CN117127229A - Magnesium-lithium alloy super-hydrophobic composite coating and preparation method thereof - Google Patents
Magnesium-lithium alloy super-hydrophobic composite coating and preparation method thereof Download PDFInfo
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- CN117127229A CN117127229A CN202311051765.3A CN202311051765A CN117127229A CN 117127229 A CN117127229 A CN 117127229A CN 202311051765 A CN202311051765 A CN 202311051765A CN 117127229 A CN117127229 A CN 117127229A
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- 229910000733 Li alloy Inorganic materials 0.000 title claims abstract description 144
- 239000001989 lithium alloy Substances 0.000 title claims abstract description 144
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 238000000576 coating method Methods 0.000 title claims abstract description 108
- 239000011248 coating agent Substances 0.000 title claims abstract description 107
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 100
- 239000002131 composite material Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 claims abstract description 111
- 238000004070 electrodeposition Methods 0.000 claims abstract description 51
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003792 electrolyte Substances 0.000 claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 18
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 10
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 10
- 238000005520 cutting process Methods 0.000 claims description 6
- 238000005553 drilling Methods 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 6
- 239000008151 electrolyte solution Substances 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 27
- 238000005260 corrosion Methods 0.000 abstract description 27
- 239000011159 matrix material Substances 0.000 abstract description 17
- 238000004140 cleaning Methods 0.000 abstract description 13
- 238000004381 surface treatment Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 19
- 239000011698 potassium fluoride Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229910000861 Mg alloy Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000010892 electric spark Methods 0.000 description 4
- 238000000840 electrochemical analysis Methods 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 230000001939 inductive effect Effects 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 240000002853 Nelumbo nucifera Species 0.000 description 2
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 2
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000003749 cleanliness Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000002057 nanoflower Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 235000003270 potassium fluoride Nutrition 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003466 welding Methods 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
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/026—Anodisation with spark discharge
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/30—Anodisation of magnesium or alloys based thereon
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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)
- Chemical Treatment Of Metals (AREA)
Abstract
The invention provides a magnesium-lithium alloy super-hydrophobic composite coating and a preparation method thereof, and belongs to the technical field of surface treatment. The preparation method provided by the invention comprises the following steps: placing the magnesium-lithium alloy into a micro-arc oxidation electrolyte for micro-arc oxidation treatment to obtain a magnesium-lithium alloy micro-arc oxidation layer; the micro-arc oxidation electrolyte is a solution containing NaOH and Na 2 SiO 3 And KF; placing the obtained magnesium-lithium alloy micro-arc oxidation layer into electrodeposition liquid for electrodeposition to obtain a magnesium-lithium alloy super-hydrophobic composite coating; the electrodeposition liquid contains Sm (NO) 3 ) 3 And CH (CH) 3 (CH 2 ) 12 COOH mixed solution. The magnesium-lithium alloy super-hydrophobic composite coating prepared by the preparation method provided by the invention has higher binding force with the matrix, and the surface of the coating can form a larger contact angle with water, so that the magnesium-lithium alloy super-hydrophobic composite coating has good hydrophobicity, self-cleaning capability and corrosion resistance.
Description
Technical Field
The invention relates to the technical field of surface treatment, in particular to a magnesium-lithium alloy super-hydrophobic composite coating and a preparation method thereof.
Background
The magnesium-lithium alloy is the lightest structural metal material, has the advantages of small density, high specific strength and specific rigidity, excellent electromagnetic shielding property, damping and shock absorbing property, good welding, machining and cold forming capabilities and the like, and can be applied to the fields of aerospace, digital 3C, mechanical manufacturing and the like. However, magnesium-lithium alloy has very active properties, wherein the corrosion potential of magnesium is-2.37V, the corrosion potential of lithium is-3.05V, and the corrosion resistance is very poor, so that the magnesium-lithium alloy is very easy to react with oxygen and water in the air to cause corrosion. The preparation of the coating for protection on the surface of the magnesium-lithium alloy is one of the most effective and most economical methods for improving the corrosion performance of the magnesium-lithium alloy.
In recent years, people obtain inspires from the phenomena of lotus leaf hydrophobicity and self-cleaning in the nature, and super-hydrophobic coatings with static contact angles larger than 150 degrees and rolling angles smaller than 10 degrees are researched. The coating has strong water-repellent capability, can isolate the contact between the corrosive medium and the matrix, and improves the corrosion resistance of the material. At present, common methods for preparing the super-hydrophobic coating comprise chemical conversion film, micro-arc oxidation, electrostatic spinning, chemical etching, electrodeposition and the like. Among them, electrodeposition is favored by industry because of its advantages of low cost, green protection, uniform coating, etc., but because electrodeposition coating has insufficient binding force with substrate, coating is easy to fall off under extreme working conditions, which greatly limits the application range of coating. The magnesium alloy micro-arc oxidation coating is a ceramic oxide layer which is grown on the surface of the magnesium alloy in situ and mainly contains magnesium oxide under the high-temperature and high-pressure environment generated by arc discharge, and has excellent adhesive force with a magnesium substrate, but the outer layer is not compact enough due to a large number of micron-sized holes in the spark discharge, and corrosive media are easily accumulated in the holes to corrode.
