KR101873096B1 - Nanotextured superhydrophobic polymer film and method of manufacturing the same - Google Patents

Abstract

The present invention relates to a nano-textured ultra-hydrophobic polymer film and a method of manufacturing the same, and a method of fabricating a nanotextured ultra-hydrophobic polymer film according to an embodiment of the present invention includes the steps of forming a porous anodic aluminum mold ; Disposing a polymer on the porous anodic aluminum mold; Forming the porous anodic aluminum mold and the polymer by hot pressing to form a nanostructured polymer structure on the polymer; And separating the polymer comprising the nanostructured polymeric structure from the porous anodic aluminum mold.

Description

TECHNICAL FIELD [0001] The present invention relates to a nano-textured ultra-hydrophobic polymer film and a method of manufacturing the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a nanotextured ultra-hydrophobic polymer film and a method for producing the same.

Superhydrophobic refers to the physical properties of the surface of an object that are extremely difficult to wet. Many organisms in nature have been reported to have perfect superhydrophobic structures with harmonization and unity of structure and function to achieve maximum performance utilizing minimal resources. For example, leaves of some plants, wings of an insect or birds' wings have the property that any contaminants from the outside are removed without special removal or contamination from the beginning. This is because the leaves of these plants, the wings of insects, and the wings of birds have super-hydrophobicity. Recently, many researchers have focused on the production of biomimetic superhydrophobic surfaces due to their wide potential applicability. In nature, leaves of many plants exhibit water repellency and self-cleaning. Among them, lotus leaves are recognized as an ideal model for engineering self-cleaning. This artificial imitation of the superhydrophobic surface is an attractive technique that is needed in various industries because it can easily remove undesirable contaminants from the surface of a premium product. A superhydrophobicity surface is generally defined as a surface capable of producing a static water contact angle (CA) greater than 150 °. Such high contact angle values on the material surface can not be achieved without geometrical supports such as periodic microscale objects, nanoscale objects, or mixtures thereof. Therefore, most superhydrophobic surfaces include nanometer scale or micrometer scale profiles of low surface energy (gamma) materials.

Fractal surface nanostructures of hydrophobic materials drastically increase the contact angle of water droplets on nanotactured surfaces. Additionally, microscale surface texturing of hydrophobic materials with average section spacing ranging from several to several hundred micrometers improved surface hydrophobicity. Different wetting states and contact angle hysteresis behavior of water droplets are possible with various hydrophobic surfaces depending on the material and surface shape. These include the following states: (1) Wenzel (a droplet pin on the surface in wet-contact mode), (2) Cassie-Baxter (CB) (3) the "lotus" state (special case of the cache-backster state), (4) the transition between Wenzel and cache-backster (occurring in most real samples).

An object to which a superhydrophobic surface is applied may exhibit properties such as waterproofing, antifouling and the like. Therefore, techniques for forming superhydrophobic surfaces can be usefully used in various industrial fields. However, the formation of artificial superhydrophobic surface is still technically inadequate.

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made to solve the above problems, and an object of the present invention is to provide a nanofiber- And a method for producing the same.

However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other matters not mentioned can be clearly understood by those skilled in the art from the following description.

According to an embodiment of the present invention, there is provided a method of preparing a porous anodic aluminum mold, comprising: preparing a porous anodic aluminum mold including a nanostructure; Disposing a polymer on the porous anodic aluminum mold; Forming the porous anodic aluminum mold and the polymer by hot pressing to form a nanostructured polymer structure on the polymer; And separating the polymer comprising the nanostructured polymeric structure from the porous anodic aluminum mold. The present invention also provides a method for preparing a nanostructured polymeric film.

According to one aspect, the step of preparing the porous anodized aluminum mold comprises: polishing aluminum; Performing primary anodization on the polished aluminum; Etching the primary anodized aluminum layer; Performing a secondary anodization on the etched anodized aluminum to form a nanostructure; And enlarging the pores of the nanostructure.

According to one aspect, the primary anodization and the secondary anodization are carried out in an electrolyte containing at least any one selected from the group consisting of perchloric acid, ethanol, sulfuric acid, chromic acid, phosphoric acid and oxalic acid, Followed by applying a voltage between 20 V and 300 V for 5 minutes to 72 hours while maintaining the temperature at 200 ° C.

According to one aspect, the step of etching the porous anodic aluminum may be performed in an etchant selected from the group consisting of chromic acid, phosphoric acid, hydrochloric acid, hydrofluoric acid, and sulfuric acid for 5 minutes ≪ / RTI > to 24 hours.

According to one aspect of the present invention, the method may further include the step of surface-treating the surface of the secondary anodized aluminum mold with a hydrophobic self-assembled monolayer or a polymer membrane after the step of enlarging the pores of the nanostructure.

According to one aspect of the present invention, the hydrophobic self-assembled monolayer or polymer membrane may be formed by using an octadecyltriethoxysilane (ODTS), a hexyltrialkoxysilane, a heptatrialkoxysilane, an octyltrialkoxysilane, Alkoxy = methoxy or ethoxy, including decyltrialkoxysilane, undecyltrialkoxysilane, dodecyltrialkoxysilane, octadecyltrialkoxysilane, and the like; Phenyl-based alkoxy silanes including phenyl trialkoxysilane; Fluorinated alkoxy silanes including heptadecafluorodecyl trialkoxysilane; But are not limited to, hexyltrichlorosilane, heptatrichlorosilane, octyltrichlorosilane, decyltrichlorosilane, undecyltrichlorosilane, dodecyltrichlorosilane, Alkylchlorosilanes including octadecyltrichlorosilane; Phenyl-based chlorosilanes containing phenyltrichlorosilane; And fluorine-based chlorosilanes including heptadecafluorododecyltrichlorosilane. In addition, the fluorine-based chlorosilane may include at least one selected from the group consisting of heptadecafluorodecyltrichlorosilane and heptadecafluorododecyltrichlorosilane.

According to one aspect, separating the polymer comprising the nanotextured polymeric structure from the porous anodic aluminum mold may include chemically etching the porous anodized aluminum mold to separate the nanotactured polymeric structure step; And separating the nanostructured polymeric structure from the porous anodized aluminum mold heated to a temperature (T) below the glass transition temperature (Tg) of the polymer; Or the like.

According to one aspect, the polymer is selected from the group consisting of polystyrene (PS), polyurethane (PU); Polyimide (PI); Polyacrylates including polymethylmethacrylate (PMMA); Polyesters including polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), and polyethylene terephthalate (PET); Polyethylene (PE), polyalkylene including polypropylene (PP); Vinyl polymers including polyvinyl chloride (PVC), polyvinylidene fluoride (PVdF); Polydimethylsiloxane (PDMS); Polyurethane; Acrylonitrile-butadiene-styrene copolymer (ABS); and acrylonitrile-butadiene-styrene copolymer (ABS).

