WO2014123376A1 - Structure ultra-hydrofuge et oléofuge et procédé de fabrication de celle-ci - Google Patents

Structure ultra-hydrofuge et oléofuge et procédé de fabrication de celle-ci Download PDF

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Publication number
WO2014123376A1
WO2014123376A1 PCT/KR2014/001036 KR2014001036W WO2014123376A1 WO 2014123376 A1 WO2014123376 A1 WO 2014123376A1 KR 2014001036 W KR2014001036 W KR 2014001036W WO 2014123376 A1 WO2014123376 A1 WO 2014123376A1
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Prior art keywords
water
super
oil repellent
roughening
oil
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English (en)
Korean (ko)
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임시형
바스왈서밋
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Kookmin University
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Kookmin University
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/20—Acidic compositions for etching aluminium or alloys thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/16—Pretreatment, e.g. desmutting

Definitions

  • the present invention relates to a super water / oil repellent structure and a method of manufacturing the same, and more particularly to a super water repellent / super water repellent property, even with a curved surface or a large structure without using a special apparatus.
  • the present invention relates to a super water / oil repellent structure capable of imparting oil repellent properties and a method of manufacturing the same.
  • water repellency and oil repellency refer to properties that are hard to get wet with water and oil, respectively, and super water repellency / super oil repellency means that the contact angle of water in contact with the surface of a solid in the field is 150 ° or more and the contact angle to oil is 150 Generally defined as the case above °.
  • Superhydrophobicity and superoleophobicity are the physical properties of the surface of the object that are extremely wet with water and oil, respectively.
  • the leaves of plants, the wings of insects, or the wings of birds are characterized by preventing any external contaminants from being removed or contaminated from the outset without special removal. This is because the leaves of plants, the wings of insects, and the wings of birds are superhydrophobic.
  • Wetability is the major surface property of solid materials, which is largely governed by both chemical composition and geometric micro / nano structure. Wet surfaces have attracted much attention due to their potential applications in various fields such as oil-water separation, antireflection, bioadhesion prevention, adhesion prevention, contamination prevention, self cleaning and fluid turbulence suppression.
  • the first technical problem to be achieved by the present invention is to provide a super water / water repellent structure having excellent super water / oil repellent properties by showing a very large contact angle with respect to the aqueous solution and the oil-based solution.
  • the second technical problem to be achieved by the present invention is to manufacture a super water / oil repellent structure that can easily give super water / oil repellent properties without requiring special manufacturing equipment even for a large or curved structure. To provide a way.
  • a third object of the present invention is to provide an electronic device or a mechanical device including a structure having super water / oil repellent properties.
  • the roughening (roughening) primary structure formed on the surface of the metal substrate; Nano-pores formed in the roughening primary structure; And a water / oil repellent layer formed on the surface of the roughening primary structure.
  • the nanopores may have a diameter of about 1 nm to about 300 nm.
  • the diameter of the nano pores may be about 10 nm to about 50 nm.
  • the metal substrate may be an aluminum (Al) substrate.
  • the roughening primary structure the same or different sidewalls and flat surfaces may be continuous.
  • the horizontal length of the flat surface may be about 500 nm to about 5 ⁇ m.
  • the nano-pores may be formed in a direction substantially perpendicular to the side wall and the flat surface of the roughening primary structure, respectively.
  • the water / oil repellent layer may include fluorine (F).
  • the water / oil repellent layer may be a layer of a fluorine-containing silane compound or a fluorine-containing thiol compound.
  • the water / oil repellent layer may not be substantially formed inside the nano-pores.
  • etching the metal substrate using an acid in order to form a roughened primary structure on a metal substrate, etching the metal substrate using an acid; Anodizing the metal substrate on which the roughening primary structure is formed to form nanopores in the roughening primary structure; And providing a water / oil repellent layer on the surface of the roughened primary structure.
  • the anodic oxidation may be performed for about 3 minutes to about 25 minutes.
  • the etching may be performed by wet etching.
  • the etching may be performed in a hydrochloric acid solution.
