CN111073500B - Film and method for producing same - Google Patents
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- CN111073500B CN111073500B CN201911293755.4A CN201911293755A CN111073500B CN 111073500 B CN111073500 B CN 111073500B CN 201911293755 A CN201911293755 A CN 201911293755A CN 111073500 B CN111073500 B CN 111073500B
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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
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
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- C—CHEMISTRY; METALLURGY
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2003/1084—Laminates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/02—Inorganic compounds
- C09K2200/0204—Elements
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0645—Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds
- C09K2200/0667—Polyamides, polyimides
Abstract
Membranes and methods of making the same are disclosed. The film comprises: the device comprises a substrate layer, a first barrier layer arranged on the surface of the substrate layer and a second barrier layer arranged on the surface of the first barrier layer, wherein: the second barrier layer comprises a two-dimensional nano material and a high polymer material. Because the material particle size of the two-dimensional nano material belongs to the nanometer level, compared with the first barrier layer, the compactness of the second barrier layer is higher, the pore size is smaller, and the second barrier layer is added on the first barrier layer, so that the overall sealing performance of the membrane can be improved, and the problems in the prior art are solved.
Description
Technical Field
The application relates to the technical field of material processing, in particular to a membrane and a preparation method thereof.
Background
With the development of society, films such as plastic films and metal foils are generally used in sealing processes in food, beverage bottles, pharmaceuticals, optical and electronic industries, and the like. The existing film is limited by preparation materials, preparation processes and the like, and tiny pores, pinholes, cracks and the like are usually formed on the surface, so that the sealing performance of the film is influenced. Therefore, it is necessary to provide a film having more excellent sealing performance to solve the problems of the prior art.
Disclosure of Invention
The embodiment of the application provides a membrane and a preparation method thereof, which are used for solving the problem of poor membrane sealing performance in the prior art.
The embodiment of the application provides a preparation method of a membrane, which comprises the following steps:
providing a substrate layer, wherein the substrate layer comprises a first barrier layer thereon;
and generating a second barrier layer on the surface of the first barrier layer by using a mixed material of a two-dimensional nano material and a high polymer material.
Preferably, the two-dimensional nanomaterial comprises any one or more of the following materials:
graphene;
functionalized graphene;
graphene oxide;
functionalized graphene oxide;
reduced graphene oxide;
a functionalized reduced graphene oxide.
Preferably, the polymer material specifically includes: a polymer material having a swelling ratio lower than a predetermined threshold value and/or a polymer material to which a swelling-suppressing additive is added.
Preferably, the generating of the second barrier layer on the surface of the first barrier layer by using a mixed material of a two-dimensional nanomaterial and a polymer material specifically includes:
and generating a second barrier layer on the surface of the first barrier layer by using a mixed material of graphene oxide and polyetherimide.
Preferably, a mixed material of graphene oxide and polyetherimide is used to form a second barrier layer on the surface of the first barrier layer, and the method specifically includes:
dissolving polyetherimide in dimethylacetamide to prepare a polyetherimide solution;
dispersing graphene oxide in dimethylacetamide to prepare a dispersion;
and mixing the prepared polyetherimide solution with the dispersion, and generating a second barrier layer on the surface of the first barrier layer by using the mixed solution.
Preferably, the generating the second barrier layer on the surface of the first barrier layer by using the mixed solution specifically includes:
uniformly coating the mixed solution on the surface of the first barrier layer;
and forming a second barrier layer on the surface of the first barrier layer by thermally-induced phase inversion or non-solvent-induced phase inversion of the uniformly coated mixed solution.
An embodiment of the present application provides a membrane, including: the device comprises a substrate layer, a first barrier layer arranged on the surface of the substrate layer and a second barrier layer arranged on the surface of the first barrier layer, wherein: the second barrier layer comprises a two-dimensional nano material and a high polymer material.