According to one aspect, the nanostructured polymeric structure may be selected from the group consisting of nano-hair, nano-pillar, nano-spike, nano-fiber, nano- -rod, and nano-wire.

According to another embodiment of the present invention there is provided a nanostructured polymeric structure formed on a polymer, said nanostructured polymeric structure having a diameter in the range of 1 nm to 300 nm, a length in the range of 1 nm to 40 μm , And an aspect ratio ranging from 1 to 140. The present invention also provides a nanotextured ultra-hydrophobic polymeric film.

According to one aspect, the nanostructured polymeric structure may be selected from the group consisting of nano-hair, nano-pillar, nano-spike, nano-fiber, nano- -rod, and nano-wire.

According to an embodiment of the present invention, there is provided a nanotextured ultra-hydrophobic polymer film produced by a method of manufacturing a nanotextured ultra-hydrophobic polymer film according to an embodiment of the present invention.

According to an embodiment of the present invention, there is provided a method of manufacturing an anodized metal mold, comprising: preparing an anodized metal mold including a nanostructure; Disposing a polymer on the anodized metal mold; Forming an anodized metal mold and the polymer by hot pressing to form a nanostructured polymer structure on the polymer; And separating the polymer comprising the nanostructured polymeric structure from the anodized metal mold. The present invention also provides a method for preparing a nanostructured superhydrophobic polymeric film.

According to one aspect, the anodized metal mold may include at least one of an anodized aluminum mold, an anodized titanium mold, or an anodized magnesium mold.

According to the method of manufacturing a nanotextured hydrophobic polymer film according to an embodiment of the present invention, a method of easily and easily forming a biomimetic superhydrophobic surface on a polymer can be provided. The manufacturing method according to one embodiment of the present invention can easily and quickly produce a superhydrophobic polymer structure, and can also repetitively super-hydrophobic surfaces using an anodized circular aluminum mold. Therefore, It can be mass-produced in an area and can be economical.

The nanotextured hydrophobic polymer film according to an embodiment of the present invention can have a nanopattern structure over a large area, maintain super hydrophobic properties such as rose petals and lotus leaves, and excel in self-cleaning effect.

FIG. 1 is a flowchart illustrating a process of manufacturing a nanotextured ultra-hydrophobic polymeric film according to an embodiment of the present invention.
2 is a detailed flowchart of a preparation step of a porous anodic aluminum mold according to an embodiment of the present invention.
FIG. 3 is a schematic view of the aluminum sheet surface for each step according to the embodiment of the present invention ((a) before each manufacturing step and (be) after each manufacturing step), (b) electrolytic polishing, (c) , (d) etching, (e) secondary anodization and subsequent pore expansion, and (f) surface modification with ODTS.
Figure 4 shows two different methods of separating an anodized aluminum mold from (a) an anodized aluminum hot press and (b, c) polymer surfaces on a soft polystyrene film, according to an embodiment of the present invention, FIG.
5 is a SEM photograph of a secondary anodized aluminum surface comprising (a) a primary anodization and a subsequent etched aluminum surface and (b, c) a porous anodized aluminum layer according to an embodiment of the present invention, according to an embodiment of the present invention.
FIG. 6 is a graph showing changes in the depth and diameter of nano pores of anodic aluminum oxide prepared under the conditions of 0 ° C. and 195 V in 0.1 M phosphoric acid according to an embodiment of the present invention.
Figure 7 is a top and cross-sectional SEM image of polystyrene nanostructures on various nanotextured polystyrene films formed through (ad) chemistry and (ej) physically anodizing aluminum mold separation according to an embodiment of the present invention. (Fig. 7 (a) and Fig. 7 (b) show the nano pillar (AR = 7.5 - 8.5 (AR = 17-23 and 17-23, respectively) in FIGS. 7 (a) and 7 (f) 110-130)).
8 is an SEM image of a polystyrene nanofiller produced by chemical etching of an AAO mold for anodic oxidation in the separation of nanostructured polymeric structures according to an embodiment of the present invention ((a) top and (b) cross-section) .
FIG. 9 is a schematic view of an embodiment of the present invention comprising (a) a hexagonally (HEX) -oriented nanopore of anodized aluminum layer, a nanotextured polymeric structure (b) nanorod, and (c) The AFM image of the polystyrene film is shown.
10 is an SEM image of the surface of (a) anodic aluminum oxide and (b) polystyrene film separated after physically separating the nanostructured polymeric structure according to an embodiment of the present invention at room temperature.
11 shows the DSC heating curve of a polystyrene having a molecular weight of 100 kDa according to an embodiment of the present invention (heating rate of 10 ° C min ^-1 ).
Figure 12 is a digital photographic image showing the contact angle of water droplets (right) versus the different types of nanotextured polymeric structures according to an embodiment of the present invention and the change in contact angle of the nanostructures on the surface textured polystyrene film.
13 is a digital photographic image of water droplets on untreated polystyrene film according to an embodiment of the present invention.
FIG. 14 is a graph showing the relationship between (ac) chemical and (df) physically anodizing aluminum polycarbonate film surface polished with polycarbonate film using an anodized aluminum mold according to an embodiment of the present invention, ((Ae) is the nanopile and (f) the different terrains of the nanohair).
15 (a) shows a schematic diagram of an anodic oxidation configuration comprising a round tube type carbon cathode (cathode) and a high purity aluminum cylindrical anode (anode) according to an embodiment of the present invention. Fig. 15 (b) is a photographic image of the aluminum cylinder rod before and after the treatment, respectively. 15 (c) is an SEM micrograph of the anodic aluminum oxide layer on the anodized circular aluminum surface. Figure 15 (d) shows a schematic view of a single process surface texturing of a polystyrene film using aluminum cylinders (drums) comprising a heated porous anodized aluminum layer for nanotexturing. FIG. 15 (e) is an SEM image of a continuous roll-pressed polystyrene film using an aluminum cylinder containing a porous anodized aluminum layer heated to 180.degree.
Fig. 16 (a) shows a rosette leaf, Fig. 16 (b) shows a lotus leaf, and Fig. 16 (c) shows an aluminum cylinder containing a porous anodized aluminum layer heated to 180 캜 on a roll- Is a digital photographic image of water droplets.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear. In addition, terms used in this specification are terms used to appropriately express the preferred embodiments of the present invention, which may vary depending on the user, the intention of the operator, or the practice of the field to which the present invention belongs. Therefore, the definitions of these terms should be based on the contents throughout this specification. Like reference symbols in the drawings denote like elements.

Throughout the specification, when a member is located on another member, it includes not only when a member is in contact with another member but also when another member exists between the two members.

Throughout the specification, when an element is referred to as "comprising ", it means that it can include other elements as well, without excluding other elements unless specifically stated otherwise.

