CN110257867B - Ni-Co/Cu super-hydrophobic coating and preparation method thereof - Google Patents

Ni-Co/Cu super-hydrophobic coating and preparation method thereof Download PDF

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CN110257867B
CN110257867B CN201910482119.XA CN201910482119A CN110257867B CN 110257867 B CN110257867 B CN 110257867B CN 201910482119 A CN201910482119 A CN 201910482119A CN 110257867 B CN110257867 B CN 110257867B
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CN110257867A (en
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林志峰
张伟
许立坤
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725th Research Institute of CSIC
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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
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • 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
    • 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
    • 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
    • C25D5/48—After-treatment of electroplated surfaces

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Abstract

The invention provides a Ni-Co/Cu super-hydrophobic coating and a preparation method thereof, belonging to the field of electrodeposition composite coatings. The coating comprises a metal matrix, a Ni-Co coating plated on the surface of the metal matrix, and a copper coating plated on the surface of the Ni-Co coating, wherein low surface energy substances are modified on the surface of the copper coating after the copper coating is oxidized into a dendritic structure. The preparation method comprises the following steps: firstly, preparing a nickel-cobalt coating on the surface of a metal matrix; then carrying out surface treatment on the nickel-cobalt plating layer, plating a copper plating layer on the surface of the nickel-cobalt plating layer, putting the composite plating layer into prepared oxidizing liquid, soaking for a certain time, taking out the composite plating layer, and drying by using cold air; finally, low surface energy modification is carried out to obtain the Ni-Co/Cu composite plating layer. The invention can effectively improve the protection effect of the Ni-Co coating, and when corrosive media such as water and the like reach the surface of the coating, the corrosive media are difficult to enter the coating due to the existence of the surface hydrophobic layer, thereby improving the corrosion prevention effect of the coating, prolonging the protection life of the coating and providing a new idea for preparing a novel metal composite coating.

Description

Ni-Co/Cu super-hydrophobic coating and preparation method thereof
Technical Field
The invention relates to the field of electrodeposition composite coatings, in particular to a preparation and application method of a Ni-Co/Cu super-hydrophobic coating.
Background
The metal and the alloy coating/plating layer thereof have better physical, chemical and mechanical properties, such as higher hardness, wear resistance, corrosion resistance and the like, so the metal and the alloy coating/plating layer thereof are widely applied to the surface treatment of steel. The nickel-cobalt (Ni-Co) alloy coating has high corrosion resistance, hardness and good wear resistance, and is widely applied to the fields of electronic and photoelectronic devices, chemical engineering and the like.
However, when the nickel-cobalt plating is applied to the working conditions of severe environments such as marine environment, the nickel-cobalt plating easily loses the protective performance. Therefore, it is one of the hot spots of the current research to improve the protection life of the nickel-cobalt plating. If researchers add other elements into the plating solution to prepare ternary or multi-element composite plating (such as Ni-Co-Cr ternary alloy plating, Ni-Co-Fe-P quaternary alloy plating, etc.), or add micro-nano particles to prepare micro-nano composite plating (Ni-Co/Al/Ni-Co/Al quaternary alloy plating, etc.)2O3Composite coating, Ni-Co/SiO2Composite plating, Ni-Co/WC nanocomposite plating, etc.). These coatings can better improve the hardness, wear resistance and the like of the Ni-Co coatings, but the improvement degree of the anticorrosion life is limited.
Disclosure of Invention
The invention aims at the defect that the corrosion resistance of the existing Ni-Co coating is easy to corrode and lose efficacy under severe working conditions, and provides a Ni-Co/Cu super-hydrophobic coating and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows:
1. the invention provides a Ni-Co/Cu super-hydrophobic plating layer, which comprises a metal substrate, a Ni-Co plating layer plated on the surface of the metal substrate, and a copper plating layer plated on the surface of the Ni-Co plating layer, wherein after the copper plating layer is oxidized into a dendritic structure, a low surface energy substance is modified on the surface of the copper plating layer, so that the Ni-Co/Cu super-hydrophobic plating layer is obtained.