Preferably, the two-dimensional nanomaterial comprises any one or more of the following materials:
graphene;
functionalized graphene;
graphene oxide;
functionalized graphene oxide;
reduced graphene oxide;
a functionalized reduced graphene oxide.
Preferably, the mass ratio of the graphene oxide in the second barrier layer is: greater than or equal to 5% and less than or equal to 40%.
Preferably, the thickness of the second barrier layer is greater than or equal to 1 nm and less than or equal to 500 nm.
The embodiment of the application adopts at least one technical scheme which can achieve the following beneficial effects:
by adopting the film provided by the embodiment of the application, the film comprises a substrate layer, a first barrier layer arranged on the surface of the substrate layer and a second barrier layer arranged on the surface of the first barrier layer, wherein: the second barrier layer comprises a two-dimensional nano material and a high polymer material. Because the material particle size of the two-dimensional nano material belongs to the nanometer level, compared with the first barrier layer, the compactness of the second barrier layer is higher, the pore size is smaller, and the second barrier layer is added on the first barrier layer, so that the overall sealing performance of the membrane can be improved, and the problems in the prior art are solved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the application and together with the description serve to explain the application and not to limit the application. In the drawings:
FIG. 1 is a schematic cross-sectional view of a film according to an embodiment of the present disclosure;
FIG. 2 is a schematic cross-sectional detail view of another film provided in an embodiment of the present application;
fig. 3 is a schematic flow chart of a specific method for preparing a membrane according to an embodiment of the present disclosure.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the technical solutions of the present application will be described in detail and completely with reference to the following specific embodiments of the present application and the accompanying drawings. It should be apparent that the described embodiments are only some of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The technical solutions provided by the embodiments of the present application are described in detail below with reference to the accompanying drawings.
As described above, the existing membrane is limited by the preparation materials, preparation processes, etc., and tiny pores, pinholes, cracks, etc. are usually formed on the surface, so that the membrane can transmit oxygen, water vapor, carbon dioxide, hydrogen sulfide, sulfur oxide, nitrogen oxide, solvent, solute, etc., thereby affecting the sealing performance.
Based on this, the present application provides a film that can solve the problems in the prior art. A schematic cross-sectional view of the membrane 10 is shown in fig. 1. As can be seen in fig. 1, the film 10 comprises a substrate layer 11, wherein at least one surface of the substrate layer 11 comprises one or more first barrier layers 12, the film 10 further comprises a second barrier layer 13 disposed on a surface of the at least one first barrier layer 12, wherein: the second barrier layer 13 includes a two-dimensional nanomaterial and a polymer material.
Wherein the substrate layer 11 is used to provide mechanical support and/or fluid flow paths, depending on the particular application. For example, in membranes used for water filtration, the substrate layer needs to provide mechanical support and fluid flow channels.
Also, the material of the substrate layer 11 may be organic and/or inorganic materials and mixtures thereof, for example, the substrate layer 11 may be a single block or a structure comprising a plurality of adjacent different blocks of material. The material of the substrate layer 11 may be a thermoplastic. The material of the base layer 11 may also be an organic polymeric resin such as, but not limited to, polyethylene terephthalate (PET), polyacrylate, polynorbornene, Polycarbonate (PC), silicone, epoxy, silicone-functionalized epoxy, or polyethylene naphthalate (PEN). The material of the further substrate layer 11 may be an ultra-thin glass layer or a metal foil or a fused ceramic, which has pores, pinholes or cracks. Furthermore, the materials of the substrate layer 11 of different industry names may include Aclar, Vectran, Tefzel, Surlyn, PET ST504, PET mylar D, Armstrong A661, Tedlar, BRP-C, PVC Black, P0100, P0130, Kapton, PVC clear, Korad, EVA, PVB, TPU, DC Sy1guards, GE RTV 615. It should be noted that a combination of materials formed by a plurality of materials is also within the scope of the present application.
For example, the material of the substrate layer 11 may be a flexible organic material such as PET, so as to prepare a flexible organic substrate layer with flexibility; the material of the base layer 11 may also be a metal material such as gold, silver, copper, etc., so that the base layer 11 of the prepared metal foil is processed using these metal materials.
