CN115110128B - Method for preparing high-stability nickel myristate super-hydrophobic coating on metal surface - Google Patents
Method for preparing high-stability nickel myristate super-hydrophobic coating on metal surface Download PDFInfo
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- CN115110128B CN115110128B CN202210702079.7A CN202210702079A CN115110128B CN 115110128 B CN115110128 B CN 115110128B CN 202210702079 A CN202210702079 A CN 202210702079A CN 115110128 B CN115110128 B CN 115110128B
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 65
- 239000002184 metal Substances 0.000 title claims abstract description 65
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 49
- 238000000576 coating method Methods 0.000 title claims abstract description 35
- CJIRDPOUAUKPJI-UHFFFAOYSA-L nickel(2+);tetradecanoate Chemical compound [Ni+2].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O CJIRDPOUAUKPJI-UHFFFAOYSA-L 0.000 title claims abstract description 34
- 239000011248 coating agent Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 100
- 238000007747 plating Methods 0.000 claims abstract description 51
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 50
- 239000007788 liquid Substances 0.000 claims abstract description 33
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000007797 corrosion Effects 0.000 claims abstract description 22
- 238000005260 corrosion Methods 0.000 claims abstract description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 20
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 17
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 17
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 16
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000004070 electrodeposition Methods 0.000 claims description 29
- 238000005238 degreasing Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000009713 electroplating Methods 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 230000003213 activating effect Effects 0.000 claims description 12
- 238000005498 polishing Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004327 boric acid Substances 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 8
- 229910001369 Brass Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004115 Sodium Silicate Substances 0.000 claims description 6
- 239000010951 brass Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 239000001488 sodium phosphate Substances 0.000 claims description 6
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 6
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 2
- 238000005530 etching Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 6
- 239000008367 deionised water Substances 0.000 abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 3
- KAKKLJAJCVHTAM-UHFFFAOYSA-N nickel;tetradecanoic acid Chemical compound [Ni].CCCCCCCCCCCCCC(O)=O KAKKLJAJCVHTAM-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 41
- 238000001035 drying Methods 0.000 description 27
- 238000005299 abrasion Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 244000137852 Petrea volubilis Species 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000011010 flushing procedure Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006355 external stress Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/025—Cleaning or pickling metallic material with solutions or molten salts with acid solutions acidic pickling pastes
-
- 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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention discloses a method for preparing a high-stability nickel myristate super-hydrophobic coating on a metal surface, and belongs to the field of super-hydrophobic coatings. Firstly, preparing a pure nickel layer on the surface of a metal sheet by using a Watt nickel plating solution; then carrying out corrosion treatment in anode corrosive liquid prepared from nickel sulfate, sulfuric acid and deionized water, so as to generate micron-sized holes; and finally, electrodepositing in a solution prepared from nickel chloride, tetradecanoic acid and absolute ethyl alcohol to obtain the nickel tetradecanoic acid super-hydrophobic coating. The invention prepares micron-sized holes by adopting an anodic corrosion method, and combines the nickel myristate particles with low surface energy to improve the stability of the super-hydrophobic coating. The preparation method has the advantages of simple preparation process and low production cost, and can widen the application field of the high-stability superhydrophobic material.
Description
Technical Field
The invention belongs to the field of super-hydrophobic coatings, and particularly relates to a method for preparing a high-stability nickel myristate super-hydrophobic coating on a metal surface.
Background
Metals such as copper, magnesium, iron and the like and alloys thereof are used as metal materials which are widely applied in industry, and are easy to be oxidized and corroded in the atmosphere environment, so that accelerated aging of products, environmental pollution and huge waste of resources are caused. It is often desirable to plate the metal surface with a plating of nickel, chromium, or the like to alleviate or solve the problem of poor corrosion resistance. However, with the development of high and new technologies, materials are also subjected to increasingly complex use environments, and the conventional single nickel plating layer cannot meet the corrosion resistance requirement under the severe environment.
