WO2020223887A1 - 一种可实现液滴饼状弹跳功能的超疏水半球阵列 - Google Patents

一种可实现液滴饼状弹跳功能的超疏水半球阵列 Download PDF

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WO2020223887A1
WO2020223887A1 PCT/CN2019/085758 CN2019085758W WO2020223887A1 WO 2020223887 A1 WO2020223887 A1 WO 2020223887A1 CN 2019085758 W CN2019085758 W CN 2019085758W WO 2020223887 A1 WO2020223887 A1 WO 2020223887A1
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hydrophobic
droplet
array
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宋金龙
黄柳
刘新
王续跃
孙玉文
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Dalian University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1681—Antifouling coatings characterised by surface structure, e.g. for roughness effect giving superhydrophobic coatings or Lotus effect
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B17/00—Methods preventing fouling
    • B08B17/02—Preventing deposition of fouling or of dust
    • B08B17/06—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement
    • B08B17/065—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement the surface having a microscopic surface pattern to achieve the same effect as a lotus flower
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/02—Etching
    • C25F3/04—Etching of light metals

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  • the invention belongs to the technical field of functional materials, and relates to a superhydrophobic hemispherical array that can realize the bounce function of a droplet cake, specifically a superhydrophobic hemispherical array that can realize the bounce function of a droplet cake.
  • the height-to-diameter ratio of the super-hydrophobic cone column array, square column array, and cylindrical array is too large, and the mechanical strength is low, and when used on the surface of the aircraft, it is easy to produce large resistance, which affects its practical application. It is extremely important to design a new structure array that can realize the droplet-like bounce function, but also has a smaller aspect ratio, higher mechanical strength, and drag reduction effect.
  • the present invention aims to provide a super-hydrophobic hemispherical array capable of realizing the bounce function of the liquid droplet cake.
  • the hemispherical array can accumulate a large amount of capillary energy and then release, so as to realize the bounce of the liquid droplet.
  • a super-hydrophobic hemispherical array capable of realizing the bounce function of droplets and cakes. It is in the shape of an upper narrow and a lower wide arc.
  • the angle between the substrate-air interface and the substrate-hemisphere interface through the external air is ⁇ , and the hemispherical structure and the substrate contact surface
  • the diameter of is d
  • the distance between adjacent hemispheres is s
  • the vertical height between the top of the hemisphere and the bottom surface of the substrate is h, respectively satisfying 70° ⁇ ⁇ ⁇ 90°, 900 ⁇ m ⁇ d ⁇ 1700 ⁇ m, s ⁇ 550 ⁇ m, 600 ⁇ m ⁇ h ⁇ 1100 ⁇ m
  • the contact angle of the superhydrophobic hemispherical array to water droplets is ⁇ 150°
  • the rolling angle ⁇ 10° is
  • the present invention proposes a new structure that can realize the bounce function of liquid droplets—superhydrophobic hemisphere array
  • the height-to-diameter ratio of the superhydrophobic hemispherical array proposed by the present invention can reach more than 0.48;
  • the superhydrophobic hemispherical array proposed by the present invention has better mechanical strength than the existing superhydrophobic cone, square and cylindrical arrays that can realize droplet cake-like bounce.
  • Figure 1 is a schematic diagram of the structural parameters of the superhydrophobic hemisphere array.
  • Fig. 4 is an electron microscope image of a magnesium alloy mold with a 300 ⁇ m hemispherical micropit array.
  • the ratio reaches 0.56; the contact angle of the superhydrophobic hemispherical array to the water droplet is 160°, and the rolling angle is 3°; 21.0 ⁇ L of the water droplet hits the superhydrophobic array and presents a pie-shaped bouncing state, as shown in FIG. 3.
  • Pretreatment Carry out acetone cleaning and degreasing on 30 mm ⁇ 40 mm ⁇ 2 mm magnesium alloy plates, then polish them with 800# and 1500# sandpaper respectively, and then ultrasonically clean with deionized water and blow dry;
  • Electrochemical machining install the magnesium alloy plate covered with dry film and the copper plate of the same size as anode and cathode on the side punching fixture, adjust the machining gap to 1 mm, and then fill the gap between the electrodes through the electrolyte circulation system 15% NaNO3 solution, and process for 2 minutes under the pulse parameters of current density 14A•cm-2, frequency 20 kHz, duty cycle 30%, and then take out the magnesium alloy plate and place it in 5% NaOH solution After soaking in medium for 4 min to remove the film, after cleaning and drying, a magnesium alloy mold with a hemispherical micropit array is obtained, as shown in Figure 4;
  • the magnesium alloy mold obtained in step (3) is subjected to nano-laser scanning processing at a frequency of 20 kHz, a power of 50 W, and a scanning speed of 200 mm/s, and then ultrasonic cleaning with deionized water. Blow dry