2. The invention also provides a preparation method of the Ni-Co/Cu super-hydrophobic coating, which comprises the steps of firstly preparing the Ni-Co coating on the surface of the metal matrix, then carrying out surface treatment on the Ni-Co coating, plating a copper coating on the surface of the Ni-Co coating, putting the composite coating into prepared oxidation liquid, soaking for a certain time, taking out the composite coating, drying by using cold air, and finally carrying out low surface energy modification to obtain the Ni-Co/Cu composite coating.
The method specifically comprises the following steps:
1) polishing a metal matrix by using sand paper, moistening by using acetone and ethanol, drying by blowing, putting into a Ni-Co plating solution, and preparing a Ni-Co plating layer on the surface of the metal matrix by using a constant current method;
2) putting the metal matrix with the Ni-Co coating into a dilute hydrochloric acid solution, soaking for a period of time, removing loose coating particles on the surface by hydrochloric acid treatment, and simultaneously increasing the roughness of the surface so as to improve the roughness of the finally obtained Ni-Co/Cu copper coating, then rinsing with ultrapure water and ethanol, and blow-drying for later use;
3) putting the prepared plating layer sample into Cu plating solution, preparing a copper plating layer under the constant potential condition, and forming a Ni-Co/Cu composite plating layer;
4) putting the Ni-Co/Cu composite coating into an oxidizing solution, and soaking for a certain time to oxidize the copper coating into rough Cu (OH)2Taking out the dendritic structure, rinsing with ultrapure water and drying;
5) and (3) putting the oxidized Ni-Co/Cu plating layer into a dodecyl mercaptan solution, soaking for a certain time, and performing low surface energy modification to obtain the Ni-Co/Cu super-hydrophobic plating layer.
As a further preferred aspect of the present invention, the metal base material is carbon steel.
As a further preferred aspect of the present invention, the Ni — Co plating solution preparation in step 1) includes the following steps:
1.1) weighing 10-30 g of NiSO4·6H2O、2~10 g CoSO4·7H2O and 1-6 g NiCl2·6H2Putting O into a 200 mL beaker, then adding 100mL deionized water, and fully stirring and dissolving to prepare a main salt solution;
1.2) weighing 1-5 g H3BO3Putting the mixture into a 50 mL beaker, adding 25 mL of deionized water, heating until the mixture is boiled, and keeping for 3-5 min;
1.3) finally adding H3BO3The solution was slowly added dropwise to the main salt solution.
As a further preferable mode of the present invention, the Ni — Co plating layer in step 1) is prepared by the following parameters: the current density is 10-80 mA/cm2The electrodeposition time is 20-50 min, the electroplating pH is 3-5, the electrodeposition temperature is 40-60 ℃, the stirring speed is 300 rpm/min, and the distance between the cathode and the anode is 3 cm.
As a further preferred aspect of the present invention, the step of preparing the Cu plating solution in step 3) includes the following steps: weighing CuCl2·2H2Adding 3-10 g of O into 100mL of deionized water, fully stirring and dissolving, and then weighing 2-10 g of Na2SO4Adding the mixture into the solution, and stirring to dissolve the mixture.
As a further preferable mode of the present invention, the parameters for preparing the Ni — Co/Cu composite plating layer in step 3) are as follows: the deposition time is 10-40 min, and the voltage is-0.1 to-0.5V/cm2The stirring rate was 300 rpm/min, and the distance between the anode and cathode was 3 cm.
Further preferably, in the step 4), when the Ni — Co/Cu composite plating layer is subjected to oxidation treatment: putting the Ni-Co/Cu plating layer into an ammonium persulfate oxidation solution, and soaking for 30 min, wherein the ammonium persulfate solution is prepared by the following steps:weighing 11 g of NaOH and H8N2O8S22.5 g, adding 200 mL of deionized water, and fully stirring and dissolving.
