CN103817059A - Preparation method for aluminum super-hydrophobic surface and product - Google Patents
Preparation method for aluminum super-hydrophobic surface and product Download PDFInfo
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- CN103817059A CN103817059A CN201210467681.3A CN201210467681A CN103817059A CN 103817059 A CN103817059 A CN 103817059A CN 201210467681 A CN201210467681 A CN 201210467681A CN 103817059 A CN103817059 A CN 103817059A
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Abstract
The invention provides a preparation method for an aluminum super-hydrophobic surface. The preparation method comprises the following steps of providing an aluminum base material; performing pretreatment on the surface of the aluminum base material; performing sand blasting on the surface of the aluminum base material after pretreatment is performed on the aluminum base material so as to form a plurality of micrometer holes in the surface of the aluminum base material; performing anodic oxidation treatment on the aluminum base material after sand blasting is performed on the aluminum base material so as to further form a plurality of nanometer holes in the inner walls of the micrometer holes formed by sand blasting; and uniformly spraying ethanol liquor of fluorosilane on the surface of the aluminum base material after anodic oxidation treatment is performed on the aluminum base material, and solidifying the ethanol liquor so as to form a fluorosilane decorating film on the surface of the aluminum base material. The invention also provides an aluminum product prepared by using the preparation method for the aluminum super-hydrophobic surface.
Description
Technical field
The present invention relates to a kind of preparation method and aluminum products obtained by this method of aluminum or aluminum alloy super hydrophobic surface.
Background technology
Research finds that the super hydrophobic surface that is greater than 150o with the contact angle of water has self-cleaning function, can also anticorrosion, waterproof and dustproof etc.In metallic substrates, super hydrophobic surface performance has a wide range of applications.It has been generally acknowledged that compound coarse structure and low surface free energy that micron combines with nanoscale are two necessary conditions that form super hydrophobic surface.The existing method that is used to form metallic aluminium surface roughness has two kinds of chemical method and electrochemical methods.Wherein chemical method normally obtains coarse structure with acid or caustic corrosion metallic aluminium, and chemical corrosion method is simple, can obtain fast micron order coarse structure, but difficult quality control, and be unfavorable for environmental protection.Described electrochemical method is generally anodizing, and anodizing easily forms uniform nanoscale coarse structure, but process time is longer, is unfavorable for large-scale production.
Summary of the invention
In view of this, the invention provides a kind of preparation method of simple and effective aluminium super hydrophobic surface.
In addition, the present invention also provides the aluminum products that a kind of said method makes.
A preparation method for aluminium super hydrophobic surface, comprises the steps:
Aluminium base is provided;
Pre-treatment is carried out in aluminium base surface;
Blasting treatment is carried out in aluminium base surface through pre-treatment, to form multiple micron-sized holes on aluminium base surface;
Aluminium base through blasting treatment is carried out to anodized, further to form multiple nano level holes on the micron order hole inwall forming in sandblast;
The ethanolic solution of silicon fluoride is evenly sprayed on through the aluminium base surface of anodized and is also solidified, to form silicon fluoride modified membrane on aluminium base surface.
A kind of aluminum products that made by the preparation method of above-mentioned aluminium super hydrophobic surface, comprise an aluminium base and be formed at the silicon fluoride cured film on this aluminium base surface, the surface of this aluminium base is covered by multiple micron-sized hole, on the inwall of described micron-sized hole, further form the nano level hole that multiple aperture sizes are less, this silicon fluoride modified membrane is formed at aluminium base and has the surface of this micron order hole and nanoscale hole, and this silicon fluoride modified membrane is to be solidify to form by the ethanolic solution of the silicon fluoride that is coated on aluminium base surface.
The preparation method of above-mentioned aluminium super hydrophobic surface forms the hole of the multiple microns of composite constructions that combine with nano-scale on the surface of aluminium base, make aluminium base surface there is the structure that is similar to lotus leaf surface, be conducive to hydrophobicly, simultaneously make aluminium base there is super-hydrophobic surface property in conjunction with the silicon fluoride modified membrane of this low-surface-energy.
