CN117922070A - Method and device for preparing film based on super-spreading of lyophilic substrate - Google Patents
Method and device for preparing film based on super-spreading of lyophilic substrate Download PDFInfo
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- CN117922070A CN117922070A CN202410118880.6A CN202410118880A CN117922070A CN 117922070 A CN117922070 A CN 117922070A CN 202410118880 A CN202410118880 A CN 202410118880A CN 117922070 A CN117922070 A CN 117922070A
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- 239000000758 substrate Substances 0.000 title claims abstract description 112
- 238000000034 method Methods 0.000 title claims abstract description 66
- 238000003892 spreading Methods 0.000 title abstract description 67
- 239000007788 liquid Substances 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 238000004132 cross linking Methods 0.000 claims abstract description 19
- 239000000243 solution Substances 0.000 claims description 199
- 239000010408 film Substances 0.000 claims description 155
- 239000002135 nanosheet Substances 0.000 claims description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
- 229910021389 graphene Inorganic materials 0.000 claims description 29
- 239000012528 membrane Substances 0.000 claims description 29
- 239000010409 thin film Substances 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 22
- 239000011521 glass Substances 0.000 claims description 17
- 229910001220 stainless steel Inorganic materials 0.000 claims description 14
- 239000010935 stainless steel Substances 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- 229910052582 BN Inorganic materials 0.000 claims description 10
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 10
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 9
- 239000005751 Copper oxide Substances 0.000 claims description 9
- 229910000431 copper oxide Inorganic materials 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
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- 239000010703 silicon Substances 0.000 claims description 8
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- 238000009832 plasma treatment Methods 0.000 claims description 7
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 239000010445 mica Substances 0.000 claims description 6
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- 239000012266 salt solution Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- VJFCXDHFYISGTE-UHFFFAOYSA-N O=[Co](=O)=O Chemical compound O=[Co](=O)=O VJFCXDHFYISGTE-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- ROUIDRHELGULJS-UHFFFAOYSA-N bis(selanylidene)tungsten Chemical compound [Se]=[W]=[Se] ROUIDRHELGULJS-UHFFFAOYSA-N 0.000 claims description 3
- HITXEXPSQXNMAN-UHFFFAOYSA-N bis(tellanylidene)molybdenum Chemical compound [Te]=[Mo]=[Te] HITXEXPSQXNMAN-UHFFFAOYSA-N 0.000 claims description 3
- OOEISWVDKCZSMS-UHFFFAOYSA-N bis(tellanylidene)vanadium Chemical compound [Te]=[V]=[Te] OOEISWVDKCZSMS-UHFFFAOYSA-N 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 229910052570 clay Inorganic materials 0.000 claims description 3
- 239000011889 copper foil Substances 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- MHWZQNGIEIYAQJ-UHFFFAOYSA-N molybdenum diselenide Chemical compound [Se]=[Mo]=[Se] MHWZQNGIEIYAQJ-UHFFFAOYSA-N 0.000 claims description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 3
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 3
- 239000000123 paper Substances 0.000 claims description 3
- 229910000338 selenium disulfide Inorganic materials 0.000 claims description 3
- JNMWHTHYDQTDQZ-UHFFFAOYSA-N selenium sulfide Chemical compound S=[Se]=S JNMWHTHYDQTDQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229960005265 selenium sulfide Drugs 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 claims description 3
- WFGOJOJMWHVMAP-UHFFFAOYSA-N tungsten(iv) telluride Chemical compound [Te]=[W]=[Te] WFGOJOJMWHVMAP-UHFFFAOYSA-N 0.000 claims description 3
- 238000011144 upstream manufacturing Methods 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
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- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 5
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
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- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
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Abstract
The invention provides a method for preparing a film based on super-spreading of a lyophilic substrate, which comprises the following steps: firstly, providing a substrate with a lyophile surface, then dripping a first solution on the lyophile surface of the substrate, forming a liquid film on the lyophile surface, finally dripping a second solution on the liquid film surface, and super-spreading the second solution on the liquid film surface, so that the second solution and the first solution undergo interfacial film-forming crosslinking curing reaction, and forming a film on the lyophile surface of the substrate. The invention also provides a device for preparing the film by super-spreading the surface of the lyophilic substrate, which is suitable for the method.
Description
Technical Field
The invention belongs to the technical field of film preparation, and particularly relates to a method and a device for preparing a film based on super-spreading of a lyophile substrate.
Background
The film material has a broad development prospect when being used as a material with special functions. The thickness of the film material is very thin, so that the volume and weight of the product can be greatly reduced, the utilization rate of the material is improved, and the energy is saved. Meanwhile, the film material is widely applied in the fields of machinery, optics, electronics, biology and the like by the performance advantages of higher hardness, higher wear resistance, higher reflectivity and the like. In addition, the production process of the film material is simple, the mass production can be realized, and the cost is low. However, the preparation technology of the film material has great difficulty, high-precision equipment and process control are needed, the performance of the film material is influenced by the preparation process and the base material, the film material is difficult to maintain stably, and the mechanical strength and the durability are also to be improved.
