CN111560633A - Method for electrodepositing Ni-P-SiC composite coating - Google Patents
Method for electrodepositing Ni-P-SiC composite coating Download PDFInfo
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- CN111560633A CN111560633A CN202010487796.3A CN202010487796A CN111560633A CN 111560633 A CN111560633 A CN 111560633A CN 202010487796 A CN202010487796 A CN 202010487796A CN 111560633 A CN111560633 A CN 111560633A
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- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
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- 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
- C25D5/18—Electroplating using modulated, pulsed or reversing current
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- 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
- C25D5/42—Pretreatment of metallic surfaces to be electroplated of light metals
- C25D5/44—Aluminium
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Abstract
The invention discloses a method for electrodepositing a Ni-P-SiC composite coating, which comprises the following steps of electroplating the Ni-P-SiC composite coating on a metal matrix, wherein the electroplating process conditions are as follows: the pH value of the electroplating solution is 3-5, the frequency of the pulse power supply is 200-2000Hz, and the duty ratio is 0.2-0.9. The coating obtained by pulse electroplating in the invention has low porosity, brightness, uniformity, compactness, good corrosion resistance and strong binding force. The quality of the plating layer obtained by pulse plating is better, so that the thickness of the plating layer can be reduced by 30-50% on the premise of the same plating layer performance, thereby saving raw materials.
Description
Technical Field
The invention relates to the field of electroplating, in particular to a method for electrodepositing a Ni-P-SiC composite coating.
Background
The electroplated chromium coating is still applied in a large amount in many important industrial fields in China due to the advantages of good finish, high hardness, strong wear resistance and corrosion resistance and the like. However, the problems of environmental pollution, health hazard and the like caused by the chromium electroplating process become chronic diseases for restricting the environment-friendly society in China. The green surface treatment technology for replacing the chromium electroplating provides a breakthrough for solving the problems, but various typical parts in the major industries of vehicle transportation, steel, mine and the like in China still lack the green technology at present.
At present, in order to improve the performances of high temperature resistance, corrosion resistance, wear resistance and the like of metal cylinder bodies, the prior surface treatment process comprises the following steps: Ni-SiC composite electroplating, hard chromium plating, micro-arc oxidation treatment, thermal spraying and the like. In the electroplating process, the existing Ni-SiC composite electroplating can improve the wear resistance, heat conductivity and lubricating oil adhesion capability of a metal matrix, but the obtained Ni-SiC composite coating has relatively low hardness and high brittleness, and the Ni-SiC composite coating is easy to fall off. In the existing hard chromium plating process, a large amount of toxic and harmful waste liquid is generated in the electroplating process, and the electroplating cost is higher.
In chinese patent CN109797413A, "Ni-P-SiC composite plating solution and method for electroplating metal substrate", a constant dc power supply is used, phosphoric acid is used in the process of preparing the plating solution, and ultrasonic stirring is used in the electroplating process, meanwhile, since the plating solution is strongly acidic and corrodes the metal surface during electroplating, secondary zinc dipping is performed on the metal surface to solve the problem of self-corrosion of the substrate in the plating solution, but the prepared Ni-P-SiC plating layer still has deficiencies in porosity, brightness, uniformity, compactness and corrosion resistance.
Disclosure of Invention
In order to solve the problems that in the prior art, a large amount of waste liquid which is difficult to treat and high in cost are generated when hard chromium is plated on the surface of metal, and a Ni-SiC composite plating layer generated in Ni-SiC composite electroplating has high brittleness, easy falling and low hardness, the invention provides a method for electrodepositing a Ni-P-SiC composite plating layer.
The purpose of the invention is realized by the following technical scheme:
a method for electrodepositing a Ni-P-SiC composite coating comprises the following steps of electroplating the Ni-P-SiC composite coating on a metal substrate, wherein the electroplating process conditions are as follows:
the pH value of the electroplating solution is 3-5, the frequency of the pulse power supply is 200-2000Hz, and the duty ratio is 0.2-0.9.
Preferably, the frequency of the pulse power supply is 600-1200Hz, and the duty ratio is 0.4-0.8.
