WO2020151288A1 - 一种仿生防粘表面及其制备方法 - Google Patents

一种仿生防粘表面及其制备方法 Download PDF

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WO2020151288A1
WO2020151288A1 PCT/CN2019/114522 CN2019114522W WO2020151288A1 WO 2020151288 A1 WO2020151288 A1 WO 2020151288A1 CN 2019114522 W CN2019114522 W CN 2019114522W WO 2020151288 A1 WO2020151288 A1 WO 2020151288A1
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preparation
rough
absolute ethanol
steel
rough body
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PCT/CN2019/114522
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French (fr)
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陆龙生
李凯凯
梁林生
谢颖熙
汤勇
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华南理工大学
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23P—METAL-WORKING NOT OTHERWISE PROVIDED FOR; COMBINED OPERATIONS; UNIVERSAL MACHINE TOOLS
    • B23P15/00—Making specific metal objects by operations not covered by a single other subclass or a group in this subclass
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/02—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions

Definitions

  • the invention belongs to the field of bionic desorption structures, and specifically relates to a bionic anti-stick surface and a preparation method thereof.
  • carbon fiber prepreg composite materials have been widely used in many fields such as aerospace, sports equipment, construction industry and electromagnetic shielding due to their high specific strength, high specific stiffness, and excellent thermal conductivity, electrical conductivity and corrosion resistance.
  • the prepreg In the production process of carbon fiber/epoxy resin prepreg, the prepreg is usually cut to a desired size and placed in a mold to manufacture parts with complex shapes.
  • the viscosity is 1000-50000 times that of water at 20°C
  • a large amount of epoxy resin and fibers adhere to the surface of the short-cutting tool and the mold, which not only causes additional energy loss, but also seriously affects
  • the prepreg molding process also increases the difficulty and cost of later cleaning.
  • Chinese patent application CN201610531105.9 discloses a manufacturing process for an anti-adhesion cutter, which uses stamping in An anti-sticking groove is formed on the surface of the cutting knife, which effectively solves the problem of adhesion of the knife surface during the vegetable cutting process, but this kind of punching groove cannot effectively solve the problem of adhesion of high-viscosity resin.
  • Chinese patent CN201610520973.7 discloses a treatment method to prevent the surface adhesion of the roller.
  • the present invention provides a bionic anti-sticking surface and a preparation method thereof, so that the chopped cutting tool and the mold surface can effectively reduce or reduce the adhesion amount of resin and fiber, and can be applied For other applications where high viscosity liquids are prevented from sticking.
  • a bionic anti-adhesive surface taking the lotus leaf with a "papillary”-like microstructure and super-phobic surface in nature as an imitation object, processing micro-nano-level "papilla”-like structures on the surface of steel, and using chemical methods to modify and reduce the steel Surface energy makes the steel surface have resin desorption performance.
  • the preparation method of the bionic anti-sticking surface includes the following steps:
  • Step one Slicing the steel, and then grinding and polishing to obtain rough blank one;
  • Step two Carry out the ultrasonic cleaning of the rough body one with deionized water, acetone and absolute ethanol in sequence, and obtain rough body two after drying;
  • Step 3 Use the nanosecond laser to process the rough blank 2, adjust the laser power, scanning rate, scanning speed and other parameters, and place the laser focus on the surface of the rough blank to obtain the rough blank 3;
  • Step four Immerse the rough body 3 in an acidic rust remover, and scrub the processed surface with a plastic brush, and then use deionized water and absolute ethanol for ultrasonic cleaning to obtain rough body 4;
  • Step 5 Immerse the rough body 4 in a mixed solution of fluorosilane (C 13 H 13 F 17 O 3 Si) and absolute ethanol for a period of time, and then wash with absolute ethanol and dry to obtain a finished product.
  • fluorosilane C 13 H 13 F 17 O 3 Si
  • the steel type is W18Cr4V.
  • the steel mentioned in step one should be cut into 40 ⁇ 40mm square samples, and then the samples should be polished with 300#, 500#, 800#, 1200#, 2000# sandpaper in sequence.
  • the drying in steps 2 and 5 is performed in a vacuum or nitrogen atmosphere.
  • the processing diameter of the "papillary"-like structure is 100-500 ⁇ m
  • the processing distance is 100-500 ⁇ m
  • the laser scanning rate is 100-800 mm/s.
