CN102912345A - Aluminium alloy surface corrosion control method - Google Patents
Aluminium alloy surface corrosion control method Download PDFInfo
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- CN102912345A CN102912345A CN2012104199462A CN201210419946A CN102912345A CN 102912345 A CN102912345 A CN 102912345A CN 2012104199462 A CN2012104199462 A CN 2012104199462A CN 201210419946 A CN201210419946 A CN 201210419946A CN 102912345 A CN102912345 A CN 102912345A
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Abstract
The invention provides an aluminium alloy surface corrosion control method, and relates to the field of metal surface coating treatment. The method comprises the following steps: cleaning and drying; preparing nano TiO2 sol; preparing aluminium alloy coated with an inorganic membrane; preparing an organic membrane solution, mixing silane coupling agent, absolute ethyl alcohol and water, adding methanoic acid to serve as a catalyst, adjusting the pH value to 9-10, sealing after stirring uniformly, placing in a water bath of 30-40 DEG C for reaction to form gel after sonic oscillation, thereby obtaining organogel; mixing organogel, tetrahydrofuran and firming agent uniformly, so as to obtain the organic membrane solution; coating the surface of the aluminium alloy, coated with the inorganic membrane, with the organic membrane solution, so as to obtain the aluminium alloy with the surface coated with the organic membrane and the inorganic membrane. According to the invention, through the sol-gel process, a compact nano TiO2 inorganic membrane is formed on the surface of the aluminium alloy, and the organic membrane is coated on the surface of the aluminium alloy, so that the aluminium alloy can achieve excellent surface corrosion resistance.
Description
Technical field
The present invention relates to metallic surface coating process field, be specifically related to a kind of aluminum alloy surface anti-corrosion method.
Background technology
The one of the main reasons of metal base corrosion is because the surface contacts with the atmosphere of electrolyte solution or humidity; produce various corrosion; and aluminium alloy surface in air can form the protective membrane of aluminum oxide, and under normal atmospheric environment, this protective membrane can be protected aluminum alloy base material effectively.But in containing electrolytical moisture, ocean surface atmospheric environment for example, spot corrosion can appear in aluminum alloy surface, and the havoc product appearance causes product to shorten work-ing life simultaneously.For the corrosion resistance nature (or salt spray resistance) that improves alloy product, usually to carry out surface treatment to aluminum alloy base material, such as anodic oxidation, baking vanish etc., but all there is larger environmental pollution in these techniques, so be badly in need of new aluminium alloy surface treatment method to replace the technology such as anodic oxidation, baking vanish.
In recent years, a lot of to metal surface treatment process research both at home and abroad, wherein vacuum coating technology (PVD) is a kind of coating technique than environmental protection in the aseptic technic, the PVD rete has high rigidity, high-wearing feature, good advantages such as chemical stability, therefore more and more wider in the application in protecting metallic surface field, and aluminium alloy is because differing greatly of its standard potential and the functional rete of many PVD very easily causes galvanic corrosion, so that alloy product lost efficacy.It is more to be formed with organic coating research in the aluminum alloy surface coating at present, and CN1341775A discloses by nine kinds of surface treatment liquids that raw material forms such as sodium lauryl sulphate, sodium hydroxide, citric acids, and forms coating by being immersed in aluminum alloy surface; CN101139500A discloses the treatment solution by compositions such as silane coupling agent, organometallic compound, silicate, phosphoric acid, by use the line rod balancedly blade coating in aluminum alloy surface, heating, drying forms coating, with outward appearance and the physical and chemical performance that improves aluminium alloy.But the thickness of coating that these two kinds of processing methodes form is thinner, and lower with aluminum alloy surface sticking power, and physical strength is bad, and scarcely high temperature resistant, coating easily comes off in corrosive medium, and preservative effect is relatively poor.Summary of the invention:
In order to overcome in the prior art, bad, the non-refractory of aluminum alloy surface protective membrane physical strength, the problem that erosion resistance is poor the invention provides a kind of aluminum alloy surface preserving method.
Purpose of the present invention adopts following technical scheme to realize.
A kind of aluminum alloy surface anti-corrosion method, its feature is in comprising the steps:
(1) cleaning and dry: pending aluminium alloy is put into the organic solution ultrasonic cleaning, then carry out rinsing with deionized water, take out described aluminium alloy oven dry;
(2) preparation nano-TiO
2Colloidal sol: prepare nano-TiO take Butyl Phthalate as raw material
2Colloidal sol;
(3) aluminium alloy of mineral membrane has been wrapped up in preparation: will clean with dried aluminium alloy and be immersed in nano-TiO
2Colloidal sol,, the taking-up aluminium alloy is put in the air and is dried, and oven dry namely gets the aluminium alloy that has wrapped up mineral membrane in the baking oven.
