WO2017028449A1 - 可拉伸的柔性超疏液薄膜及制备方法与液滴无损转移方法 - Google Patents

可拉伸的柔性超疏液薄膜及制备方法与液滴无损转移方法 Download PDF

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WO2017028449A1
WO2017028449A1 PCT/CN2015/098935 CN2015098935W WO2017028449A1 WO 2017028449 A1 WO2017028449 A1 WO 2017028449A1 CN 2015098935 W CN2015098935 W CN 2015098935W WO 2017028449 A1 WO2017028449 A1 WO 2017028449A1
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micro
inverted
nano structure
film
stretchable flexible
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French (fr)
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王智伟
吴天准
王磊
袁丽芳
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中国科学院深圳先进技术研究院
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Priority to JP2018509529A priority Critical patent/JP6619873B2/ja
Publication of WO2017028449A1 publication Critical patent/WO2017028449A1/zh

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    • 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
    • C08J7/04—Coating
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • 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
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/04—Homopolymers or copolymers of ethene
    • C09D123/08—Copolymers of ethene
    • 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
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/10—Homopolymers or copolymers of propene
    • C09D123/12—Polypropene

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  • the invention relates to a stretchable flexible super-liquid-repellent film, a preparation method thereof and a method for non-destructive liquid droplet transfer, and belongs to the technical field of micro-droplet operation control.
  • planar microfluidic chips that manipulate droplets on the surface have attracted widespread attention.
  • the planar microfluidic chip not only has the advantages of miniaturization, integration, low reagent consumption and fast analysis speed of the channel microfluidic chip, but also has many channel microfluidic chips. It has the advantages of easy direct contact with droplets, easy handling of solid samples and generation of droplet arrays, without concern for microchannel blockage caused by solid particles and bubbles.
  • an object of the present invention is to provide a stretchable flexible super-lyophobic film and a preparation method thereof, which can realize non-destructive transfer of liquid droplets.
  • the treatment can overcome the shortcomings of the existing micro-droplet operation control technology and broaden the application range of the micro-droplet operation control technology.
  • the present invention provides a method for preparing a stretchable flexible super-lyophobic film, the flow of which is shown in FIG. 1 , and specifically includes the following steps:
  • the curable elastic material is peeled off from the original template to obtain an intermediate having a micro/nano structure corresponding to the inverted micro-nano structure;
  • the cured film is peeled off and subjected to fluorination modification to obtain the stretchable flexible super-lyophobic film.
  • the super-lyophobic surface template having the inverted suspension micro-nano structure may be prepared by dry etching, or may be prepared by wet etching on a silicon substrate; preferably, the inverted-suspended micro-nano structure is T-shaped , inverted trapezoid, spherical, nail-shaped, umbrella or mushroom.
  • the fluorination modification comprises the following steps:
  • the surface of the inverted micro-nanostructure on the original template is heated by a chemical vapor deposition process, and the fluorocarbon gas source in a plasma state is deposited in all directions of the inverted micro-nanostructure to form a hydrophobicity on the surface of the inverted micro-nano structure.
  • a single molecule self-assembly process is used to chemically react on the surface of the inverted micro-nanostructure of the original template to form a hydrophobic fluorocarbon coating on the surface of the inverted micro-nanostructure;
  • the reagent (ie, fluorocarbon) used in the hydrophobic treatment includes fluorine containing trimethylchlorosilane (TMCS), hexamethyldisilazane (HMDS), and perfluorodecyltrichlorosilane (PFTS).
  • TMCS trimethylchlorosilane
  • HMDS hexamethyldisilazane
  • PFTS perfluorodecyltrichlorosilane
  • TMCS trimethylchlorosilane
  • HMDS hexamethyldisilazane
  • PFTS perfluorodecyltrichlorosilane
  • the curable elastic material comprises polydimethylsiloxane, ethylene propylene diene monomer, nitrile rubber, butadiene rubber and neoprene.