Therefore, it is needed to provide a preparation method of a coating, which has high binding force with magnesium-lithium alloy and good corrosion resistance.
Disclosure of Invention
The invention aims to provide a magnesium-lithium alloy super-hydrophobic composite coating and a preparation method thereof. The magnesium-lithium alloy super-hydrophobic composite coating prepared by the preparation method provided by the invention has higher binding force with the matrix, and the surface of the coating can form a larger contact angle with water, so that the magnesium-lithium alloy super-hydrophobic composite coating has good hydrophobic and self-cleaning capabilities and corrosion resistance.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a magnesium-lithium alloy super-hydrophobic composite coating, which comprises the following steps:
(1) Placing the magnesium-lithium alloy into a micro-arc oxidation electrolyte for micro-arc oxidation treatment to obtain a magnesium-lithium alloy micro-arc oxidation layer; the micro-arc oxidation electrolyte is a solution containing NaOH and Na 2 SiO 3 And KF;
(2) Placing the magnesium-lithium alloy micro-arc oxidation layer obtained in the step (1) into electrodeposition liquid for electrodeposition to obtain a magnesium-lithium alloy super-hydrophobic composite coating; the electrodeposition liquid contains Sm (NO) 3 ) 3 And CH (CH) 3 (CH 2 ) 12 COOH mixed solution.
Preferably, the concentration of NaOH in the micro-arc oxidation electrolyte in the step (1) is 6-10 g/L, na 2 SiO 3 The concentration of KF is 8-12 g/L, and the concentration of KF is 3-7 g/L.
Preferably, the power supply for the micro-arc oxidation treatment in the step (1) is an alternating current power supply; the duty ratio of the alternating current power supply is 8-12%, the frequency of the alternating current power supply is 480-520 Hz, and the voltage of the alternating current power supply is 280-320V.
Preferably, the micro-arc oxidation treatment in the step (1) is performed in constant-temperature circulating water; the temperature of the constant-temperature circulating water is 28-31 ℃.
Preferably, the time of the micro-arc oxidation treatment in the step (1) is 2-4 min.
Preferably, the magnesium-lithium alloy in the step (1) is pretreated before being used; the pretreatment comprises cutting, drilling, polishing, ultrasonic cleaning and drying which are sequentially carried out.
Preferably, sm (NO) in the electrodeposition liquid of the step (2) 3 ) 3 The concentration of (C) is 0.06-0.08 mol/L, CH 3 (CH 2 ) 12 The concentration of COOH is 0.08-0.12 mol/L.
Preferably, the power source for electrodeposition in the step (2) is a direct current power source; the voltage of the direct current power supply is 25-45V.
Preferably, the electrodeposition time in the step (2) is 40 to 60 minutes.
The invention also provides the magnesium-lithium alloy super-hydrophobic composite coating obtained by the preparation method.
The invention provides a preparation method of a magnesium-lithium alloy super-hydrophobic composite coating, which comprises the following steps: placing the magnesium-lithium alloy into a micro-arc oxidation electrolyte for micro-arc oxidation treatment to obtain a magnesium-lithium alloy micro-arc oxidation layer; the micro-arc oxidation electrolyte is a solution containing NaOH and Na 2 SiO 3 And KF; placing the obtained magnesium-lithium alloy micro-arc oxidation layer into electrodeposition liquid for electrodeposition to obtain a magnesium-lithium alloy super-hydrophobic composite coating; the electrodeposition liquid contains Sm (NO) 3 ) 3 And CH (CH) 3 (CH 2 ) 12 COOH mixed solution. The invention firstly carries out micro-arc oxidation on the surface of the magnesium-lithium alloy matrix, and can utilize micro-arc oxidation electrolyte and arc dischargeSo as to obtain a film layer with uniform holes; sodium silicate in the micro-arc oxidation electrolyte is a main film forming agent, so that magnesium alloy can rapidly undergo passivation reaction in the electrolyte to generate a layer of insulating film, the resistance of an electrode and a solution interface is increased, the initial voltage can be rapidly increased, and excessive anodic dissolution of a magnesium alloy matrix is prevented; sodium hydroxide and potassium fluoride in the micro-arc oxidation electrolyte are film forming promoters, which are conducive to discharging and improve the conductivity of the solution, and the pH value of the solution can be adjusted to enable the film to be more uniform and smooth, finally, in the micro-arc oxidation discharging process, electric sparks penetrate the film, bubble transfer is generated between the film and the solution, micro-arc holes are formed, the specific surface area and the roughness are higher, and the binding force between the magnesium-lithium alloy substrate and the super-hydrophobic coating can be obviously improved; then, when electrodeposition is performed in the electrodeposition liquid, sm (NO 3 ) 3 And CH (CH) 3 (CH 2 ) 12 COOH reaction to form Sm (CH) 3 (CH 2 ) 12 COO) 3 The complex can be tightly combined on the surface of the micro-arc hole film layer to form a super-hydrophobic coating, so that the surface of the magnesium-lithium alloy has higher hydrophobicity and self-cleaning capability, the contact between a corrosion medium and a magnesium-lithium alloy matrix can be isolated, and the corrosion resistance of the magnesium-lithium alloy is improved.
