CN105085952A - Stretchable flexible superlyophobic film, and preparation method and liquid drop nondestructive transfer method thereof. - Google Patents
Stretchable flexible superlyophobic film, and preparation method and liquid drop nondestructive transfer method thereof. Download PDFInfo
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- CN105085952A CN105085952A CN201510514081.1A CN201510514081A CN105085952A CN 105085952 A CN105085952 A CN 105085952A CN 201510514081 A CN201510514081 A CN 201510514081A CN 105085952 A CN105085952 A CN 105085952A
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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- 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
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- 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
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- 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
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- 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
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Abstract
The invention provides a stretchable flexible superlyophobic film, and a preparation method and liquid drop nondestructive transfer method thereof. The preparation method comprises the following steps: carrying out fluoridation modification on a template in an overhung micro/nano structure, and casting a curable elastic material; peeling the curable elastic material off the original template to obtain a micro/nano-structure intermediate corresponding to the overhung micro/nano structure; carrying out spin coating on a plastic emulsion on the intermediate; curing the plastic emulsion subjected to spin coating; and stripping the cured film, and carrying out fluoridation modification to obtain the stretchable flexible superlyophobic film. The superlyophobic film has the advantages of low wettability for almost every liquid, favorable flexibility and favorable stretchability; and the surface can be stretched, bent or the like to change the local solid-liquid contact area and curvature, thereby regulating the surface adhesion to the liquid drops and implementing nondestructive transfer of the liquid drops. The invention also provides a liquid drop control and nondestructive transfer method by using the stretchable flexible superlyophobic surface.
Description
Technical field
The present invention relates to a kind of stretchable flexibility to surpass lyophoby film and preparation method and drop and can't harm transfer method, belong to microlayer model operation control techniques field.
Background technology
In recent years, the plane micro-fluidic chip manipulating drop on surface causes to be paid close attention to widely.Compared with traditional channel microfluidic chip, plane micro-fluidic chip is except having the advantages such as channel microfluidic chip miniaturization, integrated, reagent consumption is low, analysis speed is fast, also there is the advantage not available for all multichannel micro-fluidic chips, as being easy to directly to contact drop, be convenient to process solid sample and generate droplet array, without the need to worrying the microchannel blocking etc. caused by solid particulate and bubble.
But compared with the channel microfluidic chip driven by continuous fluid with tradition, Current surface micro-fluidic chip still lacks effective liquid drop control method.Although developed that part is light-operated in recent years, electromagnetic field controlled, mechanical vibration control and sound field excitation control etc. surperficial microlayer model manipulation technology, overcome the some drawbacks based on channel microfluidic technology, but these liquid drop control technology there is very large restriction to the composition of drop, the transmission route of microfluid droplet sample and direction etc.The plane liquid drop control method of current main-stream drives liquid drop movement by electricity is wetting, by substrate implant electrode array, alternately applies voltage driven drop at Different electrodes.The implantation of electrod-array and higher driving voltage are that the system integration brings inconvenience.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of stretchable flexibility to surpass lyophoby film and preparation method, adopting this film can realize the harmless transfer of drop.
The present invention also aims to provide a kind of drop utilizing above-mentioned stretchable flexibility to surpass lyophoby film to can't harm transfer method, adopt the method can realize transporting of any composition and size microlayer model, without the need to carrying out any process to microlayer model, the deficiency of existing microlayer model operation control techniques can be overcome, widen the range of application of microlayer model operation control techniques.
For achieving the above object, the invention provides the preparation method that a kind of stretchable flexibility surpasses lyophoby film, its flow process as shown in Figure 1, specifically comprises the following steps:
(1) fluoridize and modify to having the template of hanging micro-nano structure by the feet and build curable elastomer material;
(2) after solidification, described curable elastomer material being peeled off from primary template, obtaining having the intermediate of the micro-nano structure corresponding with hanging micro-nano structure by the feet;
(3) there is the layer of surface spin coating plastics emulsion of the micro-nano structure corresponding with hanging micro-nano structure by the feet on described intermediate;
(4) the plastics emulsion of spin coating is solidified, form film;
(5) film of solidification is peeled off, carry out fluoridizing modification, obtain described stretchable flexibility and surpass lyophoby film.
