CN114775004A - Nickel-graphene super-hydrophobic coating and preparation method thereof - Google Patents
Nickel-graphene super-hydrophobic coating and preparation method thereof Download PDFInfo
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- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 62
- 238000000576 coating method Methods 0.000 title claims abstract description 53
- 239000011248 coating agent Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000007747 plating Methods 0.000 claims abstract description 75
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- 238000009713 electroplating Methods 0.000 claims abstract description 32
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
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- 238000001291 vacuum drying Methods 0.000 claims abstract description 17
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 12
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 12
- 238000012986 modification Methods 0.000 claims abstract description 9
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- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 239000006179 pH buffering agent Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000002135 nanosheet Substances 0.000 claims description 4
- 239000006174 pH buffer Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 13
- 230000007797 corrosion Effects 0.000 abstract description 13
- 238000007385 chemical modification Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 19
- 238000012360 testing method Methods 0.000 description 17
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- 238000001035 drying Methods 0.000 description 12
- 238000001878 scanning electron micrograph Methods 0.000 description 11
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
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- 239000013256 coordination polymer Substances 0.000 description 4
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- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 3
- 235000019743 Choline chloride Nutrition 0.000 description 3
- 229910003243 Na2SiO3·9H2O Inorganic materials 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 229960003178 choline chloride Drugs 0.000 description 3
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical group [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
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- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 3
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 244000137852 Petrea volubilis Species 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical class [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005258 corrosion kinetic Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical compound [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000010329 laser etching Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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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
-
- 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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
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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 relates to the technical field of metal surface protection, in particular to a nickel-graphene super-hydrophobic coating and a preparation method and application thereof. The preparation method provided by the invention comprises the following steps: electroplating in a plating solution by taking a metal matrix as a cathode and nickel as an anode, and then performing vacuum drying to obtain a nickel-graphene super-hydrophobic plating layer on the surface of the metal matrix; the plating solution comprises nickel chloride and graphene oxide; the concentration of the graphene oxide in the plating solution is 0.05-0.30 g/L; the concentration of nickel chloride in the plating solution is 210-260 g/L; the current density of the electroplating is 30-60 mA/cm2(ii) a The vacuum drying time is more than or equal to 14 days; the plating is completed without low surface energy material modification. The preparation method can prepare the super-hydrophobic coating without further chemical modification, and the super-hydrophobic coating is preparedThe super-hydrophobic coating has higher corrosion resistance.
Description
Technical Field
The invention relates to the technical field of metal surface protection, in particular to a nickel-graphene super-hydrophobic coating and a preparation method and application thereof.
Background
By inspiring natural biological materials with ordered surface configuration and super-hydrophobic characteristics, a great deal of research at present finds that the super-hydrophobic surface can directly reduce the solid/liquid contact surface, thereby greatly improving the corrosion resistance of metal and becoming an important means for metal corrosion protection. At present, various means such as an electrochemical method, electrostatic spinning, laser etching and the like have successfully developed the metal super-hydrophobic surface. The electrochemical deposition can realize the regulation and control of the surface micro-morphology by changing the plating solution formula and current parameters, and has easy operability and repeatability. At present, the super-hydrophobic surface is prepared by electrodeposition through a two-step method, firstly, a coating with a rough structure is prepared, but super-hydrophobicity cannot be realized, so that a low-surface-energy substance is required to be used for modification. However, the chemical modification method increases the preparation cost and the operation difficulty, and most of low surface energy substances (such as fluorosilane and the like) have toxicity and may cause ecological damage.
Disclosure of Invention
The invention aims to provide a nickel-graphene super-hydrophobic coating and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a nickel-graphene super-hydrophobic coating, which comprises the following steps:
electroplating in a plating solution by taking a metal matrix as a cathode and nickel as an anode, and then performing vacuum drying to obtain a nickel-graphene superhydrophobic coating on the surface of the metal matrix;
the plating solution comprises nickel chloride and graphene oxide; the concentration of the graphene oxide in the plating solution is 0.05-0.3 g/L; the concentration of nickel chloride in the plating solution is 210-260 g/L;
the current density of the electroplating is 30-60 mA/cm2；
The vacuum drying time is more than or equal to 14 days;
the low surface energy substance modification is not performed after the electroplating is completed.