(4) prepare organic coating solution: be 1: 8～12: 3～5 to mix silane coupling agent, dehydrated alcohol and water according to volume ratio, add formic acid as catalyzer, regulating pH is 9～10, rear sealing stirs, in the rearmounted 30-40 ℃ of water-bath of sonic oscillation, react to gel, namely get organogel; The add-on of formic acid is the 5-15% of silane coupling agent volume.
Be 100:(300～400 with organogel, tetrahydrofuran (THF) and solidifying agent according to mass ratio): (2～4) mix, and make organic membrane solution;
(5) coat organic membrane solution in the aluminum alloy surface of having wrapped up mineral membrane, obtain being coated with the aluminium alloy of machine film and mineral membrane.
Organic solution is ethanol, Virahol, methyl alcohol or acetone described in the step (1), ultrasonic cleaning 30～60 minutes, and bake out temperature is 70 ℃～100 ℃.
Step (2) prepares nano-TiO take Butyl Phthalate as raw material
2The concrete grammar of colloidal sol is:
According to volume ratio 1:4～8 butyl (tetra) titanate is dissolved in dehydrated alcohol, adds methyl ethyl diketone, stir 15～30 min, obtain solution A; The mol ratio of described methyl ethyl diketone and butyl (tetra) titanate is 0.3～0.5:1;
Nitric acid and deionized water are added in the dehydrated alcohol, stir 15～30 min, obtain solution B;
Solution B is added drop-wise in the solution A, and 18～25 degree stir 2～4h, obtain nano-TiO
2Colloidal sol; The mol ratio of butyl (tetra) titanate is 0.2～0.4:1 in nitric acid in the described solution B and the solution A.
Soak time 10～30 min described in the step (3), flash-off time is 0.5-1.5h in the air, and oven temperature is 80 ℃～100 ℃, and drying time is 2～4h.
The described silane coupling agent of step (4) is vinyltrimethoxy silane, γ-(methacryloxypropyl) propyl trimethoxy silicane or γ-epoxypropyl ether Trimethoxy silane; Mixing speed is 300-400 r/min, and churning time is 2～4h; The sonic oscillation time is 1h～3h; Described solidifying agent is benzoyl peroxide.
Beneficial effect: the invention provides a kind of aluminum alloy surface preserving method, form fine and close nano-TiO by sol gel process in aluminum alloy surface
2Mineral membrane utilizes nano-TiO
2Excellent photocatalysis effect, the corrosive nature of ionogen moisture again at aluminum alloy surface integument organic membrane, realizes the antiseptic property of aluminum alloy surface excellence in the reduction aluminium alloy surrounding environment.In this way the organic-inorganic film of preparation can combine with chemical bond with the metallic surface, has greatly strengthened adhesive ability and the resistance to corrosion of film.The environmental protection of material preparation technique is the environment-friendly material of desirable effectively substitute chromium hydrochlorate oxide film.
Embodiment
Further describe technical scheme of the present invention below by embodiment.
Embodiment 1:
(1) cleaning and dry: pending aluminium alloy was put into the acetone ultrasonic cleaning 30 minutes, then carry out rinsing with deionized water and remove inorganic and organic pollutant, take out aluminium alloy and put into 70 ℃ of baking oven flash baking surface waters, so that metal thoroughly eliminates rust, it is totally smooth that the surface reaches;
(2) preparation nano-TiO
2Colloidal sol: prepare nano-TiO take butyl (tetra) titanate as raw material
2Colloidal sol.
Butyl (tetra) titanate is dissolved in dehydrated alcohol, and the volume ratio of butyl (tetra) titanate and dehydrated alcohol is 1:4.Add the methyl ethyl diketone of 0.3 times of described butyl (tetra) titanate mole number as inhibitor, 20 degree stir 15 min, obtain solution A, and are stand-by;
Get the 100ml dehydrated alcohol, add the nitric acid of 10ml and the deionized water of 20ml, stirring at room 15min obtains solution B.
Solution B is added drop-wise in the solution A, and 20 degree stir 2h, obtain nano-TiO
2Colloidal sol.In the described solution B in nitric acid and the solution A mol ratio of butyl (tetra) titanate be 0.2:1.