  • the metal substrate may be aluminum (Al).
  • the method of manufacturing the super water / oil repellent structure may further include drying the metal substrate at a temperature of about 50 ° C. to about 200 ° C. between the etching and the anodizing.
  • an electronic device or a transportation device including the super water / oil repellent structure may be used in automobile / aircraft / railway / ship interior / exterior, automobile / aircraft / railway / ship or home / business / industrial refrigeration and air conditioning system (air conditioner and heat pump), television, mobile phone, computer system, portable It may be a computer, a monitor, a telephone, a printer, a keyboard, a mouse, a pump, a pipe for transporting fluid, a pipe for transporting powder, a tank for storing fluid for transport, a lighting device, a backlight unit, and the like, but is not limited thereto.
  • the super water / oil repellent structure of the present invention exhibits an extremely large contact angle with respect to the aqueous solution and the oil-based solution, thereby having an excellent super water / oil repellent property.
  • the method of manufacturing a super water / oil repellent structure of the present invention can be easily manufactured even a structure having a large or curved surface without requiring special manufacturing equipment.
  • FIG. 1 is a perspective view showing a super water / water repellent structure according to an embodiment of the present invention.
  • FIG. 2 is a partially enlarged view showing part II of FIG. 1 in detail.
  • FIG. 3 is a cross-sectional view of a cross section of an optional flat surface and sidewall of FIG. 2.
  • FIG. 4 is a flowchart illustrating a method of manufacturing a super water / oil repellent structure according to an embodiment of the present invention.
  • FIG. 5 is a conceptual diagram showing a cross section of the superhydrophilic / superoleophilic structure according to an embodiment of the present invention.
  • 6A and 6B are scanning electron microscope (SEM) images obtained by enlarging the surface of the aluminum substrate immediately after step 2 of Example 1 by about 10,000 times and about 50,000 times, respectively.
  • 7A and 7B are SEM images obtained by enlarging the surface of an aluminum substrate obtained in step 2 of Example 1 with a corrosion time of 6 minutes by about 10,000 times and about 50,000 times, respectively.
  • FIG. 8A-8D are SEM images of about 10,000 times, about 30,000 times, about 100,000 times, and about 300,000 times magnification of the surface of the aluminum substrate immediately after step 3 of Example 1.
  • FIG. 8A-8D are SEM images of about 10,000 times, about 30,000 times, about 100,000 times, and about 300,000 times magnification of the surface of the aluminum substrate immediately after step 3 of Example 1.
  • 9A and 9B are SEM images of about 10,000 times and about 100,000 times magnification of the surface of an aluminum substrate immediately after anodizing, without omitting step 2 of Example 1 according to Comparative Example 1.
  • FIG. 9A and 9B are SEM images of about 10,000 times and about 100,000 times magnification of the surface of an aluminum substrate immediately after anodizing, without omitting step 2 of Example 1 according to Comparative Example 1.
  • FIG. 10 shows planar and lateral images of water, glycerol, ethylene glycol (EG), olive oil, hexadecane, which are in turn placed on the surface of the superhydrophobic / superoil-repellent structure prepared according to Example 1.
  • FIG. 10 shows planar and lateral images of water, glycerol, ethylene glycol (EG), olive oil, hexadecane, which are in turn placed on the surface of the superhydrophobic / superoil-repellent structure prepared according to Example 1.
  • EG ethylene glycol
  • FIG. 11 is a graph showing the results obtained by averaging the contact angles of water, glycerol, ethylene glycol, olive oil, and hexadecane for the specimens prepared in Examples 2 to 5, respectively.
  • 12a to 12f are images showing the step of applying water and olive oil to the surface of the specimen.
  • first and second may be used to describe various components, but the components are not limited by the terms. The terms are used only for the purpose of distinguishing one component from another.
  • first component may be referred to as the second component, and vice versa, the second component may be referred to as the first component.
  • '/' in the description of 'water / oil repellent' and 'super water / oil repellent' means 'and'.