Accompanying drawing explanation
Fig. 1 is scanning electron microscope (SEM) photograph and the contact angle measurement result figure of the aluminium super hydrophobic surface prepared of the embodiment of the present invention 1.
Fig. 2 is scanning electron microscope (SEM) photograph and the contact angle measurement result figure of the aluminium super hydrophobic surface prepared of the embodiment of the present invention 2.
Fig. 3 is scanning electron microscope (SEM) photograph and the contact angle measurement result figure of the aluminium super hydrophobic surface prepared of the embodiment of the present invention 3.
Fig. 4 is the generalized section of preferred embodiment aluminum products of the present invention.
Main element symbol description
| |
10 |
| |
11 |
| Micron |
112 |
| Nano |
1122 |
| Silicon fluoride modified |
13 |
The following specific embodiment further illustrates the present invention in connection with above-mentioned accompanying drawing.
The specific embodiment
The preparation method of aluminium super hydrophobic surface of the present invention, mainly comprises the steps:
Aluminium base is provided.This aluminium base can be aluminum or aluminum alloy.
Aluminium base is carried out to pre-treatment.This pre-treatment can comprise cleans aluminium base to remove surface and oil contaminant; Also can be included in after oil removing is cleaned electrobrightening is carried out in aluminium base surface; After also can being further included in electrobrightening, use NaOH solution to soak aluminium base to remove the oxide-film on aluminium base surface.This pre-treatment specifically can be: first use trichloro-ethylene solution removal aluminium base surface and oil contaminant, putting it into volume ratio is in the perchloric acid and phosphoric acid solution of 1:4-1:3 again, under the 0.8-1.2A function of current, soak 3-5min and carry out surperficial electrobrightening, the NaOH solution of putting into mass concentration and be 1%-3% after distilled water flushing soaks after 0.5-2min and cleans with distilled water, the oxide-film existing to remove aluminium base surface.
Blasting treatment is carried out in aluminium base surface through pre-treatment.This blasting treatment is that employing diameter is that 80-120 object shot-peening high velocity jet arrives aluminium base surface, and the aluminium base surface after blasting treatment forms micron-sized coarse structure, has deep mixed micron hole, and the aperture of micron hole is about 10-40 μ m.
Aluminium base through blasting treatment is carried out to anodized.Anodic oxidation electrolyte used can be sulfuric acid solution.Sulfuric acid concentration can be 0.15-0.3mol/L, and electrolyte temperature is 8 ℃-12 ℃, adopts constant current mode, and constant current is 1.5A, and voltage fluctuates within the scope of 10V-25V, and oxidization time is 3-10min.On the micron hole inwall forming in sandblast through anodized, further formed the nano aperture that multiple aperture sizes are less, the aperture of these nano apertures is approximately 200nm-400nm.So, form the hole of the multiple microns of composite constructions that combine with nano-scale on the surface of aluminium base, be called for short the compound hole of micron-nanometer, make aluminium base surface there is the structure that is similar to lotus leaf surface.
Low-surface-energy modifying and decorating is carried out in aluminium base surface through anodized.The ethanolic solution of silicon fluoride is evenly sprayed on to the aluminium base surface through anodized, then solidifies, to form the silicon fluoride modified membrane of low-surface-energy on aluminium base surface.Described silicon fluoride refers to fluorine-containing silane, as 17 fluorine decyl trimethoxy silanes, ten trifluoro octyltri-ethoxysilane.The ethanolic solution of described silicon fluoride can be silicon fluoride: water: the solution that 95% ethanol is mixed to get for 5:5:90 by volume.Described solidifying can adopt 80 ℃ of-120 ℃ of high-temperature baking 30-60min.
The above-mentioned compound hole of micron-nanometer forming on aluminium base surface through blasting treatment and anodized is conducive to hydrophobic, make aluminium base have super-hydrophobic surface property in conjunction with the silicon fluoride modified membrane of low-surface-energy, aluminium base surface is greater than 150o to the static contact angle of water simultaneously.