In above-mentioned preparation method, there is the super lyophobic surface template of hanging micro-nano structure by the feet dry etching can be utilized to prepare, or, utilize wet etching to prepare on a silicon substrate; Preferably, hanging micro-nano structure described in by the feet is T-shaped, inverted trapezoidal, spherical, spike, umbrella or mushroom etc.
In above-mentioned preparation method, preferably, in step (1), described in fluoridize modification and comprise the following steps:
Use the surface of hanging micro nano structure by the feet on chemical vapor deposition method process heating primary template, fluorocarbon source of the gas under all directions of hanging micro nano structure by the feet use isoionic state deposits, and has hydrophobic fluorocarbon coating at the Surface Creation of hanging micro nano structure by the feet;
Or, use unit molecule self-assembly process to carry out chemical reaction on the surface of hanging micro nano structure by the feet of primary template, at the Surface Creation of hanging micro nano structure by the feet, there is hydrophobic fluorocarbon coating;
More preferably, the reagent (i.e. fluorocarbon) that described hydrophobic treatment adopts comprises the combination of one or more in the fluorine-containing low surface energy reagent such as trimethylchlorosilane (TMCS), hmds (HMDS) and perfluoro decyl trichlorosilane (PFTS).
In above-mentioned preparation method, preferably, in step (1), described curable elastomer material comprises the combination of one or more in polydimethylsiloxane, terpolymer EP rubber, paracril, cis-butadiene cement and neoprene latex.
In above-mentioned preparation method, in step (2) and (4), the mode of film forming can be low-temperature curing, and typical solidification value is lower than 5 DEG C.
In above-mentioned preparation method, preferably, should control the rotating speed of spin coating instrument when plastics emulsion being carried out spin coating, different rotating speeds can obtain the super lyophoby film of different thickness, in step (3), the rotating speed of described spin coating controls to forward 2000 turns to for per minute 50.
In above-mentioned preparation method, preferably, in step (3), described plastics emulsion is EVA emulsion or polypropylene emulsion etc.
In above-mentioned preparation method, preferably, in step (5), described in fluoridize modification and comprise the following steps:
Use the surface of hanging micro nano structure by the feet on chemical vapor deposition method process heating primary template, fluorocarbon source of the gas under all directions of hanging micro nano structure by the feet use isoionic state deposits, and has hydrophobic fluorocarbon coating at the Surface Creation of hanging micro nano structure by the feet;
Or, use unit molecule self-assembly process to carry out chemical reaction on the surface of hanging micro nano structure by the feet of primary template, at the Surface Creation of hanging micro nano structure by the feet, there is hydrophobic fluorocarbon coating;
More preferably, fluoridize described in and modify the reagent (i.e. fluorocarbon) adopted and comprise the combination of one or more in the fluorine-containing low surface energy reagent such as trimethylchlorosilane (TMCS), hmds (HMDS) and perfluoro decyl trichlorosilane (PFTS).
Present invention also offers a kind of stretchable flexibility and surpass lyophoby film, it is prepared by above-mentioned preparation method.This stretchable flexibility surpasses lyophoby film and has larger flexibility and larger tensility, can bend largely and stretch.
Present invention also offers a kind of drop and can't harm transfer method, it comprises the following steps:
Step 1: drop is placed in the surface that above-mentioned stretchable flexibility surpasses lyophoby film;
Step 2: the above-mentioned drop of surface contact surpassing lyophoby film by another stretchable flexibility, is captured, and shift;
Step 3: the spacing increasing micro-nano structure, reduce solid-liquid contact area, the surface making above-mentioned drop surpass lyophoby film from described stretchable flexibility comes off, and completes transfer.
The method inputs without the need to external energy, as optical, electrical magnetic field, mechanical vibration and sound field excitation etc., can realize the harmless transfer of drop.And, the composition of drop, the transmission route of microfluid droplet sample and direction etc. are not all limited, effective to any drop.
