CN106835219B - A kind of super-hydrophobic stainless steel surface coating and preparation method thereof - Google Patents
A kind of super-hydrophobic stainless steel surface coating and preparation method thereof Download PDFInfo
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- CN106835219B CN106835219B CN201710039436.5A CN201710039436A CN106835219B CN 106835219 B CN106835219 B CN 106835219B CN 201710039436 A CN201710039436 A CN 201710039436A CN 106835219 B CN106835219 B CN 106835219B
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- 239000010935 stainless steel Substances 0.000 title claims abstract description 134
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 134
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000011248 coating agent Substances 0.000 title claims description 23
- 238000000576 coating method Methods 0.000 title claims description 23
- 238000004070 electrodeposition Methods 0.000 claims abstract description 76
- 239000000463 material Substances 0.000 claims abstract description 60
- 239000002086 nanomaterial Substances 0.000 claims abstract description 57
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 27
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 239000010949 copper Substances 0.000 claims abstract description 8
- 230000005855 radiation Effects 0.000 claims abstract description 8
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims description 30
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 20
- 150000002815 nickel Chemical class 0.000 claims description 13
- 238000002425 crystallisation Methods 0.000 claims description 12
- 230000008025 crystallization Effects 0.000 claims description 12
- 239000003607 modifier Substances 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- 230000033228 biological regulation Effects 0.000 claims description 5
- 239000008139 complexing agent Substances 0.000 claims description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 3
- HCFPRFJJTHMING-UHFFFAOYSA-N ethane-1,2-diamine;hydron;chloride Chemical group [Cl-].NCC[NH3+] HCFPRFJJTHMING-UHFFFAOYSA-N 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 150000001879 copper Chemical class 0.000 claims 2
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims 2
- 239000000126 substance Substances 0.000 abstract description 7
- 230000003373 anti-fouling effect Effects 0.000 abstract description 6
- 241000894006 Bacteria Species 0.000 abstract description 5
- 230000003628 erosive effect Effects 0.000 abstract description 5
- 238000001556 precipitation Methods 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 230000004913 activation Effects 0.000 description 18
- 239000002659 electrodeposit Substances 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 238000000151 deposition Methods 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000003921 oil Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 230000008021 deposition Effects 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 239000013527 degreasing agent Substances 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000005611 electricity Effects 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- 238000005498 polishing Methods 0.000 description 6
- 238000004062 sedimentation Methods 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 230000010148 water-pollination Effects 0.000 description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001509 sodium citrate Substances 0.000 description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 3
- 239000001488 sodium phosphate Substances 0.000 description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000002519 antifouling agent Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical group [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical class NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229910000792 Monel Inorganic materials 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 208000021760 high fever Diseases 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- NFIYTPYOYDDLGO-UHFFFAOYSA-N phosphoric acid;sodium Chemical compound [Na].OP(O)(O)=O NFIYTPYOYDDLGO-UHFFFAOYSA-N 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 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
- C25D5/10—Electroplating with more than one layer of the same or of different metals
-
- 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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
- C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The present invention provides a kind of super-hydrophobic stainless steel watch finishing coats, super-hydrophobic stainless steel watch finishing coat includes the micro-nano structure being arranged in array, micro-nano structure includes micron order pointed cone and nanoscale whisker, nanoscale whisker forms petal-like structures to external radiation centered on micron order pointed cone, and the material of micro-nano structure includes at least one of nickel, copper and mickel copper alloy.Super-hydrophobic stainless steel watch finishing coat provided by the invention can effectively obstruct corrosive medium, bacterium, albumen erosion and stick, so as to realize anticorrosion and antifouling performance.The present invention also provides a kind of preparation methods of super-hydrophobic stainless steel watch finishing coat, including prepare super-hydrophobic stainless steel watch finishing coat in surface of stainless steel Direct precipitation by orientation electrodeposition process；Preparation method of the present invention is not necessarily to template, and is not limited by stainless steel material shape, modifies without organic low-surface energy substance, reduces costs, reduce process flow, and can regulate and control the growth and size of deposit.
Description
Technical field
The present invention relates to super hydrophobic material fields, and in particular to a kind of super-hydrophobic stainless steel watch finishing coat and its preparation side
Method.