  • 'water / oil repellent' means 'water repellent and oil repellent'
  • 'super water repellent / super oil repellent' means 'super water repellent and super oil repellent'.
  • the present invention provides a roughening primary structure formed on the surface of a metal substrate; Nano-pores formed in the roughening primary structure; And a water / oil repellent layer formed on the surface of the roughening primary structure.
  • FIG. 1 is a perspective view showing a super water-repellent / super-oil-repellent structure 100 according to an embodiment of the present invention
  • Figure 2 is a partial enlarged view showing in detail the portion II of FIG.
  • a super water / oil repellent structure 100 in the form of a pipe is shown.
  • the super water / oil repellent structure 100 is illustrated in the form of a pipe, but is not limited thereto, and may have various shapes such as a plane, a curved surface, a spherical surface, and a combination thereof.
  • the substrate of the super water / oil repellent structure 100 may be a metal such as copper (Cu), titanium (Ti), aluminum (Al), tungsten (W), zinc (Zn), tin (Sn), or the like.
  • the base material is preferably aluminum (Al). However, it is not limited to this.
  • a planar 104 that is substantially parallel to the surface of the super water / oil repellent structure 100 and a sidewall 102 that is substantially perpendicular to the surface may be included.
  • the fact that the side wall 102 and the flat surface 104 are substantially perpendicular does not necessarily mean that there is an angle of 90 ° between them, but rather flat surfaces 104 having different levels. It means that the side wall 102 as a plane connecting therebetween is distinguishably present with the flat surface 104.
  • the plurality of side walls 102 and the flat surface 104 may be continuous along the surface of the super water / oil repellent structure 100 with or without a certain rule.
  • the plurality of side walls 102 and the flat surface 104 do not necessarily need to be formed over the entire surface of the super water / oil repellent structure 100, but only on surfaces where super water / hydrogen performance is required. It may be.
  • the horizontal length of the flat surface 104 may be defined as the distance (W) between two furthest points of the defined edge of the flat surface 104, the range of about 500 nm to about 5 ⁇ m It can have a value.
  • the roughening primary structure 106 may be formed with a plurality of nano-pores (110).
  • the nano pores 110 may have a pore diameter of about 1 nm to about 300 nm, and more preferably may have a pore diameter of about 10 nm to about 50 nm.
  • the diameter of the nano-pores 110 is too large or too small, super water / oil repellent performance may not be expressed.
  • the diameters of the nanopores 110 become excessively large, neighboring pores 110 may merge with each other.
  • the shape of the pores formed in the plane of the pillar (pillar) standing on the plane can have a poor water-repellent / super-oil-repelling performance.
  • the diameters of the nano-pores 110 are too small, the pores contribute to the super water / oil repelling performance is too small, and thus may have insufficient super water / water repellent performance.
  • the nano pores 110 may be defined as a secondary structure of the super water / oil repellent structure 100.
  • the nano pores 110 may extend in a direction substantially perpendicular to the surfaces of the flat surface 104 and the sidewall 102.
  • the meaning that the direction of extension of the nanopores 110 is substantially perpendicular to the surfaces of the flat surface 104 and the sidewall 102 does not mean that the nanopores 110 have an angle of 90 ° therebetween.
  • the water / oil repellent layer 120 is formed on the surfaces of the flat surface 104 and the sidewall 102.
  • the water / oil repellent layer 120 may include fluorine (F), and more specifically, may be a fluorine-containing silane compound or a fluorine-containing thiol compound.
  • a plurality of nano pores 110 are formed on each surface of the substrate 101, and the inlet of the nano pores 110 is opened without being blocked by the water / oil repellent layer 120.
  • the method and material for forming the water / oil repellent layer 120 will be described in more detail in the method for manufacturing the water / oil repellent structure 100.
  • water / oil repellent layer 120 may not be substantially formed in the nanopores 110.
  • FIG. 4 is a flowchart illustrating a method of manufacturing a super water / oil repellent structure 100 according to an embodiment of the present invention.
  • Figure 4 describes a method of manufacturing a super water-repellent / super oil-repellent structure 100 according to an embodiment of the present invention.