The results of the embodiment show that the micro-arc oxidation film layer in the magnesium-lithium alloy super-hydrophobic composite coating prepared by the preparation method provided by the invention has tiny and uniform holes, the appearance of the super-hydrophobic film layer at the outermost layer is in a nano flower shape, micro-nano-scale gaps are formed between flowers, air can be captured, and the super-hydrophobic composite coating has very strong water-repellent capability; the coating is compact, no naked micro-arc oxidation coating is seen, and the coating has strong bonding force with the matrix; when the magnesium-lithium alloy super-hydrophobic composite coating is immersed in water for mirror test, water drops can be converged into spherical water drops by SiC powder to roll off, the water drops can not wet the surface of the coating, and the SiC powder can not adhere to the water drops in the sliding path, so that the self-cleaning capability is good; when electrochemical test is carried out, the magnesium-lithium alloy super-hydrophobic composite coating presents inductive reactance arc, and the modulus value at low frequency is as high as 1.7X10 5 Ω·cm 2 WhileBare LA141 magnesium-lithium alloy is only 48 omega cm 2 The low-frequency part modulus of the magnesium-lithium alloy super-hydrophobic composite coating is improved by more than 3500 times, meanwhile, the corrosion voltage of the magnesium-lithium alloy super-hydrophobic composite coating is positively moved, the corrosion current density is reduced by three orders of magnitude relative to the LA141 magnesium-lithium alloy, and the corrosion resistance is greatly improved. Therefore, the magnesium-lithium alloy super-hydrophobic composite coating prepared by the preparation method provided by the invention has higher binding force with the matrix, and the surface of the coating can form a larger contact angle with water, so that the magnesium-lithium alloy super-hydrophobic composite coating has good hydrophobic and self-cleaning capabilities and corrosion resistance.
Drawings
FIG. 1 is a scanning electron microscope image of the surface of a micro-arc oxide layer of a magnesium-lithium alloy obtained in the step (1) of the embodiment 1;
FIG. 2 is a scanning electron microscope image of the cross section of the micro-arc oxidation layer of the magnesium-lithium alloy obtained in the step (1) of the embodiment 1;
FIG. 3 is a scanning electron microscope image of the surface of the superhydrophobic layer in the superhydrophobic composite coating of magnesium-lithium alloy prepared in example 1 of the invention;
FIG. 4 is a graph showing the contact angle between the surface of the superhydrophobic composite coating of magnesium-lithium alloy prepared in example 1 and water drops;
FIG. 5 is a graph showing the test result of the "specular response" of the superhydrophobic composite coating of magnesium-lithium alloy prepared in example 2 of the invention;
FIG. 6 is a graph of the "self-cleaning" test results of the superhydrophobic composite coating of magnesium-lithium alloy prepared in example 3 of the invention;
FIG. 7 is a graph showing the test results of nano scratches of the magnesium-lithium alloy micro-arc oxide layer obtained in the step (1) and the magnesium-lithium alloy super-hydrophobic composite coating prepared in the step (2) in the embodiment 3; wherein the left graph of fig. 7 is a nano scratch test chart of the magnesium-lithium alloy micro-arc oxidation layer obtained in the step (1) of example 3, and the right graph of fig. 7 is a nano scratch test chart of the magnesium-lithium alloy super-hydrophobic composite coating prepared in the step (2) of example 3;
FIG. 8 is a Nyquist plot of the LA141 magnesium-lithium alloy used in step (1) of example 1 of the present invention;
FIG. 9 is a Nyquist plot of the superhydrophobic composite coating of magnesium-lithium alloy prepared in example 1 of the invention;
FIG. 10 is a graph showing the Bode impedance modulus of the LA141 magnesium-lithium alloy used in step (1) of example 1 of the present invention;
FIG. 11 is a graph showing the Bode impedance modulus of the superhydrophobic composite coating of magnesium-lithium alloy prepared in example 1 of the invention;
FIG. 12 is a polarization curve of the superhydrophobic composite coating of magnesium-lithium alloy prepared in example 1 of the invention.