Preferably, the concentration of the graphene oxide in the plating solution is 0.1-0.2 g/L.
Preferably, the pH value of the plating solution is 3.9-4.1.
Preferably, the plating solution further comprises a pH buffering agent, a crystallization modifier and a surfactant;
the mass ratio of the pH buffering agent to the crystallization modifier to the surfactant is (30-50): (150-200): (0.1-0.5).
Preferably, the concentration of the pH buffering agent in the plating solution is 30-50 g/L.
Preferably, the distance between the anode and the cathode is 3.8-4.2 cm.
Preferably, the current density of the electroplating is 40-50 mA/cm2。
Preferably, the electroplating is carried out under stirring conditions;
the electroplating temperature is 55-65 ℃, and the time is 10-12 min; the rotating speed of the stirring is 100-200 rpm.
The invention also provides the nickel-graphene super-hydrophobic coating prepared by the preparation method of the technical scheme, and the surface of the nickel-graphene super-hydrophobic coating is of a micro-nano multilevel structure;
the nickel-graphene super-hydrophobic coating comprises a metal nickel layer and graphene nanosheets distributed in the nickel layer.
The invention provides a preparation method of a nickel-graphene super-hydrophobic coating, which comprises the following steps: electroplating in a plating solution by taking a metal matrix as a cathode and nickel as an anode, and then performing vacuum drying to obtain a nickel-graphene super-hydrophobic plating layer on the surface of the metal matrix; the plating solution comprises nickel chloride and graphene oxide(ii) a The concentration of the graphene oxide in the plating solution is 0.05-0.3 g/L; the concentration of nickel chloride in the plating solution is 210-260 g/L; the current density of the electroplating is 30-60 mA/cm2(ii) a The vacuum drying time is more than or equal to 14 days; the low surface energy substance modification is not performed after the electroplating is completed. According to the method, an electroplating process is adopted, the composition in a plating solution and the conditions of the electroplating process are adjusted to prepare a nickel coating distributed with graphene, and after further vacuum drying treatment, a metal nickel coating with micron-sized protrusions and nano-dispersed nano-sheet graphene on the surface can be obtained; meanwhile, the graphene distributed in the nickel coating has impermeability, so that the physical shielding capacity of the coating can be further improved, and the corrosion resistance of the coating is further improved; and the preparation method does not need to use a low surface energy compound for modification.
Drawings
FIG. 1 is an SEM image and a water contact angle of a super-hydrophobic pure nickel plating layer as shown in comparative example 1 and nickel-graphene super-hydrophobic plating layers prepared in examples 1 to 4;
FIG. 2 is an SEM image and a water contact angle of the nickel-graphene superhydrophobic coating prepared in examples 5-8;
FIG. 3 is a water contact angle curve of the plating layers described in example 3 and comparative examples 2 to 5;
fig. 4 is a tafel plot of No. 20 low carbon steel plate, the superhydrophobic pure nickel plating layer described in comparative example 1, the nickel-graphene composite plating layer described in comparative example 2, and the nickel-graphene superhydrophobic plating layer described in example 6.
Detailed Description
The invention provides a preparation method of a nickel-graphene super-hydrophobic coating, which comprises the following steps:
electroplating in a plating solution by taking a metal matrix as a cathode and nickel as an anode, and then performing vacuum drying to obtain a nickel-graphene super-hydrophobic plating layer on the surface of the metal matrix;
the plating solution comprises nickel chloride and graphene oxide; the concentration of the graphene oxide in the plating solution is 0.05-0.3 g/L; the concentration of nickel chloride in the plating solution is 210-260 g/L;
the current density of the electroplating is 30-60 mA/cm2；
The vacuum drying time is more than or equal to 14 days;
the low surface energy substance modification is not performed after the electroplating is completed.
The metal substrate used in the present invention is not particularly limited, and those known to those skilled in the art can be used. In a specific embodiment of the invention, the metal matrix is a 20-size low carbon steel plate with the size of 20mm × 30mm × 2 mm.