  • the curable elastic material comprises polydimethylsiloxane, ethylene propylene diene monomer, nitrile rubber, butadiene rubber and neoprene.
  • the film formation in the steps (2) and (4), may be a low temperature curing, and a typical curing temperature is lower than 5 °C.
  • the rotational speed of the spin coater should be controlled when the plastic emulsion is spin-coated, and the super-lyophobic film of different thickness is obtained at different rotational speeds.
  • the rotational speed of the spin coating is obtained. Control is 50 to 2000 rpm.
  • the plastic emulsion is an EVA emulsion or a polypropylene emulsion or the like.
  • the fluorination modification comprises the following steps:
  • the surface of the inverted micro-nanostructure on the original template is heated by a chemical vapor deposition process, and the fluorocarbon gas source in a plasma state is deposited in all directions of the inverted micro-nanostructure to form a hydrophobicity on the surface of the inverted micro-nano structure.
  • a single molecule self-assembly process is used to chemically react on the surface of the inverted micro-nanostructure of the original template to form a hydrophobic fluorocarbon coating on the surface of the inverted micro-nanostructure;
  • the reagent used for the fluorination modification includes trimethylchlorosilane (TMCS), hexamethyldisilazane (HMDS), and perfluorodecyltrichlorosilane (PFTS).
  • TMCS trimethylchlorosilane
  • HMDS hexamethyldisilazane
  • PFTS perfluorodecyltrichlorosilane
  • the present invention also provides a stretchable flexible super-lyophobic film which is prepared by the above preparation method.
  • the stretchable flexible super-lyophobic film has greater flexibility and greater stretchability and allows for greater bending and stretching.
  • the invention also provides a method for non-destructive transfer of droplets, comprising the steps of:
  • Step 1 placing a droplet on the surface of the above stretchable flexible super-lyophobic film
  • Step 2 contacting the droplet with the surface of another stretchable flexible super-lyophobic film, grasping it, and transferring;
  • Step 3 Increasing the pitch of the micro/nano structure, reducing the solid-liquid contact area, and causing the droplets to fall off the surface of the stretchable flexible super-lyophobic film to complete the transfer.
  • the method does not require external energy input, such as light, electromagnetic field, mechanical vibration and sound field excitation, etc., and can realize non-destructive transfer of droplets.
  • external energy input such as light, electromagnetic field, mechanical vibration and sound field excitation, etc.
  • composition of the droplets, the transport path and direction of the microfluidic droplet sample, and the like there is no limitation on the composition of the droplets, the transport path and direction of the microfluidic droplet sample, and the like, and it is effective for any droplet.
  • the non-destructive transfer of droplets provided by the present invention is applicable to droplets of various kinds and characteristics or mixtures thereof.
  • the droplets comprise droplets of different kinds and characteristics, mixtures of different droplets or droplets and solid particles.
  • the liquid comprises one or a combination of an aqueous solution, milk, blood, plasma, and a biochemical agent.
  • the super-lyophobic film in the transfer process, can be utilized to have good flexibility and good stretchability, and the contact area and adhesion between the droplet and the surface can be changed by stretching to realize the loss of the droplet.
  • the transfer can also reduce the curvature of the surface by bending, thereby reducing the contact area and adhesion between the droplet and the surface, and achieving non-destructive transfer of the droplet. That is, preferably, in step 3, increasing the pitch of the micro/nano structure is achieved by stretching or bending the stretchable flexible super-lyophobic film.
  • the ultra-lyophobic surface with low wetting and low adhesion to any liquid is ideal for surface microfluidic droplet handling.
  • the invention develops a super-lyophobic surface material based on a special inverted suspension microstructure based on microelectromechanical system (MEMS) processing technology.
  • MEMS microelectromechanical system
  • the surface not only has good low wetting characteristics for almost any liquid, but also has good flexibility and pullability. Extensibility, therefore, the local solid-liquid contact area and curvature can be changed by stretching, bending, etc. of the surface to adjust the adhesion of the surface to the droplets, thereby achieving non-destructive transport of the droplets.
