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
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- electrolytic etching
- aluminum metal
- metallic aluminium
- etching
- hydrophobic film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- ing And Chemical Polishing (AREA)
Abstract
The invention relates to the preparation technology of super-hydrophobic surfaces, in particular to a method for preparing a super-hydrophobic film on an aluminum metal surface by using electrolytic etching. The method comprises the following steps of: removing oil from aluminum metal matrix for 1 to 10 minutes at room temperature in 0.1 to 2mol/L NaOH solution, cleaning the aluminum metal matrix by using deionized water and airing the aluminum metal matrix for later use; performing electrolytic etching in a constant current mode by using the aluminum metal matrix after oil removal as an anode and using a platinum electrode as a cathode, wherein the temperature of the electrolytic etching solution is 15 to 85 DEG C, the etching current density is 0.1 to 2A/cm<2> and the electrolytic etching time is 10 seconds to 5 minutes; and soaking the electrolytic etched aluminum metal matrix sample into ethanol solution containing fatty acid to perform modification for 5 minutes to 1 hour, and drying the sample to realize coverage of the super-hydrophobic film on the aluminum metal surface. The method has the advantages of simple operation, safety, short processing time and good repeatability. The prepared super-hydrophobic surface has broad application prospect in the fields of nondestructive liquid delivery, self-cleaning, water proofing, corrosion resistance and the like.
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)
1. method of utilizing electrolytic etching at metallic aluminium surface preparation super hydrophobic film is characterized in that:
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.
2. by the described method of utilizing electrolytic etching at metallic aluminium surface preparation super hydrophobic film of claim 1, it is characterized in that: 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.
3. by the described method of utilizing electrolytic etching at metallic aluminium surface preparation super hydrophobic film of claim 1, it is characterized in that: 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010268192 CN101967673A (en) | 2010-08-27 | 2010-08-27 | Method for preparing super-hydrophobic film on aluminum metal surface by using electrolytic etching |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010268192 CN101967673A (en) | 2010-08-27 | 2010-08-27 | Method for preparing super-hydrophobic film on aluminum metal surface by using electrolytic etching |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101967673A true CN101967673A (en) | 2011-02-09 |
Family
ID=43546891
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010268192 Pending CN101967673A (en) | 2010-08-27 | 2010-08-27 | Method for preparing super-hydrophobic film on aluminum metal surface by using electrolytic etching |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101967673A (en) |
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 | Preparation method and system of wear-resistant ultra-hydrophobic micro-nano composite structure on surface of aluminum alloy |
| CN112111780A (en) * | 2020-09-11 | 2020-12-22 | 山东大学 | Method for improving surface hydrophobic property and corrosion resistance of high-strength aluminum alloy, aluminum alloy material and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1639392A (en) * | 2002-01-25 | 2005-07-13 | 昭和电工株式会社 | Composite metal material and production method therefor, etched metal material and production method therefor, and electrolytic capacitor |
| WO2008151495A1 (en) * | 2007-06-15 | 2008-12-18 | Beijing University Of Chemical Technology | Super-hydrophobic double-layered-hydroxides thin film and the method for making the same |
| CN101423945A (en) * | 2007-11-02 | 2009-05-06 | 中国科学院宁波材料技术与工程研究所 | Method for preparing light metal super-hydrophobic surface |
| CN101532159A (en) * | 2009-03-10 | 2009-09-16 | 集美大学 | Preparation method for metallic aluminum super-hydrophobic surface |
| CN101970705A (en) * | 2008-03-14 | 2011-02-09 | 浦项工科大学校产学协力团 | Method for fabricating 3d structure having hydrophobic surface by dipping method |
-
2010