In addition, as for the thickness of the base layer 11, the thickness thereof may be greater than or equal to 5 micrometers and less than or equal to 250 micrometers. For example, the base layer 11 has a thickness of 5 microns, 10 microns, 15 microns, 20 microns, 30 microns, 50 microns, 80 microns, 100 microns, 110 microns, 135 microns, 150 microns, 170 microns, 195 microns, 200 microns, 220 microns, 230 microns, 250 microns, or other thickness values between 5 microns and 250 microns. In practical applications, the specific thickness of the substrate layer 11 can be determined according to specific application scenarios, the material of the substrate layer 11, and the like.
For both surfaces of the substrate layer 11, at least one surface thereof comprises one or more first barrier layers 12. For example, the substrate layer 11 includes a first barrier layer 12 on one surface and no first barrier layer 12 on the other surface; alternatively, the substrate layer 11 includes one first barrier layer 12 on one surface and one or more first barrier layers 12 on the other surface; alternatively, the base layer 11 includes a plurality of first barrier layers 12 on one surface, a plurality of first barrier layers 12 on the other surface, and the like.
For both surfaces of the substrate layer 11, specifically, one or both surfaces include the first barrier layer 12, which may be determined according to actual needs, for example, for the fields related to life and health, such as medicine, food, etc., in order to avoid pollution caused by direct contact of the substrate layer 11 with the medicine, food, etc., the first barrier layer 12 may be disposed on both surfaces of the substrate layer 11.
In addition, the specific number of the first barrier layers 12 on either surface of the base layer 11 may be generally 1. Of course, when high sealability is required, there may be a plurality of the first barrier layers 12, such as 2, 3, 4 or other numbers, and these first barrier layers 12 may be stacked on the surface of the substrate layer 11.
Generally, the greater the number of first barrier layers 12, the greater the sealability of the film 10, but at a correspondingly higher cost, the number of first barrier layers 12 may be determined in conjunction with the actual sealing needs and cost considerations.
The thickness of any one of the first barrier layers 12 may be greater than or equal to 30 microns and less than or equal to 150 microns. For example, the first barrier layer 12 has a thickness of 30 microns, 35 microns, 45 microns, 60 microns, 80 microns, 90 microns, 100 microns, 110 microns, 135 microns, 150 microns, or other thickness values between 30 microns and 150 microns.
The first barrier layer 12 may be formed using a metallic or ceramic material and may be produced by dip coating, spray coating, physical vapor deposition, Chemical Vapor Deposition (CVD), Plasma Enhanced Chemical Vapor Deposition (PECVD), magnetron sputtering, and/or reactive sputtering, or other means.
The material of the first barrier layer 12 may be a nitride, such as silicon nitride. The material of the first barrier layer 12 may also be those of organic materials, inorganic materials, ceramic materials, and any combination thereof.
For example, in one example, the material of the first barrier layer 12 is a recombination product from a reactive plasma species and deposited onto the substrate layer 11. In another example, the material of the first barrier layer 12 is an organic barrier coating material, which may generally include carbon and hydrogen, optionally with other elements such as oxygen, nitrogen, silicon, sulfur, and the like.
The material of the first barrier layer 12 may also be an inorganic material, a ceramic material, typically including oxides, nitrides, borides, or any combination thereof of elements of groups IIA, IIIA, IVA, VA, VIA, VIIA, IB, or IIB; metals of group IIIB, IVB or VB or of rare earth elements. For example, the first barrier layer 12 comprising a silicon carbide material may be deposited onto the substrate layer 11 by recombination of plasmas generated from silane and an organic material such as methane or xylene. The first barrier layer 12 comprising a carbon-containing silicon oxide material may be deposited from a plasma generated from silane, methane and oxygen, or silane and propylene oxide, or from a plasma generated from an organosilicone precursor, such as tetraethoxyorthosilicate (TE0S), Hexamethyldisiloxane (HMDS), Hexamethyldisilazane (HMDZ), or octamethylcyclotetrasiloxane (D4). The first barrier layer 12 of silicon nitride-containing material may be deposited from a plasma generated from silane and ammonia. The first barrier layer 12 comprising the carbon-containing aluminum oxynitride material may be deposited from a plasma generated, for example, from a mixture of aluminum tartrate and ammonia.