In the present invention, the metal substrate is preferably a metal substrate which is subjected to degreasing, first drying, wire bonding, packaging, polishing, cleaning, and second drying in this order. In the invention, the oil removal is preferably carried out by sequentially cleaning with acetone and ethanol; the first drying process is not particularly limited, and may be performed by a process known to those skilled in the art. In the present invention, the second drying is preferably performed by blowing with cold air. In the present invention, the encapsulation is preferably performed using epoxy resin; the grinding is preferably carried out step by using 400# to 2000# sand paper; the cleaning is preferably performed by sequentially adopting deionized water, acetone and ethanol.
Before electroplating, the invention also preferably comprises the steps of sequentially carrying out alkali washing and activation on the metal matrix; the alkaline washing liquid adopted by the alkaline washing preferably comprises 30g/L NaOH and 40g/L Na2CO325g/L of Na2SiO3·9H2O, 20g/L of Na3PO4·12H2And O. In the present invention, the time for the alkali washing is preferably 10 min. In the invention, the activating reagent used for activating is preferably a hydrochloric acid solution with the mass concentration of 10%; the time for the activation is preferably 10 s.
In the invention, the nickel is preferably a nickel plate with the purity of more than or equal to 99.6 wt%.
In the invention, the distance between the anode and the cathode is preferably 3.8-4.2 cm, more preferably 3.9-4.1 cm, and most preferably 4 cm. In the present invention, the surface to be plated of the cathode is preferably opposite to and parallel to the surface of the anode.
In the invention, the concentration of the graphene oxide in the plating solution is preferably 0.1-0.2 g/L, and more preferably 0.2 g/L.
In the invention, the concentration of the nickel chloride in the plating solution is 210-260 g/L, preferably 220-250 g/L, and more preferably 238-240 g/L. In the present invention, the nickel chloride is preferably nickel chloride hexahydrate (analytically pure AR).
In the invention, the pH value of the plating solution is preferably 3.9-4.1, and more preferably 4.0.
In the present invention, the plating solution further preferably includes a pH buffer, a crystallization modifier, and a surfactant; the mass ratio of the pH buffering agent to the crystallization modifier to the surfactant is preferably (30-50): (150-200): (0.1 to 0.5), more preferably (31 to 40): (160 to 180): (0.2-0.3), and most preferably 31:168: 0.2. In the invention, the concentration of the pH buffering agent in the plating solution is preferably 30-50 g/L, more preferably 31-40 g/L, and most preferably 31 g/L. In the present invention, the pH buffer is preferably boric acid (analytically pure AR), and the crystal modifier is preferably choline chloride (chemically pure CR); the surfactant is preferably polyethylene glycol (chemically pure CR).
In the invention, the current density of the electroplating is preferably 40-50 mA/cm2More preferably 40mA/cm2。
In the present invention, the plating is preferably performed under stirring; the electroplating temperature is preferably 55-65 ℃, more preferably 58-62 ℃, and most preferably 60 ℃, and the time is preferably 10-12 min, more preferably 10-11 min, and most preferably 10 min; the rotation speed of the stirring is preferably 100-200 rpm, more preferably 120-180 rpm, and most preferably 130-160 rpm. In the present invention, the temperature of the electroplating is preferably realized by means of water bath heating.
After the electroplating is finished, the invention also preferably comprises cleaning and drying which are carried out in sequence. In the invention, the cleaning comprises a first cleaning, a second cleaning and a third cleaning which are sequentially carried out, wherein the first cleaning is preferably carried out by adopting deionized water for washing; the second cleaning is preferably ultrasonic cleaning in deionized water; the process of the ultrasonic cleaning is not limited in any way, and can be carried out by adopting a process well known by the technical personnel in the field; the third cleaning is preferably performed by using absolute ethyl alcohol. In the present invention, the drying is preferably performed by drying with cold air.
In the present invention, the temperature of the vacuum drying is preferably room temperature, and the time is 14 days or more, preferably 14 days.
The invention also provides the nickel-graphene superhydrophobic coating prepared by the preparation method in the technical scheme, which comprises a metal nickel layer and graphene nanosheets distributed in the nickel layer.
The invention also provides application of the nickel-graphene super-hydrophobic coating in the field of metal surface protection. The method of the present invention is not particularly limited, and the method may be performed by a method known to those skilled in the art.
