CN118127589A - Preparation method of color-adjustable magnesium alloy surface corrosion-resistant composite film - Google Patents
Preparation method of color-adjustable magnesium alloy surface corrosion-resistant composite film Download PDFInfo
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 47
- 238000005260 corrosion Methods 0.000 title claims abstract description 46
- 230000007797 corrosion Effects 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims description 25
- 239000002131 composite material Substances 0.000 title claims description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 107
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000007787 solid Substances 0.000 claims abstract description 63
- 239000000463 material Substances 0.000 claims abstract description 56
- 238000005530 etching Methods 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 30
- 230000003075 superhydrophobic effect Effects 0.000 claims abstract description 17
- 239000003792 electrolyte Substances 0.000 claims abstract description 16
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 15
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 13
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 10
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 10
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 10
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 10
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 102
- 238000003756 stirring Methods 0.000 claims description 85
- 239000000243 solution Substances 0.000 claims description 39
- 238000001035 drying Methods 0.000 claims description 38
- 150000002500 ions Chemical class 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 235000019441 ethanol Nutrition 0.000 claims description 30
- 238000012545 processing Methods 0.000 claims description 29
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 27
- 238000000576 coating method Methods 0.000 claims description 27
- 239000011248 coating agent Substances 0.000 claims description 26
- 238000000926 separation method Methods 0.000 claims description 26
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 18
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- QCIARNIKNKKHFH-UHFFFAOYSA-N 7-(2-chloroethyl)-1,3-dimethylpurine-2,6-dione Chemical compound O=C1N(C)C(=O)N(C)C2=C1N(CCCl)C=N2 QCIARNIKNKKHFH-UHFFFAOYSA-N 0.000 claims description 14
- 238000007747 plating Methods 0.000 claims description 13
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 13
- 238000001704 evaporation Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000000151 deposition Methods 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 238000011068 loading method Methods 0.000 claims description 10
- 239000004570 mortar (masonry) Substances 0.000 claims description 10
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 10
- 239000011780 sodium chloride Substances 0.000 claims description 10
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 9
- 229960000583 acetic acid Drugs 0.000 claims description 9
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 9
- 239000003085 diluting agent Substances 0.000 claims description 9
- 239000003822 epoxy resin Substances 0.000 claims description 9
- 239000012362 glacial acetic acid Substances 0.000 claims description 9
- 229920000647 polyepoxide Polymers 0.000 claims description 9
- 235000010344 sodium nitrate Nutrition 0.000 claims description 9
- 235000010288 sodium nitrite Nutrition 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 238000001771 vacuum deposition Methods 0.000 claims description 8
- 238000005240 physical vapour deposition Methods 0.000 claims description 7
- 239000008139 complexing agent Substances 0.000 claims description 6
- VDRSDNINOSAWIV-UHFFFAOYSA-N [F].[Si] Chemical compound [F].[Si] VDRSDNINOSAWIV-UHFFFAOYSA-N 0.000 claims description 5
- 150000002527 isonitriles Chemical class 0.000 claims description 5
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000010884 ion-beam technique Methods 0.000 claims description 3
- 239000012459 cleaning agent Substances 0.000 claims description 2
- XVSBWQYHSLNOCU-UHFFFAOYSA-N ethenyl(dimethyl)silicon Chemical compound C[Si](C)C=C XVSBWQYHSLNOCU-UHFFFAOYSA-N 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 claims description 2
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical class [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 claims 2
- 230000001276 controlling effect Effects 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 53
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 abstract description 23
- 230000007547 defect Effects 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000000866 electrolytic etching Methods 0.000 abstract description 4
- 239000002344 surface layer Substances 0.000 abstract description 3
- 238000004381 surface treatment Methods 0.000 abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052593 corundum Inorganic materials 0.000 abstract description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 25
- 229910004298 SiO 2 Inorganic materials 0.000 description 20
- GYWIDSZAIGIHMH-UHFFFAOYSA-N ethenyl-fluoro-dimethylsilane Chemical compound C[Si](C)(F)C=C GYWIDSZAIGIHMH-UHFFFAOYSA-N 0.000 description 14
- 238000005299 abrasion Methods 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 230000003287 optical effect Effects 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- 239000011856 silicon-based particle Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- -1 silicon fluoride compound Chemical class 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000003086 colorant Substances 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 239000007888 film coating Substances 0.000 description 3
- 238000009501 film coating Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 239000003637 basic solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005536 corrosion prevention Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000009396 hybridization Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- CMXUHIBXGMHANR-UHFFFAOYSA-N trimethoxy(1,1,2,2,3,3,4,4,5,5,8,8,8-tridecafluorooctyl)silane Chemical compound CO[Si](OC)(OC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F CMXUHIBXGMHANR-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 238000009736 wetting 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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/42—Pretreatment of metallic surfaces to be electroplated of light metals
-
- 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
- C25D5/011—Electroplating using electromagnetic wave irradiation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
- C25F3/04—Etching of light metals
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The invention relates to a magnesium alloy surface treatment technology, which forms a surface with adjustable color, corrosion resistance and superhydrophobicity on the surface of a magnesium alloy. The method is characterized in that electrolyte etching is adopted for pretreatment, an electron gun is assisted by a radio frequency ion source, a film system formed by stacking multiple layers of materials is evaporated, wherein the high refractive index material is one or a combination of more than one of hybridized ZrO2 nano solid, tiO2, H4g and Nb2O5, the low refractive index material is one of SiO2 or Al2O3, and the fluorine silicon compound is used as a super-hydrophobic film layer to be the most surface layer. Wherein, the electrolytic etching is combined with the radio frequency ion source to reduce the surface defects of the material, and the film layer is more dense. The high and low refractive materials reduce stress in the film. The hydrophobic material further compensates for the defects of the oxide film.
Description
Technical Field
The invention relates to the field of magnesium alloy surface coloring, in particular to a preparation method of a color-adjustable magnesium alloy surface corrosion-resistant composite film layer.
Background
The magnesium alloy is the lightest metal in the structural material, and can effectively reduce the weight, save energy, reduce emission and protect the environment. Excellent electromagnetic shielding performance and damping performance, higher specific strength, specific rigidity and fatigue limit, good anti-vibration and noise reduction performance and cutting machining performance. Stable size, easy casting, no toxicity, easy recovery and rich reserves in crust. Magnesium alloys are widely used as the third largest metal engineering material following steel and aluminum alloys. The method is widely applied to the fields of transportation, 3C products, petrochemical industry, biomedicine, military industry, aerospace and the like.
The vapor deposition has the advantages of high-speed deposition, compact and uniform coating, high film/base bonding strength, high production efficiency, favorable reproduction, no pollution and the like, and is widely used for preparing high-quality corrosion-resistant coatings. Among them, magnetron sputtering is one of the most widely used Physical Vapor Deposition (PVD) techniques in recent decades, and the prepared film has strong bonding performance and high density. However, the current protection has two problems: (1) Magnetron sputtering is mainly used for researching different film systems, particularly metals and nitrides, and is mainly divided into four types: al, alN film system, cr and CrN film system, ti and TiCN, tiN film system, single color, low gloss brightness, and vivid color, and is difficult to meet the requirements of 3C product fashion attribute. (2) The sputtering film layer has pores and defect points, the deposition and growth mode of the film layer also causes the existence of the pores and the transition of the metal magnesium layer to high-hardness nitride, the internal stress is different, and the surface has microcracks to influence the corrosion resistance.