Background technique
Research of the China in Seawate-corrosive-resisting steel field is started late, and the foundation of marine material system is simultaneously not perfect, tradition
Material 316L stainless steel is still widely used as marine engineering equipment material, but this material is in the Nan Haihai of high temperature and humidity
Occurs serious corrosion failure in foreign environment, it is dirty that reason is mostly derived from more active marine microorganism under the conditions of high humidity high fever
Damage activity accelerates the spot corrosion to 316L stainless steel.
The method that the anticorrosion and antifouling of marine engineering equipment metal material mainly uses paint spraying at present.Traditional anti-corrosion is anti-
For dirty coating mainly with organotin and cuprous oxide for main anti-fouling agent, the addition of these anti-fouling agents causes the marine eco-environment
Destruction very serious.Recently, preparing super hydrophobic surface also in metal material surface may be implemented anticorrosion and antifouling performance.Currently,
Preparing the main method of super hydrophobic surface both at home and abroad includes: self-assembly method, etching method, sol-gal process, chemical vapor deposition, electricity
Chemical deposition, electrochemistry anodic oxidation and mechanical processing method etc..But the above method, which exists, prepares required equipment valuableness, and technique is multiple
It is miscellaneous, expensive low-surface energy substance silicon fluoride need to be used to modify, at high cost, the defects of environment is unfriendly.
Summary of the invention
To solve the above problems, the present invention provides a kind of super-hydrophobic stainless steel watch finishing coats and preparation method thereof.This hair
The preparation method simple process of bright super-hydrophobic stainless steel watch finishing coat, the super-hydrophobicity of super-hydrophobic stainless steel watch finishing coat obtained
It can be good with corrosion resistance.
First aspect present invention provides a kind of super-hydrophobic stainless steel watch finishing coat, the super-hydrophobic stainless steel watch finishing coat
Including the micro-nano structure being arranged in array, the micro-nano structure includes micron order pointed cone and nanoscale whisker, and the nanoscale is brilliant
Must centered on the micron order pointed cone to external radiation formed petal-like structures, the material of the micro-nano structure include nickel, copper and
At least one of monel.
Preferably, the surface of the micro-nano structure have oxide layer, the oxide layer with a thickness of 10nm-100nm.
Preferably, the height of the micron order pointed cone is 0.1 μm -0.7 μm, and average diameter is 0.4 μm -0.6 μm, adjacent institute
Stating the distance between micron order pointed cone is 0.2 μm -0.3 μm.
Preferably, the length of the nanoscale whisker is 100nm-250nm.
The super-hydrophobic stainless steel watch finishing coat that first aspect present invention provides includes the micro-nano structure being arranged in array, essence
Thin micro-nano two-dimensional structure and low-surface-energy characteristic has played the effect of entrapped air, can obstruct corrosive medium, bacterium, albumen
Erosion and stick, to realize anticorrosion and antifouling performance.
Second aspect of the present invention provides a kind of preparation method of super-hydrophobic stainless steel watch finishing coat, comprising:
(1) stainless steel material is provided, the stainless steel material is pre-processed；
(2) it is immersed in the electrodeposit liquid containing nickel salt and/or mantoquita using pretreated stainless steel material as cathode, it will
Nickel plate or platinum sheet carry out first time electro-deposition, the temperature of the first time electro-deposition in the surface of stainless steel as anode
Degree is 40-80 DEG C, current density 0.1-5A/dm2, electrodeposition time 50-1000s；
(3) second of electro-deposition, the temperature of second of electro-deposition are carried out in the surface of stainless steel that step (2) obtains
Degree is 40-80 DEG C, the big 7-10A/ of current density of first time electro-deposition described in the current density ratio of second of electro-deposition
dm2, second of electrodeposition time be shorter than first time electrodeposition time；After electro-deposition, in the stainless steel material table
The micro-nano structure that wheat flour must be arranged in array, to obtain super-hydrophobic stainless steel watch finishing coat；
The super-hydrophobic stainless steel watch finishing coat includes the micro-nano structure being arranged in array, and the micro-nano structure includes micron
Grade pointed cone and nanoscale whisker, the nanoscale whisker form petal-shaped knot to external radiation centered on the micron order pointed cone
Structure, the material of the micro-nano structure include at least one of nickel, copper and mickel copper alloy.