The superhydrophobic surface is a surface with a water contact angle of 150 degrees or more and a rolling angle of 10 degrees or less, shows hydrophobicity, and is widely applied to the scientific fields of anti-fog, anti-icing, oil-water separation and the like. In recent years, researchers have found that the superhydrophobic film layer can significantly reduce the contact area between the metal surface and the corrosive medium, thereby reducing or inhibiting the corrosive attack of the corrosive medium on the metal material. However, the superhydrophobic film layer has the defects of insufficient stability and poor reliability, and the surface micro-nano structure is easily damaged and loses superhydrophobic performance when the superhydrophobic film layer is subjected to external stress, so that the industrial application of the superhydrophobic film layer is limited to a great extent.
Disclosure of Invention
The invention provides a method for preparing a high-stability nickel tetradecanoate super-hydrophobic coating on a metal surface in order to solve the characteristics of insufficient stability and poor reliability of the existing super-hydrophobic surface. The method has low cost and simple process, and is suitable for industrial mass production.
The aim of the invention is achieved by the following technical scheme.
A method for preparing a high-stability nickel tetradecanoate super-hydrophobic coating on a metal surface comprises the following steps:
(1) Pretreating the metal surface;
(2) Carrying out nickel plating treatment on the pretreated metal in the step (1);
(3) Taking the metal subjected to nickel plating treatment in the step (2) as an anode, placing the anode into anode corrosive liquid for corrosion, wherein the cathode is a brass plate; the anode corrosive liquid is prepared by nickel sulfate and sulfuric acid in water;
(4) Taking the metal sheet subjected to anodic corrosion treatment in the step (3) as a cathode, and placing the cathode into an electrodeposition solution to perform electrodeposition of nickel tetradecanoate, wherein the anode is a graphite plate; the electrodeposition solution is prepared from nickel chloride and tetradecanoic acid in absolute ethanol.
Preferably, the voltage of the electrodeposition in the step (4) is 10-35V, and the time is 10-20 min.
Preferably, the voltage of the electrodeposition in the step (4) is 20-30V.
Preferably, the voltage of the electrodeposition in the step (4) is 25V and the time is 15min.
Preferably, the anodic corrosive liquid in the step (3) comprises the following components: 80-120 g/L of nickel sulfate and 160-360 ml/L of sulfuric acid. The sulfuric acid concentration was 98wt%.
Preferably, in the step (3), the anodic etching has a current density of 1 to 2A/dm 2 The time is 1-30 min.
Preferably, in the step (4), the electrodeposited product is placed in a drying oven for drying; the drying time is 60-120 min.
Preferably, the step of pretreating the metal surface in the step (1) comprises non-plating surface insulation, plating surface polishing, ultrasonic degreasing and activation; the non-plating surface insulation is to insulate the non-plating surface of the metal sheet by using epoxy resin; the plating surface is polished to remove oxides and other impurities on the surface to be plated with metal; the ultrasonic degreasing is to put the polished metal sheet into degreasing liquid for ultrasonic alkaline cleaning degreasing; the activation is to put the metal sheet after ultrasonic alkali washing treatment into an activating solution for activation; the oil removing liquid comprises 10-20 g/L of sodium hydroxide, 10-20 g/L of sodium carbonate, 10-25 g/L of sodium phosphate and 10-25 g/L of sodium silicate; the activating solution comprises 15wt% hydrochloric acid solution; the types of the sand paper for polishing are 800#, 1000#, 1200#, the ultrasonic degreasing temperature is 60-70 ℃ and the time is 3-5 min; the activation time is 5-15 s.
Preferably, the degreasing liquid and the nickel plating liquid both use distilled water as a solvent.
Preferably, the nickel plating treatment in the step (2) is to take the pretreated metal sheet in the step (1) as a cathode, and place the cathode in a nickel plating solution for nickel plating, wherein the anode is a pure nickel plate; the nickel plating solution is prepared from nickel sulfate, nickel chloride, boric acid and sodium dodecyl sulfate in water; the nickel plating solution comprises the following components: 300-360 g/L nickel sulfate, 30-60 g/L nickel chloride, 30-40 g/L boric acid and 0.05-0.15 g/L sodium dodecyl sulfate; the electroplating temperature is 45-55 ℃, the current density is 3-5A/dm < 2 >, the electroplating time is 1-2 hours, the pH of the nickel plating solution is 3.8-5.6, and the electroplating process is added with magnetic stirring of 300-500 r/min.
