技术领域technical field
本发明属于微纳加工技术领域，尤其涉及一种仿生壁虎干胶及其制备方法。The invention belongs to the technical field of micro-nano processing, and in particular relates to a bionic gecko dry glue and a preparation method thereof.
背景技术Background technique
自然界中生物体所特有的功能很大程度上与其表面微观结构有着密切关系，例如壁虎脚掌具有非常精细的微纳复合结构，约有50万根刚毛，每根刚毛具有约1000根绒毛，当其与固体表面接触时，可以产生强大的粘附力，并且能够快速脱离，使得壁虎能够快速地在垂直的天花板和平行的墙面爬行。同时壁虎脚掌的微纳复合结构具有超疏水性，污水不容易在其表面吸附、沉积，具有自清洁特征。The unique functions of organisms in nature are closely related to their surface microstructure to a large extent. For example, the paw of a gecko has a very fine micro-nano composite structure, with about 500,000 setae, and each setae has about 1,000 hairs. When in contact with a solid surface, it can produce a strong adhesive force and can quickly detach, allowing the gecko to quickly crawl on vertical ceilings and parallel walls. At the same time, the micro-nano composite structure of the gecko's feet is super-hydrophobic, and sewage is not easy to adsorb and deposit on its surface, and it has self-cleaning characteristics.
壁虎的干性粘附优于其他吸附原理，对环境和壁面具有普适性。基于此优异功能得到的仿生微纳结构(如仿生壁虎干胶)日益受到重视，在微电子、国防、生物材料等高新技术领域的应用也越来越广泛。Gecko's dry adhesion is superior to other adsorption principles, and it is universal to the environment and walls. Biomimetic micro-nano structures based on this excellent function (such as biomimetic gecko dry glue) are increasingly valued, and their applications in high-tech fields such as microelectronics, national defense, and biomaterials are becoming more and more extensive.
然而，目前已有的仿生壁虎干胶，大多是采用聚二甲基硅氧烷(PDMS)研制而成，仿生壁虎干胶存在结构不规则、粘附力不强、抗拉伸强度低等问题，另外，仿生壁虎干胶一般是基于微机电系统(MEMS)技术制备得到，其制备工艺复杂且成本高，无法精细控制壁虎的微纳结构。因此，有必要开发一种具有结构规整、粘附性高、自清洁性强、能重复使用的仿生壁虎干胶及其制备方法。However, most of the existing bionic gecko adhesives are developed from polydimethylsiloxane (PDMS), which has problems such as irregular structure, weak adhesion, and low tensile strength. , In addition, bionic gecko dry glue is generally prepared based on micro-electromechanical system (MEMS) technology, the preparation process is complex and costly, and the micro-nano structure of gecko cannot be finely controlled. Therefore, it is necessary to develop a bionic gecko dry glue with regular structure, high adhesion, strong self-cleaning property and reusability and a preparation method thereof.
发明内容Contents of the invention
有鉴于此，本发明提供了一种仿生壁虎干胶及其制备方法，所述仿生壁虎干胶的结构规则，所述仿生壁虎干胶包括基底和T型微纳米结构，其中T型微纳米结构包括柱体和设置在柱体顶部的盖体，而且所述仿生壁虎干胶的材质为乙烯-醋酸乙烯共聚物(简称EVA)，仿生壁虎干胶结构中多个盖体的存在及EVA材质使得所述仿生壁虎干胶不仅具有强效粘附力，而且还具有高透光率、高抗拉伸强度、自清洁性强等优点；所述仿生壁虎干胶的制备方法简单易操作，克服了目前加工微纳复合结构成本高、工艺复杂、难以加工规则有序结构的缺点，该方法可精细复现设计图案，且适用于仿生壁虎干胶的批量生产。In view of this, the present invention provides a bionic gecko dry glue and a preparation method thereof. The bionic gecko dry glue has a regular structure, and the bionic gecko dry glue includes a substrate and a T-shaped micro-nano structure, wherein the T-shaped micro-nano structure It includes a cylinder and a cover arranged on the top of the cylinder, and the material of the bionic gecko dry glue is ethylene-vinyl acetate copolymer (referred to as EVA). The existence of multiple covers and the EVA material in the bionic gecko dry glue structure make The bionic gecko dry glue not only has strong adhesion, but also has the advantages of high light transmittance, high tensile strength, and strong self-cleaning property; the preparation method of the bionic gecko dry glue is simple and easy to operate, which overcomes the At present, the processing cost of micro-nano composite structure is high, the process is complicated, and it is difficult to process regular and orderly structures. This method can accurately reproduce the design pattern, and is suitable for mass production of bionic gecko dry glue.
第一方面，本发明提供了一种仿生壁虎干胶，所述仿生壁虎干胶的材质为乙烯-醋酸乙烯共聚物(简称EVA)，所述仿生壁虎干胶包括基底及设置在所述基底上的多个T型微纳米结构，其中，所述T型微纳米结构包括柱体和设置在柱体顶部的盖体，所述柱体在竖直方向上的投影落入所述盖体在竖直方向上的投影范围内。In the first aspect, the present invention provides a kind of bionic gecko dry glue, the material of the bionic gecko dry glue is ethylene-vinyl acetate copolymer (referred to as EVA), the bionic gecko dry glue includes a base and is arranged on the base A plurality of T-shaped micro-nanostructures, wherein the T-shaped micro-nanostructures include a column and a cover arranged on the top of the column, and the projection of the column in the vertical direction falls into the cover in the vertical direction. Within the range of projection in the vertical direction.
优选地，所述盖体的尺寸为5-35μm，所述柱体的高度为15-25μm，相邻各柱体之间的间距为20-50μm。Preferably, the size of the cover is 5-35 μm, the height of the columns is 15-25 μm, and the distance between adjacent columns is 20-50 μm.
优选地，所述柱体在的直径或边长为4-30μm。Preferably, the diameter or side length of the cylinder is 4-30 μm.
所述柱体可以是圆柱体、长方体、正方体、圆台或棱台。The column may be a cylinder, a cuboid, a cube, a circular frustum or a prism.
所述盖体可以是圆形或方形。所述盖体的直径或边长为5-35μm。The cover can be round or square. The diameter or side length of the cover is 5-35 μm.
第二方面，本发明提供了一种仿生壁虎干胶的制备方法，包括以下步骤：In a second aspect, the present invention provides a method for preparing bionic gecko dry glue, comprising the following steps:
(1)制备微纳结构：选一基板，在所述基板表面依次旋涂第一高分子涂层、第二高分子涂层，对两层高分子涂层进行逐层刻蚀获得基于高分子涂层的负T型微纳米结构；(1) Preparation of micro-nano structure: select a substrate, spin-coat the first polymer coating and the second polymer coating on the surface of the substrate in turn, and etch the two layers of polymer coatings layer by layer to obtain polymer-based Negative T-shaped micro-nanostructure of the coating;
(2)表面疏水处理：对所述负T型微纳米结构的表面进行疏水处理，所述负T型微纳米结构的表面形成疏水薄膜；(2) surface hydrophobic treatment: the surface of the negative T-shaped micro-nanostructure is hydrophobically treated, and the surface of the negative T-shaped micro-nanostructure forms a hydrophobic film;
(3)转印：将上述疏水处理后的负T型微纳米结构经两次转印至弹性体材料，经脱膜得到负T型结构的弹性体印章；(3) Transfer printing: the negative T-shaped micro-nano structure after the above-mentioned hydrophobic treatment is transferred to the elastomer material twice, and the elastic body seal of the negative T-shaped structure is obtained through stripping;
(4)浇注：将乙烯-醋酸乙烯共聚物(简称EVA)浇注到所述负T型结构的弹性体印章内，待真空除气后，经固化、脱膜得到材质为EVA的T型微纳米结构；(4) Pouring: Pouring ethylene-vinyl acetate copolymer (EVA for short) into the elastomer seal of the negative T-shaped structure, and after vacuum degassing, T-shaped micro-nano stamps made of EVA are obtained by curing and stripping. structure;
(5)表面疏水处理：将步骤(4)获得的T型微纳米结构进行疏水处理，使所述T型微纳米结构的表面形成疏水薄膜，即得到具有多个T型微纳米结构的仿生壁虎干胶，所述仿生壁虎干胶包括基底及设置在所述基底上的多个T型微纳米结构，其中，所述T型微纳米结构包括柱体和设置在柱体顶部的盖体，所述柱体在竖直方向上的投影落入所述盖体在竖直方向上的投影范围内。(5) Surface hydrophobic treatment: the T-shaped micro-nanostructure obtained in step (4) is subjected to hydrophobic treatment, so that the surface of the T-shaped micro-nanostructure forms a hydrophobic film, that is, a bionic gecko with multiple T-shaped micro-nanostructures is obtained Dry glue, the bionic gecko dry glue includes a substrate and a plurality of T-shaped micro-nanostructures arranged on the substrate, wherein the T-shaped micro-nanostructures include a column and a cover arranged on the top of the column, so The projection of the cylinder in the vertical direction falls within the projection range of the cover in the vertical direction.
