CN101942654A - Method for immersing superhydrophobic surface of aluminum alloy in one step - Google Patents

Method for immersing superhydrophobic surface of aluminum alloy in one step Download PDF

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CN101942654A
CN101942654A CN 201010521151 CN201010521151A CN101942654A CN 101942654 A CN101942654 A CN 101942654A CN 201010521151 CN201010521151 CN 201010521151 CN 201010521151 A CN201010521151 A CN 201010521151A CN 101942654 A CN101942654 A CN 101942654A
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acid
aluminum alloy
chain fatty
fatty acid
hydrochloric acid
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CN101942654B (en
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余新泉
周荃卉
张友法
吴洁
陈锋
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Southeast University
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Abstract

The invention relates to a method for immersing the superhydrophobic surface of an aluminum alloy in one step. The method comprises the following steps of: (1) immersing the aluminum alloy in mixed solution of hydrochloric acid, long-chain fatty acid and alcohol at the bath temperature of between 30 and 70 DEG C for 5 to 25 minutes, wherein the mass ratio of the hydrochloric acid to the long-chain fatty acid to the alcohol in the mixed solution is 30-50:2-10:40-68, and the long-chain fatty acid comprises at least one of myristic acid and palmitic acid; and (2) cleaning chemically-immersed aluminum alloy through deionized water, placing the aluminum alloy in a box-type electric furnace and curing for 0.5 to 1.5 hours at the temperature of between 50 and 90 DEG C, taking the aluminum alloy out and cooling in the air. In the method, the aluminum alloy is immersed in the mixed solution of the hydrochloric acid, the long-chain fatty acid and the alcohol, and the aluminum alloy surface which has the advantages of different adherence of water drops and excellent superhydrophobic property is prepared through the double effects of constructing a surface rough structure by hydrochloric acid and constructing the surface rough structure and changing the wetting property by the long-chain fatty acid.

Description

One step immersion treatment method of aluminium alloy super hydrophobic surface
Technical field
The present invention relates to a kind of surface treatment method of easy aluminium alloy.
 
