WO2019010764A1 - 一种液滴饼状弹跳的大尺寸超疏水圆柱阵列的热压加工方法 - Google Patents

一种液滴饼状弹跳的大尺寸超疏水圆柱阵列的热压加工方法 Download PDF

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WO2019010764A1
WO2019010764A1 PCT/CN2017/099362 CN2017099362W WO2019010764A1 WO 2019010764 A1 WO2019010764 A1 WO 2019010764A1 CN 2017099362 W CN2017099362 W CN 2017099362W WO 2019010764 A1 WO2019010764 A1 WO 2019010764A1
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hot pressing
cake
cylinder array
processing method
super
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French (fr)
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宋金龙
黄柳
赵长林
高明谦
刘新
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Dalian University of Technology
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Dalian University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
    • B29C37/0053—Moulding articles characterised by the shape of the surface, e.g. ribs, high polish
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
    • B29C59/022—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing characterised by the disposition or the configuration, e.g. dimensions, of the embossments or the shaping tools therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • B01J2/30—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic using agents to prevent the granules sticking together; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
    • B29C59/022—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing characterised by the disposition or the configuration, e.g. dimensions, of the embossments or the shaping tools therefor
    • B29C2059/023—Microembossing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
    • B29C37/0003—Discharging moulded articles from the mould
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/15—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor incorporating preformed parts or layers, e.g. extrusion moulding around inserts
    • B29C48/154—Coating solid articles, i.e. non-hollow articles
    • B29C48/155—Partial coating thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/30—Extrusion nozzles or dies
    • B29C48/345—Extrusion nozzles comprising two or more adjacently arranged ports, for simultaneously extruding multiple strands, e.g. for pelletising
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0093—Other properties hydrophobic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/756—Microarticles, nanoarticles
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping

Definitions

  • the present invention belongs to the field of microfabrication technology, and relates to a hot press processing method for a large-sized super-hydrophobic cylindrical array capable of realizing droplet cake bounce.
  • Freezing rain is a common phenomenon in nature, but it is easy to cause damage to human production and life due to the attachment of freezing on solid surfaces.
  • freezing rain attached to transmission lines is likely to cause power failure in inverted towers; freezing rain adheres to highways to reduce pedestrians and cars and roads. Friction, increase traffic accidents; freezing rain attached to the wing will reduce the aircraft's lift and increase flight resistance, and serious crashes will occur.
  • the danger of freezing rain forces people to find effective ways to reduce their adhesion to solid surfaces.
  • the superhydrophobic surface has attracted the attention of researchers due to its high contact angle and low rolling angle. The researchers hope to prevent freezing rain from adhering by the phenomenon that water droplets hit the superhydrophobic surface and the liquid-solid contact is short and easy to roll off.
  • This type of structure can only be used because the diameter is too small and the aspect ratio is too large.
  • the wire electric discharge cutting method is processed.
  • the efficiency of EDM is too low, and it takes 7-8 small defects to process 2 C mx2 cm samples, making it difficult to achieve industrialized large-area processing. Therefore, it is necessary to develop a structure that can realize a droplet-like bounce but is suitable for large-area industrial processing and emits a large-area processing of a droplet-like bounce surface.
  • the technical problem to be solved by the present invention is to provide a structure capable of realizing droplet cake bounce and large-scale industrial processing, and providing a process for processing a large area of a droplet cake bounce surface.
  • the invention mainly proposes a super-hydrophobic cylindrical array with a column diameter of 0.8 mm-1.25 mm, a column spacing of 0.25 mm and a column height of 0.6 mm-1.0 mm, which can also realize droplet cake bounce, and realize the liquid through the porous array template hot-press replication method. Large-area processing of the blister-like bounce surface.
  • a hot press processing method for a large-sized superhydrophobic cylindrical array of droplet cake bounce the steps are as follows: [0006] (1) Preparation of a hot press mold: a processing diameter of 0.8 mm to 1.25 mm, a column spacing of 0.25 mm, The through hole of the metal substrate array with a depth of 0.6 mm to 1.0 mm is sanded and dried to obtain a hot pressing die; the metal substrate may be aluminum, copper, die steel or stainless steel;
  • Hot pressing Based on the prepared hot press mold, hot pressing is performed using a polymer plate, and taken out and cooled to room temperature.
  • the polymer sheet may be a PP board, a PC board, a PE board, and a PTFE board;
  • the cylindrical array proposed by the invention has a large size and a low aspect ratio, and is easy to process;
  • the invention processes a super-hydrophobic cylindrical array by using a template to replicate a macroscopic columnar array and a method of spraying a nano-coating, and the template can be reused, and the large-area processing of the droplet-shaped bounce surface can be realized simply and at low cost. ;
  • the invention mainly processes polymer materials, and has many types of materials, and the materials have the characteristics of small density, high specific strength, low heat conductivity, high insulation, and low price;
  • the superhydrophobic cylindrical array processed by the present invention can reduce the liquid-solid contact enthalpy by 60%.
  • FIG. 1 is a schematic view of a super-hydrophobic cylindrical array processed by a porous array template thermocompression replication method.
  • 2(a) is an electron micrograph of a 0.2 mm superhydrophobic PP cylinder array.
  • 2(b) is an electron micrograph of a 0.1 mm superhydrophobic PP cylinder array.
  • FIG. 3 is a diagram showing the movement of 18 water droplets striking a superhydrophobic PP cylindrical array.
  • FIG. 4 is a schematic diagram of the hydrophobicity of the prepared superhydrophobic yttrium cylindrical array.
  • the super-hydrophobic cylindrical array capable of realizing droplet cake bounce is processed by the porous array template hot press replication method, as shown in FIG. 1, the specific method is as follows:
  • the mixture is uniformly sprayed on the PP cylindrical array obtained in the step 3 to obtain a superhydrophobic PP cylindrical array.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Shaping Of Tube Ends By Bending Or Straightening (AREA)
  • Devices For Post-Treatments, Processing, Supply, Discharge, And Other Processes (AREA)