The plating solution includes the components necessary for electroplating the Ni-P-SiC composite coating, such as a nickel source, including but not limited to NiSO4 and NiCl 2; pH adjusters, including but not limited to, perboric acid; a source of phosphorus, preferably sodium hypoborate; SiC; surfactants, including but not limited to cetyltrimethylammonium bromide; and stress relief agents including, but not limited to, fatty alcohol-polyoxyethylene ether type solutions. The stress relieving agent and the surfactant can obviously improve the internal stress of the plating layer, and can be matched with mechanical stirring, so that the uniformity of the plating solution can be ensured, and the agglomeration of SiC particles in the plating solution can be prevented.
Preferably, the specific components and contents in the electroplating solution are as follows:
the plating solution can be stirred mechanically, and the rotation speed is preferably 150-200r/min, so that SiC particles in the plating solution are uniformly dispersed, the agglomeration phenomenon is prevented, and the plating layer has better uniformity.
Preferably, the electroplating temperature is 20-70 ℃, and the current density is 1-10A/dm2The time is 60-120 min.
The metal substrate is preferably subjected to a pretreatment such as sanding and polishing and surface degreasing.
When the metal matrix is light alloy such as aluminum, magnesium and titanium, preferably, the metal surface is subjected to zinc dipping treatment twice, and the zinc dipping solution in each zinc dipping treatment comprises: 100-120g/L of sodium hydroxide, 8-12g/L of zinc oxide and 20-30mL/L of triethanolamine; the treatment temperature is 20-75 deg.C, and the current density is 1-10A/dm2The treatment time is 10-100 s.
After the composite electroplating, the plated piece can be ultrasonically cleaned by deionized water, the residual plating solution on the surface of the plated piece is removed, and then the plated piece is dried.
Compared with the prior art, the invention has the following advantages and effects:
(1) compared with other redox agents, the low-cost sodium hypophosphite has the advantages of low redox potential, low cost and stable plating solution, can well control the content of phosphorus in a plating layer, can obtain a Ni-P-SiC composite plating layer with good compactness and excellent performance in a certain concentration range, but the content of the sodium hypophosphite cannot be too high, because the discharge chance of hydrogen ions on a cathode can be increased when the content is too high, and the compounding of SiC particles is hindered.
(2) The coating obtained by pulse plating has low porosity, brightness, uniformity, compactness, good corrosion resistance and strong binding force. Through the combination of the pulse current and the use of sodium hypophosphite, the porosity of the obtained plating layer can be effectively reduced under the condition of ensuring the thickness of the thinned plating layer, so that the thickness of the plating layer can be thinned by 30-50% on the premise of the same plating layer performance, and the raw materials are saved.
Drawings
FIG. 1 is a diagram of an experimental apparatus in the example.
FIG. 2 is a bar graph of hardness of products made in accordance with examples of the invention versus different coatings.
FIG. 3 is a comparison graph of polarization curves of Ni-SiC composite coatings and Ni-P-SiC composite coatings prepared by the examples of the invention.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
(1) Pretreatment of metal substrates
Mechanically flattening and pretreating an aluminum alloy substrate with the specification of 10mm × 10mm × 1.5.5 mm, cutting an aluminum alloy blank into a sheet structure with flat surface and moderate size by using a wire cutting machine, polishing by using sand paper, and firstly using 800#Coarse grinding with sandpaper, then using 1500#Abrasive paperFinely grinding, and finally using 2000#The sand paper is finely ground until the surface is smooth and bright, and then the emery diamond polishing paste is used for polishing on a polishing machine; in order to prevent the corrosion of an acid plating solution to an aluminum alloy substrate, a zinc transition layer is deposited on the aluminum alloy by twice zinc dipping, and the zinc dipping solution comprises the following components: 110g/L of sodium hydroxide, 10g/L of zinc oxide and 25mL/L of triethanolamine. The zinc immersion treatment temperature is 25 ℃, and the current density is 2A/dm2The treatment time was 60 s. After repeated washing with ethanol, the organic matter remained on the surface of the substrate is washed by a plasma cleaning machine so as to enhance the binding force between the plating layer and the substrate.
(2) Composite electroplating
Preparing a Ni-P-SiC composite coating on the surface of the aluminum alloy substrate by adopting a device shown in figure 1, wherein the plating solution comprises the following components:
wherein, SiC particles in the plating solution are dispersed by adopting a mechanical stirring mode, and the rotating speed is 200 r/min;
the current density is 4A/dm2The pH value of the plating solution is 3.5, the frequency of a pulse power supply is 1000Hz, and the duty ratio is 0.8;
the temperature is 25 deg.C and the time is 90 min.
