CN103011063B - Capillary forming method for preparing super oleophobic surface - Google Patents
Capillary forming method for preparing super oleophobic surface Download PDFInfo
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Abstract
The invention relates to the field of functional surface preparation technology, and particularly relates to a capillary forming method for a preparing super oleophobic surface. The capillary forming method is suitable for preparation of a polymer super oleophobic surface, particularly suitable for the preparation of the super oleophobic surface under a simple condition. A pre-prepared micro-nano structure surface is employed as a template by the method; the template is put on a smooth and flat substrate which is coated by a liquid state polymer film; the template is separated 5-50 [mu]m from the substrate after contact with the separate speed ranging from 0.1 [mu]m/s to 5 [mu]m/s; the liquid state polymer is aggregated in a gap between the micro-nano structure and the substrate under the action of a capillary force; and at the time, the liquid state polymer is cured, so that a preparation of a secondary groove structure. Equipment required by the method is simple, preparation of the super oleophobic surface can be realized under a simple condition, preparation cost is low, and batch preparation can be easily realized.
Description
Technical field
The present invention relates to function surface preparing technical field, refer in particular to a kind of capillary forming process preparing super oleophobic surface, it is applicable to the preparation that polymer surpasses oleophobic surface, is particularly useful for the preparation of the super oleophobic surface under simple condition.
Background technology
Super oleophobic surface refers to and drop (as fluid drop) that surface tension is less can be made on the surface of the large contact angle of its surface presentation (>130 °).Due to fluid drop can be made to have larger contact angle, the functional improvement of super hydrophobic surface has been arrived fluid environment by this surface, can realize more excellent self-cleaning and resistance reducing performance.Therefore, super oleophobic surface obtains in recent years and pays close attention to widely.
In order to realize the super oleophobic performance on surface, at present mainly through constructing secondary groove structure from the teeth outwards to realize (a kind of Novel method for designing super oleophobic surface structure, national inventing patent, application number CN201010132465.4; Ahuja A, Taylor J A, Lifton V, Sidorenko A A, Salamon T R, Lobaton E J, Kolodner P, Krupenkin T N.Nanonails:A Simple Geometrical Approach toElectrically 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.).This secondary groove structure has feature (the tip section area of the micro-nano structure 2 namely on surface substrate 1 is greater than the area of section near surface substrate 1 position on micro-nano structure 2, and the top width of micro-nano structure 2 is greater than bottom width) as shown in Figure 1.Due to the existence of secondary groove structure, the less liquid of surface tension can not be slipped in the substrate on surface along the sidewall of micro-structural, thus can construct the compound interface that liquid gas interface and liquid-solid boundary formed jointly on the contact interface of liquid with surface.Theoretical according to Cassie, this interface can make drop present larger contact angle from the teeth outwards, concerning fluid, namely achieves the super oleophobic performance on surface.
At present, the difficult point constructing super oleophobic surface is the preparation of secondary groove structure.Due to secondary groove structure complex forms, be then difficult to realize the demoulding according to template synthesis, so usually adopt Bosch technique and electrostatic spinning to realize the preparation of the secondary groove on super oleophobic surface at present.Bosch technique is wherein the typical process in micro-nano structure processing, can the sidewall shape of comparatively accurately control structure, so the different cross section of structure can be made to have different area, especially can realize the preparation of the secondary groove structure required for super oleophobic surface.But Bosch technique needs could realize on special plasma etch apparatus, and its complex process, need higher vacuum level requirements, these problems limit the popularization of Bosch technique in prepared by super oleophobic surface.The another kind of method preparing secondary groove structure is electrospinning process.The method, by be deposited on by the filament of micro fine cylindrical shape in substrate thus to construct secondary groove structure, because efficiency is higher, is used widely at present in the field of study.But because the diameter of filament in the method is very little, the secondary groove structure degree of depth of structure is limited.The secondary groove structure of this finite depth makes the super oleophobic performance on surface and stability thereof all be affected.Meanwhile, the rule due to filament arrangement is difficult to control, so adopt the method to be difficult to the controlled synthesis realizing secondary groove structure.