Throughout the specification, "superhydrophobicity" means the nature of a material in which a liquid, e.g., water droplets, can not significantly wet the surface of the material.

Throughout the specification, "Hydrophobicity" means the degree of repulsion of the surface to a liquid, e.g., water droplet.

Throughout the specification, the term "Contact angle" means the angle at which a liquid, e.g., a water droplet, faces the solid surface.

Throughout the specification, "monolithic" means an object or element of a single body of the same material.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the nanotextured ultra-hydrophobic polymer film of the present invention and a method for producing the same will be described in detail with reference to examples and drawings. However, the present invention is not limited to these embodiments and drawings.

According to an embodiment of the present invention, there is provided a method of manufacturing an anodized aluminum mold, comprising: preparing an anodized aluminum mold including a nanostructure; Disposing a polymer on the anodized aluminum mold; Forming an anodized aluminum mold and the polymer by hot pressing to form a nanostructured polymer structure on the polymer; And separating the polymer comprising the nanostructured polymeric structure from the anodized aluminum mold. The present invention also provides a method of preparing a nanostructured polymeric film.

FIG. 1 is a flowchart illustrating a process of manufacturing a nanotextured ultra-hydrophobic polymeric film according to an embodiment of the present invention. Referring to FIG. 1, a process for preparing a nanotextured ultra-hydrophobic polymeric film according to an embodiment of the present invention includes preparing an anodized aluminum mold 100, a polymer placement 200, a hot press 300, And a polymer separation step (400) comprising a nanotextured polymer structure.

According to one aspect, the anodizing aluminum mold preparation step 100 may be to prepare an anodized aluminum mold comprising nanostructures. Aluminum is very light, has a suitable strength, is not only inexpensive, but also can be used advantageously because it can clearly form a template for biomimetic hierarchical structure through various chemical etching.

According to one aspect, preparing (100) the anodized aluminum mold comprises: polishing aluminum; Performing primary anodization on the polished aluminum; Etching the primary anodized aluminum layer; Performing a secondary anodization on the etched anodized aluminum to form a nanostructure; And enlarging the pores of the nanostructure.

2 is a detailed flowchart of a preparation step of a porous anodic aluminum mold according to an embodiment of the present invention. Referring to FIG. 2, the preparation of the porous anodic aluminum mold according to an embodiment of the present invention includes an aluminum polishing step 110, a primary anodizing step 120, an etching step 130, Step 140, pore enlargement step 150, and surface treatment step 160.

According to one aspect, the aluminum polishing step 110 may be to polish the aluminum surface. The aluminum polishing may be carried out by at least one of electric polishing, mechanical polishing, chemical polishing and physical polishing, and preferably, performing electrolytic polishing. For example, in the case of electrolytic polishing, the surface roughness of aluminum can be reduced to 0.1 nm to 10 占 퐉 by applying a voltage of 10 V to 50 V for 30 seconds to 5 minutes.

According to one aspect, before the aluminum polishing step, the aluminum surface may be cleaned using at least one selected from the group consisting of acetone, alcohol, sodium hydroxide, and hydrochloric acid.

According to one aspect, the primary anodizing step 120 may be to perform primary anodization on the polished aluminum. The anodized aluminum layer may be formed on the aluminum surface by the primary anodization to form a nano dimple having a downward convex pattern for forming a nanostructure. The nanostructure may include a straight through hole (through hole pore).

According to one aspect, the primary anodization may be performed on all or a portion of the aluminum inner and outer surfaces, which may be performed on portions of the aluminum outer surface in the present invention.

According to one aspect, the primary anodization is carried out in an electrolyte containing at least any one selected from the group consisting of perchloric acid, ethanol, sulfuric acid, chromic acid, phosphoric acid and oxalic acid, while maintaining the temperature at -30 캜 to 200 캜 And applying a voltage between V and 300 V for 5 minutes to 72 hours.

According to one aspect, the etching step 130 may be to etch the primary anodized aluminum layer, e.g., a nano dimple. When the anodization layer formed by the primary anodization is removed to perform the secondary anodization step, it is possible to make the well-aligned intact ventilation holes grow.

According to one aspect of the present invention, the step of etching the anodic aluminum oxide includes a step of etching the anodic aluminum oxide in at least one of an etchant selected from the group consisting of chromic acid, phosphoric acid, hydrochloric acid, hydrofluoric acid and sulfuric acid, And may be performed for 24 hours. If the etching time is less than 5 minutes, the proper chemical arrangement of the surface of the anodized aluminum layer may not be sufficiently performed, and an undesired layer may be formed on the pores and nano structure at the time of the secondary anodization, Can not be removed, and if it exceeds 24 hours, the surface may become rather rough.

According to one aspect, the secondary anodization step 140 may be to perform a secondary anodization of the etched anodized aluminum to form a nanostructure. The nanostructure may be formed with a well-aligned straight pipe vent by the secondary anodization. The straight pipe ventilation hole may have a hexagonal column shape passing through the center. The interpolated spacing of the hexagonal pillars may be between 50 nm and 600 nm.

According to one aspect, the secondary anodization is carried out in an electrolyte containing at least any one selected from the group consisting of perchloric acid, ethanol, sulfuric acid, chromic acid, phosphoric acid and oxalic acid while maintaining the temperature at -30 to 200 ° C V to 300 V for 5 minutes to 72 hours. If the secondary anodization is performed for less than 5 minutes, a nanostructure having a sufficient height required for the super-hydrophobic property is not produced, and if it exceeds 72 hours, a fine crack may be generated on the surface.

According to one aspect, the secondary anodization may be carried out to form a surface of anodized aluminum formed with rose petals and lotus leaf-like porous nanostructures, thereby realizing a surface shape capable of controlling self-cleaning and adhesion properties .

According to one aspect, the secondary anodization time may be different from the primary anodization time. By controlling the secondary anodization time, it is possible to control the size of the nanostructure, for example, the size of the straight pipe.

According to one aspect, the pore expanding step 150 is a step of expanding the pores of the nanostructure while maintaining a temperature of 10 to 50 DEG C in at least one solution selected from the group consisting of chromic acid, phosphoric acid, hydrochloric acid, hydrofluoric acid and sulfuric acid It can be enlarging.

According to one aspect of the present invention, the pore enlargement is based on the fact that the formation of nano-structure of rose petals and lotus leaf-like is performed by equilibrium of preparation and dissolution of anodic aluminum oxide. In the case of dislocation, When the straight pipe vents of each columnar shape are immersed in the acidic solution, the pores of the pores are gradually widened. In this process, the thickness (height) of the straight pipe is not greatly changed. This phenomenon may be caused by the partial density difference of the anodic oxide layer. The diameter and the porosity of the pores can be controlled by proceeding with the pore expansion step to form a nanostructure having an intrinsic tube of a desired size.

According to one aspect, after the step of enlarging the pores of the nanostructures, a surface treatment step 160 may be further included.