  • the double soft replication process is combined with the low surface energy treatment, a super-lyophobic surface with controllable surface micro-nano structure and excellent low wetting property is obtained, and the flexibility of the super-lyophobic surface is utilized. And stretchability, so the local solid-liquid contact area and curvature can be changed by stretching, bending, etc. of the surface to adjust the adhesion of the surface to the droplets, thereby achieving non-destructive transfer and transport of the droplets.
  • the technical scheme of the invention overcomes the deficiencies of the existing micro-droplet operation control technology, does not need any processing on the micro-droplets, can realize the transport of micro-droplets of any composition and size, and broadens the application of the micro-droplet operation control technology range.
  • FIG. 1 is a schematic view showing a preparation process of a stretchable flexible super-lyophobic surface provided by the present invention
  • FIG. 2 is a schematic diagram of droplet manipulation of a stretchable flexible super-lyophobic surface provided in accordance with the present invention
  • FIG. 3 is a diagram of an actual droplet manipulation process for a stretchable flexible super-lyophobic surface provided in accordance with the present invention.
  • This embodiment provides a method for preparing a stretchable flexible super-lyophobic film, which comprises the following steps:
  • the microstructure of the PDMS intermediate with T-type micro-nanostructure on the surface is placed on the spin coater, and the liquid EVA emulsion is poured onto the surface of the intermediate body.
  • the rotation speed ranges from 50 to 2,000 rpm. Between, different spin coating speeds can be set according to the required thickness, such as a thickness of about 160 microns at 100 revolutions per minute and a thickness of about 80 microns at 300 revolutions per minute.
  • the spin-coated EVA emulsion is taken together with the PDMS intermediate, and placed in a low temperature environment below -4 ° C for curing.
  • the curing time increases with the thickness of the EVA emulsion, and it has a T-type micro after curing.
  • the nanostructured PDMS intermediate was peeled off to obtain a T-type micro-nanostructure EVA film on the surface.
  • This embodiment provides a method for non-destructive transfer of droplets, the process of which is shown in FIG. 2, which utilizes the characteristics of good lyophobic surface prepared in Example 1 with good flexibility and good stretchability for droplet manipulation and non-destruction. Transfer.
  • the method specifically includes the following steps:
  • the droplets 22 are placed on the super-lyophobic film 23;
  • the flexible transparent super-lyophobic film 21 prepared in the operation example 1 is used to take the liquid droplets from the super-lyophobic film 23;
  • the stretched super-lyophobic film 21 reduces the adhesion of the film to the droplets, causing the droplets 22 to fall off the film and thereby non-destructively transfer to any other surface.
  • This embodiment provides another method for non-destructive transfer of droplets, which can utilize the characteristics of good flexibility and good stretchability of the super-lyophobic surface prepared in Example 1 to perform droplet manipulation and non-destructive transfer.
  • the method specifically includes the following steps:
  • the droplets 22 are placed on the super-lyophobic film 23;
  • the flexible transparent super-lyophobic film 21 prepared in the operation example 1 is used to take the liquid droplets from the super-lyophobic film 23;
  • FIG. 3 is a control process diagram for achieving a non-destructive transfer of droplets based on the actual manipulation of droplets of a stretchable flexible super-lyophobic surface provided by the present invention. It can be seen from FIG. 3 that the non-destructive transport of the droplets can be well achieved by the technical solution provided by the present invention.

