CN103817059B - The preparation method and its product of aluminium super hydrophobic surface - Google Patents
The preparation method and its product of aluminium super hydrophobic surface Download PDFInfo
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- CN103817059B CN103817059B CN201210467681.3A CN201210467681A CN103817059B CN 103817059 B CN103817059 B CN 103817059B CN 201210467681 A CN201210467681 A CN 201210467681A CN 103817059 B CN103817059 B CN 103817059B
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- aluminium
- aluminium base
- super hydrophobic
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- hydrophobic surface
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Abstract
The present invention provides a kind of preparation method of aluminium super hydrophobic surface, comprises the following steps：Aluminium base is provided；Pre-treatment is carried out to aluminium base surface；Blasting treatment is carried out to the aluminium base surface through pre-treatment, to form multiple micron-sized holes on aluminium base surface；Anodized is carried out to the aluminium base through blasting treatment, further to form multiple nano level holes on the micron order hole inwall that is formed in sandblasting；The ethanol solution even application of silicon fluoride on the aluminium base surface through anodized and is solidified, to form silicon fluoride modified membrane on aluminium base surface.The present invention also provides aluminum products prepared by a kind of preparation method of above-mentioned aluminium super hydrophobic surface.
Description
Technical field
The present invention relates to a kind of preparation method of aluminum or aluminum alloy super hydrophobic surface and aluminum products obtained by this method.
Background technology
Research finds there is self-cleaning function with super hydrophobic surface of the contact angle of water more than 150o, moreover it is possible to anticorrosion, prevents
Water, dust-proof etc..Super hydrophobic surface performance has a wide range of applications in metallic substrates.It has been generally acknowledged that micron and nanoscale phase
With reference to compound coarse structure and low surface free energy be form super hydrophobic surface two necessary conditions.It is existing to be used for shape
Method into metallic aluminum surface coarse structure has two kinds of chemical method and electrochemical method.Wherein chemical method be typically with acid or
Caustic corrosion metallic aluminium obtains coarse structure, and chemical corrosion method is simple, can quickly obtain micron order coarse structure, but quality is difficult
With control, and it is unfavorable for environmental protection.The electrochemical method is generally anodizing, and anodizing easily forms uniform nanometer
Level coarse structure, but process time is longer, is unfavorable for mass producing.
The content of the invention
In view of this, the present invention provides a kind of preparation method of simple and effective aluminium super hydrophobic surface.
In addition, the present invention also provides aluminum products made from a kind of above method.
A kind of preparation method of aluminium super hydrophobic surface, comprises the following steps：
Aluminium base is provided；
Pre-treatment is carried out to aluminium base surface；
Blasting treatment is carried out to the aluminium base surface through pre-treatment, to form multiple micron-sized holes on aluminium base surface
Hole；
Anodized is carried out to the aluminium base through blasting treatment, it is enterprising with the micron order hole inwall formed in sandblasting
One step forms multiple nano level holes；
The ethanol solution even application of silicon fluoride on the aluminium base surface through anodized and is solidified, with aluminium base
Material surface forms silicon fluoride modified membrane.
A kind of aluminum products as made from the preparation method of above-mentioned aluminium super hydrophobic surface, including an aluminium base and it is formed at the aluminium
The silicon fluoride cured film of substrate surface, the surface of the aluminium base are covered by multiple micron-sized holes, the micron-sized hole
The smaller nano level hole of multiple aperture sizes is further defined on the inwall in hole, the silicon fluoride modified membrane is formed at aluminium base
Material has the surface of the micron order hole and nanoscale hole hole, and the silicon fluoride modified membrane is by the fluorine silicon coated on aluminium base surface
The ethanol solution of alkane is formed by curing.
The preparation method of above-mentioned aluminium super hydrophobic surface forms multiple microns on the surface of aluminium base and is combined with nano-scale
Composite construction hole, make aluminium base surface have similar to lotus leaf surface structure, be advantageous to it is hydrophobic, it is low in combination with this
The silicon fluoride modified membrane of surface energy makes aluminium base have super-hydrophobic surface property.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph and Contact-angle measurement result figure of aluminium super hydrophobic surface prepared by the embodiment of the present invention 1.
Fig. 2 is the scanning electron microscope (SEM) photograph and Contact-angle measurement result figure of aluminium super hydrophobic surface prepared by the embodiment of the present invention 2.
Fig. 3 is the scanning electron microscope (SEM) photograph and Contact-angle measurement result figure of aluminium super hydrophobic surface prepared by the embodiment of the present invention 3.
Fig. 4 is the diagrammatic cross-section of present pre-ferred embodiments aluminum products.