The metal layer is coated on the surface of the magnesium alloy matrix by the electrochemical plating technology, the process is simple, the cost is low, and the corrosion resistance, the wear resistance, the welding manufacturability, the electrical property and the decoration of the magnesium alloy matrix can be effectively improved. Either electroplating or electroless plating is performed by reducing metal cations in a metal salt solution to form a metal coating on the substrate surface. However, the current electrochemical plating technology also has the following problems and challenges: electroplating is difficult due to high chemical activity. Magnesium and magnesium alloys are extremely easily oxidized in air, so that a proper pretreatment process must be adopted, so that the oxidation of air is prevented, and the pretreatment layer is easy to remove during electroplating. While the quality of the coating is closely related to the collective material, in other words, different pretreatment processes must be developed for different series of magnesium alloys. In view of the high chemical activity of the substrate and the spontaneous displacement reaction of the plating solution, it is also necessary to consider how to ensure preferential progress of the plating layer formation reaction.
Prior to the electrolyte etching, the magnesium alloy surface is typically pretreated with a chemical solution. The aim of the pretreatment is to remove impurities, oxides and bad surface layers on the surface, so that the surface of the magnesium alloy is cleaner and more uniform. This can be achieved by chemical reactions in acidic or basic solutions, for example using acidic solutions (e.g. nitric acid, sulfuric acid, etc.) or basic solutions (e.g. sodium hydroxide solution).
The trapping agent has a great role in restricting the etching process, and can react with the etching agent to limit the diffusion range of the etching agent, so that the etching agent is restricted in the area near the surface of the template. The thinner the thickness of the etchant layer, the higher the processing accuracy. Therefore, a scavenger is selected that can effectively confine the etchant. OH-in the solution can react with H+ diffused to the solution body rapidly, so that the diffusion of H+ is greatly limited, the etchant can only exist on the surface of the template, the thickness of the etchant layer becomes very thin, and the capturing effect required by experiments can be achieved. So a strongly alkaline solution is an effective scavenger.
The conventional electrolytic etching cannot well control the etching precision, and adverse phenomena such as pitting and the like can occur in the etching process, so that the surface is uneven, and the subsequent adhesive force, compactness and the like are affected. How to furthest combine the principle of the capturing agent and the complexing agent to exert the maximum etching effect and control the etching precision is the research focus of the invention.
ZrO2 is an inorganic nonmetallic material having a high melting point, a large thermal expansion coefficient, a low thermal conductivity, a high abrasion resistance, and a good corrosion resistance, but their use in the treatment of optical devices has many disadvantages such as heavy and brittle optical materials produced by high density and low flexibility, and the surface of the oxide film produced is rough. Compared with inorganic materials, the organic polymer material has the advantages of light weight, excellent impact resistance, good flexibility and processability, and is beneficial to the manufacture of optical devices. The incorporation of inorganic nanostructure units with polymers can improve the mechanical and thermal properties of polymeric materials. The nanocomposite optical material can combine the advantages of organic polymer (light weight, good flexibility and impact resistance, excellent processability) and inorganic material (high refractive index, high thermal stability and other physical properties, namely optics, magnetism and the like), and the preparation of the organic-inorganic nano hybrid optical material with high refractive index performance is the research focus of the invention.
Magnesium alloys are widely used due to their excellent properties. Magnesium alloys are very sensitive in nature, resulting in being very susceptible to corrosion during application, and therefore control of corrosion of magnesium alloys has been of great concern in recent years. The superhydrophobic surface has the most remarkable effect in the magnesium alloy corrosion prevention process, and is one of the most popular corrosion prevention control means at present. The conventional high-polarity fluorine silicon compound with hydroxyl can obviously improve the solid surface energy, and has the defects that the higher the solid surface energy is, the more difficult to wet and spread, the solid surface energy cannot be firmly combined with an oxide film, more adhesive is needed to be added for adjustment, the flatness and smoothness of the surface of the hydrophobic film can be reduced to a certain extent, and the selection of a proper fluorine-silicon modified substance to increase the superhydrophobicity of the hydrophobic film is the focus of the research of the invention.
Disclosure of Invention
The invention aims to provide a method for manufacturing a low-defect, low-stress and super-hydrophobic anti-corrosion film on the surface of a magnesium alloy, which solves the problems of defects and stress cracks of the PVD treatment of the surface of the magnesium alloy at present; the invention also aims to form a magnesium alloy surface treatment technology with adjustable color and smooth hand feeling on the surface of the magnesium alloy and meeting the requirements of the 3C product shell.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
(1) Ultrasonic cleaning: before coating, firstly adopting a neutral cleaning agent to carry out ultrasonic cleaning, wherein the ultrasonic current is 1-4A, preferably 1.5-2.8A, for 2-10 minutes, preferably 3-7 minutes, and then carrying out electrolyte etching;
The ultrasonic wave further comprises electrolyte etching: the electrode is a Pt electrode, 100-150 parts by mass of 25% NaNO3, 200-240 parts by mass of 40% NaNO2, 200-240 parts by mass of 12% NaF are added, 20-40 parts by mass of 18% NaCl is added, 40-60 parts of complexing agent is added, 10-15 parts by mass of 50% hexadecyl trimethyl ammonium bromide is added, the processing voltage is 1.8-2.2V, the temperature is room temperature, the electrolytic processing time is 500-540s, and the processing time is 1500-1600s;
wherein the complexing agent in the etching and cleaning of the electrolyte is a 7- (2-chloroethyl) theophylline water solvent with the mass fraction of 10 percent.
(2) A radio frequency ion source treatment surface: hanging the etched and cleaned surface-treated material on a jig, loading the surface-treated material into a vacuum coating cavity, starting vacuumizing, wherein the vacuum degree is 1 x 10 -1-1*100 Pa, the vacuum degree is preferably 1 x 10 -1-5*100 Pa, carrying out radio-frequency ion source treatment on the surface, the working gas is Ar or N2, the energy is 700-2000ev, the treatment time is 3-30 minutes, the treatment time is preferably 10-20 minutes, the working voltage is 200-600V, and the current is 300-800MA;
(3) Plating a corrosion-resistant oxide film layer by an electron gun: evaporating a coating by adopting a PVD (physical vapor deposition) electron gun and assisting the coating by using a high-energy ion source, wherein the assisted high-energy ion beam bombards the surface of the magnesium alloy, the vacuum degree of the coating is 9 x 10 -3-3*10-2 Pa, the priority is 1 x 10 -2-2*10-2 Pa, the working gas of the coating ion source is Ar, the deposition rate of the coating is controlled to be 1.5-5 angstroms/second, the working voltage is 200-600V, and the current is 300-800MA; the coating material adopts corrosion-resistant high-refraction and low-refraction materials, and the high-refraction and low-refraction materials are matched;
The corrosion-resistant oxide film layer adopts a low-high refraction material alternating film coating sequence, the film coating sequence and the film layer thickness are controlled, and the colors of the film layer, such as blue, yellow, orange, green and the like, are regulated through light diffraction.
The specific high refractive index material of the corrosion-resistant oxide film layer is one or a combination of more of hybridized ZrO2 nano solid, tiO2, H4g and Nb2O5, and the low refractive index material is one or a combination of more of SiO2 and Al2O 3.
The preparation method of the high refractive index material hybridized ZrO2 nano solid comprises the following steps: firstly, adding 10-15 parts of epoxy resin E51 and D400 (the mass ratio is 100:64) into 50-60 parts of water, adding 70-90 parts of ZrO2 powder, adding 2-5 parts of benzyl alcohol as an accelerator, and 3.5-5 parts of acetone as a diluent, and stirring for 10min at room temperature; then adding 0.1 part of glacial acetic acid into the system, stirring for 30min at room temperature, then adding 4-6 parts of regulator into the system dropwise, stirring for 5-6h at room temperature until a uniform and transparent hybrid sol solution is formed, heating to 120 ℃ while stirring, stirring and evaporating for 2h, then drying for 40-60min at 40-50 ℃ in a vacuum drying oven, and then drying for 90-120min at 60 ℃ to obtain the hybrid ZrO2 nano solid.
Wherein the regulator is p-methylsulfonylmethyl isonitrile.