Abstract

一种液滴饼状弹跳的大尺寸超疏水圆柱阵列的热压加工方法，包括以下步骤：制备热压模具：加工直径0.8mm～1.25mm、柱间距0.25mm、深0.6mm～1.0mm的金属基体阵列通孔结构，经打磨、清洗及吹干后获得热压模具（1）；热压：使用聚合物材料于热压模具上进行真空热压，取出冷却至室温；取模：截断从通孔溢出的多余的聚合物材料（4）之后拔模即得聚合物圆柱阵列；超疏水处理：对获得的圆柱阵列进行喷涂混合液处理获得超疏水圆柱阵列，其中混合液为含纳米TiO 2颗粒的氟硅烷乙醇溶液。本方法具有简单易操作、成本低、选材料种类多、材料及模板可重复使用、所制备的圆柱阵列尺寸大等优点，有效地实现液滴饼状弹跳表面的大面积、产业化加工。

Description

一种液滴饼状弹跳的大尺寸超疏水圆柱阵列的热压加工 方法 技术领域
[0001] 本发明属于微细加工技术领域， 涉及到一种能实现液滴饼状弹跳的大尺寸超疏 水圆柱阵列的热压加工方法。
背景技术
[0002] 冻雨是自然界中的常见现象， 但因极易在固体表面附着冻结而对人类生产生活 造成破坏， 如冻雨附着输电线路易造成倒塔断电； 冻雨附着公路易降低行人及 汽车与路面摩擦力， 增加交通事故； 冻雨附着机翼会降低飞机升力并增加飞行 阻力， 严重的还会发生坠机事故。 冻雨的危害迫使人们寻找有效的方法减小其 与固体表面的粘附。 超疏水表面因具有较高接触角和较低滚动角而引起了研究 人员的关注， 研究人员希望依靠水滴撞击超疏水表面吋液-固接触吋间短并易滚 落的特征来防止冻雨附着。 水滴撞击超疏水平面吋会先铺展然后回弹最后离幵 基体， 对于固定体积的液滴， 液-固接触吋间几乎不随撞击速度而发生改变。 如 何进一步减小液 -固接触吋间对提高超疏水表面防冻雨抗结冰具有重要意义。 201 4年， Bird发现液滴撞击超疏水平面上的高 180 μηι的长条形脊状结构吋， 液滴会 破裂， 液 -固接触吋间会减小 37% (Nature. 2014, 505(7483)) 。 2015年， Gauthier 等进一步研究了超疏水平面上直径高度为几十至几百微米级的长条形脊柱状结 构对液-固接触吋间的影响， 发现即使液滴不破裂， 液-固接触吋间也显著减小 （ Nature Communications. 2015, 6(8001)) 。 同年， Liu等还发现液滴撞击超疏水平 面上横向放置的、 直径几个毫米的长条形圆柱状结构曲面也可降低液-固接触吋 间 （Nature Communications. 2015, 6(10034)) 。 尽管上述长条形脊状或横向放置 的圆柱状结构曲面可有效降低液-固接触吋间， 但实际使用吋大部分雨滴均不会 滴落在脊状或圆柱状结构曲面上， 应用价值较低。 2014年， Liu等观察到水滴撞 击超疏水亚毫米级的锥柱和方柱阵列上会出现饼状弹跳， 液-固接触吋间减小 80 %。 这种大面积的柱状阵列结构由于能保证雨滴均与之接触， 故应用价值较大。 Liu等研发出的超疏水锥柱和方柱阵列直径约 20 μηι~100 μηι, 高度约 800 μηι~120 Ο μηι, 这种类型的结构由于直径过小且高径比过大， 目前只能用电火花线切割 方法加工出。 但电火花加工效率过低， 加工 2 Cmx2 cm样品需 7~8个小吋， 难以 实现产业化大面积加工。 因此有必要研发能实现液滴饼状弹跳但又适合大面积 产业化加工的结构并幵发出液滴饼状弹跳表面大面积加工的工艺。
技术问题
[0003] 本发明所要解决的技术问题是提供一种既能实现液滴饼状弹跳又适合大面级产 业化加工的结构， 并提供液滴饼状弹跳表面大面积加工的工艺。 本发明主要提 出柱直径 0.8 mm- 1.25 mm、 柱间距 0.25 mm、 柱高 0.6 mm- 1.0 mm的超疏水圆柱 阵列也可实现液滴饼状弹跳， 并通过多孔阵列模板热压复制的方法实现液滴饼 状弹跳表面的大面积加工。
