CN104018162A - Preparation method of cathode protection coating on aluminum alloy surface - Google Patents
Preparation method of cathode protection coating on aluminum alloy surface Download PDFInfo
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- CN104018162A CN104018162A CN201410258550.3A CN201410258550A CN104018162A CN 104018162 A CN104018162 A CN 104018162A CN 201410258550 A CN201410258550 A CN 201410258550A CN 104018162 A CN104018162 A CN 104018162A
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Abstract
The invention discloses a preparation method of an aluminum-magnesium-rich alloy coating for protecting an aluminum alloy cathode. The method disclosed by the invention comprises the following steps of mixing epoxy resin, aluminum-magnesium metal micropowder, a curing agent, a solvent, an auxiliary, a coupling agent and a defoaming agent according to a certain ratio; placing the mixture into a ball mill for sufficiently grinding to ensure that all components in the mixture are uniformly distributed so as to prepare a corrosion-resistant coating; then, covering the coating on the aluminum alloy surface washed in advance and subjected to ultrasonic treatment by using a spray coating or brush coating or roller coating method; finally, curing at room temperature, and drying for 5-7d to form a cathode protective coating with high corrosion resistance on the aluminum alloy surface. The coating prepared by using the method disclosed by the invention has favorable corrosion resistance 10 times of that of a magnesium-rich coating under salt-spray and seawater environments and still can protect an aluminum alloy matrix even if the coating on the aluminum alloy surface is damaged; the method is relatively simple, good in repeatability and suitable for industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of corrosion-resistant finishes, specifically a kind of preparation method of the corrosion-resistant finishes for aluminum alloy surface galvanic protection, belongs to anticorrosion coating material technical field.
Background technology
Aluminium and the aluminium alloy advantages such as intensity is high, density is little, electrical and thermal conductivity is strong, mechanical property is excellent owing to having, workability is good are widely used in the fields such as chemical industry, aerospace industry, automobile industry, foodstuffs industry, electronics, instrument industry and shipping industry.Under field conditions (factors), aluminum alloy surface easily forms the natural oxide film of the about 4nm of thick layer, but this tunic porous, inhomogeneous and corrosion stability is poor, is difficult to resist the corrosion of severe environment.
The feature of first carrying out on its surface for corrosion of aluminium alloy, investigator adopts the method for physics or chemistry at the various protective barrier layers of its surface-coated, body material and corrosive medium is separated, to reach the object of corrosion protection.Utilize this principle; investigator adopts at aluminum alloy surface paint brush; plastics; the organic coatings such as resin coating; adopt thermospray and electric plating method to prepare metallic aluminium tectum and Ni-P tectum in aluminum alloy surface respectively; show but study, above-mentioned coating only plays protectiveness covering effect to aluminium alloy.In the time that coating is intact, the slow but infiltration that can not completely cut off corrosive medium completely of ground resistance in various degree, its provide protection mainly relies on mechanical isolation mechanism.In the time there is defect in coatingsurface or local when destroyed, accelerate the corrosion of matrix, matrix is not had to provide protection.Therefore, only depend on the protectiveness covering effect of coating can not meet anticorrosion for a long time in oceanographic engineering of aluminium alloy.