A highly stable nickel tetradecanoate superhydrophobic coating obtained by any of the above preparation methods.
Compared with the prior art, the invention has the following advantages and effects:
(1) The method for preparing the high-stability nickel tetradecanoate super-hydrophobic coating on the metal surface has the advantages of low production cost and simple process, and is suitable for industrial mass production.
(2) The invention utilizes the anode corrosion method to generate a porous structure on the surface of the traditional nickel plating layer, and combines the porous structure with the super-hydrophobic plating layer, thereby improving the stability of the super-hydrophobic plating layer.
(3) The super-hydrophobic coating prepared by the method avoids the use of fluorine-containing harmful substances, and has less harm to the environment.
Drawings
Fig. 1 is a scanning electron microscope image of an anodized nickel layer prepared in example 1 and a graph of contact angle test results at various voltages.
Fig. 2 is a three-dimensional morphology graph of the super-hydrophobic nickel tetradecanoate coating prepared in example 2 and a graph of contact angle test results after abrasion.
Fig. 3 is a scanning electron microscope image of the super-hydrophobic nickel tetradecanoate plating layer prepared in example 3 and a contact angle test result graph after abrasion.
Fig. 4 is a graph showing the infrared spectrogram of the super-hydrophobic nickel tetradecanoate coating prepared in example 4 and the contact angle test result after abrasion.
Fig. 5 is a graph showing the contact angle test result of the abrasion of the super-hydrophobic nickel tetradecanoate coating prepared in comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto. For process parameters not specifically noted, reference may be made to conventional techniques.
Example 1
A method for preparing a high-stability nickel tetradecanoate super-hydrophobic coating on a metal surface comprises the following specific operation steps:
step one: pretreatment of metal surfaces
A metal sheet having a size of 30X 40X 1 (mm) was selected, and the non-plated surface was subjected to an insulation treatment with an epoxy resin. Sequentially polishing the surface to be plated by using abrasive paper of No. 800, no. 1000 and No. 1200, repeatedly flushing with deionized water and absolute ethyl alcohol after polishing, and drying; immersing the metal sheet into degreasing liquid, ultrasonically cleaning for 4 minutes at the temperature of 65 ℃, taking out, washing with absolute ethyl alcohol, and drying, wherein the degreasing liquid is 15g/L sodium hydroxide, 15g/L sodium carbonate, 17g/L sodium phosphate and 17g/L sodium silicate; immersing the metal sheet in an activating solution for 10 seconds, taking out, washing with absolute ethyl alcohol, and drying, wherein the activating solution is a 15wt% hydrochloric acid solution.
Step two: electroplated nickel layer
Placing the metal sheet obtained in the first step into nickel plating solution as cathode, wherein the anode is pure nickel plate, the electroplating temperature is 50deg.C, and the current density is 4.5A/dm 2 Electroplating time is 1.5 hours, pH of the nickel plating solution is 4.7, and magnetic stirring of 400r/min is added in the electroplating process; the nickel plating solution is a mixed aqueous solution of 330g/L nickel sulfate, 45g/L nickel chloride, 35g/L boric acid and 0.1g/L sodium dodecyl sulfate;
step three: anodic corrosion of
Placing the metal sheet obtained in the second step into anode corrosive liquid, wherein the cathode is a brass plate, the anode corrosion temperature is 25 ℃, and the current density is 1.5A/dm 2 The time is 15min; anodeThe corrosive liquid is a mixed aqueous solution of 100g/L nickel sulfate and 260ml/L sulfuric acid (98 wt%);
step four: electrodeposition of tetradecanoic acid
Placing the metal sheet obtained in the third step into an electrodeposition solution as a cathode, wherein the anode is a graphite plate, the temperature of electrodeposition is 25 ℃, the voltages are 10, 15, 20, 25, 30, 35 and 40V respectively, and the time is 15min; the electrodeposition liquid is a mixed ethanol solution of 20g/L nickel chloride and 40g/L tetradecanoic acid; placing the electrodeposited material in a drying oven for drying; the drying time was 80min.