The preparation method of the film generally comprises a solvent evaporation method, a knife coating method, a suction filtration method, a layer-by-layer self-assembly method and a super spreading method. Wherein, the super-spreading method refers to the process of performing super-spreading film formation on the interface of gel and immiscible liquid phase. The gel surface has quasi-liquid property, and can obviously promote the spreading of the miscible liquid. The super-spreading method for preparing the film has the advantages of low energy consumption, simple process, realization of large-scale continuous preparation and realization of highly oriented arrangement of the nano-sheets. However, in the related art, the method for preparing the thin film by super-spreading needs to form a film at an interface after spreading a solution on the surface of the hydrogel, then transferring the thin film to any solid surface and drying, but the preparation of the hydrogel is complex, and the process of transferring the thin film to any solid surface further needs to be carried out under the condition that the hydrogel is wet, so that the thin film which is not dried is easy to break.
Therefore, the existing super-spreading film forming method has certain process limitations and film forming quality problems, and needs to be further improved.
Disclosure of Invention
In view of the above, in order to solve at least one technical problem in the related art and other aspects, the present invention provides a method for preparing a thin film based on super spreading of a lyophile substrate, comprising:
Step S1: a substrate having a lyophilic surface is provided.
Step S2: and (3) dropwise adding the first solution to the lyophilic surface of the substrate to form a liquid film on the lyophilic surface.
Step S3: and (3) dropwise adding a second solution to the surface of the liquid film, and super-spreading the second solution on the surface of the liquid film to enable the second solution and the first solution to undergo interfacial film forming, crosslinking and curing reaction, so that a film is formed on the lyophilic surface of the substrate.
According to an embodiment of the present invention, the material of the substrate includes one of a filter film, a filter paper, a plastic plate, a glass plate, a silicon wafer, a mica sheet, a copper foil, an aluminum foil, and a stainless steel plate.
According to an embodiment of the present invention, in the case where a material of the substrate is selected from any one of a glass plate, a silicon wafer, and a mica sheet, the substrate is subjected to a lyophilic treatment to obtain a substrate having a lyophilic surface.
According to an embodiment of the present invention, the lyophilic treatment includes subjecting the substrate to an oxygen plasma treatment to render the lyophilic surface of the substrate hydrophilic, or subjecting the substrate to a super-philic organic liquid treatment to render the lyophilic surface of the substrate lipophilic.
According to an embodiment of the present invention, the first solution includes one or more of a metal ion solution, an aldehyde solution, a quaternary ammonium salt solution, and a silane coupling agent solution; the second solution comprises a solution of one or more nanoplatelets of graphene oxide, reduced graphene, clay, titanium dioxide, cobalt trioxide, copper oxide, zinc oxide, molybdenum disulfide, tungsten disulfide, selenium disulfide, vanadium ditelluride, tungsten ditelluride, molybdenum ditelluride, tungsten diselenide, molybdenum diselenide, carbon nitride, boron nitride, silicon carbide, black phosphorus, two-dimensional metal carbide.
According to an embodiment of the present invention, the concentration of the first solution ranges from 0.05mol/L to 0.15mol/L; the concentration range of the second solution is 0.1 mg/L-20 mg/L; the volume ratio of the first solution to the second solution is 1:10-10:1.
According to an embodiment of the invention, the second solution is super-spread on the surface of the liquid film for less than or equal to 2 seconds.
According to embodiments of the present invention, the side length of the film ranges from 1cm to 2m.
In another aspect of the invention, a device for preparing a thin film by super-spreading, which is suitable for the method, is provided, and comprises a feeding unit and an interface reaction platform. Wherein the feeding unit comprises a first solution dripping assembly and a second solution dripping assembly; the interface reaction platform is a substrate with a lyophilic surface, and the lyophilic surface of the substrate sequentially receives the first solution and the second solution from the feeding unit, so that the first solution and the second solution undergo interface film forming, crosslinking and curing reaction on the substrate to obtain the film.
According to an embodiment of the invention, the device for preparing a thin film based on the super-spreading of a lyophilic substrate further comprises a collecting unit comprising a conveying assembly and a collecting assembly. The conveying assembly is suitable for driving the interface reaction platform to move, and the first solution dripping assembly is positioned at the upstream of the second solution dripping assembly according to the moving direction of the interface reaction platform; and the conveying component conveys the film obtained on the interface reaction platform to the collecting component for collection.
According to an embodiment of the invention, a first solution is first spread to form a liquid film on a substrate having a lyophilic surface; and then dropwise adding a second solution on the surface of the liquid film with the first solution, wherein the second solution is super-spread on the surface of the liquid film with the first solution, and the solute of the second solution is oriented and arranged by the super-spreading force. At the same time, the first solution is used as a cross-linking agent to cross-link with the solute of the second solution and solidify into a film through at least one effect of chemical cross-linking, electrostatic action, coordination action, cation-pi action and hydrophobic interaction. The method for preparing the film based on the hyperspreading of the lyophile substrate simplifies the process, avoids the risk of damaging the film in the preparation process, is beneficial to obtaining a complete large-area film, and has wide application prospect in the fields of electronic devices, sensing, film separation, biomedicine and the like.