For the defect of above-mentioned protective coating, vertical G.P. professor Bierwagen of the university leader's of North Dakota seminar is incorporated into the concept of zinc-rich paint galvanic protection in the coating protection design of aluminium alloy, the corrosion potential of considering pure Magnesium and magnesium alloys will be lower than the corrosion potential of aluminium, " rich magnesium coating and coating system ” ﹝ Nanna ME are developed, Bierwagen GP, Journal of Coatings Technology Research, 2004, 1 (2): 69-80. ﹞, but in actual use procedure, find that rich magnesium coating still comes with some shortcomings, magnesium powder in coating and magnesium alloy powder activity are very high, in galvanic protection process, there is strong sacrificial anode effect in magnesium powder, can produce strong galvanic action, cause organic degraded and aging acceleration in coating, affect the work-ing life of coating.Therefore many investigators carry out modification to magnesium powder, and the spending rate that reduces magnesium powder improves the corrosion resistance nature of coating.The people such as Wang Jianguo adopt the aluminium powder that has electroconductibility and the galvanic protection effect of magnesium powder is had no adverse effects to carry out modification to rich magnesium coating, replace magnesium powder with a certain amount of aluminium powder, reduce the magnesium powder content in coating, improve the corrosion resistance nature of coating.But this method does not fundamentally change the existence of magnesium powder, the anti-corrosion property energy ﹝ king that can only improve to a certain extent coating founds the state, the civilian ﹞ of the master Bi Ye of Beijing University of Chemical Technology opinion.The people such as Shashi S. Pathak carry out carbonating pre-treatment to magnesium powder,
Add to again in epoxy resin and make rich magnesium coating, make the corrosion resistance nature get of coating to the large Ti Gao of Hen ﹝ Shashi S. Pathak, Michael D. Blanton, etal, Corrosion Science, 2010, (52): 3782-92. ﹞; Jianguo Wang; the people such as Yu Zuo carry out phosphorylation pre-treatment to magnesium powder; add to again and in epoxy resin, make rich magnesium coating; coating to the protective value of aluminium alloy also get to the large Ti Gao of Hen ﹝ Jianguo Wang; Yu Zuo, etal, Applied Surface Science; 2014,15 (292): 93-97. ﹞.But above-mentioned method more complicated of magnesium powder being carried out to modification, operation is various.
Summary of the invention
The object of the invention is in order to make up the deficiencies in the prior art; a kind of method of preparing high anti-corrosion cathodic protection coatings in aluminum alloy surface is provided; the method is by adopting corrosion resistance and good and corrosion potential to add to and prepare coating in epoxy resin lower than the aluminium-magnesium alloy powder of aluminium alloy; adopt the methods such as brushing, spraying to be coated on alloy matrix aluminum; realize the corrosion-resistant protection to aluminum alloy surface and matrix, the method has the advantages that technique is simple, controllability is good.
The object of the present invention is achieved like this: according to a certain percentage aluminum magnesium alloy micro mist, epoxy resin, solvent and solidifying agent are hybridly prepared into coating; coating is fully ground in ball mill; each component in coating is uniformly distributed; and then adopt the method for spraying or brushing or roller coat coating to be coated on to the aluminum alloy surface cleaning up in advance; at room temperature solidify dry 5～7 days, can form in aluminum alloy surface the cathodic protection coatings of one deck high corrosion resistance.
From magnalium binary alloy phase diagram, aluminium-magnesium alloy powder (the quality percentage composition 40≤x≤60wt% of aluminium) is mainly by intermetallic compound β (Al
12mg
l7) phase and A1
3mg
2phase composite, β phase and A1
3mg
2be respectively-1.27V of the electropotential of phase and-1.29V, lower than the corrosion potential-0.85v(SCE of aluminium), and both corrosion electric current densities are also very little, the film that coatingsurface corrosion generates is divided into two-layer, top layer is magnesium aluminum hydroxide, and nexine is magnesium aluminum oxide, all has high aluminum concentration, both are corroded at sodium chloride solution very stable being not easy, and have good corrosion resistance nature.Therefore with respect to simple rich magnesium coating, the solidity to corrosion of coating itself is greatly improved, and can provide galvanic protection effect to aluminium alloy, thereby avoid the in the situation that of coating damage, with the corrosion of alloy matrix aluminum composition galvanic couple to acceleration aluminium alloy simultaneously.
Technical scheme of the present invention is as follows: a kind of preparation method of the rich aluminum magnesium alloy coating for aluminium alloy galvanic protection, comprises the steps:
(1) to aluminum alloy surface clean, decontamination, use distilled water ultrasonic cleaning, be then put into loft drier dry;
(2) according to a certain percentage epoxy resin, magnalium metal fine powder, solidifying agent, solvent, auxiliary agent, coupling agent, defoamer are mixed, put into ball mill and fully grind, make wherein each component be uniformly distributed and be mixed with coating;
(3) coating that adopts the method for spraying, brushing or roller coat prepared by step (2) is coated on alloy matrix aluminum, solidifies dry under room temperature.