优选地，步骤(1)中，所述基板包括硅片、塑料、石英或玻璃，但不限于此。Preferably, in step (1), the substrate includes silicon wafer, plastic, quartz or glass, but not limited thereto.
所述第一高分子涂层包括AR5460或AR5480或含有PMMA的共聚物，所述第二高分子涂层包括SU-8光刻胶，但不限于此。The first polymer coating includes AR5460 or AR5480 or a copolymer containing PMMA, and the second polymer coating includes SU-8 photoresist, but is not limited thereto.
如本发明所述的，所述AR5460、AR548为AR系列的胶，不感光，可以使用AR系列的特定溶剂AR300显影剂来溶解。所述SU-8光刻胶包括SU8-T3035，SU8-2025或SU8-2050，但不限于此。As described in the present invention, the AR5460 and AR548 are AR series glues, which are not photosensitive, and can be dissolved with AR series specific solvent AR300 developer. The SU-8 photoresist includes SU8-T3035, SU8-2025 or SU8-2050, but is not limited thereto.
优选地，步骤(1)中，所述对两层高分子涂层进行逐层刻蚀获得基于高分子涂层的负T型微纳米结构，包括：Preferably, in step (1), the two-layer polymer coating is etched layer by layer to obtain a negative T-shaped micro-nano structure based on the polymer coating, including:
使用所述第二高分子涂层的显影剂来显影所述第二高分子涂层，获得特定的微米或纳米图形；using the developer of the second polymer coating to develop the second polymer coating to obtain a specific micro or nano pattern;
使用特定溶剂通过显影后的所述第二高分子涂层来刻蚀所述第一高分子涂层；在所述第二高分子涂层和所述第一高分子涂层上形成负T型微纳米结构。Use a specific solvent to etch the first polymer coating through the developed second polymer coating; form a negative T-shaped coating on the second polymer coating and the first polymer coating micro-nanostructure.
优选地，所述显影剂包括SU-8显影剂，所述特定溶剂包括AR300显影剂或可溶解PMMA的有机溶剂。Preferably, the developer includes SU-8 developer, and the specific solvent includes AR300 developer or an organic solvent that can dissolve PMMA.
更优选地，所述可溶解PMMA的有机溶剂包括甲苯和丙酮中的一种或多种，但不限于此。More preferably, the PMMA-soluble organic solvent includes one or more of toluene and acetone, but is not limited thereto.
优选地，步骤(2)中，所述对所述T型微纳米结构的表面进行疏水处理，使所述T型微纳米结构的表面形成疏水薄膜，具体包括：Preferably, in step (2), the hydrophobic treatment is carried out on the surface of the T-type micro-nanostructure so that the surface of the T-type micro-nanostructure forms a hydrophobic film, which specifically includes:
使用化学气相沉积工艺处理加热硅基板上的T型微纳米结构的表面，T型微纳米结构的各个方向使用等离子状态下的碳氟化合物气源均匀沉积，在T型微纳米结构的表面形成具有疏水性的碳氟化合物薄膜，所述碳氟化合物包括C4F8或CF4；Chemical vapor deposition process is used to process the surface of the T-shaped micro-nano structure on the heated silicon substrate, and the T-shaped micro-nano structure is uniformly deposited in all directions using a fluorocarbon gas source in a plasma state, forming a characteristic on the surface of the T-shaped micro-nano structure Hydrophobic fluorocarbon films comprisingC4F8 orCF4;
或者，使用单分子自组装材料在T型微纳米结构的表面进行自组装形成疏水性薄膜，所述单分子自组装材料包括全氟辛基三氯硅烷(PFTS)、全氟葵基三氯硅烷或全氟十二基三氯硅烷，但不限于此。Alternatively, use a single-molecule self-assembly material to self-assemble on the surface of the T-shaped micro-nano structure to form a hydrophobic film, and the single-molecule self-assembly material includes perfluorooctyltrichlorosilane (PFTS), perfluorodecyltrichlorosilane or perfluorododecyltrichlorosilane, but not limited thereto.
优选地，步骤(3)中，所述弹性体材料包括聚二甲基硅氧烷(PDMS)、三元乙丙橡胶、丁晴橡胶、顺丁胶和氯丁胶中的一种，但不限于此。Preferably, in step (3), the elastomeric material includes one of polydimethylsiloxane (PDMS), EPDM, NBR, butadiene rubber and neoprene, but not limited to this.
优选地，所述将上述疏水处理后的负T型微纳米结构两次转印至弹性体材料，经剥离得到负T型结构的弹性体印章，具体包括：Preferably, the above-mentioned negative T-shaped micro-nano structure after the hydrophobic treatment is transferred twice to the elastomer material, and the elastomer stamp with the negative T-shaped structure is obtained after peeling off, specifically including:
将上述疏水处理后的负T型微纳米结构转印至弹性体材料，经脱膜得到T型结构的弹性体印章；Transferring the negative T-shaped micro-nano structure after the above-mentioned hydrophobic treatment to the elastomer material, and obtaining a T-shaped elastomer stamp through defilming;
再将T型结构的弹性体印章转印至弹性体材料，经脱膜得到负T型结构的弹性体印章。Then transfer the elastic body stamp with T-shaped structure to the elastic body material, and obtain the elastic body stamp with negative T-shaped structure through stripping.
优选地，所述将乙烯-醋酸乙烯共聚物(简称EVA)浇注到所述负T型结构的弹性体印章内之前，还包括：Preferably, before pouring ethylene-vinyl acetate copolymer (EVA for short) into the elastomer stamp of the negative T-shaped structure, it also includes:
将所述负T型结构的弹性体印章的表面进行疏水处理，使所述负T型结构的弹性体印章的表面形成疏水薄膜。The surface of the elastic body stamp with the negative T-shaped structure is subjected to hydrophobic treatment, so that the surface of the elastic body stamp with the negative T-shaped structure forms a hydrophobic film.
优选地，步骤(4)中，所述乙烯-醋酸乙烯共聚物(EVA)的相对分子量为1000-3000。Preferably, in step (4), the relative molecular weight of the ethylene-vinyl acetate copolymer (EVA) is 1000-3000.
更优选地，所述EVA中，醋酸乙烯的摩尔含量为20％-30％。More preferably, in the EVA, the molar content of vinyl acetate is 20%-30%.
优选地，步骤(1)中，所述在所述基板表面依次旋涂第一高分子涂层、第二高分子涂层之前，还包括：Preferably, in step (1), before the first polymer coating and the second polymer coating are sequentially spin-coated on the surface of the substrate, further comprising:
使用有机溶剂或氢氟酸清洗硅基板；将清洗后的硅基板在烘箱或者热台上烘烤。Clean the silicon substrate with an organic solvent or hydrofluoric acid; bake the cleaned silicon substrate in an oven or a hot stage.