The prepared super-hydrophobic nickel myristate coating is subjected to the following detection and characterization:
(1) Surface structure analysis: the scanning electron microscope image of the anode corrosion nickel layer prepared in the embodiment is shown in (a) in fig. 1, and after anode corrosion, a hole structure appears on the surface of the nickel layer, which is favorable for the deposition of tetradecanoic acid nickel particles therein and provides a certain structural foundation for the stability of the superhydrophobic layer.
(2) Wettability analysis: the contact angle test results of the super-hydrophobic nickel tetradecanoate plating layers prepared under different voltages in this example are shown in fig. 1 (b). Therefore, when the tetradecanoic acid is electrodeposited, the obtained coating has super-hydrophobic performance under the voltage of 10-35V.
Example 2
A method for preparing a high-stability nickel tetradecanoate super-hydrophobic coating on a metal surface comprises the following specific operation steps:
step one: pretreatment of metal surfaces
A metal sheet having a size of 30X 40X 1 (mm) was selected, and the non-plated surface was subjected to an insulation treatment with an epoxy resin. Sequentially polishing the surface to be plated by using abrasive paper of No. 800, no. 1000 and No. 1200, repeatedly flushing with deionized water and absolute ethyl alcohol after polishing, and drying; immersing the metal sheet into degreasing liquid, ultrasonically cleaning for 3 minutes at the temperature of 60 ℃, taking out, washing with absolute ethyl alcohol, and drying, wherein the degreasing liquid is 10g/L sodium hydroxide, 10g/L sodium carbonate, 10g/L sodium phosphate and 10g/L sodium silicate; immersing the metal sheet in an activating solution for 5 seconds, taking out, washing with absolute ethyl alcohol, and drying, wherein the activating solution is a 15wt% hydrochloric acid solution.
Step two: electroplated nickel layer
Placing the metal sheet obtained in the first step into nickel plating solution as cathode, wherein the anode is pure nickel plate, the electroplating temperature is 45 ℃, and the current density is 3A/dm 2 The electroplating time is 1 hour, the pH of the nickel plating solution is 3.8, and magnetic stirring of 300r/min is added in the electroplating process; the nickel plating solution is a mixed aqueous solution of 300g/L nickel sulfate, 30g/L nickel chloride, 30g/L boric acid and 0.05g/L sodium dodecyl sulfate;
step three: anodic corrosion of
Placing the metal sheet obtained in the second step into anode corrosive liquid, wherein the cathode is a brass plate, the anode corrosion temperature is 25 ℃, and the current density is 1A/dm 2 The time is 1min; the anode corrosive liquid is a mixed aqueous solution of 80g/L nickel sulfate and 160ml/L sulfuric acid (98 wt%);
step four: electrodeposition of tetradecanoic acid
Placing the metal sheet obtained in the third step into an electrodeposition solution as a cathode, wherein the anode is a graphite plate, the electrodeposition temperature is 25 ℃, the voltage is 20V, and the time is 10min; the electrodeposition liquid is a mixed ethanol solution of 10g/L nickel chloride and 20g/L tetradecanoic acid; placing the electrodeposited material in a drying oven for drying; the drying time was 60min.
The prepared anode corrosion nickel layer is subjected to the following detection and characterization:
(1) Surface morphology and roughness analysis: the three-dimensional morphology graph of the anode corrosion nickel layer prepared in the embodiment is shown in (a) of fig. 2, the surface roughness of the nickel layer after anode corrosion reaches 3.38 mu m, and the three-dimensional morphology graph provides an advantageous coarse morphology for preparing the high-stability nickel myristate super-hydrophobic coating.
(2) Stability analysis: the contact angle test result of the super-hydrophobic nickel tetradecanoate plating layer prepared in this example after abrasion by sand paper (abrasion was performed on the 800# sand paper surface at a speed of 1cm/s under a pressure of 2.63 kPa) is shown in fig. 2 (b). When the abrasion distance reaches 900 mm, the coating can still maintain superhydrophobicity.