(4) Plating a super-hydrophobic film layer: after the corrosion-resistant oxide film layer is finished, a resistance heating plating super-hydrophobic film layer is adopted.
The super-hydrophobic material is silicon fluoride, and the thickness of the super-hydrophobic material is 10-100nm.
The preparation of the specific silicon fluorine compound comprises the following steps: (1) hydrophobic modification of silica: firstly, weighing 10 parts of silicon dioxide powder, pouring the silicon dioxide powder into 30 parts of modified fluorosilane solution, stirring for 24 hours at room temperature, centrifuging the obtained silica sol for 3 times, washing with absolute ethyl alcohol, then placing into a drying oven for drying for 5 hours, and finally grinding into fine powder by using a mortar to obtain hydrophobically modified silicon dioxide; (2) preparation of fluorosilicone particles: mechanically stirring 33-38 parts of ethanol with the mass concentration of 99% and 46-52 parts of ethyl orthosilicate with the mass fraction of 98% for 30min at 50 ℃; then, 2.6-3.0 parts of ammonia water and 7.2-8.2 parts of deionized water are slowly dripped into the mixed solution, after continuous stirring is carried out for 8 hours, the modified silicon dioxide is added into the mixed solution, then stirring is continued for 12 hours, the obtained sol is placed in a centrifugal machine for centrifugal separation, the rotating speed is 6000rpm, the centrifugal separation is carried out for 10 minutes, the obtained solid is washed for 2-3 times by ethanol solution, then the centrifugal separation is carried out again, and finally the obtained solid particles are completely dried at 80 ℃, thus obtaining the fluorine-silicon particles.
The modified fluorosilane is an ethanol solution of 10% by mass of vinyldimethylsilane.
The total thickness of the film coating layer is 200-2000nm, preferably 500-1500nm.
The invention has the beneficial effects that:
1. The invention relates to a magnesium alloy surface treatment technology, which forms a surface with adjustable color, corrosion resistance and superhydrophobicity on the surface of a magnesium alloy. The method is characterized in that high-energy ion source pretreatment and auxiliary coating are adopted, so that the pore defects and stress cracks of the film layer are reduced, and the corrosion resistance of the surface anti-corrosion layer is improved; the high-low refraction oxide film reduces the film stress, and can form various colors through light diffraction, so that the magnesium alloy part has rich colors; the superhydrophobic film layer added behind the film layer is an organic silicon fluorine compound material, so that pores and cracks are further compensated; meanwhile, the super-hydrophobic film layer isolates external corrosion water vapor from contacting with the film layer, so that the corrosion resistance is further improved.
2. According to the invention, the electrolyte etching is adopted for pretreatment, and the radio frequency ion source is combined to assist the electron gun, so that the pore defects and stress cracks of the film layer are reduced, oil stains or local oxides on the surface of the magnesium alloy can be efficiently removed, the contact area of materials can be greatly increased, the uniformity of a subsequent oxide film is ensured, the surface defects of the magnesium alloy are reduced, the film layers of the subsequent oxide film plating are more compact, and the corrosion resistance of the surface corrosion-resistant layer is improved.
3. And evaporating a film system formed by stacking multiple layers of materials, wherein the high refractive index material is a hybridized ZrO2 nano material, the low refractive index material is one of SiO2 or Al2O3, and the fluorine silicon compound is used as a super-hydrophobic film layer to be the most surface layer. Wherein, the electrolytic etching is combined with the radio frequency ion source to reduce the surface defects of the material, and the film layer is more dense. The high-low refraction material reduces the stress in the film layer and can form various colors through light diffraction, so that the magnesium alloy part has rich colors;
4. The super-hydrophobic film layer is an organic silicon fluorine compound material, and further compensates for pores and cracks of the oxide film layer; meanwhile, the super-hydrophobic film layer isolates external corrosion water vapor from contacting with the film layer, so that the corrosion resistance is further improved, and the super-hydrophobic structure also provides a super-smooth hand feeling.
5. The conventional electrolytic etching cannot well control the etching precision, and adverse phenomena such as pitting and the like can occur in the etching process, so that the surface is uneven, and the subsequent adhesive force, compactness and the like are affected. According to the invention, 7- (2-chloroethyl) theophylline is added as a complexing agent to form complexes with metal ions, and the complexes can provide more soluble ions and free charges, so that the transfer of charges and the flow of current are promoted, the resistance is reduced, the conductivity is increased, a condensation core is provided, bubbles can escape from the surface in a very small time, the pitting phenomenon is reduced, the flatness and purity of the magnesium alloy surface are improved, and the adhesion and compactness of a subsequent oxide film are enhanced.
6. In addition, the free alkaline substance of the 7- (2-chloroethyl) theophylline can be used as a capturing agent to react with the etching agent, so that the diffusion range of the etching agent is limited, the etching agent is restrained in the area near the surface of the magnesium alloy, the diffusion of H+ is greatly limited, the etching thickness is enabled to be very thin, the capturing effect required by experiments can be achieved, and the etching precision is improved.
7. The radio frequency ion treatment accelerates and collides ions by applying high frequency electric field and magnetic field under vacuum environment. When the surface of the magnesium alloy is subjected to radio frequency ion treatment, the ion beam can remove impurities and oxides on the surface, and improve the crystallinity and the compactness of the surface. The treatment further improves the flatness and purity of the magnesium alloy surface, and enhances the adhesion and compactness of the subsequent oxide film.
8. Many inorganic optical materials generally exhibit good mechanical properties (e.g., high strength, high hardness, and high rigidity) and high refractive index, but their use in the processing of optical devices has many drawbacks, such as the high density and low flexibility of the optical materials produced are heavy and brittle, and the surface of the oxide films produced is rough. According to the invention, a certain content of organic matters is added into the inorganic nano ZrO2 clusters by a sol-gel method, and chemical bonds are formed between nitrile groups of organic matter side chains and the inorganic nano clusters so as to increase the compatibility between organic and inorganic components and prevent the inorganic nano clusters from coalescing in a system, so that the organic and inorganic nano hybrid optical material with high refractive index performance is prepared.
9. The p-methylsulfonyl methyl isonitrile is used as an inorganic substance to be fused and embedded into a film structure of ZrO2, so that the morphology structure of the film is changed, the roughness is improved, partial discharge in the process of preparing the oxide film is improved, the film is rough and porous, and the performance of the film is adversely affected. The surface evenness of the film layer can be improved by adding proper and proper organic matter content, but the refractive index of the organic matter is lower than that of the inorganic matter at the same time, and the refractive index is reduced when the organic matter is introduced, so that the choice of the organic matter which can improve the evenness of the film layer and improve the refractive index is the key direction of the invention.
10. And a certain organic content is increased, so that good surface flatness can be maintained, and a good hybridization system and film forming property are formed. On the one hand, the p-methylsulfonyl methyl isonitrile contains benzene rings, has high polarizability and high molar refractive index, and also contains more S atoms with small molar volume and high molar refractive index to synergistically improve the refractive index of a matrix, and on the other hand, the polar groups contained in the p-methylsulfonyl methyl isonitrile can reduce the grain size of ZrO2 particles and ensure more uniform dispersion due to electrostatic repulsion.
11. The conventional high-polarity fluorosilicone compound with hydroxyl can obviously improve the solid surface energy, and has the defects that the higher the solid surface energy is, the more difficult wetting and spreading are, the firm combination with an oxide film cannot be realized, and more binders are needed to be added for adjustment. When the ratio of the silicon dioxide to the vinyl dimethyl fluorosilane is 1:3, the silicon dioxide and the vinyl dimethyl fluorosilane show good hydrophobicity, polyethylene glycol (PEG) is used as a pore-forming agent, and a double bond structure in the vinyl dimethyl fluorosilane is subjected to polymerization reaction in the reaction process to form a firmer three-dimensional crosslinked network structure, so that the adhesive force between the silicon dioxide and an oxide film layer is improved, the surface has excellent corrosion resistance, the adhesive force and the friction resistance of the fluorine silicon compound are improved, the superhydrophobicity of the fluorine silicon compound can be increased, and a loose outer layer in the oxide film layer can be filled.