  • the metal substrate 101 is etched using an acid to form the roughened primary structure 106 on the metal substrate 101 (S1).
  • the metal substrate 101 may be etched in an acidic solution for about 10 seconds to about 10 minutes, preferably about 1 minute to about 5 minutes.
  • the etching may be performed at room temperature.
  • the etching time is too short or too long, the roughening primary structure 106 having the flat surface 104 and the sidewall 102 may not be formed.
  • the present invention is not limited thereto, and the etching time may be appropriately adjusted in consideration of the kind of the metal material, the kind of the acid, the concentration of the acid solution, and the like.
  • the acid may be any inorganic acid such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, any organic acid such as organic acetic acid, organic sulfonic acid, perfluorinated carboxylic acid, or a mixture of two or more thereof. These acids may be used as they are, or in some cases, diluted with a solvent such as water. When diluting the acid may be appropriately diluted according to the characteristics of each material, for example, in the case of using hydrochloric acid it may be diluted with deionized water in the range of about 1: 1 to about 1: 5, Dilution to about 1: 2 is preferred.
  • hydrochloric acid it may be diluted with deionized water in the range of about 1: 1 to about 1: 5, Dilution to about 1: 2 is preferred.
  • the wet etching using the acid solution is merely immersing the metal substrate 101, a space such as a chamber is not necessarily required, and it may be easily performed even on a large metal substrate.
  • the etched metal substrate 101 may be washed with deionized water (DI water) and then dried at an elevated temperature.
  • DI water deionized water
  • the drying may be performed at a temperature of about 50 ° C. to 200 ° C. for about 5 minutes to 3 hours, but is not limited thereto.
  • the metal substrate 101 is anodized (S2).
  • S2 Methods of anodic oxidation of metal materials are well known to those of ordinary skill in the art.
  • the metal substrate 101 is immersed in a sulfuric acid solution, oxalic acid solution, citric acid solution, sodium nitrate solution, sodium chloride solution, chromic acid solution, or phosphoric acid solution and voltage is applied using the metal substrate 101 as an anode.
  • the voltage may be about 10 V to about 30 V.
  • the anodic oxidation may be performed at room temperature for about 1 minute to about 30 minutes, preferably about 3 minutes to about 25 minutes.
  • the anodic oxidation is merely immersing the metal substrate 101 in the solution, so a space such as a chamber is not necessarily required and can be easily performed on a large metal substrate. .
  • the water / oil repellent layer 120 is formed on the surface of the metal substrate 101 (S3).
  • the water / oil repellent layer 120 serves to modify the surface of the metal substrate 101.
  • the surface of the metal substrate 101 may be fluorinated.
  • the metal substrate 101 may be immersed in a chemical solution for water / oil repellent treatment.
  • the material for forming the water / oil repellent layer 120 may be a fluorine-containing silane compound, a fluorine-containing thiol compound, a fluorine-containing polymer, or the like, but is not limited thereto.
  • the metal substrate 101 may be coated with the materials listed above to form the water / oil repellent layer.
  • the coating method may be spin coating, dip coating, or the like, but is not limited thereto.
  • Non-limiting examples of materials for forming the water / oil repellent layer 120 include compounds of Formula 1 below:
  • R 1 is alkyl fluoride which is-(CH 2 ) p (CF 2 ) m CF 3 , and X is hydrogen; Halogen atoms selected from the group consisting of F, Cl, Br, I; C 1 -C 10 alkoxy group; C 3 -C 8 aromaticalkoxy group; And a C 2 -C 8 heteroaromatic alkoxy group having at least one selected from the group consisting of O, N, S, and P as a hetero element, n is an integer of 1 to 3, p is an integer of 0 to 3, m is an integer of 0-17.