Main element symbol description
| Aluminum products | 10 |
| Aluminium base | 11 |
| Micron hole | 112 |
| Nano aperture | 1122 |
| Silicon fluoride modified membrane | 13 |
Following embodiment will combine above-mentioned accompanying drawing and further illustrate the present invention.
Embodiment
The preparation method of the aluminium super hydrophobic surface of the present invention, mainly comprises the following steps：
Aluminium base is provided.The aluminium base can be aluminum or aluminum alloy.
Pre-treatment is carried out to aluminium base.The pre-treatment may include to clean aluminium base to remove surface and oil contaminant；It may additionally include
Electrobrightening is carried out to aluminium base surface after oil removing cleaning；It can also further comprise soaking aluminium with NaOH solution after electrobrightening
Base material is to remove the oxide-film on aluminium base surface.The pre-treatment is concretely：First aluminium base table is removed using trichloro ethylene solution
Face greasy dirt, then volume ratio is put it into as 1：4-1:In 3 perchloric acid and phosphoric acid solution, soaked under the 0.8-1.2A functions of current
3-5min carries out surface electrobrightening, is put into after distilled water flushing in the NaOH solution that mass concentration is 1%-3% and soaks 0.5-
Cleaned after 2min with distilled water, to remove oxide-film existing for aluminium base surface.
Blasting treatment is carried out to the aluminium base surface through pre-treatment.The blasting treatment is the spray using a diameter of 80-120 mesh
Ball is ejected into aluminium base surface at a high speed, and the aluminium base surface after blasting treatment forms micron-sized coarse structure, the depth be present not
One micron hole, the aperture of micron hole is about 10-40 μm.
Anodized is carried out to the aluminium base through blasting treatment.Electrolyte used in anodic oxidation can be that sulfuric acid is molten
Liquid.Sulfuric acid concentration can be 0.15-0.3mol/L, and electrolyte temperature is 8 DEG C -12 DEG C, and using constant current mode, constant current is
1.5A, voltage fluctuate in the range of 10V-25V, oxidization time 3-10min.The micron formed through anodized in sandblasting
The smaller nano aperture of multiple aperture sizes is further defined on hole inwall, the aperture of these nano apertures is about
200nm-400nm.In this way, the hole for the composite construction that multiple microns are combined with nano-scale is formed on the surface of aluminium base,
The compound hole of abbreviation micron-nanometer, make aluminium base surface that there is the structure similar to lotus leaf surface.
Low-surface-energy modifying and decorating is carried out to the aluminium base surface through anodized.The ethanol solution of silicon fluoride is equal
The even aluminium base surface being sprayed on through anodized, then solidifies, to form the fluorine silicon of low-surface-energy on aluminium base surface
Alkane modified membrane.The silicon fluoride refers to fluorine-containing silane, such as 17 fluorine decyl trimethoxy silanes, ten trifluoro octyl group triethoxies
Silane.The ethanol solution of the silicon fluoride can be by silicon fluoride：Water：95% ethanol is 5 by volume：5：90 are mixed to get
Solution.The solidification can use 80 DEG C of -120 DEG C of high-temperature baking 30-60min.
It is above-mentioned to be advantageous to through blasting treatment and anodized in the compound hole of micron-nanometer that aluminium base surface is formed
It is hydrophobic, make aluminium base that there is super-hydrophobic surface property, i.e. aluminium base surface in combination with the silicon fluoride modified membrane of low-surface-energy
150o is more than to the static contact angle of water.
Referring to Fig. 4, the aluminum products 10 as made from the preparation method of above-mentioned aluminium super hydrophobic surface include an aluminium base 11 and
It is formed at the silicon fluoride modified membrane 13 on the surface of aluminium base 11.The aluminium base 11 can be aluminum or aluminum alloy.The surface of aluminium base 11
By multiple microns of holes 112（One is illustrate only in Fig. 4）Covered, the aperture of the micron hole 112 is about 10 μm of -40 μ
m.The smaller nano aperture 1122 of multiple aperture sizes is further defined on the inwall of the micron hole 112（Only show in Fig. 4
One is gone out）, the aperture of these nano apertures is about 200nm-400nm.That is, the surface of the aluminium base 11 forms multiple microns
With the hole of composite construction that nano-scale is combined, the compound hole of abbreviation micron-nanometer, there is the surface of aluminium base 11 similar
In the structure of lotus leaf surface.The silicon fluoride modified membrane 13, which is formed at aluminium base 11, has the surface of the compound hole of the micron-nanometer,
And the silicon fluoride modified membrane 13 has the surface scan structure of aluminium base 11, i.e. silicon fluoride modified membrane 13 does not cram aluminium base substantially
The micron hole 112 and nano aperture 1122 on 11 surfaces, make aluminum products 10 that there is the surface shape essentially identical with its aluminium base 11
Looks.Silicon fluoride modified membrane 13 is formed by curing by the ethanol solution of the silicon fluoride coated on the surface of aluminium base 11.