The nickel-graphene superhydrophobic coating provided by the invention, the preparation method and the application thereof are described in detail below with reference to examples, but the nickel-graphene superhydrophobic coating and the preparation method and the application thereof are not to be construed as limiting the scope of the invention.
Examples 1 to 4
The plating solution comprises the following components: 238g/L of nickel chloride hexahydrate (analytically pure AR), 31g/L of boric acid (analytically pure AR), 168g/L of choline chloride (chemically pure CP), 0.2g/L of polyethylene glycol (chemically pure CP) and 0.05g/L (example 1), 0.10g/L (example 2), 0.20g/L (example 3) and 0.30g/L (example 4) of graphene oxide respectively;
a metal matrix: a No. 20 low carbon steel plate with the size of 20mm multiplied by 30mm multiplied by 2 mm;
removing oil on the metal substrate by using acetone and ethanol, welding a wire after drying, packaging by using epoxy resin, polishing a working surface (to-be-plated surface) step by using 400# to 2000# abrasive paper, cleaning by using deionized water, acetone and ethanol in sequence, and drying by cold air for later use;
subjecting the metal matrix to alkaline solution (containing 30g/L NaOH and 40g/L Na) at bath temperature of 65 deg.C2CO325g/L of Na2SiO3·9H2O, 20g/L Na3PO4·12H2O) performing alkaline washing for 10min to remove surface oil stains, and then activating for 10s in a hydrochloric acid solution with the mass concentration of 10% to obtain a pretreated metal matrix;
taking the pretreated metal matrix as a cathode, a nickel plate with the purity of 99.6 percent as an anode, wherein the distance between the cathode and the anode is 4cm, the surface to be plated of the cathode is preferably opposite to and parallel to the surface of the anode, and electroplating is carried out in the plating solution (the electroplating temperature is 60 ℃, the stirring rotating speed is 150rpm, and the current density is 40 mA/cm)2And the time is 10min), after electroplating is finished, washing with deionized water, performing ultrasonic cleaning in the deionized water, cleaning with absolute ethyl alcohol, blow-drying with cold air, and performing vacuum drying for 14 days to obtain the nickel-graphene superhydrophobic coating.
Comparative example 1
Referring to examples 1 to 4, the difference is that graphene oxide is not included in the plating solution, and a pure nickel plating layer is obtained.
Test example 1
SEM test and hydrophobic property test were performed on the pure nickel plating layer described in comparative example 1 and the nickel-graphene superhydrophobic plating layers prepared in examples 1 to 4, and the test results are shown in fig. 1, where (a) is an SEM image and a water contact angle of the pure nickel plating layer described in comparative example 1, (b) is an SEM image and a water contact angle of the nickel-graphene superhydrophobic plating layer described in example 1, (c) is an SEM image and a water contact angle of the nickel-graphene superhydrophobic plating layer described in example 2, (d) is an SEM image and a water contact angle of the nickel-graphene superhydrophobic plating layer described in example 3, and (e) is an SEM image and a water contact angle of the nickel-graphene superhydrophobic plating layer described in example 4; as can be seen from FIG. 1, the plating surface of the pure nickel plating layer presents a randomly distributed nano-scale sheet structure; the plating surface of the nickel-graphene super-hydrophobic plating layer prepared in the embodiments 1-3 has a cluster structure, the cluster is a combination of a micron-sized protrusion and a nanoscale sheet layer, and the cluster structure is more and more obvious; the surface of the coating of the nickel-graphene superhydrophobic coating prepared in the embodiment 4 has irregular micron-sized nodular protrusions; the micro-morphology of the nickel-graphene superhydrophobic coating prepared in the embodiments 1-4 has water contact angles of 151 °, 140 °, 147 ° and 156 ° in sequence, wherein the nickel-graphene superhydrophobic coating in the embodiment 3 has the strongest hydrophobicity.