Preferably, the current density of second of electro-deposition is 8-15A/dm2, the time of second of electro-deposition is
1s-500s。
Preferably, by surface that step (3) obtains have micro-nano structure coating stainless steel material be placed in temperature be 10 DEG C-
5d-30d is stored in the environment that 40 DEG C and humidity are 10%-50%, the surface of the micro-nano structure is oxidized, to obtain super thin
Water stainless steel watch finishing coat.
Preferably, the concentration of the nickel salt in the electrodeposit liquid and/or mantoquita is 0.1-3mol/L.
Preferably, the electrodeposit liquid further includes the complexing agent of 0.1-1mol/L and the crystallization modifier of 0.1-3mol/L,
The complexing agent is one or more of citrate, borate and acetate, and the crystallization modifier is ethylenediamine hydrochloric acid
Salt.
Preferably, the pH value of the electrodeposit liquid is 1.0-7.0.
The preparation method for a kind of super-hydrophobic stainless steel watch finishing coat that second aspect of the present invention provides, by orienting electro-deposition
For method in surface of stainless steel Direct precipitation prepares coating, preparation method is simple to operation, is not necessarily to template, and not by stainless steel
Expect shape limitation, super-hydrophobic stainless steel surface coating surface obtained is made of micron order pointed cone and nanoscale whisker, is in array
Shape distribution, has preferable ultra-hydrophobicity and antibacterium Adhesion property, modifies without organic low-surface energy substance, reduces
Cost, reduces process flow, and can regulate and control the growth and size of deposition morphology.
To sum up, beneficial effect of the present invention includes the following aspects:
1, super-hydrophobic stainless steel watch finishing coat provided by the invention includes the micro-nano structure being arranged in array, and fine is micro-
Two-dimensional structure of receiving has played the effect of entrapped air with low-surface-energy characteristic, can obstruct the erosion of corrosive medium, bacterium, albumen
With stick, to realize anticorrosion and antifouling performance；
2, the preparation method of super-hydrophobic stainless steel watch finishing coat provided by the invention, preparation method is simple to operation, reduces
Cost, reduces process flow, and can regulate and control the growth and size of deposition morphology.
Detailed description of the invention
Fig. 1 is the microscopic appearance figure of super-hydrophobic stainless steel watch finishing coat made from the embodiment of the present invention 1；
Fig. 2 is the shape appearance figure that micron order pointed cone made from the embodiment of the present invention 1 passes through atomic force microscope observation；
Fig. 3 is the hydrophily macro-test and contact angle of super-hydrophobic stainless steel watch finishing coat made from the embodiment of the present invention 1
Test chart.
Specific embodiment
The following is a preferred embodiment of the present invention, it is noted that for those skilled in the art
For, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also considered as
Protection scope of the present invention.
In a first aspect, the present invention provides a kind of super-hydrophobic stainless steel watch finishing coat, super-hydrophobic stainless steel watch finishing coat packet
The micro-nano structure being arranged in array is included, micro-nano structure includes micron order pointed cone and nanoscale whisker, and nanoscale whisker is with micron order
Petal-like structures are formed to external radiation centered on pointed cone, the material of micro-nano structure includes nickel, at least one in copper and mickel copper alloy
Kind.
In the present invention, super-hydrophobic stainless steel watch finishing coat is arranged in surface of stainless steel.
In the present invention, the height of micron order pointed cone is 0.1 μm -0.7 μm.
In the present invention, the height of micron order pointed cone is 0.4 μm -0.6 μm.
In the present invention, the average diameter of micron order pointed cone is 0.4 μm -0.6 μm.
In the present invention, the average diameter of micron order pointed cone is 0.4 μm, 0.5 μm or 0.6 μm.
In the present invention, the distance between adjacent micron order pointed cone is 0.2 μm -0.3 μm.
In the present invention, the length of nanoscale whisker is 100nm-250nm.
In the present invention, the length of nanoscale whisker is 200nm.
In the present invention, the surface of micro-nano structure has an oxide layer, oxide layer with a thickness of 10nm-100nm.
In the present invention, oxide layer with a thickness of 10nm-50nm.
In the present invention, oxide layer with a thickness of 10nm-20nm.
In the present invention, oxide layer is nickel oxide and/or copper oxide.