  • the processing diameter of the "papillary" structure is 100 ⁇ m.
  • the processing distance of the "papillary"-like structure is 100 ⁇ m.
  • the laser scanning rate is 100 mm/s.
  • the processing diameter of the "papillary"-like structure is 100 ⁇ m
  • the processing distance is 100 ⁇ m
  • the laser scanning rate is 100 mm/s.
  • the time for the rough body to be immersed in the acidic rust remover in step 4 is 4-6 minutes.
  • the volume ratio of fluorosilane to absolute ethanol used for immersion in step 5 is 1:10.
  • the reaction time for the rough body 4 in step 5 to be immersed in the mixed solution is 2.5-3h.
  • the sample drying temperature in step 5 is 70 ⁇ 80°C, and the drying time is 20 ⁇ 30min; It is further preferred that the drying temperature is 80°C and the drying time is 30min.
  • a bionic anti-sticking surface prepared by the above-mentioned preparation method.
  • the material selected in the present invention is tungsten high-speed steel W18Cr4V, which has high hardness, high wear resistance and red hardness; in the first step, the surface of the steel is polished with different sandpaper to remove the surface oxide layer and make the surface of the steel have a certain The flatness of the laser processing ensures that the size and spacing of the laser processing are uniform; in the second and fifth steps, the steel is dried in a vacuum or nitrogen atmosphere to avoid an oxide layer on the surface of the steel during the heating process, which affects the quality of the finished product; In the third, the nanosecond laser is used to etch the surface of the steel, which has little thermal effect on the materials around the processing part, and some molten metal particles are attached to the "papilla" to form a micro-nano hierarchical structure, which is transformed from the Wenzel model to the Cassie The model is more likely to repel viscous liquids; in the fourth step, an acidic rust remover is used to remove the high-temperature oxide layer on the processed surface, and the
  • the silanol and the hydroxyl on the surface of the steel sheet undergo dehydration reaction, which makes the fluorosilane molecules connect in the form of covalent bonds.
  • the surface energy of the steel is reduced, so that the finished product can effectively prevent the adhesion of viscous liquids such as resin.
  • the anti-adhesive surface preparation method of the present invention is simple, has strong operability, and has excellent anti-resin adhesion ability. It can be applied to cutting tools, mold surfaces and other anti-adhesive liquid adhesion during the production of carbon fiber/epoxy resin prepreg. Attached occasions, etc.
  • Figure 1 is a schematic diagram of the covalent bond connection between fluorosilane and the surface of micro-nano "papilla” structure steel.
  • Example 2 is a scanning electron microscope image of the surface microstructure of high-speed steel with the best desorption effect prepared in Example 3 of the present invention.
  • Fig. 3 is a super-depth microscope image of the surface microstructure of high-speed steel with the best desorption effect prepared in Example 3 of the present invention.
  • FIG. 4 is a diagram of the surface state of the high-speed steel with the best desorption effect obtained in Example 3 with a volume of 4 ⁇ l epoxy resin droplets.
  • FIG. 1 The schematic diagram of the covalent bond connection between the fluorosilane and the surface of the micro-nano "papilla” structure steel in the bionic anti-adhesive surface of the present invention is shown in Figure 1, where 1 is the non-polar hydrophobic long chain of the fluorosilane molecule; 2 is the high-speed steel substrate; 3 is the micro-nano "papilla”-like structure on the surface of the high-speed steel; 4 is the covalent bond between the fluorosilane and the surface of the high-speed steel.
  • a bionic anti-sticking surface the specific steps of the preparation process are as follows:
  • Step 1 Use tungsten high-speed steel W18Cr4V to cut the steel into 40 ⁇ 40mm square samples, and then use 300#, 500#, 800#, 1200#, 2000# sandpaper to polish the samples to remove the oxide layer on the steel surface and ensure The surface has a certain degree of flatness, and a rough blank is obtained;
  • Step two Carry out the ultrasonic cleaning of the rough billet one with deionized water, acetone and absolute ethanol in sequence to remove impurities and oil stains on the steel surface, and vacuum dry to obtain the rough billet two;
  • Step 3 Use nanosecond lasers to process "papillae" structures of different diameters with diameters of 100 ⁇ m, 200 ⁇ m, 300 ⁇ m, 400 ⁇ m, 500 ⁇ m, spacing of 100 ⁇ m, and laser scanning rate of 200mm/s to obtain rough three.
