CN104178773A - Chromium-free environmental-friendly silicon-contained aluminum and aluminum alloy surface treating agent and preparation method thereof - Google Patents
Chromium-free environmental-friendly silicon-contained aluminum and aluminum alloy surface treating agent and preparation method thereof Download PDFInfo
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- CN104178773A CN104178773A CN201410410563.8A CN201410410563A CN104178773A CN 104178773 A CN104178773 A CN 104178773A CN 201410410563 A CN201410410563 A CN 201410410563A CN 104178773 A CN104178773 A CN 104178773A
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- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 72
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 title abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 50
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 17
- 239000010941 cobalt Substances 0.000 claims abstract description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- 239000010703 silicon Substances 0.000 claims abstract description 15
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 13
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000010936 titanium Substances 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 6
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 5
- 238000002161 passivation Methods 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 239000004411 aluminium Substances 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000005530 etching Methods 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 12
- 238000007598 dipping method Methods 0.000 claims description 11
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 11
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 11
- 239000012756 surface treatment agent Substances 0.000 claims description 10
- 238000005238 degreasing Methods 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 235000019353 potassium silicate Nutrition 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 239000001488 sodium phosphate Substances 0.000 claims description 6
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 101710194948 Protein phosphatase PhpP Proteins 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 4
- 238000007601 warm air drying Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims 2
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 150000001868 cobalt Chemical class 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 150000003608 titanium Chemical class 0.000 claims 1
- -1 vitriol Chemical compound 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 39
- 238000005260 corrosion Methods 0.000 abstract description 39
- 238000000034 method Methods 0.000 abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011651 chromium Substances 0.000 abstract description 2
- 238000007739 conversion coating Methods 0.000 abstract description 2
- 239000003112 inhibitor Substances 0.000 abstract description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 229910052804 chromium Inorganic materials 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- 231100000614 poison Toxicity 0.000 abstract 1
- 239000003440 toxic substance Substances 0.000 abstract 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 24
- 239000011780 sodium chloride Substances 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 7
- 229910000077 silane Inorganic materials 0.000 description 7
- 238000011282 treatment Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009396 hybridization Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 description 2
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 2
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 238000013532 laser treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002481 rotproofing Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000026676 system process Effects 0.000 description 1
- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Chemical Treatment Of Metals (AREA)
Abstract
The invention relates to a chromium-free environmental-friendly silicon-contained aluminum and aluminum alloy surface treating agent and a preparation method thereof. The method comprises the following step: adding an organic corrosion inhibitor by taking TEOS as a silicon source and taking an aqueous solution of an inorganic salt or an organic alkoxide of cobalt, titanium or zirconium as a hydrolysis accelerant so as to prepare an organic-inorganic hybrid passivation solution. According to the method, chromium, fluorine and other toxic substances are not adopted. The method is simple in process and low in cost, and a conversion coating is excellent in corrosion resistance. Thus, the method is suitable for industrial production and can be used for replacing a chromate process. As a result, the method has a wide market application prospect.
Description
Technical field
The invention belongs to field of metal surface treatment, be specifically related to a kind of chromium-free environment-friendly type aluminium and the anticorrosion conversion film of aluminum alloy surface and preparation method.
Background technology
Adopt chromic salt technology to carry out surface anticorrosion processing to aluminum and aluminum alloy mateial, sexavalent chrome causes serious environmental pollution to environment, has formed serious consequence, has endless trouble.Trend of Chrome-free treatment technology becomes current important research topic, realizes Trend of Chrome-free processing completely and will benefit throughout the ages.
Aluminum and aluminum alloy mateial has widespread use in fields such as building, chemical, aerospace, mechano-electronic, communications and transportation.Such material surface can form the oxide film that one deck is very thin in air, but this tunic is still easy to make it be subject to heavy corrosion in various corrosive mediums, seawater and atmospheric environment, cannot effectively protect aluminium and alloy product.