Examples 5 to 8
The plating solution comprises the following components: 238g/L of nickel chloride hexahydrate (analytically pure AR), 31g/L of boric acid (analytically pure AR), 168g/L of choline chloride (chemically pure CP), 0.2g/L of polyethylene glycol (chemically pure CP) and 0.2g/L of graphene oxide (concentration of 0.2 g/L);
metal matrix: a No. 20 low carbon steel plate with the size of 20mm multiplied by 30mm multiplied by 2 mm;
removing oil on the metal substrate by using acetone and ethanol, welding a wire after drying, packaging by using epoxy resin, polishing a working surface (to-be-plated surface) step by using 400# to 2000# abrasive paper, cleaning by using deionized water, acetone and ethanol in sequence, and drying by cold air for later use;
subjecting the metal matrix to alkaline washing at 65 deg.C in water bath (containing 30g/L NaOH and 40g/L Na)2CO325g/L of Na2SiO3·9H2O, 20g/L Na3PO4·12H2O) performing alkali washing for 10min to remove oil stains on the surface, and then activating in a hydrochloric acid solution with the mass concentration of 10% for 10s to obtain a pretreated metal matrix;
taking the pretreated metal matrix as a cathode, a nickel plate with the purity of 99.6 percent as an anode, wherein the distance between the cathode and the anode is 4 +/-0.2 cm, the surface to be plated of the cathode is preferably opposite to and parallel to the surface of the anode, and electroplating is carried out in the plating solution (the electroplating temperature is 60 ℃, the stirring rotating speed is 150rpm, and the current density is 30mA/cm respectively2(example 5) 40mA/cm2(example 6) 50mA/cm2(example 7) and 60mA/cm2(example 8) for 10min), rinsing with deionized water after the completion of electroplating, ultrasonic cleaning in deionized water, cleaning with absolute ethanol, and cooling with cold airAnd (4) drying by blowing, and performing vacuum drying for 14 days to obtain the nickel-graphene super-hydrophobic coating.
Test example 2
Performing SEM test and hydrophobic property test on the nickel-graphene super-hydrophobic coating prepared in the examples 5-8, wherein the test results are shown in FIG. 2, wherein (a) is an SEM image and a water contact angle of the nickel-graphene super-hydrophobic coating prepared in the example 5, the deposition morphology is relatively flat, the sheet structure on the surface of the coating is dominant, and a small amount of clusters appear; (b) an SEM image and a water contact angle of the nickel-graphene superhydrophobic coating of the embodiment 6 are shown, the surface of the coating has a cluster structure, and the cluster is a combination of micron-sized protrusions and nanoscale sheets; (c) an increase in surface cluster size for SEM images and water contact angles of the nickel-graphene superhydrophobic plating described in example 7; (d) is SEM image and water contact angle of the nickel-graphene super-hydrophobic coating described in example 8; the surface structure of the plating layer is obviously deteriorated, and the surface of the plating layer begins to generate nodular bulges and is accompanied with the formation of microcracks; the water contact angles of the nickel-graphene superhydrophobic coatings prepared in the embodiments 5-8 are 138 degrees, 156 degrees, 154 degrees and 145 degrees in sequence, wherein the nickel-graphene superhydrophobic coating in the embodiment 6 is strongest in hydrophobicity.
Example 9
Referring to example 6, except that the vacuum drying time was 20 days.
Comparative examples 2 to 5
Referring to example 6, except that the vacuum drying time was 0 day (comparative example 2), 3 days (comparative example 3), 6 days (comparative example 4), and 10 days (comparative example 5), respectively.
Test example 3
The coatings described in examples 3 and 9 and comparative examples 2 to 5 were subjected to a hydrophobic property test, and the test results are shown in fig. 3, and it can be seen from fig. 3 that the nickel-graphene coating prepared from steel has a hydrophilic surface with a contact angle of only 24.5 °, and the contact angle of the coating gradually increases with the increase of the vacuum drying time, and reaches a stable value (156.1 ℃) after 14 days; the insert in the lower right corner of fig. 3 is a real image of the droplet on the surface of the nickel-graphene plating layer in example 3, and thus it can be seen that the droplet is spherical at different positions.