In the present invention, super-hydrophobic stainless steel watch finishing coat includes the micro-nano structure being arranged in array, and micro-nano structure includes micro-
The surface of meter level pointed cone and nanoscale whisker, micron order pointed cone and nanoscale whisker is oxidized to form oxide layer, the table of oxide layer
Face can it is lower, can obstruct corrosive medium, bacterium, albumen erosion and stick.
The super-hydrophobic stainless steel watch finishing coat that first aspect present invention provides, nanoscale whisker is centered on micron order pointed cone
Petal-like structures are formed to external radiation, fine micro-nano two-dimensional structure and low-surface-energy characteristic have played the work of entrapped air
With, can effectively obstruct corrosive medium, bacterium, albumen erosion and stick, so as to realize anticorrosion and antifouling performance.
Second aspect, the present invention provides a kind of preparation methods of super-hydrophobic stainless steel watch finishing coat, comprising:
(1) stainless steel material is provided, stainless steel material is pre-processed；
(2) it is immersed in the electrodeposit liquid containing nickel salt and/or mantoquita using pretreated stainless steel material as cathode, it will
Nickel plate or platinum sheet carry out first time electro-deposition in surface of stainless steel, the temperature of first time electro-deposition is 40-80 as anode
DEG C, current density 0.1-5A/dm2, electrodeposition time 50-1000s；
(3) second of electro-deposition is carried out in the surface of stainless steel that step (2) obtains, the temperature of second of electro-deposition is
40-80 DEG C, the big 7-9A/dm of current density of the current density ratio first time electro-deposition of second of electro-deposition2, second of electro-deposition
Time is shorter than first time electrodeposition time；After electro-deposition, the micro-nano knot being arranged in array is made in surface of stainless steel
Structure, to obtain super-hydrophobic stainless steel watch finishing coat；
Super-hydrophobic stainless steel watch finishing coat includes the micro-nano structure being arranged in array, micro-nano structure include micron order pointed cone and
Nanoscale whisker, nanoscale whisker form petal-like structures, the material of micro-nano structure to external radiation centered on micron order pointed cone
Including at least one of nickel, copper and mickel copper alloy.
In the present invention, stainless steel material is austenitic stainless steel.
In the present invention, stainless steel material is 316L stainless steel.
In the present invention, the pretreatment of stainless steel material is successively to carry out at oil removal treatment and acid-wash activation to stainless steel material
Reason.
In the present invention, the temperature of oil removal treatment is 70 DEG C -90 DEG C, time 5min-20min.
In the present invention, the temperature of acid-wash activation is room temperature, time 1min-6min.
In the present invention, carrying out oil removal treatment to stainless steel material is that stainless steel material is placed in alkaline degreaser to remove
Oil, alkaline degreaser include that concentration is 10g/L-40g/L sodium hydroxide, 20g/L-50g/L sodium carbonate, 10g/L-30g/L phosphoric acid
Sodium and 5g/L-10g/L alkyl polyoxyethylene ether.
In the present invention, the solvent in alkaline degreaser is distilled water.
In the present invention, to stainless steel material carry out acid-wash activation processing for by stainless steel material be placed in acid-wash activation liquid into
The processing of row acid-wash activation, acid-wash activation liquid include the hydrochloric acid solution that volume ratio is 5mL/L-20mL/L, the vinegar of 5mL/L-10mL/L
The phosphoric acid solution of acid solution and 5mL/L-10mL/L.
In the present invention, the concentration of hydrochloric acid solution is 35%, and the concentration of acetum is 99.3%, and the concentration of phosphoric acid solution is
85.0%.
After pre-processing to stainless steel material, the quality and electro-deposition modified layer of subsequent electrodeposition modified layer can be improved
With the binding force of material.
In the present invention, nickel salt is nickeliferous or nickeliferous and its alloying metal ions salt.
In the present invention, nickel salt is at least one of nickeliferous sulfate, chlorate or acetate.
In the present invention, mantoquita is at least one of sulfate, chlorate or the acetate of cupric.
In the present invention, the concentration of nickel salt and/or mantoquita in electrodeposit liquid is 0.1-3mol/L.
In the present invention, electrodeposit liquid further includes the complexing agent of 0.1-1mol/L and the crystallization modifier of 0.1-3mol/L, network
Mixture is one or more of citrate, borate and acetate, and crystallization modifier is ethylenediamine-hydrochloride.
