CN103305068A - Surface treatment liquid capable of enhancing corrosion-resistant property of oxidation film of magnesium alloy or aluminum alloy and treatment method thereof - Google Patents
Surface treatment liquid capable of enhancing corrosion-resistant property of oxidation film of magnesium alloy or aluminum alloy and treatment method thereof Download PDFInfo
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- CN103305068A CN103305068A CN2013102595125A CN201310259512A CN103305068A CN 103305068 A CN103305068 A CN 103305068A CN 2013102595125 A CN2013102595125 A CN 2013102595125A CN 201310259512 A CN201310259512 A CN 201310259512A CN 103305068 A CN103305068 A CN 103305068A
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Abstract
The invention provides surface treatment liquid capable of enhancing the corrosion-resistant property of the oxidation film of a magnesium alloy or an aluminum alloy and a treatment method thereof. According to the treatment method, the magnesium alloy or the aluminum alloy which is treated through micro-arc oxidation and anodic oxidation is immersed into a tetrahydrofuran solution of polystyrene and maleic anhydride grafted polystyrene, or the tetrahydrofuran solution is sprayed onto the surface of the magnesium alloy or the aluminum alloy so that a compact polystyrene coating is formed on the surface of the oxidation film of the magnesium alloy or the aluminum alloy and fills holes and microcracks formed in the surface of the oxidation film, thus improving the corrosion-resistant property of the magnesium alloy or the aluminum alloy.
Description
Technical field:
The present invention relates to a kind of surface treatment method that improves magnesium alloy or Process on Aluminum Alloy Oxidation Film corrosion resistance nature, the organic coating that specially refers to magnesium alloy or aluminum alloy differential arc oxidation and anodized surface is processed.
Background technology:
Magnesium alloy is with lightweight, and specific tenacity is high, and good processing characteristics and the good characteristics such as electromagnetic wave shielding are described as the green metal structured material of 21 century; Aluminium alloy has that proportion is little, and specific tenacity is high, and good heat-conductivity conducting performance and excellent castibility are widely used in fields such as space flight and aviation, electronics and carrier vehicles.Yet magnesium alloy and aluminium alloy all can suffer serious corrosion in malaria or marine atmosphere.Therefore, rotproofing is carried out on its surface, improving corrosion resistance nature is the major issue that magnesium alloy and aluminium alloy are used needs solution.
At present, magnesium alloy and aluminum alloy surface protection processing method mainly contain chemical conversion and process, and the organism application is processed, anodic oxidation treatment, and differential arc oxidation is processed, the methods such as plating or electroless plating processing.Wherein, anodic oxidation treatment can significantly improve mechanical property and the corrosion resisting property of metal, also has simultaneously stronger adsorptivity, and the differential arc oxidation that grows up on anodizing technology basis processing is a kind of new technology at non-ferrous metal surface in situ growth ceramic layer, it has with the metallic matrix bonding force strong, the heat-resisting characteristic such as shock-resistant, wear-resistant, corrosion-resistant, the surfacecti proteon effect is far above traditional surface treatment method.Yet, no matter be anode oxide film or micro-arc oxidation films, outside surface all exists many holes or tiny crack, and corrosive medium can infiltrate matrix from these field at micro-defects, causes its solidity to corrosion to descend.Defective for magnesium alloy and Process on Aluminum Alloy Oxidation Film, main adopt heat-hydration sealing of hole, chromic salt and silicate, rare earth oxide, organic acid etc. to carry out sealing of hole to process, adopt the thermoplasticss such as the thermosetting resin such as sol-gel method or acrylic resin, Resins, epoxy, aminoresin and polypropylene to carry out surface treatment.The sealing of holes such as heat-hydration sealing of hole, chromic salt and silicate, rare earth oxide, organic acid are processed the bore portions sealing is diminished, and are difficult to complete closed micropore bottom and tiny crack; The sol-gel method complex treatment process, and the colloidal sol of larger particles is difficult for entering fenestra; Currently used thermoset macromolecule material can not recycle, and coating is difficult to after because of damages such as bump, scrapings repair; And the polypropylene that has adopted in the thermoplastic material needs to be heated in xylene solvent and could dissolve under 120 ℃ the temperature, and in use needs heat tracing, in addition, and volatile poisonous dimethylbenzene gas in heat-processed, practical application.
