phosphorus alloy corrosion-resistant layer on the stainless steel substrate, controlling the temperature of the electroplating solution to be 60-90 ℃, controlling the cathode current density to be 10-30A/dm 2, and maintaining the uniformity and stability of the electroplating solution on the cathode surface by adopting a cathode movement or air stirring mode;
and S5, taking and cleaning, namely taking out the workpiece, cleaning and drying the workpiece when the nickel-phosphorus alloy corrosion-resistant layer electroplated on the stainless steel substrate reaches the required thickness.
3. The surface treatment method for improving corrosion resistance of stainless steel according to claim 2, wherein in step S1, the pH of the plating solution is controlled to 2 to 3.
4. The surface treatment method for improving corrosion resistance of stainless steel according to claim 2, wherein the hydrochloric acid solution has a concentration of 10% to 20% and a dipping time of 20 to 40 seconds in step S2.
5. The surface treatment method for improving corrosion resistance of stainless steel according to claim 2, wherein in step S3, the pre-plating solution consists of: 150-250 g/L of nickel chloride and 150-200 ml/L of hydrochloric acid, wherein the preplating current density is 5-10A/dm 2, the electroplating is carried out for 30-60 seconds at room temperature, and the thickness of the preplating layer is 0.2-1 μm.
6. The surface treatment method for improving corrosion resistance of stainless steel according to claim 2, wherein the temperature of the plating solution in step S4 is controlled to 70 to 80 ℃ and the cathode current density is 15 to 25A/dm 2.
7. The surface treatment method for improving corrosion resistance of stainless steel according to claim 2, wherein the thickness of the nickel-phosphorus alloy corrosion resistant layer in step S5 is 30 to 100 μm.
8. The surface treatment method for improving corrosion resistance of stainless steel according to claim 2, wherein the nickel-phosphorus alloy corrosion resistant layer in step S5 contains more than 8wt% of phosphorus, and the nickel-phosphorus alloy is a single-phase amorphous alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210588606.6A CN114717614A (en) | 2022-05-27 | 2022-05-27 | Electroplating solution and surface treatment method for improving corrosion resistance of stainless steel by using same |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210588606.6A CN114717614A (en) | 2022-05-27 | 2022-05-27 | Electroplating solution and surface treatment method for improving corrosion resistance of stainless steel by using same |
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|---|---|---|---|---|
| WO2003066936A2 (en) * | 2002-02-06 | 2003-08-14 | Liqun Feng | Commercial process for electroplating nickel-phosphorus coatings |
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-
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