CN101967673A - Method for preparing super-hydrophobic film on aluminum metal surface by using electrolytic etching - Google Patents
Method for preparing super-hydrophobic film on aluminum metal surface by using electrolytic etching Download PDFInfo
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- CN101967673A CN101967673A CN 201010268192 CN201010268192A CN101967673A CN 101967673 A CN101967673 A CN 101967673A CN 201010268192 CN201010268192 CN 201010268192 CN 201010268192 A CN201010268192 A CN 201010268192A CN 101967673 A CN101967673 A CN 101967673A
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- electrolytic etching
- metal aluminum
- etching
- electrolytic
- aluminum substrate
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000000866 electrolytic etching Methods 0.000 title claims abstract description 37
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 17
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 46
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000005530 etching Methods 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 8
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 6
- 239000000194 fatty acid Substances 0.000 claims abstract description 6
- 229930195729 fatty acid Natural products 0.000 claims abstract description 6
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract 11
- 239000002184 metal Substances 0.000 claims abstract 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract 6
- 239000000758 substrate Substances 0.000 claims abstract 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 13
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 claims description 2
- 238000005238 degreasing Methods 0.000 claims 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000004140 cleaning Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000004411 aluminium Substances 0.000 description 34
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002848 electrochemical method Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000001311 chemical methods and process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 244000101724 Apium graveolens Dulce Group Species 0.000 description 1
- 235000015849 Apium graveolens Dulce Group Nutrition 0.000 description 1
- 235000010591 Appio Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及超疏水表面的制备技术，具体是一种利用电解刻蚀在金属铝表面制备超疏水膜的方法。将金属铝基体在室温0.1～2mol/L NaOH溶液中除油1～10min后，用去离子水清洗晾干，备用；将除油后的金属铝基体作为阳极，铂电极为阴极，以恒电流模式进行电解刻蚀，电解刻蚀液温度为15～85℃，刻蚀电流密度为0.1～2A/cm2，电解刻蚀时间为10s～5min；将电解刻蚀后的金属铝基体试样浸入含脂肪酸的乙醇溶液中修饰5min～1h后，干燥，即实现金属铝表面覆超疏水膜。本法操作简单，安全，加工时间短，重复性好。所制得超疏水表面在液体无损失输送、自清洁、防水、耐腐蚀等领域有广泛的应用前景。The invention relates to a preparation technology of a super-hydrophobic surface, in particular to a method for preparing a super-hydrophobic film on the surface of metal aluminum by electrolytic etching. Degrease the metal aluminum substrate in a 0.1-2mol/L NaOH solution at room temperature for 1-10 minutes, wash and dry it with deionized water, and set aside; use the degreased metal aluminum substrate as the anode, and the platinum electrode as the cathode, and use a constant current Electrolytic etching is carried out in the electrolytic etching mode, the temperature of the electrolytic etching solution is 15-85°C, the etching current density is 0.1-2A/cm 2 , and the electrolytic etching time is 10s-5min; the metal aluminum substrate sample after electrolytic etching is immersed in After being modified in ethanol solution containing fatty acid for 5 minutes to 1 hour, it is dried to realize super-hydrophobic film on the surface of metal aluminum. This method is simple, safe, short processing time and good repeatability. The prepared superhydrophobic surface has broad application prospects in the fields of liquid loss-free transportation, self-cleaning, waterproof, and corrosion resistance.
Description
Technical field
The present invention relates to the technology of preparing of super hydrophobic surface, specifically is a kind of method of utilizing electrolytic etching at metallic aluminium surface preparation super hydrophobic film.
Background technology
Since the scientist of the nineties in last century Japan and Germany delivers the research work of fractal surface and plant surface, caused worldwide very big concern greater than 150 ° super hydrophobic surface with the contact angle of water.Discover that super hydrophobic surface not only has self-cleaning function, but also have anti-conduction of current, protection against corrosion, waterproof, function such as antifog, anti-pollution.Therefore, it is with a wide range of applications in fields such as liquid conveying, trace analyses.