Summary of the invention:
For the problem that prior art exists, one of purpose of the present invention is to provide the surface processing solution of a kind of magnesium alloy or aluminum alloy differential arc oxidation film and anode oxide film; A further object of the present invention is to utilize this solution that the surface treatment method of a kind of magnesium alloy or aluminum alloy differential arc oxidation film and anode oxide film is provided.
A kind of surface treatment liquid that improves magnesium alloy or Process on Aluminum Alloy Oxidation Film corrosion resistance nature adds maleic anhydride grafted polystyrene in the tetrahydrofuran (THF) under-10～35 ℃, and the mass concentration of maleic anhydride grafted polystyrene is 5～18%.
Add and also to comprise polystyrene in the tetrahydrofuran (THF), the total mass concentration of polystyrene and maleic anhydride grafted polystyrene is 5～18%, and maleic anhydride grafted polystyrene is not less than 10% of polystyrene and maleic anhydride grafted polystyrene total mass.
Utilize described surface treatment liquid to improve the method for magnesium alloy or Process on Aluminum Alloy Oxidation Film corrosion resistance nature, magnesium alloy and Al alloy parts that differential arc oxidation or anodic oxidation treatment are crossed immerse in the described surface processing solution, take out behind 5～15min and dry, perhaps surface processing solution is sprayed to workpiece surface, after being incubated 1～30min under 180～250 ℃ the temperature, cool off again.
The inventive method can at room temperature be filled into polystyrene and make its sealing in magnesium alloy or the Process on Aluminum Alloy Oxidation Film hole, and forms the organic coating of one deck densification on the oxide film surface, significantly improves the corrosion resistance nature of magnesium alloy or aluminium alloy.Simultaneously, polystyrene belongs to thermoplastic material, when coating causes local failure because scraping waits, can by this local heating fusing is repaired fast, prolong the work-ing life of coating.In addition, can in treatment soln, add pigment, the coating of preparation different colours.
Description of drawings:
To be differential arc oxidation AZ31 magnesium alloy adopt surface topography map after the surface treatment liquid of mass concentration 15% is processed through the present invention to Fig. 1;
Fig. 2 is the polarization curve of AZ31 magnesium alloy in 3.5%NaCl solution; (a is the differential arc oxidation sample, and b is that the present invention processes sample)
Fig. 3 is the ac impedance spectroscopy of differential arc oxidation AZ31 magnesium alloy in 3.5%NaCl solution;
Fig. 4 is differential arc oxidation AZ31 magnesium alloy ac impedance spectroscopy in 3.5%NaCl solution after the present invention adopts the surface treatment liquid of mass concentration 15% to process;
Fig. 5 is the saline soak corrosion photo before and after the present invention of differential arc oxidation AZ31 magnesium alloy processes;
To be differential arc oxidation 2519 aluminium alloys adopt surface topography map after the surface treatment liquid of mass concentration 15% is processed through the present invention to Fig. 6;
Fig. 7 is the polarization curves of 2519 aluminium alloys in 3.5%NaCl solution; (a is the differential arc oxidation sample, and b is that the present invention processes sample)
Fig. 8 is the ac impedance spectroscopies of differential arc oxidation 2519 aluminium alloys in 3.5%NaCl solution;
Fig. 9 is differential arc oxidation 2519 aluminium alloys ac impedance spectroscopies in 3.5%NaCl solution after the present invention adopts the surface treatment liquid of mass concentration 15% to process;
To be differential arc oxidation AZ31 magnesium alloy adopt surface topography map after the surface treatment liquid of mass concentration 5% is processed through the present invention to Figure 10;
Figure 11 is differential arc oxidation AZ31 magnesium alloy polarization curve in 3.5%NaCl solution after the present invention adopts the surface treatment liquid of mass concentration 5% to process;
Figure 12 is differential arc oxidation AZ31 magnesium alloy ac impedance spectroscopy in 3.5%NaCl solution after the present invention adopts the surface treatment liquid of mass concentration 5% to process;
To be differential arc oxidation AZ31 magnesium alloy adopt surface topography map after the surface treatment liquid of mass concentration 10% is processed through the present invention to Figure 13;
Figure 14 is differential arc oxidation AZ31 magnesium alloy polarization curve in 3.5%NaCl solution after the present invention adopts the surface treatment liquid of mass concentration 10% to process;
Figure 15 is differential arc oxidation AZ31 magnesium alloy ac impedance spectroscopy in 3.5%NaCl solution after the present invention adopts the surface treatment liquid of mass concentration 10% to process;
Embodiment:
Be intended to further specify the present invention below in conjunction with embodiment, and unrestricted the present invention.