  • non-limiting examples of materials for forming the water / oil repellent layer 120 include the following materials: 1H, 1H-perfluorooctyltrichlorosilane, 1H, 1H-perfluorodecyltrichloro Rosilane, 1H, 1H-perfluorododecyltrichlorosilane, 1H, 1H-perfluorooctyltriethoxysilane, 1H, 1H-perfluorodecyltriethoxysilane, 1H, 1H-perfluorodode Siltriethoxysilane, 1H, 1H-perfluorooctyltrimethoxysilane, 1H, 1H-perfluorodecyltrimethoxysilane, 1H, 1H-perfluorododecyltrimethoxysilane, 1H, 1H- Perfluororododecyltrimethoxysilane, 1H, 1H
  • non-limiting examples of materials for forming the water / oil repellent layer 120 include the following polysiloxane-based materials.
  • the polysiloxane-based material may be linear, branched, or cyclic polydimethylsiloxane;
  • polysiloxanes having hydroxyl groups in the molecular chain silanol-terminated polydimethylsiloxanes, silanol-terminated polydiphenylsiloxanes, diphenylsilanol-terminated polydimethylsiloxanes, carbinol-terminated polydimethylsiloxanes, hydroxys Polysiloxanes such as propyl-terminated polydimethylsiloxane, and polydimethylhydroxyalkylene oxide methylsiloxane; Polysiloxanes having amino groups in the molecular chain as bis (aminopropyldimethyl) siloxanes, aminopropyl-terminated polydimethylsiloxa
  • the metal substrate 101 may be heated to an elevated temperature to fix the water / oil repellent layer 120.
  • it may be heated for 10 minutes to 3 hours at a temperature of about 40 °C to 150 °C.
  • the metal substrate 101 may be cleaned using an organic solvent, deionized water, or the like before the heating.
  • the heating temperature is excessively high, there is a fear that the roughened primary structure and the pore structure (secondary structure) formed on the surface are damaged.
  • the heating temperature is excessively low, the time taken for fixing the water / oil repellent layer 120 may be long.
  • the super water / oil repellent structure described above may be applied to various electronic devices or transportation devices.
  • the electronic device or transportation device may be used in automobile / aircraft / railway / ship interior / exterior, automobile / aircraft / railway / ship or home / business / industrial refrigeration and air conditioning system (air conditioner and heat pump), television, mobile phone, computer system, portable It may be a computer, a monitor, a telephone, a printer, a keyboard, a mouse, a pump, a pipe for transporting fluid, a pipe for transporting powder, a tank for storing fluid for transport, a lighting device, a backlight unit, and the like, but is not limited thereto.
  • mold or harmful substances grow on the surface of water-repellent components by water / oil repellent treatment on the components of domestic / business / industrial refrigeration and air-conditioning systems, including refrigeration and air-conditioning systems for automobiles, aircraft, ships, railways, etc.
  • the surface can be implemented to retard the formation of ice, frost, etc. by utilizing the above water-repellent / oil-repellent properties at sub-zero temperatures, such surfaces are used in automotive, aircraft, railway and home / business / industrial refrigeration air conditioning system (air conditioner and Heat pump) to improve the energy efficiency of the entire system.
  • FIG. 5 is a conceptual view showing a cross-section of the super hydrophilic / superoleophilic structure 200 according to an embodiment of the present invention.
  • the superhydrophilic / superoleophilic structure 200 omits only the treatment of the water / oil repellent layer in the superhydrophobic / superoil repellent structure 100 described above, and thus the flat surface 204 and the substrate 201. It has a roughening primary structure 206 that includes sidewalls 202. In addition, a plurality of pores 210 are formed in the flat surface 204 and the side wall 202, which has been described in detail in the description regarding the super water / oil repellent structure 100. Omit.
  • the horizontal length of the flat surface 204 may be defined as the distance W between two furthest points of the edge of the defined flat surface 204 and may have a value ranging from about 500 nm to about 5 ⁇ m. Can be.
  • the method of manufacturing the superhydrophilic / superoleophilic structure 200 comprises the steps of forming a water / oil repellent layer in the method of manufacturing the superhydrophobic / superhydrophobic structure 100 described with reference to FIG. 4. (S3) may be omitted. That is, in order to form the roughened primary structure 206 on the metal substrate 201, the metal substrate 201 may be etched using an acid, and then the metal substrate 201 may be anodized. The anodic oxidation may be performed at room temperature for about 1 minute to about 30 minutes, preferably about 3 minutes to about 25 minutes.