The first barrier layer 12 comprising an organic material in some embodiments may be formed by: spin coating, flow coating, knife coating, extrusion, gravure or microgravure printing, dip coating, spray coating, vacuum deposition, Chemical Vapor Deposition (CVD), Plasma Enhanced Chemical Vapor Deposition (PECVD), or similar methods such as radio frequency plasma enhanced chemical vapor deposition (RF-PECVD), expanding thermal-plasma chemical vapor deposition, reactive sputtering, electron-cyclotron resonance plasma enhanced chemical vapor deposition (ecrpevd), Inductively Coupled Plasma Enhanced Chemical Vapor Deposition (ICPECVD), sputter deposition, evaporation, layer deposition, or a combination of these methods.
The film 10 further comprises a second barrier layer 13 disposed on a surface of the at least one first barrier layer 12. For example, in fig. 1, the film 10 includes a second barrier layer 13 disposed on a surface of a first barrier layer 12; as shown in fig. 2, a plurality of second barrier layers 13 may be further included, and the second barrier layers are respectively disposed on the surfaces of the plurality of first barrier layers 12. Of course, for each first barrier layer 12, a corresponding second barrier layer 13 may be provided on the surface thereof. The greater the number of the second barrier layers 13, the better the sealing effect is, but the higher the corresponding manufacturing cost is, the number of the second barrier layers 13 can be determined by combining the requirements of sealing performance, cost and other factors.
The thickness of the second barrier layer 13 may be the same as or different from the thickness of the first barrier layer 12, and in general, the thickness of the second barrier layer 13 may be greater than or equal to 1 nm and less than or equal to 500 nm. For example, the thickness of the second barrier layer 13 is 1 nm, 3 nm, 7 nm, 10 nm, 16 nm, 30 nm, 50 nm, 70 nm, 100 nm, 140 nm, 170 nm, 200 nm, 230 nm, 270 nm, 300 nm, 350 nm, 390 nm, 400 nm, 420 nm, 450 nm, 480 nm, 500 nm or other thickness values between 1 nm and 500 nm.
As the material of the second barrier layer 13, a material having higher density or larger specific surface area than that of the first barrier layer 12 is generally used, so that the barrier or adsorption property of the second barrier layer 13 is larger than that of the first barrier layer 12.
Since the specific surface area of the two-dimensional nanomaterial is large and the adsorbability is strong, the second barrier layer 13 can be prepared by using the two-dimensional nanomaterial. The two-dimensional nanomaterial may comprise any one or a combination of materials: graphene; functionalized graphene; graphene oxide; functionalized graphene oxide; reduced graphene oxide; a functionalized reduced graphene oxide. The second barrier layer 13 is made of, for example, graphene oxide.
In addition, because the particle size of the two-dimensional nanomaterial belongs to the nanometer level, compared with the first barrier layer 12, the second barrier layer 13 prepared from the two-dimensional nanomaterial has higher compactness and smaller pore size, and the sealing performance of the whole membrane can be improved by adding the second barrier layer 13 on the first barrier layer 12. In particular, materials such as graphene, functionalized graphene, graphene oxide, functionalized graphene oxide, reduced graphene oxide, and functionalized reduced graphene oxide generally have extremely large specific surface areas due to the structure of the materials including single-layer graphite, and the single-layer graphite is overlapped and staggered with each other, so that the compactness is high, the pore size is small, and the sealing performance is excellent.