Embodiment 1
1. at room temperature maleic anhydride grafted polystyrene is added in the tetrahydrofuran (THF), the mass concentration of maleic anhydride grafted polystyrene is 15%;
2. treatment process: magnesium alloy or Al alloy parts that differential arc oxidation or anodic oxidation treatment are crossed immerse in the described surface processing solution, take out behind 5～15min and dry, perhaps surface processing solution is sprayed to workpiece surface, after being incubated 1～30min under 210 ℃ the temperature, cool off again.
To carry out following experiment through the AZ31 magnesium alloy sample of above-mentioned art breading:
1. scanning electron microscope: as shown in Figure 1, differential arc oxidation AZ31 magnesium alloy sample is after the present invention adopts the surface treatment liquid of mass concentration 15% to process, and the surface exists micropore hole and tiny crack hardly.
2. electrokinetic potential polarization curve test: as shown in Figure 2, differential arc oxidation AZ31 magnesium alloy sample is after the present invention adopts the surface treatment liquid of mass concentration 15% to process, and the sample corrosion electric current density drops to 10
-9Acm
-2, than low approximately 4 orders of magnitude of differential arc oxidation sample.
3. electrochemical AC impedance is composed: shown in Figure 4 such as Fig. 3, the AZ31 magnesium alloy soaks the initial stage resistance value and improve approximately 2 orders of magnitude, and the speed that resistance value descends obviously reduces after the surface treatment liquid that adopts mass concentration 15% through the present invention is processed.Differential arc oxidation sample resistance value after soaking through 120h drops to 10
3Ω .cm
2, and resistance value still was higher than 10 after sample soaked 1104h after the present invention adopts the surface treatment liquid of mass concentration 15% to process
4Ω .cm
2
4. room temperature brine soaking experiment: as shown in Figure 5, untreated differential arc oxidation sample hot spot namely occurs soaking 48h, and when immersion proceeded to 96h, sample surfaces was covered with the white corrosion product, and had the part matrix exposed; By comparison, adopt the sample after the surface treatment liquid of mass concentration 15% is processed not have considerable change early stage in immersion through the present invention, when being dipped to 336h, sample surfaces just begins to occur hot spot, and when immersion proceeded to 552h, the quantity of hot spot and area did not obviously increase yet.
To carry out following experiment through 2519 aluminum alloy samples of above-mentioned art breading:
1. scanning electron microscope: as shown in Figure 6, after differential arc oxidation 2519 aluminum alloy samples adopted the surface treatment liquid of mass concentration 15% to process through the present invention, sample surfaces existed micropore hole and tiny crack hardly.
2. electrokinetic potential polarization curve test: as shown in Figure 7, adopt the surface treatment liquid of mass concentration 15% to process through the present invention after the corrosion electric current density of sample than low approximately 4 orders of magnitude of differential arc oxidation sample, the corrosion potential 80mV that shuffled.