Refer to Fig. 4, the aluminum products 10 that made by the preparation method of above-mentioned aluminium super hydrophobic surface comprise an aluminium base 11 and are formed at the silicon fluoride modified membrane 13 on these aluminium base 11 surfaces.This aluminium base 11 can be aluminum or aluminum alloy.The surface of aluminium base 11 is only shown one in multiple microns of hole 112(Fig. 4) cover, the aperture of described micron hole 112 is about 10 μ m-40 μ m.On the inwall of described micron hole 112, further form in nano aperture 1122(Fig. 4 that multiple aperture sizes are less and only shown one), the aperture of these nano apertures is approximately 200nm-400nm.That is, the surface of this aluminium base 11 forms the hole of the multiple microns of composite constructions that combine with nano-scale, is called for short the compound hole of micron-nanometer, makes aluminium base 11 surfaces have the structure that is similar to lotus leaf surface.This silicon fluoride modified membrane 13 is formed at aluminium base 11 and has the surface of the compound hole of this micron-nanometer, and this silicon fluoride modified membrane 13 has the surface scan structure of aluminium base 11, be micron hole 112 and the nano aperture 1122 that silicon fluoride modified membrane 13 is not crammed aluminium base 11 surfaces substantially, aluminum products 10 are had and the essentially identical surface topography of its aluminium base 11.Silicon fluoride modified membrane 13 is to be solidify to form by the ethanolic solution of the silicon fluoride that is coated on aluminium base 11 surfaces.
The compound hole of micron-nanometer on aluminum products 10 surfaces is conducive to hydrophobic, makes aluminum products 10 have super-hydrophobic surface property in conjunction with the silicon fluoride modified membrane 13 of low-surface-energy simultaneously.
Below in conjunction with specific embodiment, the present invention is further elaborated.
Embodiment 1
1) first use trichloro-ethylene solution removal aluminium flake surface and oil contaminant, putting it into volume ratio is in the perchloric acid and phosphoric acid solution of 1:3 again, under the 0.8A function of current, soak 3min and carry out surperficial electrobrightening, after distilled water flushing, put into mass concentration and be 2% NaOH solution and soak after 1min and clean with distilled water, the oxide-film existing to remove aluminium base surface.
2) adopting diameter is that 100 object shot-peening high velocity jet are to aluminium base surface, at the deep mixed micron hole of aluminium base surface formation.
3) aluminium base is carried out to anodized.Anodic oxidation electrolyte used is sulfuric acid solution.Sulfuric acid concentration is 0.3mol/L, and electrolyte temperature is 8 ℃-12 ℃, and voltage is 10V-25V, and making current constant is 1.5A, and the processing time is 3min.Anodized has further formed the nano aperture that multiple aperture sizes are less on described micron hole inwall.
4) 17 fluorine decyl trimethoxy silanes, water, 95% ethanol are prepared to the rear aluminium base surface that is evenly sprayed on by 5:5:90, then at 120 ℃, toast 40min, on aluminium base, make super hydrophobic surface.
Aluminium super hydrophobic surface prepared by embodiment 1 and the contact angle of water are 152o.The scanning electron microscope (SEM) photograph of aluminium super hydrophobic surface prepared by embodiment 1 and contact angle measurement result figure join Fig. 1.
1) first use trichloro-ethylene solution removal aluminium flake surface and oil contaminant, putting it into volume ratio is in the perchloric acid and phosphoric acid solution of 1:4 again, under the 1A function of current, soak 3min and carry out surperficial electrobrightening, after distilled water flushing, put into mass concentration and be 2% NaOH solution and soak after 1min and clean with distilled water, the oxide-film existing to remove aluminium base surface.
2) adopting diameter is that 80 object shot-peening high velocity jet are to aluminium base surface, at the deep mixed micron hole of aluminium base surface formation.