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Abstract

本发明提供了一种可拉伸的柔性超疏液薄膜及制备方法与液滴无损转移方法。制备方法包括：对具有倒悬微纳结构的模板进行氟化修饰并浇筑可固化弹性材料；将可固化弹性材料从原始模板上剥离，得到具有与倒悬微纳结构相对应的微纳结构的中间体；在中间体上旋涂塑料乳液；将旋涂的塑料乳液固化；将固化的薄膜剥离，进行氟化修饰，得到可拉伸的柔性超疏液薄膜。该超疏液薄膜不仅对几乎任何液体都具有良好的低润湿特性，具有良好的柔韧性和可拉伸性，可以通过对表面的拉伸、弯曲等操作改变局部的固液接触面积和曲率，调节表面对液滴的粘附力，实现液滴的无损转移。本发明还提供了通过可拉伸的柔性超疏液表面实现液滴操控和无损转移的方法。

Description

可拉伸的柔性超疏液薄膜及制备方法与液滴无损转移方法 技术领域
本发明涉及一种可拉伸的柔性超疏液薄膜及制备方法与液滴无损转移方法，属于微液滴操作控制技术领域。
背景技术
近年来，在表面操控液滴的平面微流控芯片引起了广泛的关注。与传统的通道微流控芯片相比，平面微流控芯片除了具有通道微流控芯片小型化、集成化、试剂消耗低、分析速度快等优点以外，还具有诸多通道微流控芯片所不具备的优点，如易于直接接触液滴，便于处理固体样品和生成液滴阵列，无需担心固体颗粒和气泡所引起的微通道堵塞等。
然而，与传统通过连续流体驱动的通道微流控芯片相比，当前表面微流控芯片仍缺少有效的液滴操控方法。近年来虽然发展了部分光控、电磁场控制、机械振动控制及声场激励控制等的表面微液滴操控技术，克服了基于通道微流控技术的部分缺点，但是这些液滴操控技术对液滴的成分、微流体液滴样品的传输路径和方向等都有很大的限制。当前主流的平面液滴操控方法是通过电润湿驱动液滴运动，通过在基底植入电极阵列，交替性地在不同电极施加电压驱动液滴。电极阵列的植入和较高的驱动电压为系统集成带来了诸多不便。
发明内容
为解决上述技术问题，本发明的目的在于提供一种可拉伸的柔性超疏液薄膜及制备方法，采用该薄膜可以实现液滴的无损转移。
本发明的目的还在于提供一种利用上述可拉伸的柔性超疏液薄膜的液滴无损转移方法，采用该方法可以实现任何成分和大小微液滴的输运，无需对微液滴进行任何处理，能够克服现有的微液滴操作控制技术的不足，拓宽微液滴操作控制技术的应用范围。
为达到上述目的，本发明提供了一种可拉伸的柔性超疏液薄膜的制备方法，其流程如图1所示，具体包括以下步骤：
(1)对具有倒悬微纳结构的模板进行氟化修饰并浇筑可固化弹性材料；
(2)在固化之后，将所述可固化弹性材料从原始模板上剥离，得到具有与倒悬微纳结构相对应的微纳结构的中间体；
(3)在所述中间体上具有与倒悬微纳结构相对应的微纳结构的一层表面旋涂塑料乳液；
(4)将旋涂的塑料乳液固化，形成薄膜；
(5)将固化的薄膜剥离，进行氟化修饰，得到所述可拉伸的柔性超疏液薄膜。
在上述制备方法中，具有倒悬微纳结构的超疏液表面模板可以利用干法刻蚀制备，或者，利用湿法蚀刻在硅基板上制备得到；优选地，所述倒悬微纳结构为T形、倒梯形、球形、钉状、伞状或蘑菇状等。
在上述制备方法中，优选地，在步骤(1)中，所述氟化修饰包括以下步骤：
使用化学气相沉积工艺处理加热原始模板上的倒悬微纳米结构的表面，在倒悬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进行沉积，在倒悬微纳米结构的表面生成具有疏水性的碳氟化合物涂层；
