CN103992668A - Aluminum alloy umbrella skeleton surface coating as well as preparation and application method thereof - Google Patents
Aluminum alloy umbrella skeleton surface coating as well as preparation and application method thereof Download PDFInfo
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- CN103992668A CN103992668A CN201410231316.1A CN201410231316A CN103992668A CN 103992668 A CN103992668 A CN 103992668A CN 201410231316 A CN201410231316 A CN 201410231316A CN 103992668 A CN103992668 A CN 103992668A
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- aluminium alloy
- umbrella frame
- titanium
- coating material
- alloy umbrella
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- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 72
- 238000000576 coating method Methods 0.000 title claims abstract description 64
- 239000011248 coating agent Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000010936 titanium Substances 0.000 claims abstract description 54
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 53
- 239000007788 liquid Substances 0.000 claims abstract description 44
- 239000006185 dispersion Substances 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 40
- 238000005034 decoration Methods 0.000 claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005516 engineering process Methods 0.000 claims abstract description 5
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 4
- 239000003085 diluting agent Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 14
- 230000032683 aging Effects 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 239000002612 dispersion medium Substances 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- -1 poly(oxyethylene glycol) Polymers 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 4
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 4
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 4
- ULRCHFVDUCOKTE-UHFFFAOYSA-N 3-[3-aminopropyl(diethoxy)silyl]oxybutan-1-amine Chemical compound NCCC[Si](OCC)(OCC)OC(C)CCN ULRCHFVDUCOKTE-UHFFFAOYSA-N 0.000 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 229940075507 glyceryl monostearate Drugs 0.000 claims description 3
- 229960003511 macrogol Drugs 0.000 claims description 3
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- AUEJBKCWXPYRGZ-UHFFFAOYSA-N 1,1'-biphenyl diethoxysilane Chemical compound C(C)O[SiH2]OCC.C1(=CC=CC=C1)C1=CC=CC=C1 AUEJBKCWXPYRGZ-UHFFFAOYSA-N 0.000 claims description 2
- ZDZYGYFHTPFREM-UHFFFAOYSA-N 3-[3-aminopropyl(dimethoxy)silyl]oxypropan-1-amine Chemical compound NCCC[Si](OC)(OC)OCCCN ZDZYGYFHTPFREM-UHFFFAOYSA-N 0.000 claims description 2
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910015900 BF3 Inorganic materials 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 11
- 238000005260 corrosion Methods 0.000 abstract description 11
- 230000003647 oxidation Effects 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 239000000049 pigment Substances 0.000 abstract description 5
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 230000001681 protective effect Effects 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 238000010907 mechanical stirring Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 238000003618 dip coating Methods 0.000 description 4
- 230000001680 brushing effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910001773 titanium mineral Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention belongs to the technical field of hybrid coatings, and discloses an aluminum alloy umbrella skeleton surface coating as well as a preparation and application method thereof. A coating material comprises the following components in percentage by weight: 20-90% of SiO2 organic-inorganic hybrid sol, 5-80% of titanium black dispersion liquid and 0-75% of diluent. The aluminum alloy umbrella skeleton surface coating adopts an organic-inorganic hybrid method, introduces a titanium black pigment into a system for preparing the SiO2 hybrid sol by using a sol-gel technology, and adopts the comprehensive excellent performances of organic-inorganic hybrid coatings and good dispersion performance and high blackness covering performance of the titanium black pigment, so that the obtained coating material disclosed by the invention can obtain various characteristics and functions such as high hardness, high adhesion, wear resistance and scratch resistance, corrosion resistance and the like when a coating with a micron-level thickness is formed on the surface of an aluminum alloy umbrella skeleton, and can reach the characteristics of black decoration on the surface of the umbrella skeleton. A black organic-inorganic hybrid protective and decorative coating can be used for replacing the anodic oxidation treatment of the aluminum alloy umbrella skeleton.
Description
Technical field
The invention belongs to hybrid coating technical field, particularly a kind of have that corrosion-resistant, high rigidity, strong adhesive force, black are ornamental, coat-thickness is micron order, top coat and the preparation and application thereof that can play to aluminium alloy umbrella frame surface protection and black decoration function.