(3) aluminium alloy of mineral membrane has been wrapped up in preparation: will clean with dried aluminium alloy and be immersed in nano-TiO
2Colloidal sol soaks 10min, takes out and dry 1h in air, continues oven dry 2h in 80 ℃ baking oven, has obtained wrapping up the aluminium alloy of mineral membrane.
(4) preparation of organic membrane solution: vinyltrimethoxy silane is placed in the beaker, add dehydrated alcohol and water, the formic acid that adds again silane volume 15% is made catalyzer, regulate pH value to 9, after stirring 2h under the 400rpm condition and making each evenly miscible mutually, with the solution good seal, carry out sonic oscillation 1h at Ultrasonic Cleaners with electric blender, be placed at last in 35 ℃ of water-baths and react to gel, namely get organogel; The volume ratio of vinyltrimethoxy silane, dehydrated alcohol and water is 1:8:3.
Get organogel and be put in the beaker, add the tetrahydrofuran (THF) (THF) of 3 times of organogel quality and make its dissolving, add the solidifying agent benzoyl peroxide of organogel quality 2%, adopt magnetic stirrer to stir, this solution is organic membrane solution.
(5) coat organic membrane solution with lifting coating device in the aluminum alloy surface of having wrapped up mineral membrane, obtain the aluminium alloy that the surface has coated organic membrane and mineral membrane.The residence time of aluminium alloy in organic membrane solution is 1min, and pull rate is 27cm/min, repeatedly film 3 times, both.
Embodiment 2:
(1) cleaning and dry: pending aluminium alloy was put into the ethanol ultrasonic cleaning 60 minutes, then carry out rinsing with deionized water and remove inorganic and organic pollutant, take out aluminium alloy and put into 100 ℃ of baking oven flash baking surface waters, so that metal thoroughly eliminates rust, it is totally smooth that the surface reaches;
(2) preparation nano-TiO
2Colloidal sol: prepare nano-TiO take butyl (tetra) titanate as raw material
2Colloidal sol.
Butyl (tetra) titanate is dissolved in dehydrated alcohol, and the volume ratio of butyl (tetra) titanate and dehydrated alcohol is 1:8.Add the methyl ethyl diketone of 0.5 times of described butyl (tetra) titanate mole number as inhibitor, 25 degree stir 30min, obtain solution A, and are stand-by;
Get the 100ml dehydrated alcohol, add the nitric acid of 10ml and the deionized water of 20ml, 25 degree stir 30min, obtain solution B.
Solution B is added drop-wise in the solution A, and 25 degree stir 4h, obtain nano-TiO
2Colloidal sol.In the described solution B in nitric acid and the solution A mol ratio of butyl (tetra) titanate be 0.4:1.
(3) aluminium alloy of mineral membrane has been wrapped up in preparation: will clean with dried aluminium alloy and be immersed in nano-TiO
2Colloidal sol soaks 30min, takes out and dry 1.5h in air, continues oven dry 4h in 100 ℃ baking oven, has obtained wrapping up the aluminium alloy of mineral membrane.
(4) preparation of organic membrane solution: γ-(methacryloxypropyl) propyl trimethoxy silicane is placed in the beaker, add dehydrated alcohol and water, the formic acid that adds again γ-(methacryloxypropyl) propyl trimethoxy silicon volume 10% is made catalyzer, regulate pH value to 10, after stirring 4h and make each evenly miscible mutually with electric blender, with the solution good seal, carry out sonic oscillation 3h at Ultrasonic Cleaners, be placed at last in 40 ℃ of water-baths and react to gel, namely get organogel; The volume ratio of γ-(methacryloxypropyl) propyl trimethoxy silicane, dehydrated alcohol and water is 1:12:5.
Get organogel and be put in the beaker, add the tetrahydrofuran (THF) (THF) of 4 times of organogel quality and make its dissolving, add the solidifying agent benzoyl peroxide of organogel quality 4%, adopt magnetic stirrer to stir, this solution is organic membrane solution.
(5) coat organic membrane solution with lifting coating device in the aluminum alloy surface of having wrapped up mineral membrane, obtain the aluminium alloy that the surface has coated organic membrane and mineral membrane.The residence time of aluminium alloy in organic membrane solution is 1min, and pull rate is 27cm/min, repeatedly film 3 times, both.