Background technology
The super hydrophobic surface technology is applied to metallic substance, the effect that can play automatically cleaning, inhibition surface corrosion and surface oxidation, reduction frictional coefficient and strengthen the frost resistance performance, and therefore, the preparation metal super-hydrophobic surface has important application prospects.Prepare in the whole bag of tricks of super hydrophobic surface at existing metallic substance, the major technique characteristics are by making up suitable Rough Metal Surface, modifying the low surface energy material then on prepared uneven surface, i.e. substep preparation technology.Method as employing chemical etchings such as Shen has been constructed coarse structure on the surface of metallic aluminium, copper and zinc, further use silicon fluoride that the surface is modified after, obtain super hydrophobic surface, water droplet with the surface contact angle reach more than 150 °; Wang research group adopts Beck reagent that aluminium is carried out etching, and then modifies with the low surface energy material, has made the hydrophobic performance surface of good.Guo etc. are immersed in the certain density aqueous sodium hydroxide solution etching with aluminium alloy and modify low-surface-energy material more from the teeth outwards after for some time, thereby have obtained and the stable super hydrophobic surface of water droplet contact angle up to 161 °.Xiao etc. at first carry out aluminium flake the coarse processing of hydroxylation as substrate, again it is immersed in and forms the PEI coating in polymine (PEI) aqueous solution, the aluminium flake that will be formed with the PEI coating then is immersed in stearic acid (STA) and N, in the mixing solutions of N ˊ-dicyclohexylcarbodiimide (DCCD), interact by carboxyl among the STA and the amino among the PEI, make on the coating absorption STA self-assembled monolayer, obtained contact angle at last and be 166 ° based superhydrophobic thin films.
At present, existing a lot of for the preparation method of aluminium alloy super hydrophobic surface, but mainly be in conceptual phase, in more existing technologies of preparing, because preparation process or adopt special preparation equipment and technology, or adopt expensive low surface energy material to modify, cause the preparation cost height, complicated operation, poor controllability etc., be not suitable for industrialized mass production, as electrochemical deposition method, template, self-assembly method or the like.Even some is expected to realize also still have problems such as technology is easy inadequately, preparation cost height among some preparation methods of suitability for industrialized production.For example, the method that employing chemical etchings such as Zhou Feng combine with anodic oxidation is constructed coarse structure in aluminum alloy surface, utilizes silicon fluoride to carry out finishing again, prepares the aluminium alloy super hydrophobic surface, complicated process of preparation, and preparation cost is high.The treatment process that Wu Xuedong etc. mention in " a kind of preparation method of light metal super-hydrophobic surface " (patent CN200710156490.4), make up microtexture by anodic oxidation treatment, adopt silicon fluoride to carry out the method for finishing again, also be that preparation technology was divided into for two steps, and costing an arm and a leg of coating materials be not from solving the problem of simplifying technology, reducing cost in essence.Xi Jinming etc. are in the electrochemical process described in " preparation method who is used for the super hydrophobic surface of anti-corrosion of metal and self-cleaning effects " (patent No. CN200710177876.3), the ethanolic soln that adopts lipid acid is as electrolyte solution, make the metallic surface deposition one deck on the negative electrode have anticorrosion and soap self-cleaning effects by electrochemical action, thus the metallic surface that obtains having superhydrophobic characteristic.The employing of lipid acid has reduced cost to a certain extent, the method of galvanic deposit has also been abandoned general branch one-step preparation method, but electrochemical process complexity, poor controllability, low and the comprehensive cost of efficient is not effectively reduced, and is not suitable for large-scale industrial production and promotes, and therefore seeks a kind of truly simple and easy to do, with low cost, and the method for can obtained performance good super hydrophobic surface is still the emphasis of present people's research.
Longer chain fatty acid not only can be used as the low surface energy modifier, and the acidity of himself can also be to metallic surface generation effect, and uneven surface is constructed and the dual function of wetting property change thereby play, and provides effective thinking for simplifying super hydrophobic surface preparation technology.And longer chain fatty acid also has with low cost, only contains C, H, three kinds of elements of O, and environmentally safe is to advantage such as the selectivity of modification of surfaces is little.