Background technology
At present umbrella frame material on the market has five kinds, is respectively wooden, irony, aluminium alloy, stainless steel and advanced composite material, and aluminum alloy materials density is low, quality is light, intensity is high, plasticity is good, can conveniently be processed into different shape, thereby uses the most extensive.As umbrella frame with aluminium alloy structure material require meet corrosion-resistant, wear-resistant, can be ornamental etc. requirement, but undressed umbrella frame aluminium alloy structure parts are easily corrosion in moist atmosphere, and aluminium alloy structure parts surface appearance color is single, processing and manufacturing vestige is obvious, therefore be difficult to meet the requirement of umbrella frame material strong corrosion resistant, weather resisteant and high-decoration.
In order to overcome the defect of the aspects such as aluminium alloy umbrella frame surface hardness, wearability, erosion resistance, increase the service life, and raising decorative effect, surface treatment becomes an indispensable ring in aluminium alloy use, and anodizing technology is at present most widely used and the most successful.By anodic oxidation, can be at the oxide film of aluminium Surface Creation hard, clear, obviously improve corrosion resistance nature, surface hardness and the wear resistance of aluminum alloy material, after the suitable painted processing of process, also can make aluminium alloy umbrella frame can have better decorate properties.But anode oxidation process flow process is very complicated, comprise dress extension-oil removing-washing-caustic corrosion-hot water wash-cold wash-pickling-washing-anodic oxidation-washing-deionization washing-sealing-washing-dry multiple steps, and in treating processes, produce a large amount of heavy metal wastewater therebies and waste gas, serious environment pollution, environmental issue is serious.
Although the anode oxidation process of umbrella frame aluminium alloy and flow process are in constantly modified and optimization, but current method cannot meet the double requirements of not only simple to operate but also environmental protection all the time, still not mature enough in production and application process, still need to make great efforts seeking breakthrough.
Summary of the invention
In order to overcome the shortcoming and deficiency of above-mentioned prior art; primary and foremost purpose of the present invention is to provide a kind of black hybrid inorganic-organic protected decoration coating that can be used for substitution of Al alloy umbrella frame anodic oxidation treatment, reaches the object that aluminium alloy umbrella frame surface is played to protection and black decoration function.Described hybrid coating is thinner, can obtain the multifrequency nature functions such as corrosion-resistant, high rigidity, strong adhesive force at micron order thickness, is added with the titanium mineral black of high hiding rare in coating simultaneously, has the effect of umbrella frame surface being carried out to black decoration.
Another object of the present invention is to provide a kind of and above-mentionedly has that corrosion-resistant, high rigidity, strong adhesive force, black are ornamental, coat-thickness is the preparation and application of micron-sized aluminium alloy umbrella frame surface hydridization protected decoration coating.
Object of the present invention realizes by following proposal:
A kind of alternative aluminium alloy umbrella frame anodic oxidation treatment, have that corrosion-resistant, high rigidity, strong adhesive force, black are ornamental, coat-thickness is micron-sized aluminium alloy umbrella frame surface hydridization protected decoration coating, it is characterized in that the component that comprises following weight percentage meter: SiO
2hybrid inorganic-organic colloidal sol 30 ~ 90%, black dispersion liquid 10 ~ 60 % of titanium and thinner 0 ~ 50 %.
Described thinner is at least one in methyl alcohol, ethanol, Virahol, propyl carbinol, ethyl acetate.
Described SiO
2hybrid inorganic-organic colloidal sol is prepared by following methods: hydridization presoma, organic solvent and water mixed, adds catalyzer, and heating reflux reaction, room temperature ageing, obtains SiO
2hybrid inorganic-organic colloidal sol.
By percentage to the quality, described SiO
2in hybrid inorganic-organic colloidal sol preparation feedback system, hydridization presoma content is that 5 ~ 60 %, organic solvent content are that 30 ~ 80 %, water-content are that 0.1 ~ 20 % and catalyst content are 0.001 ~ 2 %.
In order to realize better the present invention, described heating reflux reaction is condensing reflux 1 ~ 3 h at 40 ~ 75 DEG C preferably.
In order to realize better the present invention, the time of described ageing is preferably 8 ~ 80h.