Pure nickel coatings, Ni-P coatings and Ni-SiC coatings were further prepared by conventional adjustment of the raw materials based on the same preparation conditions as described above for comparison.
(3) Vickers hardness test
The vickers hardness test was performed on the plated article prepared through the above process, the load of a durometer was 200g, the load time was 15s, and the measurement results are shown in fig. 2, in which the hardness value of the substrate was 63.71HV, the hardness value of the pure nickel plating layer was 194.76HV, the hardness value of the Ni-P plating layer was 750.64HV, the hardness value of the Ni-SiC plating layer was 782.21, and the hardness value of the Ni-P-SiC plating layer was 836.48 HV.
(4) Testing corrosion resistance;
the adopted electrochemical workstation is of the type of Shanghai Chenghua CHI760E
Electrolyte solution prepared: 3.5 wt.% NaCl solution
Reference electrode: Ag/AgCl
Counter electrode: pt sheet
A working electrode: Ni-P coating or Ni-P-SiC coating
Polarization curve test range: open circuit potential +/-500 mV; the scanning rate is as follows: 10mV s-1
The resulting corrosion polarization curve is shown in FIG. 3, and the specific corrosion current density versus ratio is shown in Table 1 below. The corrosion resistance of the Ni-P-SiC composite coating is superior to that of the Ni-SiC composite coating, which shows that the corrosion resistance of the Ni-SiC composite coating can be greatly improved by adding phosphorus.
TABLE 1 comparison table of open-circuit potential and corrosion current of Ni-SiC composite coating and Ni-P-SiC composite coating
| Type of coating | Self-corrosion potential (V vs. Ag/AgCl) | Corrosion current (A/cm)2) |
| Ni-P | -0.634 | 6.10×10-5 |
| Ni-P-SiC | -0.563 | 1.24×10-5 |
Comparative example 1
(1) Pretreatment of metal substrates
Mechanically flattening and pretreating Q235 steel with specification of 10mm × 10mm × 1.5.5 mm, cutting a steel blank into a sheet structure with flat surface and moderate size by using a wire cutting machine, polishing by using sand paper, and firstly polishing by using 600#Coarse grinding with sandpaper, then using 1200#The sand paper is finely ground and finally 1500 are used#The sand paper is finely ground until the surface is smooth and bright, and then the emery diamond polishing paste is used for polishing on a polishing machine; after repeated washing with ethanol, the organic matter remained on the surface of the substrate is washed by a plasma cleaning machine so as to enhance the binding force between the plating layer and the substrate.
(2) Composite electroplating
Preparing a Ni-P-SiC composite coating on the surface of the Q235 steel by adopting a device shown in figure 1, wherein the plating solution comprises the following components:
the current density is 4A/dm2The pH value of the plating solution is 4.0.
The mechanical stirring mode is adopted, the rotating speed is 200r/min, the temperature is 25 ℃, the time is 120min, and the power supply is a direct current power supply.
(3) Vickers hardness test
The plated piece prepared by the above process was subjected to vickers hardness test, and the load of the durometer was 200g and the load time was 15 seconds.
The measured Vickers hardness value of a sample is about 750HV at most, the hardness of the sample is greatly improved compared with that of pure steel, the corrosion resistance of the steel is improved to a certain extent due to the addition of phosphorus, and the wear resistance is also improved to a certain extent due to the addition of SiC.
Example 2
(1) Pretreatment of metal substrates
Mechanically flattening and pretreating Q235 steel with specification of 10mm × 10mm × 1.5.5 mm, cutting a steel blank into a sheet structure with flat surface and moderate size by using a wire cutting machine, polishing by using sand paper, and firstly polishing by using 600#Coarse grinding with sandpaper, then using 1200#The sand paper is finely ground and finally 1500 are used#Is finely ground to the surfaceLeveling and polishing, and polishing on a polishing machine by using carborundum diamond polishing paste; after repeated washing with ethanol, the organic matter remained on the surface of the substrate is washed by a plasma cleaning machine so as to enhance the binding force between the plating layer and the substrate.