According to one aspect, the surface treatment step 160 may be a surface treatment with a hydrophobic self-assembled monolayer on the surface of the secondary anodized aluminum mold.

According to one aspect of the present invention, the hydrophobic self-assembled monolayer or polymer membrane may be formed by using an octadecyltriethoxysilane (ODTS), a hexyltrialkoxysilane, a heptatrialkoxysilane, an octyltrialkoxysilane, Alkoxy = methoxy or ethoxy, including decyltrialkoxysilane, undecyltrialkoxysilane, dodecyltrialkoxysilane, octadecyltrialkoxysilane, and the like; Phenyl-based alkoxy silanes including phenyl trialkoxysilane; Fluorinated alkoxy silanes including heptadecafluorodecyl trialkoxysilane; But are not limited to, hexyltrichlorosilane, heptatrichlorosilane, octyltrichlorosilane, decyltrichlorosilane, undecyltrichlorosilane, dodecyltrichlorosilane, Alkylchlorosilanes including octadecyltrichlorosilane; Phenyl-based chlorosilanes containing phenyltrichlorosilane; And fluorine-based chlorosilanes including heptadecafluorododecyltrichlorosilane. In addition, the fluorine-based chlorosilane may include at least one selected from the group consisting of heptadecafluorodecyltrichlorosilane and heptadecafluorododecyltrichlorosilane.

According to one aspect of the present invention, when an anodized aluminum surface including a nanostructure formed by the two-step anodization process including the primary anodization and the secondary anodization is coated with the hydrophobic self-assembled monolayer or polymer membrane, The surface energy is reduced on the surface, and the contact angle with respect to water can be increased to be modified into a hydrophobic surface. The surface of the anodized aluminum may be given super-hydrophobicity and self-cleaning effect may be exhibited.

According to one aspect, the anodized aluminum mold may be in the form of a square, a square sheet, or a cylindrical rod shape. In the case of the sheet-like anodized aluminum mold, it can be pressed onto the polymer and can be stamped. In the case of the cylindrical rod-shaped anodized aluminum mold, it can be roll-pressed on the polymer.

According to one aspect of the present invention, it is possible to repeatedly form nanoparticles of nanoparticulate nanoparticles on a polymer by using the porous anodic aluminum molds prepared as described above, so that it is possible to mass produce a superhydrophobic polymer structure.

According to one aspect, the polymer placement step 200 may be to place the polymer on the anodized aluminum mold. The polymer can be easily placed on an object having various shapes due to flexibility and flexibility. The polymer may be economical because it is easy to handle and low in manufacturing cost.

According to one aspect of the present invention, when the polymer is disposed on the anodized aluminum mold, the temperature can be maintained at a temperature higher than the glass transition temperature (Tg) of the polymer.

According to one aspect, the polymer may be a thermoplastic polymer. Thermoplastic polymers cause plastic deformation when heated, but they are reversibly hardened by cooling. When the thermoplastic polymer is used for the transfer of the anodized aluminum mold, the polymer is softened by the hot press so that the structure such as the nano structure of the mold is easily transferred. When the polymer is cooled, the structure formed through the transfer can be well maintained do.

According to one aspect, the polymer is selected from the group consisting of polystyrene (PS), polyurethane (PU); Polyimide (PI); Polyacrylates including polymethylmethacrylate (PMMA); Polyesters including polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), and polyethylene terephthalate (PET); Polyethylene (PE), polyalkylene including polypropylene (PP); Vinyl polymers including polyvinyl chloride (PVC), polyvinylidene fluoride (PVdF); Polydimethylsiloxane (PDMS); Polyurethane; Acrylonitrile-butadiene-styrene copolymer (ABS); and acrylonitrile-butadiene-styrene copolymer (ABS).

According to one aspect, the thickness of the polymer may be from several micrometers to 1,000 micrometers. The thickness of the polymer may be greater than the depth of the nanostructures formed in the anodized aluminum mold and may form nanostructured polymer structures only in the upper region of the polymer.

According to one aspect, the hot pressing step 300 may be to hot-press the anodized aluminum mold and the polymer to form a nanostructured polymeric structure on the polymer.

According to one aspect of the present invention, there is provided a method of fabricating an anodized aluminum sheet, comprising the steps of: applying a predetermined pressure to upper and lower support layers through a polymer disposed on the anodized aluminum mold between upper and lower support substrate substrates, So as to fill the space between them.

According to one aspect, the hot press may be carried out in a temperature range of 40 ° C to 250 ° C and a pressure range of 50 N / m to 500 kN / m.

According to one aspect, it may be to form a nanotextured polymeric structure having a diameter in the range of 10 nm to 300 nm, a length in the range of 10 nm to 40 m, and an aspect ratio in the range of 1 to 140 in the upper region of the polymer.

According to one aspect, a polymer separation step (400) comprising a nanotextured polymer structure may be performed by separating the polymer comprising the nanotextured polymer structure from the anodized aluminum mold.

According to one aspect, separating the polymer comprising the nanostructured polymeric structure from the anodized aluminum mold comprises at least one of a chemical separation step (not shown) and a physical separation step (not shown) Lt; / RTI >

According to one aspect, the chemical separation step may be to chemically etch the anodized aluminum mold using chemical wet etching to separate the nanostructured polymeric structure.

According to one aspect, the physical separation step comprises using physical dry separation, wherein the nanotexturing is performed from the anodized aluminum mold heated to a temperature ( T ) below the glass transition temperature (Tg) of the polymer, To separate the resulting polymeric structures. The nano-textured polymer structure may have a different structure depending on the temperature.

According to one aspect, the nanostructured polymeric structure may be selected from the group consisting of nano-hair, nano-pillar, nano-spike, nano-fiber, nano- -rod, and nano-wire.

According to one aspect, the nanostructured polymeric structure can be nanotextured into a nanofiller shape by the chemical separation, and may be nanotextured into a shape such as a nano spike or a nano-hair by the physical separation have.

According to the method of manufacturing a nanotextured hydrophobic polymer film according to an embodiment of the present invention, a method of easily and easily forming a biomimetic superhydrophobic surface on a polymer can be provided. By using the manufacturing method of the present invention, it is possible to easily and quickly produce the superhydrophobic polymer structure, and the superhydrophobic surface can be repetitively repeated using the anodized aluminum mold, so that the super-hydrophobic polymer structure can be mass- It can be economical.

According to another embodiment of the present invention, there is provided a nanostructured polymeric structure formed on a polymer, the nanostructured polymeric structure having a diameter in the range of 10 nm to 300 nm, a length in the range of 10 nm to 40 μm , And an aspect ratio ranging from 1 to 140. The present invention also provides a nanotextured ultra-hydrophobic polymeric film.