As a further preferred aspect of the present invention, the low surface energy modification in step 5) refers to: taking 10 ml of dodecyl mercaptan, placing the dodecyl mercaptan into a glass bottle, hanging a sample in the glass bottle, placing the glass bottle into a thermostat, setting the temperature at 60 ℃, maintaining the temperature for 60 min, and preparing a super-hydrophobic Ni-Co/Cu coating, wherein the preparation steps of the modifying solution are as follows: 5-10 g of dodecyl mercaptan is added into 100mL of ethanol and fully stirred to be dissolved.
Compared with the prior art, the Ni-Co/Cu super-hydrophobic coating and the preparation method thereof have the beneficial effects that:
firstly, preparing a nickel-cobalt coating on the surface of a metal substrate; then carrying out surface treatment on the nickel-cobalt plating layer, plating a copper plating layer on the surface of the nickel-cobalt plating layer, putting the composite plating layer into prepared oxidizing liquid, soaking for a certain time, taking out the composite plating layer, and drying by using cold air; finally, low surface energy modification is carried out to obtain the Ni-Co/Cu composite plating layer. The invention can effectively improve the protection effect of the Ni-Co coating, and when corrosive media such as water and the like reach the surface of the coating, the corrosive media are difficult to enter the coating due to the existence of the surface hydrophobic layer, thereby improving the corrosion prevention effect of the coating, prolonging the protection life of the coating and providing a new idea for preparing a novel metal composite coating.
Drawings
FIG. 1 is an SEM image of the carbon steel and Ni-Co plating of example 1 (a carbon steel, b Ni-Co plating);
FIG. 2 is the Ni-Co/Cu plating layer after oxidation and low surface energy modification (a oxidized Ni-Co/Cu plating layer, b Ni-Co/Cu plating layer after low surface energy substance treatment) of example 1;
FIG. 3 is the contact angles of the Ni-Co plating, the Ni-Co/Cu plating and the Ni-Co/Cu superhydrophobic plating of example 1 (a contact angle of the Ni-Co plating, b contact angle of the Ni-Co/Cu plating, c contact angle of the Ni-Co/Cu plating after oxidation and treatment with a low surface energy substance);
FIG. 4 is a polarization diagram of the carbon steel, Ni-Co plating and Ni-Co/Cu superhydrophobic plating of example 1.
Detailed Description
The Ni-Co/Cu super-hydrophobic coating and the preparation method thereof according to the present invention will be described in detail below with reference to FIG. 1.
The invention provides a Ni-Co/Cu super-hydrophobic plating layer, which comprises a metal substrate, a Ni-Co plating layer plated on the surface of the metal substrate, and a copper plating layer plated on the surface of the Ni-Co plating layer, wherein after the copper plating layer is oxidized into a dendritic structure, a low surface energy substance is modified on the surface of the copper plating layer, so that the Ni-Co/Cu super-hydrophobic plating layer is obtained.
The method comprises the steps of firstly preparing a Ni-Co coating on the surface of a metal matrix, and then carrying out surface treatment on the Ni-Co coating in a dilute hydrochloric acid solution, wherein the hydrochloric acid treatment can remove loose metal particles on the surface and can increase the roughness of the surface, so that the roughness of the finally obtained Ni-Co/Cu copper coating is improved. After the treatment is finished, plating a layer of copper plating layer on the surface of the Ni-Co plating layer, putting the composite plating layer into prepared oxidizing liquid for oxidation, and oxidizing the Cu plating layer on the surface into rough Cu (OH)2And (3) a dendritic structure, which is one of the key steps for preparing the super-hydrophobic coating, and finally performing low surface energy modification to enable hydrophobic molecules to be adsorbed to the surface of the structure only, thus obtaining the Ni-Co/Cu composite coating. The method specifically comprises the following steps:
1) polishing a metal matrix by using sand paper, moistening by using acetone and ethanol, drying by blowing, putting into a Ni-Co plating solution, and preparing a Ni-Co plating layer on the surface of the metal matrix by using a constant current method;
2) putting the metal matrix with the Ni-Co coating into a dilute hydrochloric acid solution, soaking for a period of time, removing loose coating particles on the surface by hydrochloric acid treatment, and simultaneously increasing the roughness of the surface so as to improve the roughness of the finally obtained Ni-Co/Cu copper coating, then rinsing with ultrapure water and ethanol, and blow-drying for later use;
3) putting the prepared plating layer sample into Cu plating solution, preparing a copper plating layer under the constant potential condition, and forming a Ni-Co/Cu composite plating layer;
4) putting the Ni-Co/Cu composite coating into an oxidizing solution, and soaking for a certain time to oxidize the copper coating into roughCu (OH)2Taking out the dendritic structure, rinsing with ultrapure water and drying;
5) and (3) putting the oxidized Ni-Co/Cu plating layer into a dodecyl mercaptan solution, soaking for a certain time, and performing low surface energy modification to obtain the Ni-Co/Cu super-hydrophobic plating layer.