Drop provided by the invention can't harm transfer and is applicable to drop or its mixture of various different sorts and characteristic, and preferably, described drop comprises the mixture of the drop of different sorts and characteristic, the mixture of different drop or drop and solid particulate; More preferably, described liquid comprises the combination of one or more in the aqueous solution, milk, blood, blood plasma and biochemical reagents.
In above-mentioned transfer method, in transfer process, super lyophoby film can be utilized to have the feature of good snappiness and good stretchiness, drop and surperficial contact area and adhesive power is changed by stretching, realize the harmless transfer of drop, also by bending the curvature reducing surface, thus drop and surperficial contact area and adhesive power can be reduced, realizing the harmless transfer of drop.Namely preferably, in step 3, the spacing increasing micro-nano structure surpasses the realization of lyophoby film by stretching or bending described stretchable flexibility.
To any liquid to there being low super lyophobic surface that is wetting, low adhesion characteristics to be the ideal chose that surperficial Microfluidic droplet manipulates.The present invention is based on MEMS (micro electro mechanical system) (MEMS) processing technology develops based on special super lyophobic surface material of hanging microstructure by the feet, this surface not only all has good low wetting property to almost any liquid, and there is good snappiness and tensility, therefore can by the solid-liquid contact area of the stretching of effects on surface, the operation change local such as bending and curvature, reconciliation statement in the face of the adhesive power of drop, thus realizes the harmless of drop and transports.
In the inventive solutions, owing to using dual soft duplication process in conjunction with low surface energy process, obtain the super lyophobic surface that controlled, the low wetting property of surface micro-nano structure is excellent, utilize snappiness and tensility that this super lyophobic surface is good, therefore can by the solid-liquid contact area of the stretching of effects on surface, the operation change local such as bending and curvature, reconciliation statement in the face of the adhesive power of drop, thus realizes the harmless transfer of drop and transports.Technical scheme of the present invention overcomes the deficiency of existing microlayer model operation control techniques, without the need to carrying out any process to microlayer model, can realize transporting of any composition and size microlayer model, widens the range of application of microlayer model operation control techniques.
Accompanying drawing explanation
Fig. 1 is that stretchable flexibility provided by the invention surpasses lyophobic surface preparation flow schematic diagram;
Fig. 2 is the liquid drop control schematic diagram surpassing lyophobic surface based on stretchable flexibility provided by the invention;
Fig. 3 is the actual liquid drop control procedure chart surpassing lyophobic surface based on stretchable flexibility provided by the invention.
Embodiment
In order to there be understanding clearly to technical characteristic of the present invention, object and beneficial effect, existing following detailed description is carried out to technical scheme of the present invention, but can not be interpreted as to of the present invention can the restriction of practical range.
Embodiment 1
Present embodiments provide the preparation method that a kind of stretchable flexibility surpasses lyophoby film, it comprises the following steps:
(1) after the primary template with T-shaped micro-nano structure being cleaned up drying, be placed in thermal station, the temperature of thermal station is set to 150 DEG C, the clean slide glass of a slice is placed on the side of template, preheating 3 minutes, takes out perfluoro decyl trichlorosilane (PFTS), drips on 2 slide glasss in thermal station with Dispette, one glassware is buckled in the primary template surface in thermal station, thermal station heats 4 minutes to obtain best hydrophobic effect.
(2) glassware of back-off is taken off, curable elastomer material polydimethylsiloxane (PDMS) good for configured in advance is poured in culture dish, put in the vacuum drying oven of 80 DEG C, vacuumizing and toasting makes curable elastomer material PDMS solidify for 2 hours, can obtain the intermediate that surface has T-shaped micro nano structure after being peeled off by curable elastomer material PDMS.
(3) microstructure one side surface with the PDMS intermediate of T-shaped micro nano structure is upwards placed on spin coating instrument, liquid EVA emulsion is poured over intermediate surface, speed range forwards between per minute 2000 turns from per minute 50, different spin speed can be set according to desired thickness, as thickness during per minute 100 turns about 160 microns, thickness about 80 microns during per minute 300 turns.
(4) the EVA emulsion after spin coating is taken off in the lump together with PDMS intermediate, be positioned in the low temperature environment of less than-4 DEG C and solidify, set time increases with the thickness of EVA emulsion, after solidification, it is peeled off from the PDMS intermediate with T-shaped micro nano structure, obtain surface and there is T-shaped micro nano structure eva film.
