CN102417792B - Preparation method of antifouling material having crossed regular microstructure on surface - Google Patents
Preparation method of antifouling material having crossed regular microstructure on surface Download PDFInfo
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- CN102417792B CN102417792B CN2011103762183A CN201110376218A CN102417792B CN 102417792 B CN102417792 B CN 102417792B CN 2011103762183 A CN2011103762183 A CN 2011103762183A CN 201110376218 A CN201110376218 A CN 201110376218A CN 102417792 B CN102417792 B CN 102417792B
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Abstract
The invention relates to a preparation method of an antifouling material having a crossed regular microstructure on the surface. The method comprises the following steps of: etching a microstructure with a crossed pattern on a photomask, and arranging crossed cylindrical basic units with conical tail ends in a staggered way to form an array; forming a microstructure of a specified depth on the surface of a silicon chip by adopting a plasma deep silicon etching process; and preparing the antifouling material with themicrostructure by adopting a method for rolling over and copying polydimethylsiloxane. Due to the adoption of the crossed pattern of the microstructure and the arrangement mode, the contact area between a fouling organism and the material is reduced, the surface hydrophobicity of the material is enhanced, and adhesion of fouling organisms such as ulva spores, diatoms, barnacle larvae and the like can be effectively prevented. According to the material, an antifouling effect is achieved by using the microstructure on the surface, and loss is avoided; and moreover, the antifouling material can be self-cleaned under the action of water current erosion, is an environmentally-friendly antifouling material, and can be used for preventing and eliminating bio-fouling on the surfaces of ships and marine structural objects under marine environment.
Description
Technical field:
The present invention relates to prevent and kill off under a kind of marine environment boats and ships and the stained anti-fouling material of marine structure surface biological, particularly relate to the preparation method that a kind of surface has the anti-fouling material of cross rule micro-structural, belong to the marine anti-pollution technical field.
Background technology:
Marine biofouling is that the marine growth of battalion's set life and epiphytism is grown in hull bottom or artificial facility is surperficial, and causes the phenomenon of adverse effect.These biologies are called as marine fouling organism, comprise microbe, sea-plant and marine animal etc.Coastal area of china has recorded more than 600 and has planted fouling organism, and wherein topmost monoid is algae, hydra, sponge, imperial cyprid, Bivalve, barnacle and Ascidian etc.Marine fouling organism is attached to the works surface in seawater, as boats and ships, dock, harbour, oil platform, submarine cable, buoy, power plant's cooling pipe, fishing net etc., cause serious harm and economic loss, as cause ship resistance increase, pipeline obstruction, the reduction of cooling device thermal conductivity, catch reduction etc.The marine anti-pollution technology is be used to preventing that marine organisms from adhering to stained technology, and the most frequently used method is to add an overcoat on soaking of boats and ships or works extra large surface, at works surface label copper sheet, pitching etc., is generally to adopt nonpolluting coating as previously now.
Nonpolluting coating has polytype, as antifouling formulation, low-surface-energy type.Antifouling formulation coating forms fouling organism is attached with inhibiting concentration layer, thereby prevent biodeterioration by the release of anti-fouling agent.The patented invention of British patent GB1457590 a kind of antifouling paint that contains triphenyltin, its anti-fouling effect reached more than 5 years.Yet this nonpolluting coating that contains toxic agent causes serious adverse effect to the marine eco-environment, the organotin use that is under an embargo gradually.Low-surface-energy type coating is to utilize the not viscosity of its low-surface-energy, and marine fouling organism is difficult in its surface attachment, though adhere to also insecure and easily come off, to reach antifouling purpose.The invention of US Patent No. 4910252 adopts room curing silicon rubber to make a kind of low surface energy anti-fouling paint, and its antifouling phase can reach more than 2 years.US Patent No. 6265515 has been introduced a kind of silicon-fluororesin low surface energy anti-fouling paint, makes with poly-(methyl hydrogen siloxane) and the nine fluorine hexenes reactions of trimethyl silyl end-blocking, and this coating has the long antifouling phase.
Except common antifouling formulation and low-surface-energy type, the nonpolluting coating based on other new principle is arranged also.As the entrap gas nonpolluting coating of world patent 97-291571 invention, this coating forms osmotic membrane, the entrap gas with control surface tension force by hydrophobic microfilament.Form the entrap gas thin layer between surface and water body, reduce the hydrodynamic drag of coating, prevent sea marine organism pollution.Japanese Patent Publication 5-2284261 has invented the antifouling paint of a kind of pliability and excellent spring, makes halobiontic adhesive strength very low, can remove easily with water under high pressure, and elastic layer can not peeled off or be destroyed yet.The base-material of above-mentioned coating can be elastic epoxy resin or elastic polyurethane latex.US Patent No. 20100227111 has been invented the dirty coating of a kind of surface fiber chemoprevention, by thickness at least at 50 microns, length at least 3 millimeters fibrous.The thickness of fiber and length ratio are 0.01 at least, and the density of fibre columns is lower than 40fibres/mm
2This fiber coat can be applied directly on the ocean materials such as rope, building fittings and hull.