Drawings
FIG. 1 is a flow chart of a method for preparing a thin film by super-spreading in an embodiment of the invention;
FIG. 2 is a schematic diagram of an apparatus for preparing a thin film by super-spreading in the embodiment of the present invention;
FIG. 3 is an optical photograph of the film prepared in example 1 of the present invention;
FIG. 4 is a scanning electron microscope image of the thin film in example 1 of the present invention;
FIG. 5 is a photograph showing the contact angle of a graphene oxide solution on the surface of a glass plate before oxygen plasma surface treatment in example 2 of the present invention;
FIG. 6 is a photograph showing the contact angle of a graphene oxide solution on the surface of a glass plate subjected to oxygen plasma surface treatment in example 2 of the present invention;
FIG. 7 is an optical photograph of the film prepared in example 2 of the present invention;
FIG. 8 is a scanning electron microscope image of the thin film in example 2 of the present invention;
FIG. 9 is a wide-angle X-ray scattering diagram of the film prepared in example 2 of the present invention;
FIG. 10 is an azimuthal plot of the film produced in example 2 of the present invention versus orientation factor;
FIG. 11 is an optical photograph of the film prepared in example 3 of the present invention;
FIG. 12 is a scanning electron microscope image of the thin film in example 3 of the present invention;
FIG. 13 is an optical photograph of the film prepared in example 4 of the present invention;
FIG. 14 is an optical photograph of the film prepared in example 5 of the present invention;
FIG. 15 is an optical photograph of the film prepared in example 6 of the present invention;
FIG. 16 is a wide-angle X-ray scattering chart of the film prepared in comparative example 1 of the present invention;
FIG. 17 is an azimuthal plot of the film prepared in comparative example 1 of the present invention;
FIG. 18 is a wide-angle X-ray scattering chart of the film prepared in comparative example 2 of the present invention;
FIG. 19 is an azimuthal plot of the film prepared in comparative example 2 of the present invention.
In the drawings and the specification, the reference numerals have the following meanings:
1.A feeding unit;
11. A first solution drip assembly;
12. A second solution drip assembly;
2. An interface reaction platform;
3. a collection unit;
31. A transfer assembly;
32. and a collection assembly.
Detailed Description
The present invention will be further described in detail below with reference to specific embodiments and with reference to the accompanying drawings, in order to make the objects, technical solutions and advantages of the present invention more apparent.
The endpoints of the ranges and any values disclosed in the present invention are not limited to the precise range or value, and the range or value should be understood to include values close to the range or value. For numerical ranges, one or more new numerical ranges may be obtained in combination with each other between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point values, and are to be considered as specifically disclosed in the present invention.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The terms "comprises," "comprising," and/or the like, as used herein, specify the presence of stated features, steps, operations, and/or components, but do not preclude the presence or addition of one or more other features, steps, operations, or components.
All terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art unless otherwise defined. It should be noted that the terms used herein should be construed to have meanings consistent with the context of the present specification and should not be construed in an idealized or overly formal manner.
It is to be noted that unless otherwise defined, technical or scientific terms used herein should be taken in a general sense as understood by one of ordinary skill in the art to which the present invention belongs. If, throughout, reference is made to "first," "second," etc., the description of "first," "second," etc., is used merely for distinguishing between similar objects and not for understanding as indicating or implying a relative importance, order, or implicitly indicating the number of technical features indicated, it being understood that the data of "first," "second," etc., may be interchanged where appropriate.
In the present invention, unless explicitly specified and limited otherwise, the terms "mounted," "connected," "secured," and the like are to be construed broadly and include, for example, either permanently connected, removably connected, or integrally formed therewith; may be mechanically connected, may be electrically connected or may communicate with each other; can be directly connected or indirectly connected through an intermediate medium, and can be communicated with the inside of two elements or the interaction relationship of the two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
In the description of the present invention, it should be understood that the terms "longitudinal," "length," "circumferential," "front," "rear," "left," "right," "top," "bottom," "inner," "outer," and the like indicate an orientation or a positional relationship based on that shown in the drawings, merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the subsystem or element in question must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention.
Like elements are denoted by like or similar reference numerals throughout the drawings. Conventional structures or constructions will be omitted when they may cause confusion in the understanding of the invention. And the shape, size and position relation of each component in the figure do not reflect the actual size, proportion and actual position relation. In addition, in the present invention, any reference signs placed between parentheses shall not be construed as limiting the claim.
Similarly, in the foregoing description of exemplary embodiments of the invention, various features of the invention are sometimes grouped together in a single embodiment, figure, or description thereof for the purpose of streamlining the disclosure and aiding in the understanding of one or more of the various disclosed aspects. The description of the terms "one embodiment," "some embodiments," "example," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present invention.
The super-spreading film-forming has the advantages that the structure and the performance of the polymer film can be influenced by fine adjustment and control of the orientation of solute molecules of the spreading solution through the magnitude and the direction of the super-spreading force, so that the polymer film with specific functions can be obtained.