In the present invention, the pH value of electrodeposit liquid is 1.0-7.0.
In the present invention, the pH value of electrodeposit liquid is 1.0,2.0,3.0,4.0,5.0,6.0 or 7.0.
In the present invention, contain crystallization modifier in electrodeposit liquid, in deposition process, crystallization modifier is to metal difference crystal face
Have the function of Characteristic Adsorption, keeps the speed of growth of the crystal on different crystal faces different, to be easily formed petal-like structures.
In the present invention, stainless steel material, nickel plate or platinum sheet and constant-current supply are connected by circuit by conducting wire.
In the present invention, direct current or pulse current is may be selected in electro-deposition electric current.
In the present invention, the current density of second of electro-deposition is 8-15A/dm2。
In the present invention, the time of first time electro-deposition is 500s-1000s.
In the present invention, the time of second of electro-deposition is 1s-500s.
In the present invention, the time of second of electro-deposition is 1s-400s.
In the present invention, the time of second of electro-deposition is 1s-50s.
In the present invention, it is 10 that the surface that step (3) obtains, which is placed in temperature with the stainless steel material of micro-nano structure coating,
5d-30d is stored in the environment that DEG C -40 DEG C and humidity are 10%-50%, the surface of micro-nano structure is oxidized, to obtain super thin
Water stainless steel watch finishing coat.After electro-deposition, under condition of storage of the invention, pointed cone and nanoscale nickel whisker in the micron-scale
Surface forms oxide layer, and the surface of oxide layer can be lower, to facilitate steady in surface of stainless steel formation ultra-hydrophobicity
The presence of fixed surface covering, simultaneous oxidation layer will not influence the pattern of micro-nano structure.
In the present invention, in first electrodeposition process, the metal ion under the conditions of cathodic polarization in surface of stainless steel fills
Sufficient supply area generates shelf depreciation effect, is locally there is the generation of elemental metals salient point, with the increase of polarized current density,
The extension of polarization time continues to discharge at metal salient point, forms the growth and focusing of multiple crystal grain.And it cannot get metal ion
The region of abundance supply, i.e. concave point, these concave points are distributed between the pointed cone structure that the salient point gradually grown up is formed, increase micro-
The roughness on micro-nano structure surface, subsequent micro-nano structure surface are covered by low-surface energy substance nickel oxide (NiO), improve micro-nano knot
The hydrophobic performance of structure.Crystallization modifier can be adsorbed on some particular crystal plane in electrodeposition process, inhibit the extension of the crystal face raw
It is long.During double electrodeposition under the conditions of larger current electro-deposition cathodic polarization, suction of the crystallization modifier in metal longitudinal direction crystal face
Attached situation is different, and micron order pointed cone structure slows down in longitudinal growth speed at this time, and the growth in crystal face (100) and (111) obtains
It must develop, ultimately form petal-like structures.
In the present invention, principles of electro-deposition is oriented using electrochemistry, by regulating and controlling electro-deposition electric current and electrodeposition time twice
The horizontal and vertical growth of micro-nano structure is controlled, to obtain super-hydrophobic stainless steel watch finishing coat in stainless steel surface.It is super-hydrophobic
Stainless steel watch finishing coat includes the micro-nano structure being arranged in array, and orientation electro-deposition control condition includes: to obtain micron order
The longitudinal growth of pointed cone array structure, i.e. micron order pointed cone deposit for the first time in surface of stainless steel longitudinal growth, implementation, in order to
The cross growth of cone cell array structure is obtained, i.e. secondary deposition is implemented in the growth of nanoscale whisker.It is in after orientation electro-deposition
The micro-nano structure of array arrangement.