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
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Abstract

一种可实现液滴饼状弹跳功能的超疏水半球阵列，其呈上窄下宽圆弧形状，其中基体-气界面经外部气体至基体-半球界面的夹角为α，半球结构与基体接触面的直径为d，相邻半球之间的间距为s，半球顶端距基体底面的垂直高度为h，分别满足70°≤α≤90°，900μm≤d≤1700μm，s≤550μm，600μm≤h≤1100μm；所述的超疏水半球阵列对水滴的接触角≥150°、滚动角≤10°。该超疏水半球阵列不仅可呈现液滴饼状弹跳现象，且较现有可实现饼状弹跳功能的柱状阵列具有更好的机械强度。

Description

一种可实现液滴饼状弹跳功能的超疏水半球阵列 技术领域
本发明属于功能材料技术领域，涉及到一种超疏水半球阵列，且可实现液滴饼状弹跳功能，具体为一种可实现液滴饼状弹跳功能的超疏水半球阵列。
 背景技术
近年来，针对冻雨可能造成的输电线断裂、飞机飞行阻力增加、车辆与路面摩擦力降低等安全问题，研究人员一直致力于依靠水滴撞击特定超疏水表面时液-固接触时间短且易滚落的特征来防止冻雨附着。考虑到对固定体积的液滴，液-固接触时间几乎不随撞击速度而发生改变，如何进一步减小液-固接触时间对提高超疏水表面防冻雨抗结冰具有重要意义。2013-2015年间，研究人员陆续发现液滴撞击超疏水表面上高180 μm的长条形脊状结构（Nature. 2013, 503:385-388）、直径高度为几十至几百微米级的长条形脊柱状结构（Nature Communications. 2015, 6:8001）及横向放置的直径几个毫米的长条形圆柱状结构曲面（Nature Communications. 2015, 6:10034）时，液-固接触时间均有一定程度的降低。然而，实际应用时大部分雨滴均不会滴落在上述脊状或圆柱状结构曲面上，应用价值较低。
直到2014年，Liu等率先报道了水滴撞击直径20 μm ~ 100 μm、高度800 μm ~ 1200 μm、间距100 μm的超疏水锥柱和方柱阵列上会出现饼状弹跳（Nature Physics, 2014, 10:515-519），液-固接触时间减小约80%。这类亚毫米级柱状结构均能保证雨滴与之接触，应用价值较大。2016年，Hecksher等成功将尺度放大近百倍，在水气球撞击间距为1.85 cm的钉子板阵列时实现宏观饼状弹跳功能（European Journal of Physics, 2016, 38）。2017年，申请人也发现直径≤ 1250 μm、高度600 μm ~ 1000 μm、间距≤ 250 μm的超疏水圆柱阵列也可实现液滴饼状弹跳（ACS nano, 2017, 11:9259-9267，专利号201710555340.4和201710568996.X），且该尺寸易于大面积加工。但超疏水锥柱阵列、方柱阵列以及圆柱阵列的高径比过大，机械强度偏低，且用于飞机表面时易产生大的阻力，影响其实际应用。设计出既可实现液滴饼状弹跳功能，又具有较小高径比、较高机械强度、减阻效果的新型结构阵列异常重要。
 技术问题
本发明旨在提供一种可实现液滴饼状弹跳功能的超疏水半球阵列，液滴撞击超疏水半球阵列时，该半球阵列可聚集大量的毛细能进而释放，实现液滴饼状弹起。
 技术解决方案
本发明的技术方案：
一种可实现液滴饼状弹跳功能的超疏水半球阵列，呈上窄下宽圆弧形状，其中基体-气界面经外部气体至基体-半球界面的夹角为α，半球结构与基体接触面的直径为d，相邻半球之间的间距为s，半球顶端距基体底面的垂直高度为h，分别满足70° ≤ α ≤ 90°，900 μm ≤ d ≤ 1700 μm，s ≤ 550 μm，600 μm ≤ h ≤ 1100 μm；所述的超疏水半球阵列对水滴的接触角≥ 150°、滚动角≤ 10°。
 有益效果
本发明的有益效果：
（1）本发明提出了一种可实现液滴饼状弹跳功能的新型结构——超疏水半球阵列；
（2）本发明提出的超疏水半球阵列的高径比可达0.48以上；