The alloy that described aluminum magnesium alloy micro mist preferably becomes with pure metal magnesium mixed smelting taking pure metallic aluminum is as raw material, the particle diameter of making by powder-making technique is the micro-fine metal powder of 10～35 μ m, wherein the quality percentage composition X of pure metallic aluminum is 40≤X≤60wt%, the quality percentage composition Y of pure metal magnesium is 60≤Y≤40wt%, the percentage composition of pure metallic aluminum and pure metal magnesium and be 100%; The shape of described metal powder can be spherical metal powder, scaled metal powder and profiled metal powder.
Described magnalium metal fine powder, solidifying agent, solvent, auxiliary agent, coupling agent, defoamer, the preferred usage ratio of epoxy resin are 0.65～0.8:0.2～0.6:2.0～0.6:0.005～0.01:0.02～0.06:0.1～0.2:1.
Described solidifying agent preferred polyamide.The preferred dimethylbenzene of described solvent and propyl carbinol mix by 7:3.One in the preferred organobentonite of described auxiliary agent or White Carbon black.One in the preferred titanate coupling agent of described coupling agent or silane coupling agent.The preferred silicone oil of described defoamer or mineral oil defoaming agent.
The time of described ball mill grinding is preferably 0.5～4 hour; Time curing dry under described room temperature is preferred: 5～7 days.
Further preferred preparation method, comprises the steps:
(1) to aluminum alloy surface clean, decontamination, with distilled water ultrasonic cleaning 10 ~ 20min, be then put into loft drier and dry; The alloy becoming with pure metal magnesium mixed smelting taking pure metallic aluminum is as raw material, and the particle diameter of making taking powder-making technique is the micro-fine metal powder of 10～35 μ m;
(2) magnalium metal fine powder, solidifying agent, solvent, auxiliary agent, coupling agent, defoamer, epoxy resin are mixed according to amount ratio 0.65～0.8:0.2～0.6:2.0～0.6:0.005～0.01:0.02～0.06:0.1～0.2:1, put into ball mill, fully grind 1 ~ 4 hour with the stirring velocity of 20 ~ 50Hz, wherein each component is uniformly distributed, is mixed with coating;
(3) coating that adopts the method for spraying, brushing or roller coat prepared by step (2) is evenly coated on alloy matrix aluminum, is then placed under room temperature and solidifies dry 5 ~ 7 days.
The present invention compared with prior art, has the following advantages:
1) technological process of the present invention is relatively simple, reproducible, is applicable to suitability for industrialized production;
2) coating that the present invention makes has good corrosion resistance nature, and the corrosion resistance nature under salt mist environment and briny environment is 10 times of rich magnesium coating;
3), after the coating damage that the present invention makes, still can protect alloy matrix aluminum.
embodiment
Below by embodiment, the present invention is described in further details, these embodiment are only used for illustrating the present invention, do not limit the scope of the invention.
Embodiment 1 adopts following steps to realize the present invention:
(1) to aluminum alloy surface clean, decontamination, with distilled water ultrasonic cleaning 15min, be then put into loft drier and dry; The alloy becoming with pure metal magnesium mixed smelting taking pure metallic aluminum is as raw material, and wherein the quality percentage composition of aluminium is 60%, and the quality percentage composition of magnesium is 40%, and the particle diameter of making taking powder-making technique is the micro-fine metal powder of 30 μ m;
(2) solvent, White Carbon black, alkane coupling agent, silicon oil foam killer, the epoxy resin that magnalium metal fine powder, polymeric amide, dimethylbenzene and propyl carbinol are mixed by 7:3 mix according to amount ratio 0.65:0.2:2.0:0.006:0.02:0.15:1, put into ball mill, fully grind 1 hour with the stirring velocity of 25Hz, wherein each component is uniformly distributed, is mixed with coating;
(3) coating that adopts the method for spraying prepared by step (2) is evenly coated on alloy matrix aluminum, is then placed under room temperature and solidifies dry 5 days.
End to be dried, after coating is stable, open circuit potential is-1.05V, salt fog cabinet corrosion 100 days, observation coating was still intact, has good corrosion resistance nature.