The present invention utilizes simple constant-current supply and electrolytic cell, the electrodeposit liquid of design environment close friend, thus in material table
Face electro-deposition goes out the micro-nano structure of specific morphology, obtains ultra-hydrophobicity using specific morphology structure and ingredient, is without the use of and appoints
What low-surface energy substance.It solves the valuableness of equipment needed for prior art preparation, complex process, and uses expensive low surface
Energy substance silicon fluoride modification, at high cost, the disagreeableness disadvantage of environment.The present invention is by using pretreatment activating, in electrodeposit liquid
It is middle addition specific molecular structure and certain concentration crystallization modifier, regulate and control in electrodeposition process different depositing current densities and
It is time, horizontal and vertical in the Characteristic Adsorption of different crystal faces and different electro-deposition current regulation micro-nano structures using crystallization modifier
Discharge growth, obtain the micro-nano super hydrophobic surface of regulatable size and the direction of growth.Solve traditional electro-deposition techniques without
Method regulates and controls the shortcomings that growth and size of deposition morphology.
In the present invention, orientation electro-deposition method includes pre-treatment, orients electro-deposition, post-processing.Micro-nano used in the present invention
Structure coating can be not necessarily to template, not by stainless steel material by orientation electrodeposition process in surface of stainless steel Direct precipitation
Shape limitation, has preferable ultra-hydrophobicity afterwards after post treatment, modifies, reduces without organic low-surface energy substance
Cost reduces process flow.Oriented the obtained coating of electrodeposition process of the present invention, surface is by micrometer nickel pointed cone and nanoscale
Pointed cone whisker composition, is distributed in array-like, has preferable ultra-hydrophobicity and antibacterium Adhesion property.
The preparation method for the super-hydrophobic stainless steel watch finishing coat that second aspect of the present invention provides, preparation method is simple, preparation
Cost is relatively low, is suitble to industrialized mass production, has been made super thin with preferable ultra-hydrophobicity and antibacterium Adhesion property
Water coating.
Embodiment 1:
A kind of preparation method of super-hydrophobic stainless steel watch finishing coat, comprising:
(1) 316L stainless steel is provided as basis material, and 316L stainless steel material is successively used into 800#, 1000#,
2000# silicon carbide paper polishing surface, is cleaned with distilled water and ethyl alcohol respectively after polishing, then with acetone and ethyl alcohol to 316L
Stainless steel is cleaned by ultrasonic 20min respectively.Oil removal treatment is carried out to stainless steel using alkaline degreaser, alkaline degreaser includes concentration
It is removed for 10g/L sodium hydroxide, 20g/L sodium carbonate, 10g/L sodium phosphate and 5g/L alkyl polyoxyethylene ether except oil temperature is 70 DEG C
The oily time is 20min.Then acid-wash activation processing is carried out using acid-wash activation liquid, acid-wash activation liquid includes 5mL/L hydrochloric acid
(35%), 5mL/L acetic acid (99.3%) and 5mL/L phosphoric acid (85.0%), at room temperature, acid-wash activation time are 6min,
Then it is cleaned, is dried with nitrogen with distilled water and ethyl alcohol, storage is stand-by.
(2) it is immersed in the electrodeposit liquid containing nickel salt using pretreated stainless steel material as cathode, the electricity containing nickel salt
Deposition liquid includes the nickel sulfate that concentration is 0.1mol/L, and concentration is the sodium citrate of 0.1mol/L, and concentration is the second of 0.1mol/L
Diamine hydrochloride is 1.0 using 10% ammonium hydroxide or 10% hydrochloric acid solution regulation electrodeposit liquid pH value；It, will using platinum sheet as anode
Stainless steel material, platinum sheet and constant-current supply connect into circuit, apply cathodic polarization electric current to stainless steel material, in stainless steel material
Surface carries out electro-deposition twice, and the temperature of first time electro-deposition is 40 DEG C, and depositing current density size is 5A/dm2, sedimentation time
For 1000s；The temperature of second of electro-deposition is 40 DEG C, and deposition current size is 12A/dm2, sedimentation time 500s；Electro-deposition
After, the micro-nano structure being arranged in array is made in surface of stainless steel；
(3) surface is had the stainless steel material of the micro-nano structure coating of array arrangement be placed in temperature is 10 DEG C and humidity is
30d is stored in 10% environment, the surface of micro-nano structure is oxidized, to obtain super-hydrophobic stainless steel watch finishing coat.