（3）本发明提出的超疏水半球阵列较现有的可实现液滴饼状弹跳的超疏水锥柱、方柱及圆柱阵列具有更好的机械强度。
 附图说明
图1是超疏水半球阵列结构参数的示意图。
图2是α = 71°、d = 1570 μm、s = 160 μm、h = 890 μm的超疏水半球阵列的结构图。
图3是21.0 μL水滴撞击α = 71°、d = 1570 μm、s = 160 μm、h = 890 μm的超疏水半球阵列的运动情况。
图4是300 μm的半球微坑阵列的镁合金模具的电镜图。
 本发明的实施方式
下面结合附图和技术方案，进一步说明本发明的具体实施方式。
实施例
本发明的一种可实现液滴饼状弹跳功能的超疏水半球阵列，如图2所示，呈上窄下宽圆弧形状，其中基体-气界面经外部气体至基体-半球界面的夹角为α = 71°，半球结构与基体接触面的直径为d = 1570 μm，相邻半球之间的间距为s = 160 μm，半球顶端距基体底面的垂直高度为h = 890 μm，且高径比达到0.56；所述的超疏水半球阵列对水滴的接触角为160°，滚动角为3°；21.0 μL水滴撞击该超疏水阵列呈现饼状弹跳状态，如图3所示。
上述可实现液滴饼状弹跳功能的超疏水半球阵列的加工工艺，步骤如下：
（1）预处理：对30 mm × 40 mm × 2 mm的镁合金板进行丙酮清洗除油，然后分别用800#和1500#砂纸打磨进行打磨去除，再用去离子水超声清洗，吹干；
（2）掩膜制备：依次将光致抗蚀干膜HT200和掩膜孔径600 μm、中心距1.9 mm的掩膜板贴于预处理后的镁合金板上，然后在波长360 nm的紫外光下照射30 s以引发光聚合反应，再在质量分数5%的Na2CO3溶液中显影2 min，从而复制图案到干膜上；
（3）电解加工：分别将覆有干膜的镁合金板和同尺寸的铜板作为阳极和阴极安装在侧冲夹具上，调整加工间隙为1 mm，然后通过电解液循环系统使极间充满质量分数15%的NaNO3溶液，并在电流密度14A•cm-2、频率20 kHz、占空比30%的脉冲参数下加工2 min，再将镁合金板取出并置于质量分数5%的NaOH溶液中浸泡4 min去膜，经清洗、吹干后获得有半球微坑阵列的镁合金模具，如图4所示；
（4）微纳结构构建：对步骤（3）中得到的镁合金模具在频率20 kHz、功率50 W、扫描速度200 mm/s参数下进行纳米激光扫描加工，然后进行去离子水超声清洗，吹干；
（5）复制加工：利用PDMS模块胶对步骤（4）中得到的镁合金模具进行浇注，经真空环境下脱泡2 h、60℃下加热6 h进行固化，然后直接徒手脱模得到PDMS半球阵列；
（6）超疏水处理：将步骤（3）中得到的PDMS半球阵列置于质量分数1%的氟硅烷乙醇溶液中修饰40 min，取出烘干，即得到超疏水半球阵列，如图2所示。

Claims (1)

  1. 一种可实现液滴饼状弹跳功能的超疏水半球阵列，其特征在于：该超疏水半球阵列呈上窄下宽圆弧形状，其中基体-气界面经外部气体至基体-半球界面的夹角为α，半球结构与基体接触面的直径为d，相邻半球之间的间距为s，半球顶端距基体底面的垂直高度为h，分别满足70° ≤ α ≤ 90°，900 μm ≤ d ≤ 1700 μm，s ≤ 550 μm，600 μm ≤ h ≤ 1100 μm，且高径比h / d ≥ 0.48；所述的超疏水半球对水滴的接触角≥ 150°、滚动角≤ 10°。
PCT/CN2019/085758 2019-05-07 2019-05-07 一种可实现液滴饼状弹跳功能的超疏水半球阵列 Ceased WO2020223887A1 (zh)

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US17/042,462 US11767455B2 (en) 2019-05-07 2019-05-07 Superhydrophobic hemispherical array which can realize droplet pancake bouncing phenomenon

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