Easily there are spot corrosion, intergranular corrosion, stress corrosion crack and Peeling Corrosion etc. in aluminium and aluminum alloy surface, so aluminium and alloy product must carry out rotproofing to its surface before using.The various corrosion that how to take effective measures inhibition aluminium and alloy product become a great problem of current scientific research and industrial production application.Be most widely used at present and ripe be hexavalent chromate treatment technology.Because it can significantly improve the erosion resistance of matrix and cheap price is used widely.But hexavalent chromium (Cr
6+) strong carcinogenesis human body and environment are had to great harm.On February 13rd, 2003, European Union has issued " waste electronic andelectrical equipment instruction " and " about restriction in electronic electric equipment, using some objectionable impurities instruction ", and the use of chromic salt in metal treatment is prohibited the most at last.China also announces on March 6th, 2002, intends, from July, 2002, carcinogenic compound sexavalent chrome (chromic salt) is carried out to the use of limiting the quantity of, and Bing Yu European Union synchronously cancels and uses chromic salt before in July, 2006.Therefore seek a kind of cheap, environmental friendliness, Trend of Chrome-free and corrosion resisting property and be better than the material of chromic salt and focus and the difficult point that production technique becomes current research.In addition, conventional aluminum surface treatment method also has: rare earth conversion processing, phosphate conversion, anodic oxidation, ion implantation, laser treatment, collosol and gel conversion film etc.
The Trend of Chrome-free passivating solution of most study is that zirconium titanium is that conversion film and silane are conversion film (JP2004018992A, US6638369, CN200610046516.5, CN10218122A) at present.Adopting the metal inorganic salts such as zirconium, titanium is the main component of film forming liquid, under special organism and other Additives, can form thinner conversion film at aluminium and aluminum alloy surface.But aluminium and aluminum alloy surface are after zirconium titanium system processes, its corrosion resistance nature is lower than chromic salt, and a large amount of adding still of fluorion can cause very large harm to environment, and form film and do not have color to be difficult to directly judge that film forming is good and bad, to work, produce and bring inconvenience.It is main component that organosilane film adopts silane coupling agent, by adding of various additives, controls its hydrolytic polymerization, in aluminum alloy surface, forms silane conversion film.After silane surface treatment, the group of outside has stronger hydrophobicity.Higher and its surface hydrophobicity of the physical strength of silane film hinders corrosive medium and is diffused into aluminium and alloy matrix aluminum, can effectively improve its antiseptic property.But pure silane film silane film/metal interface bonding strength a little less than.Sol-gel method is generally taked in the preparation of silane film.And this method also can be prepared various ceramic coatings at aluminium and aluminum alloy surface, such as silicon-dioxide, aluminum oxide, zirconium white, cerium oxide and complex oxide film etc.Therefore the silicon that, adopts the method for collosol and gel to prepare organic inorganic hybridization is the focus (CN101717930A, CN102140667A, CN 102677039 A) that aluminium and aluminum alloy surface treatment solution have become current research.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of chromium-free environment-friendly type aluminium and the anticorrosion conversion film of aluminum alloy surface and preparation method are provided.This preparation method's technical process is simple, cost is low, treatment temp is low, the treatment time is short, has improved corrosion resistance nature and the practical life of conversion film.
summary of the invention
The present invention adopts TEOS as silicon source, usings cobalt, zirconium, Ti-inorganic salt or the organic alkoxide aqueous solution as hydrolytic accelerating agent, adds organic inhibitor, has prepared organic and inorganic passivating solution.By aluminium and aluminium alloy are carried out to dip treating, obtain the good organic-inorganic conversion film of solidity to corrosion, performance is better than chromic salt to be processed, and is produced on a large scale.
detailed Description Of The Invention
Technical solution of the present invention is as follows:
Aluminium and aluminum alloy surface pre-treatment, concrete steps are as follows:
(1) washing
Aluminum alloy surface is cleaned to twice with deionized water spray, each 2-5min.Or aluminium alloy is soaked in deionized water to 5-20min.