12. Since a large number of nano-pore structures are formed after the vinyl dimethyl fluorosilane is modified, the pore structures can inhibit reflected light and scattered light from escaping from the surface and convert the reflected light and the scattered light into incident light to pass through the sample, thereby increasing the transmittance of visible light, and the nano-pore structures and part of nano-particles can also keep the anti-reflection high transparency of the surface and keep certain superhydrophobicity.
Drawings
FIG. 1 is a diagram of a film-attached layer structure.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the specific embodiments, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. All other embodiments of the present invention, based on embodiments of the present inventive articles, which would be within the purview of one of ordinary skill in the art without the exercise of inventive faculty, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products available commercially without the manufacturer's attention.
The magnesium alloy used in the examples and comparative examples of the present invention was AZ31 pellets, with a size of 2 cm.times.2cm.times.1mm.
Example 1
The embodiment provides a preparation method of a color-adjustable corrosion-resistant composite film layer on the surface of a magnesium alloy, which comprises the following steps:
(1) Pretreatment: ultrasonic cleaning is adopted, the current is 2A, the time is 5 minutes, and the treatment time of the ion source treatment vacuum degree is 3 x 10 0 Pa is 10 minutes. Then carrying out electrolyte etching, wherein the electrode is Pt,120 parts of NaNO3 with the mass fraction of 25%, 220 parts of NaNO2 with the mass fraction of 40%, 220 parts of NaF with the mass fraction of 12%, adding 30 parts of 18% NaCl, adding 50 parts of 7- (2-chloroethyl) theophylline water solvent with the mass fraction of 10%, adding 12 parts of hexadecyl trimethyl ammonium bromide with the mass fraction of 50%, wherein the processing voltage is 2.0V, the temperature is room temperature, the electrolytic processing time is 520s, and the processing time is 1550s; hanging the etched and cleaned film on a jig, loading the film into a vacuum coating cavity, and starting vacuumizing, wherein the vacuum degree of the radio frequency ion source treatment is 3 x 100Pa, and the treatment time is 10 minutes.
(2) The preparation method of the high refractive index material hybridized ZrO2 nano solid comprises the following steps: firstly, adding 12 parts of epoxy resin E51 and D400 (the mass ratio is 100:64) into 55 parts of water, adding 80 parts of ZrO2 powder, adding 3 parts of benzyl alcohol as an accelerator and 4.2 parts of acetone as a diluent, and stirring for 10 minutes at room temperature; then adding 0.1 part of glacial acetic acid into the system, stirring for 30min at room temperature, then adding 5 parts of p-methylsulfonyl methyl isonitrile into the system dropwise, stirring for 5.5h at room temperature until a uniform and transparent hybrid sol solution is formed, heating to 120 ℃ while stirring, stirring and evaporating for 2h, drying for 50min at 45 ℃ in a vacuum drying oven, and drying for 105min at 60 ℃ to obtain the hybrid ZrO2 nano solid.
(3) The preparation of the fluorine silicon compound comprises the following steps: firstly, weighing 10 parts of silicon dioxide powder, pouring the silicon dioxide powder into 30 parts of ethanol solution of 10% of vinyl dimethyl fluorosilane by mass fraction, stirring for 24 hours at room temperature, centrifuging the obtained silica sol for 3 times, washing with absolute ethanol, putting into a drying oven for drying for 5 hours, and finally grinding into fine powder by using a mortar to obtain hydrophobically modified silicon dioxide; mechanically stirring 35 parts of 99% ethanol and 50 parts of 98% ethyl orthosilicate at 50 ℃ for 30min; then, 2.8 parts of ammonia water and 7.6 parts of deionized water are slowly dripped into the mixed solution, after continuous stirring for 8 hours, the modified silicon dioxide is added into the mixed solution, then stirring is continued for 12 hours, the obtained sol is placed in a centrifugal machine for centrifugal separation, the rotating speed is 6000rpm, the obtained solid is subjected to centrifugal separation for 10 minutes, the obtained solid is subjected to 3 times of washing by ethanol solution, then the obtained solid is subjected to centrifugal separation again, and finally the obtained solid particles are completely dried at 80 ℃ to obtain the fluorine-silicon particles.
(4) The vacuum degree of the coating is 1.5 x10 < -2 > Pa, the thickness of the film layer is SiO2 (154 nm)/hybrid ZrO2 nanometer (62 nm)/SiO 2 (84 nm)/hybrid ZrO2 nanometer (58 nm)/SiO 2 (51 nm)/hybrid ZrO2 nanometer (25 nm)/SiO 2 (109 nm), and the auxiliary ion source is AR. The deposition rate was 3 a/s. After the completion, the silicon fluoride compound is continuously evaporated, and the film layer is 30nm.
Example 2
(1) Pretreatment: ultrasonic cleaning is adopted, the current is 2A, the time is 3 minutes, and the treatment time of the ion source treatment vacuum degree is 3 x 10 0 Pa is 6 minutes. Then carrying out electrolyte etching, wherein the electrode is a Pt electrode, 100 parts of NaNO3 with the mass fraction of 25%, 240 parts of NaNO2 with the mass fraction of 40%, 240 parts of NaF with the mass fraction of 12%, adding 20 parts of 18% NaCl, adding 60 parts of 7- (2-chloroethyl) theophylline water solvent with the mass fraction of 10%, 10 parts of hexadecyl trimethyl ammonium bromide with the mass fraction of 50%, the processing voltage is 2.2V, the temperature is room temperature, the electrolytic processing time is 540s, and the processing time is 1500s; hanging the etched and cleaned film on a jig, loading the film into a vacuum coating cavity, and starting vacuumizing, wherein the vacuum degree of the radio frequency ion source treatment is 3 x 100Pa, and the treatment time is 6 minutes.
(2) The preparation method of the high refractive index material hybridized ZrO2 nano solid comprises the following steps: firstly, adding 10 parts of epoxy resin E51 and D400 (the mass ratio is 100:64) into 60 parts of water, adding 70 parts of ZrO2 powder, adding 5 parts of benzyl alcohol as an accelerator, and stirring for 10 minutes at room temperature, wherein 3.5 parts of acetone is used as a diluent; then adding 0.1 part of glacial acetic acid into the system, stirring for 30min at room temperature, then adding 6 parts of p-methylsulfonyl methyl isonitrile into the system dropwise, stirring for 6h at room temperature until a uniform and transparent hybrid sol solution is formed, heating to 120 ℃ while stirring, stirring and evaporating for 2h, drying for 60min at 40 ℃ in a vacuum drying oven, and drying for 90min at 60 ℃ to obtain the hybrid ZrO2 nano solid.
(3) The preparation of the fluorine silicon compound comprises the following steps: firstly, weighing 10 parts of silicon dioxide powder, pouring the silicon dioxide powder into 30 parts of ethanol solution of 10% of vinyl dimethyl fluorosilane by mass fraction, stirring for 24 hours at room temperature, centrifuging the obtained silica sol for 3 times, washing with absolute ethanol, putting into a drying oven for drying for 5 hours, and finally grinding into fine powder by using a mortar to obtain hydrophobically modified silicon dioxide; mechanically stirring 33 parts of ethanol with the mass concentration of 99% and 52 parts of ethyl orthosilicate with the mass fraction of 98% for 30min at 50 ℃; then, 2.6 parts of ammonia water and 8.2 parts of deionized water are slowly dripped into the mixed solution, after continuous stirring for 8 hours, the modified silicon dioxide is added into the mixed solution, then stirring is continued for 12 hours, the obtained sol is placed in a centrifugal machine for centrifugal separation, the rotating speed is 6000rpm, the obtained solid is subjected to centrifugal separation for 10 minutes, the obtained solid is subjected to 2 times of cleaning by ethanol solution, then the obtained solid is subjected to centrifugal separation again, and finally the obtained solid particles are completely dried at 80 ℃, so that the fluorine-silicon particles can be obtained.