In order to realize better the present invention, described hydridization presoma is tetraethoxy, methyl silicate, γ-aminopropyltrimethoxysilane, γ-aminopropyl triethoxysilane, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane, N-β (aminoethyl)-γ-aminopropyl triethoxysilane, Union carbide A-162, methyltrimethoxy silane, 2-(3,4-epoxy cyclohexane base) ethyl triethoxysilane, 2-(3,4-epoxy cyclohexane) ethyl trimethoxy silane, γ-(2,3-glycidoxy) propyl trimethoxy silicane, 3-glycidyl ether oxygen base propyl-triethoxysilicane, the two ethyl-silicone ethane of 1,2-, the two silica-based ethane of trimethoxy of 1,2-, propyl trimethoxy silicane, phenyl triethoxysilane, phenyltrimethoxysila,e, phenylbenzene diethoxy silane, dimethoxydiphenylsilane, dimethyldiethoxysilane, dimethyldimethoxysil,ne, urea propyl-triethoxysilicane, urea propyl trimethoxy silicane, at least one in γ-methacryloxypropyl trimethoxy silane and γ-methacryloxypropyl triethoxyl silane.
Described catalyzer is at least one in formic acid, acetic acid, sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, hydrofluoric acid, phosphoric acid, boric acid, aluminum chloride, iron(ic) chloride, boron trifluoride, ammoniacal liquor and sodium hydroxide.
Described organic solvent is at least one in methyl alcohol, ethanol and Virahol.
The black dispersion liquid of titanium is prepared by following methods:
Black titanium powder, dispersing auxiliary, dispersion medium, through dispersion grinding, are made to the black dispersion liquid of titanium.
By percentage to the quality, to prepare the black content of powder of titanium in system be that 5 ~ 60 %, dispersing auxiliary content are that 0.05 ~ 5 %, dispersion medium content are 35 ~ 90 % to the black dispersion liquid of described titanium.
In order to realize better the present invention, described dispersion grinding is preferably being disperseed 10 ~ 80min with 400 ~ 4000rpm, then grinds 15 ~ 120min with ball milling method, makes the black dispersion liquid of titanium.
In order to realize better the present invention, the black size of described titanium is 1nm ~ 3 μ m.
Described dispersing auxiliary is at least one in ethylene glycol, Macrogol 200, poly(oxyethylene glycol) 400, calcium stearate, barium stearate, glyceryl monostearate, ethylene group bis-stearamides.
Described dispersion medium is at least one in methyl alcohol, ethanol, propyl carbinol, Virahol.
The preparation method of aluminium alloy umbrella frame coating material of the present invention, comprises the following steps: 30 ~ 90 wt% SiO
2hybrid inorganic-organic colloidal sol, the black dispersion liquid of 10 ~ 60 wt% titanium and 0 ~ 50wt% mixing diluents, and stir, aluminium alloy umbrella frame coating material obtained.
The present invention also provides a kind of above-mentioned alternative aluminium alloy umbrella frame anodic oxidation treatment, it is corrosion-resistant to have, high rigidity, strong adhesive force, black are ornamental, coat-thickness is the using method of micron-sized aluminium alloy umbrella frame surface hydridization protected decoration coated material, concrete technology is: aluminium alloy umbrella frame coating material is coated in to aluminium alloy umbrella frame surface, leave standstill after levelling, under 60 DEG C ~ 200 DEG C conditions, toast 10 ~ 60 min, obtain hybrid inorganic-organic protected decoration coating.
Preferably, the method for described coating can be the either method that those skilled in the art use, and comprises the one in dip-coating, showering, spraying and brushing.
Preferably, the thickness of described hybrid inorganic-organic protected decoration coating is 1 ~ 300 μ m.
Alternative aluminium alloy umbrella frame anodic oxidation treatment aluminium alloy umbrella frame of the present invention surface hydridization protected decoration coated material applies the coat-thickness obtaining and can be low to moderate 1 ~ 300 μ m, both there is the excellent properties such as corrosion-resistant, high rigidity, strong adhesive force, black be ornamental, and can be widely used in the surfacecti proteon of aluminium alloy umbrella frame and decorate.