Example 1
The invention relates to a Ni-Co/Cu super-hydrophobic coating, which comprises the following steps:
1. the substrate material is Q235 carbon steel, and is cut and packaged by epoxy resin to ensure that the working area is 1 cm2And polishing the substrate by using No. 2000 abrasive paper to remove surface corrosion products, cleaning by using acetone and ethanol, and drying for later use.
2. Preparation of Ni-Co plating solution: weighing 20 g of NiSO4·6H2O、5 g CoSO4·7H2O and 3 g NiCl2·6H2O was placed in a 200 mL beaker, then 100mL deionized water was added and dissolved with thorough stirring. Weighing 3 g H3BO3Put into a 50 mL beaker, add 25 mL deionized water, heat until boiling, and maintain for 4 min. Finally, H is put3BO3The solution was slowly added dropwise to the main salt solution.
3. Preparation of Cu plating solution: weighing CuCl2·2H2O5 g is added into 100mL deionized water, fully stirred and dissolved, and then 5 g Na is weighed2SO4Adding the mixture into the solution, and stirring to dissolve the mixture.
4. Preparation parameters of the Ni-Co plating layer: the current density is 40 mA/cm2The electrodeposition time is 30 min, the electroplating pH is 4, the electrodeposition temperature is 50 ℃, the stirring speed is 300 rpm/min, and the distance between the cathode and the anode is 3 cm. The SEM of the surface of the prepared Ni-Co plating layer is shown in figure 1.
5. Preparation parameters of the Ni-Co/Cu plating layer are as follows: the deposition time is 30 min, and the voltage is-0.2V/cm2The stirring rate was 300 rpm/min, and the distance between the anode and cathode was 3 cm.
6. Oxidation treatment of Ni-Co/Cu plating layer: putting the Ni-Co/Cu plating layer into an oxidizing solution, and soaking for 30 min (the solution is prepared and called)Taking 11 g of NaOH and H8N2O8S22.5 g, adding 200 mL of deionized water, and fully stirring and dissolving to obtain the product).
7. Low surface energy modification: 10 mL of dodecyl mercaptan is taken out and put into a glass bottle, a sample is hung in the glass bottle and put into a constant temperature box, the temperature is set at 60 ℃, and the constant temperature box is maintained for 60 min, so that the super-hydrophobic Ni-Co/Cu coating is prepared (configuration of a modifying solution: 7g of dodecyl mercaptan is added into 100mL of ethanol and fully stirred to be dissolved).
The prepared super-hydrophobic Ni-Co/Cu plating layer is shown in figure 2, and a dendritic structure is formed on the surface of the matrix after oxidation as can be seen from figure 2. The contact angle test (figure 3) shows that the plating layer has good super-hydrophobic performance, and the contact angle can reach 158 degrees. Therefore, when the coating is soaked in corrosive media such as seawater and the like, the super-hydrophobic layer on the surface can shield the entry of the corrosive media such as water and the like, so that the protection effect of the Ni-Co coating is greatly improved. The polarization curve test (fig. 4) shows that the plating layer has good corrosion resistance.