第三方面，本发明提供了一种仿生壁虎干胶的制备方法，包括以下步骤：In a third aspect, the present invention provides a method for preparing bionic gecko dry glue, comprising the following steps:
(1)制备微纳结构：选一硅基板，利用光刻技术将掩膜版上的微图案转移到所述硅基板上，并通过干法刻蚀工艺在硅基板上进行刻蚀，获得T型微纳米结构；(1) Preparation of micro-nano structure: select a silicon substrate, use photolithography technology to transfer the micro-pattern on the mask plate to the silicon substrate, and etch the silicon substrate through a dry etching process to obtain T Type micro-nano structure;
(2)表面疏水处理：对所述T型微纳米结构的表面进行疏水处理，使所述T型微纳米结构的表面形成疏水薄膜；(2) Surface hydrophobic treatment: carry out hydrophobic treatment to the surface of the T-shaped micro-nanostructure, so that the surface of the T-shaped micro-nanostructure forms a hydrophobic film;
(3)转印：将上述疏水处理后的T型微纳米结构转印至弹性体材料，经脱膜得到负T型结构的弹性体印章；(3) Transfer printing: transfer the T-shaped micro-nano structure after the above-mentioned hydrophobic treatment to the elastomer material, and obtain an elastomer stamp with a negative T-shaped structure through stripping;
(4)浇注：将乙烯-醋酸乙烯共聚物(简称EVA)浇注到所述负T型结构的弹性体印章内，待真空除气后，经固化、脱膜得到材质为EVA的T型微纳米结构；(4) Pouring: Pouring ethylene-vinyl acetate copolymer (EVA for short) into the elastomer seal of the negative T-shaped structure, and after vacuum degassing, T-shaped micro-nano stamps made of EVA are obtained by curing and stripping. structure;
(5)表面疏水处理：将步骤(4)获得的T型微纳米结构进行疏水处理，使所述T型微纳米结构的表面形成疏水薄膜，即得到具有多个T型微纳米结构的仿生壁虎干胶，所述仿生壁虎干胶包括基底及设置在所述基底上的多个T型微纳米结构，其中，所述T型微纳米结构包括柱体和设置在柱体顶部的盖体，所述柱体在竖直方向上的投影落入所述盖体在竖直方向上的投影范围内。(5) Surface hydrophobic treatment: the T-shaped micro-nanostructure obtained in step (4) is subjected to hydrophobic treatment, so that the surface of the T-shaped micro-nanostructure forms a hydrophobic film, that is, a bionic gecko with multiple T-shaped micro-nanostructures is obtained Dry glue, the bionic gecko dry glue includes a substrate and a plurality of T-shaped micro-nanostructures arranged on the substrate, wherein the T-shaped micro-nanostructures include a column and a cover arranged on the top of the column, so The projection of the cylinder in the vertical direction falls within the projection range of the cover in the vertical direction.
优选地，步骤(1)中，所述硅基板为表面具有热生长的二氧化硅薄膜的硅基板。Preferably, in step (1), the silicon substrate is a silicon substrate with a thermally grown silicon dioxide film on its surface.
优选地，步骤(1)中，所述通过干法刻蚀工艺在硅基板上进行刻蚀，获得T型微纳米结构，具体包括：将硅基板通过气相刻蚀工艺或通过深层反应离子刻蚀工艺进行刻蚀，直至获得T型微纳米结构。Preferably, in step (1), the etching on the silicon substrate through a dry etching process to obtain a T-type micro-nano structure specifically includes: the silicon substrate is etched through a vapor phase etching process or through deep reactive ion etching The etching process is carried out until a T-shaped micro-nano structure is obtained.
进一步优选地，所述通过深层反应离子刻蚀工艺进行刻蚀，具体包括：利用分时复用的工艺以C4F8和SF6气体交替进行等离子沉积和刻蚀，再通过高密度等离子体垂直轰击硅基板，从而各向异性地刻蚀硅基板。Further preferably, the etching by deep reactive ion etching process specifically includes: using a time-division multiplexing process to alternately perform plasma deposition and etching with C4 F8 and SF6 gases, and then pass high-density plasma The silicon substrate is bombarded vertically to etch the silicon substrate anisotropically.
优选地，步骤(2)中，所述对所述T型微纳米结构的表面进行疏水处理，使所述T型微纳米结构的表面形成疏水薄膜，具体包括：Preferably, in step (2), the hydrophobic treatment is carried out on the surface of the T-type micro-nanostructure so that the surface of the T-type micro-nanostructure forms a hydrophobic film, which specifically includes:
使用化学气相沉积工艺处理加热硅基板上的T型微纳米结构的表面，T型微纳米结构的各个方向使用等离子状态下的碳氟化合物气源均匀沉积，在T型微纳米结构的表面形成具有疏水性的碳氟化合物薄膜，所述碳氟化合物包括C4F8或CF4；Chemical vapor deposition process is used to process the surface of the T-shaped micro-nano structure on the heated silicon substrate, and the T-shaped micro-nano structure is uniformly deposited in all directions using a fluorocarbon gas source in a plasma state, forming a characteristic on the surface of the T-shaped micro-nano structure Hydrophobic fluorocarbon films comprisingC4F8 orCF4;
或者，使用单分子自组装材料在T型微纳米结构的表面进行自组装形成疏水性薄膜，所述单分子自组装材料包括全氟辛基三氯硅烷、全氟葵基三氯硅烷或全氟十二基三氯硅烷。Alternatively, use a single-molecule self-assembly material to self-assemble on the surface of the T-shaped micro-nanostructure to form a hydrophobic film, and the single-molecule self-assembly material includes perfluorooctyltrichlorosilane, perfluorodecyltrichlorosilane or perfluorodecyltrichlorosilane. Dodecyltrichlorosilane.
优选地，步骤(3)中，所述弹性体材料包括聚二甲基硅氧烷(PDMS)、三元乙丙橡胶、丁晴橡胶、顺丁胶和氯丁胶中的一种，但不限于此。Preferably, in step (3), the elastomeric material includes one of polydimethylsiloxane (PDMS), EPDM, NBR, butadiene rubber and neoprene, but not limited to this.
如本发明所述的，所述将上述疏水处理后的T型微纳米结构转印至弹性体材料，经脱膜得到负T型结构的弹性体印章，具体是将弹性体材料浇注所述疏水处理后的T型微纳米结构，待弹性体材料固化后，揭膜，得到负T型结构的弹性体印章。As described in the present invention, the T-shaped micro-nano structure after the above-mentioned hydrophobic treatment is transferred to the elastomer material, and an elastomer stamp with a negative T-shaped structure is obtained through stripping, specifically, the elastomer material is poured into the hydrophobic After the treated T-shaped micro-nano structure, after the elastomer material is solidified, the film is peeled off to obtain an elastomer stamp with a negative T-shaped structure.
优选地，所述将乙烯-醋酸乙烯共聚物(简称EVA)浇注到所述负T型结构的弹性体印章内之前，还包括：Preferably, before pouring ethylene-vinyl acetate copolymer (EVA for short) into the elastomer stamp of the negative T-shaped structure, it also includes:
将所述负T型结构的弹性体印章的表面进行疏水处理，使所述负T型结构的弹性体印章的表面形成疏水薄膜。The surface of the elastic body stamp with the negative T-shaped structure is subjected to hydrophobic treatment, so that the surface of the elastic body stamp with the negative T-shaped structure forms a hydrophobic film.
优选地，步骤(4)中，所述固化是在温度为0-5℃下固化4-6h。Preferably, in step (4), the curing is at a temperature of 0-5° C. for 4-6 hours.
优选地，步骤(1)中，所述利用光刻技术将掩膜版上的微图案转移到所述硅基板上之前，还包括：Preferably, in step (1), before transferring the micropattern on the mask plate to the silicon substrate by using photolithography technology, it also includes:
使用有机溶剂或氢氟酸清洗硅基板；将清洗后的硅基板在烘箱或者热台上烘烤。Clean the silicon substrate with an organic solvent or hydrofluoric acid; bake the cleaned silicon substrate in an oven or a hot stage.
所述仿生壁虎干胶包括基底和T型微纳米结构，其中T型微纳米结构包括柱体和设置在柱体顶部的盖体，盖体的存在，可以增加仿生壁虎干胶的粘附能力，相对于附图7的柱体上具有多个纤细的分叉结构而言，本申请中柱体顶部的所述盖体的表面积较大，各个盖体不会发生交叉纠缠或倒塌，与壁面之间的接触较大，粘附能力强。The bionic gecko dry glue includes a substrate and a T-shaped micro-nano structure, wherein the T-shaped micro-nano structure includes a column and a cover arranged on the top of the column. The presence of the cover can increase the adhesion of the bionic gecko dry glue, Compared with the multiple slender bifurcated structures on the cylinder in Fig. 7, the cover at the top of the cylinder in this application has a larger surface area, and each cover will not be entangled or collapsed, and the gap between the cover and the wall The contact between them is large and the adhesion ability is strong.
本发明中，使用弹性体材料将硅基板上的T型微纳米结构或两层高分子涂层上的负T型微纳米结构转印而制成负T型结构的弹性体印章，然后借助负T型结构的弹性体印章的软复制方法，可将上述微纳结构多次转印至在乙烯-醋酸乙烯共聚物(简称EVA)上，得到材质为EVA的仿生壁虎干胶。In the present invention, the T-shaped micro-nanostructure on the silicon substrate or the negative T-shaped micro-nanostructure on the two-layer polymer coating is transferred by using an elastomer material to make an elastic body stamp with a negative T-shaped structure, and then the The soft replication method of the elastic body stamp with T-shaped structure can transfer the above-mentioned micro-nano structure to ethylene-vinyl acetate copolymer (referred to as EVA) multiple times to obtain the bionic gecko dry glue made of EVA.