The coarse structure of micro-/ nano yardstick and low surface free energy are two prerequisites on constructing super-drainage surface, because on plane surface, be merely able at most contact angle is increased to about 119 ° by reducing surface free energy, therefore, the structure of the coarse structure of micro-/ nano yardstick is the key of artificial preparation super hydrophobic surface.Reported that at present the method that is used to construct the fine coarse structure in metallic aluminium surface mainly comprises two kinds of chemical process and electrochemical methods.Compare with chemical process, electrochemical method has favorable reproducibility, is not subjected to the advantages such as restriction of material lattice.At present, the electrochemical method that is adopted in the report is an anode oxidation method, for example people (Shibuichi S such as Shibuichi S, Yamamoto T, Onda T, et al.Journal of Colid andinterface science, 1998,208:287) at acid solution continuous current 10mA/cm
2Handle metallic aluminium 3h under the condition, the aluminium surface generates the aluminum oxide rete of coarse structure, can obtain super hydrophobic surface after the low surface energy material is modified.People such as Zhang Qin (Zhang Qin; Zhu Yuanrong; Huang Zhiyong. SCI; 2009; 30 (11): 2210-2214. opens celery, Zhu Yuanrong. a kind of preparation method of metallic aluminum super-hydrophobic surface [P]. and Chinese patent, application number: 200910111202.2.) developed chemical corrosion/anodic oxidation combining method; to the aluminium sample anodic oxidation 20min after the chemical corrosion, after the modification promptly at aluminium surface preparation super hydrophobic surface.But in above-mentioned two kinds of methods, anodizing time is all longer, and complicated operation, and this just limits the application of this method in industry.
Summary of the invention
The purpose of this invention is to provide a kind of quick, simple, the cheap method of electrolytic etching of utilizing at metallic aluminium surface preparation super hydrophobic film.
For achieving the above object, the technical solution used in the present invention is:
A kind of method of utilizing electrolytic etching at metallic aluminium surface preparation super hydrophobic film:
1) alkali cleaning oil removing: the metallic aluminium matrix behind oil removing 1～10min, is dried with washed with de-ionized water in room temperature 0.1～2mol/L NaOH solution, standby;
2) electrolytic etching: as anode, platinum electrode is a negative electrode, carries out electrolytic etching with constant current mode with the metallic aluminium matrix after the oil removing, and the electrolytic etching liquid temp is 15～85 ℃, and the etching current density is 0.1～2A/cm
2, the electrolytic etching time is 10s～5min;
3) low finishing: the metallic aluminium matrix sample behind the electrolytic etching is immersed modify 5min～1h in the ethanolic soln of fatty acids after, drying realizes that promptly the metallic aluminium surface covers super hydrophobic film.
The electrolytic solution of described electrolytic etching is the acidic aqueous solution of chloride ion-containing, and wherein chlorine ion concentration is 0.5～4mol/L, pH＜5.The ethanolic soln of described fatty acids, wherein lipid acid is CH
3(CH
2)
nCOOH, n=10～16, concentration is 10-2～1mol/L.
The advantage that the present invention had: the present invention adopts the method for electrolytic etching in metallic aluminium surface construction micro-rough structure, continue with after modifying the low surface energy material, obtains the super hydrophobic film surface.The present invention adopts the method for electrolytic etching to make metallic aluminium generation spot corrosion, forms coarse microtexture, reaches super-hydrophobic state after the low surface energy material is modified, and the treatment time is shortened greatly.
Description of drawings
Fig. 1 prepares the contact angle measuring result figure of super hydrophobic surface at the metallic aluminium matrix for the embodiment of the invention 1.
Fig. 2 prepares the contact angle measuring result figure of super hydrophobic surface at the metallic aluminium matrix for the embodiment of the invention 2.
Embodiment
The invention will be further described below by embodiment, and its purpose only is better to understand content of the present invention, and unrestricted protection scope of the present invention:
Embodiment 1
(1) metallic aluminium behind the oil removing 10min, is dried with washed with de-ionized water in immersing room temperature 1mol/L NaOH solution, standby.
(2) with the metallic aluminium after the oil removing as anode, platinum electrode is a negative electrode, in the 1mol/L hydrochloric acid soln with constant current density 0.5A/cm
2Carry out electrolytic etching, wherein, etching temperature is 25 ℃, and etching time is 200s.
(3) the aluminium sample behind the electrolytic etching is immersed modify 5min in the ethanolic soln contain the 0.1mol/L TETRADECONIC ACID after, drying can obtain super hydrophobic surface.Water droplet is 148.2 ± 3 ° (referring to Fig. 1) at the aluminium surface contact angle.
Embodiment 2
(1) metallic aluminium behind the oil removing 10min, is dried with washed with de-ionized water in immersing room temperature 1mol/L NaOH solution, standby.
(2) with the metallic aluminium after the oil removing as anode, platinum electrode is a negative electrode, at 2mol/L HCl+0.5mol/L H
2SO
4In the solution with constant current density 0.5A/cm
2Carry out electrolytic etching, wherein, etching temperature is 25 ℃, and etching time is 60s.
(3) the aluminium sample behind the electrolytic etching is immersed modify 5min in the ethanolic soln contain the 0.1mol/L TETRADECONIC ACID after, drying can obtain super hydrophobic surface.Water droplet is 148.7 ± 3 ° (referring to Fig. 2) at the aluminium surface contact angle.
Embodiment 3
(1) metallic aluminium behind the oil removing 5min, is dried with washed with de-ionized water in immersing room temperature 2mol/L NaOH solution, standby.