  • Step 4 Immerse the rough body 3 in an acidic rust remover for 5 minutes, and scrub the processed surface with a plastic brush to remove the high-temperature oxide layer on the processed surface, and then use deionized water and absolute ethanol for ultrasonic cleaning to obtain rough body 4;
  • Step 5 Immerse the rough body No. 4 in a mixed solution of fluorosilane (C 13 H 13 F 17 O 3 Si) and absolute ethanol for 3 hours, and then vacuum dry it at 80°C for 30 min to obtain the final sample.
  • fluorosilane C 13 H 13 F 17 O 3 Si
  • absolute ethanol absolute ethanol
  • the final sample was tested for the contact angle and rolling angle of water and resin, and the volume of water and resin droplets was 4 ⁇ l.
  • the test result is that the surface of the sample with a diameter of 100 ⁇ m, a spacing of 100 ⁇ m, and a laser scanning rate of 200mm/s has the best effect on repelling water and resin.
  • Its water contact angle and rolling angle are 155.3° and 3.3°, respectively.
  • the contact angle and rolling angle are 147.1° and 10.4°, respectively. Therefore, the "papillae" prepared in this embodiment have a diameter of 100 ⁇ m, a spacing of 100 ⁇ m, and a laser scanning rate of 200 mm/s on the surface of the sample, which has a good anti-resin adhesion effect.
  • step 3 the diameter of the laser processing "papilla" structure is 100 ⁇ m, the spacing is 100 ⁇ m, 200 ⁇ m, 300 ⁇ m, 400 ⁇ m, 500 ⁇ m, and the scanning rate is 200 mm/s.
  • the final sample was tested for the contact angle and rolling angle of water and resin, and the volume of water and resin droplets was 4 ⁇ l.
  • the test result is that the surface of the sample with a diameter of 100 ⁇ m, a spacing of 100 ⁇ m, and a laser scanning rate of 200mm/s has the best effect on repelling water and resin.
  • Its water contact angle and rolling angle are 155.3° and 3.3°, respectively.
  • the contact angle and rolling angle are 147.5° and 9.4°, respectively. Therefore, the "papillae" prepared in this embodiment have a diameter of 100 ⁇ m, a spacing of 100 ⁇ m, and a laser scanning rate of 200 mm/s on the surface of the sample, which has a good anti-resin adhesion effect.
  • step 3 the diameter of the laser processing "papillary" structure is 100 ⁇ m, the spacing is 100 ⁇ m, and the scanning rate is 800 mm/s, 400 mm/s, 300 mm/s, 200 mm/s. s, 100mm/s.
  • the final sample was tested for the contact angle and rolling angle of water and resin, and the volume of water and resin droplets was 4 ⁇ l.
  • the test result is that the "papillary" diameter is 100 ⁇ m, the spacing is 100 ⁇ m, and the laser scanning rate is 100mm/s.
  • the surface of the sample has the best effect of repelling water and resin. Its water contact angle and rolling angle are 157.2° and 2.8°, respectively. The contact angle and rolling angle are 149.7° and 7.3°, respectively. Therefore, the surface of the bionic protruding structure steel prepared in this embodiment has a better resin adhesion prevention effect. And compared with the optimal sample surface in Examples 1 and 2, the test effect of this sample is better.
  • Figure 2 is a scanning electron microscope image of the sample surface with a "papilla" diameter of 100 ⁇ m, a spacing of 100 ⁇ m, and a laser scanning rate of 100mm/s;
  • Figure 3 is a super-depth microscope image of the microstructure of the sample surface;
  • Figure 4 is a volume of 4 ⁇ l epoxy resin The state diagram of the droplet on the surface of the sample.
  • a surface with no biomimetic "papilla” structure is prepared.
  • the specific steps of the preparation process are as follows:
  • Step 1 Use tungsten high-speed steel W18Cr4V to cut the steel into 40 ⁇ 40mm square samples, and then use 300#, 500#, 800#, 1200#, 2000# sandpaper to polish the samples to remove the oxide layer on the steel surface and ensure The surface has a certain degree of flatness, and a rough blank is obtained;
  • Step two The rough billet is sequentially ultrasonically cleaned with deionized water, acetone and absolute ethanol to remove impurities and oil stains on the surface of the steel, and vacuum-dried to obtain a final sample.
  • the contact angles of water and resin on the sample surface are 84.1° and 59.6°, respectively.
