CN101817500A - Hydrophilic material surface super hydrophobic functional shift micro structure design method - Google Patents
Hydrophilic material surface super hydrophobic functional shift micro structure design method Download PDFInfo
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- CN101817500A CN101817500A CN201010132449A CN201010132449A CN101817500A CN 101817500 A CN101817500 A CN 101817500A CN 201010132449 A CN201010132449 A CN 201010132449A CN 201010132449 A CN201010132449 A CN 201010132449A CN 101817500 A CN101817500 A CN 101817500A
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Abstract
The invention provides a hydrophilic material super hydrophobic surface micro nano structure design method, relating to the micro nano structure function surface design preparation technical field. Protuberance ratio of micro structure is calculated according to super hydrophobic contact angle requirement; and meanwhile maximum period of micro structure is determined according to use condition; and finally, contact status of liquid and micro structure surface is verified according to the designed micro structure and structure parameter. The invention realizes surface super hydrophobic performance by controlling the form of micro structure without carrying out coating treatment on the surface, thus the super hydrophobic performance of micro structure surface can not be influenced when the structure form of the interior of micro structure is not changed even if the material is partially abrased, super hydrophobic surface has stable performance, and the performance is effective for long term.
Description
Technical field
The present invention relates to micro-nano structure function surface design preparing technical field, refer in particular to a kind of new construction that designs to realize the surface structure design method of water wetted material surface super hydrophobic performance, it is applicable to that having the self-cleaning anti-pollution requirement and requiring surfacing is the superhydrophobic surface structure design analysis of non-coating material situation.
Background technology
Super hydrophobic surface is to instigate water droplet to present the surface of big contact angle (θ＞150 °) from the teeth outwards, because it has the self-cleaning anti-pollution effect, is with a wide range of applications in industry.At present, the technology of the hydrophobic material surface being carried out modifying super hydrophobicity is applied in the engineering gradually, the transformation that part super hydrophobic surface modification technology is used to hold the preparation of food container and is used for the body of wall outward appearance, because this modification technology has adopted the method for polymeric coating layer, environment is caused certain pollution, there is potential harm in human body.Therefore, in engineering was used, it was significant to develop the without pollution super hydrophobic surface with self-cleaning anti-pollution.
General super hydrophobic surface is based on all that two kinds of theories prepare, and wherein a kind of is the Wenzel theory, and a kind of is the Cassie theory.1936, the Wenzel theory that Wenzel proposes thought that water droplet contacts closely with groove part on rough surface, according to analyzing and the definition of Young contact angle obtains the contact angle that liquid is in the Wenzel state on the surface:
cosθ
W＝rcosθ (1)
θ wherein
WBe drop is in the Wenzel state on micro-structure surface contact angle, r is the roughness of micro-structure surface, refers to the ratio of true area with the floor projection on surface on surface, and its value is greater than 1, and θ is the intrinsic contact angle that forms the material of micro-structure surface.According to above formula, as can be seen, the contact angle of water droplet on hydrophobic material (θ＞90 °) micro-structure surface is bigger than the contact angle on the smooth surface in same material, and the contact angle of water droplet on water-wetted surface (θ＜90 °) micro-structure surface is littler than the contact angle at the smooth surface of same material.This means,, adopt water wetted material can not prepare super hydrophobic surface (θ according to the Wenzel theory
W＞150 °).Nineteen forty-four, Cassie and Baxer have proposed the Cassie theory, think the compound interface that exists solid liquid interface and gas-liquid interface to constitute when liquid contacts with micro-structure surface on the interface, liquid contacts with gas at the groove position on surface, contacts with solid in the protruding part.According to analysis, the liquid-drop contact angle computing formula that obtains being in the Cassie state is:
cosθ
C＝f(cosθ+1)-1 (2)
θ wherein
CExpress liquid is in the contact angle of Cassie contact condition on super hydrophobic surface, f represents the ratio ratio of the projected area of liquid-surface contact portion (the liquid-solid contact area with) of liquid-solid effective contact area and apparent contact area, θ is the intrinsic contact angle that forms the material of micro-structure surface, under this guide of theory, many bionical super hydrophobic surfaces are progressively prepared.People such as Onda at first notice the rough surface ultra-hydrophobicity, and they analyze the actual conditions of rough surface, adopt improved Wenzel formula that super-hydrophobic mechanism is described.After this, the research of super hydrophobic surface has obtained remarkable progress, has proposed serial method for preparing super-hydrophobic surface and has studied the performance of super hydrophobic surface as domestic river thunder seminar.