Detailed Description
The invention provides a preparation method of a magnesium-lithium alloy super-hydrophobic composite coating, which comprises the following steps:
(1) Placing the magnesium-lithium alloy into a micro-arc oxidation electrolyte for micro-arc oxidation treatment to obtain a magnesium-lithium alloy micro-arc oxidation layer; the micro-arc oxidation electrolyte is a solution containing NaOH and Na 2 SiO 3 And KF;
(2) Placing the magnesium-lithium alloy micro-arc oxidation layer obtained in the step (1) into electrodeposition liquid for electrodeposition to obtain a magnesium-lithium alloy super-hydrophobic composite coating; the electrodeposition liquid contains Sm (NO) 3 ) 3 And CH (CH) 3 (CH 2 ) 12 COOH mixed solution.
The magnesium-lithium alloy is placed in a micro-arc oxidation electrolyte for micro-arc oxidation treatment, so that a magnesium-lithium alloy micro-arc oxidation layer is obtained.
The source of the magnesium-lithium alloy is not particularly required, and the magnesium-lithium alloy prepared by the conventional commercial method or the conventional method in the field can be adopted. In the present invention, the magnesium-lithium alloy is preferably LA141 magnesium-lithium alloy.
In the invention, the magnesium-lithium alloy is preferably pretreated before use; the pretreatment preferably includes cutting, drilling, polishing, ultrasonic cleaning, and drying, which are sequentially performed. The invention has no special requirements for the specific operations of cutting, drilling, polishing, ultrasonic cleaning and drying, and conventional methods well known in the art can be adopted. According to the invention, the magnesium-lithium alloy is subjected to the pretreatment, the cutting and drilling are utilized to obtain proper size and facilitate connection conduction to carry out micro-arc oxidation treatment, and then the polishing, ultrasonic cleaning and drying are utilized to remove oxides and impurities on the surface of the magnesium-lithium alloy, so that the surface of the magnesium-lithium alloy is smoother and cleaner, and the formed composite film layer is more favorable to be tightly combined on the surface of the magnesium-lithium alloy.
In the invention, the micro-arc oxidation electrolyte contains NaOH and Na 2 SiO 3 And KF. In the present invention, the solvent of the micro-arc oxidation electrolyte is preferably deionized water. According to the invention, sodium silicate is used as a main film forming agent, so that magnesium alloy can rapidly undergo passivation reaction in electrolyte to generate a layer of insulating film, the resistance of an electrode and a solution interface is increased, the initial voltage can be rapidly increased, and excessive anodic dissolution of a magnesium alloy matrix is prevented; sodium hydroxide and potassium fluoride are used as film forming promoters, so that the electric discharge is facilitated, the conductivity of the solution is improved, the pH value of the solution can be regulated to enable the film to be more uniform and smooth, finally, in the micro-arc oxidation discharge process, electric sparks penetrate the film, bubble transfer is generated between the film and the solution, micro-arc holes are formed, the specific surface area and the roughness are high, and the binding force between a magnesium-lithium alloy matrix and the super-hydrophobic coating can be remarkably improved.
In the present invention, the concentration of NaOH in the electrodeposition bath is preferably 6 to 10g/L, more preferably 7 to 9g/L; na in the electrodeposition liquid 2 SiO 3 The concentration of (2) is preferably 8 to 12g/L, more preferably 9 to 11g/L; the concentration of KF in the electrodeposition liquid is preferably 3 to 7g/L, more preferably 4 to 6g/L. The concentration of each substance in the micro-arc oxidation electrolyte is controlled within the range, so that the uniform and tiny holes of the formed micro-arc oxidation film layer can be ensured, the follow-up super-hydrophobic film layer is more favorably and tightly combined on the surface of the micro-arc oxidation film layer, and the film layer and the substrate have higher bonding force.
In the invention, the power supply for the micro-arc oxidation treatment is preferably an alternating current power supply; the duty ratio of the alternating current power supply is preferably 8-12%, more preferably 9-11%; the frequency of the alternating current power supply is preferably 480-520 Hz, more preferably 490-510 Hz; the voltage of the ac power supply is preferably 280 to 320V, more preferably 290 to 310V. The invention is more beneficial to uniformly depositing the micro-arc oxidation electrolyte to form a film layer and forming uniform and tiny holes under the discharge action of electric sparks by adopting the alternating current power supply and controlling the parameters of the alternating current power supply in the range.
In the invention, the micro-arc oxidation treatment is preferably carried out in constant-temperature circulating water; the temperature of the constant temperature circulating water is preferably 28-31 ℃. The micro-arc oxidation treatment is carried out under the condition of constant-temperature circulating water, so that the micro-arc oxidation electrolyte can be ensured not to be obviously heated under the action of higher current, the temperature of the electrolyte is stabilized in a lower range, the uniform deposition of the micro-arc oxidation electrolyte is ensured to form a film layer, and uniform and tiny holes are formed under the discharge action of electric sparks.