  • the sample is placed at 90°, and the water and resin still adhere to the surface of the sample. It can be seen that the smooth surface prepared by this comparative example is resistant to resin.
  • the adhesion ability is far worse than that of Examples 1, 2, and 3.
  • the combination of the biomimetic "papilla" structure and fluorosilane (C 13 H 13 F 17 O 3 Si) in the present invention improves the anti-adhesion performance of the steel surface Great improvement.
  • a surface with no biomimetic "papilla” structure is prepared.
  • the specific steps of the preparation process are as follows:
  • Step 1 Use tungsten high-speed steel W18Cr4V to cut the steel into 40 ⁇ 40mm square samples, and then use 300#, 500#, 800#, 1200#, 2000# sandpaper to polish the samples to remove the oxide layer on the steel surface and ensure The surface has a certain degree of flatness, and a rough blank is obtained;
  • Step two Carry out the ultrasonic cleaning of the rough billet one with deionized water, acetone and absolute ethanol in sequence to remove impurities and oil stains on the surface of the steel to obtain a rough billet two;
  • Step 3 Immerse the second rough body in a mixed solution of fluorosilane (C 13 H 13 F 17 O 3 Si) and absolute ethanol for 3 hours, and then vacuum dry it at 80°C for 30 min to obtain the final sample.
  • fluorosilane C 13 H 13 F 17 O 3 Si
  • the contact angles of water and resin on the sample surface are 107.7° and 79.6°, respectively.
  • the sample is placed at 90°, and the water and resin still adhere to the surface of the sample. It can be seen that the smooth surface prepared by this comparative example is resistant to resin.
  • the adhesion ability is far worse than that of Examples 1, 2, and 3.
  • the combination of the biomimetic "papilla" structure and fluorosilane (C 13 H 13 F 17 O 3 Si) in the present invention improves the anti-adhesion performance of the steel surface Great improvement.
