CN103030099A - Gas-assisted forming method for producing ultra-oleophobic surface - Google Patents
Gas-assisted forming method for producing ultra-oleophobic surface Download PDFInfo
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Abstract
The invention relates to the technical field of production of functional surfaces, in particular to a gas-assisted forming method for producing an ultra-oleophobic surface, which is applicable to production of the ultra-oleophobic surface of a polymer, in particular to production of the ultra-oleophobic surface under a simple condition. The gas-assisted forming method for producing the ultra-oleophobic surface comprises the following steps: putting a liquid polymer into a container; covering a porous template on the surface of the liquid polymer, and fixing the position of the porous template so as to expose a part of the surface of the liquid polymer; sending the container into a vacuum drying box, vacuumizing, and expanding air confined between the liquid polymer and template pores under the action of pressure difference to form a spherical crown-shaped pore array; and curing the polymer so as to produce a secondary groove structure. Less equipment is required in the two-step forming method; by the two-step forming method, the ultra-oleophobic surface can be produced under the simple condition; the production cost is low; and batch production is easy.
Description
Technical field
The present invention relates to the function surface preparing technical field, refer in particular to a kind of gas assist formation method for preparing super oleophobic surface, the preparation that it is applicable to the super oleophobic surface of polymer is particularly useful for the preparation of the super oleophobic surface under the simple and easy condition.
Background technology
Super oleophobic surface refers to that the drop (such as the fluid drop) that can make surface tension less presents 130 ° of large contact angles (〉 on its surface) the surface.Similar with super hydrophobic surface, this surface has excellent self-cleaning and resistance reducing performance, is particularly useful for the fluid environment.Therefore, super oleophobic surface has obtained paying close attention to widely in recent years.
Existing document (a kind of Novel method for designing super oleophobic surface structure, national inventing patent, application number CN201010132465.4; AhujaA, Taylor J A, Lifton V, Sidorenko AA, Salamon T R, Lobaton E J, Kolodner P, Krupenkin T N.Nanonails:A Simple Geometrical Approach to Electrically Tunable Superlyophobic Surfaces.Langmuir2008,24:9-14. and Tut eja A, Choi W, Ma M, Mabry J M, Mazzella S A, Rutledge G C, McKinley G H, Cohen RE.Designing SuperoleophobicSurfaces.Science2007,318:1618-1622.) show, the super oleophobic function on surface can be by realizing at surface structure secondary groove structure.Be the preparation of lip-deep secondary groove structure so realize the difficult point of the super oleophobic performance in surface.These secondary groove structures have the tip section area greater than micro-nano structure near the characteristic of the area of section at substrate position (as shown in Figure 1, the top width of the secondary groove structure 2 in the substrate 1 of surface is greater than the bottom width), so be difficult to realize the demoulding (macrostructure on top is blocked by die hole) by common template.In order to construct the surface with secondary groove structure, method commonly used is Bosch technique and the electrospinning process in the micro-nano processing method at present.Although Bosch technique can be controlled the shape of micro-nano structure well, because it needs expensive equipment and stricter vacuum condition, so Bosch technique also is not promoted use at super oleophobic surface aspect preparing.The cost of electrospinning process has advantage, but the secondary groove structure of its generation is formed by the nanoscale filament of random deposition, so there are two limitations in the method: the one, controllability and the repdocutbility of secondary groove structure are very poor, the 2nd, the secondary groove structure that the filament of nanoscale forms is obvious not, so in the situation that fluctuation occurs in the drop free energy, be easy to the phenomenon (i.e. super oleophobic state conversion phenomena) that the Cassie contact interface between drop and the surface is damaged occurs, make super oleophobic state labile.
In a word, the difficult point of super oleophobic surface preparation is the structure of secondary groove structure, and prepares at present high equipment and the preparation process complexity of Bosch arts demand price of super oleophobic surface method, and electrospinning process prepares the poor controllability of secondary groove structure.For realizing the simple and easy controlled preparation of super oleophobic surface, the present invention proposes a kind of gas assist formation method based on the polymer thermal deformation.
Summary of the invention
The purpose of this invention is to provide a kind of gas assist formation method for the preparation of super oleophobic surface, realize the controlled preparation of the super oleophobic surface of the polymeric material under the simple and easy condition.