Example 2
The invention relates to a Ni-Co/Cu super-hydrophobic coating, which comprises the following steps:
1. the base material is Q255 carbon steel, cutting and packaging with epoxy resin to enable the working area to be 1 cm2, polishing the base body with No. 2000 abrasive paper to remove surface corrosion products, cleaning with acetone and ethanol, and blow-drying for later use.
2. Preparation of Ni-Co plating solution: weighing 10 g of NiSO4·6H2O、2 g CoSO4·7H2O and 1 g NiCl2·6H2O was placed in a 200 mL beaker, then 100mL deionized water was added and dissolved with thorough stirring. Weighing 1 g H3BO3Put into a 50 mL beaker, add 25 mL deionized water, heat until boiling, and maintain for 3 min. Finally, H is put3BO3The solution was slowly added dropwise to the main salt solution.
3. Preparation of Cu plating solution: weighing CuCl2·2H2O3 g is added into 100mL deionized water, fully stirred and dissolved, and then 2 g Na is weighed2SO4Adding the above solutionAnd (4) stirring and dissolving.
4. Preparation parameters of the Ni-Co plating layer: the current density is 10 mA/cm2The electrodeposition time is 20 min, the electroplating pH is 3, the electrodeposition temperature is 40 ℃, the stirring speed is 300 rpm/min, and the distance between the cathode and the anode is 3 cm.
5. Preparation parameters of the Ni-Co/Cu plating layer are as follows: the deposition time is 10 min, and the voltage is-0.1V/cm2The stirring rate was 300 rpm/min, and the distance between the anode and cathode was 3 cm.
6. Oxidation treatment of Ni-Co/Cu plating layer: putting the Ni-Co/Cu plating layer into an oxidizing solution, and soaking for 30 min (the solution is prepared by weighing 11 g of NaOH and H8N2O8S22.5 g, adding 200 mL of deionized water, and fully stirring and dissolving to obtain the product).
7. Low surface energy modification: 10 mL of dodecyl mercaptan is taken out and put into a glass bottle, a sample is hung in the glass bottle and put into a constant temperature box, the temperature is set at 60 ℃, and the constant temperature box is maintained for 60 min, so that the super-hydrophobic Ni-Co/Cu coating is prepared (configuration of a modifying solution: 5 g of dodecyl mercaptan is added into 100mL of ethanol and fully stirred to be dissolved).
Example 3
The invention relates to a Ni-Co/Cu super-hydrophobic coating, which comprises the following steps:
1. the base material is Q275 carbon steel, cutting and packaging with epoxy resin to enable the working area to be 1 cm2, polishing the base body with No. 2000 abrasive paper to remove surface corrosion products, cleaning with acetone and ethanol, and blow-drying for later use.
2. Preparation of Ni-Co plating solution: weighing 15 g of NiSO4·6H2O、4 g CoSO4·7H2O and 2 g NiCl2·6H2O was placed in a 200 mL beaker, then 100mL deionized water was added and dissolved with thorough stirring. Weighing 4 g H3BO3Put into a 50 mL beaker, add 25 mL deionized water, heat until boiling, and maintain for 4 min. Finally, H is put3BO3The solution was slowly added dropwise to the main salt solution.
3. Preparation of Cu plating solution: weighing CuCl2·2H2O4 g, adding 100In mL deionized water, fully stirred and dissolved, and then 7g of Na is weighed2SO4Adding the mixture into the solution, and stirring to dissolve the mixture.
4. Preparation parameters of the Ni-Co plating layer: the current density was 30 mA/cm2The electrodeposition time is 40 min, the electroplating pH is 5, the electrodeposition temperature is 45 ℃, the stirring speed is 300 rpm/min, and the distance between the cathode and the anode is 3 cm.
5. Preparation parameters of the Ni-Co/Cu plating layer are as follows: the deposition time is 20 min, and the voltage is-0.3V/cm2The stirring rate was 300 rpm/min, and the distance between the anode and cathode was 3 cm.
6. Oxidation treatment of Ni-Co/Cu plating layer: putting the Ni-Co/Cu plating layer into an oxidizing solution, and soaking for 30 min (the solution is prepared by weighing 11 g of NaOH and H8N2O8S22.5 g, adding 200 mL of deionized water, and fully stirring and dissolving to obtain the product).