In a word, current preparation surpasses in oleophobic surface method, the equipment that Bosch technique needs price high and preparation process is complicated, and in electrospinning process, prepare the poor controllability of secondary groove structure, this have impact on super oleophobic performance and the stability thereof on surface to a great extent.For realizing the simple and easy preparation of controlled super oleophobic surface, the present invention proposes a kind of capillary forming process of the capillary effect based on liquid polymer.
Summary of the invention
The object of this invention is to provide a kind of capillary forming process for the preparation of super oleophobic surface, realize the controlled synthesis of the super oleophobic surface of the polymeric material under simple condition.
The present invention realizes by following technical proposals:
A kind of capillary forming process for the preparation of super oleophobic surface, be: with previously prepared good micro-nano structure surface as template, template being positioned over one is coated with in the smooth straight substrate of liquid polymer film, after contact, template and substrate are separated 5 ~ 50 μm, the velocity interval be separated is between 0.1 μm/s to 5 μm/s, liquid polymer is gathered in the gap of micro-nano structure and substrate under the effect of capillary force, and now liquid towards polymer is cured the preparation that can realize secondary groove structure.
In said method, the template adopted can be prepared by multiple method, needs the top of the micro-nano structure ensured in template to be in same plane.
In said method, the method that smooth straight substrate covers liquid thin polymer film is first dripped in smooth straight substrate by a small amount of (volume <20 μ L) liquid polymer, then by methods such as even glue, liquid polymer is sprawled as the film of thickness between 0.1 μm to 20 μm in smooth straight substrate.
In said method, liquid polymer can be by the polymer of photocuring or heat cure for the polymer of liquid, also can adopt thermoplastic polymer, now need polymer to be heated to more than its fusing point to ensure that it is in liquid state under normality.
In said method, template being positioned over the smooth straight suprabasil process being coated with liquid polymer film is first by smooth straight sole placing flat, be coated with the surface of polymer upward, then by template near smooth straight substrate, in close process, the micro-nano structure surface of template down.
In said method, the time of contact between template and smooth straight substrate is less than 5s, is filled in the gap of micro-nano structure to prevent liquid polymer.
In said method, the distance range that template and substrate separate is 5 ~ 50 μm, for the distance between accurate Control architecture and substrate, method by adding given thickness wedge clearance gauge between template and substrate carrys out command range, this process need slowly carries out, and the velocity interval of separation is between 0.1 μm/s to 5 μm/s.
In said method, liquid polymer rule be gathered in the gap of micro-nano structure and substrate under the effect of capillary force is that the distance that micro-nano structure arrives substrate is little apart from the distance of substrate compared with the bottom, gap of micro-nano structure, and after of short duration contact, liquid polymer is attached on the top of micro-nano structure, because the distance of template and substrate increases, make the height on micro-nano structure top higher than the height on the liquid polymer surface at balance place, the effect that the liquid polymer be attached on micro-nano structure is subject to gravity has the trend of down moving, and the liquid polymer being in balance place is subject to the trend of the oriented micro-nano structure motion of effect of the liquid polymer on micro-nano structure, final liquid polymers is under the acting in conjunction of adhesive force and gravity, because himself has surface tension, thus form the little secondary groove-like structure of the large lower section of upper section.
In said method, after forming secondary groove structure, need to be cured process to polymer, the method of solidification process depends on adopted polymer type, if select the polymer of thermal curable or photocuring, corresponding employing heat cure and process for photocuring, when then solidifying according to thermoplastic polymer, adopt the method for cooling curing.
The present invention has following technical advantage:
Required equipment is simple, and can realize the preparation of super oleophobic surface under simple condition, preparation cost is low, easily batch preparation.
Employing template is prepared, and has the advantage of the cost effective of template.
Regulating by adjusting template structure and the distance between template and substrate of the secondary groove structure that preparation is surperficial.
Accompanying drawing explanation
Fig. 1 secondary groove structure schematic diagram
Fig. 2 capillary deformation method flow process
Fig. 3 capillary deformation method principle
1 surface substrate, 2 two groove structures, 3 micro-nano structure templates, 4 liquid polymers films, 5 smooth straight substrates, 6 surfaces with secondary groove structure.
Detailed description of the invention
Implementation detail and the working condition of the concrete technology that the present invention proposes are described below in conjunction with Fig. 2 and Fig. 3.