In practical applications, when the second barrier layer 13 is made of two-dimensional nano materials, a certain amount of polymer material with a swelling ratio lower than a preset threshold value can be added thereto, so that the second barrier layer 13 is made of a mixed material after the polymer material is added, and thus the swelling phenomenon of the second barrier layer 13 is suppressed by using the material characteristics of the polymer material. The predetermined threshold value may be determined for polymer materials having a swelling ratio below a predetermined threshold value, and for those cases where a strict limitation of swelling is required, the predetermined threshold value may be lower, such as 1 ml per gram, 1.1 ml per gram, or other values equal to or greater than about 1 ml per gram.
For example, due to the very low swelling ratio of Polyetherimide (PEI) (below a preset threshold), PEI may be added to the two-dimensional nanomaterial and then the mixed material is used to make the second barrier layer 13.
In addition, it is also possible to add a polymer material to which a swelling inhibiting additive is added to the two-dimensional nanomaterial and then prepare the second barrier layer 13 from a mixed material, thereby inhibiting the swelling phenomenon by the swelling inhibiting additive added.
Fig. 2 is a schematic structural diagram of a film in practical application, which includes a substrate layer 11; the first barrier layer 12 is arranged on the surface of the substrate layer 11, and the first barrier layer 12 comprises a pinhole 121 due to defects of a preparation process, a preparation material and the like; the surface of the first barrier layer 12 comprises a second barrier layer 13, and the second barrier layer 13 comprises nanoscale material particles 131 of two-dimensional nanomaterials and PEI. The nano-scale material particles 131 in the second barrier layer 13 block the pinholes 121 in the first barrier layer 12, thereby increasing the overall sealing performance of the membrane.
When a polymer material having a swelling ratio lower than a preset threshold value or a polymer material containing a swelling-inhibiting additive is added to the two-dimensional nanomaterial, the higher the mass ratio of the two-dimensional nanomaterial in the mixed material is, the higher the sealing performance of the second barrier layer 13 prepared from the mixed material is, but the higher the preparation cost is generally. In practical applications, the mass ratio of the two-dimensional nanomaterial in the added mixed material may be greater than or equal to 5% and less than or equal to 40%, in combination with factors such as cost and sealing performance. For example, when graphene oxide is used as the two-dimensional nanomaterial, the mass ratio thereof may be 5% or more and 40% or less. For example, it may be 5%, 7%, 11%, 18%, 20%, 25%, 29%, 32%, 37%, 40%, or other values between 5% and 40%.
Since the metal material has high denseness, a metal material such as gold, silver, or aluminum may be used as the material of the second barrier layer 13, and particularly, the second barrier layer 13 may be formed on the surface of the first barrier layer 12 by magnetron sputtering of the metal material. The magnetron sputtering method has low cost and simple operation, and can generally reduce the manufacturing cost of the second barrier layer 13.
In addition, it should be noted that the second barrier layer 13 is generated by using the surface of the first barrier layer 12 made of the dense metal material in a magnetron sputtering manner, and since the dense metal material does not chemically react with the first barrier layer 12 in the magnetron sputtering manner, the second barrier layer 13 may be peeled off from the outer surface of the first barrier layer 12 in physical manners such as scratching and reverse flushing if necessary, and then the second barrier layer 13 is generated again, so as to achieve the purpose of recycling, and contribute to environmental protection and cost reduction.
For example, when the second barrier layer 13 has a groove, a crack, or the like after a long time use, the second barrier layer 13 may be peeled off from the outer surface of the first barrier layer 12, and a new second barrier layer 13 may be regenerated, and the other parts may be recycled.
With the film 10 provided in the embodiment of the present application, the film 10 includes a substrate layer 11, a first barrier layer 12 disposed on a surface of the substrate layer 11, and a second barrier layer 13 disposed on a surface of the first barrier layer, where: the second barrier layer 13 includes a two-dimensional nanomaterial and a polymer material. Because the material particle size of the two-dimensional nano material belongs to the nanometer level, compared with the first barrier layer 12, the compactness of the second barrier layer 13 is higher, the pore size is smaller, and the sealing performance of the whole membrane can be improved by adding the second barrier layer 13 on the first barrier layer 12, thereby solving the problems in the prior art.