或者，使用单分子自组装工艺在原始模板的倒悬微纳米结构的表面进行化学反应，在倒悬微纳米结构的表面生成具有疏水性的碳氟化合物涂层；
更优选地，所述疏水处理采用的试剂(即碳氟化合物)包括三甲基氯硅烷(TMCS)、六甲基二硅胺(HMDS)和全氟癸基三氯硅烷(PFTS)等含氟低表面能试剂中的一种或几种的组合。
在上述制备方法中，优选地，在步骤(1)中，所述可固化弹性材料包括聚二甲基硅氧烷、三元乙丙橡胶、丁腈橡胶、顺丁胶和氯丁胶中的一种或几种的组合。
在上述制备方法中，在步骤(2)和(4)中，成膜的方式可以是低温固化，典型的固化温度为低于5℃。
在上述制备方法中，优选地，将塑料乳液进行旋涂时应控制旋涂仪的转速，不同的转速会得到不同厚度的超疏液薄膜，在步骤(3)中，所述旋涂的转速控制为每分钟50转到2000转。
在上述制备方法中，优选地，在步骤(3)中，所述塑料乳液为EVA乳液或聚丙烯乳液等。
在上述制备方法中，优选地，在步骤(5)中，所述氟化修饰包括以下步骤：
使用化学气相沉积工艺处理加热原始模板上的倒悬微纳米结构的表面，在倒悬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进行沉积，在倒悬微纳米结构的表面生成具有疏水性的碳氟化合物涂层；
或者，使用单分子自组装工艺在原始模板的倒悬微纳米结构的表面进行化学反应，在倒悬微纳米结构的表面生成具有疏水性的碳氟化合物涂层；
更优选地，所述氟化修饰采用的试剂(即碳氟化合物)包括三甲基氯硅烷(TMCS)、六甲基二硅胺(HMDS)和全氟癸基三氯硅烷(PFTS)等含氟低表面能试剂中的一种或几种的组合。
本发明还提供了一种可拉伸的柔性超疏液薄膜，其是通过上述制备方法制备的。该可拉伸的柔性超疏液薄膜具有较大的柔性和较大的可拉伸性，可以进行较大程度的弯曲和拉伸。
本发明还提供了一种液滴无损转移方法，其包括以下步骤：
步骤1：将液滴置于上述可拉伸的柔性超疏液薄膜的表面；
步骤2：用另一可拉伸的柔性超疏液薄膜的表面接触上述液滴，将其抓取，并进行转移；
步骤3：增大微纳结构的间距，减小固液接触面积，使上述液滴从所述可拉伸的柔性超疏液薄膜的表面脱落，完成转移。
该方法无需外部能量输入，如光、电磁场、机械振动及声场激励等，可实现液滴的无损转移。而且，对于液滴的成分、微流体液滴样品的传输路径和方向等均没有限定，对任何液滴有效。
本发明提供的液滴无损转移适用于各种不同种类和特性的液滴或其混合物，优选地，所述液滴包括不同种类和特性的液滴、不同液滴的混合物或者液滴与固体颗粒的混合物；更优选地，所述液体包括水溶液、牛奶、血液、血浆和生化试剂中的一种或几种的组合。
在上述转移方法中，在转移过程中，可以利用超疏液薄膜具有良好柔韧性和良好拉伸性的特点，通过拉伸改变液滴与表面的接触面积和粘附力，实现液滴的无损转移，也可以通过弯曲减小表面的曲率，从而减小液滴与表面的接触面积和粘附力，实现液滴的无损转移。即优选地，在步骤3中，增加微纳结构的间距通过拉伸或者弯曲所述可拉伸的柔性超疏液薄膜实现。
对任何液体有低润湿、低粘附特性的超疏液表面是表面微流控液滴操控的理想选择。本发明基于微机电系统(MEMS)加工技术开发了基于特殊倒悬微结构的超疏液表面材料，该表面不仅对几乎任何液体都具有良好的低润湿特性，而且具有良好的柔韧性和可拉伸性，因此可以通过对表面的拉伸、弯曲等操作改变局部的固液接触面积和曲率，调节表面对液滴的粘附力，从而实现液滴的无损输运。