In the present invention, the time of the micro-arc oxidation treatment is preferably 2 to 4 minutes. The invention can ensure that the magnesium-lithium alloy micro-arc oxidation layer has proper thickness by controlling the time of the micro-arc oxidation treatment within the range.
After the micro-arc oxidation is completed, the method preferably carries out ultrasonic cleaning and drying on the products of the micro-arc oxidation treatment in sequence to obtain the magnesium-lithium alloy micro-arc oxidation layer. The invention has no special requirements on the ultrasonic cleaning and drying operation, and can ensure that the treated film layer has higher cleanliness. According to the invention, after micro-arc oxidation is completed, ultrasonic cleaning and drying are carried out, so that residual micro-arc oxidation electrolyte and unfixed particles in holes of the magnesium-lithium alloy micro-arc oxidation layer can be removed, the film layer has higher cleanliness, and the super-hydrophobic coating is more favorably tightly combined on the surface of the film layer.
After the magnesium-lithium alloy micro-arc oxidation layer is obtained, the obtained magnesium-lithium alloy micro-arc oxidation layer is placed in electrodeposition liquid for electrodeposition, and the magnesium-lithium alloy super-hydrophobic composite coating is obtained.
In the present invention, the electrodeposition liquid contains Sm (NO 3 ) 3 And CH (CH) 3 (CH 2 ) 12 COOH mixed solution. In the present invention, the solvent of the electrodeposition liquid is preferably ethanol. The invention can lead Sm (NO 3 ) 3 And CH (CH) 3 (CH 2 ) 12 COOH reaction to form Sm (CH) 3 (CH 2 ) 12 COO) 3 The complex is tightly combined on the surface of the micro-arc hole film layer to form a super-hydrophobic composite coating, so that the surface of the magnesium-lithium alloy has higher hydrophobicity and self-cleaning capability, the contact between a corrosion medium and a magnesium-lithium alloy matrix can be isolated, and the corrosion resistance of the magnesium-lithium alloy is improved.
In the present invention, sm (NO 3 ) 3 The concentration of (2) is preferably 0.06 to 0.08mol/L, more preferably 0.07 to 0.075mol/L; CH in the electrodeposition liquid 3 (CH 2 ) 12 The concentration of COOH is preferably 0.08 to 0.12mol/L, more preferably 0.09 to 0.11mol/L. The concentration of each substance in the electrodeposition liquid is controlled within the range, so that the formed super-hydrophobic film layer can be ensured to be more uniform, smooth and compact.
In the present invention, the power source for electrodeposition is preferably a direct current power source; the voltage of the direct current power supply is preferably 25 to 45V. The invention can ensure that the formed super-hydrophobic layer is even, smooth and compact by adopting the direct current power supply to carry out electrodeposition and controlling the voltage thereof within the range.
In the present invention, the electrodeposition is preferably performed in constant temperature circulating water; the temperature of the constant temperature circulating water is preferably 28-31 ℃. According to the invention, through electrodeposition under the condition of constant-temperature circulating water, the temperature of the electrodeposition liquid is kept stable without being influenced by current, and the formation of a compact and uniform superhydrophobic layer in the electrodeposition process is ensured.
In the present invention, the time of the electrodeposition is preferably 40 to 60 minutes. The invention is more beneficial to obtaining the super-hydrophobic layer with proper thickness by controlling the electrodeposition time within the range.
The magnesium-lithium alloy super-hydrophobic composite coating prepared by the preparation method provided by the invention has good corrosion resistance, and the preparation method is simple and feasible, the parameters are easy to control, and the cost is low.
The invention also provides the magnesium-lithium alloy super-hydrophobic composite coating obtained by the preparation method.
In the invention, the magnesium-lithium alloy super-hydrophobic composite coating preferably comprises a micro-arc oxidation layer and a super-hydrophobic layer which are sequentially arranged on the surface of the magnesium-lithium alloy. The micro-arc oxidation layer and the super-hydrophobic layer are combined, so that the composite coating has high binding force and corrosion resistance.
In the invention, the thickness of the micro-arc oxidation layer is preferably 10-15 mu m; the average diameter of the holes of the micro-arc oxidation layer is preferably 1-2 mu m. The invention is more beneficial to the high binding force between the composite coating and the matrix and between the micro-arc oxidation layer and the super-hydrophobic layer by controlling the thickness of the micro-arc oxidation layer and the average diameter of the holes in the range.
In the present invention, the thickness of the superhydrophobic layer is preferably 30 to 40 μm. The thickness of the super-hydrophobic layer is controlled within the range, so that the composite coating and the matrix have high binding force and excellent corrosion resistance.