In the related art, the super-spreading is realized on the surface of the gel, but the inherent characteristics of the hydrogel that absorbs water and loses water make the film inevitably have the problems of secondary transfer and film breakage during the peeling or curing process, and it is difficult to prepare a complete large-size film. In addition, the existing super-spreading method for preparing the film generally adopts a sodium alginate high-molecular crosslinking system and a metal ion crosslinking system, but a small-molecular crosslinking system such as quaternary ammonium salt, a silane coupling agent and the like is not realized. Therefore, in the invention, aiming at the defects of the related technology, a super-spreading film forming method based on a lyophile substrate is designed, namely, on the basis of a conventional substrate with a lyophile surface, a liquid film is firstly obtained by spreading a first solution, a gel-like liquid film surface is created, then a second solution is dripped on the liquid film surface as a spreading solution, the second solution spontaneously or under the effect of super-spreading force on the liquid film surface is subjected to orientation arrangement, and the film is obtained under the condition of super-spreading through cross-linking and solidification of the first solution and the second solution. Wherein, the contact angle of the liquid film surface formed by the second solution and the first solution in the super spreading process is 0 degree.
FIG. 1 is a flow chart of a method for preparing a thin film by super-spreading in an embodiment of the present invention.
The invention provides a method for preparing a film based on super-spreading of a lyophilic substrate, which is shown in figure 1 and comprises the steps S1-S3.
Step S1: a substrate having a lyophilic surface is provided.
Step S2: and (3) dropwise adding the first solution to the lyophilic surface of the substrate to form a liquid film on the lyophilic surface.
Step S3: and (3) dropwise adding a second solution to the surface of the liquid film, and super-spreading the second solution on the surface of the liquid film to enable the second solution and the first solution to undergo interfacial film forming, crosslinking and curing reaction, so that a film is formed on the lyophilic surface of the substrate.
According to an embodiment of the invention, a first solution is first spread to form a liquid film on a substrate having a lyophilic surface; and then dropwise adding a second solution on the surface of the liquid film with the first solution, wherein the second solution is super-spread on the surface of the liquid film with the first solution, and the solute of the second solution is oriented and arranged by the super-spreading force. Simultaneously, the first solution is used as a cross-linking agent to rapidly cross-link the solute of the second solution and solidify into a film through at least one effect of chemical cross-linking, electrostatic action, coordination action, cation-pi action and hydrophobic interaction. The method for preparing the film by using the super-spreading provided by the invention simplifies the process, avoids the risk of damage of the film in the preparation process, is favorable for obtaining a complete large-area film, and has wide application prospects in the fields of electronic devices, sensing, film separation, biomedicine and the like.
According to an embodiment of the present invention, the material of the substrate includes one of a filter film, a filter paper, a glass plate, a plastic plate, a silicon wafer, a mica sheet, a copper foil, an aluminum foil, and a stainless steel plate.
According to the embodiment of the invention, the material of the substrate has the advantages of wider application range and simpler and more convenient operation, and the prepared film can be directly dried on the substrate without transferring, so that the process is simplified, and the film is prevented from being damaged.
According to an embodiment of the present invention, in the case where a material of the substrate is selected from any one of a glass plate, a silicon wafer, and a mica sheet, the substrate is subjected to a lyophilic treatment to obtain a substrate having a lyophilic surface.
According to the embodiment of the invention, the surface of the substrate material is lyophilic, so that the first solution can be rapidly and fully spread on the surface of the substrate to form a liquid film, and a basic environment is established for the super-spreading of the second solution.
According to an embodiment of the present invention, the lyophilic treatment includes subjecting the substrate to an oxygen plasma treatment to render the lyophilic surface of the substrate hydrophilic, or subjecting the substrate to a super-philic organic liquid treatment to render the surface of the substrate lipophilic.
According to an embodiment of the present invention, the substrate is subjected to oxygen plasma treatment for 10 minutes, and hydroxy carboxyl functional groups are introduced into the surface of the substrate to make the surface of the substrate material hydrophilic. The super-organophilic liquid treatment comprises the step of treating the substrate by adopting a chemical modification treatment or a surface coating treatment, wherein nonpolar groups are introduced to the surface of the substrate through chemical modification, and the surface coating treatment enables the surface of the substrate material to be organophilic liquid through hydrophobic coating.
In some specific embodiments, the treatment of the chemical modification comprises: cleaning the surface of the substrate, activating the surface of the substrate through plasma treatment, soaking the substrate in a perfluorodecyl triethoxysilane solution for 2 hours, taking out and drying the substrate, and making the surface of the substrate have lipophilicity.
In some specific embodiments, the treatment of the surface coating comprises: and cleaning the surface of the substrate, coating the coating on the surface of the substrate, and drying and curing to obtain the lipophilic lyophile surface substrate. Wherein the coating operation comprises spraying, brushing or dipping; coatings include polymeric coatings (e.g., polypropylene, polyethylene, and polytetrafluoroethylene), silicon-based coatings (e.g., silicone oils and other silicon-based polymers), and paraffin waxes.