Mechanism of the present invention is:
The present invention utilizes hybrid inorganic-organic method, prepares SiO at sol-gel technique
2in hybrid collosol system, introduce titanium mineral black, utilize the comprehensive excellent properties of hybrid inorganic-organic coating, and titanium mineral black good dispersion and high blackness opacifying property, while making gained coated material of the present invention form micron order thickness coatings on aluminium alloy umbrella frame surface, both can obtain high rigidity, high adhesive force, wear-resisting scratch resistance, the multifrequency nature function such as anticorrosive, and can reach black decorative characteristic is carried out in umbrella frame surface again.This black hybrid inorganic-organic protected decoration coating can be used for substitution of Al alloy umbrella frame anodic oxidation treatment.
Described titanium is black is a kind of novel black pigment, gradually by people's extensive concern and employing.Black titanium oxide compound is a kind of titanium suboxide or mixed valence titanium oxide, as TiO, and Ti
2o
3,≤TiO
2n-1(1≤n≤10) etc.The advantage of black titanium oxide compound is that black purity is high, and thermostability is very high, has good dispersiveness in organic solvent and water, and opacifying power, resistance to acids and bases, solvent resistance are good, poisons without chemistry; Its particle diameter can reach micron order or nano level, has very strong tinting strength, is the extraordinary black pigment of a kind of prospect.
The present invention, with respect to prior art, has following advantage and beneficial effect:
1, the anodised traditional treatment method in organic-inorganic hybridized coatings of the present invention alternative aluminium alloy umbrella frame surface, this hybrid coating can obtain high rigidity, high adhesive force, wear-resisting scratch resistance, the multifrequency nature function such as anticorrosive at micron order thickness, has the effect of umbrella frame surface being carried out to black decoration simultaneously;
2, hybrid inorganic-organic protected decoration coated material of the present invention, technical process is very simple, and there is no the discharge of heavy metal wastewater thereby and poisonous fume.The hazardous solvent such as containing benezene not in system, has energy-conserving and environment-protective, with low cost, easy and simple to handle, nontoxic, the operating efficiency high of constructing.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
(1) SiO
2the preparation of hybrid inorganic-organic colloidal sol: add dimethoxydiphenylsilane 10 g, tetraethoxy 5 g, 2-(3,4-epoxy cyclohexane) ethyl trimethoxy silane 5 g, ethanol 50 g and water 5 g in reactor, stirring at room temperature is even; Then add the mixing liquid of 0.1 g hydrochloric acid (37 %) and 2 g water, condensing reflux 2 h under 55 DEG C of conditions; Finally ageing 8h at ambient temperature, obtains SiO
2hybrid inorganic-organic colloidal sol;
(2) preparation of the black dispersion liquid of titanium: adding the black powder of the titanium (trade mark: Type S in mechanical stirring container, particle diameter: 60nm, Mitsubishi) 5g, ethylene glycol 1g, Virahol 94g disperse 30min under 400 rpm conditions, then grind 120min with ball milling method, make the black dispersion liquid of titanium.
SiO prepared by step (1)
2the black dispersion liquid 30g of titanium, ethyl acetate 5g that hybrid inorganic-organic colloidal sol 30 g are prepared with step (1) stir 60 min to mixing, and obtain aluminium alloy umbrella frame coating material; Adopt dip-coating method, prepared aluminium alloy umbrella frame coating material is coated with and is contained in aluminium alloy umbrella frame surface, under 120 DEG C of conditions, toast 40 min, obtain hybrid inorganic-organic protected decoration coating.
Test result:
Coat-thickness: 12 μ m;
Hardness HV(carries out according to GB/T 4340.1-2009): 370;
Salt fog resistance: >250 h.
Embodiment 2
(1) SiO
2the preparation of hybrid inorganic-organic colloidal sol: add Union carbide A-162 10 g, tetraethoxy 15 g, dimethoxydiphenylsilane 5 g, Virahol 50 g and water 3 g in reactor, stirring at room temperature is even; Then add the mixing liquid of 0.05 g sulfuric acid and 2 g water, condensing reflux 1h under 75 DEG C of conditions; Finally ageing 40h at ambient temperature, obtains SiO
2hybrid inorganic-organic colloidal sol;
(2) preparation of the black dispersion liquid of titanium: adding the black powder of titanium (particle diameter: 1 ~ 3 μ m in mechanical stirring container, Ke Le pigment company limited) 60g, Macrogol 200 2g, ethanol 38g, under 3000 rpm conditions, disperse 10min, then grind 100min with ball milling method, make the black dispersion liquid of titanium.