在本发明的技术方案中，由于使用双重软复制工艺结合低表面能处理，获得了表面微纳结构可控、低润湿特性优良的超疏液表面，利用该超疏液表面良好的柔韧性和可拉伸性，因此可以通过对表面的拉伸、弯曲等操作改变局部的固液接触面积和曲率，调节表面对液滴的粘附力，从而实现液滴的无损转移和输运。本发明的技术方案克服了现有的微液滴操作控制技术的不足，无需对微液滴进行任何处理，可实现任何成分和大小微液滴的输运，拓宽微液滴操作控制技术的应用范围。
附图说明
图1为本发明提供的可拉伸的柔性超疏液表面制备流程示意图；
图2为基于本发明提供的可拉伸的柔性超疏液表面的液滴操控示意图；
图3为基于本发明提供的可拉伸的柔性超疏液表面的实际液滴操控过程图。
具体实施方式
为了对本发明的技术特征、目的和有益效果有更加清楚的理解，现对本发明的技术方案进行以下详细说明，但不能理解为对本发明的可实施范围的限定。
实施例1
本实施例提供了一种可拉伸的柔性超疏液薄膜的制备方法，其包括以下步骤：
(1)将具有T型微纳结构的原始模板清洗干净干燥后，置于热台上，热台的温度设为150℃，在模板的旁边放置一片干净的载玻片，预热3分钟，取出全氟癸基三氯硅烷(PFTS)，用一次性吸管滴加两点在热台上的载玻片上，将一玻璃器皿扣在热台上的原始模板表面，热台加热4分钟以取得最好的疏水效果。
(2)取下倒扣的玻璃器皿，将事先配置好的可固化弹性材料聚二甲基硅氧烷(PDMS)倒入培养皿内，放进80℃的真空干燥箱中，抽真空并烘烤2小时使得可固化弹性材料PDMS固化，将可固化弹性材料PDMS剥离后可获得表面具有T型微纳米结构的中间体。
(3)将表面具有T型微纳米结构的PDMS中间体的微结构一面向上置于旋涂仪上，将液态EVA乳液倾倒在中间体表面，转速范围从每分钟50转到每分钟2000转之间，可以根据所需厚度设置不同的旋涂速度，如每分钟100转时厚度约160微米，每分钟300转时厚度约80微米。
(4)将旋涂后的EVA乳液连同PDMS中间体一并取下，放置于-4℃以下的低温环境中固化，固化时间随EVA乳液的厚度而增加，固化后将其从具有T型微纳米结构的PDMS中间体上剥离，获得表面具有T型微纳米结构EVA薄膜。
(5)将具有T型微纳结构的EVA薄膜支撑两端悬空置于热台上，热台的温度设为70℃，在薄膜的旁边放置一片干净的载玻片，预热3分钟，用一次性吸管滴加数滴全氟癸基三氯硅烷(PFTS)在热台上的载玻片上，将一玻璃器皿扣在热台上，热台上加热30分钟以取得最好的疏水效果，得到可拉伸的柔性超疏液薄膜。
实施例2
本实施例提供了一种液滴无损转移方法，其过程如图2所示，其利用实施例1制备的超疏液表面具有良好柔韧性和良好拉伸性的特点可以进行液滴操控和无损转移。该方法具体包括以下步骤：
首先，将液滴22置于超疏液薄膜23上；
其次，操作实施例1制备出的柔性透明超疏液薄膜21将液滴从超疏液薄膜23上抓取；
最后，拉伸超疏液薄膜21降低薄膜对液滴的粘附力，使得液滴22从薄膜上掉落，从而无损转移到其他任何表面上。
实施例3
本实施例提供了另外一种液滴无损转移方法，其利用实施例1制备的超疏液表面具有良好柔韧性和良好拉伸性的特点可以进行液滴操控和无损转移。该方法具体包括以下步骤：
首先，将液滴22置于超疏液薄膜23上；
其次，操作实施例1制备出的柔性透明超疏液薄膜21将液滴从超疏液薄膜23上抓取；
最后，通过弯曲超疏液薄膜21改变薄膜与液滴接触处的局部曲率降低薄膜对液滴的粘附力，使得液滴22从薄膜上掉落，从而无损转移到其他任何表面上。
图3是基于本发明提供的可拉伸的柔性超疏液表面的实际操控液滴实现液滴无损转移的操控过程图。从图3可以看出，采用本发明所提供的技术方案能够很好地实现液滴的无损输运。