According to an embodiment of the present invention, the first solution includes one or more of a metal ion solution, an aldehyde solution, a quaternary ammonium salt solution, and a silane coupling agent solution; the second solution comprises a solution of one or more nanoplatelets of graphene oxide, reduced graphene, clay, titanium dioxide, cobalt trioxide, copper oxide, zinc oxide, molybdenum disulfide, tungsten disulfide, selenium disulfide, vanadium ditelluride, tungsten ditelluride, molybdenum ditelluride, tungsten diselenide, molybdenum diselenide, carbon nitride, boron nitride, silicon carbide, black phosphorus, two-dimensional metal carbide (MXene). In the second solution, the solvent comprises one or more of water, ethanol, isopropanol, acetone, N-dimethylformamide, dimethyl sulfoxide and dichloromethane.
In some specific embodiments, when the first solution is a metal ion solution, the metal ions include at least one of Na+、K+、Li+、Ag+、Mg2+、Cu2+、Ca2+、Zn2+、Fe3+、Al3+; when the first solution is an aldehyde solution, glutaraldehyde is preferable; when the first solution is a quaternary ammonium salt solution, the quaternary ammonium salt comprises at least one of octadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium bromide and tetramethyl ammonium bromide; when the first solution is a silane coupling agent, the silane comprises at least one of 3-aminopropyl triethoxysilane, [3- (methacryloyloxy) propyl ] trimethoxysilane, vinyltriethoxysilane, and vinyltrimethoxysilane.
According to the embodiment of the invention, during the super-spreading process, the spreading acting force enables the nano-sheet solutes (such as graphene oxide and other nano-sheets) of the second solution to be oriented and arranged, and the acting force mainly originates from the acting force of the super-spreading shear liquid flow, and then the film is obtained through crosslinking and solidification. When the first solution is a metal ion, the metal ion interacts with the nano-sheet solute of the second solution through electrostatic interaction, cation-pi interaction, coordination bond or other types of chemical bonds so as to influence the stability, mobility and arrangement mode of the nano-sheets; when the aldehyde solution is contacted with the nano-sheet solute of the second solution, the nano-sheet solute in the second solution is arranged along a specific direction in the super-spreading process under the action of the super-spreading shearing liquid flow, and then the aldehyde solution is crosslinked and fixed; when the first solution is quaternary ammonium salt solution, the nano-sheets serving as solutes of the second solution are driven to self-assemble through electrostatic interaction and hydrophobic interaction; when the first solution is a silane coupling agent, the silane coupling agent generates hydroxyl, and the hydroxyl and the carboxyl on the surface of the second solution nano-sheet solute are subjected to dehydration reaction, so that crosslinking and curing are realized.
According to an embodiment of the present invention, the concentration of the first solution ranges from 0.05mol/L to 5mol/L; the concentration range of the second solution is 0.1 mg/L-20 mg/L; the volume ratio of the first solution to the second solution is 1:10-10:1.
According to an embodiment of the invention, the second solution is super-spread on the surface of the liquid film for less than or equal to 2 seconds.
According to embodiments of the present invention, the side length of the film ranges from 1cm to 2m.
According to the embodiment of the invention, the film is formed rapidly and stably on the basis of super-spreading by applying the preparation method of the invention. Meanwhile, the film is not required to be transferred to another substrate for curing, and can be directly dried at room temperature on the substrate or transferred into an oven for drying, so that the film with the substrate or the self-supporting film can be prepared by a simpler method, and the maximum spreadable size of the film is 2 meters.
FIG. 2 is a schematic diagram of an apparatus for preparing a thin film by super-spreading in the examples of the present invention.
In another aspect of the present invention, a device for preparing a thin film by super-spreading based on a lyophilic substrate, which is suitable for the above-mentioned method, is provided, and as shown in fig. 2, the device for preparing a thin film by super-spreading comprises a feeding unit 1 and an interfacial reaction platform 2. Wherein the feed unit 1 comprises a first solution drop assembly 11 and a second solution drop assembly 12; the interface reaction platform 2 is a substrate with a lyophilic surface, and the lyophilic surface of the substrate sequentially receives the first solution and the second solution from the feeding unit, so that the first solution and the second solution undergo an interface film forming, crosslinking and curing reaction on the substrate to obtain a film.
According to the embodiment of the invention, the substrate is placed on the interface reaction platform 2, and the first solution dripping component 11 and the second solution dripping component 12 of the feeding unit 1 respectively drip the first solution and the second solution into the interface reaction platform 2 in sequence, so that the super-spreading film-forming reaction is completed.
According to an embodiment of the present invention, the device for preparing a thin film based on the super-spreading of a lyophilic substrate further comprises a collecting unit 3, the collecting unit 3 comprising a transfer assembly 31 and a collecting assembly 32. Wherein the conveying component 31 is suitable for driving the interface reaction platform 2 to move, and the first solution dripping component 11 is positioned at the upstream of the second solution dripping component 12 according to the moving direction of the interface reaction platform 2; the transfer module 31 transfers the thin film obtained on the interface reaction platform 2 to the collection module 32 for collection.
According to an embodiment of the present invention, when preparing a large-sized thin film, the interface reaction platform 2 is driven to move by the transfer assembly 31 of the collecting unit 3, thereby continuously dropping the first solution and the second solution, and realizing the preparation of the large-sized thin film. The resulting film may be collected by collection assembly 32 after drying. In some embodiments, the collection assembly 32 is preferably a roller structure.