(2) Composite electroplating
Preparing a Ni-P-SiC composite coating on the surface of the Q235 steel by adopting a device shown in figure 1, wherein the plating solution comprises the following components:
the current density is 4A/dm2The pH value of the plating solution is 4.0.
The mechanical stirring mode is adopted, the rotating speed is 200r/min, the temperature is 25 ℃, the time is 120min, the frequency of a pulse power supply is 1000Hz, and the duty ratio is 0.8.
(3) Vickers hardness test
The plated piece prepared by the above process was subjected to vickers hardness test, and the load of the durometer was 200g and the load time was 15 seconds.
Compared with the direct current deposition of the comparative example 1, the steel sample prepared by the pulse current in the example 2 has the surface hardness of about 800HV at most, and the thickness of the coating is reduced from about 20 μm to about 15 μm. Compared with a plating layer obtained by direct current electrodeposition, the Ni-P-SiC plating layer prepared by pulse electrodeposition has the advantages that the porosity of the plating layer is obviously reduced, the compactness is better, generally, the porosity of the plating layer can be increased along with the reduction of the thickness of the plating layer, and the porosity of the plating layer prepared by adopting pulse current reaches 0.4/cm when the thickness is 15 mu m2And in the aspect of wear resistance, the coating is 7-8 times of that of a pure nickel coating, and when the addition amount of sodium hypophosphite is 25g/L, the coating has the strongest corrosion resistance.
One of the advantages of the pulse current used in this embodiment is that it is possible to prepare a Ni-P-SiC plating layer having a surface with preferred orientations of (111) crystal plane and (200) crystal plane, which is advantageous to obtain a higher hardness of the plating layer. Further, as the plating time is prolonged, the preferential direction of the plating layer is changed from the (111) crystal plane to the (200) crystal plane, and the hardness is gradually decreased.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (7)
1. A method for electrodepositing a Ni-P-SiC composite coating comprises the step of electroplating the Ni-P-SiC composite coating on a metal substrate, and is characterized in that the electroplating process conditions are as follows:
the pH value of the electroplating solution is 3-5, the frequency of the pulse power supply is 200-2000Hz, and the duty ratio is 0.2-0.9.
2. The method of claim 1, wherein the frequency of the pulse power source is 600-1200Hz and the duty ratio is 0.4-0.8.
3. The method of electrodepositing a Ni-P-SiC composite coating of claim 1, wherein the plating solution comprises a nickel source, a pH adjusting agent, sodium hypoborate, SiC, a surfactant, and a stress relief agent.
4. The method for electrodepositing the Ni-P-SiC composite coating according to claim 3, wherein the specific components and contents in the electroplating solution are as follows:
5. the method for electrodepositing the Ni-P-SiC composite coating according to claim 4, wherein the plating solution is mechanically stirred at a rotation speed of 150-200 r/min.
6. The method of electrodepositing a Ni-P-SiC composite coating according to claim 1, wherein the electroplating temperature is 20 to 70 ℃ and the current density is 1 to 10A/dm2The time is 60-120 min.
7. The method for electrodepositing the Ni-P-SiC composite coating according to claim 1, wherein the metal matrix is aluminum, magnesium or titanium, and the surface of the metal matrix is subjected to zinc dipping treatment twice before the electroplating, and the zinc dipping solution in each zinc dipping treatment comprises: 100-120g/L of sodium hydroxide, 8-12g/L of zinc oxide and 20-30mL/L of triethanolamine; the treatment temperature is 20-75 deg.C, and the current density is 1-10A/dm2The treatment time is 10-100 s.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113549980A (en) * | 2021-04-27 | 2021-10-26 | 济南大学 | Energy-saving preparation method of nickel-based composite coating |
| CN115747906A (en) * | 2022-11-28 | 2023-03-07 | 国网重庆市电力公司电力科学研究院 | Anti-corrosion metal material and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113549980A (en) * | 2021-04-27 | 2021-10-26 | 济南大学 | Energy-saving preparation method of nickel-based composite coating |
| CN113549980B (en) * | 2021-04-27 | 2024-01-05 | 济南大学 | Energy-saving preparation method of nickel-based composite coating |
| CN115747906A (en) * | 2022-11-28 | 2023-03-07 | 国网重庆市电力公司电力科学研究院 | Anti-corrosion metal material and preparation method thereof |
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