3) aluminium base is carried out to anodized.Anodic oxidation electrolyte used is sulfuric acid solution.Sulfuric acid concentration is 0.3mol/L, and electrolyte temperature is 8 ℃-12 ℃, and voltage is 10V-25V, and the processing time is 3min.Anodized has further formed the nano aperture that multiple aperture sizes are less on described micron hole inwall.
4) 17 fluorine decyl trimethoxy silanes, water, 95% ethanol are prepared to the rear aluminium base surface that is evenly sprayed on by 5:5:90, then at 120 ℃, toast 40min, on aluminium base, make super hydrophobic surface.
Aluminium super hydrophobic surface prepared by embodiment 2 and the contact angle of water are 157o.The scanning electron microscope (SEM) photograph of aluminium super hydrophobic surface prepared by embodiment 2 and contact angle measurement result figure join Fig. 2.
Embodiment 3
1) first use trichloro-ethylene solution removal aluminium flake surface and oil contaminant, putting it into volume ratio is in the perchloric acid and phosphoric acid solution of 1:4 again, under the 1A function of current, soak 3min and carry out surperficial electrobrightening, after distilled water flushing, put into mass concentration and be 3% NaOH solution and soak after 0.5min and clean with distilled water, the oxide-film existing to remove aluminium base surface.
2) adopting diameter is that 120 object shot-peening high velocity jet are to aluminium base surface, at the deep mixed micron hole of aluminium base surface formation.
3) aluminium base is carried out to anodized.Anodic oxidation electrolyte used is sulfuric acid solution.Sulfuric acid concentration is 0.3mol/L, and electrolyte temperature is 8 ℃-12 ℃ (PLSCONFM or modifications), and voltage is 10V-25V, and the processing time is 3min.Anodized has further formed the nano aperture that multiple aperture sizes are less on described micron hole inwall.
4) 17 fluorine decyl trimethoxy silanes, water, 95% ethanol are prepared to the rear aluminium base surface that is evenly sprayed on by 5:5:90, then at 100 ℃, toast 40min, on aluminium base, make super hydrophobic surface.
Aluminium super hydrophobic surface prepared by embodiment 3 and the contact angle of water are 150o.The scanning electron microscope (SEM) photograph of aluminium super hydrophobic surface prepared by embodiment 3 and contact angle measurement result figure join Fig. 3.
Claims (9)
1. a preparation method for aluminium super hydrophobic surface, comprises the steps:
Aluminium base is provided;
Pre-treatment is carried out in aluminium base surface;
Blasting treatment is carried out in aluminium base surface through pre-treatment, to form multiple micron-sized holes on aluminium base surface;
Aluminium base through blasting treatment is carried out to anodized, further to form multiple nano level holes on the micron order hole inwall forming in sandblast;
The ethanolic solution of silicon fluoride is evenly sprayed on through the aluminium base surface of anodized and is also solidified, to form silicon fluoride modified membrane on aluminium base surface.
2. the preparation method of aluminium super hydrophobic surface as claimed in claim 1, is characterized in that: this aluminium base is aluminum or aluminum alloy.
3. the preparation method of aluminium super hydrophobic surface as claimed in claim 1, is characterized in that: this blasting treatment is that employing diameter is that 80-120 object shot-peening high velocity jet is to aluminium base surface.
4. the preparation method of aluminium super hydrophobic surface as claimed in claim 1, is characterized in that: the aperture of described micron order hole is 10 μ m-40 μ m.
5. the preparation method of aluminium super hydrophobic surface as claimed in claim 4, it is characterized in that: this anodized electrolyte used is sulfuric acid solution, sulfuric acid concentration is 0.15 mol/L-0.3mol/L, and electrolyte temperature is 8 ℃-12 ℃, voltage is 10V-25V, and the processing time is 3min-10min.
6. the preparation method of aluminium super hydrophobic surface as claimed in claim 1, is characterized in that: the ethanolic solution of described silicon fluoride is the solution that silicon fluoride, water, 95% ethanol are mixed to get for 5:5:90 by volume; Described curing referring at 80 ℃-120 ℃ toasted this aluminium base 30min-60min.