Summary of the invention
The invention provides an a kind of step immersion treatment method of simple and easy to do aluminium alloy super hydrophobic surface, the present invention adopts a step infusion method to replace the substep preparation technology who generally uses, the structure and the infiltrating change of surface roughness are carried out simultaneously, obtained super-hydrophobic aluminum alloy surface.
The present invention adopts following technical scheme:
An a kind of step immersion treatment method of aluminium alloy super hydrophobic surface the treating method comprises the following step:
(1) aluminium alloy is immersed in hydrochloric acid, longer chain fatty acid and the alcoholic acid mixing solutions, soaking bath temperature is 30 ℃ ~ 70 ℃, soak time is 5min ~ 25min, hydrochloric acid in the described mixing solutions, longer chain fatty acid and alcoholic acid mass ratio are: 30 ~ 50: 2 ~ 10: 40 ~ 68, and described longer chain fatty acid comprises a kind of in myristic acid and the palmitinic acid at least;
(2) aluminium alloy after chemical immersion is handled places cabinet-type electric furnace after washed with de-ionized water, and 50 ℃ ~ 90 ℃ following solidification treatment 0.5 ~ 1.5 hour, air cooling was taken out in the back.
Technological method provided by the invention has following advantage:
The present invention adopts hydrochloric acid, longer chain fatty acid and alcoholic acid mixing solutions cheaply, treatment process by step immersion aluminium alloy, make the structure and the infiltrating change of aluminum alloy surface coarse structure carry out simultaneously, greatly simplify preparation technology, obtained ideal aluminium alloy super hydrophobic surface.This method is device simple not only, and is easy to operate, and technology is easy, and agents useful for same is with low cost, significantly reduced preparation cost, is easy to industrialized mass production and uses.
1. the aluminum alloy materials through mixing solutions one step immersion treatment has good ultra-hydrophobicity, contact angle can be up to 160 ° about, and stick very little.
2. adopt a step infusion method, the structure of surface roughness and infiltrating change are carried out simultaneously, greatly simplified preparation technology.
3. the reagent that adopts pollutes little, easily handle, and [(per 500 grams of the price of myristic acid and palmitinic acid are all about 25 yuan) substitute siloxanes, the silicon fluoride (about 1000 yuan of per 5 grams of price) that generally uses] with low cost reduced preparation cost significantly.
4.Preparation technology and required equipment are simple, easy handling, efficient height, and comprehensive cost is cheap, is easy to industrialized mass production and uses.
Description of drawings:
Fig. 1 is that a step infusion method (myristic acid) is handled the state graph on this surface of the sem photograph of back aluminum alloy surface coarse structure and water droplet.
Fig. 2 is that a step infusion method (myristic acid) is handled the adhesion figure of back water droplet in aluminum alloy surface.
Fig. 3 is that a step infusion method (palmitinic acid) is handled the state graph of back water droplet in aluminum alloy surface.
Fig. 4 is that a step infusion method (palmitinic acid) is handled the adhesion figure of back water droplet in aluminum alloy surface.
Fig. 5 is that a step infusion method (palmitinic acid and myristic acid mixed solution) is handled the state graph of back water droplet in aluminum alloy surface.
Fig. 6 is that a step infusion method (palmitinic acid and myristic acid mixed solution) is handled the adhesion figure of back water droplet in aluminum alloy surface.
Fig. 7 is that a step infusion method (palmitinic acid and myristic acid mixed solution) is handled the state graph of back water droplet in aluminum alloy surface.
Fig. 8 is that a step infusion method (palmitinic acid and myristic acid mixed solution) is handled the adhesion figure of back water droplet in aluminum alloy surface.
Embodiment
Embodiment 1
Preparation hydrochloric acid, myristic acid and alcoholic acid mixing solutions, mixing solutions is: hydrochloric acid: myristic acid: ethanol mass ratio 42: 5: 53.The A356 aluminium alloy is carried out chemical immersion handle in mixing solutions, soaking temperature is 40 ℃ (water-baths), and soak time is 8min, with at its surface construction coarse structure and carry out finishing.To the aluminium alloy washed with de-ionized water after the immersion treatment, remove the residual reaction agent, place cabinet-type electric furnace to be heated to 80 ℃ at last and solidified 0.5 hour, air cooling is taken out in the back.
Sample is through after a step, infusion method was handled, surface tissue as shown in Figure 1, lower left corner illustration is for amplifying pattern.After testing, the contact angle of sample and water is 163 ° (the A356 aluminium alloy before handling is 52 ° with the contact angle of water), accordingly water droplet at the state of sample surfaces shown in the illustration of Fig. 1 upper right corner.The adhesion situation as shown in Figure 2.
 