(5) eva film with T-shaped micro-nano structure is supported two ends are unsettled is placed in thermal station, the temperature of thermal station is set to 70 DEG C, the clean slide glass of a slice is placed on the side of film, preheating 3 minutes, drip on the slide glass of several perfluoro decyl trichlorosilanes (PFTS) in thermal station with Dispette, one glassware is buckled in thermal station, thermal station heats 30 minutes to obtain best hydrophobic effect, obtain stretchable flexibility and surpass lyophoby film.
Embodiment 2
Present embodiments provide a kind of drop and can't harm transfer method, as shown in Figure 2, the feature that its super lyophobic surface utilizing embodiment 1 to prepare has good snappiness and good stretchiness can carry out liquid drop control and harmless transfer to its process.The method specifically comprises the following steps:
First, drop 22 is placed on super lyophoby film 23;
Secondly, the flexible and transparent that operation embodiment 1 is prepared surpasses lyophoby film 21 and is captured from super lyophoby film 23 by drop;
Finally, the super lyophoby film 21 that stretches reduces the adhesive power of film to drop, and drop 22 is dropped from film, thus harmless transfers on other any surfaces.
Embodiment 3
Present embodiments provide another drop and can't harm transfer method, the feature that its super lyophobic surface utilizing embodiment 1 to prepare has good snappiness and good stretchiness can carry out liquid drop control and harmless transfer.The method specifically comprises the following steps:
First, drop 22 is placed on super lyophoby film 23;
Secondly, the flexible and transparent that operation embodiment 1 is prepared surpasses lyophoby film 21 and is captured from super lyophoby film 23 by drop;
Finally, the local curvature being changed film and drop contact place by bending super lyophoby film 21 reduces the adhesive power of film to drop, and drop 22 is dropped from film, thus can't harm and transfer on other any surfaces.
Fig. 3 is that the actual manipulation drop surpassing lyophobic surface based on stretchable flexibility provided by the invention realizes the manipulation procedure chart that drop can't harm transfer.As can be seen from Figure 3, adopt technical scheme provided by the present invention can realize the harmless of drop well to transport.
Claims (10)
1. stretchable flexibility surpasses a preparation method for lyophoby film, and it comprises the following steps:
(1) fluoridize and modify to having the template of hanging micro-nano structure by the feet and build curable elastomer material;
(2) after solidification, described curable elastomer material being peeled off from primary template, obtaining having the intermediate of the micro-nano structure corresponding with hanging micro-nano structure by the feet;
(3) there is the layer of surface spin coating plastics emulsion of the micro-nano structure corresponding with hanging micro-nano structure by the feet on described intermediate;
(4) the plastics emulsion of spin coating is solidified, form film;
(5) film of solidification is peeled off, carry out fluoridizing modification, obtain described stretchable flexibility and surpass lyophoby film.
2. preparation method according to claim 1, wherein, described in hang micro-nano structure by the feet be T-shaped, inverted trapezoidal, spherical, spike, umbrella or mushroom.
3. preparation method according to claim 1, wherein, in step (1), described in fluoridize modification and comprise the following steps:
Use the surface of hanging micro nano structure by the feet on chemical vapor deposition method process heating primary template, fluorocarbon source of the gas under all directions of hanging micro nano structure by the feet use isoionic state deposits, and has hydrophobic fluorocarbon coating at the Surface Creation of hanging micro nano structure by the feet;
Or, use unit molecule self-assembly process to carry out chemical reaction on the surface of hanging micro nano structure by the feet of primary template, at the Surface Creation of hanging micro nano structure by the feet, there is hydrophobic fluorocarbon coating;
Preferably, fluoridize described in and modify the reagent adopted and comprise the combination of one or more in trimethylchlorosilane, hmds and perfluoro decyl trichlorosilane.
4. preparation method according to claim 1, wherein, in step (1), described curable elastomer material comprises the combination of one or more in polydimethylsiloxane, terpolymer EP rubber, paracril, cis-butadiene cement and neoprene latex.