According to one aspect, the nanostructured polymeric structure may be selected from the group consisting of nano-hair, nano-pillar, nano-spike, nano-fiber, nano- -rod, and nano-wire. Depending on the shape of the nanostructured polymeric structure, the water contact angle may be different.

According to one aspect of the present invention, the nanotextured ultra-hydrophobic polymer film may be manufactured by the method of manufacturing the nanotextured ultra-hydrophobic polymer film according to an embodiment of the present invention.

According to one aspect, the nanotextured polymer film has a water contact angle of 100 DEG or more, preferably 120 DEG or more, more preferably 130 DEG or more, still more preferably 140 DEG or more, still more preferably , More preferably at least 150 °, and even more preferably at least 160 °, which may exhibit superhydrophobic properties.

According to one aspect, the nanocontacted polymeric structure may have a different water contact angle depending on the aspect ratio, and the water contact angle may also increase with increasing aspect ratio. For example, when the aspect ratio of the nanotextured polymer structure is 2 to 100, the contact angle is 100 to 150, and when the aspect ratio of the nanotextured polymer structure is 100 to 140, the contact angle is 150 to 165 Lt; / RTI >

According to one aspect, the anodized metal mold may include at least one of an anodized aluminum mold, an anodized titanium mold, or an anodized magnesium mold.

The nanotextured hydrophobic polymer film according to an embodiment of the present invention can have a nanopattern structure over a large area, maintains super hydrophobic properties such as rose petals and lotus leaves, and has excellent self-cleaning effect. The nano-textured super-hydrophobic polymer film can be applied to any field where super-hydrophobicity is required. For example, it can be used variously when it is intended to prevent loss caused by water, or to prevent or prevent pollution. For example, waterproofing, antifouling, anti-freezing, anti-fogging, self-cleaning and the like.

Hereinafter, the present invention will be described more specifically with reference to Examples, but the technical scope of the present invention is not limited to these Examples.

[ Example ]

The water repellency of the polymer film surface can be easily adjusted by hot pressing a softened polystyrene (PS) film into a monolithic porous anodized aluminum oxide (AAO) mold. High density nanopile and nano hair on the polystyrene film surface were produced by physical or chemical separation of the anodized aluminum mold from the surface-pressed polystyrene film. The resulting nanostructures on polystyrene showed various aspect ratios (AR) of 2 to 130, depending on the viscoelastic response of the polymer chains during the aluminum oxide hot press and subsequent separation. The contact angle values for water droplets on nano-textured polystyrene films varied significantly from 91 ° to 160 ° with increasing aspect ratio. Using a hot press and physical exfoliation of a porous aluminum oxide-covered aluminum columnar bar, one-pot large area nanotextured polystyrene films with superhydrophobic properties similar to rose petals and lotus leaves were prepared . The following shows the specific manufacturing process and characteristics of a large-area nanotextured polystyrene film.

≪ Substance, polymer film and anodized aluminum production >

All acids and solvents were purchased from Aldrich and used without further purification. Polystyrene (PS, molecular weight, Mw = 100 kDa, Aldrich) was compression molded and the film thickness was between 250 μm and 300 μm. High purity aluminum sheets (99.999% Goodfellow, 3 x 5 cm ² and 1 mm thick) and cylinder bars were used for aluminum anodization.

FIG. 3 is a schematic view of the surface of an aluminum sheet in each step according to an embodiment of the present invention ((a) before each manufacturing step and (be) after each manufacturing step), (b) electrolytic polishing, (c) , (d) etching, (e) secondary anodization and subsequent pore expansion, and (f) surface modification with ODTS.

Anodized aluminum nano-molds for the surface texturing process of polymer films were prepared by the following steps: (1) aluminum electrolytic polishing, (2) primary aluminum anodization, (3) anodic aluminum etching, (4) Car aluminum anodization, and (5) pore enlargement (widening). The resulting aluminum surface after each step is schematically shown in Fig. First, the high purity aluminum sheet was electrochemically polished at a constant current in a 500 ml electrolyte mixture containing perchloric acid and ethanol (1: 4 by volume ratio) at 7 DEG C (FIG. A well-defined porous anodized aluminum layer was produced on an electrolytically polished aluminum sheet by two stages of anodic oxidation and subsequent pore expansion (FIG. 3 (c) - FIG. 3 (e)). The primary anodization of aluminum was carried out in an aqueous solution of 0.1 M phosphoric acid (85% H ₃ PO ₄ , Aldrich) at 195 V and 0 ° C for 24 hours. Then, the positive electrode aluminum oxide layer is produced as a result is, of 1.8% by weight of chromic acid (H ₂ CrO _4), and 6% by weight of phosphoric acid (H ₃ PO ₄₎ containing an aqueous etchant anodized aluminum overnight at 60 ℃ in that Lt; / RTI > The secondary anodization was carried out under the same conditions as the previous anodization except that the time was different. The nano pores formed in the anodized aluminum layer were then immersed in 0.1 M phosphoric acid (H ₃ PO ₄ ) solution at 30 ° C and expanded to about 200 nm. Finally, additional surface treatment of the porous anodized aluminum layer was performed to induce proper wettability between the anodized aluminum surface and the polymer chains. In particular, the anodized aluminum template was UV-O ₃ -treated and silanized inside the chamber by vapor phase octadecyltrichlorosilane (ODTS, 97%, Aldrich) at 150 ° C for 1 hour. The treated sample was rinsed several times with excess toluene to induce the ODTS monolayer (the yellow-coated layer in Figure 3f) bound on the anodized surface.

<Surface Textured  Preparation of polymer film>

4 is a schematic view illustrating a process of manufacturing a nanostructured polystyrene film according to an embodiment of the present invention. FIG. 4 shows a surface texturing method of a polystyrene film that may include various nanostructures. First, the compression-molded polystyrene film was heated in a furnace filled with nitrogen (N2) controlled through a pressure gauge at 140 DEG C and 180 DEG C (the glass transition temperature of the polymer used in the examples of the present invention temperature (Tg)) and placed on an ODTS-treated anodic aluminum template (Fig. 4 (a)). The degree of polystyrene filling of the anodized aluminum nano pores was varied using various pressure conditions (FIG. 4 (b)). Finally, the porous anodic aluminum template laminated to the polymer film was removed by a conventional chemical etching (Fig. 4 (c)) or by physically separating the anodized aluminum mold (Fig. 4 (d)) . The polystyrene film was removed from the anodized aluminum template at a constant rate of 5 mm s &lt; ^{-1 &} gt ;. When the film was still able to deform at a temperature (T) below the glass transition temperature (Tg), it was below the glass transition temperature (Tg) of the polymer.