Claims (10)

  1. 一种可拉伸的柔性超疏液薄膜的制备方法，其包括以下步骤：
    (1)对具有倒悬微纳结构的模板进行氟化修饰并浇筑可固化弹性材料；
    (2)在固化之后，将所述可固化弹性材料从原始模板上剥离，得到具有与倒悬微纳结构相对应的微纳结构的中间体；
    (3)在所述中间体上具有与倒悬微纳结构相对应的微纳结构的一层表面旋涂塑料乳液；
    (4)将旋涂的塑料乳液固化，形成薄膜；
    (5)将固化的薄膜剥离，进行氟化修饰，得到所述可拉伸的柔性超疏液薄膜。
  2. 根据权利要求1所述的制备方法，其中，所述倒悬微纳结构为T形、倒梯形、球形、钉状、伞状或蘑菇状。
  3. 根据权利要求1所述的制备方法，其中，在步骤(1)中，所述氟化修饰包括以下步骤：
    使用化学气相沉积工艺处理加热原始模板上的倒悬微纳米结构的表面，在倒悬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进行沉积，在倒悬微纳米结构的表面生成具有疏水性的碳氟化合物涂层；
    或者，使用单分子自组装工艺在原始模板的倒悬微纳米结构的表面进行化学反应，在倒悬微纳米结构的表面生成具有疏水性的碳氟化合物涂层；
    优选地，所述氟化修饰采用的试剂包括三甲基氯硅烷、六甲基二硅胺和全氟癸基三氯硅烷中的一种或几种的组合。
  4. 根据权利要求1所述的制备方法，其中，在步骤(1)中，所述可固化弹性材料包括聚二甲基硅氧烷、三元乙丙橡胶、丁腈橡胶、顺丁胶和氯丁胶中的一种或几种的组合。
  5. 根据权利要求1所述的制备方法，其中，在步骤(3)中，所述旋涂的转速控制为每分钟50转到2000转。
  6. 根据权利要求1或5所述的制备方法，其中，在步骤(3)中，所述塑料乳液为EVA乳液或聚丙烯乳液。
  7. 根据权利要求1所述的制备方法，其中，在步骤(5)中，所述氟化修饰包括以下步骤：
    使用化学气相沉积工艺处理加热原始模板上的倒悬微纳米结构的表面，在倒悬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进行沉积，在倒悬微纳米结构的表面生成具有疏水性的碳氟化合物涂层；
    或者，使用单分子自组装工艺在原始模板的倒悬微纳米结构的表面进行化学反应，在倒悬微纳米结构的表面生成具有疏水性的碳氟化合物涂层；
    优选地，所述氟化修饰采用的试剂包括三甲基氯硅烷、六甲基二硅胺和全氟癸基三氯硅烷中的一种或几种的组合。
  8. 一种可拉伸的柔性超疏液薄膜，其是通过权利要求1-7任一项所述的制备方法制备的。
  9. 一种液滴无损转移方法，其包括以下步骤：
    步骤1：将液滴置于权利要求8所述的可拉伸的柔性超疏液薄膜的表面；
    步骤2：用另一权利要求8所述的可拉伸的柔性超疏液薄膜的表面接触所述液滴，将其抓取，并进行转移；
    步骤3：增大微纳结构的间距，减小固液接触面积，使所述液滴从所述可拉伸的柔性超疏液薄膜的表面脱落，完成转移；
    优选地，所述液滴包括不同种类和特性的液滴、不同液滴的混合物或者液滴与固体颗粒的混合物；更优选地，所述液体包括水溶液、牛奶、血液、血浆和生化试剂中的一种或几种的组合。
  10. 根据权利要求9所述的方法，其中，在步骤3中，增加微纳结构的间距通过拉伸或者弯曲所述可拉伸的柔性超疏液薄膜实现。
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