The present invention realizes by following technical scheme:
A kind of gas assist formation method for the preparation of super oleophobic surface, be: (1) is contained in liquid polymer in the container, the hole class template is covered the liquid polymer surface and fixes its position, allow outside the surface of partially liq polymer is exposed to, (2) container is sent in the vacuum drying chamber vacuumized, the air that is limited between liquid polymer and pattern hole is expanded under pressure difference, form the hole array of spherical crown shape, be cured preparation that processing can realize secondary groove structure to polymer this moment.
In the said method, employed template is pore array template or groove array mould plate, and its inner air can be closed when requiring template one side with holes or groove to contact with liquid polymers.
In the said method, employed liquid polymer can be the material that normal temperature is in liquid state and can realizes by the method for heat cure or photocuring solidifying, also can be thermoplastic, namely in the situation that the higher material of temperature has certain flowing and deformation performance, thermoplastic need to be when the operation be increased to 10 ~ 30 ° of C more than the fusion temperature of thermoplastic with the temperature of employed template, polymer.
In the said method, liquid polymer is contained in the container of an opening, and the thickness of liquid polymers is 0.5 ~ 10mm, according to the thickness requirement of final super oleophobic surface is determined, makes polymer thickness equal the thickness of desired super oleophobic surface.
In the said method, the mode that template is covered liquid polymer surfaces is at first to throw in three certain thickness locating pieces in liquid polymers, make upper surface and the polymer liquid level of locating piece in the same plane, pore array template is positioned on these three locating pieces, and faces down with one of porose array.
In the said method, pore array template is the overlie polymer liquid level fully, is beneficial to the follow-up processing that vacuumizes, and the pressure of liquid level is equated with vacuum pressure.
In the said method, with container put into behind the vacuum drying chamber it is vacuumized after, the pressure of liquid level equates with vacuum pressure, and the inner residual air in the hole on the pore array template has certain pressure intensity, this is so that there is certain pressure difference in the liquid level of inside, hole, thereby liquid level is deformed.
In the said method, the pressure difference of the liquid level both sides of inside, hole is △ P=P
In-P
Vacuum, P wherein
InBe the gas pressure intensity of inside, hole, P
VacuumBeing vacuum pressure, setting by vacuum drying chamber, in order to construct the secondary groove structure, is the situation of array of circular apertures for the structure on the template, and vacuum pressure need to satisfy
For micro groove structure, vacuum pressure need to satisfy
Wherein H is the degree of depth of structure, P
0Be atmospheric pressure, R is the radius of circular hole, and γ is the surface tension of liquid polymer, and W is width of mini longitudinal channels.
In the said method, need at last the liquid towards polymer to be cured processing, solidifying the method for processing decides according to the character of employed polymer, if polymer is the polymer of thermal curable or photocuring, then adopt heat cure or process for photocuring, if polymer is thermoplastic polymer, then the liquid polymer cooling can be realized solidifying.
The present invention has following technical advantage:
Required equipment is simple, can realize the preparation of super oleophobic surface under simple and easy condition, and preparation cost is low, easily in batches preparation.
Can regulating by regulating vacuum pressure of the secondary groove structure on preparation surface.
Employed template can repeatedly be used, and has the advantage of template.
Description of drawings
Fig. 1 secondary groove structure schematic diagram.
Fig. 2 gas assist formation method flow process.
Concern schematic diagram between pore array template, liquid polymers and the locating piece in Fig. 3 gas assist formation method.
Fig. 4 gas assist formation method principle (a) is the situation of pore array template, (b) is the situation of slot template.
1 surperficial substrate, 2 secondary groove structures, 3 pore array templates, 4 gases, 5 liquid polymers, 6 have the surface of secondary groove structure, and 7 hold the container of liquid polymer, 8 locating pieces.
The specific embodiment
Implementation detail and the working condition of the concrete technology that the present invention proposes are described below in conjunction with Fig. 2-Fig. 4.
The gas assist formation method flow process of the super oleophobic surface of preparation as shown in Figure 2, by pore array template 3 being covered liquid polymer 5 surfaces, reduce by vacuumizing the pressure that makes liquid internal, thereby so that the pressure of air 4 is greater than the liquid level pressure of liquid polymer 5, the liquid level that contacts with air is deformed, realize the shaping of secondary groove structure, then liquid towards polymer 5 is cured and processes and the demoulding, can obtain the required surface with secondary groove structure 6.