- 2010-08-27 CN CN 201010268192 patent/CN101967673A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1639392A (en) * | 2002-01-25 | 2005-07-13 | 昭和电工株式会社 | Composite metal material and production method therefor, etched metal material and production method therefor, and electrolytic capacitor |
| WO2008151495A1 (en) * | 2007-06-15 | 2008-12-18 | Beijing University Of Chemical Technology | Super-hydrophobic double-layered-hydroxides thin film and the method for making the same |
| CN101423945A (en) * | 2007-11-02 | 2009-05-06 | 中国科学院宁波材料技术与工程研究所 | Method for preparing light metal super-hydrophobic surface |
| CN101970705A (en) * | 2008-03-14 | 2011-02-09 | 浦项工科大学校产学协力团 | Method for fabricating 3d structure having hydrophobic surface by dipping method |
| CN101532159A (en) * | 2009-03-10 | 2009-09-16 | 集美大学 | Preparation method for metallic aluminum super-hydrophobic surface |
Non-Patent Citations (2)
| Title |
|---|
| 《无机化学学报》 20081130 刘通等 超疏水表面改善铝基材料的抗海水腐蚀性能 1859-1863 1-3 第24卷, 第11期 2 * |
| 《高等学校化学学报》 20091130 张芹等 化学/电化学腐蚀法快速制备超疏水金属铝 2210-2214 1-3 第30卷, 第11期 2 * |
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 | Preparation method and system of wear-resistant ultra-hydrophobic micro-nano composite structure on surface of aluminum alloy |
| CN110938860B (en) * | 2019-12-23 | 2021-08-20 | 西安科技大学 | Preparation method and system of wear-resistant ultra-hydrophobic micro-nano composite structure on surface of aluminum alloy |
| CN112111780A (en) * | 2020-09-11 | 2020-12-22 | 山东大学 | Method for improving surface hydrophobic property 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 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103276429B (en) | The preparation method of the super hydrophobic surface of aluminum or aluminum alloy | |
| JP6004181B2 (en) | Anodized film and method for producing the same | |
| Zhang et al. | Study on a novel manufacturing process of membrane electrode assemblies for solid polymer electrolyte water electrolysis | |
| CN101967673A (en) | Method for preparing super-hydrophobic film on aluminum metal surface by using electrolytic etching | |
| CN102304741A (en) | Anodic oxidation method for preparing aluminum-based super-hydrophobic film | |
| CN102618913B (en) | Method for preparing titanium or titanium alloy super-hydrophobic surface | |
| JP2008138288A6 (en) | Surface treatment method of aluminum material before painting | |
| CN110359044A (en) | A kind of preparation method of steel matrix surface ultra-hydrophobic water film | |
| CN103966643A (en) | Method for preparing titanium-alloy super-hydrophobic surface with low roughness | |
| CN105887156B (en) | Preparation method of highly ordered porous anodic aluminum oxide film | |
| CN101967663A (en) | Method for preparing super-hydrophobic alloy film on surface of metal matrix | |
| CN105088314A (en) | Method for constructing super-hydrophobic membrane layer on surface of micro-arc oxidation ceramic layer of magnesium alloy | |
| CN105621540A (en) | Method for degrading antibiotic pharmaceutical wastewater | |
| CN102965720A (en) | Method for preparing aluminum-base super-amphiphobic surface | |
| CN108677221A (en) | A kind of titanium-based β-MnO2Composite coating anode and preparation method thereof | |
| CN105297073A (en) | Preparation method of copper-based titanium black electrode plate | |
| CN105937037B (en) | Application of the anti-corrosion electrode in the selectivity of Organic electro-synthesis reaction and yield is improved | |
| CN106044963A (en) | Preparation method titanium-based polyaniline-doped lead dioxide composite electrode material | |
| CN109518221A (en) | A kind of surface is rich in the gradient distribution Ni―Ti anode and preparation method thereof of iridium dioxide | |
| KR101668542B1 (en) | Metal material surface treatment method, and metal material | |
| CN102383162A (en) | Method for preparing super-hydrophobic aluminum alloy with low carbon, energy saving and environmental protection | |
| CN107937920B (en) | For ocean platform cathodic protection reparation oxide anode material and preparation process | |
| CN104451819A (en) | Method for constructing superhydrophobic aluminum surface with high stability | |
| CN107317043B (en) | Preparation method of graphene/tin dioxide sandwich structure film on surface of aluminum alloy bipolar plate | |
| CN103147112A (en) | Electrolyte as well as application and method for preparing micro-arc oxidation film on zirconium alloy cladding of nuclear fuel rod by an electrolyte |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20110209 |