The compound hole of micron-nanometer on the surface of aluminum products 10 is advantageous to hydrophobic, is repaiied in combination with the silicon fluoride of low-surface-energy
Decorations film 13 makes aluminum products 10 have super-hydrophobic surface property.
With reference to specific embodiment, the present invention will be described in further detail.
Embodiment 1
1）Aluminum flake surface greasy dirt first is removed using trichloro ethylene solution, then puts it into volume ratio as 1：3 perchloric acid and
In phosphoric acid solution, 3min progress surface electrobrightenings are soaked under the 0.8A functions of current, it is dense that quality is put into after distilled water flushing
Spend in the NaOH solution for 2% after soaking 1min and cleaned with distilled water, to remove oxide-film existing for aluminium base surface.
2）Aluminium base surface is ejected at a high speed using the shot-peening of a diameter of 100 mesh, formed on aluminium base surface deep mixed
Micron hole.
3）Aluminium base is subjected to anodized.Electrolyte used in anodic oxidation is sulfuric acid solution.Sulfuric acid concentration is
0.3mol/L, electrolyte temperature are 8 DEG C -12 DEG C, voltage 10V-25V, and it is 1.5A, processing time 3min to make electric current constant.
Anodized further defines the smaller nano aperture of multiple aperture sizes on the micron hole inwall.
4) 17 fluorine decyl trimethoxy silanes, water, 95% ethanol are pressed 5：5：90 prepare rear even application in aluminium base
Surface, 40min is then toasted at 120 DEG C, super hydrophobic surface is made on aluminum substrates.
Aluminium super hydrophobic surface and the contact angle of water prepared by embodiment 1 is 152o.Aluminium super hydrophobic surface prepared by embodiment 1
Scanning electron microscope (SEM) photograph and Contact-angle measurement result figure join Fig. 1.
Embodiment 2
1）Aluminum flake surface greasy dirt first is removed using trichloro ethylene solution, then puts it into volume ratio as 1：4 perchloric acid and
In phosphoric acid solution, 3min progress surface electrobrightenings are soaked under the 1A functions of current, mass concentration is put into after distilled water flushing
To be cleaned in 2% NaOH solution after immersion 1min with distilled water, to remove oxide-film existing for aluminium base surface.
2）Aluminium base surface is ejected at a high speed using the shot-peening of a diameter of 80 mesh, formed on aluminium base surface deep mixed
Micron hole.
3）Aluminium base is subjected to anodized.Electrolyte used in anodic oxidation is sulfuric acid solution.Sulfuric acid concentration is
0.3mol/L, electrolyte temperature are 8 DEG C -12 DEG C, voltage 10V-25V, processing time 3min.Anodized is described
The smaller nano aperture of multiple aperture sizes is further defined on micron hole inwall.
4) 17 fluorine decyl trimethoxy silanes, water, 95% ethanol are pressed 5：5：90 prepare rear even application in aluminium base
Surface, 40min is then toasted at 120 DEG C, super hydrophobic surface is made on aluminum substrates.
Aluminium super hydrophobic surface and the contact angle of water prepared by embodiment 2 is 157o.Aluminium super hydrophobic surface prepared by embodiment 2
Scanning electron microscope (SEM) photograph and Contact-angle measurement result figure join Fig. 2.
Embodiment 3
1）Aluminum flake surface greasy dirt first is removed using trichloro ethylene solution, then puts it into volume ratio as 1：4 perchloric acid and
In phosphoric acid solution, 3min progress surface electrobrightenings are soaked under the 1A functions of current, mass concentration is put into after distilled water flushing
To be cleaned in 3% NaOH solution after immersion 0.5min with distilled water, to remove oxide-film existing for aluminium base surface.
2）Aluminium base surface is ejected at a high speed using the shot-peening of a diameter of 120 mesh, formed on aluminium base surface deep mixed
Micron hole.
3）Aluminium base is subjected to anodized.Electrolyte used in anodic oxidation is sulfuric acid solution.Sulfuric acid concentration is
0.3mol/L, electrolyte temperature are 8 DEG C -12 DEG C（PLSCONFM or modification）, voltage 10V-25V, processing time 3min.Anode
Oxidation processes further define the smaller nano aperture of multiple aperture sizes on the micron hole inwall.
4) 17 fluorine decyl trimethoxy silanes, water, 95% ethanol are pressed 5：5：90 prepare rear even application in aluminium base
Surface, 40min is then toasted at 100 DEG C, super hydrophobic surface is made on aluminum substrates.
Aluminium super hydrophobic surface and the contact angle of water prepared by embodiment 3 is 150o.Aluminium super hydrophobic surface prepared by embodiment 3
Scanning electron microscope (SEM) photograph and Contact-angle measurement result figure join Fig. 3.