In existing super hydrophobic surface, adopt at present extensively hydrophobic material to carry out the method for structure of modification and carry out the method that the hydrophobic material coating handles and realize the ultra-hydrophobicity on surface on body structure surface, the work of water wetted material being carried out modifying super hydrophobicity yet there are no report.In fact, the contact condition of the starting stage that liquid contacts with the water wetted material micro-structure surface is shown in Fig. 1 left end, liquid under the effect of interfacial tension rapidly to the micro-structural internal extended, the contact angle θ constant (this angle is suitable with the intrinsic contact angle) that keeps liquid level and groove walls in this process, and finally contact with micro-structure surface formation Wenzel.These are different with the situation on the hydrophobic material coating shown in Fig. 1 right-hand member.Therefore, the ultra-hydrophobicity on water wetted material surface is difficult to realize.
In a word, significant in realization without pollution self-cleaning anti-pollution at structure super hydrophobic surface on the water wetted material, and be difficult to realize ultra-hydrophobicity by the general micro-structure surface that water wetted material forms.
Summary of the invention
The purpose of this invention is to provide a kind of water wetted material super hydrophobic surface micro-nano structure method for designing, the ultra-hydrophobicity of realizing extensive material is especially realized the super hydrophobic surface transformation of non-coating type.
The present invention realizes by following technical scheme:
A kind of water wetted material super hydrophobic surface micro-nano structure method for designing is: calculate protuberance ratio of micro structure according to super hydrophobic contact angle requirement; Determine the maximum cycle of micro-structural simultaneously according to service condition; At last, according to the micro-structural of design and the contact condition of structural parameters checking liquid and micro-structure surface.
In the said method, the micro-structural of designed water wetted material super hydrophobic surface is the mini column array structure of versions such as polygon, circle and non-regular sections shape, is furnished with more the periodicity groove of small scale (accompanying drawing 2 (a)) or is T type version (accompanying drawing 2 (b)) on microtrabeculae.
In the said method, the protuberance ratio of micro-structural is meant the gross area on structure top and the ratio of the horizontal projected area on surface, for the post array surface, if the cycle of structure on the both direction in surperficial section be respectively L
1And L
2, the apex area of single micro-structural is A, then protuberance ratio is: f
1=A/ (L
1* L
2), f wherein
1Be protuberance ratio.The protuberance ratio of super hydrophobic surface is calculated by Cassie formula and the given required liquid-drop contact angle of super hydrophobic surface: f
2=(cos θ
C+ 1)/(cos θ+1), θ
CBe the super hydrophobic contact angle on designed surface, θ is the intrinsic contact angle of water on smooth surface; f
1≤ f
2, otherwise readjust f
1In three parameter L
1, L
2And A.
In the said method, the maximum cycle that is calculated micro-structural by pressure difference obtains by the mechanical analysis to liquid level.Liquid level bears the effect to liquid of liquid internal pressure, gas pressure intensity and microstructured edge, for guaranteeing that liquid is in the Cassie state on super hydrophobic surface, need satisfy equation: (P-P
0) (L
1* L
2-A)＜-S γ cos α＜S γ, wherein P is a liquid internal pressure, P
0Be atmospheric pressure, S is the girth of raised structures top end surface, and γ is the surface tension of liquid water, and α is the contact angle between liquid level and the vertical wall of micro-structural.Can determine the maximum cycle of micro-structural by this equation.
In the said method, the contact condition on checking liquid and surface is realized by the angle beta (referring to accompanying drawing 2) of the formation between investigation liquid vapour interface and the true wall of micro-structural and the relation of the advancing contact angle of liquid on smooth surface.Choose the structural cycle L less than the max architecture cycle, this moment, β can try to achieve by geometrical relationship:
Liquid advancing contact angle from the teeth outwards is suitable with the intrinsic contact angle, and the approximate intrinsic contact angle that adopts is handled, if β＞θ, then liquid is in the Wenzel state on general micro-structure surface, otherwise then is in the Cassie state.
The present invention has following technical advantage:
Form by the control micro-structural realizes the ultra-hydrophobicity on surface, and be not coating to be carried out on the surface handle, even therefore the part wearing and tearing take place in material, as long as the version of micro-structural inside does not change, the ultra-hydrophobicity of micro-structure surface can not be affected, the super hydrophobic surface stable performance, permanently effective.
It is super-hydrophobic not adopt polymeric coating layer to realize, can realize the modifying super hydrophobicity of inorganic material, and environmentally safe is harmless, is particularly useful for holding the super-hydrophobic container of food.
Because inorganic material has hear resistance and light resistance, place the environment micro-structure surface can not take place to wear out and distribute for a long time, have the scope of application comparatively widely.