所用EVA的成膜固化温度低、透光性高，成膜性能好，固化后形成的EVA膜的抗拉伸、抗弹性形变的能力较强，且对水、油均有较好的阻挡作用，使得所制得的仿生壁虎干胶可保持高质量的超疏水超疏油性能，自清洁性强，不仅具有强效粘附力，而且还具有高透光率、高抗拉伸强度等优点。The EVA used has low film-forming and curing temperature, high light transmittance, and good film-forming performance. The EVA film formed after curing has strong resistance to stretching and elastic deformation, and has a good blocking effect on water and oil. , so that the prepared bionic gecko dry glue can maintain high-quality superhydrophobic and superoleophobic properties, strong self-cleaning, not only has strong adhesion, but also has the advantages of high light transmittance, high tensile strength, etc. .
此外，弹性体材料的易脱模、高精度、耐用性，中间制得的负T型结构的弹性体印章可以多次重复利用，使用于质为EVA的仿生壁虎干胶的批量、高精度生产，同时还可显著降低仿生壁虎干胶的生产成本。In addition, the elastomer material is easy to release, high-precision, and durable. The elastomer stamp with a negative T-shaped structure can be reused many times, and it is used in the batch and high-precision production of bionic gecko dry glue made of EVA. , and can also significantly reduce the production cost of bionic gecko dry glue.
与现有技术相比，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
1、所述仿生壁虎干胶包括基底和T型微纳米结构，其中T型微纳米结构包括柱体和设置在柱体顶部的盖体，而且所述仿生壁虎干胶的材质为乙烯-醋酸乙烯共聚物(简称EVA)，仿生壁虎干胶中盖体的存在及EVA材质使得所述仿生壁虎干胶不仅具有强效粘附力，而且还具有高透光率、高抗拉伸强度、自清洁性强等优点；1. The bionic gecko dry glue includes a substrate and a T-shaped micro-nano structure, wherein the T-shaped micro-nano structure includes a cylinder and a cover arranged on the top of the cylinder, and the material of the bionic gecko dry glue is ethylene-vinyl acetate Copolymer (referred to as EVA), the existence of the cover in the bionic gecko dry glue and the EVA material make the bionic gecko dry glue not only have strong adhesion, but also have high light transmittance, high tensile strength, self-cleaning Strong and other advantages;
2、所述仿生壁虎干胶的制备方法简单易操作，克服了目前加工微纳复合结构成本高、工艺复杂、难以加工规则有序结构的缺点，该方法可精细复现设计图案，且适用于仿生壁虎干胶的批量生产。2. The preparation method of the biomimetic gecko dry glue is simple and easy to operate, which overcomes the shortcomings of high cost, complicated process and difficulty in processing regular and orderly structures in the current processing of micro-nano composite structures. Mass production of bionic gecko dry glue.
附图说明Description of drawings
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单的介绍。In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings that are required in the description of the embodiments or the prior art.
图1是本发明实施例1中仿生壁虎干胶的制备方法的流程图；Fig. 1 is the flow chart of the preparation method of bionic gecko dry glue in the embodiment 1 of the present invention;
图2是本发明实施例1中仿生壁虎干胶的结构示意图；Fig. 2 is a schematic structural view of the bionic gecko dry glue in Example 1 of the present invention;
图3是图1是本发明实施例3中仿生壁虎干胶的制备方法的流程图；Fig. 3 is Fig. 1 is the flow chart of the preparation method of bionic gecko dry glue in the embodiment 3 of the present invention;
图4为本发明实施例3的经一次转印得到的脱膜处理前的T型结构的弹性体印章的结构示意图；4 is a schematic structural view of an elastomer stamp with a T-shaped structure obtained by one transfer printing in Example 3 of the present invention before the release treatment;
图5是本发明实施例1的仿生壁虎干胶与材质为PDMS的仿生壁虎干胶的粘附力性能比对图；Fig. 5 is a comparison chart of the adhesion performance between the bionic gecko dry glue of Example 1 of the present invention and the bionic gecko dry glue made of PDMS;
图6是本发明实施例3-4的仿生壁虎干胶与材质为PDMS的仿生壁虎干胶的纵向剥离力与预压力的变化关系对比图；Fig. 6 is a comparison diagram of the relationship between the longitudinal peeling force and the pre-pressure of the bionic gecko dry glue of Example 3-4 of the present invention and the bionic gecko dry glue made of PDMS;
图7是现有技术中的仿生壁虎干胶的结构示意图。Fig. 7 is a schematic structural view of the bionic gecko dry glue in the prior art.
具体实施方式detailed description
下面结合附图及实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。应当指出，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。The technical solutions in the embodiments of the present invention are clearly and completely described below in conjunction with the accompanying drawings and embodiments. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. It should be pointed out that the specific embodiments described here are only used to explain the present invention, not to limit the present invention.
实施例1Example 1
参见附图1的仿生壁虎干胶的制备方法的流程图，本实施例提供的一种仿生壁虎干胶的制备方法，包括以下步骤：Referring to the flowchart of the preparation method of the bionic gecko dry glue of accompanying drawing 1, a kind of preparation method of the bionic gecko dry glue provided in this embodiment comprises the following steps:
S101、制备微纳结构：选一硅基板，该硅基板为表面具有热生长的、厚度为300nm的二氧化硅薄膜的硅基板，在上述硅基板上旋涂光刻胶，曝光、显影，将设计好的掩膜版上的微尺度图形转移到旋涂的光刻胶表面；采用反应离子刻蚀法将光刻胶上的图形进一步转移到SiO2薄表面，具体是以光刻胶为掩模、利用CF4或CHF3气体等离子刻蚀刻蚀SiO2薄膜，直到露出硅表面，之后用去胶液或丙酮洗去光刻胶，并经过O2等离子清洗；S101. Preparation of micro-nano structure: select a silicon substrate, which is a silicon substrate with a thermally grown silicon dioxide film with a thickness of 300 nm on the surface, spin-coat photoresist on the above-mentioned silicon substrate, expose and develop, and The micro-scale pattern on the designed mask plate is transferred to the surface of the spin-coated photoresist; the pattern on the photoresist is further transferred to the thin surface ofSiO2 by reactive ion etching, specifically using the photoresist as a mask Mold, use CF4 or CHF3 gas plasma etching to etch the SiO2 film until the silicon surface is exposed, then wash off the photoresist with glue remover or acetone, and clean it with O2 plasma;
然后通过深层反应离子刻蚀工艺进行刻蚀硅基板，具体如下，利用分时复用的工艺以C4F8和SF6气体交替进行等离子沉积和刻蚀，再通过高密度等离子体垂直轰击硅基板，从而各向异性地刻蚀硅基板，直至获得T型微纳米结构。Then the silicon substrate is etched by a deep reactive ion etching process, specifically as follows, using a time-division multiplexing process to alternately perform plasma deposition and etching with C4 F8 and SF6 gases, and then vertically bombard the silicon with high-density plasma substrate, so that the silicon substrate is etched anisotropically until a T-shaped micro-nano structure is obtained.
S102、表面疏水处理：对上述T型微纳米结构的表面进行疏水处理，使所述T型微纳米结构的表面形成疏水薄膜，所述疏水处理具体为：S102. Surface hydrophobic treatment: perform hydrophobic treatment on the surface of the T-shaped micro-nano structure, so that the surface of the T-shaped micro-nano structure forms a hydrophobic film, and the hydrophobic treatment specifically includes:
使用化学气相沉积工艺处理加热硅基板上的T型微纳米结构的表面，T型微纳米结构的各个方向使用等离子状态下的碳氟化合物C4F8气源均匀沉积，在T型微纳米结构的表面形成具有疏水性的C4F8薄膜；Chemical vapor deposition process is used to process the surface of the T-shaped micro-nano structure on the heated silicon substrate. The T-shaped micro-nano structure is uniformly deposited in all directions by using the fluorocarbon C4 F8 gas source in the plasma state. On the T-shaped micro-nano structure A hydrophobic C4 F8 film is formed on the surface;
S103、转印：将上述疏水处理后的T型微纳米结构转印至弹性体材料，经脱膜得到负T型结构的弹性体印章，具体为：S103. Transfer printing: transfer the T-shaped micro-nano structure after the hydrophobic treatment to the elastomer material, and obtain an elastomer stamp with a negative T-shaped structure after stripping, specifically:
使用聚二甲基硅氧烷(PDMS)作为弹性体材料，其前驱体与固化剂以10:1混合，抽真空使混合液中的气泡浮至表面并破裂，再放入70℃烤箱中烤约1小时固化，待PDMS固化后，脱膜，得到负T型结构的弹性体印章。Use polydimethylsiloxane (PDMS) as the elastomer material, mix its precursor and curing agent at a ratio of 10:1, vacuumize to make the air bubbles in the mixture float to the surface and burst, and then bake in an oven at 70°C After about 1 hour of curing, after the PDMS is cured, the film is removed to obtain an elastomer stamp with a negative T-shaped structure.