Due to the stained surface that occurs in biological, the character of the surface of solids can the appreciable impact fouling organism adheres to behavior.Therefore, build special surface and can develop the nontoxic anti-fouling material that makes new advances.The microstructure of the surface of solids can affect bacterium, algae spore and adhere to behavior and desorption behavior without vertebra larva etc.But not all surface with microstructure can prevent biological attachment, and fouling organism is easily adhered on some coarse surface all the better.It is most important that the surface micro-structure that can prevent biological attachment has the parameters such as special geometric parameter, particularly size, the degree of depth, Area Ratio, pattern, curvature.Therefore, the particular design of surface micro-structure is the key of this nontoxic anti-fouling material of exploitation.
Summary of the invention:
The object of the invention is to bring the problem of serious harm for the biodeterioration on boats and ships in marine environment and marine structure surface, the preparation method of the anti-fouling material of the micro-structural that a kind of surface has the special geometric parameter is provided.This micro-structural is the cross column, has certain height and Area Ratio, can suppress preferably marine growth the adhering at material surface such as algae spore, diatom and kentrogon.
In order to realize the foregoing invention purpose, the preparation method of anti-fouling material that a kind of surface of the present invention has cross rule micro-structural is as follows:
The processing method of this micro-structural is: adopt the electron beam lithography method, etch the micro-structural with cruciform pattern on photomask, elementary cell is the cross column, and end is tapered, and is staggered, forms array; Then at the dark silicon etching process of silicon chip surface using plasma, form the micro-structural of prescribed depth: the height of micro-structural is the 5-20 micron, hip cross is divided into projection, and this distance is from the cross top to the distance of bottom, its projection area with sidewall area than being 0.46-0.11; This structure cross is partly the pit that forms after etching.
The strong point of described micro-structural cross is 15 microns, and cross is wide is 3 microns, and the elementary cell spacing is 3.4 microns.
The preparation of anti-fouling material: silicon chip is kept flat, have micro-structural one facing up, utilize disposable adhesive tape tape edge to enclose, form take silicon chip the end of as the upper shed container take adhesive tape as wall; Then with the dimethyl silicone polymer fluid drips at silicon chip surface, make dimethyl silicone polymer be paved with silicon chip surface; Putting into vacuum desiccator vacuumizes and removes bubble; Standing until dimethyl silicone polymer solidifies, until after curing, the dimethyl silicone polymer film being opened from the edge fully under room temperature condition, can form the anti-fouling material that the surface has cross rule micro-structural at the dimethyl silicone polymer material surface.
The present invention is the organic silicon antifouling material that a kind of surface has cross rule micro-structural, the characteristics of this micro-structural are that top upper surface cross area and sidewall area ratio are less, interface curvature is larger, can greatly reduce the contact area of fouling organism and storeroom, the attachment site of fouling organism is reduced, thereby be not easy to adhere to, even adhere to also easy desorption; And the water contact angle of this material is larger, is 140 degree, near super-hydrophobic state, thereby makes fouling organism also be not easy to adhere to.Adhere to experiment through ulva spores, diatom and kentrogon and show, this material has anti-adhesion performance preferably.The microstructure characteristic on this material use surface is carried out antifouling, and do not produce loss, and can carry out automatically cleaning under certain current scour speed, be a kind of long-acting environment friendly anti-fouling material based on new principle, new ideas.
Description of drawings:
Fig. 1 is the arrangement mode figure of micro-structural cruciform pattern.
Fig. 2 is the concrete dimensional drawing of micro-structural elementary cell.
Fig. 3 is the stereoscan photograph of the micro-structural of 5 microns height.
Fig. 4 is the stereoscan photograph of the micro-structural of 20 microns height.
Embodiment:
Embodiment 1: the preparation of cross fine structure material
Utilize electron beam lithography preparation to have the photomask of pattern shown in Figure 1, the micro-structural arrangement mode as shown in Figure 1, this figure is the vertical view directly over material surface, Fig. 1 medium scale unit be micron.Etch the micro-structural with cruciform pattern, elementary cell is the cross column, and is staggered, form array, the strong point of cross is 15 microns, and cross is wide is 3 microns, the elementary cell spacing is 3.4 microns, concrete size as shown in Figure 2, in figure, the unit of scale be micron; Then utilize dark silicon etching method to carry out etching to silicon chip, 40min is etched to 20 microns of the degree of depth, can prepare 20 micrometer depth, has the silicon chip of cross recess patterns.The stereoscan photograph of micro-structural as shown in Figure 4.