5. preparation method according to claim 1, wherein, in step (3), the rotating speed of described spin coating controls to forward 2000 turns to for per minute 50.
6. preparation method according to claim 1 or 5, wherein, in step (3), described plastics emulsion is EVA emulsion or polypropylene emulsion.
7. preparation method according to claim 1, wherein, in step (5), described in fluoridize modification and comprise the following steps:
Use the surface of hanging micro nano structure by the feet on chemical vapor deposition method process heating primary template, fluorocarbon source of the gas under all directions of hanging micro nano structure by the feet use isoionic state deposits, and has hydrophobic fluorocarbon coating at the Surface Creation of hanging micro nano structure by the feet;
Or, use unit molecule self-assembly process to carry out chemical reaction on the surface of hanging micro nano structure by the feet of primary template, at the Surface Creation of hanging micro nano structure by the feet, there is hydrophobic fluorocarbon coating;
Preferably, fluoridize described in and modify the reagent adopted and comprise the combination of one or more in trimethylchlorosilane, hmds and perfluoro decyl trichlorosilane.
8. stretchable flexibility surpasses a lyophoby film, and it is prepared by the preparation method described in any one of claim 1-7.
9. drop can't harm a transfer method, and it comprises the following steps:
Step 1: drop is placed in the surface that stretchable flexibility according to claim 8 surpasses lyophoby film;
Step 2: drop described in the surface contact surpassing lyophoby film by another stretchable flexibility according to claim 8, is captured, and shift;
Step 3: the spacing increasing micro-nano structure, reduce solid-liquid contact area, the surface making described drop surpass lyophoby film from described stretchable flexibility comes off, and completes transfer;
Preferably, described drop comprises the mixture of the drop of different sorts and characteristic, the mixture of different drop or drop and solid particulate; More preferably, described liquid comprises the combination of one or more in the aqueous solution, milk, blood, blood plasma and biochemical reagents.
10. method according to claim 9, wherein, in step 3, the spacing increasing micro-nano structure surpasses the realization of lyophoby film by stretching or bending described stretchable flexibility.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510514081.1A CN105085952B (en) | 2015-08-20 | 2015-08-20 | Stretchable flexible super lyophoby film and preparation method and the lossless transfer method of drop |
| JP2018509529A JP6619873B2 (en) | 2015-08-20 | 2015-12-25 | Pullable flexible ultra-phophophobic film, method for producing the same, and method for non-destructive transfer of droplets |
| PCT/CN2015/098935 WO2017028449A1 (en) | 2015-08-20 | 2015-12-25 | Stretchable flexible super-lyophobic film, preparation method, and liquid-drop nondestructive transfer method |
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| CN201510514081.1A CN105085952B (en) | 2015-08-20 | 2015-08-20 | Stretchable flexible super lyophoby film and preparation method and the lossless transfer method of drop |
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| CN105085952A true CN105085952A (en) | 2015-11-25 |
| CN105085952B CN105085952B (en) | 2018-02-06 |
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| CN201510514081.1A Active CN105085952B (en) | 2015-08-20 | 2015-08-20 | Stretchable flexible super lyophoby film and preparation method and the lossless transfer method of drop |
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| WO2017028449A1 (en) * | 2015-08-20 | 2017-02-23 | 中国科学院深圳先进技术研究院 | Stretchable flexible super-lyophobic film, preparation method, and liquid-drop nondestructive transfer method |
| CN106756777A (en) * | 2016-11-28 | 2017-05-31 | 山东大学 | A kind of method and application by straining regulation and control wrinkled surface hydrophilic and hydrophobic reversible transition |
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| WO2017028449A1 (en) * | 2015-08-20 | 2017-02-23 | 中国科学院深圳先进技术研究院 | Stretchable flexible super-lyophobic film, preparation method, and liquid-drop nondestructive transfer method |
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Also Published As
| Publication number | Publication date |
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| CN105085952B (en) | 2018-02-06 |
| JP2018526505A (en) | 2018-09-13 |
| WO2017028449A1 (en) | 2017-02-23 |
| JP6619873B2 (en) | 2019-12-11 |
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