(2) degreasing and alkaline etching
Aluminum alloy sample after washing is carried out to degreasing and alkaline etching.Dosing composition is: sodium hydroxide 5-30g, sodium carbonate 0.5-2g, sodium phosphate or tripoly phosphate sodium STPP 0.1-2g, water glass 0.1-2g, Sodium dodecylbenzene sulfonate or sodium laurylsulfonate 0.1-1g, water 100mL.Aluminium alloy is soaked to 2-20min in alkaline etching dosing.Then use washed with de-ionized water 2 times.
(3) neutralization and washing
Aluminium alloy dipping after alkaline etching is flooded to 1-10min in neutralizer.Neutralizer consists of nitric acid or the aqueous sulfuric acid of 10-40wt%.Then use deionized water wash 2 times.
Preferably, in above-mentioned steps (1), deionized water spray cleans 3-5min.Or in deionized water, soak 8-15min.
Preferably, in above-mentioned steps (2), sodium hydroxide: sodium carbonate: (sodium phosphate or tripoly phosphate sodium STPP): water glass: (sodium laurylsulfonate or Sodium dodecylbenzene sulfonate): the mass ratio of water is (10-25g): (0.6-1.5g): (0.2-1.5g): (0.1-0.8g): (0.1-0.8g): 100g.In alkaline etching dosing, soak 3-18min.
Preferably, in above-mentioned steps (3), neutralizer consists of nitric acid or the aqueous sulfuric acid of 15-35wt%, and soak time is 3-8min.
Silicon is a preparation for aluminium and the anticorrosion conversion film of aluminum alloy surface, and concrete steps are as follows:
(1) TEOS is joined in the mixing solutions of water and methyl alcohol or ethanol.The adding proportion of TEOS, water, (methyl alcohol or ethanol) is (5-20mL): (2-10mL): (2-10mL).Magnetic agitation.
(2), by the inorganic salt of cobalt, zirconium, titanium or organic alkoxide, Sodium dodecylbenzene sulfonate or sodium laurylsulfonate join in certain water gaging, stir.Cobalt: zirconium: the mol ratio of titanium is 1:(0-0.5): (0-0.5), cobalt: water: the mol ratio of (Sodium dodecylbenzene sulfonate or sodium laurylsulfonate) is 1:(100-500): (0.1-1), the mol ratio of cobalt: TEOS is 1:(10-200).
(3) mixed solution in step (1) is positioned over to 25-65
oin the water bath with thermostatic control of C, stir.Mixed solution in step (2) is dropwise joined in step (1) mixed solution.Adding speed is 0.1-1mL/s, continues reaction 0.5-5h.Obtain passivating solution.
(4) by the aluminium alloy dipping 5-60min in passivating solution after processing.With deionized water, clean, then at 25-150
odry or warm air drying in C baking oven.
Preferably, in above-mentioned steps (1), the adding proportion of TEOS, water, (methyl alcohol or ethanol) is (8-18mL): (5-10mL): (3-8mL).
Preferably, in above-mentioned steps (2), cobalt: zirconium: the mol ratio of titanium is 1:(0-0.4): (0-0.4), cobalt: water: the mol ratio of (Sodium dodecylbenzene sulfonate or sodium laurylsulfonate) is 1:(150-450): (0.2-0.8), the mol ratio of cobalt: TEOS is 1:(20-150).
Preferably, in above-mentioned steps (3), water bath with thermostatic control 30-60
oc, adding speed is 0.2-0.8mL/s, continues reaction 1-4h.
Preferably, in above-mentioned steps (4), aluminium alloy dipping is 8-50min in passivating solution, and drying temperature is 35-120
oc.
The present invention compared with prior art, has the following advantages:
(1) the present invention adopts cheap TEOS as silicon source, and the silicon that cobalt, zirconium, Ti-inorganic salt or the organic alkoxide aqueous solution prepared organic inorganic hybridization as hydrolytic accelerating agent of usining is aluminium surface treatment agent.Can form stronger protective membrane at aluminium and aluminum alloy surface, effectively avoid the shortcoming of simple organic or inorganic treatment agent.