Then, get dimethyl silicone polymer 20g and put into dixie cup, add silane coupler 2g, stir with glass bar, put into vacuum desiccator, be evacuated to 580Pa, keep 10min.Silicon chip adhesive tape tape edge, pour dimethyl silicone polymer into, cover whole silicon chip surface, then put into vacuum desiccator, be evacuated to 170Pa, after keeping 30min, take out to place under room temperature condition and after curing 48h, the dimethyl silicone polymer film is opened from the edge, prepare the dimethyl silicone polymer anti-fouling material that the surface has cross rule micro-structural.
Embodiment 2:
Utilize electron beam lithography preparation to have the photomask of pattern shown in Figure 1, the micro-structural arrangement mode as shown in Figure 1, this figure is the vertical view directly over material surface, Fig. 1 medium scale unit be micron.Etch the micro-structural with cruciform pattern, elementary cell is the cross column, and is staggered, form array, the strong point of cross is 15 microns, and cross is wide is 3 microns, the elementary cell spacing is 3.4 microns, concrete size as shown in Figure 2, in figure, the unit of scale be micron; Then utilize dark silicon etching method to carry out etching to silicon chip, etching depth was 5 microns in 10 minutes, can prepare 5 micrometer depth, had the silicon chip of cross recess patterns.The stereoscan photograph of micro-structural as shown in Figure 3.
Then, get dimethyl silicone polymer 20g and put into dixie cup, add silane coupler 2g, stir with glass bar, put into vacuum desiccator, be evacuated to 580Pa, keep 10min.Silicon chip adhesive tape tape edge, pour dimethyl silicone polymer into, cover whole silicon chip surface, then put into vacuum desiccator, be evacuated to 170Pa, after keeping 30min, take out to place under room temperature condition and after curing 48h, the dimethyl silicone polymer film is opened from the edge, prepare the dimethyl silicone polymer anti-fouling material that the surface has cross rule micro-structural.
Embodiment 3: the surface contact angle of cross fine structure material is measured
Measure having cross rule micro-structural dimethyl silicone polymer material and there is no the static contact angle of the dimethyl silicone polymer material of micro-structural of embodiment 1 preparation with the Static Contact angle measuring instrument.Through measuring, the static contact angle that there is no the dimethyl silicone polymer material of micro-structural is 111.9 °, and the static contact angle with cross micro-structural dimethyl silicone polymer material of embodiment 1 preparation is 140.7 °.The existence of surface micro-structure has significantly improved the hydrophobicity of material.
Embodiment 4: the ulva spores of cross fine structure material adheres to test
The anti-fouling material of embodiment 1 preparation is carried out ulva spores adhere to test, take the dimethyl silicone polymer material that there is no micro-structural as contrast.Be 1 * 10 with the ulva spores that newly discharges with the dilution of sterilization seawater
5The concentration of individual/ml, after 24 hours, ulva spores is 43/mm at the control material adhesion amount
2, ulva spores is 8/mm in the anti-fouling material surface attachment amount of embodiment 1 preparation
2, inhibiting rate is 81.4%; Adopt the material after rotary drum adheres to ulva spores to wash away 5min with the tangential velocity of 3 joints, carried out centrifugal desorption test, the volume residual of ulva spores on control material is 14/mm
2, desorption rate is 67.4%, and volume residual is 0/mm on micro-structural anti-fouling material surface
2, desorption rate is 100%.Visible surface has the cross fine structure material not only makes ulva spores be difficult to adhere to, and makes its easier desorption, has better ulva spores with respect to contrast low surface energy organic silicon material and prevents and kill off performance.
Embodiment 5: the diatom of cross fine structure material adheres to test
The anti-fouling material of embodiment 1 preparation is carried out diatom adhere to test, take the dimethyl silicone polymer material that there is no micro-structural as contrast.Be 1 * 10 with small-sized boat-shaped algae with the dilution of sterilization seawater
5The concentration of individual/ml, after 24 hours, diatom is 67/mm at the control material adhesion amount
2, be 13/mm in the anti-fouling material surface attachment amount of embodiment 1 preparation
2, inhibiting rate is 80.6%; Adopt the material after rotary drum adheres to diatom to wash away 5min with the tangential velocity of 3 joints, carried out centrifugal desorption test, the volume residual of diatom on control material is 35/mm
2, desorption rate is 47.8%, and volume residual is 0/mm on micro-structural anti-fouling material surface
2, desorption rate is 100%.Visible surface has cross rule micro-structural anti-fouling material not only makes diatom be difficult to adhere to, and makes its easier desorption, has better diatom with respect to contrast low surface energy organic silicon material and prevents and kill off performance.