  • Table 1 summarizes the important parameters and technical effects of Examples 1 to 3 and Comparative Examples 1 and 2.

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Abstract

一种仿生防粘表面的制备方法，包括如下步骤：(1)对钢片打磨抛光，以去除表面氧化层并保证平整度；(2)利用有机溶剂去除表面油污；(3)利用纳秒激光对钢片进行刻蚀，形成规则排列的微"乳突"结构；(4)利用酸性除锈剂去除钢片经刻蚀形成的氧化层；(5)将钢片置入氟硅烷和乙醇的混合溶液中反应一段时间，干燥后得到防粘表面。还公开了一种仿生防粘表面。

Description

一种仿生防粘表面及其制备方法 技术领域
本发明属于仿生脱附结构领域，具体涉及一种仿生防粘表面及其制备方法。
 背景技术
近年来，碳纤维预浸料复合材料因其高比强度、高比刚度以及优良的导热、导电和耐腐蚀等性能，被广泛应用于航空航天、运动器材、建筑工业及电磁屏蔽等多个领域。
在碳纤维/环氧树脂预浸料的生产过程中，通常将预浸料切割成所需尺寸并置入模具中以制造具有复杂形状的部件。但由于环氧树脂具有高粘性（在20℃下，粘度是水的1000-50000倍），使得短切刀具和模具表面粘附大量环氧树脂和纤维，不仅造成额外的能量损耗，而且严重影响预浸料成型工艺且增加了后期清理难度和费用。
为能够有效解决工业和生活中的粘附问题，一些防粘附的结构或涂层受到了广泛关注，如中国专利申请CN201610531105.9公开了一种防粘附切刀的制作工艺，利用冲压在切刀表面形成防粘槽，有效解决了切菜过程中刀面的粘附问题，但这种冲压槽无法有效解决高粘度树脂的粘附问题。中国专利CN201610520973.7公开了一种防止滚筒表面粘附的处理方法，通过在滚筒表面喷涂特氟龙涂层，能够有效降低表面的杂质粘附，防止滚筒被腐蚀，提高了使用效率和节约了维护成本，但是现有涂层强度低、易脱落的问题，使得涂层应用具有局限性。针对碳纤维预浸料成型过程中树脂的粘附问题，目前还缺乏一种行之有效的解决方法。短切刀具和模具表面的脱附性、高强度和耐腐蚀等性能成为了预浸料加工成型工艺中亟待解决的关键性问题。
 技术问题
为解决现有技术的缺点和不足之处，本发明提供一种仿生防粘表面及其制备方法，使得短切刀具和模具表面能够有效的减少或降低树脂和纤维的粘附量，并能够适用于其他防止高黏度液体粘连的应用场合。
 技术解决方案
本发明的目的至少通过如下技术方案之一实现。
一种仿生防粘表面，以自然界中具有“乳突”状微结构超疏性表面的荷叶为模仿对象，在钢材表面加工微纳米级“乳突”状结构，并利用化学法修饰降低钢材表面能，使得钢材表面具有树脂脱附性能。
所述仿生防粘表面，其制备方法包括以下步骤：
步骤一  将钢材切片，然后进行打磨抛光，得到粗坯一；
步骤二  将所述粗坯一依次用去离子水、丙酮和无水乙醇进行超声波清洗，干燥后得到粗坯二；
步骤三  利用纳秒激光对粗坯二进行加工，调整激光功率、扫描速率、扫描速度等参数，并将激光焦点置于粗坯二表面，得到粗坯三；
步骤四  将所述粗坯三浸入酸性除锈剂中，并用塑料刷刷洗加工表面，然后依次用去离子水、无水乙醇进行超声波清洗，得到粗坯四；
步骤五  将所述粗坯四浸入氟硅烷(C 13H 13F 17O 3Si)和无水乙醇的混合溶液中反应一段时间，然后经无水乙醇清洗，干燥得到成品。
作为优选的，步骤一中，钢材型号为W18Cr4V。
作为优选的，步骤一中所述钢材要先切割成40×40mm方形样片，再将样片依次用300#、500#、800#、1200#、2000#砂纸进行打磨抛光。
作为优选的，步骤二、五中所述干燥是在真空或氮气氛围中进行。
作为优选的，步骤三中“乳突”状结构加工直径100-500μm、加工间距100-500μm、激光扫描速率为100-800mm/s。
作为优选的，步骤三中，“乳突”状结构加工直径100μm。
作为优选的，步骤三中，“乳突”状结构加工间距100μm。
作为优选的，步骤三中，激光扫描速率100mm/s。
最优选的，步骤三中“乳突”状结构加工直径100μm、加工间距100μm、激光扫描速率为100mm/s。
作为优选的，步骤四中粗坯三浸入酸性除锈剂的时间为4 ~ 6min。
作为优选的，步骤五中浸渍所用氟硅烷与无水乙醇的体积比为1 : 10。
作为优选的，步骤五中粗坯四浸入混合溶液中反应的时间为2.5 ~ 3h。
作为优选的，步骤五中样品干燥的温度为70 ~ 80℃，干燥的时间为20 ~ 30min；进一步优选干燥温度为80℃，干燥时间为30min。
由以上所述的制备方法制得的一种仿生防粘表面。
 有益效果
本发明采用上述技术方案，具有如下有益效果：