The magnesium-lithium alloy super-hydrophobic composite coating provided by the invention has high binding force with the matrix, excellent corrosion resistance and wider application prospect.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A preparation method of a magnesium-lithium alloy super-hydrophobic composite coating comprises the following steps:
(1) Placing the pretreated magnesium-lithium alloy into a micro-arc oxidation electrolyte for micro-arc oxidation treatment, and then sequentially performing ultrasonic cleaning and drying to obtain a magnesium-lithium alloy micro-arc oxidation layer (marked as MAO); the micro-arc oxidation electrolyte is NaOH and Na 2 SiO 3 And KF;
specifically: cutting LA141 magnesium-lithium alloy into 50mm multiplied by 20mm multiplied by 0.35mm, drilling small holes with phi 3mm on the surface of the alloy, penetrating pure aluminum wires, sequentially polishing with 400# abrasive paper, 600# abrasive paper, 1000# abrasive paper and 1500# abrasive paper, sequentially ultrasonically cleaning with acetone and ethanol, and finally drying for later use.
With 8g/LNaOH, 10g/LNa 2 SiO 3 Preparing micro-arc oxidation electrolyte by 5g/LKF and deionized water, placing the pretreated LA141 magnesium-lithium alloy into the prepared micro-arc oxidation electrolyte, and carrying out micro-arc oxidation treatment by adopting an alternating current power supply (three-phase power), wherein the parameters of the alternating current power supply are as follows: duty cycle 10%, frequency 500Hz, voltage 300V, time 3min; after the micro-arc oxidation is finished, ultrasonic cleaning is carried out for 10min by using alcohol, and then the magnesium-lithium alloy micro-arc oxidation layer (marked as MAO) is obtained after taking out and drying by using a blower to blow;
(2) Placing the magnesium-lithium alloy micro-arc oxidation layer obtained in the step (1) into electrodeposition liquid for electrodeposition to obtain a magnesium-lithium alloy super-hydrophobic composite coating (marked as MAO-SHS); the electrodeposition liquid is Sm (NO) 3 ) 3 And CH (CH) 3 (CH 2 ) 12 A mixed solution of COOH;
specifically: taking the magnesium-lithium alloy micro-arc oxidation layer obtained in the step (1) as a cathode, taking a Pt electrode as an anode, and putting the anode and the cathode in parallel into 0.074mol/L Sm (NO) 3 ) 3 、0.1mol/LCH 3 (CH 2 ) 12 In an ethanol solution of COOH, adjusting the distance between two polar plates to be 2cm, switching on a direct current power supply, adjusting the voltage of the direct current power supply to be 40V, and carrying out electrodeposition for 40min, taking out a sample, and naturally air-drying to obtain the magnesium-lithium alloy super-hydrophobic composite coating (marked as MAO-SHS).
The magnesium-lithium alloy super-hydrophobic composite coating prepared by the preparation method comprises a micro-arc oxidation layer and a super-hydrophobic layer which are sequentially arranged on the surface of the magnesium-lithium alloy; the thickness of the micro-arc oxidation layer is 10.63 mu m; the average diameter of the holes of the micro-arc oxidation layer is 1-2 mu m; the thickness of the superhydrophobic layer was 34 μm.
Example 2
The electrodeposition time in step (2) of example 1 was replaced with 50min, and the other technical features were the same as those of example 1.
The magnesium-lithium alloy super-hydrophobic composite coating prepared by the preparation method comprises a micro-arc oxidation layer and a super-hydrophobic layer which are sequentially arranged on the surface of the magnesium-lithium alloy; the thickness of the micro-arc oxidation layer is 10.5 mu m; the average diameter of the holes of the micro-arc oxidation layer is 1-2 mu m; the thickness of the super-hydrophobic layer is 35.6 μm.
Note that: although parameters are consistent when the micro-arc oxidation layer is obtained in the micro-arc oxidation step, a certain error exists in multiple experiments, and the thickness error of the micro-arc oxidation layer is +/-0.97 mu m.
Example 3
The electrodeposition time in step (2) of example 1 was replaced with 60min, and the other technical features were the same as those of example 1.
The magnesium-lithium alloy super-hydrophobic composite coating prepared by the preparation method comprises a micro-arc oxidation layer and a super-hydrophobic layer which are sequentially arranged on the surface of the magnesium-lithium alloy; the thickness of the micro-arc oxidation layer is 10.56 mu m; the average diameter of the holes of the micro-arc oxidation layer is 1-2 mu m; the thickness of the superhydrophobic layer is 32.3 μm.
Note that: since the trend of the influence of the electrodeposition time on the deposition thickness is not increased in proportion, the thickness is increased and then decreased in a certain period of time, and since the electrodeposition driving force is larger as the electrodeposition time is prolonged, a small part of the film layer is peeled off.