Example 3
A method for preparing a high-stability nickel tetradecanoate super-hydrophobic coating on a metal surface comprises the following specific operation steps:
step one: pretreatment of metal surfaces
A metal sheet having a size of 30X 40X 1 (mm) was selected, and the non-plated surface was subjected to an insulation treatment with an epoxy resin. Sequentially polishing the surface to be plated by using abrasive paper of No. 800, no. 1000 and No. 1200, repeatedly flushing with deionized water and absolute ethyl alcohol after polishing, and drying; immersing the metal sheet into degreasing liquid, ultrasonically cleaning for 4 minutes at the temperature of 65 ℃, taking out, washing with absolute ethyl alcohol, and drying, wherein the degreasing liquid is 15g/L sodium hydroxide, 15g/L sodium carbonate, 17g/L sodium phosphate and 17g/L sodium silicate; immersing the metal sheet in an activating solution for 10 seconds, taking out, washing with absolute ethyl alcohol, and drying, wherein the activating solution is a 15wt% hydrochloric acid solution.
Step two: electroplated nickel layer
Placing the metal sheet obtained in the first step into nickel plating solution as cathode, wherein the anode is pure nickel plate, the electroplating temperature is 50deg.C, and the current density is 4.5A/dm 2 Electroplating time is 1.5 hours, pH of the nickel plating solution is 4.7, and magnetic stirring of 400r/min is added in the electroplating process; the nickel plating solution is a mixed aqueous solution of 330g/L nickel sulfate, 45g/L nickel chloride, 35g/L boric acid and 0.1g/L sodium dodecyl sulfate;
step three: anodic corrosion of
Placing the metal sheet obtained in the second step into anode corrosive liquid, wherein the cathode is a brass plate, the anode corrosion temperature is 25 ℃, and the current density is 1.5A/dm 2 The time is 15min; the anode corrosive liquid is a mixed aqueous solution of 100g/L nickel sulfate and 260ml/L sulfuric acid (98 wt%);
step four: electrodeposition of tetradecanoic acid
Placing the metal sheet obtained in the third step into an electrodeposition solution as a cathode, wherein the anode is a graphite plate, the electrodeposition temperature is 25 ℃, the voltage is 25V, and the time is 15min; the electrodeposition liquid is a mixed ethanol solution of 20g/L nickel chloride and 40g/L tetradecanoic acid; placing the electrodeposited material in a drying oven for drying; the drying time was 80min.
The prepared super-hydrophobic nickel myristate coating is subjected to the following detection and characterization:
(1) Surface topography analysis: the scanning electron microscope image of the super-hydrophobic nickel tetradecanoate plating layer prepared in this example is shown in (a) of figure 3,
(2) Stability analysis: the contact angle test result of the super-hydrophobic nickel tetradecanoate plating layer prepared in this example after abrasion by sand paper (abrasion was performed on the 800# sand paper surface at a speed of 1cm/s under a pressure of 2.63 kPa) is shown in fig. 3 (b). When the abrasion distance reaches 1200 mm, the coating can still maintain superhydrophobicity.
Example 4
A method for preparing a high-stability nickel tetradecanoate super-hydrophobic coating on a metal surface comprises the following specific operation steps:
step one: pretreatment of metal surfaces
A metal sheet having a size of 30X 40X 1 (mm) was selected, and the non-plated surface was subjected to an insulation treatment with an epoxy resin. Sequentially polishing the surface to be plated by using abrasive paper of No. 800, no. 1000 and No. 1200, repeatedly flushing with deionized water and absolute ethyl alcohol after polishing, and drying; immersing the metal sheet into degreasing liquid, ultrasonically cleaning for 5 minutes at the temperature of 70 ℃, taking out, washing with absolute ethyl alcohol, and drying, wherein the degreasing liquid is 20g/L sodium hydroxide, 20g/L sodium carbonate, 25g/L sodium phosphate and 25g/L sodium silicate; immersing the metal sheet in an activating solution for 15 seconds, taking out, washing with absolute ethyl alcohol, and drying, wherein the activating solution is a 15wt% hydrochloric acid solution.