Embodiment 2
Preparation hydrochloric acid, palmitinic acid and alcoholic acid mixing solutions, mixing solutions is: hydrochloric acid: palmitinic acid: ethanol mass ratio 40: 7: 53.The A356 aluminium alloy is carried out chemical immersion handle in mixing solutions, soaking temperature is 50 ℃ (water-baths), and soak time is 6min, with at its surface construction coarse structure and carry out finishing.To the aluminium alloy washed with de-ionized water after the immersion treatment, remove the residual reaction agent, place cabinet-type electric furnace to be heated to 60 ℃ at last and solidified 1 hour, air cooling is taken out in the back.
Sample is through after a step, infusion method was handled, and after testing, the contact angle of sample and water is 160 ° (being 52 °) before the processing, and water droplet at the state of sample surfaces as shown in Figure 3 accordingly.The adhesion situation as shown in Figure 4.
 
Embodiment 3
Preparation hydrochloric acid, myristic acid, palmitinic acid and alcoholic acid mixing solutions, mixing solutions is: hydrochloric acid: myristic acid: palmitinic acid: ethanol mass ratio 45: 2: 8: 45.The A356 aluminium alloy is carried out chemical immersion handle in mixing solutions, soaking temperature is 55 ℃ (water-baths), and soak time is 9min, with at its surface construction coarse structure and carry out finishing.To the aluminium alloy washed with de-ionized water after the immersion treatment, remove the residual reaction agent, place cabinet-type electric furnace to be heated to 60 ℃ at last and solidified 1 hour, air cooling is taken out in the back.
Sample is through after a step, infusion method was handled, and after testing, the contact angle of sample and water is 161 ° (being 52 °) before the processing, and water droplet at the state of sample surfaces as shown in Figure 5 accordingly.The adhesion situation as shown in Figure 6.
 
Embodiment 4
Preparation hydrochloric acid, myristic acid, palmitinic acid and alcoholic acid mixing solutions, mixing solutions is: hydrochloric acid: myristic acid: palmitinic acid: ethanol mass ratio 30: 5: 9: 56.The A356 aluminium alloy is carried out chemical immersion handle in mixing solutions, soaking temperature is 70 ℃ (water-baths), and soak time is 5min, with at its surface construction coarse structure and carry out finishing.To the aluminium alloy washed with de-ionized water after the immersion treatment, remove the residual reaction agent, place cabinet-type electric furnace to be heated to 60 ℃ at last and solidified 1 hour, air cooling is taken out in the back.
Sample is through after a step, infusion method was handled, and after testing, the contact angle of sample and water is 159 ° (being 52 °) before the processing, and water droplet at the state of sample surfaces as shown in Figure 7 accordingly.The adhesion situation as shown in Figure 8.
Embodiment 4
An a kind of step immersion treatment method of aluminium alloy super hydrophobic surface the treating method comprises the following step:
(1) aluminium alloy is immersed in hydrochloric acid, in longer chain fatty acid and the alcoholic acid mixing solutions, soaking bath temperature is 30 ℃ ~ 70 ℃, soak time is 5min ~ 25min, hydrochloric acid in the described mixing solutions, longer chain fatty acid and alcoholic acid mass ratio are: 30 ~ 50: 2 ~ 10: 40 ~ 68, described longer chain fatty acid comprises a kind of in myristic acid and the palmitinic acid at least, in the present embodiment, soaking bath temperature is 30 ℃, 44 ℃ or 70 ℃, soak time is 5min, 22min or 25min, hydrochloric acid in the described mixing solutions, longer chain fatty acid and alcoholic acid mass ratio are: 30: 2: 68,35:8:57 or 50: 10: 40
(2) aluminium alloy after chemical immersion is handled is after washed with de-ionized water, place cabinet-type electric furnace, 50 ℃ ~ 90 ℃ following solidification treatment 0.5 ~ 1.5 hour, in the present embodiment, can select 50 ℃, 75 ℃ or 90 ℃ of following solidification treatment 0.5,1.0 or 1.5 hours, air cooling is taken out in the back.