Figure 4 shows two different methods of separating an anodized aluminum mold from (a) an anodized aluminum hot press and (b, c) polymer surfaces on a soft polystyrene film, according to an embodiment of the present invention, FIG. In Figure 4 (a), the molten polystyrene phase begins to penetrate into the anodized aluminum pores and then fills the pores, either partially or wholly, depending on the temperature. Figure 4 (b) shows the polystyrene nanopillar formed on the textured film surface after chemically etching the anodized aluminum mold. Referring to Figure 4 (d), during dry separation, each polystyrene nano-domain is deformed and the surface of the film comprising the nanospikes or nanohair is textured.

<Characteristics>

The morphology of the prepared anodized aluminum layer nanotextured polymer films was observed using a scanning electron microscope (SEM, JSM-7610F, JEOL) and an atomic force microscope (AFM, Multimode 8, Bruker). The contact angle values for water droplets on the surface textured polymer film were measured using an optical device including Nikon D7000. Each test was repeated 10 times and the contact angle values were averaged.

<Results and Discussion>

Various nanopillar and nano hair structures on polymer films show that they can be efficiently fabricated from porous anodic aluminum templates. Highly ordered anodic aluminum nano-pores from sheet of aluminum were developed using two-stage aluminum anodization in 0.1 M aqueous phosphoric acid (H ₃ PO ₄ ) solution at 0 ° C and 195 V. 5 is an SEM micrograph of a secondary anodized aluminum surface comprising (a) a primary anodization and subsequent etched aluminum surface and (b, c) a porous anodic aluminum layer according to an embodiment of the present invention. Secondary aluminum anodization was performed on the etched aluminum surface after removing the primary anodized aluminum layer (Fig. 5 (a)) with hexagonal (HEX) -filled nano dimples having an average spacing of 500 nm . Figures 5 (b) and 5 (c) show top and cross-sectional SEM shapes of the porous anodized aluminum layer formed on the anodized and etched aluminum surface. The initial porosity of the secondary anodized aluminum layer was steadily expanded in 0.1 M phosphoric acid (H ₃ PO ₄ ) solution (at 30 ° C) until the average diameter (Dave) was 200 nm; This is due to the time-dependent pore change in the anodized aluminum (Figure 6). The anodized aluminum template has a diameter (Dave) of 200 nm and a height (Have) of 1.6 mu m.

To introduce the various nanostructures onto the polymer film, a polystyrene film about 300 탆 thick was placed on the anodized aluminum mold and both sides of the polystyrene / anodized aluminum sample were interposed between the supporting substrates. Thereafter, a constant pressure was applied to the sample using a spring clamp (spring constant of 200 N / m), and then the sample was heated inside the tube furnace. After thermo-pressing under various environmental temperature and pressure conditions, a thermally soft polystyrene film in direct contact with an anodized aluminum layer at a depth of 1.6 탆 has a porous nanorodular space, as shown in Figure 2 (b) ). &Lt; / RTI &gt; Finally, the polystyrene film laminated on the anodized aluminum layer was chemically or physically separated (Fig. 4 (c) and Fig. 4 (d)).

Figures 7 (a) and 7 (b) show that general nanotextured polystyrene films produced by chemical separation of anodized aluminum / aluminum molds. The aluminum and anodized aluminum layers were dissolved in 5% sodium hydroxide (NaOH) and 0.1 M water-soluble phosphoric acid (H ₃ PO ₄ ) (at 30 ° C), respectively. Less than a few microns of polystyrene and 1.6 microns long on a treated polystyrene film having an interplanar spacing (Delta) of about 500 nm can be formed without any clumping of the nanostructures or bundles between the polymer pillars, Vertically arranged. The cluster rapidly aggravated the back surface area of the nanotextured film, which degraded the ability of the textured surface to repel water. This cluster phenomenon was more severe for the higher aspect ratio (AR) values of the vertical polymer domains. The behavior of aggregation between nanodomains with critical length (L _c ) was estimated using Equation (1) below:

<Formula 1>

In the above Equation 1, D _poly , E, and W _ad are the average cross-sectional diameter of the cylindrical polymer domain, the domain coefficient, and the adhesive energy per contact area between adjacent pillars, respectively.

<Equation 1>, the system the same dimension polystyrene nano-pillars arranged in the (Δ = 500 nm and Dpoly = 200 nm) based on ^- the maximum critical length for the (E = 3.0 GPa and ^{Dpoly = 80 mJm 2) (L} c ) Value was about 2.7 탆. This explains why thin hair with a very high aspect ratio (AR) is difficult to handle through chemical etching procedures without any aggregation or shrinkage. High aspect ratio (AR) pillars (greater than 10) on treated polystyrene films tend to cluster and disintegrate during the wet mold separation process (Figure 8). Clustering behavior can occur regardless of the value of AR due to imperfect spacing between the porous anodized aluminum layers used for molding or imprinting.

Figure 9 shows additional AFM topography and phase images of a nanopillar on a textured polystyrene film by filling a partially and fully anodized aluminum mold according to an embodiment of the present invention (AFM topography (top) and phase (A) a hexagonal (HEX) -filled anodized aluminum layer, (b) a nanorod, and (c) a nanopillar on a polystyrene textured film).

The height of the 400 nm to 450 nm nanopillar (aspect ratio 2.0-2.25) clearly shows the highest convex structure in the N ₂ - atmosphere, indicating that the polystyrene melt phase was partially filled with anodic oxide aluminum pores with a depth of 1.6 μm at 160 ° C. 9 (a) and 9 (b)). In addition, the polymer nanopillars were fabricated through the complete filling of ODTS-treated anodized aluminum with molten polystyrene above 180 ° C following a subsequent etching of the aluminum / anodized aluminum layer. Each pillar represents the highest indentation point with improved interfacial adhesion between polystyrene and ODTS-treated anodized aluminum surfaces (Figure 9 (d)). Due to unexpected interlocking points, physical polystyrene-mold separation is difficult to keep the polystyrene domains at room temperature without cutting (FIG. 10); Most of the polystyrene domains are cut during the pulling process leading to irregular size nano-domains on the textured film.