3. electrochemical AC impedance is composed: shown in Figure 9 such as Fig. 8, at the immersion initial stage, the resistance value of 2519 aluminium alloys is than high approximately 2 orders of magnitude of differential arc oxidation sample after the present invention adopts the surface treatment liquid of mass concentration 15% to process.And after the 572h immersion, the resistance value of differential arc oxidation sample drops to 10
3Ω .cm
2And resistance value still was higher than 10 after sample soaked 1104h after the present invention adopts the surface treatment liquid of mass concentration 15% to process
5Ω .cm
2
1. at room temperature polystyrene and maleic anhydride grafted polystyrene are added in the tetrahydrofuran (THF), the total mass concentration of polystyrene and maleic anhydride grafted polystyrene is 5%, and maleic anhydride grafted polystyrene is not less than 10% of polystyrene and maleic anhydride grafted polystyrene total mass;
2. treatment process: the magnesium alloy workpiece that differential arc oxidation or anodic oxidation treatment are crossed immerses in the described surface processing solution, take out behind 5～15min and dry, perhaps surface processing solution is sprayed to workpiece surface, after being incubated 1～30min under 210 ℃ the temperature, cool off again.
To carry out following experiment through the AZ31 magnesium alloy sample of above-mentioned art breading:
1. scanning electron microscope: as shown in figure 10, after differential arc oxidation AZ31 magnesium alloy sample adopted the surface treatment liquid of mass concentration 5% to process through the present invention, the most hole of sample surfaces and tiny crack were covered by the polystyrene-coated of layer.
2. electrokinetic potential polarization curve test: as shown in figure 11, differential arc oxidation AZ31 magnesium alloy sample is after the present invention adopts the surface treatment liquid of mass concentration 5% to process, and the sample corrosion electric current density drops to 10
-6A.cm
-2
3. electrochemical AC impedance is composed: as shown in figure 12, at the immersion initial stage, though differential arc oxidation AZ31 magnesium alloy adopts the resistance value after the surface treatment liquid of mass concentration 5% is processed to compare the not raising of differential arc oxidation sample through the present invention, but the speed that resistance value descends significantly reduces, and resistance value is apparently higher than 10 after soaking 1104h
3Ω .cm
2
1. at room temperature polystyrene and maleic anhydride grafted polystyrene are added in the tetrahydrofuran (THF), the total mass concentration of polystyrene and maleic anhydride grafted polystyrene is 10%, and maleic anhydride grafted polystyrene is not less than 10% of polystyrene and maleic anhydride grafted polystyrene total mass;
2. treatment process: the magnesium alloy workpiece that differential arc oxidation or anodic oxidation treatment are crossed immerses in the described surface processing solution, take out behind 5～15min and dry, perhaps surface processing solution is sprayed to workpiece surface, after being incubated 1～30min under 210 ℃ the temperature, cool off again.
To carry out following experiment through the AZ31 magnesium alloy sample of above-mentioned art breading:
1. scanning electron microscope: as shown in figure 13, after differential arc oxidation AZ31 magnesium alloy sample adopted the surface treatment liquid of mass concentration 10% to process through the present invention, sample surfaces was covered by the thicker polystyrene-coated of one deck, and only remaining minority micropore is not filled fully.
2. electrokinetic potential polarization curve test: as shown in figure 14, differential arc oxidation AZ31 magnesium alloy sample is after the present invention adopts the surface treatment liquid of mass concentration 10% to process, and the sample corrosion electric current density drops to 10
-7A.cm
-2
3. electrochemical AC impedance is composed: as shown in figure 15, differential arc oxidation AZ31 magnesium alloy is after the surface treatment liquid that adopts mass concentration 10% through the present invention is processed, immersion initial stage resistance value improves approximately 1 order of magnitude, and the speed that resistance value descends obviously reduces, and resistance value still is higher than 10 after soaking 1104h
4Ω .cm
2
Claims (3)
1. a surface treatment liquid that improves magnesium alloy or Process on Aluminum Alloy Oxidation Film corrosion resistance nature is characterized in that, under-10～35 ℃ maleic anhydride grafted polystyrene is added in the tetrahydrofuran (THF), and the mass concentration of maleic anhydride grafted polystyrene is 5～18%.