(2) with the metallic aluminium after the oil removing as anode, platinum electrode is a negative electrode, in the 2mol/L hydrochloric acid soln with constant current density 1A/cm
2Carry out electrolytic etching, wherein, etching temperature is 15 ℃, and etching time is 300s.
(3) immersion of the aluminium sample behind the electrolytic etching is contained 1mol/L CH
3(CH
2)
nCOOH, behind the modification 20min, drying can obtain super hydrophobic surface in the ethanolic soln of n=10.
Embodiment 4
(1) metallic aluminium behind the oil removing 8min, is dried with washed with de-ionized water in immersing room temperature 0.1mol/L NaOH solution, standby.
(2) with the metallic aluminium after the oil removing as anode, platinum electrode is a negative electrode, in the 4mol/L hydrochloric acid soln with constant current density 1.5A/cm
2Carry out electrolytic etching, wherein, etching temperature is 40 ℃, and etching time is 100s.
(3) immersion of the aluminium sample behind the electrolytic etching is contained 0.8mol/L CH
3(CH
2)
nCOOH, behind the modification 40min, drying can obtain super hydrophobic surface in the ethanolic soln of n=16.
Embodiment 5
(1) metallic aluminium behind the oil removing 2min, is dried with washed with de-ionized water in immersing room temperature 0.5mol/L NaOH solution, standby.
(2) with the metallic aluminium after the oil removing as anode, platinum electrode is a negative electrode, in the 3mol/L hydrochloric acid soln with constant current density 2A/cm
2Carry out electrolytic etching, wherein, etching temperature is 80 ℃, and etching time is 40s.
(3) immersion of the aluminium sample behind the electrolytic etching is contained 0.5mol/L CH
3(CH
2)
nCOOH, behind the modification 10min, drying can obtain super hydrophobic surface in the ethanolic soln of n=13.
Claims (3)
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| CN 201010268192 CN101967673A (en) | 2010-08-27 | 2010-08-27 | Method for preparing super-hydrophobic film on aluminum metal surface by using electrolytic etching |
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| CN 201010268192 CN101967673A (en) | 2010-08-27 | 2010-08-27 | Method for preparing super-hydrophobic film on aluminum metal surface by using electrolytic etching |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104425654A (en) * | 2013-08-28 | 2015-03-18 | 上海晶玺电子科技有限公司 | Etching method |
| CN104532337A (en) * | 2015-01-09 | 2015-04-22 | 中国矿业大学 | Electro erosion method for rapidly preparing iron base super-hydrophobic surface in large area |
| RU2567776C1 (en) * | 2014-10-24 | 2015-11-10 | Федеральное государственное бюджетное учреждение науки Институт химии Дальневосточного отделения Российской академии наук (ИХ ДВО РАН) | Method for producing protective superhydrophobic coatings on aluminium alloys |
| CN110938860A (en) * | 2019-12-23 | 2020-03-31 | 西安科技大学 | A kind of preparation method and system of wear-resistant super-sparse micro-nano composite structure on aluminum alloy surface |
| CN112111780A (en) * | 2020-09-11 | 2020-12-22 | 山东大学 | A method for improving the surface hydrophobicity and corrosion resistance of high-strength aluminum alloy, aluminum alloy material and application |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104425654A (en) * | 2013-08-28 | 2015-03-18 | 上海晶玺电子科技有限公司 | Etching method |
| CN104425654B (en) * | 2013-08-28 | 2017-08-25 | 上海晶玺电子科技有限公司 | Engraving method |
| RU2567776C1 (en) * | 2014-10-24 | 2015-11-10 | Федеральное государственное бюджетное учреждение науки Институт химии Дальневосточного отделения Российской академии наук (ИХ ДВО РАН) | Method for producing protective superhydrophobic coatings on aluminium alloys |
| CN104532337A (en) * | 2015-01-09 | 2015-04-22 | 中国矿业大学 | Electro erosion method for rapidly preparing iron base super-hydrophobic surface in large area |
| CN110938860A (en) * | 2019-12-23 | 2020-03-31 | 西安科技大学 | A kind of preparation method and system of wear-resistant super-sparse micro-nano composite structure on aluminum alloy surface |
| CN110938860B (en) * | 2019-12-23 | 2021-08-20 | 西安科技大学 | A kind of preparation method and system of wear-resistant super-sparse micro-nano composite structure on aluminum alloy surface |
| CN112111780A (en) * | 2020-09-11 | 2020-12-22 | 山东大学 | A method for improving the surface hydrophobicity and corrosion resistance of high-strength aluminum alloy, aluminum alloy material and application |
| CN112111780B (en) * | 2020-09-11 | 2021-10-12 | 山东大学 | Method for improving surface hydrophobic property and corrosion resistance of high-strength aluminum alloy, aluminum alloy material and application |
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Open date: 20110209 |