问题的解决方案
技术解决方案
[0004] 本发明的技术方案：
[0005] 一种液滴饼状弹跳的大尺寸超疏水圆柱阵列的热压加工方法， 步骤如下： [0006] ( 1) 制备热压模具： 加工直径 0.8 mm~1.25 mm、 柱间距 0.25 mm、 深为 0.6 m m~1.0 mm的金属基体阵列通孔， 打磨清洗吹干得到热压模具； 所述的金属基体 可为铝、 铜、 模具钢、 不锈钢；
[0007] (2) 热压： 基于制备的热压模具， 使用聚合物板进行热压， 取出冷却至室温
； 所述的聚合物板可为 PP板、 PC板、 PE板及 PTFE板；
[0008] (3) 取模： 截断从通孔溢出的多余的聚合物材料之后拔模即可得到聚合物圆 柱阵列；
[0009] (4) 超疏水处理： 喷涂含纳米 110 2颗粒的氟硅烷乙醇混合溶液， 晾干后获得 超疏水圆柱阵列； 所述的混合溶液中纳米 Ti0 2颗粒与氟硅烷的乙醇溶液 （氟硅 烷的质量分数为 lwt.%) 的质量比不低于 1:25。
发明的有益效果
有益效果
[0010] 本发明的有益效果： [0011] ( 1) 本发明提出的圆柱阵列尺寸较大且高径比低， 易加工；
[0012] (2) 本发明采用模板复制宏观柱状阵列和喷涂纳米涂层的方法加工超疏水圆 柱阵列， 且模板可重复使用， 可简单、 低成本地实现液滴饼状弹跳表面的大面 积加工；
[0013] (3) 本发明主要加工聚合物材料， 可选材料种类较多， 且材料具有密度小、 比强度高、 传热性低、 绝缘性高、 价格低等特点；
[0014] (4) 本发明加工出的超疏水圆柱阵列可使液-固接触吋间减小 60%。
对附图的简要说明
附图说明
[0015] 图 1是多孔阵列模板热压复制方法加工超疏水圆柱阵列的示意图。
[0016] 图 2(a)是 0.2 mm的超疏水 PP圆柱阵列的电镜图。
[0017] 图 2(b)是 0.1 mm的超疏水 PP圆柱阵列的电镜图。
[0018] 图 3是 18 水滴撞击超疏水 PP圆柱阵列的运动情况。
[0019] 图 4是制备的超疏水 ΡΡ圆柱阵列的疏水示意图。
[0020] 图中： 1铝基阵列通孔模具； 2钻头； 3热压； 4聚合物材料；
[0021] 5压力机上端压板； 6加热加压； 7压力机下端基板； 8截断取模； 9喷涂。
本发明的实施方式
[0022] 以下结合附图和技术方案， 进一步说明本发明的具体实施方式。
[0023] 实施例：
[0024] 利用多孔阵列模板热压复制方法加工可实现液滴饼状弹跳的超疏水圆柱阵列， 如图 1所示， 具体方法如下：
[0025] ( 1) 制备热压模具： 分别用 800#和1500#砂纸打磨和去离子水超声清洗 6061铝 板 （厚 l mm) ， 用以去除表面氧化层和油污； 借助钻削技术加工直径 1.05 mm、 柱间距 0.25 mm、 深 1.0 mm的阵列通孔结构， 利用 1500#砂纸打磨去除表面毛刺
， 并经去离子水超声清洗后吹干；
[0026] (2) 热压： 将步骤 1中制备的阵列通孔模具置于压力机下端基板上， 再将 PP材 料固定在上端压板上， 然后将基板温度调整为 180°C， 调整压力为 2000 Pa， 加热 lO min后撤去压力， 取出模具材料并冷却至室温；
[0027] (3) 取模： 截断步骤 2中从通孔溢出的多余的 PP材料， 多余材料可重复利用， 之后拔模即可得到 PP圆柱阵列， 其表面结构如图 2所示；
[0028] (4) 超疏水处理： 配备含纳米 110 2颗粒的氟硅烷乙醇混合溶液， 其中 50 g氟 硅烷的乙醇溶液 （氟硅烷质量分数为 lwt.%) 中含 6 g纳米 Ti0 2颗粒 （40 nm直径
) ； 将该混合液均匀喷涂于步骤 3中得到的 PP圆柱阵列上获得超疏水 PP圆柱阵列