Because of the advantage of proper heat treatment of the anodized aluminum / aluminum mold, the polystyrene nano domain embedded in the warm anodized aluminum mold during physical separation can be tuned to have various forms such as spikes or hair depending on the temperature (T) -independent viscosity of the polystyrene . Polystyrene is generally fragile in a glass state below the glass transition temperature (Tg). For the 100 kDa polystyrene used in the present invention, the glass transition temperature (Tg) was about 105 ° C (FIG. 11). However, it can be seen that it is possible to produce at a process temperature of 60 DEG C below the glass transition temperature (Tg) and to induce pseudo-plastic deformation. Additionally, it is believed that the glass transition temperature (Tg) inside the anodized aluminum may be similar to the glass transition temperature of the bulk polystyrene domain, since the domain radius is about 100 nm; A thickness-dependent reduction of the glass transition temperature (Tg) was not reported in the polystyrene film. It is noted that the method of physical exfoliation of some polystyrene films laminated from an anodized aluminum mold was carried out in a warm anodized aluminum mold. At 40 ° C <T <60 ° C, the polystyrene nano-domains can be deformed under uniaxial stress at a strain rate of about 5 mm s ^-1 . In this case, the nanodomains are deformed, elongate and begin to break in the necked (or modified) region, creating a 1.0 micron to 1.2 micron height polystyrene spike on the textured polystyrene film (E) and (f) of FIG. 7). At temperatures above T (T) (still lower than the glass transition temperature (Tg) of bulk polystyrene), the nano-domains of the polystyrene inside the anodized aluminum layer can be sufficiently modified during the physical removal process. For example, the polystyrene domains resulted in hairy fibrils of 75 &lt; 0 &gt; C and lengths of up to 7 [mu] m at 80 [deg.] C (FIG. 7 (h) and FIG. 7 (j)). The diameter (Dpoly) value of the polystyrene nano hair was thinned to 15 to 20 nm. The aspect ratio value was calculated based on the ratio of height (L) to diameter (Dpoly) at half maximum height for this nanostructure. Figure 7 shows a top and cross-sectional SEM topography of a polystyrene nanostructure on a textured polystyrene film with physically anodized aluminum mold separation, showing (ad) chemical and (ej) different topographic shapes according to an embodiment of the present invention. . Figures 7 (a) and 7 (b) show the nanopillar (AR = 2.0-2.25), Figure 7 (c) and Figure 7 (AR = 17-23 and 110-130, respectively) of the spike (AR = 12-13), FIG. 5 (g) and FIG. 5 (j) .

Figure 12 is a digital photographic image showing the contact angle of water droplets (right) for different types of nanotactured polymeric structures and the change in contact angle of nanostructures on surface textured polystyrene films according to an embodiment of the present invention 12 (a) shows a pillar (AR = 2.0-2.25), Fig. 12 (b) shows a pillar (AR = 7.5-8.5) (D) and (e) show the hair (AR = 17 - 23 and 110 - 130, respectively) and Fig. 12 (f) show the θwater variation dependent on the corresponding aspect ratio. The water repellent surface textured polystyrene film having different aspect ratio nanostructures was examined by measuring the contact angle of the water droplet, and the result is shown in FIG. 12 (f). As shown in Figures 12 (a) to 12 (e), polystyrene pillar, spikes and hair were formed with different contact angles. The water contact angle obtained a maximum value of 160 DEG on the very long polystyrene hair on the supporting film (Fig. 12 (e)). 13 is a digital photographic image of water droplets on untreated polystyrene film according to an embodiment of the present invention. The water contact angle of 160 ° can be compared to 91 ° obtained on the flat polystyrene surface of FIG. The highest contact angle of the water droplets on the hair structured polystyrene film showed about 80% increase in the contact angle on the flat surface.

FIG. 14 is a graph showing the relationship between (ac) chemical and (df) physically anodizing aluminum polycarbonate film surface polished with polycarbonate film using an anodized aluminum mold according to an embodiment of the present invention, Image. Fig. 14 (a-e) shows the type of the different topography of the nanofiller and Fig. 14 (f) nanohair. Referring to FIG. 14, the most substantial point of the present invention is that the superfine hydrophobic polymer film can be easily reproduced using a monolithic porous anodic aluminum mold using the controlled pressure, and then the chemical / physical separation I can do it.

Figure 15 (a) shows a schematic diagram of an anodic oxidation configuration comprising a round tubular carbon cathode (cathode) and a high purity aluminum cylindrical bar anode (anode). Fig. 15 (b) is a photographic image of each aluminum cylinder bar before and after the treatment. 15 (c) is an SEM micrograph of the anodic aluminum oxide layer on the anodized circular aluminum surface. Figure 15 (d) shows a schematic of single-process surface texturing of a polystyrene film using aluminum cylinders (drums) comprising a heated porous anodization layer for nanotexturing. Figure 15 (e) is an SEM image of a continuous roll-pressed polystyrene film using an aluminum cylinder (drum) comprising a porous anodized aluminum layer heated to 180 ° C. To extend the surface nano-texturing process for large-area polymer films, an anodic oxidation configuration having a round tube-type carbon cathode and a highly refined aluminum cylindrical bar anode was designed (see Fig. 15 (a)). The same anodizing step was carried out with an aluminum crown bar having a diameter of 3 cm and a height of 5 cm. Fig. 15 (b) shows the shape of the aluminum cylindrical bar after each treatment. After the pore enlargement, the anodized aluminum layer on the circular aluminum shows a hexagonal-filled nanopore having a diameter (Dave) of 500 nm and a height (H) of 1.5 占 퐉 (FIG. 15 (c)). The polystyrene film was continuously roll-pressed and separated using a porous anodized aluminum / aluminum crown rod heated at 180 占 폚 as shown in Figure 15 (d); Texturing was very similar to hot pressing and physical separation of anodized aluminum mold plates (Fig. 4 (d)). The resulting textured polystyrene film exhibited a very large nano hair structure. Resulting from the polystyrene domain peeling inside the anodized aluminum pores (Fig. 15 (e)). As a result, the one - step anodic hot rolled aluminum roll press provided a large - scale, short - time process for hydrophobic polymer film texturing.

The water contact angle values on a roll-pressed polystyrene film were compared with representative water-contact angle values of hyperspeed rose leaves and lotus leaves. The water-sprayed droplets were sprayed on three surfaces. Figure 16 (a) is a digital photograph of water droplets on a roll-pressed polystyrene film with an aluminum cylinder containing rose leaf (b) a lotus leaf and (c) a porous anodized aluminum layer heated to 180 & to be. As shown in Fig. 16, the roll-pressed polystyrene film exhibited similar water repellency properties, such as rose leaves and lotus leaves, indicating a supersonic water characteristic with &amp;thetas; water ranging from 145 DEG to 160 DEG. The superhydrophobic non-stick behavior on the nano-hair textured polystyrene film is evident in Fig. Figure 16 shows the contact geometry on a rose petal, lotus leaf polystyrene film with nanotextured surface morphology of 10 [mu] l to 20 [mu] l water droplets injected from a syringe.

<Conclusion>

An easy method for producing nano hair on the polymer film surface has been developed. The formation of this structure was controlled using an anodized aluminum template using a multilayer porous structure and a nano-producing process. Porous anodized aluminum treated polystyrene (PS) films exhibited various nanoturified surfaces including vertically standing domains (similar spacing of 500 nm). These domains were changed from nanorods to nanohair, which exhibit various aspect ratios (AR) values ranging from 1 to tens, depending on the viscoelasticity of the polystyrene film processed during hot pressing and separation of the porous anodized aluminum mold. The water contact angle value of the nanotextured polystyrene film changed from 91 ° to 160 ° as the aspect ratio increased. Large-area large-area nanotextured polystyrene films exhibiting submergence properties similar to rose leaves and lotus leaves by hot pressing and physical exfoliation using a porous anodic aluminum covered aluminum cylindrical rod. The hot porous anodic aluminum roll press method provides a multipurpose path that can be applied to any object having a variety of shapes with a large area and a super hydrophobic surface since the manufacturing process is simple to manufacture a super hydrophobic polymer film.