SiO prepared by step (1)
2the black dispersion liquid 10g of titanium, propyl carbinol 20g that hybrid inorganic-organic colloidal sol 50 g are prepared with step (1) stir 60 min to mixing, and obtain aluminium alloy umbrella frame coating material; Adopt brushing method, prepared aluminium alloy umbrella frame coating material is coated with and is contained in aluminium alloy umbrella frame surface, under 60 DEG C of conditions, toast 60 min, obtain hybrid inorganic-organic protected decoration coating.
Test result:
Coat-thickness: 20 μ m;
Hardness HV(carries out according to GB/T 4340.1-2009): 325;
Salt fog resistance: >300 h.
Embodiment 3
(1) SiO
2the preparation of hybrid inorganic-organic colloidal sol: add γ-methacryloxypropyl trimethoxy silane 3 g, dimethyldimethoxysil,ne 1.9g, ethanol 60 g, Virahol 4.34g and water 10 g in reactor, stirring at room temperature is even; Then add the mixing liquid of 0.57 g aluminum chloride and 2 g water, condensing reflux 3 h under 40 DEG C of conditions; Finally ageing 60h at ambient temperature, obtains SiO
2hybrid inorganic-organic colloidal sol;
(2) preparation of the black dispersion liquid of titanium: adding the black powder of the titanium (trade mark: Type M in mechanical stirring container, particle diameter: 80 ~ 100nm, Mitsubishi) 20g, poly(oxyethylene glycol) 400 5g, ethanol 75g, under 1500rpm condition, disperse 40min, then grind 80min with ball milling method, make the black dispersion liquid of titanium.
SiO prepared by step (1)
2the black dispersion liquid 12g of titanium that hybrid inorganic-organic colloidal sol 48 g are prepared with step (1) stirs 60 min to mixing, and obtains aluminium alloy umbrella frame coating material; Adopt showering method, prepared aluminium alloy umbrella frame coating material is coated with and is contained in aluminium alloy umbrella frame surface, under 200 DEG C of conditions, toast 10 min, obtain hybrid inorganic-organic protected decoration coating.
Test result:
Coat-thickness: 10 μ m;
Hardness HV(carries out according to GB/T 4340.1-2009): 360;
Salt fog resistance: >200 h.
Embodiment 4
(1) SiO
2the preparation of hybrid inorganic-organic colloidal sol: add N-β (aminoethyl)-γ-aminopropyl triethoxysilane 20g, methyl silicate 15g, phenyl triethoxysilane 13 g, methyl alcohol 36g and water 0.4 g in reactor, stirring at room temperature is even; Then add the mixing liquid of 0.8 g nitric acid and 2 g water, condensing reflux 2h under 40 DEG C of conditions; Finally ageing 80h at ambient temperature, obtains SiO
2hybrid inorganic-organic colloidal sol;
(2) preparation of the black dispersion liquid of titanium: adding the black powder of the titanium (trade mark: Type S in mechanical stirring container, particle diameter: 60nm, Mitsubishi) 60g, calcium stearate 5g, Virahol 35g, under 4000 rpm conditions, disperse 20min, then grind 15min with ball milling method, make the black dispersion liquid of titanium.
SiO prepared by step (1)
2the black dispersion liquid 20g of titanium, ethanol 4g that hybrid inorganic-organic colloidal sol 56 g are prepared with step (1) stir 60 min to mixing, and obtain aluminium alloy umbrella frame coating material; Adopt spraying method, prepared aluminium alloy umbrella frame coating material is coated with and is contained in aluminium alloy umbrella frame surface, under 160 DEG C of conditions, toast 20 min, obtain hybrid inorganic-organic protected decoration coating.
Test result:
Coat-thickness: 15 μ m;
Hardness HV(carries out according to GB/T 4340.1-2009): 380;
Salt fog resistance: >350 h.