Claims

权利要求书 [权利要求 1] 一种液滴饼状弹跳的大尺寸超疏水圆柱阵列的热压加工方法， 其特征 在于， 步骤如下：
(1) 制备热压模具： 加工直径 0.8 mm~1.25 mm、 柱间距 0.25 mm、 深为 0.6 mm~1.0 mm的金属基体阵列通孔， 清洗吹干得到热压模具；
(2) 热压： 基于制备的热压模具， 使用聚合物板进行热压， 取出冷 却至室温；
(3) 取模： 截断从通孔溢出的多余的聚合物材料后拔模， 即得到聚 合物圆柱阵列；
(4) 超疏水处理： 喷涂含纳米 110 2颗粒的氟硅烷乙醇混合溶液， 晾 干后获得超疏水圆柱阵列； 所述的混合溶液中纳米 TiO 2颗粒与氟硅 烷的乙醇溶液的质量比不低于 1:25; 其中， 氟硅烷的乙醇溶液中的氟 硅烷质量分数为 lwt.%。
2.根据权利要求 1所述的热压加工方法， 其特征在于， 所述的金属基 体的材质为铝、 铜、 模具钢或不锈钢。
3.根据权利要求 1或 2所述的热压加工方法， 其特征在于， 所述的聚合 物板为 PP板、 PC板、 PE板或 PTFE板。
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