7. the preparation method of aluminium super hydrophobic surface as claimed in claim 1, is characterized in that: described silicon fluoride is 17 fluorine decyl trimethoxy silanes.
8. the preparation method of aluminium super hydrophobic surface as claimed in claim 1, is characterized in that: described silicon fluoride is ten trifluoro octyltri-ethoxysilane.
9. aluminum products of being prepared by the preparation method of the aluminium super hydrophobic surface described in above-mentioned 1-8 item any one.
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| CN201210467681.3A CN103817059B (en) | 2012-11-19 | 2012-11-19 | The preparation method and its product of aluminium super hydrophobic surface |
| TW101144388A TWI577837B (en) | 2012-11-19 | 2012-11-27 | Surface treatment method for aluminum or aluminum alloy and aluminum article made thereby |
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| CN201210467681.3A CN103817059B (en) | 2012-11-19 | 2012-11-19 | The preparation method and its product of aluminium super hydrophobic surface |
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| CN103817059B CN103817059B (en) | 2018-04-03 |
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Cited By (7)
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| CN104131322A (en) * | 2014-07-11 | 2014-11-05 | 华南理工大学 | Aluminum product surface super-hydrophobic film and making method thereof |
| CN104451814A (en) * | 2014-12-01 | 2015-03-25 | 中国科学院海洋研究所 | Protection method for preventing marine atmosphere from corroding metals |
| CN104726832A (en) * | 2013-12-20 | 2015-06-24 | 中国科学院兰州化学物理研究所 | Alumina self-cleaning film preparation method |
| CN105568345A (en) * | 2016-03-17 | 2016-05-11 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for metal plate anodizing |
| CN105761840A (en) * | 2016-05-27 | 2016-07-13 | 国网河南省电力公司周口供电公司 | Method for preparing superhydrophobic wire |
| CN109774111A (en) * | 2017-11-13 | 2019-05-21 | 洛阳尖端技术研究院 | A kind of hydrophobic plastic film and preparation method thereof |
| CN111315683A (en) * | 2017-10-09 | 2020-06-19 | 吉凯恩航空透明系统有限公司 | Hydrophobic coating of metals incorporating anodic and rare earth oxides and method of application thereof |
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| CN105401200B (en) * | 2015-12-10 | 2018-03-02 | 国网河北能源技术服务有限公司 | A kind of preparation method on Super-hydrophobic aluminium surface |
| US10907258B1 (en) | 2016-08-25 | 2021-02-02 | Arrowhead Center, Inc. | Surface modification of metals and alloys to alter wetting properties |
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| CN104451814A (en) * | 2014-12-01 | 2015-03-25 | 中国科学院海洋研究所 | Protection method for preventing marine atmosphere from corroding metals |
| CN105568345A (en) * | 2016-03-17 | 2016-05-11 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for metal plate anodizing |
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| CN111315683A (en) * | 2017-10-09 | 2020-06-19 | 吉凯恩航空透明系统有限公司 | Hydrophobic coating of metals incorporating anodic and rare earth oxides and method of application thereof |
| JP2021508004A (en) * | 2017-10-09 | 2021-02-25 | ジーケイエヌ エアロスペース トランスパランシー システムズ インコーポレイテッド | Hydrophobic coatings for metals, including anodized and rare earth oxides, and how to apply them |
| CN111315683B (en) * | 2017-10-09 | 2022-02-01 | 吉凯恩航空透明系统有限公司 | Hydrophobic coating of metals incorporating anodic and rare earth oxides and method of application thereof |
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| CN109774111A (en) * | 2017-11-13 | 2019-05-21 | 洛阳尖端技术研究院 | A kind of hydrophobic plastic film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI577837B (en) | 2017-04-11 |
| TW201420815A (en) | 2014-06-01 |
| CN103817059B (en) | 2018-04-03 |
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