Employed template is pore array template or groove array mould plate, its inner air can be closed when requiring template one side with holes or groove to contact with liquid polymers, so the hole on the template 3 or the edge of groove need at grade, to realize the sealing to air.Employed liquid polymer 5 has two kinds of selections, and a kind of is to realize that by the method for heat cure or photocuring the normal temperature that solidifies is in liquid material, such as PDMS; Another kind is thermoplastic, but 10 ~ 30 ° of C make it be in liquid state more than needing in use its temperature is increased to the fusion temperature of thermoplastic.Ready liquid polymer 5 need to be contained in the container 7 of an opening (as shown in Figure 3), the thickness of liquid polymers is 0.5 ~ 10mm, according to the thickness requirement of final super oleophobic surface is determined, make polymer thickness equal the thickness of desired super oleophobic surface.For template being covered on the liquid polymer surface, the locating piece 8 that three thickness equate with liquid polymer thickness need to be positioned in the container, the surface of the porose array of Form board tape or groove structure is contacted with the upper surface of locating piece down.In order to make vacuum pumping affect liquid internal pressure, need to guarantee the incomplete overlie polymer liquid level of template, as shown in Figure 3, liquid polymers is paved with the bottom of container, and template only is square scope, guarantees can contact with air at the extraneous liquid level of template (namely send in the vacuum environment and can contact with vacuum environment).
After container 7 is admitted to vacuum environment, because the part surface of liquid polymers 5 directly contacts with vacuum environment, so the pressure of liquid polymer 5 liquid levels equates with vacuum pressure, again because liquid has the effect of transmitting pressure, the liquid level pressure of the liquid polymer that is covered by template 3 also equates with vacuum pressure, at this moment, the pressure of the air of the hole on the template 3 or groove restriction is the environmental stress (atmospheric pressure) when covering template 3 on the liquid polymer, is △ P=P so there is pressure difference in the liquid polymer liquid level both sides in hole or groove
0-P
Vacuum,P wherein
0Be atmospheric pressure, P
VacuumBe vacuum pressure.Under pressure difference and the capillary effect of liquid polymer, the liquid level in hole or the groove will deform, and as shown in Figure 4, (a) be the situation in hole, (b) be the situation of groove.After distortion is finished because gas volume changes, in the hole in or the interior pressure of groove become Pin, this moment, liquid level was in poised state, satisfied the Laplace deformation rule of liquid level, namely to the circular hole situation, liquid level forms the structure of approximate spherical crown shape, for the groove situation, and the shape on the liquid level forming section face of cylinder.In order to construct the secondary groove structure, need spherical crown surface greater than the hemisphere face shape, and the part face of cylinder is greater than the shape of semi-cylindrical, so require vacuum pressure to meet some requirements.Be the situation of array of circular apertures for the structure on the template, vacuum pressure need to satisfy
For micro groove structure, vacuum pressure need to satisfy
Wherein H is the degree of depth of structure, P
0Be atmospheric pressure, R is the radius of circular hole, and γ is the surface tension of liquid polymer, and W is width of mini longitudinal channels.
After the secondary groove structure forms, also need the liquid towards polymer to be cured processing, solidifying the method for processing decides according to the character of employed polymer, if polymer is the polymer of thermal curable or photocuring, then adopt heat cure or process for photocuring, the instruction that the method reference polymer of solidifying is processed if polymer is thermoplastic polymer, then can realize the liquid polymer cooling to solidify.
Be shaped and prepared micro-nano structure surface 6 taken off (demoulding) from template 3 and container 7 after complete, can obtain the surface 6 with secondary groove structure.Existing analysis result shows (Ahuja A, Taylor J A, Lifton V, Sidorenko AA, Salamon T R, Lobaton E J, Kolodner P, Krupenkin T N.Nanonails:A Simple Geometrical Approach to Electrically Tunable Superlyophobic Surfaces.Langmuir2008,24:9-14. and Tuteja A, Choi W, Ma M, Mabry J M, Mazzella S A, Rutledge G C, McKinley G H, Cohen RE.Designing Superoleophobic Surfaces.Science2007,318:1618-1622.), super oleophobic performance can be realized in this type of surface.