Embodiment 5
(1) SiO
2the preparation of hybrid inorganic-organic colloidal sol: add 3-glycidyl ether oxygen base propyl-triethoxysilicane 20 g, tetraethoxy 7.5 g, urea propyl-triethoxysilicane 15g, ethanol 20 g, Virahol 5.5 g and water 13.3g in reactor, stirring at room temperature is even; Then add the mixing liquid of 1.7 g sodium hydroxide and 2 g water, condensing reflux 3h under 50 DEG C of conditions; Finally ageing 40h at ambient temperature, obtains SiO
2hybrid inorganic-organic colloidal sol;
(2) preparation of the black dispersion liquid of titanium: adding the black powder of the titanium (trade mark: Type M in mechanical stirring container, particle diameter: 80 ~ 100nm, Mitsubishi) 8.9g, barium stearate 0.1g, Virahol 84g, propyl carbinol 6g, under 2000 rpm conditions, disperse 50min, then grind 50min with ball milling method, make the black dispersion liquid of titanium.
SiO prepared by step (1)
2the black dispersion liquid 30g of titanium, methyl alcohol 5g that hybrid inorganic-organic colloidal sol 15g is prepared with step (1) stir 60 min to mixing, and obtain aluminium alloy umbrella frame coating material; Adopt dip-coating method, prepared aluminium alloy umbrella frame coating material is coated with and is contained in aluminium alloy umbrella frame surface, under 80 DEG C of conditions, toast 30min, obtain hybrid inorganic-organic protected decoration coating.
Test result:
Coat-thickness: 50 μ m;
Hardness HV(carries out according to GB/T 4340.1-2009): 320;
Salt fog resistance: >300h.
Embodiment 6
(1) SiO
2the preparation of hybrid inorganic-organic colloidal sol: add phenyl triethoxysilane 10 g, tetraethoxy 5 g, dimethyldimethoxysil,ne 18 g, urea propyl trimethoxy silicane 15 g, Virahol 28 g and water 1.2 g in reactor, stirring at room temperature is even; Then add the mixing liquid of 0.8 g ammoniacal liquor (25 %) and 2 g water, condensing reflux 2 h under 55 DEG C of conditions; Finally ageing 70h at ambient temperature, obtains SiO
2hybrid inorganic-organic colloidal sol;
(2) preparation of the black dispersion liquid of titanium: adding the black powder of the titanium (trade mark: Type M in mechanical stirring container, particle diameter: 80 ~ 100nm, Mitsubishi) 20g, glyceryl monostearate 0.5g, Virahol 79.5g, under 3000 rpm conditions, disperse 80min, then grind 70min with ball milling method, make the black dispersion liquid of titanium.
SiO prepared by step (1)
2the black dispersion liquid 6g of titanium prepared by hybrid inorganic-organic colloidal sol 54 g and step (1), stirs 60 min to mixing, and obtains aluminium alloy umbrella frame coating material; Adopt showering method, prepared aluminium alloy umbrella frame coating material is coated with and is contained in aluminium alloy umbrella frame surface, under 170 DEG C of conditions, toast 20min, obtain hybrid inorganic-organic protected decoration coating.
Test result:
Coat-thickness: 100 μ m;
Hardness HV(carries out according to GB/T 4340.1-2009): 350;
Salt fog resistance: >250 h.
Embodiment 7
(1) SiO
2the preparation of hybrid inorganic-organic colloidal sol: add 2-(3 in reactor, 4-epoxy cyclohexane base) ethyl triethoxysilane 10 g, propyl trimethoxy silicane 3 g, 1, two ethyl-silicone ethane 3 g of 2-, ethanol 28 g, methyl alcohol 20g and water 14 g, stirring at room temperature is even; Then add the mixing liquid of 0.0008 g phosphoric acid (85 %) and 2 g water, condensing reflux 3 h under 60 DEG C of conditions; Finally ageing 30h at ambient temperature, obtains SiO
2hybrid inorganic-organic colloidal sol;
(2) preparation of the black dispersion liquid of titanium: adding the black powder of the titanium (trade mark: Type S in mechanical stirring container, particle diameter: 60nm, Mitsubishi) 40g, ethylene group bis-stearamides 3g, propyl carbinol 57g, under 1000 rpm conditions, disperse 30min, then grind 120min with ball milling method, make the black dispersion liquid of titanium.