It should be noted that the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, other embodiments that may be obtained by those of ordinary skill in the art without making any inventive effort are within the scope of the present invention.
Example 1
Taking a cellulose filter membrane with a lyophile surface as a substrate, and placing the substrate on an interface reaction platform.
CaCl 2 solution with the concentration of 0.5mol is taken as a first solution (the solvent is water), caCl 2 solution is dripped on the lyophilic surface of the cellulose filter membrane substrate through a first solution dripping assembly, and a liquid film is formed on the lyophilic surface. Simultaneously, the transmission assembly drives the cellulose filter membrane to move from the first solution dripping assembly to the second solution dripping assembly.
Taking a two-dimensional metal carbide (MXene) solution with the concentration of 5mg/mL as a second solution (the solvent is water), dripping the MXene solution to the surface of the liquid film through a second solution dripping component, enabling the MXene solution to be super-spread on the surface of the liquid film, generating crosslinking, and reacting for 2min to obtain the film. Wherein, the MXene nano-sheets are arranged in an orientation way by the spreading acting force in the super spreading process, and Ca 2+ is used for crosslinking the MXene nano-sheets and rapidly fixing the orientation structure.
And (3) placing the cellulose filter membrane with the membrane in a baking oven at 40 ℃ for drying for 6 hours, washing with deionized water, and placing in the baking oven at 40 ℃ again for drying for 6 hours to obtain the MXene membrane with the cellulose filter membrane substrate.
Fig. 3 and 4 are an optical photograph and a scanning electron microscope image, respectively, of the thin film prepared in example 1 of the present invention.
As shown in figures 3 and 4, the method for preparing the film by using the super-spreading method provided by the invention has the advantages of compact film structure, uniform appearance and no surface damage. The film had a thickness of about 1 μm and an area of 8cm. Times.8 cm.
Example 2
The clean glass plate is put into an oxygen plasma surface treatment instrument for 10 minutes, then taken out, the clean glass plate is taken as a substrate, and the substrate is placed on an interface reaction platform.
Fig. 5 and 6 are photographs showing contact angles of graphene oxide solutions on the surfaces of glass plates before and after oxygen plasma surface treatment in example 2 of the present invention, respectively.
As shown in fig. 5 and 6, the graphene oxide solution failed to achieve super-spreading on the glass plate before oxygen plasma treatment. After oxygen plasma treatment, the glass plate became hydrophilic, and the graphene oxide solution was super-spread with a contact angle of 0 degrees.
3-Aminopropyl triethoxysilane solution with the concentration of 1% is taken as a first solution (the solvent is water), and the 3-aminopropyl triethoxysilane solution is dropwise added to the lyophilic surface of the glass substrate through a first solution dropwise adding component, so that a liquid film is formed on the lyophilic surface of the glass plate substrate. Meanwhile, the conveying assembly drives the glass plate substrate to move from the first solution dripping assembly to the second solution dripping assembly.
Taking a graphene oxide solution with the concentration of 1mg/mL as a second solution (the solvent is water), dripping the graphene oxide solution to the surface of the liquid film through a second solution dripping component, enabling the graphene oxide solution to be super-spread on the surface of the liquid film, and performing crosslinking, and reacting for 5min to obtain the film. The spreading acting force in the super spreading process enables the graphene oxide two-dimensional nano-sheets to be arranged in an oriented mode, and the 3-aminopropyl triethoxysilane is used for crosslinking the graphene oxide nano-sheets and rapidly fixing an oriented structure.
And (3) placing the glass plate with the film in a baking oven at 40 ℃ for 6 hours to obtain the graphene oxide film with the nano-sheets arranged in a layer-by-layer orientation mode.
Fig. 7 and 8 are an optical photograph and a scanning electron microscope image, respectively, of the thin film prepared in example 2 of the present invention.
As shown in figures 7 and 8, the method for preparing the film by using the super-spreading method provided by the invention has the advantages of compact film structure, uniform appearance and no surface damage. The film had a thickness of about 2 μm and an area of 3 cm. Times.6 cm.
Fig. 9 and 10 are wide angle X-ray scattering (WAXS) and azimuthal images, respectively, of the film prepared in example 2 of the invention.
As shown in FIGS. 9 and 10, the method for preparing the film by using the super-spreading method provided by the invention has high orientation degree of the film, wherein the orientation factor is as high as 0.86.
Example 3
And taking a nylon filter membrane with a lyophile surface as a substrate, and placing the substrate on an interface reaction platform.
And (3) taking a hexadecyl trimethyl ammonium bromide solution (ethanol is used as a solvent) with the concentration of 0.1mol/L as a first solution, dropwise adding the hexadecyl trimethyl ammonium bromide solution to the lyophilic surface of the nylon filter membrane substrate through a first solution dropwise adding component, and forming a liquid film on the lyophilic surface of the nylon filter membrane substrate. Simultaneously, the conveying component drives the nylon filter membrane substrate to move from the first solution dripping component to the second solution dripping component.