And (2) observing the microstructure on the surface and the microstructure on the section of the magnesium-lithium alloy micro-arc oxidation layer obtained in the step (1) in the embodiment 1 by adopting a scanning electron microscope, wherein the observed scanning electron microscope images are respectively shown in figures 1-2.
As can be seen from fig. 1, the surface of the micro-arc oxide layer in example 1 has uniform and micro holes, and the average size of the holes is about 1-2 μm; and as can be seen from fig. 2, the membrane layer structure at the section of the micro-arc oxidation layer is tightly combined with the LA141 magnesium-lithium alloy matrix.
And observing the microstructure of the surface of the superhydrophobic layer in the superhydrophobic composite coating of the magnesium-lithium alloy prepared in the embodiment 1 by adopting a scanning electron microscope, wherein the observed scanning electron microscope is shown in fig. 3.
As can be seen from fig. 3, the surface morphology of the superhydrophobic layer presents a nano flower shape, and micro-nano-scale gaps are formed among flowers, so that air can be captured, and a geometric condition is provided for superhydrophobic performance; and the coating structure is compact, and no naked micro-arc oxidation coating is seen, which indicates that the super-hydrophobic layer finishes the hole sealing treatment of the micro-arc oxidation layer.
And (3) performing a contact angle test on the surface of the magnesium-lithium alloy super-hydrophobic composite coating prepared in the embodiment 1, namely dripping a drop of deionized water on the surface of the magnesium-lithium alloy super-hydrophobic composite coating to form a water drop, and forming a contact angle between the water drop and a coating interface, wherein the obtained contact angle test result is shown in a graph shown in fig. 4.
As can be seen from fig. 4, the contact angle formed by the interface of the water drop and the coating is 151.8 degrees, and the contact angle level of 150 degrees on the surface of the lotus leaf in nature can be reached, which indicates that the magnesium-lithium alloy super-hydrophobic composite coating prepared by the invention has excellent hydrophobic and self-cleaning capabilities.
The magnesium-lithium alloy super-hydrophobic composite coating prepared in example 2 was subjected to a "specular reaction" test, i.e., the magnesium-lithium alloy super-hydrophobic composite coating was placed in a beaker containing deionized water, and the test results are shown in fig. 5.
As can be seen from fig. 5, since the superhydrophobic coating realizes water repellency by trapping air to form an air layer at the coating interface, when the superhydrophobic coating is immersed in water, the refractive index is also changed due to the change of the medium, resulting in macroscopically representing that the superhydrophobic coating is converted from white in air to silver in an aqueous solution. The magnesium-lithium alloy super-hydrophobic composite coating prepared by the invention has excellent water repellency.
The "self-cleaning" test of the magnesium-lithium alloy super-hydrophobic composite coating prepared in example 3, that is, placing SiC powder (for simulating soil) on the magnesium-lithium alloy super-hydrophobic composite coating, and respectively dripping a drop of deionized water with different volumes on the powder surface, wherein the test results are shown in fig. 6.
As can be seen from fig. 6, siC powder on the surface of the superhydrophobic composite coating of the magnesium-lithium alloy is adsorbed into water drops, and neither the water drops nor the SiC powder adhere to the surface of the coating, i.e. the path of the water drops sliding off the surface of the coating remains clean, which indicates that the superhydrophobic composite coating of the magnesium-lithium alloy prepared by the invention has excellent self-cleaning capability.
Respectively carrying out nano scratch test on the magnesium-lithium alloy micro-arc oxidation layer obtained in the step (1) in the embodiment 3 and the magnesium-lithium alloy super-hydrophobic composite coating prepared in the step (2), wherein the obtained test results are shown in fig. 7; wherein the left graph of fig. 7 is a nano scratch test chart of the magnesium-lithium alloy micro-arc oxidation layer obtained in the step (1) of example 3, and the right graph of fig. 7 is a nano scratch test chart of the magnesium-lithium alloy super-hydrophobic composite coating prepared in the step (2) of example 3.
As can be seen from fig. 7, the binding force of the magnesium-lithium alloy micro-arc oxidation layer obtained in the step (1) in the embodiment 3 is 4970mN, and the binding force of the magnesium-lithium alloy super-hydrophobic composite coating prepared in the step (2) in the embodiment 3 is 6390mN. Therefore, the binding force of the composite coating is superior to that of a single micro-arc oxidation layer, and the pinning (meshing) effect formed by the micro-arc oxidation layer is proved to be capable of remarkably improving the adhesive force of the super-hydrophobic layer.
Electrochemical tests are carried out on the LA141 magnesium-lithium alloy used in the step (1) of the embodiment 1 and the magnesium-lithium alloy super-hydrophobic composite coating prepared in the step (2) through a Wuhan Korst electrochemical workstation, a three-electrode system is selected, a saturated calomel electrode is selected as a reference electrode, an electrolyte is 3.5wt.% sodium chloride solution, an open circuit point test is carried out for 600 seconds, then an electrochemical impedance test is carried out, and the set scanning frequency range is from 10 5 Hz to 10 -2 Hz, disturbance amplitude is 10mV, and the obtained Nyquist plots are shown in FIGS. 8-9, respectively.