SiO prepared by step (1)
2the black dispersion liquid 9g of titanium, ethanol 30g that hybrid inorganic-organic colloidal sol 21 g are prepared with step (1) stir 60 min to mixing, and obtain aluminium alloy umbrella frame coating material; Adopt brushing method, prepared aluminium alloy umbrella frame coating material is coated with and is contained in aluminium alloy umbrella frame surface, under 200 DEG C of conditions, toast 10min, obtain hybrid inorganic-organic protected decoration coating.
Test result:
Coat-thickness: 20 μ m;
Hardness HV(carries out according to GB/T 4340.1-2009): 450;
Salt fog resistance: >200 h.
Embodiment 8
(1) SiO
2the preparation of hybrid inorganic-organic colloidal sol: add γ-aminopropyltrimethoxysilane 10 g, methyl silicate 10 g, Union carbide A-162 16 g, ethanol 43.2g and water 0.08g in reactor, stirring at room temperature is even; Then add 0.72 g formic acid, condensing reflux 3 h under 70 DEG C of conditions; Finally ageing 40h at ambient temperature, obtains SiO
2hybrid inorganic-organic colloidal sol;
(2) preparation of the black dispersion liquid of titanium: adding the black powder of the titanium (trade mark: Type M in mechanical stirring container, particle diameter: 80 ~ 100nm, Mitsubishi) 30g, ethylene glycol 3g, Virahol 77g, under 3000 rpm conditions, disperse 60min, then grind 80min with ball milling method, make the black dispersion liquid of titanium.
SiO prepared by step (1)
2the black dispersion liquid 9g of titanium, Virahol 9g that hybrid inorganic-organic colloidal sol 42g is prepared with step (1) stir 60 min to mixing, and obtain aluminium alloy umbrella frame coating material; Adopt dip-coating method, prepared aluminium alloy umbrella frame coating material is coated with and is contained in aluminium alloy umbrella frame surface, under 60 DEG C of conditions, toast 60 min, obtain hybrid inorganic-organic protected decoration coating.
Test result:
Coat-thickness: 300 μ m;
Hardness HV(carries out according to GB/T 4340.1-2009): 300;
Salt fog resistance: >500 h.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. an aluminium alloy umbrella frame coating material, is characterized in that the component that comprises following weight percentage meter: SiO
2hybrid inorganic-organic colloidal sol 30 ~ 90 %, black dispersion liquid 10 ~ 60 % of titanium and thinner 0 ~ 50%.
2. aluminium alloy umbrella frame coating material according to claim 1, is characterized in that: described thinner is at least one in methyl alcohol, ethanol, Virahol, propyl carbinol, ethyl acetate.
3. aluminium alloy umbrella frame coating material according to claim 1, is characterized in that: described SiO
2hybrid inorganic-organic colloidal sol is prepared by following methods: hydridization presoma, organic solvent and water mixed, adds catalyzer, and heating reflux reaction, room temperature ageing, obtains SiO
2hybrid inorganic-organic colloidal sol;
The black dispersion liquid of described titanium is prepared by following methods: black titanium powder, dispersing auxiliary, dispersion medium, through dispersion grinding, are made to the black dispersion liquid of titanium.
4. aluminium alloy umbrella frame coating material according to claim 3, is characterized in that: by percentage to the quality, and described SiO
2in hybrid inorganic-organic colloidal sol preparation feedback system, hydridization presoma content is that 5 ~ 60 %, organic solvent content are that 30 ~ 80 %, water-content are that 0.1 ~ 20 % and catalyst content are 0.001 ~ 2 %; Described heating reflux reaction is condensing reflux 1 ~ 3 h at 40 ~ 75 DEG C preferably; The time of described ageing is preferably 8 ~ 80h;
By percentage to the quality, the black dispersion liquid of described titanium prepares in system that the black content of powder of titanium is 5 ~ 60%, dispersing auxiliary content is that 0.05 ~ 5 %, dispersion medium content are 35 ~ 90 %; Described dispersion grinding is preferably being disperseed 10 ~ 80min with 400 ~ 4000rpm, then grinds 15 ~ 120min with ball milling method, makes the black dispersion liquid of titanium.