Claims (1)

1. one of an aluminium alloy super hydrophobic surface go on foot the immersion treatment method, it is characterized in that the treating method comprises the following step:
(1) aluminium alloy is immersed in hydrochloric acid, longer chain fatty acid and the alcoholic acid mixing solutions, soaking bath temperature is 30 ℃ ~ 70 ℃, soak time is 5min ~ 25min, hydrochloric acid in the described mixing solutions, longer chain fatty acid and alcoholic acid mass ratio are: 30 ~ 50: 2 ~ 10: 40 ~ 68, described longer chain fatty acid comprises a kind of in myristic acid and the palmitinic acid at least
(2) aluminium alloy after chemical immersion is handled places cabinet-type electric furnace after washed with de-ionized water, and 50 ℃ ~ 90 ℃ following solidification treatment 0.5 ~ 1.5 hour, air cooling was taken out in the back.
CN2010105211513A 2010-10-27 2010-10-27 Method for immersing superhydrophobic surface of aluminum alloy in one step Expired - Fee Related CN101942654B (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102230169A (en) * 2011-06-13 2011-11-02 哈尔滨工业大学 Method for constructing super-hydrophobic membrane on surface of copper matrix
CN104138829A (en) * 2013-05-07 2014-11-12 刘也卓 Polyamino acid adjusted and controlled super-hydrophobic surface material constructed in a biomineralization way and the preparation method thereof
CN105926498A (en) * 2016-05-12 2016-09-07 江苏固格澜栅防护设施有限公司 Protective fence with surface being coated with drainage layers and manufacturing method
CN106048685A (en) * 2016-06-30 2016-10-26 上海电力学院 Preparation method of super-hydrophobic surface of aluminum alloy
CN106086835A (en) * 2016-07-27 2016-11-09 昆明理工大学 A kind of aluminum and the preparation method of superhydrophobic surface of aluminum alloy
CN107761085A (en) * 2017-10-31 2018-03-06 哈尔滨工业大学 A kind of method that one-step method prepares aluminium base super hydrophobic surface
CN107755228A (en) * 2017-09-22 2018-03-06 浙江海洋大学 It is a kind of that super-hydrophobic and oleophobic surface method is prepared on aluminium alloy matrix surface
FR3127438A1 (en) * 2021-09-27 2023-03-31 Alphi METHOD FOR REDUCING THE ADHERENCE OF FOREIGN BODIES TO THE SURFACE OF A METALLIC SUBSTRATE

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101532159A (en) * 2009-03-10 2009-09-16 集美大学 Preparation method for metallic aluminum super-hydrophobic surface
CN101812680A (en) * 2010-04-30 2010-08-25 西北师范大学 Method for performing super-hydrophobic treatment on surface of metal copper

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101532159A (en) * 2009-03-10 2009-09-16 集美大学 Preparation method for metallic aluminum super-hydrophobic surface
CN101812680A (en) * 2010-04-30 2010-08-25 西北师范大学 Method for performing super-hydrophobic treatment on surface of metal copper

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102230169A (en) * 2011-06-13 2011-11-02 哈尔滨工业大学 Method for constructing super-hydrophobic membrane on surface of copper matrix
CN104138829A (en) * 2013-05-07 2014-11-12 刘也卓 Polyamino acid adjusted and controlled super-hydrophobic surface material constructed in a biomineralization way and the preparation method thereof
CN105926498A (en) * 2016-05-12 2016-09-07 江苏固格澜栅防护设施有限公司 Protective fence with surface being coated with drainage layers and manufacturing method
CN106048685A (en) * 2016-06-30 2016-10-26 上海电力学院 Preparation method of super-hydrophobic surface of aluminum alloy
CN106086835A (en) * 2016-07-27 2016-11-09 昆明理工大学 A kind of aluminum and the preparation method of superhydrophobic surface of aluminum alloy
CN107755228A (en) * 2017-09-22 2018-03-06 浙江海洋大学 It is a kind of that super-hydrophobic and oleophobic surface method is prepared on aluminium alloy matrix surface
CN107761085A (en) * 2017-10-31 2018-03-06 哈尔滨工业大学 A kind of method that one-step method prepares aluminium base super hydrophobic surface
FR3127438A1 (en) * 2021-09-27 2023-03-31 Alphi METHOD FOR REDUCING THE ADHERENCE OF FOREIGN BODIES TO THE SURFACE OF A METALLIC SUBSTRATE

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