Embodiment 3
(1) cleaning and dry: pending aluminium alloy was put into the ethanol ultrasonic cleaning 45 minutes, then carry out rinsing with deionized water and remove inorganic and organic pollutant, take out aluminium alloy and put into 85 ℃ of baking oven flash baking surface waters, so that metal thoroughly eliminates rust, it is totally smooth that the surface reaches;
(2) preparation nano-TiO
2Colloidal sol: prepare nano-TiO take butyl (tetra) titanate as raw material as raw material
2Colloidal sol.
Butyl (tetra) titanate is dissolved in dehydrated alcohol, and the volume ratio of butyl (tetra) titanate and dehydrated alcohol is 1:6.Be incorporated as the methyl ethyl diketone of 0.4 times of butyl (tetra) titanate mole number as inhibitor, 18 degree stir 20min, obtain solution A, and are stand-by;
Get the 100ml dehydrated alcohol, add the nitric acid of 10ml and the deionized water of 20ml, 18 degree stir 15min, obtain solution B.
Solution B is added drop-wise in the solution A, and 20 ℃ are stirred 2h, obtain nano-TiO
2Colloidal sol.In the described solution B in nitric acid and the solution A mol ratio of butyl (tetra) titanate be 0.3:1.
(3) aluminium alloy of mineral membrane has been wrapped up in preparation: will clean and dried aluminium alloy immersion nano-TiO
2Colloidal sol soaks 20min, takes out and dry 0.5h in air, continues oven dry 3h in 90 ℃ baking oven, has obtained wrapping up the aluminium alloy of mineral membrane.
(4) preparation of organic membrane solution: γ-epoxypropyl ether Trimethoxy silane is placed in the beaker, add dehydrated alcohol and water, the formic acid that adds again γ-epoxypropyl ether Trimethoxy silane volume 5% is made catalyzer, regulate pH value to 9.5, stir 3h(rotating speed 300rpm with electric blender) make each evenly miscible mutually after, with the solution good seal, carry out sonic oscillation 2h at Ultrasonic Cleaners, be placed at last in 30 ℃ of water-baths and react to gel, namely get organogel; The volume ratio of γ-epoxypropyl ether Trimethoxy silane, dehydrated alcohol and water is 1:10:4.
Get organogel and be put in the beaker, add the tetrahydrofuran (THF) (THF) of 3.5 times of organogel quality and make its dissolving, add the solidifying agent benzoyl peroxide of organogel quality 3%, adopt magnetic stirrer to stir, this solution is organic membrane solution.
(5) lift coating device with constant speed and coat organic membrane solution in the aluminum alloy surface of having wrapped up mineral membrane, obtain the aluminium alloy that the surface has coated organic membrane and mineral membrane.The residence time of aluminium alloy in coating solution is 1min, and pull rate is 27cm/min, repeatedly film 3 times, both.
Al-alloy parts and the untreated Al-alloy parts got after embodiment 1,2 and 3 processes carry out salt fog and brine soaking experiment, the result shows that the surface corrosion in corrosive atmosphere of untreated Al-alloy parts is serious, produce a large amount of corrosion impurity, and treated Al-alloy parts surface in 16 days salt fog and brine soaking experiment is unchanged, and the organic-inorganic film on Al-alloy parts surface has good adhesive ability and resistance to corrosion.
Claims (5)
1. aluminum alloy surface anti-corrosion method, its feature is in comprising the steps:
(1) cleaning and dry: pending aluminium alloy is put into the organic solution ultrasonic cleaning, then carry out rinsing with deionized water, take out described aluminium alloy oven dry;
(2) preparation nano-TiO
2Colloidal sol: prepare nano-TiO take Butyl Phthalate as raw material
2Colloidal sol;
(3) aluminium alloy of mineral membrane has been wrapped up in preparation: will clean with dried aluminium alloy and be immersed in nano-TiO
2Colloidal sol,, the taking-up aluminium alloy is put in the air and is dried, and oven dry namely gets the aluminium alloy that has wrapped up mineral membrane in the baking oven;
(4) prepare organic coating solution: be 1: 8～12: 3～5 to mix silane coupling agent, dehydrated alcohol and water according to volume ratio, add formic acid as catalyzer, regulating pH is 9～10, rear sealing stirs, in the rearmounted 30-40 ℃ of water-bath of sonic oscillation, react to gel, namely get organogel; The add-on of formic acid is the 5-15% of silane coupling agent volume;
Be 100:(300～400 with organogel, tetrahydrofuran (THF) and solidifying agent according to mass ratio): (2～4) mix, and make organic membrane solution;
(5) coat organic membrane solution in the aluminum alloy surface of having wrapped up mineral membrane, obtain being coated with the aluminium alloy of machine film and mineral membrane.