S104、将对所述负T型结构的弹性体印章进行疏水处理，所述疏水处理同步骤S102；S104. Perform hydrophobic treatment on the elastomer stamp with a negative T-shaped structure, and the hydrophobic treatment is the same as step S102;
S105、浇注：将分子量为2000的乙烯-醋酸乙烯共聚物(简称EVA)浇注到所述负T型结构的弹性体印章内，待真空除气后，置于5℃下固化5h，经脱膜得到材质为EVA的T型微纳米结构；S105. Pouring: pour ethylene-vinyl acetate copolymer (referred to as EVA) with a molecular weight of 2000 into the elastomer stamp with a negative T-shaped structure, and after vacuum degassing, place it at 5°C for 5 hours and remove the film. The T-shaped micro-nano structure whose material is EVA is obtained;
S106、表面疏水处理：将上述获得的T型微纳米结构进行疏水处理，使所述T型微纳米结构的表面形成疏水薄膜，即得到具有多个T型微纳米结构的仿生壁虎干胶，其中，所述疏水处理同步骤S102。S106. Surface hydrophobic treatment: perform hydrophobic treatment on the T-shaped micro-nano structure obtained above, so that the surface of the T-shaped micro-nano structure forms a hydrophobic film, that is, obtain a bionic gecko dry glue with multiple T-shaped micro-nano structures, wherein , the hydrophobic treatment is the same as step S102.
本发明实施例得到的仿生壁虎干胶的结构示意图如图2所示，包括基底11及设置在基底11上的多个T型微纳米结构，其中，所述T型微纳米结构包括柱体12和设置在柱体顶部的盖体13，柱体12在竖直方向上的投影落入盖体13在竖直方向上的投影范围内。柱体12可以是圆柱体、长方体、正方体、圆台或棱台。盖体13可以是圆形或方形。The schematic diagram of the structure of the bionic gecko dry glue obtained in the embodiment of the present invention is shown in Figure 2, including a substrate 11 and a plurality of T-shaped micro-nanostructures arranged on the substrate 11, wherein the T-shaped micro-nanostructures include pillars 12 and the cover 13 arranged on the top of the column, the projection of the column 12 in the vertical direction falls within the projection range of the cover 13 in the vertical direction. The cylinder 12 can be a cylinder, a cuboid, a cube, a circular frustum or a prism. The cover body 13 can be round or square.
本实施例中，盖体13为圆形，盖体13的直径为15μm。柱体12为圆柱体，柱体12的高度为22μm，柱体12横截面的直径为12μm，相邻各柱体之间的间距为50μm。In this embodiment, the cover body 13 is circular, and the diameter of the cover body 13 is 15 μm. The cylinder 12 is a cylinder, the height of the cylinder 12 is 22 μm, the diameter of the cross section of the cylinder 12 is 12 μm, and the distance between adjacent cylinders is 50 μm.
对比实施例1Comparative Example 1
为了突出本发明实施例的有益效果，采用PDMS作为浇注到负T型结构的弹性体印章的材料，即最后得到的仿生壁虎干胶的材质为PDMS，仿生壁虎干胶的其他结构参数同实施例1。In order to highlight the beneficial effects of the embodiments of the present invention, PDMS is used as the material of the elastic body stamp poured into the negative T-shaped structure, that is, the material of the finally obtained bionic gecko dry glue is PDMS, and other structural parameters of the bionic gecko dry glue are the same as those in the embodiment 1.
当两者的仿生壁虎干胶的微结构面积均为0.5cm2，在砝码给定预压力(2N)时，对本实施例1(5b)、对比实施例1(5a)制得的仿生壁虎干胶进行纵向和切向粘附力的性能对比测试，其结果如图5所示，其中，纵向是指垂直于仿生壁虎干胶所接触的壁面，切向是指给仿生壁虎干胶一个平行于壁面的力。对比实施例1的PDMS仿生壁虎干胶在纵向、切向的最大承重200g，实施例1的EVA仿生壁虎干胶在纵向、切向的最大承重300g。以上对比说明材质为EVA的仿生壁虎干胶粘附性优于PDMS仿生壁虎干胶。When the microstructure area of the bionic gecko dry glue of both is 0.5cm2 , when the pre-pressure (2N) is given by the weight, the bionic gecko obtained in the present embodiment 1 (5b) and the comparative example 1 (5a) The performance comparison test of the dry glue in the longitudinal direction and the tangential direction is shown in Figure 5. The longitudinal direction refers to the wall surface that is perpendicular to the contact of the bionic gecko dry glue, and the tangential direction refers to giving the bionic gecko dry glue a parallel surface. force on the wall. The PDMS biomimetic gecko dry glue of Comparative Example 1 has a maximum load-bearing capacity of 200g in the longitudinal and tangential directions, and the EVA biomimetic gecko dry glue of Example 1 has a maximum load-bearing capacity of 300g in the longitudinal and tangential directions. The above comparison shows that the bionic gecko dry glue made of EVA has better adhesion than PDMS bionic gecko dry glue.
实施例2Example 2
一种仿生壁虎干胶的制备方法，包括以下步骤：A preparation method of bionic gecko dry glue, comprising the following steps:
(1)制备微纳结构：选一硅基板，该硅基板为表面具有热生长的、厚度为300nm的二氧化硅薄膜的硅基板，在上述硅基板上旋涂光刻胶，曝光、显影，将设计好的掩膜版上的微尺度图形转移到旋涂的光刻胶表面；采用反应离子刻蚀法将光刻胶上的图形进一步转移到SiO2薄表面，具体是以光刻胶为掩模、利用CF4或CHF3气体等离子刻蚀刻蚀SiO2薄膜，直到露出硅表面，之后用去胶液或丙酮洗去光刻胶，并经过O2等离子清洗；(1) Preparation of micro-nano structure: choose a silicon substrate, the silicon substrate is a silicon substrate with thermal growth on the surface and a silicon dioxide film with a thickness of 300nm, spin-coat photoresist on the above-mentioned silicon substrate, expose, develop, Transfer the micro-scale pattern on the designed mask to the surface of the spin-coated photoresist; use the reactive ion etching method to further transfer the pattern on the photoresist to the thin surface of SiO2 , specifically use the photoresist as the mask, use CF4 or CHF3 gas plasma etching to etch the SiO2 film until the silicon surface is exposed, then wash off the photoresist with glue remover or acetone, and clean it with O2 plasma;
然后通过气相刻蚀工艺进行刻蚀硅基板，直至获得T型微纳米结构，具体如下：利用XeF2气相刻蚀工艺处理硅表面；最后，利用CVD化学气相沉积工艺处理经XeF2气相刻蚀工艺刻蚀硅。Then, the silicon substrate is etched by a vapor phase etching process until a T-shaped micro-nano structure is obtained, as follows: the silicon surface is treated by a XeF2 vapor phase etching process; finally, theXeF2 vapor phase etching process is processed by a CVD chemical vapor deposition process. Etch silicon.