And taking a graphene oxide solution (the solvent is N, N-dimethylformamide) with the concentration of 2mg/mL as a second solution, dropwise adding the graphene oxide solution to the surface of the liquid film through a second solution dropwise adding component, so that the graphene oxide solution is super-spread on the surface of the liquid film, and is crosslinked, and reacting for 2 minutes to obtain the film. The spreading acting force in the super spreading process enables the graphene oxide two-dimensional nano-sheets to be arranged in an oriented mode, and cetyl trimethyl ammonium bromide drives the graphene oxide nano-sheets to self-assemble.
And (3) placing the nylon filter membrane with the membrane in a baking oven at 40 ℃ for 6 hours to obtain the graphene oxide membrane with the nano-sheets arranged in a layer-by-layer orientation mode.
Fig. 11 and 12 are an optical photograph and a scanning electron microscope image, respectively, of the thin film prepared in example 3 of the present invention.
As shown in figures 11 and 12, the method for preparing the film by using the super-spreading method provided by the invention has the advantages of compact film structure, uniform appearance and no surface damage. The film had a thickness of about 3 μm and an area of 4 cm. Times.8 cm.
Example 4
And taking a nylon filter membrane with a lyophile surface as a substrate, and placing the substrate on an interface reaction platform.
CaCl 2 (water is used as a solvent) with the concentration of 1mol/L is used as a first solution, caCl 2 solution is dripped on the lyophilic surface of the nylon filter membrane substrate through a first solution dripping assembly, and a liquid film is formed on the lyophilic surface of the nylon filter membrane substrate. Simultaneously, the conveying component drives the nylon filter membrane substrate to move from the first solution dripping component to the second solution dripping component.
Taking copper oxide nano-sheet dispersion liquid (water is used as a solvent) with the concentration of 10mg/mL as a second solution, dripping the copper oxide nano-sheet dispersion liquid to the surface of a liquid film through a second solution dripping component, so that the copper oxide solution is super-spread on the surface of the liquid film, cross-linking is carried out, and after 2min of reaction, ca 2+ ions are used for cross-linking the copper oxide nano-sheet and rapidly fixing the orientation structure of the copper oxide nano-sheet.
And (3) placing the nylon filter membrane with the membrane in a baking oven at 40 ℃ for 6 hours to obtain the copper oxide membrane with the nano-sheets arranged in a layer-by-layer orientation mode.
FIG. 13 is an optical photograph of the film prepared in example 4 of the present invention.
As shown in FIG. 13, the method for preparing the film by using the super-spreading method provided by the invention has no damage to the surface of the film. The film area was 17.5cm. Times.17.5 cm.
Example 5
And taking a nylon filter membrane with a lyophile surface as a substrate, and placing the substrate on an interface reaction platform.
CaCl 2 (water is used as a solvent) with the concentration of 1mol/L is used as a first solution, caCl 2 solution is dripped on the lyophilic surface of the nylon filter membrane substrate through a first solution dripping assembly, and a liquid film is formed on the lyophilic surface of the nylon filter membrane substrate. Simultaneously, the conveying component drives the nylon filter membrane substrate to move from the first solution dripping component to the second solution dripping component.
Taking a boron nitride nano-sheet dispersion liquid (the solvent is isopropanol and water) with the concentration of 2mg/mL as a second solution, dripping the boron nitride nano-sheet dispersion liquid onto the surface of a liquid film through a second solution dripping component, so that the boron nitride solution is super-spread on the surface of the liquid film, and is crosslinked, and reacting for 2min to obtain the film. Wherein, the spreading acting force in the super spreading process makes the boron nitride nano-sheets in orientation arrangement, ca 2+ ions cross-link the boron nitride nano-sheets and rapidly fix the orientation structure of the boron nitride nano-sheets.
And (3) placing the nylon filter membrane with the membrane in a baking oven at 40 ℃ for 6 hours to obtain the boron nitride membrane with the nano-sheets arranged in a layer-by-layer orientation mode.
FIG. 14 is an optical photograph of the film prepared in example 5 of the present invention.
As shown in FIG. 14, the method for preparing the film by using the super-spreading method provided by the invention has no damage to the surface of the film. The film area was 4cm by 3cm.
Example 6
Cleaning the surface of the stainless steel plate, putting the stainless steel plate into an oxygen plasma surface treatment instrument for treatment for 10 minutes, taking out the stainless steel plate, soaking the stainless steel plate into a perfluorodecyl triethoxysilane solution for 2 hours, taking out the stainless steel plate, and drying the stainless steel plate. The stainless steel plate is used as a substrate, and the substrate is placed on an interface reaction platform.
And (3) taking a calcium chloride solution (the solvent is N, N-dimethylformamide) with the concentration of 0.004mol/L as a first solution, dropwise adding the calcium chloride solution to the lyophilic surface of the stainless steel plate substrate through a first solution dropwise adding component, and forming a liquid film on the lyophilic surface of the stainless steel plate substrate. Meanwhile, the conveying assembly drives the stainless steel plate substrate to move from the first solution dripping assembly to the second solution dripping assembly.