2. described aluminum alloy surface anti-corrosion method according to claim 1, it is characterized in that: organic solution is ethanol, Virahol, methyl alcohol or acetone described in the step (1), ultrasonic cleaning 30～60 minutes, bake out temperature is 70 ℃～100 ℃.
3. described aluminum alloy surface anti-corrosion method according to claim 2, it is characterized in that: step (2) prepares nano-TiO take Butyl Phthalate as raw material
2The concrete grammar of colloidal sol is:
According to volume ratio 1:4～8 butyl (tetra) titanate is dissolved in dehydrated alcohol, adds methyl ethyl diketone, stir 15～30 min, obtain solution A; The mol ratio of described methyl ethyl diketone and butyl (tetra) titanate is 0.3～0.5:1;
Nitric acid and deionized water are added in the dehydrated alcohol, stir 15～30 min, obtain solution B;
Solution B is added drop-wise in the solution A, and 18～25 degree stir 2～4h, obtain nano-TiO
2Colloidal sol; The mol ratio of butyl (tetra) titanate is 0.2～0.4:1 in nitric acid in the described solution B and the solution A.
4. described aluminum alloy surface anti-corrosion method according to claim 3 is characterized in that: soak time 10～30 min described in the step (3), and flash-off time is 0.5-1.5h in the air, and oven temperature is 80 ℃～100 ℃, and drying time is 2～4h.
5. described aluminum alloy surface anti-corrosion method according to claim 4, it is characterized in that: the described silane coupling agent of step (4) is vinyltrimethoxy silane, γ-(methacryloxypropyl) propyl trimethoxy silicane or γ-epoxypropyl ether Trimethoxy silane; Mixing speed is 300-400 r/min, and churning time is 2～4h; The sonic oscillation time is 1h～3h; Described solidifying agent is benzoyl peroxide.
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Cited By (8)
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| CN103668189A (en) * | 2013-12-09 | 2014-03-26 | 常熟市大康汽车座垫有限责任公司 | Aluminum alloy surface anticorrosion method |
| CN103695904A (en) * | 2013-12-26 | 2014-04-02 | 常熟市美尔特金属制品有限公司 | Metal surface treatment method |
| CN103757619A (en) * | 2013-12-26 | 2014-04-30 | 常熟市美尔特金属制品有限公司 | Metal surface treating agent |
| CN104018144A (en) * | 2014-06-20 | 2014-09-03 | 合肥长城制冷科技有限公司 | Aluminum alloy surface anticorrosion process |
| CN104612369A (en) * | 2014-12-30 | 2015-05-13 | 南京信息工程大学 | Anti-microbial plastic-wood floor and preparing method thereof |
| CN105274516A (en) * | 2015-11-04 | 2016-01-27 | 合肥海源机械有限公司 | Micro-emulsified forming liquid for cured film of aluminum alloy and preparation method of micro-emulsified forming liquid |
| CN105331964A (en) * | 2015-09-29 | 2016-02-17 | 安徽瑞林汽配有限公司 | Rust-protection aluminum alloy curing film and preparation method thereof |
| CN105331962A (en) * | 2015-09-29 | 2016-02-17 | 安徽岳塑汽车工业股份有限公司 | Forming liquid of anticorrosion aluminum alloy curing film and preparation method of forming liquid |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103668189A (en) * | 2013-12-09 | 2014-03-26 | 常熟市大康汽车座垫有限责任公司 | Aluminum alloy surface anticorrosion method |
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| CN104612369A (en) * | 2014-12-30 | 2015-05-13 | 南京信息工程大学 | Anti-microbial plastic-wood floor and preparing method thereof |
| CN105331964A (en) * | 2015-09-29 | 2016-02-17 | 安徽瑞林汽配有限公司 | Rust-protection aluminum alloy curing film and preparation method thereof |
| CN105331962A (en) * | 2015-09-29 | 2016-02-17 | 安徽岳塑汽车工业股份有限公司 | Forming liquid of anticorrosion aluminum alloy curing film and preparation method of forming liquid |
| CN105274516A (en) * | 2015-11-04 | 2016-01-27 | 合肥海源机械有限公司 | Micro-emulsified forming liquid for cured film of aluminum alloy and preparation method of micro-emulsified forming liquid |
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