(2)表面疏水处理：对上述T型微纳米结构的表面进行疏水处理，使所述T型微纳米结构的表面形成疏水薄膜，所述疏水处理具体为：(2) Surface hydrophobic treatment: carry out hydrophobic treatment to the surface of the above-mentioned T-shaped micro-nanostructure, so that the surface of the T-shaped micro-nanostructure forms a hydrophobic film, and the hydrophobic treatment is specifically:
使用化学气相沉积工艺处理加热硅基板上的T型微纳米结构的表面，T型微纳米结构的各个方向使用等离子状态下的碳氟化合物CF4气源均匀沉积，在T型微纳米结构的表面形成具有疏水性的CF4薄膜；Chemical vapor deposition process is used to process the surface of the T-shaped micro-nano structure on the heated silicon substrate. All directions of the T-shaped micro-nano structure are uniformly deposited by the fluorocarbon CF4 gas source in the plasma state. On the surface of the T-shaped micro-nano structure Form a hydrophobicCF4 film;
(3)转印：将上述疏水处理后的T型微纳米结构转印至弹性体材料，使用丁晴橡胶作为弹性体材料为顺丁胶，待顺丁胶固化后，经脱膜得到负T型结构的弹性体印章；(3) Transfer printing: transfer the T-shaped micro-nano structure after the above-mentioned hydrophobic treatment to the elastomer material, use NBR as the elastomer material to be butadiene rubber, and after the butadiene rubber is cured, the negative T is obtained by stripping Elastomer stamps with type structure;
(4)将对所述负T型结构的弹性体印章进行疏水处理，所述疏水处理同步骤(2)；(4) carry out hydrophobic treatment to the elastomer seal of described negative T-shaped structure, described hydrophobic treatment is the same as step (2);
(5)浇注：将乙烯-醋酸乙烯共聚物(简称EVA)浇注到所述负T型结构的弹性体印章内，待真空除气后，置于4℃下固化6h，脱膜得到材质为EVA的T型微纳米结构；(5) Pouring: Pouring ethylene-vinyl acetate copolymer (EVA for short) into the elastomer stamp with a negative T-shaped structure, and after vacuum degassing, place it at 4°C to cure for 6 hours, and the material is EVA after stripping. The T-shaped micro-nano structure;
(6)表面疏水处理：将步骤(4)获得的T型微纳米结构进行疏水处理，使所述T型微纳米结构的表面形成疏水薄膜，即得到具有多个T型微纳米结构的仿生壁虎干胶，其中，所述疏水处理同步骤(2)。(6) Surface hydrophobic treatment: the T-shaped micro-nanostructure obtained in step (4) is subjected to hydrophobic treatment, so that the surface of the T-shaped micro-nanostructure forms a hydrophobic film, that is, a bionic gecko with multiple T-shaped micro-nanostructures is obtained Dry glue, wherein, the hydrophobic treatment is the same as step (2).
本发明实施例得到的仿生壁虎干胶，其材质为EVA，仿生壁虎干胶包括基底及设置在基底上的多个T型微纳米结构，其中，每个T型微纳米结构包括柱体和设置在柱体顶部的盖体，柱体在竖直方向上的投影落入盖体在竖直方向上的投影范围内。盖体13可以是圆形或方形，柱体12可以是圆柱体、长方体、正方体、圆台或棱台。The bionic gecko dry glue obtained in the embodiment of the present invention is made of EVA, and the bionic gecko dry glue includes a base and a plurality of T-shaped micro-nano structures arranged on the base, wherein each T-shaped micro-nano structure includes a column and a set For the cover on the top of the column, the projection of the column in the vertical direction falls within the range of the projection of the cover in the vertical direction. The cover body 13 can be circular or square, and the column body 12 can be a cylinder, a cuboid, a cube, a circular frustum or a prism.
本实施例中，盖体13为圆形，盖体13的直径为为25μm。柱体12为圆柱体，柱体12的高度为20μm，柱体12横截面的直径为22μm，相邻各柱体之间的间距为50μm。In this embodiment, the cover body 13 is circular, and the diameter of the cover body 13 is 25 μm. The cylinder 12 is a cylinder, the height of the cylinder 12 is 20 μm, the diameter of the cross section of the cylinder 12 is 22 μm, and the distance between adjacent cylinders is 50 μm.
实施例3Example 3
参见附图3的仿生壁虎干胶的制备方法的流程图，本实施例提供的一种仿生壁虎干胶的制备方法，包括以下步骤：Referring to the flowchart of the preparation method of the bionic gecko dry glue of accompanying drawing 3, a kind of preparation method of the bionic gecko dry glue provided in this embodiment comprises the following steps:
S301、制备微纳结构：选一硅基板，在所述基板表面依次旋涂AR5460、SU8-T3035光刻胶分别作为第一高分子涂层、第二高分子涂层，之后使用SU-8显影剂来显影第二高分子涂层，获得特定的微米或纳米图形；S301. Prepare micro-nano structure: select a silicon substrate, spin-coat AR5460 and SU8-T3035 photoresist on the surface of the substrate sequentially as the first polymer coating and the second polymer coating, and then use SU-8 to develop agent to develop the second polymer coating to obtain specific micro or nano patterns;
使用AR300显影剂通过显影后的第二高分子涂层来刻蚀第一高分子涂层；在第二高分子涂层和第一高分子涂层上形成负T型微纳米结构；Use AR300 developer to etch the first polymer coating through the developed second polymer coating; form a negative T-shaped micro-nano structure on the second polymer coating and the first polymer coating;
S302、表面疏水处理：对上述负T型微纳米结构的表面进行疏水处理，使所述负T型微纳米结构的表面形成疏水薄膜，所述疏水处理具体为：S302. Surface hydrophobic treatment: perform hydrophobic treatment on the surface of the above-mentioned negative T-shaped micro-nano structure, so that the surface of the negative T-shaped micro-nano structure forms a hydrophobic film, and the hydrophobic treatment specifically includes:
使用全氟辛基三氯硅烷(PFTS)作为单分子自组装材料，使其在T型微纳米结构的表面进行自组装形成疏水性薄膜，具体是将PFTS放在密闭容器，加热至100℃，高温处理5min，使气化的PFTS与负T型微结构的表面发生化学反应，生成具有疏水性的氟基薄膜。Use perfluorooctyltrichlorosilane (PFTS) as a single-molecule self-assembly material to self-assemble on the surface of the T-shaped micro-nano structure to form a hydrophobic film. Specifically, put PFTS in an airtight container and heat it to 100°C. After high temperature treatment for 5 minutes, the vaporized PFTS chemically reacts with the surface of the negative T-shaped microstructure to form a hydrophobic fluorine-based film.
S303、转印：将上述疏水处理后的负T型微纳米结构经两次转印至弹性体材料，经脱膜得到负T型结构的弹性体印章，具体为：S303. Transfer printing: transfer the negative T-shaped micro-nano structure after the hydrophobic treatment to the elastomer material twice, and obtain an elastomer stamp with a negative T-shaped structure after stripping, specifically:
使用聚二甲基硅氧烷(PDMS)作为弹性体材料，其前驱体与固化剂以10:1混合，抽真空使混合液中的气泡浮至表面并破裂，再放入70℃烤箱中烤约1小时固化，待PDMS固化后，脱膜，得到T型结构的弹性体印章；Use polydimethylsiloxane (PDMS) as the elastomer material, mix its precursor and curing agent at a ratio of 10:1, vacuumize to make the air bubbles in the mixture float to the surface and burst, and then bake in an oven at 70°C After about 1 hour of curing, after the PDMS is cured, the film is removed to obtain a T-shaped elastomer stamp;
再将T型结构的弹性体印章的表面通过疏水处理形成一疏水薄膜，具体步骤同步骤S302；然后再浇注同一弹性体材料PDMS，抽真空，加热固化后剥离，得到负T型结构的弹性体印章。Then, the surface of the T-shaped elastomer stamp is hydrophobically treated to form a hydrophobic film, the specific steps are the same as step S302; then the same elastomer material PDMS is poured, vacuumized, heated and cured, and then peeled off to obtain a negative T-shaped elastomer. seal.
S304、将对所述负T型结构的弹性体印章进行疏水处理，所述疏水处理同步骤S102；S304. Perform hydrophobic treatment on the elastomer stamp with negative T-shaped structure, and the hydrophobic treatment is the same as step S102;
S305、浇注：将乙烯-醋酸乙烯共聚物(简称EVA)浇注到所述负T型结构的弹性体印章内，待真空除气后，置于5℃下固化，脱膜得到材质为EVA的T型微纳米结构；S305. Pouring: Pouring ethylene-vinyl acetate copolymer (EVA for short) into the elastomer stamp with a negative T-shaped structure, and after vacuum degassing, place it at 5°C for curing, and remove the film to obtain a T stamp made of EVA. Type micro-nano structure;
S306、表面疏水处理：将上述获得的T型微纳米结构进行疏水处理，使所述T型微纳米结构的表面形成疏水薄膜，即得到具有多个T型微纳米结构的仿生壁虎干胶，其中，所述疏水处理同步骤S302。S306. Surface hydrophobic treatment: perform hydrophobic treatment on the T-shaped micro-nano structure obtained above, so that the surface of the T-shaped micro-nano structure forms a hydrophobic film, that is, obtain a bionic gecko dry glue with multiple T-shaped micro-nano structures, wherein , the hydrophobic treatment is the same as step S302.