As can be seen from fig. 8, capacitive arcs exist at high and medium frequencies, inductive arcs exist at low frequencies, and the inductive loops are related to Mg dissolution, indicating that pitting of the LA141 magnesium-lithium alloy matrix occurs; whereas the nyquist plot of MAO-SHS of FIG. 9 has two distinct capacitive arcs, no inductive arcs occur. The magnesium-lithium alloy super-hydrophobic composite coating prepared by the invention has excellent corrosion resistance.
Electrochemical tests were carried out on the LA141 magnesium-lithium alloy used in the step (1) of example 1 and the magnesium-lithium alloy super-hydrophobic composite coating prepared in the step (2) by the same method as the electrochemical test, and the obtained Bode impedance modulus diagrams are shown in figures 10-11 respectively.
As can be seen from FIGS. 10 to 11, the magnesium-lithium alloy is super-hydrophobicThe modulus of the water composite coating is as high as 1.7X10 at low frequency 5 Ω·cm 2 While the LA141 magnesium-lithium alloy is only 48 omega cm 2 Namely, the modulus of the composite coating is improved by 3500 times, and the corrosion resistance is greatly improved.
The superhydrophobic composite coating of the magnesium-lithium alloy prepared in example 1 was electrochemically tested by the wuhan koste electrochemical workstation, a three-electrode system was selected, a saturated calomel electrode was selected as the reference electrode, 3.5wt.% sodium chloride solution was used as the electrolyte, a scanning potential ranging from-2.5 v to +2.5v was selected, the scanning speed was 1mV/s, and the polarization graph obtained by the test was shown in fig. 12.
As can be seen from fig. 12, after the magnesium-lithium alloy is protected by the MAO-SHS composite coating, the corrosion voltage is forward shifted, the corrosion current density is reduced by three orders of magnitude, and the corrosion resistance is greatly improved.
In conclusion, the magnesium-lithium alloy super-hydrophobic composite coating prepared by the preparation method provided by the invention has higher binding force with the matrix, and the surface of the coating can form a larger contact angle with water, so that the coating has good hydrophobic and self-cleaning capabilities and corrosion resistance.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the magnesium-lithium alloy super-hydrophobic composite coating is characterized by comprising the following steps of:
(1) Placing the magnesium-lithium alloy into a micro-arc oxidation electrolyte for micro-arc oxidation treatment to obtain a magnesium-lithium alloy micro-arc oxidation layer; the micro-arc oxidation electrolyte is a solution containing NaOH and Na 2 SiO 3 And KF;
(2) Placing the magnesium-lithium alloy micro-arc oxidation layer obtained in the step (1) into electrodeposition liquid for electrodeposition to obtain a magnesium-lithium alloy super-hydrophobic composite coating; the electrodeposition liquid contains Sm (NO) 3 ) 3 And CH (CH) 3 (CH 2 ) 12 COOH mixed solution.
2. The preparation method according to claim 1, wherein the concentration of NaOH in the micro-arc oxidation electrolyte solution in the step (1) is 6-10 g/L, na 2 SiO 3 The concentration of KF is 8-12 g/L, and the concentration of KF is 3-7 g/L.
3. The method of claim 1, wherein the power source for the micro-arc oxidation treatment in step (1) is an ac power source; the duty ratio of the alternating current power supply is 8-12%, the frequency of the alternating current power supply is 480-520 Hz, and the voltage of the alternating current power supply is 280-320V.
4. The method according to claim 1 or 3, wherein the micro-arc oxidation treatment in the step (1) is performed in constant temperature circulating water; the temperature of the constant-temperature circulating water is 28-31 ℃.
5. The method according to claim 1 or 3, wherein the time of the micro-arc oxidation treatment in the step (1) is 2 to 4 minutes.
6. The method of claim 1, wherein the magnesium-lithium alloy in step (1) is pretreated prior to use; the pretreatment comprises cutting, drilling, polishing, ultrasonic cleaning and drying which are sequentially carried out.
7. The method of claim 1, wherein Sm (NO 3 ) 3 The concentration of (C) is 0.06-0.08 mol/L, CH 3 (CH 2 ) 12 The concentration of COOH is 0.08-0.12 mol/L.
8. The method of claim 1, wherein the power source for electrodeposition in step (2) is a dc power source; the voltage of the direct current power supply is 25-45V.
9. The method according to claim 1 or 8, wherein the electrodeposition time in the step (2) is 40 to 60 minutes.
10. The superhydrophobic composite coating of magnesium-lithium alloy according to any one of claims 1-9.
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