Based on the same concept as the film 10 provided in the embodiments of the present application, the embodiments of the present application also provide a method for producing the film 10, and for the production method, reference may be made to the embodiments of the structural portion of the film 10, if unclear. As shown in fig. 3, a specific flow diagram of the preparation method is shown, which comprises the following steps:
step S31: a substrate layer is provided, wherein the substrate layer includes a first barrier layer thereon.
Step S32: and generating a second barrier layer on the surface of the first barrier layer by using a mixed material of the two-dimensional nano material and the high polymer material.
The two-dimensional nano material can be graphene, functionalized graphene, graphene oxide, functionalized graphene oxide, reduced graphene oxide, functionalized reduced graphene oxide and other materials or a combination of the materials, and because the structure of the two-dimensional nano material comprises single-layer graphite, the specific surface area is very large, and the single-layer graphite is overlapped and staggered with each other, the compactness is high, the pore size is small, and the sealing performance is excellent. The polymer material may be one having a swelling ratio lower than a predetermined threshold value, or one to which a swelling-suppressing additive is added.
In order to facilitate understanding of the preparation method, the preparation method will be described below with reference to specific examples. In this example, the two-dimensional nanomaterial is in particular graphene oxide and the polymeric material is in particular PEI with a very low swelling ratio (below a preset threshold).
Therefore, the second barrier layer can be generated on the surface of the first barrier layer by using the mixed material of the graphene oxide and the PEI.
At this point, the polyetherimide may be dissolved in Dimethylacetamide (DMAC) to prepare a PEI solution. For example, a PEI solution can be prepared by placing 200g of PEI in 500ml of dimethylacetamide, stirring for 30 to 60 minutes, dissolving the PEI sufficiently, and then allowing the dissolved PEI to stand overnight for 24 hours to defoam.
The graphene oxide can also be dispersed in dimethylacetamide to prepare a dispersion. For example, 10g of one or more graphene oxide flakes are dispersed in 500ml of dimethylacetamide by stirring or sonication to form a dispersion.
And mixing the prepared dispersion with a PEI solution, and after mixing, generating a second barrier layer on the surface of the first barrier layer by using the mixed solution. Generally, the mixed solution may be uniformly coated on the surface of the first barrier layer, and then the uniformly coated mixed solution is subjected to thermal induced phase inversion (TIPS) or non-solvent induced phase inversion (NIPS) to form a second barrier layer of graphene oxide and PEI on the surface of the first barrier layer.
It is to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in the process, method, article, or apparatus that comprises the element.
The above are merely examples of the present application and are not intended to limit the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the scope of the claims of the present application.
Claims (3)
1. A method of making a membrane, comprising:
providing a substrate layer, wherein two surfaces of the substrate layer are respectively provided with a first barrier layer;
generating a second barrier layer on the surface of the first barrier layer by using a mixed material of a two-dimensional nano material and polyetherimide, wherein the method comprises the following steps:
dissolving polyetherimide in dimethylacetamide to prepare a polyetherimide solution;
dispersing a two-dimensional nano material in dimethylacetamide to prepare a dispersion;
mixing the prepared polyetherimide solution with the dispersion;
uniformly coating the mixed solution on the surface of the first barrier layer;
and carrying out thermal initiation phase inversion or non-solvent initiation phase inversion on the uniformly coated mixed solution to form the second barrier layer on the surface of the first barrier layer.
2. The method of claim 1, wherein the two-dimensional nanomaterial is selected from the group consisting of graphene, functionalized graphene, graphene oxide, functionalized graphene oxide, reduced graphene oxide, functionalized reduced graphene oxide.
3. The method of claim 1, wherein the second barrier layer has a thickness greater than or equal to 1 nanometer and less than or equal to 500 nanometers.
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