Embodiment
Optional holes array mould plate, aperture are 50 μ m, and pitch of holes is 70 μ m, and hole depth is 50 μ m, and silicon materials prepare by lithography process.Container is selected glass dish.Liquid polymer is selected PDMS.It is the locating piece of 2mm that locating piece 8 is selected thickness.
The set-up procedure of PDMS is, at first in two prescriptions of the ratio weighing PDMS of 10:1, taking a morsel after two prescriptions are fully mixed is poured in the glass dish.Before toppling over, glass dish needs horizontal positioned, and three locating pieces are put into glass dish, notes when toppling over observing, and treats that PDMS just floods locating piece and namely stops to topple over.Afterwards ready template is lain in a horizontal plane on three locating pieces.Container is transferred in the vacuum drying chamber, noticed in this process guaranteeing that the glass dish bottom is in level.According to
Calculate vacuum pressure, with the die parameters substitution and consider that the surface tension of PDMS is 0.015N/m, calculate P
Vacuum＜73800Pa, this adopts common vacuum drying chamber to meet the demands.According to the result who calculates, selecting vacuum pressure is 0.6 atmospheric pressure, after vacuum pressure is stable, liquid polymers is cured processing.Solidifying the process of processing is: the temperature in the vacuum drying chamber is risen to 60 ° of C, react and take out container after 2 hours.The PDMS that solidifies is taken off in container, and take off template and locating piece, can obtain required this surface, the surface with secondary groove structure and have in theory super oleophobic performance.
Claims (5)
1. gas assist formation method for preparing super oleophobic surface, it is characterized in that may further comprise the steps: (1) is contained in liquid polymer in the container, the hole class template is covered the liquid polymer surface and fixes its position, allow outside the surface of partially liq polymer is exposed to, (2) container is sent in the vacuum drying chamber vacuumized, the air that is limited between liquid polymer and pattern hole is expanded under pressure difference, form the hole array of spherical crown shape, be cured preparation that processing can realize secondary groove structure to polymer this moment.
2. described method according to claim 1 is characterized in that, described template is pore array template or groove array mould plate, and its inner air can be closed when template one side with holes or groove contacted with liquid polymers.
3. described method according to claim 1 is characterized in that, employed liquid polymer is the material that normal temperature is in liquid state and can realizes by the method for heat cure or photocuring solidifying; Thermoplastic in the time of perhaps.
4. described method according to claim 1 is characterized in that, liquid polymer is contained in the container of an opening, and the thickness of liquid polymers is 0.5 ~ 10 mm.
5. described method according to claim 1, it is characterized in that, the mode that template is covered liquid polymer surfaces is at first to throw in three certain thickness locating pieces in liquid polymers, make upper surface and the polymer liquid level of locating piece in the same plane, pore array template is positioned on these three locating pieces, and faces down with one of porose array.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112225172A (en) * | 2020-09-29 | 2021-01-15 | 江苏大学 | Method for preparing surface of near-cylindrical-surface micro-groove array based on air mold method |
| CN112299363A (en) * | 2020-09-29 | 2021-02-02 | 江苏大学 | Method for preparing microstructure array surface with smooth inclined bottom surface based on air mold method |
| CN114454507A (en) * | 2022-01-26 | 2022-05-10 | 江苏大学 | Inverted gas expansion forming method of inclined micropore array |
| GB2601647A (en) * | 2020-09-29 | 2022-06-08 | Univ Jiangsu | Air mold method-based method for preparing near-cylindrical microgroove array surface |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100166964A1 (en) * | 2008-12-26 | 2010-07-01 | Pusan National University Industry University Cooperation Foundation | Method for attaching micro bubble array on plate surface |
| CN101819125A (en) * | 2010-03-24 | 2010-09-01 | 江苏大学 | Method for designing stable superhydrophobic surface of grating structure |