7. Low surface energy modification: 10 mL of dodecyl mercaptan is taken out and put into a glass bottle, a sample is hung in the glass bottle and put into a constant temperature box, the temperature is set at 60 ℃, and the constant temperature box is maintained for 60 min, so that the super-hydrophobic Ni-Co/Cu coating is prepared (configuration of a modifying solution: 8 g of dodecyl mercaptan is added into 100mL of ethanol and fully stirred to be dissolved).
Example 4
The invention relates to a Ni-Co/Cu super-hydrophobic coating, which comprises the following steps:
1. the base material is Q275 carbon steel, cutting and packaging with epoxy resin to enable the working area to be 1 cm2, polishing the base body with No. 2000 abrasive paper to remove surface corrosion products, cleaning with acetone and ethanol, and blow-drying for later use.
2. Preparation of Ni-Co plating solution: weighing 30 g of NiSO4·6H2O、10 g CoSO4·7H2O and 6 g NiCl2·6H2O was placed in a 200 mL beaker, then 100mL deionized water was added and dissolved with thorough stirring. Weighing 5 g H3BO3Put into a 50 mL beaker, add 25 mL deionized water, heat until boiling, and maintain for 5 min. Finally, H is put3BO3The solution was slowly added dropwise to the main salt solution.
3. Preparation of Cu plating solution: weighing CuCl2·2H2O10 g is added into 100mL deionized water, fully stirred and dissolved, and then 10 g of Na is weighed2SO4Adding the mixture into the solution, and stirring to dissolve the mixture.
4. Preparation parameters of the Ni-Co plating layer: the current density is 80 mA/cm2The electrodeposition time is 50 min, the electroplating pH is 5, the electrodeposition temperature is 60 ℃, the stirring speed is 300 rpm/min, and the distance between the cathode and the anode is 3 cm.
5. Preparation parameters of the Ni-Co/Cu plating layer are as follows: the deposition time is 40 min, and the voltage is-0.5V/cm2The stirring rate was 300 rpm/min, and the distance between the anode and cathode was 3 cm.
6. Oxidation treatment of Ni-Co/Cu plating layer: putting the Ni-Co/Cu plating layer into an oxidizing solution, and soaking for 30 min (the solution is prepared by weighing 11 g of NaOH and H8N2O8S22.5 g, adding 200 mL of deionized water, and fully stirring and dissolving to obtain the product).
7. Low surface energy modification: 10 mL of dodecyl mercaptan is taken out and put into a glass bottle, a sample is hung in the glass bottle and put into a constant temperature box, the temperature is set at 60 ℃, and the constant temperature box is maintained for 60 min, so that the super-hydrophobic Ni-Co/Cu coating is prepared (configuration of a modifying solution: 10 g of dodecyl mercaptan is added into 100mL of ethanol and fully stirred to be dissolved).
While the preferred embodiments of the present application have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all alterations and modifications as fall within the scope of the application.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present application without departing from the spirit and scope of the application. Thus, if such modifications and variations of the present application fall within the scope of the claims of the present application and their equivalents, the present application is intended to include such modifications and variations as well.
In addition to the technical features described in the specification, the technology is known to those skilled in the art.