(2) preparation technology of conversion treating solution is simple, and cost is low, and treatment temp is low, and the time is short, is suitable for large-scale industrial production, and application prospect is good.
(3) prepared conversion film tool is evenly fine and close, has excellent corrosion resistance nature.
Accompanying drawing explanation
Fig. 1 is the following example naked aluminium electrokinetic potential polarization curve used
Fig. 2 is the electrokinetic potential polarization curve of embodiment 1 gained conversion film
Fig. 3 is naked aluminium surface SEM figure in the following example
Fig. 4 is embodiment 1 gained aluminum alloy surface conversion film SEM figure
Embodiment
Below in conjunction with embodiment, the present invention will be further described, but be not limited to this.
embodiment 1
(1) aluminum alloy surface pre-treatment
By 10g sodium hydroxide, 1g sodium carbonate, 0.3g sodium phosphate, 0.3g water glass and 0.1g sodium laurylsulfonate join in 100g deionized water, stir and form solution.Aluminum alloy surface, with after deionized water wash 2 times, is immersed in above-mentioned degreasing and alkaline etching liquid and soaks 8min.Then use deionized water washed twice.In the salpeter solution of 15wt%, flood 2min again.Then use deionized water washed twice.
(2) preparation of the anticorrosion conversion film of aluminum alloy surface
By 0.1g Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, 0.05g zirconium nitrate, 0.05g titanium sulfate, 0.01g Sodium dodecylbenzene sulfonate joins in 10mL water and obtains mixed solution A.40
ounder C water bath with thermostatic control agitation condition, solution A is dropwise joined and contains 10mLTEOS, in the mixing solutions B of 5mL water and 5mL ethanol, continue reaction 3h and obtain passivating solution.By in step (1) through pretreated aluminium alloy dipping to 20min in passivating solution.Then take out, deionized water wash twice, 80
odry in C baking oven.
Corrosion potential in 3.5wt% sodium chloride solution is-0.50V, and corrosion current is 1.0e-006A, and protection ratio is 99.0%.
Naked aluminium electrokinetic potential polarization curve used when Fig. 1 is embodiment 1, from scheming, the corrosion potential of naked aluminium in 3.5wt% sodium chloride solution be-1.276V, and corrosion current is 1.004e-004A, and corrosion current is easy to more greatly be corroded by various corrosive mediums.Fig. 2 is the electrokinetic potential polarization curve of embodiment 1 gained conversion film, and as seen from the figure, the corrosion potential of conversion film in 3.5wt% sodium chloride solution is-0.50V that corrosion current is 1.0e-006A.Corrosion current compared with I so that aluminium and aluminum alloy surface well protected.Fig. 3 is naked aluminium surface SEM figure in the following example, and as seen from the figure, naked aluminium surface exists more hole and crack, and surface irregularity is easy to be corroded by various corrosive mediums.Fig. 4 is embodiment 1 gained aluminum alloy surface conversion film SEM figure, and as seen from the figure, surface conversion coating is consisted of fine and close hybrid organic-inorganic film, does not have hole, and compact structure is high to aluminium and aluminum alloy surface protection ratio.
embodiment 2
As described in Example 1, difference is that in step (1), the add-on of sodium hydroxide is 20g.Corrosion potential in 3.5wt% sodium chloride solution is-0.497V, and corrosion current is 1.19e-006A, and protection ratio is 98.81%.
embodiment 3
As described in Example 1, difference is not add zirconium nitrate and titanium sulfate in step (2).Corrosion potential in 3.5wt% sodium chloride solution is-0.627V, and corrosion current is 5.43e-006A, and protection ratio is 94.57%.
embodiment 4
As described in Example 1, difference is to add 0.1g zirconium iso-propoxide in step (2), 0.1g tetrabutyl titanate, and regulate pH=4 with acetic acid.Corrosion potential in 3.5wt% sodium chloride solution is-0.539V, and corrosion current is 9.72e-007A, and protection ratio is 99.03%.