Prepare the capillary deformation method of super oleophobic surface as shown in Figure 2, the capillary effect mainly through liquid polymer constructs the surface with secondary groove structure.The template 3 adopted can be prepared by multiple method, and as methods such as Replica molding, Laser Processing, lithography process, same template can repeatedly use, so the preparation cost of this method is minimized.The requirement of template 3 demand fulfillment is that the top of micro-nano structure is in the same plane.
For realizing capillary forming process, need to cover liquid thin polymer film 4 in smooth straight substrate 5, the method covered first drips in smooth straight substrate 5 by a small amount of (volume <20 μ L) liquid polymer 4, then by methods such as even glue, liquid polymer 4 is sprawled as the film of thickness between 0.1 μm to 20 μm in smooth straight substrate 5.The liquid polymer 4 used can be by the polymer of photocuring or heat cure for the polymer of liquid, also can adopt thermoplastic polymer, now need polymer to be heated to more than its fusing point to ensure that it is in liquid state under normality.
After getting out the smooth straight substrate 5 of Covering Liguid thin polymer film 4, template 3 is positioned over and is coated with in the smooth straight substrate 5 of liquid polymer film 4, its process is: first by smooth straight substrate 5 horizontal positioned, be coated with the surface of polymer 4 upward, again by template 3 near smooth straight substrate 5, in close process, the micro-nano structure surface of template is down.Time of contact between template 3 and smooth straight substrate 5 is less than 5s, is filled in the gap of micro-nano structure to prevent liquid polymer 4.
After keeping certain time of contact, template 3 and substrate 5 are separated certain distance, distance range is 5 ~ 50 μm, process separately carrys out command range by the method adding given thickness wedge clearance gauge between template 3 and substrate 5, this process need slowly carries out, and the velocity interval of separation is between 0.1 μm/s to 5 μm/s.
After being separated, the liquid polymer between template 3 and substrate 5 forms structure as shown in Figure 3 under the effect of adhesive force, surface tension and gravity.Micro-nano structure (position outstanding downwards) in template 3 is little apart from the distance of substrate compared with the bottom, gap of micro-nano structure to the distance of substrate, liquid polymer 4 is after of short duration contact, liquid polymer is attached on the top of micro-nano structure, when distance between template 3 and substrate 5 increases, due to the adhesive force effect between micro-nano structure and liquid polymer, liquid polymer will by micro-nano structure from substrate be glutinous, under the effect of polymer surfaces tension force, the version that liquid polymer will be formed as accompanying drawing 3.Now, because liquid polymer is also subject to the effect of gravity, so the structure formed is the middle part shape that carefully two ends are thick, i.e. the planform of similar secondary groove-like.
After liquid polymer forms secondary groove structure, process is cured and the demoulding to polymer, final secondary groove structure surface 6 can be obtained.In the process, the method for solidification process depends on adopted polymer type, if select the polymer of thermal curable or photocuring, corresponding employing heat cure and process for photocuring, adopts the method for cooling curing when then solidifying according to thermoplastic polymer.The surface obtained after shaping is for having the surface of secondary groove structure.Existing analysis result shows (AhujaA, Taylor JA, Lifton V, SidorenkoAA, SalamonT R, Lobaton E J, Kolodner P, Krupenkin T N.Nanonails:A Simple Geometrical Approach to Electrically TunableSuperlyophobic Surfaces.Langmuir2008,24:9-14.), this type of surface can realize super oleophobic performance.
Embodiment
Micro-nano structure template adopts silicon base template, and prepared by photolithographic process, photolithographic process is a kind of micro-nano technology technique of maturation, is not described specifically herein.The micro-nano structure of prepared template is: version is cylindrical-array, and the diameter of micro-cylinder is 30 μm, be highly 50 μm of intercolumniations is 100 μm.