5. aluminium alloy umbrella frame coating material according to claim 3, is characterized in that: described hydridization presoma is tetraethoxy, methyl silicate, γ-aminopropyltrimethoxysilane, γ-aminopropyl triethoxysilane, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane, N-β (aminoethyl)-γ-aminopropyl triethoxysilane, Union carbide A-162, methyltrimethoxy silane, 2-(3,4-epoxy cyclohexane base) ethyl triethoxysilane, 2-(3,4-epoxy cyclohexane) ethyl trimethoxy silane, γ-(2,3-glycidoxy) propyl trimethoxy silicane, 3-glycidyl ether oxygen base propyl-triethoxysilicane, the two ethyl-silicone ethane of 1,2-, the two silica-based ethane of trimethoxy of 1,2-, propyl trimethoxy silicane, phenyl triethoxysilane, phenyltrimethoxysila,e, phenylbenzene diethoxy silane, dimethoxydiphenylsilane, dimethyldiethoxysilane, dimethyldimethoxysil,ne, urea propyl-triethoxysilicane, urea propyl trimethoxy silicane, at least one in γ-methacryloxypropyl trimethoxy silane and γ-methacryloxypropyl triethoxyl silane.
6. aluminium alloy umbrella frame coating material according to claim 3, is characterized in that: described catalyzer is at least one in formic acid, acetic acid, sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, hydrofluoric acid, phosphoric acid, boric acid, aluminum chloride, iron(ic) chloride, boron trifluoride, ammoniacal liquor and sodium hydroxide;
Described organic solvent is at least one in methyl alcohol, ethanol and Virahol.
7. aluminium alloy umbrella frame coating material according to claim 3, is characterized in that: the black size of described titanium is 1nm ~ 3 μ m;
Described dispersing auxiliary is at least one in ethylene glycol, Macrogol 200, poly(oxyethylene glycol) 400, calcium stearate, barium stearate, glyceryl monostearate, ethylene group bis-stearamides;
Described dispersion medium is at least one in methyl alcohol, ethanol, propyl carbinol, Virahol.
8. according to a preparation method for the aluminium alloy umbrella frame coating material described in claim 1 ~ 7 any one, it is characterized in that comprising following concrete steps: 30 ~ 90 wt% SiO
2hybrid inorganic-organic colloidal sol, the black dispersion liquid of 10 ~ 60 wt% titanium and 0 ~ 50 wt% mixing diluents, and stir, aluminium alloy umbrella frame coating material obtained.
9. one kind according to the using method of the aluminium alloy umbrella frame coating material described in claim 1 ~ 7 any one, it is characterized in that concrete technology is: aluminium alloy umbrella frame coating material is coated in to aluminium alloy umbrella frame surface, leave standstill after levelling, under 60 DEG C ~ 200 DEG C conditions, toast 10 ~ 60 min, obtain hybrid inorganic-organic protected decoration coating; The thickness of described hybrid inorganic-organic protected decoration coating is 1 ~ 300 μ m.
10. be used for carrying out surfacecti proteon and decoration at aluminium alloy umbrella frame according to the aluminium alloy umbrella frame coating material described in claim 1 ~ 7 any one.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114273614A (en) * | 2021-12-28 | 2022-04-05 | 绍兴上虞明炀伞业有限公司 | Preparation process of multi-fold umbrella rib of beach umbrella |
| CN115232518A (en) * | 2022-07-13 | 2022-10-25 | 三棵树涂料股份有限公司 | Silicon modified high-stain-resistance interior wall coating and preparation method thereof |
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| CN114273614A (en) * | 2021-12-28 | 2022-04-05 | 绍兴上虞明炀伞业有限公司 | Preparation process of multi-fold umbrella rib of beach umbrella |
| CN115232518A (en) * | 2022-07-13 | 2022-10-25 | 三棵树涂料股份有限公司 | Silicon modified high-stain-resistance interior wall coating and preparation method thereof |
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