embodiment 5
As described in Example 1, difference is after solution A being mixed with solution B in step (2), to continue to obtain passivating solution after reaction 4.5h.Corrosion potential in 3.5wt% sodium chloride solution is-0.873v, and corrosion current is 1.972e-005A, and protection ratio is 80.28%.
embodiment 6
As described in Example 1, difference is that in step (2), surface washing after pretreated aluminium alloy floods 40min in passivating solution is dry.Corrosion potential in 3.5wt% sodium chloride solution is-0.357V, and corrosion current is 2.87e-006A, and protection ratio is 97.13%.
embodiment 7
As described in Example 1, difference be in step (2) by passivating solution dipping after aluminium alloy 120
odry in C baking oven.Corrosion potential in 3.5wt% sodium chloride solution is-0.441V, and corrosion current is 5.5e-006A, and protection ratio is 94.5%.
embodiment 8
As described in Example 1, difference is, in step (2), the aluminium alloy after dipping in passivating solution is adopted to warm air drying.Corrosion potential in 3.5wt% sodium chloride solution is-0.463V, and corrosion current is 1.5e-006A, and protection ratio is 98.5%.
embodiment 9
As described in Example 1, difference is 60 in step (2)
ounder C water bath with thermostatic control agitation condition, solution A is joined in solution B.Corrosion potential in 3.5wt% sodium chloride solution is-0.782v, and corrosion current is 8.57e-006A, and protection ratio is 91.43%.
embodiment 10
(1) aluminum alloy surface pre-treatment
By 10g sodium hydroxide, 1g sodium carbonate, 0.3g sodium phosphate, 0.3g water glass and 0.1g sodium laurylsulfonate join in 100g deionized water, stir and form solution.Aluminum alloy surface, with after deionized water wash 2 times, is immersed in above-mentioned degreasing and alkaline etching liquid and soaks 8min.Then use deionized water washed twice.In the salpeter solution of 15wt%, flood 2min again.Then use deionized water washed twice.
(2) preparation of the anticorrosion conversion film of aluminum alloy surface
40
ounder C water bath with thermostatic control agitation condition, to containing 10mLTEOS, in the mixing solutions B of 5mL water and 5mL ethanol, add acetic acid, regulate pH=4, continue reaction 3h and obtain passivating solution.By in step (1) through pretreated aluminium alloy dipping to 20min in passivating solution.Then take out, deionized water wash twice, 80
odry in C baking oven.
Corrosion potential in 3.5wt% sodium chloride solution is-0.682V, and corrosion current is 8.83e-006A, and protection ratio is 91.17%.
Claims (12)
1. the preparation of degreasing and alkaline etching agent, comprises the following steps:
(1) aluminum alloy sample after washing is carried out to degreasing and alkaline etching, dosing composition is: sodium hydroxide 5-30g, sodium carbonate 0.5-2g, sodium phosphate or tripoly phosphate sodium STPP 0.1-2g, water glass 0.1-1g, Sodium dodecylbenzene sulfonate or sodium laurylsulfonate 0.1-1g, water 100mL, aluminium alloy is soaked to 2-20min in alkaline etching dosing, then use washed with de-ionized water 2 times;
(2) aluminium alloy dipping after alkaline etching is flooded to 1-10min in neutralizer, neutralizer consists of nitric acid or the aqueous sulfuric acid of 10-40wt%, then uses deionized water wash 2 times.
2. the preparation method of degreasing as claimed in claim 1 and alkaline etching agent, is characterized in that sodium hydroxide described in claims (1): sodium carbonate: (sodium phosphate or tripoly phosphate sodium STPP): water glass: (sodium laurylsulfonate or Sodium dodecylbenzene sulfonate): the mass ratio of water is (5-30g): (0.5-2g): (0.1-2g): (0.1-1g): (0.1-1g): 100g.