Step two: electroplated nickel layer
Placing the metal sheet obtained in the first step into nickel plating solution as cathode, wherein the anode is a pure nickel plate, the electroplating temperature is 55 ℃, and the current density is 5A/dm 2 Electroplating time is 2 hours, pH of the nickel plating solution is 5.6, and magnetic stirring of 500r/min is added in the electroplating process; the nickel plating solution is a mixed aqueous solution of 360g/L nickel sulfate, 60g/L nickel chloride, 40g/L boric acid and 0.15g/L sodium dodecyl sulfate;
step three: anodic corrosion of
Placing the metal sheet obtained in the second step into anode corrosive liquid, wherein the cathode is a brass plate, the anode corrosion temperature is 25 ℃, and the current density is 2A/dm 2 The time is 30min; the anode corrosive liquid is a mixed aqueous solution of 120g/L nickel sulfate and 360ml/L sulfuric acid (98 wt%);
step four: electrodeposition of tetradecanoic acid
Placing the metal sheet obtained in the third step into an electrodeposition solution as a cathode, wherein the anode is a graphite plate, the electrodeposition temperature is 25 ℃, the voltage is 30V, and the time is 20min; the electrodeposition liquid is a mixed ethanol solution of 30g/L nickel chloride and 60g/L tetradecanoic acid; placing the electrodeposited material in a drying oven for drying; the drying time was 120min.
The prepared super-hydrophobic nickel myristate coating is subjected to the following detection and characterization:
(1) Chemical component analysis: the Fourier transform infrared spectrogram of the super-hydrophobic nickel myristate coating prepared in the embodiment is shown in (a) of fig. 4, and compared with the infrared spectrogram of pure tetradecanoic acid, the infrared spectrogram of the super-hydrophobic nickel myristate coating is 2918cm -1 And 2850cm -1 The two nearby peak positions are basically the same, and are symmetrical telescopic vibration and antisymmetric telescopic vibration of C-H respectively; is located at 1702cm in tetradecanoic acid -1 The peak position at which corresponds to the carboxyl group (-COOH) in tetradecanoic acid, whereas in the spectrum of the superhydrophobic surface, the peak position at which disappears, but at 1633cm -1 And 1555cm -1 Two new peaks appear, which correspond to salts of carboxylic acid groups.
(2) Stability analysis: the contact angle test result of the super-hydrophobic nickel tetradecanoate plating layer prepared in this example after abrasion by sand paper (abrasion was performed on the 800# sand paper surface at a speed of 1cm/s under a pressure of 2.63 kPa) is shown in fig. 4 (b). When the abrasion distance reaches 750 mm, the coating can still maintain superhydrophobicity.
Comparative example 1
On the basis of example 3, other conditions and steps are controlled unchanged, the third step is omitted, a nickel myristate super-hydrophobic coating is prepared on the metal surface, and the following characterization is carried out:
(1) Stability analysis: the contact angle test result of the nickel tetradecanoate super-hydrophobic coating prepared in the comparative example after abrasion is shown in fig. 5, and when the abrasion distance reaches only 450 mm, the coating loses super-hydrophobicity.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (8)
1. The method for preparing the high-stability nickel tetradecanoate super-hydrophobic coating on the metal surface is characterized by comprising the following steps of:
(1) Pretreating the metal surface;
(2) Carrying out nickel plating treatment on the pretreated metal in the step (1);
(3) Taking the metal subjected to nickel plating treatment in the step (2) as an anode, placing the anode into anode corrosive liquid for corrosion, wherein the cathode is a brass plate; the anode corrosive liquid is prepared by nickel sulfate and sulfuric acid in water;
(4) Taking the metal sheet subjected to anodic corrosion treatment in the step (3) as a cathode, and placing the cathode into an electrodeposition solution to perform electrodeposition of nickel tetradecanoate, wherein the anode is a graphite plate; the electrodeposition solution is prepared from nickel chloride and tetradecanoic acid in absolute ethyl alcohol;
the anode corrosive liquid in the step (3) comprises the following components: 80-120 g/L of nickel sulfate and 160-360 ml/L of sulfuric acid;
in the step (3), the current density of the anodic etching is 1-2A/dm 2 The time is 1-30 min.