Description of drawings
Fig. 1 water on the water wetted material micro-structure surface with the hydrophobic coating micro-structural on contact schematic diagram
Fig. 2 water wetted material super-drainage structure form
A) T type micro-structural periodicity groove micro-structural b)
1. air, 2. liquid, 3. hydrophobic coating, 4. water wetted material micro-structural
The specific embodiment
Further specify substantive features of the present invention and marked improvement below in conjunction with Fig. 2 by concrete enforcement, but the present invention absolutely not only only limits to described embodiment.
(square column form structure, cross section structure are the version of Fig. 2 (a) to embodiment 1, and environmental condition and parameter are: P-P
0=1kPa, θ=50 °, liquid 2 is water, γ=0.072N/m, θ
C=150 °):
Calculate the protuberance ratio of water wetted material micro-structure surface 4 according to the Cassie computing formula.f＝(cosθ
C+1)/(cosθ+1)＝0.08155；
To square column type formula, L
1=L
2=L, A=(Lf)
2, S=4Lf then has L
Max＜4f γ/[(P-P
0) (1-f
2)]=23.6 μ m, wherein L
MaxBe maximum cycle.
Selecting structural cycle for use is the water wetted material micro-structural 4 of L=1 μ m, calculates liquid 2 and the interface of air 1 formation and the angle beta of the formation between the micro-structural wall in the micro-structural,
Be far smaller than liquid water 2 50 ° of the lip-deep intrinsic contact angles of smooth water wetted material, therefore, liquid water 2 is in the Cassie contact condition on water wetted material micro-structure surface 4.
Therefore, adopt designed structural parameters can realize the big contact angle (contact angle reach 150 °) of liquid water on water wetted material micro-structure surface 4.
(square column form structure, cross section structure are the version of Fig. 2 (b) to embodiment 2, and environmental condition and parameter are: P-P
0=10kPa, θ=50 °, liquid 2 is water, γ=0.072N/m, θ
C=150 °):
Calculate the protuberance ratio of water wetted material micro-structure surface 4 according to the Cassie computing formula.f＝(cosθ
C+1)/(cosθ+1)＝0.08155；
To square column type formula, L
1=L
2=L, A=(Lf)
2, S=4Lf then has L
Max＜4f γ [(P-P
0) (1-f
2)]=23.6 μ m, wherein L
MaxBe maximum cycle.
Selecting structural cycle for use is the water wetted material micro-structural 4 of L=1 μ m, calculates liquid 2 and the interface of air 1 formation and the angle beta of the formation between the micro-structural wall of micro-structural inside,
Be far smaller than 50 ° of the intrinsic contact angle of liquid water 2 on smooth water-wetted surface, liquid water 2 is in the Cassie contact condition on water wetted material micro-structure surface 4.
Therefore, adopt designed structural parameters can realize the big contact angle (contact angle reach 150 °) of liquid water on water wetted material micro-structure surface 4.
Claims (4)
1. water wetted material super hydrophobic surface micro-nano structure method for designing, it is characterized in that, this method is carried out as follows: at first select the mini column array structure of polygon, circle or non-regular sections shape microstructure form for use, and be furnished with the periodicity groove of small scale more or be T type version on microtrabeculae; Calculate protuberance ratio of micro structure according to super hydrophobic contact angle requirement again; Determine the maximum cycle of micro-structural simultaneously according to service condition; At last, according to the microstructure form of design and the contact condition of structural parameters checking liquid and micro-structure surface.
2. method for designing according to claim 1, it is characterized in that: the protuberance ratio of micro-structural is meant the gross area on structure top and the ratio of the horizontal projected area on surface, for the micro-pillar array surface, if the cycle of structure on the both direction in surperficial section be respectively L
1And L
2, the apex area of single micro-structural is A, then protuberance ratio is: f
1=A/ (L
1* L
2), f wherein
1Be protuberance ratio; Protuberance ratio for super hydrophobic surface is calculated by Cassie formula and the given required liquid-drop contact angle of super hydrophobic surface: f
2=(cos θ
C+ 1)/(cos θ+1), θ
CBe the super hydrophobic contact angle on designed surface, θ is the intrinsic contact angle of water on smooth surface; f
1≤ f
2, otherwise readjust f
1In three parameter L
1, L
2And A.
3. method for designing according to claim 1 is characterized in that: the formula of determining the micro-structural maximum cycle is: (P-P
0) (L
1* L
2-A)＜-S γ cos α＜S γ, wherein P is a liquid internal pressure, P
0Be atmospheric pressure, S is the girth of raised structures top end surface, and γ is the surface tension of liquid water, and α is the contact angle between liquid level and the vertical wall of micro-structural.