Super-hydrophobic stainless steel watch finishing coat made from embodiment 1 is used into transmission electron microscope observing, Fig. 1 is the embodiment of the present invention
The microscopic appearance figure of super-hydrophobic stainless steel watch finishing coat made from 1；From (a), (b) to (c), successively (scale is followed successively by for amplification step by step
1 μm, 200nm, 100nm), it, can from Fig. 1 (b) and (c) from Fig. 1 (a) it can be seen that array distribution is presented in Ni-based micro-nano structure
Horizontal and vertical development structure is presented to Ni-based micro-nano structure, nanoscale nickel whisker is centered on micrometer nickel pointed cone to external radiation
Form petal-like structures.Wherein, the length of nanoscale whisker is within the scope of 100nm-250nm.
Fig. 2 is the shape appearance figure that micron order pointed cone made from the embodiment of the present invention 1 passes through atomic force microscope observation；From Fig. 2
In as can be seen that micron order pointed cone height be 0.1 μm -0.7 μm, average diameter be 0.4 μm -0.6 μm, adjacent micron order pointed cone
The distance between be 0.2 μm -0.3 μm.
Embodiment 2:
A kind of preparation method of super-hydrophobic stainless steel watch finishing coat, comprising:
(1) 316L stainless steel is provided as basis material, and stainless steel material is successively used into 800#, 1000#, 2000# water
Dry sanding paper polishing surface, is cleaned with distilled water and ethyl alcohol respectively after polishing, then with acetone and ethyl alcohol to 316L stainless steel
It is cleaned by ultrasonic 20min respectively.Oil removal treatment is carried out to stainless steel using alkaline degreaser, alkaline degreaser includes that concentration is 40g/
L sodium hydroxide, 50g/L sodium carbonate, 30g/L sodium phosphate and 10g/L alkyl polyoxyethylene ether, except oil temperature is 90 DEG C, when oil removing
Between be 5min.Then using acid-wash activation liquid carry out acid-wash activation processing, acid-wash activation liquid include 20mL/L hydrochloric acid (35%),
10mL/L acetic acid (99.3%) and 10mL/L phosphoric acid (85.0%), at room temperature, acid-wash activation time are 1min, are then used
Distilled water and ethyl alcohol cleaning, are dried with nitrogen, storage is stand-by.
(2) it is immersed in the electrodeposit liquid containing mantoquita using pretreated stainless steel material as cathode, the electricity containing nickel salt
Deposition liquid includes the copper sulphate that concentration is 3mol/L, and concentration is the sodium citrate of 1mol/L, and concentration is the ethylenediamine salt of 3mol/L
Hydrochlorate is 3.0 using 10% ammonium hydroxide or 10% hydrochloric acid solution regulation electrodeposit liquid pH value；Using platinum sheet as anode, by platinum sheet and
Constant-current supply connects into circuit, applies cathodic polarization electric current to stainless steel material, and it is heavy to carry out electricity twice in surface of stainless steel
Product, the temperature of first time electro-deposition are 80 DEG C, and depositing current density size is 0.1A/dm2, sedimentation time 50s；Second of electricity
The temperature of deposition is 80 DEG C, and deposition current size is 8.0A/dm2, sedimentation time 1s；After electro-deposition, in stainless steel
The copper-based micro-nano structure being arranged in array is made in material surface；
(3) surface is had the stainless steel material of the micro-nano structure coating of array arrangement be placed in temperature is 40 DEG C and humidity is
5d is stored in 50% environment, the surface of micro-nano structure is oxidized, to obtain super-hydrophobic stainless steel watch finishing coat.
Embodiment 3:
A kind of preparation method of super-hydrophobic stainless steel watch finishing coat, comprising:
(1) 316L stainless steel is provided as basis material, and stainless steel material is successively used into 800#, 1000#, 2000# water
Dry sanding paper polishing surface, is cleaned with distilled water and ethyl alcohol respectively after polishing, then with acetone and ethyl alcohol to 316L stainless steel
It is cleaned by ultrasonic 20min respectively.Oil removal treatment is carried out to stainless steel using alkaline degreaser, alkaline degreaser includes that concentration is 30g/
L sodium hydroxide, 30g/L sodium carbonate, 20g/L sodium phosphate and 8g/L alkyl polyoxyethylene ether, except oil temperature is 80 DEG C, the oil removing time
For 10min.Then using acid-wash activation liquid carry out acid-wash activation processing, acid-wash activation liquid include hydrochloric acid 10mL/L (35%),
8mL/L acetic acid (99.3%) and 8mL/L phosphoric acid (85.0%), at room temperature, acid-wash activation time are 4min, then with steaming
Distilled water and ethyl alcohol cleaning, are dried with nitrogen, storage is stand-by.