| CN102020237A (en) * | 2010-03-24 | 2011-04-20 | 江苏大学 | Novel method for designing super oleophobic surface structure |
| US20110287203A1 (en) * | 2010-05-24 | 2011-11-24 | Integran Technologies Inc. | Articles with super-hydrophobic and/or self-cleaning surfaces and method of making same |
| CN102448692A (en) * | 2009-02-17 | 2012-05-09 | 伊利诺伊大学评议会 | Methods for fabricating microstructures |
| CN102787364A (en) * | 2012-08-07 | 2012-11-21 | 中国科学院大连化学物理研究所 | Manufacturing method and application of PDMS (Polydimethylsiloxane) polymer chip with arc sunk holes |
-
2012
- 2012-12-25 CN CN201210569812.9A patent/CN103030099B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100166964A1 (en) * | 2008-12-26 | 2010-07-01 | Pusan National University Industry University Cooperation Foundation | Method for attaching micro bubble array on plate surface |
| CN102448692A (en) * | 2009-02-17 | 2012-05-09 | 伊利诺伊大学评议会 | Methods for fabricating microstructures |
| CN101819125A (en) * | 2010-03-24 | 2010-09-01 | 江苏大学 | Method for designing stable superhydrophobic surface of grating structure |
| CN102020237A (en) * | 2010-03-24 | 2011-04-20 | 江苏大学 | Novel method for designing super oleophobic surface structure |
| US20110287203A1 (en) * | 2010-05-24 | 2011-11-24 | Integran Technologies Inc. | Articles with super-hydrophobic and/or self-cleaning surfaces and method of making same |
| CN102787364A (en) * | 2012-08-07 | 2012-11-21 | 中国科学院大连化学物理研究所 | Manufacturing method and application of PDMS (Polydimethylsiloxane) polymer chip with arc sunk holes |
Cited By (17)
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|---|---|---|---|---|
| JP2022550505A (en) * | 2020-09-29 | 2022-12-02 | 江▲蘇▼大学 | Method for fabricating micro-groove array surfaces with near-cylindrical surfaces based on air forming |
| CN112225172B (en) * | 2020-09-29 | 2024-03-19 | 江苏大学 | Method for preparing near cylindrical surface micro-groove array surface based on air model method |
| WO2022068448A1 (en) * | 2020-09-29 | 2022-04-07 | 江苏大学 | Air mold method-based method for preparing near-cylindrical microgroove array surface |
| WO2022068191A1 (en) * | 2020-09-29 | 2022-04-07 | 江苏大学 | Method for preparing microstructure array surface with smooth inclined bottom face on basis of air molding method |
| CN112225172A (en) * | 2020-09-29 | 2021-01-15 | 江苏大学 | Method for preparing surface of near-cylindrical-surface micro-groove array based on air mold method |
| GB2601647A (en) * | 2020-09-29 | 2022-06-08 | Univ Jiangsu | Air mold method-based method for preparing near-cylindrical microgroove array surface |
| CN112299363A (en) * | 2020-09-29 | 2021-02-02 | 江苏大学 | Method for preparing microstructure array surface with smooth inclined bottom surface based on air mold method |
| JP2022551783A (en) * | 2020-09-29 | 2022-12-14 | 江▲蘇▼大学 | Method for fabricating smooth sloping bottom microcavity array surface based on air forming method |
| GB2601647B (en) * | 2020-09-29 | 2023-02-01 | Univ Jiangsu | Method for preparing microgroove array surface with nearly cylindrical surface based on air molding method |
| JP7202743B2 (en) | 2020-09-29 | 2023-01-12 | 江▲蘇▼大学 | Method for fabricating smooth sloping bottom microcavity array surface based on air forming method |
| JP7202756B2 (en) | 2020-09-29 | 2023-01-12 | 江▲蘇▼大学 | Method for fabricating micro-groove array surfaces with near-cylindrical surfaces based on air forming |
| US11655144B2 (en) | 2020-09-29 | 2023-05-23 | Jiangsu University | Method for preparing micro-cavity array surface product with inclined smooth bottom surface based on air molding method |
| CN112299363B (en) * | 2020-09-29 | 2024-03-19 | 江苏大学 | Preparation method of smooth inclined bottom surface microstructure array surface based on air die method |
| US11731321B2 (en) | 2020-09-29 | 2023-08-22 | Jiangsu University | Method for preparing microgroove array surface with nearly cylindrical surface based on air molding method |
| CN114454507A (en) * | 2022-01-26 | 2022-05-10 | 江苏大学 | Inverted gas expansion forming method of inclined micropore array |
| CN114454507B (en) * | 2022-01-26 | 2023-09-26 | 江苏大学 | Inverted gas expansion forming method of inclined micropore array |
| WO2023142479A1 (en) * | 2022-01-26 | 2023-08-03 | 江苏大学 | Inverted gas expansion forming method for inclined micropore array |
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