Claims (4)

1. A preparation method of a Ni-Co/Cu super-hydrophobic coating is characterized in that firstly, a Ni-Co coating is prepared on the surface of a metal matrix, then the surface of the Ni-Co coating is treated, a copper coating is plated on the surface of the Ni-Co coating, the composite coating is put into prepared oxidation liquid, soaked for a certain time, taken out and dried by cold air, and finally low surface energy modification is carried out, so that the Ni-Co/Cu super-hydrophobic composite coating is obtained; the method specifically comprises the following steps:
1) polishing a metal matrix by using sand paper, moistening by using acetone and ethanol, drying by blowing, putting into a Ni-Co plating solution, and preparing a Ni-Co plating layer on the surface of the metal matrix by using a constant current method;
2) putting the metal matrix with the Ni-Co coating into a dilute hydrochloric acid solution, soaking for a period of time, removing loose coating particles on the surface by hydrochloric acid treatment, and simultaneously increasing the roughness of the surface so as to improve the roughness of the finally obtained Ni-Co/Cu copper coating, then rinsing with ultrapure water and ethanol, and blow-drying for later use;
3) putting the prepared plating layer sample into Cu plating solution, preparing a copper plating layer under the constant potential condition, and forming a Ni-Co/Cu composite plating layer;
4) putting the Ni-Co/Cu composite plating layer into an oxidizing solution, soaking for a certain time to oxidize the copper plating layer into a dendritic structure, taking out, rinsing with ultrapure water, and drying;
5) putting the oxidized Ni-Co/Cu plating layer into a dodecyl mercaptan solution, soaking for a certain time, and performing low surface energy modification to obtain a Ni-Co/Cu super-hydrophobic plating layer;
the step 1) comprises the preparation of Ni-Co plating solution, and comprises the following steps:
1.1) weighing 10-30 g of NiSO4·6H2O、2~10 g CoSO4·7H2O and 1-6 g NiCl2·6H2Putting O into a 200 mL beaker, then adding 100mL deionized water, and fully stirring and dissolving to prepare a main salt solution;
1.2) weighing 1-5 g H3BO3Put into a 50 mL beaker, added with 25 mL deionized water,heating until boiling, and maintaining for 3-5 min;
1.3) finally adding H3BO3Slowly dripping the solution into the main salt solution; the preparation parameters of the Ni-Co plating layer are as follows: the current density is 10-80 mA/cm2The electrodeposition time is 20-50 min, the electroplating pH is 3-5, the electrodeposition temperature is 40-60 ℃, the stirring speed is 300 rpm/min, and the distance between the cathode and the anode is 3 cm;
the step 3) comprises the preparation of Cu plating solution, and comprises the following steps: weighing CuCl2·2H2Adding 3-10 g of O into 100mL of deionized water, fully stirring and dissolving, and then weighing 2-10 g of Na2SO4Adding the mixture into the solution, and stirring for dissolving; the preparation parameters of the Ni-Co/Cu composite plating layer are as follows: the deposition time is 10-40 min, the voltage is-0.1 to-0.5V, the stirring speed is 300 rpm/min, and the distance between the cathode and the anode is 3 cm;
when the Ni-Co/Cu composite plating layer is subjected to oxidation treatment in the step 4): putting the Ni-Co/Cu plating layer into an ammonium persulfate oxidation solution, and soaking for 30 min, wherein the ammonium persulfate solution is prepared by the following steps: weighing 11 g of NaOH and H8N2O8S22.5 g, adding 200 mL of deionized water, and fully stirring and dissolving.
2. The method for preparing the Ni-Co/Cu super-hydrophobic coating according to claim 1, wherein the low surface energy modification in the step 5) is: putting 10 ml of dodecyl mercaptan into a glass bottle, hanging a sample in the glass bottle, putting the glass bottle into a thermostat, setting the temperature at 60 ℃, and maintaining for 60 min to prepare a super-hydrophobic Ni-Co/Cu coating; the preparation method of the modification solution comprises the following steps: 5-10 g of dodecyl mercaptan is added into 100mL of ethanol and fully stirred to be dissolved.
3. The method for preparing the Ni-Co/Cu superhydrophobic coating according to claim 1 or 2, wherein the metal matrix material is carbon steel.
4. The Ni-Co/Cu super-hydrophobic coating prepared by the method of any one of claims 1 or 2, wherein the super-hydrophobic coating comprises a metal substrate, a Ni-Co coating plated on the surface of the metal substrate, and a copper coating plated on the surface of the Ni-Co coating, wherein after the copper coating is oxidized into a dendritic structure, a low surface energy substance is modified on the surface of the copper coating, so that the Ni-Co/Cu super-hydrophobic coating is obtained.
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