And taking a graphene oxide solution (the solvent is N, N-dimethylformamide) with the concentration of 2mg/mL as a second solution, dropwise adding the graphene oxide solution to the surface of the liquid film through a second solution dropwise adding component, so that the graphene oxide solution is super-spread on the surface of the liquid film, and is crosslinked, and reacting for 2 minutes to obtain the film. Wherein, the spreading acting force in the super spreading process makes the graphene oxide two-dimensional nano-sheets arranged in an orientation way, and Ca 2+ cross-links the graphene oxide nano-sheets and rapidly fixes the orientation structure.
And (3) placing the stainless steel plate with the film in a baking oven at 40 ℃ for 6 hours to obtain the graphene oxide film with the nano-sheets arranged in a layer-by-layer orientation mode.
FIG. 15 is an optical photograph of the film prepared in example 6 of the present invention.
As shown in FIG. 15, the method for preparing the film by using the super-spreading method provided by the invention has no damage to the surface of the film. The film area was 7 cm. Times.6 cm.
Comparative example 1
Directly mixing 1% of 3-aminopropyl triethoxysilane solution and 1mg/mL of graphene oxide solution, and drying in a baking oven at 40 ℃ for 6 hours to obtain the film.
FIGS. 16 and 17 are a wide-angle X-ray scattering chart and an azimuthal chart, respectively, of the film prepared in comparative example 1 of the present invention.
As shown in fig. 16 and 17, the method of preparing a film by direct mixing has a poor degree of orientation of the film, wherein the orientation factor is 0.11.
Comparative example 2
Pouring 1mg/mL graphene oxide solution into a culture dish, and drying in a baking oven at 40 ℃ for 12 hours to obtain the film.
Fig. 18 and 19 are a wide-angle X-ray scattering chart and an azimuthal chart, respectively, of the film prepared in comparative example 2 of the present invention.
As shown in fig. 18 and 19, the method for preparing the film by direct baking has a low degree of orientation of the film, wherein the orientation factor is 0.59.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the invention thereto, but to limit the invention thereto, and any modifications, equivalents, improvements and equivalents thereof may be made without departing from the spirit and principles of the invention.
Claims (10)
1. A method for preparing a film based on superspreading of a lyophile substrate comprising:
Providing a substrate with a lyophilic surface;
dropwise adding a first solution to the lyophilic surface of the substrate to form a liquid film on the lyophilic surface;
and dropwise adding a second solution to the surface of the liquid film, wherein the second solution is super-spread on the surface of the liquid film, so that the second solution and the first solution undergo interfacial film-forming crosslinking curing reaction, and a film is formed on the lyophilic surface of the substrate.
2. The method of claim 1, wherein the substrate material comprises one of a filter membrane, filter paper, plastic sheet, glass sheet, silicon wafer, mica sheet, copper foil, aluminum foil, stainless steel sheet.
3. The method according to claim 2, wherein the substrate is subjected to a lyophilic treatment to obtain a substrate having a lyophilic surface in the case where the material of the substrate is selected from any one of a glass plate, a silicon wafer, a mica sheet.
4. A method according to claim 3, wherein the lyophilic treatment comprises subjecting the substrate to an oxygen plasma treatment to render the lyophilic surface of the substrate hydrophilic or to a superorganophilic liquid treatment to render the lyophilic surface of the substrate lipophilic.
5. The method according to claim 1 or 4, wherein,
The first solution comprises one or more of a metal ion solution, an aldehyde solution, a quaternary ammonium salt solution and a silane coupling agent solution;
The second solution comprises a solution of one or more nano-sheets of graphene oxide, reduced graphene, clay, titanium dioxide, cobalt trioxide, copper oxide, zinc oxide, molybdenum disulfide, tungsten disulfide, selenium disulfide, vanadium ditelluride, tungsten ditelluride, molybdenum ditelluride, tungsten diselenide, molybdenum diselenide, carbon nitride, boron nitride, silicon carbide, black phosphorus, and two-dimensional metal carbide.
6. The method of claim 5, wherein,
The concentration range of the first solution is 0.05 mol/L-5 mol/L;
The concentration range of the second solution is 0.1 mg/L-20 mg/L;
the volume ratio of the first solution to the second solution is 1:10-10:1.
7. The method of claim 6, wherein the second solution is super-spread on the liquid film surface for less than or equal to 2 seconds.
8. The method of claim 1, wherein the film has a side length in the range of 1cm to 2m.
9. A lyophilic substrate-based superspreading preparation film device suitable for use in the method of any one of claims 1 to 8, comprising:
a feed unit (1) comprising a first solution drop assembly (11) and a second solution drop assembly (12);
The interface reaction platform (2) is a substrate with a lyophile surface, and the lyophile surface of the substrate sequentially receives the first solution and the second solution from the feeding unit (1) so that the first solution and the second solution undergo an interface film-forming crosslinking curing reaction on the substrate to obtain a film.
10. The device according to claim 9, wherein the device further comprises a collecting unit (3), the collecting unit (3) comprising a conveying assembly (31) and a collecting assembly (32);
wherein the conveying component (31) is suitable for driving the interface reaction platform (2) to move, and the first solution dripping component (11) is positioned upstream of the second solution dripping component (12) according to the moving direction of the interface reaction platform (2);
The conveying component (31) conveys the thin film obtained on the interface reaction platform (2) to the collecting component for collection (32).
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