Embodiment 2 adopts following steps to realize the present invention:
(1) to aluminum alloy surface clean, decontamination, with distilled water ultrasonic cleaning 10min, be then put into loft drier and dry; The alloy becoming with pure metal magnesium mixed smelting taking pure metallic aluminum is as raw material, and wherein the quality percentage composition of aluminium is 50%, and the quality percentage composition of magnesium is 50%, and the particle diameter of making taking powder-making technique is the micro-fine metal powder of 10 μ m;
(2) solvent, organobentonite, titanate coupling agent, mineral oil, the epoxy resin that magnalium metal fine powder, polymeric amide, dimethylbenzene and propyl carbinol are mixed by 7:3 mix according to amount ratio 0.75:0.4:1.0:0.01:0.03:0.1:1, put into ball mill, fully grind 3 hours with the stirring velocity of 35Hz, wherein each component is uniformly distributed, is mixed with coating;
(3) coating that adopts the method for brushing prepared by step (2) is evenly coated on alloy matrix aluminum, is then placed under room temperature and solidifies dry 6 days.
End to be dried, after coating is stable, open circuit potential is-0.96V, salt fog cabinet corrosion 100 days, observation coating was still intact, has good corrosion resistance nature.
Embodiment 3 adopts following steps to realize the present invention:
(1) to aluminum alloy surface clean, decontamination, with distilled water ultrasonic cleaning 20min, be then put into loft drier and dry; The alloy becoming with pure metal magnesium mixed smelting taking pure metallic aluminum is as raw material, and wherein the quality percentage composition of aluminium is 40%, and the quality percentage composition of magnesium is 60%, and the particle diameter of making taking powder-making technique is the micro-fine metal powder of 25 μ m;
(2) solvent, White Carbon black, titanate coupling agent, silicon oil foam killer, the epoxy resin that magnalium metal fine powder, polymeric amide, dimethylbenzene and propyl carbinol are mixed by 6:4 mix according to amount ratio 0.8:0.5:1.5:0.008:0.04:0.1:1, put into ball mill, fully grind 4 hours with the stirring velocity of 25Hz, wherein each component is uniformly distributed, is mixed with coating;
(3) coating that adopts the method for spraying prepared by step (2) is evenly coated on alloy matrix aluminum, is then placed under room temperature and solidifies dry 6 days.
End to be dried, after coating is stable, open circuit potential is-0.91V, salt fog cabinet corrosion 100 days, observation coating was still intact, has good corrosion resistance nature.
Embodiment 4 adopts following steps to realize the present invention:
(1) to aluminum alloy surface clean, decontamination, with distilled water ultrasonic cleaning 18min, be then put into loft drier and dry; The alloy becoming with pure metal magnesium mixed smelting taking pure metallic aluminum is as raw material, and wherein the quality percentage composition of aluminium is 60%, and the quality percentage composition of magnesium is 40%, and the particle diameter of making taking powder-making technique is the micro-fine metal powder of 35 μ m;
(2) solvent, organobentonite, silane coupling agent, mineral oil, the epoxy resin that magnalium metal fine powder, polymeric amide, dimethylbenzene and propyl carbinol are mixed by 7:3 mix according to amount ratio 0.7:0.5:1.2:0.006:0.02:0.2:1, put into ball mill, fully grind 1 hour with the stirring velocity of 25Hz, wherein each component is uniformly distributed, is mixed with coating;
(3) coating that adopts the method for roller coat prepared by step (2) is evenly coated on alloy matrix aluminum, is then placed under room temperature and solidifies dry 7 days.
End to be dried, after coating is stable, open circuit potential is-0.89V, salt fog cabinet corrosion 100 days, observation coating was still intact, has good corrosion resistance nature.
Claims (10)
1. for a preparation method for the rich aluminum magnesium alloy coating of aluminium alloy galvanic protection, it is characterized in that: comprise the steps:
(1) to aluminum alloy surface clean, decontamination, use distilled water ultrasonic cleaning, be then put into loft drier dry;
(2) according to a certain percentage epoxy resin, magnalium metal fine powder, solidifying agent, solvent, auxiliary agent, coupling agent, defoamer are mixed, put into ball mill and fully grind, make wherein each component be uniformly distributed and be mixed with coating;
(3) coating that adopts the method for spraying, brushing or roller coat prepared by step (2) is coated on alloy matrix aluminum, solidifies dry under room temperature.