4. method for designing according to claim 1 is characterized in that: the contact condition of checking liquid and micro-structure surface realizes that by following decision condition formula is: choose the structural cycle L less than the max architecture cycle, this moment, β can try to achieve by geometrical relationship:
If β＞θ, then liquid is in the Wenzel state on general micro-structure surface, otherwise then is in the Cassie state.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583214A (en) * | 2011-01-11 | 2012-07-18 | 成功大学 | Super-hydrophobic microstructure |
| CN102627256A (en) * | 2012-04-16 | 2012-08-08 | 北京大学 | Micro-nano integrated processing technology based three-dimensional anti-drag micro-channel structure and preparation method thereof |
| CN102690128A (en) * | 2012-06-01 | 2012-09-26 | 大连海事大学 | Regulating device and method for super hydrophobic surface wettability |
| CN103011063A (en) * | 2012-12-25 | 2013-04-03 | 江苏大学 | Capillary forming method for preparing super oleophobic surface |
| CN103466539A (en) * | 2013-08-29 | 2013-12-25 | 中国科学院深圳先进技术研究院 | Super-lyophobic surface and preparation method thereof |
| CN103569950A (en) * | 2013-10-11 | 2014-02-12 | 中国科学院深圳先进技术研究院 | Preparation method of super-lyophobic surface |
| CN103693613A (en) * | 2013-12-27 | 2014-04-02 | 大连海事大学 | Surface wettability regulation and control device based on film transformation and regulation and control method |
| CN105220185A (en) * | 2015-10-29 | 2016-01-06 | 广东工业大学 | A kind of preparation method of super oleophobic micro-pillar array Surface Texture |
| CN105236342A (en) * | 2015-08-27 | 2016-01-13 | 中国科学院深圳先进技术研究院 | Gecko-inspired biomimetic dry glue and preparation method thereof |
| CN105550476A (en) * | 2016-01-25 | 2016-05-04 | 大连理工大学 | Stable superhydrophobic surface design method for periodically arranged microcolumn structure |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583214A (en) * | 2011-01-11 | 2012-07-18 | 成功大学 | Super-hydrophobic microstructure |
| CN102627256B (en) * | 2012-04-16 | 2015-06-24 | 北京大学 | Micro-nano integrated processing technology based three-dimensional anti-drag micro-channel structure and preparation method thereof |
| CN102627256A (en) * | 2012-04-16 | 2012-08-08 | 北京大学 | Micro-nano integrated processing technology based three-dimensional anti-drag micro-channel structure and preparation method thereof |
| CN102690128A (en) * | 2012-06-01 | 2012-09-26 | 大连海事大学 | Regulating device and method for super hydrophobic surface wettability |
| CN103011063A (en) * | 2012-12-25 | 2013-04-03 | 江苏大学 | Capillary forming method for preparing super oleophobic surface |
| CN103011063B (en) * | 2012-12-25 | 2015-07-08 | 江苏大学 | Capillary forming method for preparing super oleophobic surface |
| CN103466539A (en) * | 2013-08-29 | 2013-12-25 | 中国科学院深圳先进技术研究院 | Super-lyophobic surface and preparation method thereof |
| CN103569950A (en) * | 2013-10-11 | 2014-02-12 | 中国科学院深圳先进技术研究院 | Preparation method of super-lyophobic surface |
| CN103693613A (en) * | 2013-12-27 | 2014-04-02 | 大连海事大学 | Surface wettability regulation and control device based on film transformation and regulation and control method |
| CN105236342A (en) * | 2015-08-27 | 2016-01-13 | 中国科学院深圳先进技术研究院 | Gecko-inspired biomimetic dry glue and preparation method thereof |
| CN105220185A (en) * | 2015-10-29 | 2016-01-06 | 广东工业大学 | A kind of preparation method of super oleophobic micro-pillar array Surface Texture |
| CN105550476A (en) * | 2016-01-25 | 2016-05-04 | 大连理工大学 | Stable superhydrophobic surface design method for periodically arranged microcolumn structure |
| CN105550476B (en) * | 2016-01-25 | 2018-07-13 | 大连理工大学 | A kind of method for designing stable superhydrophobic surface of periodic arrangement micro-column structure |
| CN110318902A (en) * | 2019-04-23 | 2019-10-11 | 天津大学 | Hydrophobic type cylinder jacket outer surface structure and hydrophobic type cylinder jacket |
| CN112624032A (en) * | 2020-12-14 | 2021-04-09 | 南京工业大学 | Preparation method of composite reentrant angle micrometer structure with super-amphiphobicity |
| WO2023274227A1 (en) * | 2021-06-30 | 2023-01-05 | Saint-Gobain Glass France | Product component having microstructure part, method for obtaining information therefrom, identification device and processing method |
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