2. surface treatment liquid according to claim 1, it is characterized in that, add and also to comprise polystyrene in the tetrahydrofuran (THF), the total mass concentration of polystyrene and maleic anhydride grafted polystyrene is 5～18%, and maleic anhydride grafted polystyrene is not less than 10% of polystyrene and maleic anhydride grafted polystyrene total mass.
3. utilize claim 1 or 2 described surface treatment liquids to improve the method for magnesium alloy or Process on Aluminum Alloy Oxidation Film corrosion resistance nature, it is characterized in that, magnesium alloy or Al alloy parts that differential arc oxidation or anodic oxidation treatment are crossed immerse in the described surface processing solution, take out behind 5～15min and dry, perhaps surface processing solution is sprayed to workpiece surface, after being incubated 1～30min under 180～250 ℃ the temperature, cool off again.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103556205A (en) * | 2013-11-14 | 2014-02-05 | 桂林理工大学 | Method for coloring magnesium alloy composite film by micro-arc oxidation |
| CN103726058A (en) * | 2014-01-19 | 2014-04-16 | 黑龙江慧田知识产权服务有限公司 | Preservative treatment process for aluminum alloy |
| CN104109854A (en) * | 2014-06-19 | 2014-10-22 | 锐展(铜陵)科技有限公司 | Long-lasting aluminum alloy surface treating agent with long shelf life |
| CN104707771A (en) * | 2013-12-16 | 2015-06-17 | 哈尔滨怀远科技发展有限公司 | Aluminum alloy antiseptic treatment technology |
| CN104711583A (en) * | 2013-12-16 | 2015-06-17 | 哈尔滨中太致远科技发展有限公司 | Aluminum alloy corrosion resistance method |
| CN104722463A (en) * | 2013-12-24 | 2015-06-24 | 哈尔滨中亿投资咨询有限责任公司 | Alloy anti-corrosion treatment process |
| CN106700663B (en) * | 2017-01-09 | 2018-08-07 | 中南大学 | A kind of preparation method of resin coated copper bronze |
| CN110126182A (en) * | 2019-04-20 | 2019-08-16 | 浙江师范大学 | A kind of processing method of metal-rubber composite-gasket |
| CN111455429A (en) * | 2020-04-22 | 2020-07-28 | 哈尔滨工业大学 | Titanium surface super-hydrophobic composite coating and preparation method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103556205A (en) * | 2013-11-14 | 2014-02-05 | 桂林理工大学 | Method for coloring magnesium alloy composite film by micro-arc oxidation |
| CN104707771A (en) * | 2013-12-16 | 2015-06-17 | 哈尔滨怀远科技发展有限公司 | Aluminum alloy antiseptic treatment technology |
| CN104711583A (en) * | 2013-12-16 | 2015-06-17 | 哈尔滨中太致远科技发展有限公司 | Aluminum alloy corrosion resistance method |
| CN104722463A (en) * | 2013-12-24 | 2015-06-24 | 哈尔滨中亿投资咨询有限责任公司 | Alloy anti-corrosion treatment process |
| CN103726058A (en) * | 2014-01-19 | 2014-04-16 | 黑龙江慧田知识产权服务有限公司 | Preservative treatment process for aluminum alloy |
| CN104109854A (en) * | 2014-06-19 | 2014-10-22 | 锐展(铜陵)科技有限公司 | Long-lasting aluminum alloy surface treating agent with long shelf life |
| CN106700663B (en) * | 2017-01-09 | 2018-08-07 | 中南大学 | A kind of preparation method of resin coated copper bronze |
| CN110126182A (en) * | 2019-04-20 | 2019-08-16 | 浙江师范大学 | A kind of processing method of metal-rubber composite-gasket |
| CN111455429A (en) * | 2020-04-22 | 2020-07-28 | 哈尔滨工业大学 | Titanium surface super-hydrophobic composite coating and preparation method thereof |
| CN111455429B (en) * | 2020-04-22 | 2021-05-04 | 哈尔滨工业大学 | Titanium surface super-hydrophobic composite coating and preparation method thereof |
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| CN103305068B (en) | 2016-08-17 |
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