Claims (9)
1. a kind of preparation method of aluminium super hydrophobic surface, comprises the following steps：
Aluminium base is provided；
Pre-treatment is carried out to aluminium base surface；
Blasting treatment is carried out to the aluminium base surface through pre-treatment, to form multiple micron-sized holes on aluminium base surface；
Anodized is carried out to the aluminium base through blasting treatment, with the micron order hole inwall that is formed in sandblasting further
Multiple nano level holes are formed, make aluminium base surface that there is the structure similar to lotus leaf surface；
The ethanol solution even application of silicon fluoride on the aluminium base surface through anodized and is solidified, with aluminium base table
Face forms silicon fluoride modified membrane, and it by silicon fluoride, water, 95% ethanol is 5 by volume that the ethanol solution of the silicon fluoride, which is,：5：
90 solution being mixed to get.
2. the preparation method of aluminium super hydrophobic surface as claimed in claim 1, it is characterised in that：The aluminium base is that aluminium or aluminium close
Gold.
3. the preparation method of aluminium super hydrophobic surface as claimed in claim 1, it is characterised in that：The blasting treatment is to use diameter
Aluminium base surface is ejected into for the shot-peening of 80-120 mesh at a high speed.
4. the preparation method of aluminium super hydrophobic surface as claimed in claim 1, it is characterised in that：The aperture of the micron order hole
For 10 μm -40 μm.
5. the preparation method of aluminium super hydrophobic surface as claimed in claim 4, it is characterised in that：The anodized institute electricity consumption
Solution liquid is sulfuric acid solution, and sulfuric acid concentration 0.15mol/L-0.3mol/L, electrolyte temperature is 8 DEG C -12 DEG C, voltage 10V-
25V, processing time 3min-10min.
6. the preparation method of aluminium super hydrophobic surface as claimed in claim 1, it is characterised in that：It is described solidification refer to 80 DEG C-
Aluminium base 30min-60min is toasted at 120 DEG C.
7. the preparation method of aluminium super hydrophobic surface as claimed in claim 1, it is characterised in that：The silicon fluoride was the 17 fluorine last of the ten Heavenly stems
Base trimethoxy silane.
8. the preparation method of aluminium super hydrophobic surface as claimed in claim 1, it is characterised in that：The silicon fluoride is that ten trifluoros are pungent
Ethyl triethoxy silicane alkane.
9. aluminum products prepared by a kind of preparation method of aluminium super hydrophobic surface as described in above-mentioned 1-8 items any one.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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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| CN103817059A CN103817059A (en) | 2014-05-28 |
| CN103817059B true CN103817059B (en) | 2018-04-03 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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 |
| 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 |
| 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 |
| CN105761840B (en) * | 2016-05-27 | 2017-11-03 | 国家电网公司 | A kind of preparation method of super-hydrophobic wire |
| US10907258B1 (en) | 2016-08-25 | 2021-02-02 | Arrowhead Center, Inc. | Surface modification of metals and alloys to alter wetting properties |
| 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 |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2005343016A (en) * | 2004-06-03 | 2005-12-15 | Nippon Sheet Glass Co Ltd | Water super-repellent film-coated article |
| JP5006394B2 (en) * | 2006-07-05 | 2012-08-22 | ポステック アカデミー−インダストリー ファンデーション | Extremely hydrophobic surface processing method |
| JP2008104936A (en) * | 2006-10-25 | 2008-05-08 | National Institute Of Advanced Industrial & Technology | Water superrepellent aluminum foil and method of manufacturing the same |
| CN100558472C (en) * | 2007-01-12 | 2009-11-11 | 华南理工大学 | The preparation method of aluminium and aluminium alloy super hydrophobic surface |
| CN101423945B (en) * | 2007-11-02 | 2010-10-27 | 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 |
| CN101270260B (en) * | 2008-01-28 | 2010-12-15 | 南京工业大学 | Ultra-hydrophobic surface coating material and preparation method thereof |
| CN101429672A (en) * | 2008-11-19 | 2009-05-13 | 东南大学 | Surface treating method for sea water corrosion-resistant metal aluminum or aluminum alloy |
| CN101417278B (en) * | 2008-11-28 | 2011-07-06 | 江苏大学 | Ultra hydrophobic surface preparation method |
| 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 |
| CN102286768B (en) * | 2011-09-07 | 2013-02-27 | 大连理工大学 | Process method for preparing superhydrophobic magnesium alloy surfaces |
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- 2012-11-19 CN CN201210467681.3A patent/CN103817059B/en not_active Expired - Fee Related
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| CN103817059A (en) | 2014-05-28 |
| TWI577837B (en) | 2017-04-11 |
| TW201420815A (en) | 2014-06-01 |
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