本发明选材为钨系高速钢W18Cr4V，该钢材具有高硬度、高耐磨性和红硬性；所述步骤一中，利用不同砂纸对钢材表面进行打磨抛光，去除表面氧化层并使得钢材表面具有一定的平整度，保证激光加工的结构大小和间距均匀；所述步骤二、五中，在真空或氮气氛围中烘干钢材，避免在加热过程中钢材表面出现氧化层，影响成品质量；所述步骤三中，利用纳秒激光对钢材表面进行刻蚀，对加工部位周围材料的热影响较小，且部分熔融金属颗粒附着在“乳突”上，形成微纳分级结构，从Wenzel模型转化为Cassie模型更易排斥黏性液体；所述步骤四中，利用酸性除锈剂去除加工表面高温氧化层，反应时间为4 ~ 6min，避免长时间反应腐蚀“乳突”结构；所述步骤五中，氟硅烷(C 13H 13F 17O 3Si)的硅烷基水解生成硅羟基，而金属表面具有亲水性，硅羟基与钢片表面羟基发生脱水反应，使得氟硅烷分子以共价键的形式连接在钢片表面上，降低了钢材的表面能，使得成品能够有效防止树脂等黏性液体的附着。本发明的防粘表面制备方法简单，可操作性强，具有优良的防树脂粘附能力，可应用于碳纤维/环氧树脂预浸料生产过程中的刀具、模具表面和其他防黏性液体粘附场合等。
附图说明
图1为氟硅烷与微纳米“乳突”结构钢材表面共价键连接示意图。
图2为本发明实施例3中制得的脱附效果最优的高速钢表面微结构扫描电镜图。
图3为本发明实施例3中制得的脱附效果最优的高速钢表面微结构超景深显微镜图。
图4为体积4μl环氧树脂液滴在实施例3中制得的脱附效果最优的高速钢表面状态图。
 本发明的实施方式
下面结合实施例对本发明作进一步详细的描述，但本发明的实施方式不限于此。
本发明仿生防粘表面中氟硅烷与微纳米“乳突”结构钢材表面共价键连接示意图如图1所示，其中，1为氟硅烷分子非极性疏水长链；2为高速钢基底；3为高速钢表面微纳米“乳突”状结构；4为氟硅烷与高速钢表面结合的共价键。
实施例 1
一种仿生防粘表面，其制备过程具体步骤如下：
步骤一  选用钨系高速钢W18Cr4V，将钢材切割成40×40mm方形样片，再将样片依次用300#、500#、800#、1200#、2000#砂纸进行打磨抛光，去除钢材表面氧化层并保证表面具有一定的平整度，得到粗坯一；
步骤二  将所述粗坯一依次用去离子水、丙酮和无水乙醇进行超声波清洗，去除钢材表面杂质和油污，并真空干燥后得到粗坯二；
步骤三  利用纳秒激光加工不同直径的“乳突”结构，直径分别为100μm、200μm、300μm、400μm、500μm，间距为100μm，激光扫描速率200mm/s，获得粗坯三。
步骤四  将粗坯三浸入酸性除锈剂5min，并用塑料刷刷洗加工表面，去除加工表面高温氧化层，然后依次用去离子水、无水乙醇进行超声波清洗，得到粗坯四；
步骤五  将粗坯四浸入氟硅烷(C 13H 13F 17O 3Si)和无水乙醇的混合溶液中3h，然后在80℃条件下真空干燥30 min，得到最终样品。
在此实施例中，对最终样品进行了水和树脂的接触角、滚动角测试，水和树脂液滴体积为4μl。测试结果为“乳突”直径为100μm，间距为100μm，激光扫描速率为200mm/s的样品表面排斥水和树脂的效果最优，其水接触角和滚动角分别为155.3°和3.3°，树脂接触角和滚动角分别为147.1°和10.4°。因此本实施例中制备的“乳突”直径为100μm，间距为100μm，激光扫描速率为200mm/s的样品表面具有较好防树脂粘附效果。
实施例 2
与实施例1的不同点在于，步骤三中，激光加工“乳突”结构直径为100μm，间距分别为100μm、200μm、300μm、400μm、500μm，扫描速率为200mm/s。
在此实施例中，对最终样品进行了水和树脂的接触角、滚动角测试，水和树脂液滴体积为4μl。测试结果为“乳突”直径为100μm，间距为100μm，激光扫描速率为200mm/s的样品表面排斥水和树脂的效果最优，其水接触角和滚动角分别为155.3°和3.3°，树脂接触角和滚动角分别为147.5°和9.4°。因此本实施例中制备的“乳突”直径为100μm，间距为100μm，激光扫描速率为200mm/s的样品表面具有较好防树脂粘附效果。
实施例 3
与上述实施例1的不同点在于，步骤三中，激光加工“乳突”结构直径为100μm，间距分别为100μm，扫描速率为800 mm/s 、400 mm/s 、300 mm/s 、200mm/s、100mm/s。