(4) The vacuum degree of the coating is 1.2 x 10 < -2 > Pa, and the thickness of the film is SiO2 (264 nm)/hybridized ZrO2 nanometer (52 nm)/SiO 2 (94 nm)/hybridized ZrO2 nanometer (62 nm)/SiO 2 (83 nm)/hybridized ZrO2 nanometer (61 nm)/SiO 2 (166 nm) hybridized ZrO2 nanometer (60 nm)/SiO 2 (90 nm). The auxiliary ion source was AR and the deposition rate was 2 a/s. After the completion, the silicon fluoride compound is continuously evaporated, and the film layer is 42nm.
Example 3
(1) Pretreatment: ultrasonic cleaning is adopted, the current is 2A, the time is 3 minutes, and the treatment time of the ion source treatment vacuum degree is 3 x 10 0 Pa is 6 minutes. Then carrying out electrolyte etching, wherein the electrode is Pt,150 parts of NaNO3 with the mass fraction of 25%, 200 parts of NaNO2 with the mass fraction of 40%, 200 parts of NaF with the mass fraction of 12%, adding 40 parts of 18% NaCl, adding 40 parts of 7- (2-chloroethyl) theophylline water solvent with the mass fraction of 10%, 15 parts of cetyltrimethylammonium bromide with the mass fraction of 50%, the processing voltage is 1.8V, the temperature is room temperature, the electrolytic processing time is 500s, and the processing time is 1600s; hanging the etched and cleaned film on a jig, loading the film into a vacuum coating cavity, and starting vacuumizing, wherein the radio frequency time is 3 minutes, the ion source treatment vacuum degree is 3 x 100Pa, and the treatment time is 6 minutes.
(2) The preparation method of the high refractive index material hybridized ZrO2 nano solid comprises the following steps: firstly, adding 10 parts of epoxy resin E51 and D400 (the mass ratio is 100:64) into 60 parts of water, adding 70 parts of ZrO2 powder, adding 5 parts of benzyl alcohol as an accelerator, and stirring for 10 minutes at room temperature, wherein 3.5 parts of acetone is used as a diluent; then adding 0.1 part of glacial acetic acid into the system, stirring for 30min at room temperature, then adding 6 parts of p-methylsulfonyl methyl isonitrile into the system dropwise, stirring for 6h at room temperature until a uniform and transparent hybrid sol solution is formed, heating to 120 ℃ while stirring, stirring and evaporating for 2h, drying for 60min at 40 ℃ in a vacuum drying oven, and drying for 90min at 60 ℃ to obtain the hybrid ZrO2 nano solid.
(3) The preparation of the fluorine silicon compound comprises the following steps: firstly, weighing 10 parts of silicon dioxide powder, pouring the silicon dioxide powder into 30 parts of ethanol solution of 10% of vinyl dimethyl fluorosilane by mass fraction, stirring for 24 hours at room temperature, centrifuging the obtained silica sol for 3 times, washing with absolute ethanol, putting into a drying oven for drying for 5 hours, and finally grinding into fine powder by using a mortar to obtain hydrophobically modified silicon dioxide; mechanically stirring 38 parts of 99% ethanol and 46 parts of 98% ethyl orthosilicate at 50 ℃ for 30min; then, 3.0 parts of ammonia water and 7.2 parts of deionized water are slowly dripped into the mixed solution, after continuous stirring for 8 hours, the modified silicon dioxide is added into the mixed solution, then stirring is continued for 12 hours, the obtained sol is placed in a centrifugal machine for centrifugal separation, the rotating speed is 6000rpm, the obtained solid is subjected to centrifugal separation for 10 minutes, the obtained solid is subjected to 3 times of washing by ethanol solution, then the obtained solid is subjected to centrifugal separation again, and finally the obtained solid particles are completely dried at 80 ℃ to obtain the fluorine-silicon particles.
(4) The vacuum degree of the coating is 1.2 x 10 < -2 > Pa, and the thickness of the film is SiO2 (146 nm)/hybrid ZrO2 nanometer (100 nm)/SiO 2 (111 nm)/hybrid ZrO2 nanometer (88 nm)/SiO 2 (144 nm)/hybrid ZrO2 nanometer (13 nm)/SiO 2 (262 nm)/hybrid ZrO2 nanometer (66 nm)/SiO 2 (115 nm). The auxiliary ion source was AR and the deposition rate was 3.5 a/sec. After the completion, the silicon fluoride compound is continuously evaporated, and the film layer is 42nm.
Example 4
(1) Pretreatment: ultrasonic cleaning is adopted, the current is 3A, the time is 6 minutes, and the treatment time of the ion source treatment vacuum degree is 3 x 10 0 Pa and the treatment time is 10 minutes. Then carrying out electrolyte etching, wherein the electrode is Pt,150 parts of NaNO3 with the mass fraction of 25%, 200 parts of NaNO2 with the mass fraction of 40%, 200 parts of NaF with the mass fraction of 12%, adding 40 parts of 18% NaCl, adding 40 parts of 7- (2-chloroethyl) theophylline water solvent with the mass fraction of 10%, 15 parts of cetyltrimethylammonium bromide with the mass fraction of 50%, the processing voltage is 1.8V, the temperature is room temperature, the electrolytic processing time is 500s, and the processing time is 1600s; hanging the etched and cleaned film on a jig, loading the film into a vacuum coating cavity, and starting vacuumizing, wherein the vacuum degree of the radio frequency ion source treatment is 3 x 100Pa, and the treatment time is 10 minutes.
(2) The preparation method of the high refractive index material hybridized ZrO2 nano solid comprises the following steps: firstly, adding 15 parts of epoxy resin E51 and D400 (the mass ratio is 100:64) into 50 parts of water, adding 90 parts of ZrO2 powder, adding 2 parts of benzyl alcohol as an accelerator and 5 parts of acetone as a diluent, and stirring for 10 minutes at room temperature; then adding 0.1 part of glacial acetic acid into the system, stirring for 30min at room temperature, then adding 4 parts of p-methylsulfonyl methyl isonitrile into the system dropwise, stirring for 5h at room temperature until a uniform and transparent hybrid sol solution is formed, heating to 120 ℃ while stirring, stirring and evaporating for 2h, drying for 60min at 50 ℃ in a vacuum drying oven, and drying for 120min at 60 ℃ to obtain the hybrid ZrO2 nano solid.
(3) The preparation of the fluorine silicon compound comprises the following steps: firstly, weighing 10 parts of silicon dioxide powder, pouring the silicon dioxide powder into 30 parts of ethanol solution of 10% of vinyl dimethyl fluorosilane by mass fraction, stirring for 24 hours at room temperature, centrifuging the obtained silica sol for 3 times, washing with absolute ethanol, putting into a drying oven for drying for 5 hours, and finally grinding into fine powder by using a mortar to obtain hydrophobically modified silicon dioxide; mechanically stirring 38 parts of 99% ethanol and 46 parts of 98% ethyl orthosilicate at 50 ℃ for 30min; then, 3.0 parts of ammonia water and 7.2 parts of deionized water are slowly dripped into the mixed solution, after continuous stirring for 8 hours, the modified silicon dioxide is added into the mixed solution, then stirring is continued for 12 hours, the obtained sol is placed in a centrifugal machine for centrifugal separation, the rotating speed is 6000rpm, the obtained solid is subjected to centrifugal separation for 10 minutes, the obtained solid is subjected to 3 times of washing by ethanol solution, then the obtained solid is subjected to centrifugal separation again, and finally the obtained solid particles are completely dried at 80 ℃ to obtain the fluorine-silicon particles.