3. the preparation method of degreasing as claimed in claim 1 and alkaline etching agent, is characterized in that described in claims (1) that aluminium alloy soak time in alkaline etching dosing is 2-20min.
4. the preparation method of degreasing as claimed in claim 1 and alkaline etching agent, is characterized in that nitric acid or aqueous sulfuric acid that described in claims (2), neutralizer is 10-40wt%, and dipping time is 1-10min.
5. silicon is a preparation for aluminium and aluminum alloy surface treatment agent, comprises the following steps:
(1) TEOS is joined in the mixing solutions of water and methyl alcohol or ethanol, the adding proportion of TEOS, water, methyl alcohol or ethanol is (5-20mL): (2-10mL): (2-10mL), magnetic agitation obtains solution A;
(2) inorganic salt of cobalt, zirconium, titanium or organic alkoxide are joined in certain water gaging, stir, then add a certain amount of Sodium dodecylbenzene sulfonate or sodium laurylsulfonate to obtain mixing solutions B, cobalt: zirconium: the mol ratio of titanium is 1:(0-0.5): (0-0.5), cobalt: water: the mol ratio of (Sodium dodecylbenzene sulfonate or sodium laurylsulfonate) is 1:(100-500): (0.1-1), the mol ratio of cobalt: TEOS is 1:(0.01-0.1);
(3) mixed liquor A in step (1) is positioned over to 25-65
oin the water bath with thermostatic control of C, stir, the mixed liquid B in step (2) is dropwise joined in step (1) mixed solution, adding speed is 0.1-1mL/s, continues reaction 0.5-5h, obtains passivating solution;
(4) by the aluminium alloy dipping 5-60min in passivating solution after processing, with deionized water, clean, then at 25-150
odry or warm air drying in C baking oven.
6. silicon as claimed in claim 5 is the preparation method of aluminium and aluminum alloy surface treatment agent, it is characterized in that described in claims (1) TEOS in solution A: water: the adding proportion of (methyl alcohol or ethanol) is (5-20mL): (2-10mL): (2-10mL).
7. silicon as claimed in claim 5 is the preparation method of aluminium and aluminum alloy surface treatment agent, it is characterized in that described in claims (2) cobalt in solution B: zirconium: the mol ratio of titanium is 1:(0-0.5): (0-0.5), cobalt: water: the mol ratio of (Sodium dodecylbenzene sulfonate or sodium laurylsulfonate) is 1:(100-500): (0.1-1), the mol ratio of cobalt: TEOS is 1:(10-200).
8. silicon as claimed in claim 5 is the preparation method of aluminium and aluminum alloy surface treatment agent, it is characterized in that described in claims (2) that cobalt salt in solution B, zirconates, titanium salt are its nitrate, vitriol, chlorate or organic alkoxide.
9. silicon as claimed in claim 5 is the preparation method of aluminium and aluminum alloy surface treatment agent, it is characterized in that described in claims (3), mixed liquor A stirs in water bath with thermostatic control, and temperature is 25-65
oc.
10. silicon as claimed in claim 5 is the preparation method of aluminium and aluminum alloy surface treatment agent, what it is characterized in that mixed liquid B described in claims (3) adds mode for dropwise adding, adding speed is 0.1-1mL/s, and adding the rear continuation reaction times is 0.5-5h.
11. silicon as claimed in claim 5 are the preparation method of aluminium and aluminum alloy surface treatment agent, it is characterized in that the dipping time in passivating solution of aluminium alloy described in claims (4) is 5-60min.
12. silicon as claimed in claim 5 are the preparation method of aluminium and aluminum alloy surface treatment agent, it is characterized in that after passivation, adopting 25-150 described in claims (4)
odry or warm air drying in C baking oven.
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| CN105177561A (en) * | 2015-08-21 | 2015-12-23 | 山东大学 | Aluminum or aluminum alloy protection chromium-free passivation solution, preparation method and aluminum or aluminum alloy surface protection method thereof |
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