图4为本实施例3的S303中经一次转印得到的脱膜处理前的T型结构的弹性体印章的结构示意图，其中21表示硅基板，22表示第一高分子涂层，23表示第二高分子涂层，22、23共同构成的结构之间形成负T型微纳米结构，当向负T型微纳米结构浇注24表示的弹性体材料PDMS后，24构成T型微纳米结构，将24表示的部分经脱膜后得到T型结构的弹性体印章。Fig. 4 is the schematic structural view of the elastomer stamp of the T-shaped structure obtained through one transfer in S303 of the present embodiment 3 before the release treatment, wherein 21 represents the silicon substrate, 22 represents the first polymer coating, and 23 represents the first polymer coating The two polymer coatings, 22 and 23 form a negative T-shaped micro-nano structure between the structures. When the elastic material PDMS represented by 24 is poured into the negative T-shaped micro-nano structure, 24 forms a T-shaped micro-nano structure. The part represented by 24 obtains the elastomer stamp of T-shaped structure after stripping.
本发明实施例最终得到的仿生壁虎干胶的结构示意图如图2所示，包括基底11及设置在基底11上的多个T型微纳米结构，其中，所述T型微纳米结构包括柱体12和设置在柱体顶部的盖体13，柱体12在竖直方向上的投影落入盖体13在竖直方向上的投影范围内。盖体13可以是圆形或方形，柱体12可以是圆柱体、长方体、正方体、圆台或棱台。The schematic diagram of the structure of the bionic gecko dry glue finally obtained in the embodiment of the present invention is shown in Figure 2, including a substrate 11 and a plurality of T-shaped micro-nanostructures arranged on the substrate 11, wherein the T-shaped micro-nanostructures include cylinders 12 and a cover 13 arranged on the top of the column, the projection of the column 12 in the vertical direction falls within the projection range of the cover 13 in the vertical direction. The cover body 13 can be circular or square, and the column body 12 can be a cylinder, a cuboid, a cube, a circular frustum or a prism.
本实施例3中，盖体13为方形，盖体13的边长为10μm。柱体12为圆柱体，柱体12的高度为20μm，柱体12横截面的直径为7μm，相邻各柱体之间的间距为40μm。In the third embodiment, the cover body 13 is square, and the side length of the cover body 13 is 10 μm. The cylinder 12 is a cylinder, the height of the cylinder 12 is 20 μm, the diameter of the cross section of the cylinder 12 is 7 μm, and the distance between adjacent cylinders is 40 μm.
实施例4Example 4
一种仿生壁虎干胶的制备方法，包括以下步骤：A preparation method of bionic gecko dry glue, comprising the following steps:
(1)制备微纳结构：选一玻璃作为基板，在所述基板表面依次旋涂AR5480、SU8-2050光刻胶分别作为第一高分子涂层、第二高分子涂层，之后使用SU-8显影剂来显影第二高分子涂层，获得特定的微米或纳米图形；(1) Preparation of micro-nano structure: choose a glass as the substrate, spin-coat AR5480 and SU8-2050 photoresist on the surface of the substrate as the first polymer coating and the second polymer coating respectively, and then use SU- 8 developers to develop the second polymer coating to obtain specific micro or nano patterns;
使用AR300显影剂通过显影后的第二高分子涂层来刻蚀第一高分子涂层；在第二高分子涂层和第一高分子涂层上形成负T型微纳米结构；Use AR300 developer to etch the first polymer coating through the developed second polymer coating; form a negative T-shaped micro-nano structure on the second polymer coating and the first polymer coating;
(2)表面疏水处理：对上述负T型微纳米结构的表面进行疏水处理，使所述负T型微纳米结构的表面形成疏水薄膜，所述疏水处理具体为：(2) Surface hydrophobic treatment: carry out hydrophobic treatment to the surface of the above-mentioned negative T-shaped micro-nanostructure, so that the surface of the negative T-shaped micro-nanostructure forms a hydrophobic film, and the hydrophobic treatment is specifically:
使用化学气相沉积工艺处理所述负T型微纳米结构的表面，负T型微纳米结构的各个方向使用等离子状态下的碳氟化合物气源(C4F8或CF4)均匀沉积，在负T型微纳米结构的表面生成具有疏水性的碳氟化合物薄膜。The surface of the negative T-shaped micro-nanostructure is processed by chemical vapor deposition process, and the negative T-shaped micro-nanostructure is uniformly deposited in each direction using a fluorocarbon gas source (C4 F8 or CF4 ) in a plasma state. A hydrophobic fluorocarbon film is formed on the surface of the T-shaped micro-nano structure.
(3)转印：将上述疏水处理后的负T型微纳米结构经两次转印至弹性体材料，经脱膜得到负T型结构的弹性体印章，具体为：(3) Transfer printing: The above-mentioned negative T-shaped micro-nano structure after the hydrophobic treatment is transferred to the elastomer material twice, and the elastomer seal with the negative T-shaped structure is obtained after stripping, specifically:
使用聚二甲基硅氧烷(PDMS)作为弹性体材料，其前驱体与固化剂以10:1混合，抽真空使混合液中的气泡浮至表面并破裂，再放入70℃烤箱中烤约1小时固化，待PDMS固化后，脱膜，得到T型结构的弹性体印章；Use polydimethylsiloxane (PDMS) as the elastomer material, mix its precursor and curing agent at a ratio of 10:1, vacuumize to make the air bubbles in the mixture float to the surface and burst, and then bake in an oven at 70°C After about 1 hour of curing, after the PDMS is cured, the film is removed to obtain a T-shaped elastomer stamp;
再将T型结构的弹性体印章的表面通过疏水处理，离子状态下的碳化合物气源(C4F8或CF4)均匀沉积，形成一疏水薄膜，具体步骤同步骤(2)；然后再浇注同一弹性体材料PDMS，抽真空，加热固化后剥离，得到负T型结构的弹性体印章。Then, the surface of the elastic body stamp with T-shaped structure is subjected to hydrophobic treatment, and the carbon compound gas source (C4 F8 or CF4 ) in the ionic state is uniformly deposited to form a hydrophobic film. The specific steps are the same as step (2); and then Pouring the same elastomer material PDMS, evacuating, heating and curing, and peeling off to obtain an elastomer stamp with a negative T-shaped structure.
(4)将对所述负T型结构的弹性体印章进行疏水处理，所述疏水处理同步骤(2)；(4) carry out hydrophobic treatment to the elastomer seal of described negative T-shaped structure, described hydrophobic treatment is the same as step (2);
(5)浇注：将乙烯-醋酸乙烯共聚物(简称EVA)浇注到所述负T型结构的弹性体印章内，待真空除气后，置于5℃下固化，脱膜得到材质为EVA的T型微纳米结构；(5) Pouring: Pouring ethylene-vinyl acetate copolymer (referred to as EVA) into the elastomer stamp of the negative T-shaped structure, and after vacuum degassing, place it at 5°C to solidify, and remove the film to obtain a stamp made of EVA. T-shaped micro-nano structure;
(6)表面疏水处理：将上述获得的T型微纳米结构进行疏水处理，使所述T型微纳米结构的表面形成疏水薄膜，即得到具有多个T型微纳米结构的仿生壁虎干胶，其中，所述疏水处理同步骤(2)。(6) surface hydrophobic treatment: the T-shaped micro-nanostructure obtained above is subjected to hydrophobic treatment, so that the surface of the T-shaped micro-nanostructure forms a hydrophobic film, that is, a bionic gecko dry glue with multiple T-shaped micro-nanostructures is obtained, Wherein, the hydrophobic treatment is the same as step (2).
本发明实施例得到的仿生壁虎干胶的材质为EVA，该仿生壁虎干胶包括基底及设置在基底上的多个T型微纳米结构，其中，每个T型微纳米结构包括柱体和设置在柱体顶部的盖体，柱体在竖直方向上的投影落入盖体在竖直方向上的投影范围内。The material of the bionic gecko dry glue obtained in the embodiment of the present invention is EVA, and the bionic gecko dry glue includes a substrate and a plurality of T-shaped micro-nano structures arranged on the substrate, wherein each T-shaped micro-nano structure includes a column and a set of T-shaped micro-nano structures. For the cover on the top of the column, the projection of the column in the vertical direction falls within the range of the projection of the cover in the vertical direction.