The vacuum degree of the coating is 1.0 x 10 < -2 > Pa, and the thickness of the film is SiO2 (88 nm)/hybridized ZrO2 nanometer (89 nm)/SiO 2 (36 nm)/hybridized ZrO2 nanometer (87 nm)/SiO 2 (88 nm)/hybridized ZrO2 nanometer (65 nm)/SiO 2 (222 nm) hybridized ZrO2 nanometer (111 nm)/Al 2O3 (159 nm). The auxiliary ion source was AR gas and the deposition rate was 2.5 a/sec. After the completion, the silicon fluoride compound is continuously evaporated, and the film layer is 50nm.
Comparative example 1
This comparative example differs from example 1 in that 7- (2-chloroethyl) theophylline of step (1) is malic acid, and the remainder is the same as in example 1.
Comparative example 2
The present comparative example differs from example 1 in that the pretreatment of step (1) does not include an electrolyte etching process, specifically:
(1) Pretreatment: ultrasonic cleaning is adopted, the current is 2A, the time is 5 minutes, and the treatment time of the ion source treatment vacuum degree is 3 x 100Pa and the treatment time is 10 minutes. After cleaning, hanging the film on a jig, loading the film into a vacuum coating cavity, and starting vacuumizing, wherein the vacuum degree of the radio frequency ion source treatment is 3 x 100Pa, and the treatment time is 10 minutes.
(2) The preparation method of the high refractive index material hybridized ZrO2 nano solid comprises the following steps: firstly, adding 12 parts of epoxy resin E51 and D400 (the mass ratio is 100:64) into 55 parts of water, adding 80 parts of ZrO2 powder, adding 3 parts of benzyl alcohol as an accelerator and 4.2 parts of acetone as a diluent, and stirring for 10 minutes at room temperature; then adding 0.1 part of glacial acetic acid into the system, stirring for 30min at room temperature, then adding 5 parts of p-methylsulfonyl methyl isonitrile into the system dropwise, stirring for 5.5h at room temperature until a uniform and transparent hybrid sol solution is formed, heating to 120 ℃ while stirring, stirring and evaporating for 2h, drying for 50min at 45 ℃ in a vacuum drying oven, and drying for 105min at 60 ℃ to obtain the hybrid ZrO2 nano solid.
(3) The preparation of the fluorine silicon compound comprises the following steps: firstly, weighing 10 parts of silicon dioxide powder, pouring the silicon dioxide powder into 30 parts of ethanol solution of 10% of vinyl dimethyl fluorosilane by mass fraction, stirring for 24 hours at room temperature, centrifuging the obtained silica sol for 3 times, washing with absolute ethanol, putting into a drying oven for drying for 5 hours, and finally grinding into fine powder by using a mortar to obtain hydrophobically modified silicon dioxide; mechanically stirring 35 parts of 99% ethanol and 50 parts of 98% ethyl orthosilicate at 50 ℃ for 30min; then, 2.8 parts of ammonia water and 7.6 parts of deionized water are slowly dripped into the mixed solution, after continuous stirring for 8 hours, the modified silicon dioxide is added into the mixed solution, then stirring is continued for 12 hours, the obtained sol is placed in a centrifugal machine for centrifugal separation, the rotating speed is 6000rpm, the obtained solid is subjected to centrifugal separation for 10 minutes, the obtained solid is subjected to 3 times of washing by ethanol solution, then the obtained solid is subjected to centrifugal separation again, and finally the obtained solid particles are completely dried at 80 ℃ to obtain the fluorine-silicon particles.
(4) The vacuum degree of the coating is 1.5 x10 < -2 > Pa, the thickness of the film layer is SiO2 (154 nm)/hybrid ZrO2 nanometer (62 nm)/SiO 2 (84 nm)/hybrid ZrO2 nanometer (58 nm)/SiO 2 (51 nm)/hybrid ZrO2 nanometer (25 nm)/SiO 2 (109 nm), and the auxiliary ion source is AR. The deposition rate was 3 a/s. After the completion, the silicon fluoride compound is continuously evaporated, and the film layer is 30nm.
Comparative example 3
The comparative example differs from example 1 in the amount of 7- (2-chloroethyl) theophylline added in step (1), the specific pretreatment being: ultrasonic cleaning is adopted, the current is 2A, the time is 5 minutes, and the treatment time of the ion source treatment vacuum degree is 3 x 10 0 Pa is 10 minutes. Then carrying out electrolyte etching, wherein the electrode is Pt,120 parts of NaNO3 with the mass fraction of 25%, 220 parts of NaNO2 with the mass fraction of 40%, 220 parts of NaF with the mass fraction of 12%, adding 30 parts of 18% NaCl, adding 80 parts of 7- (2-chloroethyl) theophylline water solvent with the mass fraction of 10%, adding 12 parts of hexadecyl trimethyl ammonium bromide with the mass fraction of 50%, wherein the processing voltage is 2.0V, the temperature is room temperature, the electrolytic processing time is 520s, and the processing time is 1550s; hanging the etched and cleaned film on a jig, loading the film into a vacuum film plating cavity, and starting vacuumizing, wherein the vacuum degree of the radio frequency ion source treatment is 3 x 100Pa, and the treatment time is 10 minutes; the procedure is as in example 1.
Comparative example 4
The comparative example differs from example 1 in the amount of 7- (2-chloroethyl) theophylline added in step (1), the specific pretreatment being: ultrasonic cleaning is adopted, the current is 2A, the time is 5 minutes, and the treatment time of the ion source treatment vacuum degree is 3 x 10 0 Pa is 10 minutes. Then carrying out electrolyte etching, wherein the electrode is Pt,120 parts of NaNO3 with the mass fraction of 25%, 220 parts of NaNO2 with the mass fraction of 40%, 220 parts of NaF with the mass fraction of 12%, adding 30 parts of 18% NaCl, adding 30 parts of 7- (2-chloroethyl) theophylline water solvent with the mass fraction of 10%, adding 12 parts of hexadecyl trimethyl ammonium bromide with the mass fraction of 50%, the processing voltage is 2.0V, the temperature is room temperature, the electrolytic processing time is 520s, and the processing time is 1550s; hanging the etched and cleaned film on a jig, loading the film into a vacuum film plating cavity, and starting vacuumizing, wherein the vacuum degree of the radio frequency ion source treatment is 3 x 100Pa, and the treatment time is 10 minutes; the procedure is as in example 1.
Comparative example 5
The comparative example is different from example 1 in that the hybridized ZrO2 nano-solid in step (2) is not subjected to hybridization treatment, and the specific process is as follows:
(1) Pretreatment: ultrasonic cleaning is adopted, the current is 2A, the time is 5 minutes, and the treatment time of the ion source treatment vacuum degree is 3 x 10 0 Pa is 10 minutes. Then carrying out electrolyte etching, wherein the electrode is Pt,120 parts of NaNO3 with the mass fraction of 25%, 220 parts of NaNO2 with the mass fraction of 40%, 220 parts of NaF with the mass fraction of 12%, adding 30 parts of 18% NaCl, adding 50 parts of 7- (2-chloroethyl) theophylline water solvent with the mass fraction of 10%, adding 12 parts of hexadecyl trimethyl ammonium bromide with the mass fraction of 50%, wherein the processing voltage is 2.0V, the temperature is room temperature, the electrolytic processing time is 520s, and the processing time is 1550s; hanging the etched and cleaned film on a jig, loading the film into a vacuum coating cavity, and starting vacuumizing, wherein the vacuum degree of the radio frequency ion source treatment is 3 x 100Pa, and the treatment time is 10 minutes.