The material of liquid polymers and smooth straight substrate all selects PDMS, first two formulas of PDMS are weighed in the ratio of 10:1, by getting after two formulas fully mixing ~ 50 μ L are poured on a smooth silicon chip surface and prepare smooth straight substrate, silicon chip is positioned on horizontal surface, after PDMS has freely sprawled, the silicon chip being loaded with PDMS is sent in vacuum drying chamber, react 2 hours under being placed in the environment of 60 ° of C, after solidification, take off PDMS duplicate from silicon chip can obtain smooth straight substrate.After preparing smooth straight substrate, smooth straight substrate is positioned on smooth silicon chip to keep its planarization, liquid for ~ 5 μ L PDMS is poured in smooth straight substrate, and the silicon chip placing PDMS substrate (carrying PDMS liquid polymers) is transferred on sol evenning machine, carry out even glue process by the speed of 1000 revs/min, obtain liquid PDMS thin polymer film.Then silicon template is contacted with liquid polymer ~ 3s after between silicon template and substrate, add the clearance gauge that thickness is 30 μm, make the distance between silicon template and substrate reach 30 μm.Keep this state and sent in vacuum drying chamber by the silicon chip being loaded with substrate being warming up to 60 ° of C, be separated silicon chip template and PDMS substrate after 2 hours through overcuring, now substrate surface has secondary groove structure, this superficial theory has super oleophobic performance.
Claims (4)
1. prepare the capillary forming process of super oleophobic surface for one kind, it is characterized in that, with previously prepared good micro-nano structure surface as template, template being positioned over one is coated with in the smooth straight substrate of liquid polymer film, after contact, template and substrate are separated 5 ~ 50 μm, the velocity interval be separated is between 0.1 μm/s to 5 μm/s, liquid polymer is gathered in the gap of micro-nano structure and substrate under the effect of capillary force, and now liquid towards polymer is cured the preparation that can realize secondary groove structure; Wherein, the method that smooth straight substrate covers liquid thin polymer film is first dripped in smooth straight substrate by volume <20 μ L liquid polymer, then liquid polymer is sprawled as the film of thickness between 0.1 μm to 20 μm in smooth straight substrate.
2. method according to claim 1, it is characterized in that, the top of the described micro-nano structure surface as template is in same plane.
3. method according to claim 1, it is characterized in that, described liquid polymer is for the polymer of liquid and by the polymer of photocuring or heat cure under normality, or adopts thermoplastic polymer, and polymer is heated to more than its fusing point to ensure that it is in liquid state.
4. method according to claim 3, it is characterized in that, template being positioned over the smooth straight suprabasil process being coated with liquid polymer film is first by smooth straight sole placing flat, be coated with the surface of polymer upward, again by template near smooth straight substrate, in close process, the micro-nano structure surface of template is down.
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| 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 |
| CN108939280B (en) * | 2018-04-13 | 2021-05-18 | 杭州电子科技大学 | Preparation method of SU8 microneedle array patch |
| CN108545694B (en) * | 2018-06-21 | 2020-06-30 | 西安建筑科技大学 | Super-hydrophobic film with singular microstructure and preparation method thereof |
| CN109987578A (en) * | 2019-04-09 | 2019-07-09 | 电子科技大学 | A method of constructing single concave inward structure on micro-column sublist face |
| CN110346078B (en) * | 2019-07-30 | 2021-02-19 | 天津大学 | Capacitive flexible pressure sensor and preparation method and application thereof |
| CN110346079B (en) * | 2019-07-30 | 2021-02-19 | 天津大学 | Capacitive flexible pressure sensor based on pre-stretching method and preparation method and application thereof |
| 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 |
| CN112250033A (en) * | 2020-09-29 | 2021-01-22 | 江苏大学 | Super-oleophobic surface preparation method based on structure dipping-in-situ dragging forming |
| 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 |
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| US20060177532A1 (en) * | 2005-02-04 | 2006-08-10 | Molecular Imprints, Inc. | Imprint lithography method to control extrusion of a liquid from a desired region on a substrate |
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| CN101817500A (en) * | 2010-03-24 | 2010-09-01 | 江苏大学 | Hydrophilic material surface super hydrophobic functional shift micro structure design method |
| CN102020237A (en) * | 2010-03-24 | 2011-04-20 | 江苏大学 | Novel method for designing super oleophobic surface structure |
| CN102427083A (en) * | 2011-11-10 | 2012-04-25 | 中山大学 | Water and oil repellency surface microstructure and manufacturing method thereof |
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