Test example 4
A 20# mild steel plate (corresponding to 20# steel in fig. 4), the superhydrophobic pure nickel plating layer described in comparative example 1, the nickel-graphene composite plating layer described in comparative example 2 (corresponding to the nickel-graphene plating layer just prepared in fig. 4), and the nickel-graphene superhydrophobic plating layer described in example 6 were subjected to corrosion resistance tests:
the testing process comprises the following steps: using a princeton 2273 electrochemical workstation, the experimental cell was a three-electrode system: the working electrode has an area of 1cm2The counter electrode of the sample to be tested (i.e. 20# mild steel plate, the super-hydrophobic pure nickel coating described in comparative example 1 and the nickel-graphene super-hydrophobic coating described in example 6) was 4cm in area2The reference electrode was a saturated potassium chloride electrode (SCE), using a gold capillary to reduce solution resistance. The test medium is sodium chloride solution with the mass concentration of 3.5%, and the electrokinetic potential polarization test range is as follows: the relative open circuit potential is +/-250 mV, and the scanning rate is 0.3mV-1And the test temperature is room temperature, and Power Suit software is used for carrying out Tafel area extrapolation fitting to obtain corrosion kinetic parameters such as corrosion potential, corrosion current density and the like, as shown in FIG. 4, as can be seen from FIG. 4, the corrosion current density of a sample with a coating is obviously lower than that of a No. 20 low carbon steel plate, and the corrosion current density of the nickel-graphene superhydrophobic coating described in example 6 is also obviously lower than that of the superhydrophobic pure nickel coating described in comparative example 1. The corrosion current densities of the 20# mild steel plate, the pure nickel plating layer described in the comparative example 1 and the nickel-graphene superhydrophobic plating layer described in the example 6 are 1.53 × 10-5A/cm2、1.48×10-7A/cm2And 2.32X 10-8A/cm2. It can be known that the corrosion current of example 6 is reduced by 1 order of magnitude compared with the corrosion current of comparative example 1 and by 3 orders of magnitude compared with No. 20 mild steel plate, which indicates that the nickel-graphene super-hydrophobic coating prepared by the invention has stronger corrosion resistance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A preparation method of a nickel-graphene super-hydrophobic coating is characterized by comprising the following steps:
electroplating in a plating solution by taking a metal matrix as a cathode and nickel as an anode, and then performing vacuum drying to obtain a nickel-graphene super-hydrophobic plating layer on the surface of the metal matrix;
the plating solution comprises nickel chloride and graphene oxide; the concentration of the graphene oxide in the plating solution is 0.05-0.3 g/L; the concentration of nickel chloride in the plating solution is 210-260 g/L;
the current density of the electroplating is 30-60 mA/cm2；
The vacuum drying time is more than or equal to 14 days;
the low surface energy substance modification is not performed after the electroplating is completed.
2. The method according to claim 1, wherein the concentration of graphene oxide in the plating solution is 0.1 to 0.2 g/L.
3. The method according to claim 1 or 2, wherein the plating solution has a pH of 3.9 to 4.1.
4. The method of claim 3, wherein the plating solution further comprises a pH buffer, a crystallization modifier, and a surfactant;
the mass ratio of the pH buffering agent to the crystallization modifier to the surfactant is (30-50): (150-200): (0.1-0.5).
5. The method according to claim 4, wherein the concentration of the pH buffer in the plating solution is 30 to 50 g/L.
6. The method according to claim 1, wherein the distance between the anode and the cathode is 3.8 to 4.2 cm.
7. The method according to claim 1, wherein the plating current density is 40 to 50mA/cm2。
8. The production method according to claim 1 or 7, wherein the electroplating is performed under a condition of stirring;
the electroplating temperature is 55-65 ℃, and the time is 10-12 min; the rotating speed of the stirring is 100-200 rpm.
9. The nickel-graphene superhydrophobic coating prepared by the preparation method according to any one of claims 1 to 8, wherein the surface of the nickel-graphene superhydrophobic coating is of a micro-nano multilevel structure;
the nickel-graphene super-hydrophobic coating comprises a metal nickel layer and graphene nanosheets distributed in the nickel layer.
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| US20170298528A1 (en) * | 2014-10-08 | 2017-10-19 | The Swatch Group Research And Development Ltd | Self-lubricating composite coating |
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| US20170298528A1 (en) * | 2014-10-08 | 2017-10-19 | The Swatch Group Research And Development Ltd | Self-lubricating composite coating |
| CN111334831A (en) * | 2020-04-14 | 2020-06-26 | 广州康滤净化科技有限公司 | Graphene composite copper filtering membrane prepared by chemical method and preparation method thereof |
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