(2) The preparation of the fluorine silicon compound comprises the following steps: firstly, weighing 10 parts of silicon dioxide powder, pouring the silicon dioxide powder into 30 parts of ethanol solution of 10% of vinyl dimethyl fluorosilane by mass fraction, stirring for 24 hours at room temperature, centrifuging the obtained silica sol for 3 times, washing with absolute ethanol, putting into a drying oven for drying for 5 hours, and finally grinding into fine powder by using a mortar to obtain hydrophobically modified silicon dioxide; mechanically stirring 35 parts of 99% ethanol and 50 parts of 98% ethyl orthosilicate at 50 ℃ for 30min; then, 2.8 parts of ammonia water and 7.6 parts of deionized water are slowly dripped into the mixed solution, after continuous stirring for 8 hours, the modified silicon dioxide is added into the mixed solution, then stirring is continued for 12 hours, the obtained sol is placed in a centrifugal machine for centrifugal separation, the rotating speed is 6000rpm, the obtained solid is subjected to centrifugal separation for 10 minutes, the obtained solid is subjected to 3 times of washing by ethanol solution, then the obtained solid is subjected to centrifugal separation again, and finally the obtained solid particles are completely dried at 80 ℃ to obtain the fluorine-silicon particles.
(3) The vacuum degree of the coating is 1.5 x 10 < -2 > Pa, the thickness of the film layer is SiO2 (154 nm)/ZrO 2 (62 nm)/SiO 2 (84 nm)/ZrO 2 (58 nm)/SiO 2 (51 nm)/ZrO 2 (25 nm)/SiO 2 (109 nm), and the auxiliary ion source is AR. The deposition rate was 3 a/s. After the completion, the silicon fluoride compound is continuously evaporated, and the film layer is 30nm.
Comparative example 6
This comparative example differs from example 1 in that the p-methylsulfonylmethyl isonitrile in step (2) is tetrabutylzirconate, and the remainder is the same as example 1.
Comparative example 7
The present comparative example is different from example 1 in that the addition amount of p-methylsulfonylmethyl isonitrile in step (2) is different, and the preparation of the specific high refractive index material hybrid ZrO2 nano solid is: firstly, adding 12 parts of epoxy resin E51 and D400 (the mass ratio is 100:64) into 55 parts of water, adding 80 parts of ZrO2 powder, adding 3 parts of benzyl alcohol as an accelerator and 4.2 parts of acetone as a diluent, and stirring for 10 minutes at room temperature; then adding 0.1 part of glacial acetic acid into the system, stirring for 30min at room temperature, then adding 10 parts of p-methylsulfonyl methyl isonitrile dropwise into the system, stirring for 5.5h at room temperature until a uniform and transparent hybrid sol solution is formed, heating to 120 ℃ while stirring, stirring and evaporating for 2h, then drying for 50min at 45 ℃ in a vacuum drying oven, and drying for 105min at 60 ℃ to obtain a hybrid ZrO2 nano solid; the procedure is as in example 1.
Comparative example 8
The present comparative example is different from example 1 in that the addition amount of p-methylsulfonylmethyl isonitrile in step (2) is different, and the preparation of the specific high refractive index material hybrid ZrO2 nano solid is: firstly, adding 12 parts of epoxy resin E51 and D400 (the mass ratio is 100:64) into 55 parts of water, adding 80 parts of ZrO2 powder, adding 3 parts of benzyl alcohol as an accelerator and 4.2 parts of acetone as a diluent, and stirring for 10 minutes at room temperature; then adding 0.1 part of glacial acetic acid into the system, stirring for 30min at room temperature, then adding 2 parts of p-methylsulfonyl methyl isonitrile dropwise into the system, stirring for 5.5h at room temperature until a uniform and transparent hybrid sol solution is formed, heating to 120 ℃ while stirring, stirring and evaporating for 2h, then drying for 50min at 45 ℃ in a vacuum drying oven, and drying for 105min at 60 ℃ to obtain a hybrid ZrO2 nano solid; the procedure is as in example 1.
Comparative example 9
This comparative example differs from example 1 in that the vinyldimethylsiloxane in step (3) is trimethoxytridecafluoron-octylsilane, and the remainder are the same as in example 1.
Comparative example 10
This comparative example differs from example 1 in the amount of added vinyldimethylfluorosilane in step (3), and the specific fluorosilicone compound was produced as follows: firstly, weighing 10 parts of silicon dioxide powder, pouring the silicon dioxide powder into 50 parts of ethanol solution of 10% of vinyl dimethyl fluorosilane by mass fraction, stirring for 24 hours at room temperature, centrifuging the obtained silica sol for 3 times, washing with absolute ethanol, putting into a drying oven for drying for 5 hours, and finally grinding into fine powder by using a mortar to obtain hydrophobically modified silicon dioxide; mechanically stirring 35 parts of 99% ethanol and 50 parts of 98% ethyl orthosilicate at 50 ℃ for 30min; then, 2.8 parts of ammonia water and 7.6 parts of deionized water are slowly dripped into the mixed solution, after continuous stirring for 8 hours, the modified silicon dioxide is added into the mixed solution, then stirring is continued for 12 hours, the obtained sol is placed in a centrifuge for centrifugal separation, the rotation speed is 6000rpm, the obtained solid is centrifuged for 10 minutes, the obtained solid is washed for 3 times by ethanol solution, then the solid particles obtained finally are centrifuged again, and the fluorine silicon particles are obtained after the final solid particles are completely dried at 80 ℃, and the rest is the same as in example 1.
Comparative example 11
This comparative example differs from example 1 in the amount of added vinyldimethylfluorosilane in step (3), and the specific fluorosilicone compound was produced as follows: firstly, weighing 10 parts of silicon dioxide powder, pouring the silicon dioxide powder into 10 parts of ethanol solution of 10% of vinyl dimethyl fluorosilane by mass fraction, stirring for 24 hours at room temperature, centrifuging the obtained silica sol for 3 times, washing with absolute ethanol, putting into a drying oven for drying for 5 hours, and finally grinding into fine powder by using a mortar to obtain hydrophobically modified silicon dioxide; mechanically stirring 35 parts of 99% ethanol and 50 parts of 98% ethyl orthosilicate at 50 ℃ for 30min; then, 2.8 parts of ammonia water and 7.6 parts of deionized water are slowly dripped into the mixed solution, after continuous stirring for 8 hours, the modified silicon dioxide is added into the mixed solution, then stirring is continued for 12 hours, the obtained sol is placed in a centrifuge for centrifugal separation, the rotation speed is 6000rpm, the obtained solid is centrifuged for 10 minutes, the obtained solid is washed for 3 times by ethanol solution, then the solid particles obtained finally are centrifuged again, and the fluorine silicon particles are obtained after the final solid particles are completely dried at 80 ℃, and the rest is the same as in example 1.
The testing method comprises the following steps:
(1) Contact angle: the contact angle tester is adopted, the dropping liquid adopts pure water, the water drops are dropped on the surface of the film layer, the light is used for photographing, and then the measuring software on the computer is used for testing the water drop angle.
(2) Color: the color of the returned light of the sample can be visually observed, and a color meter can be used.
The contact angles and color results for examples 1-4 are shown in Table 1.
Table 1 test effect of examples
| Examples | Contact angle | Color of |
| 1# | 115 Degrees | Blue color |
| 2# | 115 Degrees | Yellow colour |
| 3# | 115 Degrees | Orange color |
| 4# | 115 Degrees | Green colour |
(3) The corrosion potential test method is as follows: the Gamry electrochemical working station is selected for carrying out corrosion potential test on the examples 1-4 and the comparative examples 1-11, firstly, a sample to be tested is immersed into a NaCl solution with the corrosion medium of 3.5wt% for 30min to stabilize open-circuit potential, then, the sample to be tested is adopted as a working electrode, a platinum electrode is adopted as a counter electrode, a Saturated Calomel Electrode (SCE) is adopted as a reference electrode to form a three-electrode system for measurement, a tafel potential polarization curve of the material is measured, and the corrosion potential is calculated by using a linear extrapolation method.