(2) it is immersed in the electrodeposit liquid containing nickel salt using pretreated stainless steel material as cathode, the electricity containing nickel salt
Deposition liquid includes the nickel sulfate that concentration is 2mol/L, and concentration is the sodium citrate of 0.5mol/L, and concentration is the second two of 0.5mol/L
Amine hydrochlorate is 7.0 using 10% ammonium hydroxide or 10% hydrochloric acid solution regulation electrodeposit liquid pH value；Using platinum sheet as anode, by platinum
Plate and constant-current supply connect into circuit, apply cathodic polarization electric current to stainless steel material, carry out twice in surface of stainless steel
Electro-deposition, the temperature of first time electro-deposition are 50 DEG C, and depositing current density size is 5A/dm2, sedimentation time 500s；Second
The temperature of secondary electro-deposition is 50 DEG C, and deposition current size is 15A/dm2, sedimentation time 50s；After electro-deposition, stainless
The micro-nano structure being arranged in array is made in steel material surface；
(3) surface is had the stainless steel material of the micro-nano structure of array arrangement be placed in temperature is 20 DEG C and humidity is 30%
Environment in store 20d, the surface of micro-nano structure is oxidized, to obtain super-hydrophobic stainless steel watch finishing coat.
Effect example
For the performance for verifying super-hydrophobic stainless steel watch finishing coat produced by the present invention, the present invention also provides effect implementations
Example.
Super-hydrophobic stainless steel watch finishing coat made from embodiment 1 is subjected to hydrophily macro-test and contact angle test, knot
Fruit is as shown in figure 3, Fig. 3 is the hydrophily macro-test of super-hydrophobic stainless steel watch finishing coat made from the embodiment of the present invention 1 and connects
Feeler test chart.Fig. 3 (a) and (b) are untreated 316L stainless steel surface hydrophily macro-test and contact angle test；Figure
3 (c) and (d) be the obtained 316L stainless steel surface hydrophily macro-test and contact with Ni-based micro-nano structure of embodiment 1
Angle test.The 316L stainless steel obtained with Ni-based micro-nano structure of embodiment 1 has good ultra-hydrophobicity, and contact angle reaches
To 153.74 °, and the contact angle of untreated 316L stainless steel is only 104.65 °.
To sum up, super-hydrophobic stainless steel watch finishing coat made from preparation method through the embodiment of the present invention has good super
Hydrophobic performance.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (8)
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| CN108823617A (en) * | 2018-06-25 | 2018-11-16 | 宁波中材钰翔新材料科技有限公司 | A kind of preparation method of super water repellent metal mesh |
| CN109468668B (en) * | 2018-12-10 | 2020-10-23 | 深圳先进技术研究院 | A kind of preparation method and application of platinum nanocone array structure |
| CN111304602B (en) * | 2018-12-11 | 2023-07-21 | 深圳先进技术研究院 | Superhydrophobic diamond-like composite layer structure and its preparation method |
| CN110468437B (en) * | 2019-08-15 | 2021-11-12 | 胜利油田金岛实业有限责任公司胜岛石油机械厂 | Preparation method of corrosion-resistant structure of petroleum stainless steel pipeline |
| CN111807314A (en) * | 2020-06-23 | 2020-10-23 | 南开大学 | Copper oxide nanowhisker material for rapid sterilization of large contact surfaces |
| CN111850660A (en) * | 2020-07-15 | 2020-10-30 | 大连理工大学 | A simple preparation device for the inner surface of superhydrophobic tube based on electroplating method |
| CN112853414B (en) * | 2020-12-25 | 2021-12-24 | 山东科技大学 | A kind of preparation method of modification-free superhydrophobic copper layer and its application |
| CN112853420B (en) * | 2021-01-14 | 2022-05-24 | 同曦集团有限公司 | A kind of fluorine-free super-hydrophobic self-cleaning antibacterial anti-mildew anti-virus stainless steel and preparation method thereof |
| CN113445107B (en) * | 2021-06-28 | 2022-05-13 | 中国石油大学(华东) | Ni-PTFE-SiC super-hydrophobic anticorrosive coating and preparation method thereof |
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