  • the step of forming a water / oil repellent layer on the surface of the roughened primary structure 206 is omitted, the layer of the fluorine-based compound is not formed on the surface of the roughened primary structure 206.
  • Step 1 Aluminum substrate in planar form (thickness 0.81 mm, Al 95.8-98.6 wt%, Mg 0.8-1.2 wt%, Si 0.4-0.8 wt%, Cr 0.04-0.35 wt%, Cu 0.15-0.4 wt%, Fe 0.7 Wt% max, Zn 0.25 wt% max, Mn 0.15 wt% max, Ti 0.15 wt% max) were ultrasonically rinsed in acetone ethanol and deionized water (DI water) for 3 minutes and dried in a nitrogen atmosphere.
  • DI water deionized water
  • Step 2 The washed aluminum substrate was then etched for 3 minutes by immersion in an acidic solution at room temperature mixed with deionized water and HCl in a volume ratio of 2: 1. The etched aluminum substrate was again washed with deionized water and then dried at a temperature of 120 ° C. for 1 hour.
  • 5A and 5B are scanning electron microscope (SEM) images obtained by magnifying 10,000 times and 50,000 times the surface of an aluminum substrate obtained by etching for 3 minutes, respectively. As shown in FIGS. 5A and 5B, a roughening primary structure having sidewalls and a flat surface was formed.
  • FIGS. 7A and 7B are scanning electron microscope (SEM) images obtained by enlarging the surface of an aluminum substrate obtained by etching for 6 minutes separately from Example 1 by 10,000 times and 50,000 times, respectively. As shown in FIGS. 7A and 7B, a roughening primary structure having colorful sidewalls and flat surfaces was formed.
  • Step 3 The dried aluminum substrate was anodized for 10 minutes while applying a constant voltage of 25 V in a sulfuric acid solution (1M) at 10 ° C. After the anodic oxidation was completed, the aluminum substrate was rinsed with deionized water and dried in air.
  • FIGS. 8A to 8D show SEM images of 10,000, 30,000, 100,000, and 300,000 times magnification of the surface of the aluminum substrate immediately after anodizing for 10 minutes, respectively. As shown in Figure 8a to 8d it could be confirmed that a number of fine pores (pore) are formed.
  • Step 4 Finally, the aluminum substrate thus prepared was immersed in a 1H, 1H, 2H, 2H-perfluorooctyltrichlorosilane solution diluted to 0.5% concentration in n-hexane solvent for 8 minutes. Then, the aluminum substrate was removed from the solution, washed with n-hexane, and then heated by drying for 30 minutes on a hot plate heated to 100 ° C to prepare a super water / oil repellent structure.
  • Example 1 Specimen was prepared in the same manner as in Example 1, except that Step 2 was omitted in Example 1.
  • FIGS. 9A and 9B show SEM images of 10,000 times and 100,000 times magnification of the surface of the aluminum substrate immediately after anodizing for 10 minutes, respectively. As shown in Figure 9a and 9b, it was confirmed that a large number of fine pores (pores) are formed, but the roughening primary structure is not formed.
  • Example 1 Specimen was prepared in the same manner as in Example 1 except that Step 3 was omitted in Example 1.
  • the contact angles of water, glycerol, ethylene glycol, olive oil, and hexadecane were measured for the specimens prepared in Example 1 and Comparative Examples 1 to 3, respectively. 5 ⁇ l of each of the fluids was added dropwise to at least five places on the specimens, and contact angles were measured using a Phoenix 300 Touch device from SEO. The contact angle was a tangent line method, and the optical image of each droplet was a digital camera manufactured by SONY.
  • Example 1 showed significantly better water / oil repellency compared to other structures.
  • the structure of Example 1 has an excellent contact angle of more than 150 degrees for olive oil and hexadecane that does not have remarkable oil repellency.