Embodiment 6: the barnacle that the surface has cross rule fine structure material adheres to test
The anti-fouling material of embodiment 1 preparation is carried out kentrogon adhere to test, take the dimethyl silicone polymer material that there is no micro-structural as contrast.Bi-material is put into respectively container, add filtering sea, then add respectively 20 kentrogons, cultivate under room temperature condition, observe moving about and adhesion condition of kentrogon every day, after 3 days, the barnacle on control material surface adheres to, and micro-structural anti-fouling material surface is not adhered to.The anti-fouling material that visible surface has cross rule micro-structural is difficult for adhering to kentrogon.
Claims (1)
1. a surface has the preparation method of the anti-fouling material of cross rule micro-structural, it is characterized in that: the processing method of micro-structural is: adopt the electron beam lithography method, etch the micro-structural with cruciform pattern on photomask, elementary cell is the cross column, end is tapered, staggered, form array; Then at the dark silicon etching process of silicon chip surface using plasma, form the micro-structural of prescribed depth: the height of micro-structural is the 5-20 micron, hip cross is divided into projection, and this distance is from the cross top to the distance of bottom, its projection area with sidewall area than being 0.46-0.11; This structure cross is partly the pit that forms after etching; The preparation of anti-fouling material: silicon chip is kept flat, have micro-structural one facing up, utilize disposable adhesive tape tape edge to enclose, form take silicon chip the end of as the upper shed container take adhesive tape as wall; Then with the dimethyl silicone polymer fluid drips at silicon chip surface, make dimethyl silicone polymer be paved with silicon chip surface; Putting into vacuum desiccator vacuumizes and removes bubble; Standing until dimethyl silicone polymer solidifies, until after curing, the dimethyl silicone polymer film being opened from the edge fully under room temperature condition, can form the anti-fouling material that the surface has cross rule micro-structural at the dimethyl silicone polymer material surface; The strong point of described micro-structural cross is 15 microns, and cross is wide is 3 microns, and the elementary cell spacing is 3.4 microns.
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| CN103043595A (en) * | 2012-12-14 | 2013-04-17 | 于晓勇 | Mildew proof antibacterial material with bionic micrometer structure surface and preparation method thereof |
| CN104044694B (en) * | 2014-07-01 | 2016-08-17 | 中国船舶重工集团公司第七二五研究所 | A kind of self adaptation micro structure anti-fouling anti-drag material and preparation method thereof |
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| CN107034470B (en) * | 2017-04-10 | 2019-07-12 | 武汉理工大学 | A kind of preparation method of the topological structure antifouling surface with different scale groove |
| CN107128437A (en) * | 2017-05-10 | 2017-09-05 | 吉林大学 | A kind of bionical rust resistance and corrosion resistance submersible shell |
| CN107177050B (en) * | 2017-07-10 | 2019-03-19 | 中国船舶重工集团公司第七二五研究所 | A kind of micro-structure cooperates with anti-fouling material and preparation method thereof with antifouling activity substance |
| CN109337105B (en) * | 2018-06-12 | 2021-03-16 | 中国船舶重工集团公司第七二五研究所 | Method for preparing hydrophilic-hydrophobic interaction distribution microstructure surface |
| CN111944420A (en) * | 2020-07-21 | 2020-11-17 | 青岛理工大学 | Marine antifouling coating with bionic synergistic effect and preparation method thereof |
| CN117125215A (en) * | 2021-02-24 | 2023-11-28 | 北京丰润铭科贸有限责任公司 | Bionic anti-biological parasitic flexible ship bottom material and structure |
| CN115678078A (en) * | 2022-11-03 | 2023-02-03 | 中国科学院半导体研究所 | Transferable super-hydrophobic film and preparation method thereof |
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|---|---|---|---|---|
| EP1115798B1 (en) * | 1998-06-25 | 2004-03-10 | CSL Silicones Inc. | One-part organopolysiloxane rubber composition for use as a corrosion protection coating on metals |
| CN101260262A (en) * | 2008-04-15 | 2008-09-10 | 中国船舶重工集团公司第七二五研究所 | Antifouling material capable of forming concave-convex micro-structure surface and preparation method thereof |
| JP2009263458A (en) * | 2008-04-23 | 2009-11-12 | Shirakawa Kazuko | Surface treatment composition and surface treating method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1115798B1 (en) * | 1998-06-25 | 2004-03-10 | CSL Silicones Inc. | One-part organopolysiloxane rubber composition for use as a corrosion protection coating on metals |
| CN101260262A (en) * | 2008-04-15 | 2008-09-10 | 中国船舶重工集团公司第七二五研究所 | Antifouling material capable of forming concave-convex micro-structure surface and preparation method thereof |
| JP2009263458A (en) * | 2008-04-23 | 2009-11-12 | Shirakawa Kazuko | Surface treatment composition and surface treating method |
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