本实施例4中，盖体13为方形，盖体13的边长为10μm。柱体12为圆柱体，柱体12的高度为20μm，柱体12横截面的直径为7μm，相邻柱体之间的间距为50μm。In Embodiment 4, the cover body 13 is square, and the side length of the cover body 13 is 10 μm. The cylinder 12 is a cylinder, the height of the cylinder 12 is 20 μm, the diameter of the cross section of the cylinder 12 is 7 μm, and the distance between adjacent cylinders is 50 μm.
效果实施例1Effect Example 1
将实施例3、实施例4制得的仿生壁虎干胶，考察其在不同预压力(0.5N，2N，4N，6N，8N，10N)下的纵向剥离力的变化关系，同时为了突出本发明的有益效果，将材质为PDMS的代表仿生壁虎干胶作为对比，结果如图5所示，其中EVA 3、PDMS 3代表仿生壁虎干胶的盖体的直径为10μm，相邻柱体之间的间距为40μm；EVA 4、PDMS 4代表仿生壁虎干胶的盖体的直径为10μm，相邻柱体之间的间距为50μm。With the biomimetic gecko dry glue that embodiment 3, embodiment 4 make, investigate its longitudinal stripping force change relationship under different preloads (0.5N, 2N, 4N, 6N, 8N, 10N), simultaneously in order to highlight the present invention Compared with the representative bionic gecko dry glue made of PDMS, the results are shown in Figure 5, where EVA 3 and PDMS 3 represent the bionic gecko dry glue. The diameter of the cover body is 10 μm, and the distance between adjacent columns The spacing is 40 μm; EVA 4 and PDMS 4 represent biomimetic gecko dry glue, the cover body has a diameter of 10 μm, and the spacing between adjacent columns is 50 μm.
从图5可以看出，当预压紧力超过临界值时，接触表面发生塑性变形，在一定范围内，纵向剥离力随预压力的增加而增大。在同样的预压力下，EVA仿生壁虎干胶的纵向剥离力明显大于PDMS仿生壁虎干胶，这说明EVA材质的粘附性优于PDMS；由于EVA的可拉伸高于400％，EVA的弹性模量(约84MPa)远大于PDMS，与界面接触时表现更大的粘附强度。同一材质的仿生壁虎干胶，在相同的盖体直径、相同预压力下，相邻柱体之间的间距越大，其纵向剥离力越小。It can be seen from Figure 5 that when the pre-compression force exceeds the critical value, the contact surface undergoes plastic deformation, and within a certain range, the longitudinal peel force increases with the increase of the pre-compression force. Under the same preload, the longitudinal peeling force of EVA biomimetic gecko dry glue is significantly greater than that of PDMS biomimetic gecko dry glue, which shows that the adhesion of EVA material is better than that of PDMS; because the stretchability of EVA is higher than 400%, the elasticity of EVA The modulus (about 84MPa) is much larger than that of PDMS, and it exhibits greater adhesion strength when in contact with the interface. For bionic gecko dry glue of the same material, under the same cover diameter and the same preload, the larger the distance between adjacent cylinders, the smaller the longitudinal peeling force.
需要说明的是，本申请所提供的实施例仅仅是示意性的。所属领域的技术人员可以清楚地了解到，为了描述的方便和简洁，在上述实施例中，对各个实施例的描述都各有侧重，某个实施例中没有详述的部分，可以参见其他实施例的相关描述。在本发明实施例、权利要求以及附图中揭示的特征可以独立存在也可以组合存在。It should be noted that the embodiments provided in this application are only illustrative. Those skilled in the art can clearly understand that, for the convenience and brevity of description, in the above-mentioned embodiments, the descriptions of each embodiment have their own emphasis. Description of the example. The features disclosed in the embodiments of the present invention, the claims and the drawings can exist independently or in combination.
| Application Number | Priority Date | Filing Date | Title |
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| CN201510536851.2ACN105236342B (en) | 2015-08-27 | 2015-08-27 | A kind of bionic gecko dry glue and preparation method thereof |
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| CN201510536851.2ACN105236342B (en) | 2015-08-27 | 2015-08-27 | A kind of bionic gecko dry glue and preparation method thereof |
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| CN105236342Btrue CN105236342B (en) | 2017-08-25 |
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| CN201510536851.2AActiveCN105236342B (en) | 2015-08-27 | 2015-08-27 | A kind of bionic gecko dry glue and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106378894A (en)* | 2016-09-09 | 2017-02-08 | 清华大学 | Gecko-imitated dry adhesion surface, product with gecko-imitated dry adhesion surface and manufacturing method of product |
| CN106495497B (en)* | 2016-09-21 | 2019-03-08 | 华北电力大学 | A kind of preparation method of surface anti-reflection self-cleaning structure |
| CN106497442A (en)* | 2016-10-09 | 2017-03-15 | 宁波大学 | A kind of magnetic control dry glue device and preparation method thereof |
| CN108017035A (en)* | 2016-10-28 | 2018-05-11 | 中国科学院深圳先进技术研究院 | A kind of bionic gecko dry glue and preparation method thereof |
| CN107010590B (en)* | 2017-03-31 | 2019-07-30 | 西安交通大学 | A kind of across the scale dry adhesion composite construction and its preparation process of millimicro three-level |
| CN107221578B (en)* | 2017-06-01 | 2018-08-21 | 西南交通大学 | A kind of manufacturing method of " I " type structure PDMS matrixes |
| CN109703220B (en)* | 2017-10-26 | 2021-02-19 | Tcl科技集团股份有限公司 | Composite stamp and preparation method thereof and method for transferring quantum dots |
| CN108272775A (en)* | 2018-03-20 | 2018-07-13 | 苏州十方生物科技有限公司 | Integrated Traditional Chinese medicine plaster based on bionical high viscosity macromolecule micro-nano and preparation method |
| CN109761189A (en)* | 2019-01-10 | 2019-05-17 | 中国科学院长春光学精密机械与物理研究所 | A kind of preparation method and application of polymer microfibrous structure |
| CN109987578A (en)* | 2019-04-09 | 2019-07-09 | 电子科技大学 | A method for constructing a single concave structure on the surface of a micropillar |
| CN110003775B (en)* | 2019-04-17 | 2020-11-13 | 河南科技大学 | A kind of preparation method of super-hydrophobic high-adhesion coating and composite material with super-hydrophobic high-adhesion coating |
| CN112590083B (en)* | 2020-12-10 | 2022-06-10 | 南京航空航天大学 | Method for preparing bionic adhesion material based on micro-nano additive |
| CN116766169A (en)* | 2023-07-06 | 2023-09-19 | 河海大学 | A stiffness-adjustable soft actuator based on directional biomimetic adhesive materials |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3690936A (en)* | 1970-02-02 | 1972-09-12 | Phillips Petroleum Co | Adhesive material for bonding vinyl chloride polymers to substrates |
| US7608070B2 (en)* | 2004-09-30 | 2009-10-27 | Kimberly-Clark Worldwide, Inc. | Foam-based fasteners |
| CN101817500B (en)* | 2010-03-24 | 2014-04-09 | 江苏大学 | Microstructure design and method for superhydrophobic function conversion on the surface of hydrophilic materials |
| CN101823685B (en)* | 2010-04-30 | 2012-03-28 | 华中科技大学 | A kind of preparation method of biomimetic micro-nano structure |
| CN101837946B (en)* | 2010-05-14 | 2011-11-30 | 华中科技大学 | Method for preparing dry adhesive |
| RU2455331C1 (en)* | 2010-12-14 | 2012-07-10 | Государственное образовательное учреждение высшего профессионального образования "Южно-Российский государственный университет экономики и сервиса" (ГОУ ВПО "ЮРГУЭС") | Environmentally safe melt adhesive based on ethylene and vinyl acetate copolymer |
| US9956743B2 (en)* | 2010-12-20 | 2018-05-01 | The Regents Of The University Of California | Superhydrophobic and superoleophobic nanosurfaces |
| CN102427083A (en)* | 2011-11-10 | 2012-04-25 | 中山大学 | Water and oil repellency surface microstructure and manufacturing method thereof |
| 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 |
| Publication number | Publication date |
|---|---|
| CN105236342A (en) | 2016-01-13 |
| Publication | Publication Date | Title |
|---|---|---|
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