  • FIG. 10 shows planar and lateral images of water, glycerol, ethylene glycol (EG), olive oil, hexadecane (left to right) disposed sequentially on the surface of the super water / oil repellent structure prepared according to Example 1; .
  • the surface of the super water-repellent / super-oil-repellent structure was found to exhibit super water-repellent / super-oil repellent properties by showing an extremely large contact angle.
  • Example 1 showed significantly better slip properties compared to other structures.
  • the structures of Comparative Examples 1 to 3 were also shown to have very small slip angles of about 5 degrees and about 20 degrees, respectively, for olive oil and hexadecane, which are not significantly oil repellent.
  • Example 1 In addition, in order to determine the effect of the anodic oxidation time on the water / oil repellent properties, the method of Example 1 was followed, but the specimen was prepared by changing the anodic oxidation time as follows.
  • a specimen was prepared in the same manner as in Example 1, except that the anodic oxidation time was 25 minutes.
  • a specimen was prepared in the same manner as in Example 1, except that the anodic oxidation time was 30 minutes.
  • a specimen was prepared in the same manner as in Example 1, except that the anodic oxidation time was 3 minutes.
  • a specimen was prepared in the same manner as in Example 1, except that the anodic oxidation time was 1 minute.
  • a specimen was prepared in the same manner as in Example 1 except that Step 4 was omitted from Example 1.
  • the contact angle was substantially 0 degrees.
  • 12a to 12f are images showing the step of applying water and olive oil to the surface of the specimen.
  • the left side of each figure shows the scene of adding water to the pipette, and the right side shows the scene of adding olive oil to the pipette.
  • droplets of olive oil are being transferred to the specimen surface.
  • the droplets of the olive oil and the pipette are not yet separated in the image to the right of FIG. 12b, so that the contact angle is not a step to discuss.
  • the olive oil droplet is not yet completely separated from the pipette, because the volume flow rate of the liquid supplied to each pipette is slightly different, and the surface energy varies depending on the viscosity of each fluid, etc. The time required to separate from the pipette varies.
  • the water droplets delivered to the specimen surface could be seen to spread out over a larger area and the olive oil droplets were also separated from the pipette. Note that this image looks like a drop of olive oil with a constant contact angle, but it should be noted that the contact angle of olive oil should not be measured from this image because the olive oil is currently spreading.
  • the olive oil spreads wider than in FIG. 12E, and thus the droplet height was considerably lowered.
  • the edges of the olive oil droplets penetrate into the specimen surface without forming a contact angle, the specimen surface was confirmed to be superoleophilic.
  • the present invention can be usefully applied to the electronics industry and the mechanical industry.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrochemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Laminated Bodies (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)

Abstract

La présente invention concerne une structure ultra-hydrofuge et ultra-oléofuge, et un procédé de fabrication de celle-ci, et plus spécifiquement, une structure ultra-hydrofuge et ultra-oléofuge et un procédé de fabrication de celle-ci, la structure comprenant : une première structure de rugosification formée sur la surface d'un substrat métallique ; des nanopores formés sur la première structure de rugosification ; et une couche hydrofuge et oléofuge formée sur la surface de la première structure de rugosification. La structure ultra-hydrofuge et ultra-oléofuge de la présente invention présente des propriétés ultra-hydrofuges et ultra-oléofuges remarquables, présentant un angle de contact extrêmement élevé et un angle de glissement faible par rapport à une solution aqueuse et une solution huileuse. De plus, il est possible de fabriquer aisément une structure de grande taille ou incurvée sans matériel de fabrication spécial en utilisant le procédé pour fabriquer la structure ultra-hydrofuge et ultra-oléofuge de la présente invention.
PCT/KR2014/001036 2013-02-08 2014-02-06 Structure ultra-hydrofuge et oléofuge et procédé de fabrication de celle-ci Ceased WO2014123376A1 (fr)

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KR1020130014570A KR101569460B1 (ko) 2013-02-08 2013-02-08 초발수/초발유 구조물 및 그의 제조 방법
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