(4) The abrasion resistance test method is as follows: the abrasion resistance test is carried out on an M2000 type abrasion machine, the lower roller of the abrasion machine is made of GCr15 steel, the hardness is HRC61, the rotating speed is 200r/min, and the pressure is 300N. The abrasion resistance is evaluated by a weighing method, the samples of the examples 1-4 and the comparative examples 1-11 are cleaned by absolute ethyl alcohol and dried by a blower before the abrasion resistance test, then the mass M1 of the sample is measured by an electronic balance (3 times of measurement and average value taking are carried out), the sample is cleaned by absolute ethyl alcohol again after 3 minutes of pre-abrasion, and the mass M2 of the sample is measured by the electronic balance again (3 times of measurement and average value taking are carried out) after the sample is dried by the blower; after continuing the abrasion for 15min, M3 was measured (3 times in succession, taking the average value) and the abrasion loss m=m2-M3 of the final sample was repeated. The results are shown in Table 2.
Table 2 test results
Claims (10)
1. A preparation method of a color-adjustable magnesium alloy surface corrosion-resistant composite film layer is characterized by comprising the following steps:
(1) Ultrasonic cleaning: before coating, firstly adopting neutral cleaning agent to make ultrasonic cleaning, and making ultrasonic current be 1-4A for 2-10 min;
(2) A radio frequency ion source treatment surface: hanging the etched and cleaned surface-treated material on a jig, loading the surface-treated material into a vacuum coating cavity, starting vacuumizing, wherein the vacuum degree is 1 x 10 -1-1*100 Pa, carrying out radio frequency ion source treatment on the surface, the working gas is Ar or N2, the energy is 700-2000ev, the treatment time is 3-30 minutes, the working voltage is 200-600V, and the current is 300-800MA;
(3) Plating a corrosion-resistant oxide film layer by an electron gun: evaporating the coating by adopting a PVD (physical vapor deposition) electron gun and assisting the coating by using a high-energy ion source, wherein the assisted high-energy ion beam bombards the surface of the magnesium alloy, the vacuum degree of the coating is 9 x 10 -3-3*10-2 Pa, the working gas of the coating ion source is Ar, the deposition rate of the coating is controlled to be 1.5-5 angstroms/second, the working voltage is 200-600V, and the current is 300-800MA; the coating material adopts corrosion-resistant high-refraction and low-refraction materials, and the high-refraction and low-refraction materials are matched;
(4) Plating a super-hydrophobic film layer: after the corrosion-resistant oxide film layer is finished, a resistance heating plating super-hydrophobic film layer is adopted.
2. The method for preparing the color-adjustable magnesium alloy surface corrosion-resistant composite film layer, as set forth in claim 1, is characterized in that:
the ultrasonic cleaning further comprises electrolyte etching: the electrode is a Pt electrode, 100-150 parts by mass of 25% NaNO3, 200-240 parts by mass of 40% NaNO2, 200-240 parts by mass of 12% NaF are added, 20-40 parts by mass of 18% NaCl is added, 40-60 parts of complexing agent is added, 10-15 parts by mass of 50% hexadecyl trimethyl ammonium bromide is added, the processing voltage is 1.8-2.2V, the temperature is room temperature, the electrolytic processing time is 500-540s, and the processing time is 1500-1600s.
3. The method for preparing the color-adjustable magnesium alloy surface corrosion-resistant composite film layer, as claimed in claim 2, is characterized in that:
wherein the complexing agent in the etching and cleaning of the electrolyte is a 7- (2-chloroethyl) theophylline water solvent with the mass fraction of 10 percent.
4. The method for preparing the color-adjustable magnesium alloy surface corrosion-resistant composite film layer, as set forth in claim 1, is characterized in that:
the corrosion-resistant oxide film layer adopts the sequence of alternately coating films of low-high refractive materials, and the color of the film layer is regulated by controlling the sequence of the high-low refractive materials of the coating films and the thickness of the film layer.
5. The method for preparing the color-adjustable magnesium alloy surface corrosion-resistant composite film layer, as set forth in claim 1, is characterized in that:
the high refractive index material of the corrosion-resistant oxide film layer in the specific step (3) is one or more of hybridized ZrO2 nano solid, tiO2, H4g and Nb2O5, and the low refractive index material is one or more of SiO2 and Al2O 3.
6. The method for preparing the color-adjustable magnesium alloy surface corrosion-resistant composite film layer according to claim 5, which is characterized by comprising the following steps:
The preparation method of the high refractive index material hybridized ZrO2 nano solid comprises the following steps: firstly, adding 10-15 parts of epoxy resin E51 and D400 (the mass ratio is 100:64) into 50-60 parts of water, adding 70-90 parts of ZrO2 powder, adding 2-5 parts of benzyl alcohol as an accelerator, and 3.5-5 parts of acetone as a diluent, and stirring for 10min at room temperature; then adding 0.1 part of glacial acetic acid into the system, stirring for 30min at room temperature, then adding 4-6 parts of regulator into the system dropwise, stirring for 5-6h at room temperature until a uniform and transparent hybrid sol solution is formed, heating to 120 ℃ while stirring, stirring and evaporating for 2h, then drying for 40-60min at 40-50 ℃ in a vacuum drying oven, and then drying for 90-120min at 60 ℃ to obtain the hybrid ZrO2 nano solid.
7. The method for preparing the color-adjustable magnesium alloy surface corrosion-resistant composite film layer, as set forth in claim 6, is characterized in that:
Wherein the regulator is p-methylsulfonylmethyl isonitrile.
8. The method for preparing the color-adjustable magnesium alloy surface corrosion-resistant composite film layer, as set forth in claim 1, is characterized in that:
The super-hydrophobic material is silicon fluoride, and the thickness of the super-hydrophobic material is 10-100nm.
9. The method for preparing the color-adjustable magnesium alloy surface corrosion-resistant composite film layer, as claimed in claim 8, is characterized in that:
The preparation of the specific silicon fluorine compound comprises the following steps: (1) hydrophobic modification of silica: firstly, weighing 10 parts of silicon dioxide powder, pouring the silicon dioxide powder into 30 parts of modified fluorosilane solution, stirring for 24 hours at room temperature, centrifuging the obtained silica sol for 3 times, washing with absolute ethyl alcohol, then placing into a drying oven for drying for 5 hours, and finally grinding into fine powder by using a mortar to obtain hydrophobically modified silicon dioxide; (2) preparation of fluorosilicone particles: mechanically stirring 33-38 parts of ethanol with the mass concentration of 99% and 46-52 parts of ethyl orthosilicate with the mass fraction of 98% for 30min at 50 ℃; then, 2.6-3.0 parts of ammonia water and 7.2-8.2 parts of deionized water are slowly dripped into the mixed solution, after continuous stirring is carried out for 8 hours, the modified silicon dioxide is added into the mixed solution, then stirring is continued for 12 hours, the obtained sol is placed in a centrifugal machine for centrifugal separation, the rotating speed is 6000rpm, the centrifugal separation is carried out for 10 minutes, the obtained solid is washed for 2-3 times by ethanol solution, then the centrifugal separation is carried out again, and finally the obtained solid particles are completely dried at 80 ℃, thus obtaining the silicon fluorine particles.
10. The method for preparing the color-adjustable magnesium alloy surface corrosion-resistant composite film layer, as claimed in claim 9, is characterized in that:
The modified fluorosilane is an ethanol solution of 10% by mass of vinyldimethylsilane.
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