(1) a hot press using a single-dimensional porous anodic aluminum mold having highly-aligned nanopores (Dave = 200 nm and Lave = 1.6 m), and (2) By chemically or physically separating the nanofillers and nanofilaments of the nanofillers and nanofilms, demonstrating the ease and efficiency of various nanofiltration of nanofiller and nanofiber polymer films. Porous anodized aluminum-treated polystyrene (PS) films are used in a variety of nanostructures including vertically standing domains (similar spacing of 500 nm) from nano pillar to nano hair, yielding wide aspect ratio values in the range of 2 to 120 - textured surface. The water contact angle values of the nanotextured polystyrene films varied greatly from 91 ° to 160 ° with increasing aspect ratio. Port large-area nanotextured polystyrene films exhibiting ultra-low water characteristics similar to rose petals and lotus leaves by hot press and physical exfoliation using porous anodized aluminum-covered aluminum crown bars .

While the invention has been shown and described with reference to certain preferred embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. This is possible. Therefore, the scope of the present invention should not be limited by the described embodiments, but should be determined by the equivalents of the appended claims, as well as the appended claims.

Claims (14)

Preparing a porous anodic aluminum mold comprising a nanostructure;
Disposing a polymer on the porous anodic aluminum mold;
Forming the porous anodic aluminum mold and the polymer by hot pressing the polymer at a temperature ranging from 40 ° C to 250 ° C and a pressure range of 50 N / m to 500 kN / m to form a nanotetrained polymer structure on the polymer; And
Separating the polymer comprising the nanostructured polymeric structure from the porous anodic aluminum mold;
Lt; / RTI &gt;
The step of preparing the porous anodic aluminum mold comprises:
Polishing aluminum;
Performing primary anodization on the polished aluminum;
Etching the primary anodized aluminum layer;
Performing secondary anodization on the etched primary anodized aluminum to form a nanostructure; And
Expanding the pores of the nanostructure while maintaining a temperature of 10 ° C to 50 ° C in at least one solution selected from the group consisting of chromic acid, phosphoric acid, hydrochloric acid, hydrofluoric acid, and sulfuric acid
/ RTI &gt;
The step of performing the primary anodization includes
The polished aluminum surface is anodized to form the primary anodized aluminum layer having a nano dimple having a downward convex pattern,
The step of forming the nanostructure
And performing the secondary anodization to form a nanostructure having a hexagonal columnar shape penetrating through the center, wherein an interpore interval of the hexagonal column is 50 nm to 600 nm,
The step of forming a nanostructured polymeric structure on the polymer comprises:
Forming a nanotactured polymeric structure having a diameter in the range of 10 nm to 300 nm, a length in the range of 10 nm to 40 m, and an aspect ratio in the range of 1 to 140 in the upper region of the polymer,
Wherein the nanotextured polymer structure has a different water contact angle depending on the aspect ratio of the nanotextured polymer structure. delete The method according to claim 1,
Wherein the primary anodization and the secondary anodization are carried out in the following order:
In an electrolyte containing at least one selected from the group consisting of perchloric acid, ethanol, sulfuric acid, chromic acid, phosphoric acid, and oxalic acid, a voltage of 20 V to 300 V is applied for 5 minutes to 72 For a period of time equal to or longer than the time required for the preparation of the nanotextured superhydrophobic polymeric film. The method according to claim 1,
The step of etching the porous anodized aluminum comprises:
Is carried out in an etchant selected from the group consisting of chromic acid, phosphoric acid, hydrochloric acid, hydrofluoric acid and sulfuric acid for 5 minutes to 24 hours while maintaining the temperature at 20 to 100 ° C. &Lt; / RTI &gt; The method according to claim 1,
After the step of enlarging the pores of the nanostructure,
Surface-treating the surface of the secondary anodized aluminum mold with a hydrophobic self-assembled monolayer or a hydrophobic self-assembled polymer membrane;
Wherein the nanofibrous polymeric film further comprises at least one hydrophobic polymer. 6. The method of claim 5,
The hydrophobic self-assembled monolayer or the hydrophobic self-assembled polymer membrane may be formed of a material selected from the group consisting of octadecyltriethoxysilane (ODTS), hexyltrialkoxysilane, heptatrialkoxysilane, octyltrialkoxysilane, Alkylalkoxysilanes including decyltrialkoxysilane, undecyltrialkoxysilane, dodecyltrialkoxysilane, octadecyltrialkoxysilane, and the like; Phenyl-based alkoxy silanes including phenyl trialkoxysilane; Fluorinated alkoxy silanes including heptadecafluorodecyl trialkoxysilane; But are not limited to, hexyltrichlorosilane, heptatrichlorosilane, octyltrichlorosilane, decyltrichlorosilane, undecyltrichlorosilane, dodecyltrichlorosilane, Alkylchlorosilanes including octadecyltrichlorosilane; Phenyl-based chlorosilanes containing phenyltrichlorosilane; And fluorine-based chlorosilanes including heptadecafluorododecyltrichlorosilane. 2. The method according to claim 1, wherein the fluorine-based chlorosilane is at least one selected from the group consisting of heptadecafluorodecyltrichlorosilane and heptadecafluorododecyltrichlorosilane. The method according to claim 1,
Separating the polymer comprising the nanostructured polymeric structure from the porous anodic aluminum mold,
Chemically etching the porous anodic aluminum mold to separate the nanostructured polymeric structure; And
Separating the nanostructured polymeric structure from the porous anodized aluminum mold heated to a temperature (T) of from 40 ° C to a glass transition temperature (Tg) of the polymer;
&Lt; / RTI &gt;
(Process for the preparation of nanotextured superhydrophobic polymeric film). The method according to claim 1,
The polymer may be selected from the group consisting of polystyrene (PS), polyurethane (PU); Polyimide (PI); Polyacrylates including polymethylmethacrylate (PMMA); Polyesters including polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), and polyethylene terephthalate (PET); Polyethylene (PE), polyalkylene including polypropylene (PP); Vinyl polymers including polyvinyl chloride (PVC), polyvinylidene fluoride (PVdF); Polydimethylsiloxane (PDMS); Polyurethane; Acrylonitrile-acrylonitrile-butadiene-styrene copolymer (ABS). 2. The method of claim 1, The method according to claim 1,
The nanotextured polymeric structure may be selected from the group consisting of nano-hair, nano-pillar, nano-spike, nano-fiber, nano- Wherein the nanofibers comprise at least one selected from the group consisting of nano-wires. delete delete delete delete delete

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