2. The method of claim 1, wherein the voltage of the electrodeposition in step (4) is 10-35V for 10-20 min.
3. The method of claim 2, wherein the voltage of the electrodeposition in step (4) is 20-30V.
4. A method according to claim 3, wherein the voltage of the electrodeposition in step (4) is 25V for 15min.
5. The method of claim 1, wherein the electrodeposition bath composition of step (4) is: 10-30 g/L of nickel chloride and 20-60 g/L of tetradecanoic acid.
6. The method of claim 1, wherein the step of pre-treating the metal surface of step (1) comprises non-plating insulation, plating polishing, ultrasonic degreasing and activation; the non-plating surface insulation is to insulate the non-plating surface of the metal sheet by using epoxy resin; the plating surface is polished to remove oxides and other impurities on the surface to be plated with metal; the ultrasonic degreasing is to put the polished metal sheet into degreasing liquid for ultrasonic alkaline cleaning degreasing; the activation is to put the metal sheet after ultrasonic alkali washing treatment into an activating solution for activation; the oil removing liquid comprises 10-20 g/L of sodium hydroxide, 10-20 g/L of sodium carbonate, 10-25 g/L of sodium phosphate and 10-25 g/L of sodium silicate; the activating solution comprises 15wt% hydrochloric acid solution; the temperature of ultrasonic degreasing is 60-70 ℃ and the time is 3-5 min; the activation time is 5-15 s.
7. The method according to claim 1, wherein the nickel plating treatment in the step (2) is to place the pretreated metal sheet in the step (1) as a cathode in a nickel plating solution for nickel plating, and the anode is a pure nickel plate; the nickel plating solution is prepared from nickel sulfate, nickel chloride, boric acid and sodium dodecyl sulfate in water; the nickel plating solution comprises the following components: 300-360 g/L of nickel sulfate, 30-60 g/L of nickel chloride, 30-40 g/L of boric acid and 0.05-0.15 g/L of sodium dodecyl sulfate; the temperature of the electroplating is 45-55 ℃, and the current density is 3-5A/dm 2 The electroplating time is 1-2 hours, the pH of the nickel plating solution is 3.8-5.6, and magnetic stirring of 300-500 r/min is added in the electroplating process.
8. A highly stable nickel tetradecanoate superhydrophobic coating obtained by the method of any one of claims 1-7.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1283916A (en) * | 1968-09-28 | 1972-08-02 | Plessey Co Ltd | Improvements relating to electro-deposition |
| JPS59104442A (en) * | 1982-12-02 | 1984-06-16 | Masahide Ichikawa | Preparation of porous metal nickel |
| CN101007304A (en) * | 2007-01-12 | 2007-08-01 | 华南理工大学 | Processing method of aluminum and aluminum alloy super hydrophobic surface |
| CN103952732A (en) * | 2014-04-11 | 2014-07-30 | 华南理工大学 | Metal super-hydrophobic surface and preparation method thereof |
| CN105256342A (en) * | 2015-10-19 | 2016-01-20 | 华南理工大学 | Copper-based super-hydrophobic surface and preparation method thereof |
-
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- 2022-06-21 CN CN202210702079.7A patent/CN115110128B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1283916A (en) * | 1968-09-28 | 1972-08-02 | Plessey Co Ltd | Improvements relating to electro-deposition |
| JPS59104442A (en) * | 1982-12-02 | 1984-06-16 | Masahide Ichikawa | Preparation of porous metal nickel |
| CN101007304A (en) * | 2007-01-12 | 2007-08-01 | 华南理工大学 | Processing method of aluminum and aluminum alloy super hydrophobic surface |
| CN103952732A (en) * | 2014-04-11 | 2014-07-30 | 华南理工大学 | Metal super-hydrophobic surface and preparation method thereof |
| CN105256342A (en) * | 2015-10-19 | 2016-01-20 | 华南理工大学 | Copper-based super-hydrophobic surface and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| "Fabrication of super-hydrophobic nickel film on copper substrate with improved corrosion inhibition by electrodeposition process";Zhen Yang等;《COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS》;第560卷;第205-212页 * |
| Yuze Ye等."Achieving hierarchical structure with superhydrophobicity and enhanced anti-corrosion via electrochemical etching and chemical vapor deposition".《Applied Surface Science》.2022,第610卷第1-13页. * |
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