在此实施例中，对最终样品进行了水和树脂的接触角、滚动角测试，水和树脂液滴体积为4μl。测试结果为“乳突”直径为100μm，间距为100μm，激光扫描速率为100mm/s的样品表面排斥水和树脂的效果最优，其水接触角和滚动角分别为157.2°和2.8°，树脂接触角和滚动角分别为149.7°和7.3°。因此本实施例制备的仿生突起结构钢材表面具有较好防树脂粘附效果。且与实施例1、2中的最优样品表面相比，该样品的测试效果更好。图2为“乳突”直径为100μm，间距为100μm，激光扫描速率为100mm/s的样品表面扫描电镜图像；图3为该样品表面微结构超景深显微镜图像；图4为体积4μl环氧树脂液滴在该样品表面状态图。
对比例 1
一种未构筑仿生“乳突”结构表面，其制备过程具体步骤如下：
步骤一  选用钨系高速钢W18Cr4V，将钢材切割成40×40mm方形样片，再将样片依次用300#、500#、800#、1200#、2000#砂纸进行打磨抛光，去除钢材表面氧化层并保证表面具有一定的平整度，得到粗坯一；
步骤二  将所述粗坯一依次用去离子水、丙酮和无水乙醇进行超声波清洗，去除钢材表面杂质和油污，并真空干燥后得到最终样品。
在此对比例中，样品表面水和树脂的接触角分别为84.1°和59.6°，将样品呈90°放置，水和树脂仍粘附的样品表面，可见该对比例制备的光滑表面其防树脂粘附能力远差于实施例1、2、3，本发明中的仿生“乳突”结构和氟硅烷(C 13H 13F 17O 3Si)结合处理使钢材表面的防粘附性能得到了很大提升。
对比例 2
一种未构筑仿生“乳突”结构表面，其制备过程具体步骤如下：
步骤一  选用钨系高速钢W18Cr4V，将钢材切割成40×40mm方形样片，再将样片依次用300#、500#、800#、1200#、2000#砂纸进行打磨抛光，去除钢材表面氧化层并保证表面具有一定的平整度，得到粗坯一；
步骤二  将所述粗坯一依次用去离子水、丙酮和无水乙醇进行超声波清洗，去除钢材表面杂质和油污，得到粗坯二；
步骤三  将粗坯二浸入氟硅烷(C 13H 13F 17O 3Si)和无水乙醇的混合溶液中3h，然后在80℃条件下真空干燥30 min，得到最终样品。
在此对比例中，样品表面水和树脂的接触角分别为107.7°和79.6°，将样品呈90°放置，水和树脂仍粘附的样品表面，可见该对比例制备的光滑表面其防树脂粘附能力远差于实施例1、2、3，本发明中的仿生“乳突”结构和氟硅烷(C 13H 13F 17O 3Si)结合处理使钢材表面的防粘附性能得到了很大提升。
表1对实施例1~3和对比例1、2的重要参数和技术效果进行了总结。
表1
Figure 674125dest_path_image001
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化等形式，均应为等效的置换方式，都应包含在本发明权力要求的保护范围之内。

Claims (10)

  1. 一种仿生防粘表面的制备方法，其特征在于，包括如下步骤：
    步骤一  将钢材切片，然后进行打磨抛光，得到粗坯一；
    步骤二  将所述粗坯一依次用去离子水、丙酮和无水乙醇进行超声波清洗，干燥后得到粗坯二；
    步骤三  利用纳秒激光在粗坯二表面加工微“乳突”状结构，得到粗坯三；
    步骤四  将所述粗坯三浸入酸性除锈剂中，并用塑料刷刷洗加工表面，然后依次用去离子水、无水乙醇进行超声波清洗，得到粗坯四；
    步骤五  将所述粗坯四浸入氟硅烷和无水乙醇的混合溶液中反应，然后经无水乙醇清洗，最后干燥得到成品。
  2. 根据权利要求1所述的制备方法，其特征在于，步骤一中所述钢材要先切割成40×40mm方形样片，再将样片依次用300#、500#、800#、1200#、2000#砂纸进行打磨抛光。
  3. 根据权利要求1所述的制备方法，其特征在于，步骤二、五中所述干燥是在真空或氮气氛围中进行。
  4. 根据权利要求1所述的制备方法，其特征在于，步骤三中“乳突”状结构加工直径100-500μm、加工间距100-500μm、激光扫描速率为100-800mm/s。
  5. 根据权利要求4所述的制备方法，其特征在于，步骤三中“乳突”状结构加工直径100μm、加工间距100μm、激光扫描速率为100mm/s。
  6. 根据权利要求1所述的制备方法，其特征在于，步骤四中粗坯三浸入酸性除锈剂的时间为4 ~ 6min。
  7. 根据权利要求1所述的制备方法，其特征在于，步骤五中浸渍所用氟硅烷与无水乙醇的体积比为1 : 10。
  8. 根据权利要求1所述的制备方法，其特征在于，步骤五中粗坯四浸入混合溶液中反应的时间为2.5 ~ 3h。
  9. 根据权利要求1所述的制备方法，其特征在于，步骤五中样品干燥的温度为70 ~ 80℃，干燥的时间为20 ~ 30min。
  10. 由权利要求1-9任一项所述的制备方法制得的一种仿生防粘表面。
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