2. preparation method according to claim 1, it is characterized in that: described aluminum magnesium alloy micro mist is that the alloy that becomes with pure metal magnesium mixed smelting taking pure metallic aluminum is as raw material, the particle diameter of making by powder-making technique is the micro-fine metal powder of 10～35 μ m, wherein the quality percentage composition X of pure metallic aluminum is 40≤X≤60wt%, the quality percentage composition Y of pure metal magnesium is 60≤Y≤40wt%, the percentage composition of pure metallic aluminum and pure metal magnesium and be 100%; Described metal powder is the one in spherical metal powder, scaled metal powder and profiled metal powder.
3. preparation method according to claim 1, is characterized in that: the usage ratio of described magnalium metal fine powder, solidifying agent, solvent, auxiliary agent, coupling agent, defoamer, epoxy resin is 0.65～0.8:0.2～0.6:2.0～0.6:0.005～0.01:0.02～0.06:0.1～0.2:1.
4. preparation method according to claim 1 and 2, is characterized in that: described solidifying agent is polymeric amide.
5. preparation method according to claim 1 and 2, is characterized in that: described solvent is that dimethylbenzene and propyl carbinol mix by 7:3.
6. preparation method according to claim 1 and 2, is characterized in that: described auxiliary agent is organobentonite or White Carbon black.
7. preparation method according to claim 1 and 2, is characterized in that: described coupling agent is titanate coupling agent or silane coupling agent.
8. preparation method according to claim 1 and 2, is characterized in that: described defoamer is silicone oil or mineral oil.
9. preparation method according to claim 1 and 2, is characterized in that: the time of described ball mill grinding is 0.5～4 hour; Under described room temperature, solidifying the dry time is: 5～7 days.
10. a preparation method as claimed in claim 1, is characterized in that: comprise following concrete steps:
(1) to aluminum alloy surface clean, decontamination, use distilled water ultrasonic cleaning, be then put into loft drier dry; The alloy becoming with pure metal magnesium mixed smelting taking pure metallic aluminum is as raw material, and the particle diameter of making taking powder-making technique is the micro-fine metal powder of 10～35 μ m;
(2) magnalium metal fine powder, solidifying agent, solvent, auxiliary agent, coupling agent, defoamer, epoxy resin are mixed according to amount ratio 0.65～0.8:0.2～0.6:2.0～0.6:0.005～0.01:0.02～0.06:0.1～0.2:1, put into ball mill, fully grind 1 ~ 4 hour with the stirring velocity of 10 ~ 50Hz, wherein each component is uniformly distributed, is mixed with coating;
(3) coating that adopts the method for spraying, brushing or roller coat prepared by step (2) is evenly coated on alloy matrix aluminum, is then placed under room temperature and solidifies dry 5 ~ 7 days.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105779982A (en) * | 2016-05-17 | 2016-07-20 | 广东海洋大学 | Chrome-free metal surface conversion liquid and conversion coating preparation method |
| CN106752150A (en) * | 2016-12-23 | 2017-05-31 | 河南圣华原铝业有限公司 | A kind of aluminium alloy environment protection type corrosion resistant coating and its coating processes |
| CN113199021A (en) * | 2021-04-09 | 2021-08-03 | 宁波职业技术学院 | High-performance magnesium alloy composite powder for building material and preparation method thereof |
| CN113881322A (en) * | 2021-11-15 | 2022-01-04 | 齐威 | Coating for magnesium-rich alloy coating and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105779982A (en) * | 2016-05-17 | 2016-07-20 | 广东海洋大学 | Chrome-free metal surface conversion liquid and conversion coating preparation method |
| CN106752150A (en) * | 2016-12-23 | 2017-05-31 | 河南圣华原铝业有限公司 | A kind of aluminium alloy environment protection type corrosion resistant coating and its coating processes |
| CN113199021A (en) * | 2021-04-09 | 2021-08-03 | 宁波职业技术学院 | High-performance magnesium alloy composite powder for building material and preparation method thereof |
| CN113881322A (en) * | 2021-11-15 | 2022-01-04 | 齐威 | Coating for magnesium-rich alloy coating and preparation method thereof |
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